JP7156121B2 - Addition-curable silicone adhesive composition - Google Patents

Description

The present invention relates to addition-curable silicone adhesive compositions.

Addition-curing silicone adhesives use a platinum-catalyzed hydrosilylation reaction as a curing mechanism, and generally adhere to a substrate by curing the liquid material in an environment of 100 to 150°C. . However, from the viewpoints of increased costs due to the introduction and operation of heating equipment, deterioration of productivity due to the provision of heating and cooling times, and consideration for the environment, two-part room temperature curing silicone adhesives have been proposed. (See Patent Documents 1 to 7).

In this two-component material, the main agent, platinum catalyst, cross-linking agent, and other components are individually packaged in the form of a first agent and a second agent. By mixing the first agent and the second agent, It has the advantage that it can be rapidly cured and adhered to a substrate even at room temperature.
On the other hand, when such two-liquid materials are stored in the atmosphere, air and moisture enter the first and second parts, resulting in foaming during curing and reduced adhesion to substrates. There is a problem that the phenomenon that the adhesive is degraded is observed, and the reliability as an adhesive is impaired.

JP 2008-169386 A JP 2009-221312 A JP 2009-292901 A Japanese Patent Publication No. 2010-539308 JP 2012-117059 A JP 2013-018850 A JP 2013-60493 A

The present invention has been made in view of the above circumstances, and after mixing, it cures quickly at room temperature to exhibit adhesion to substrates such as metals and resins, and can be stored for a long time in the state before mixing. It is an object of the present invention to provide an addition-curable silicone adhesive composition that suppresses foaming during curing even after curing and that does not deteriorate in adhesion to substrates.

As a result of intensive studies to solve the above problems, the present inventors have carefully examined the structure of the cross-linking agent to be used, further reduced the ratio of Si—H groups used to alkenyl groups, and used one molecule as an adhesiveness imparting agent. The present inventors have found that by adding a silane compound or a siloxane compound having an alkenyl group and a trialkoxy group therein, it is possible to suppress foaming during curing and a decrease in adhesion to the substrate over time, and completed the present invention.

That is, the present invention
1. (A) at least one of (i) and (ii) below;
(i) Linear organopolysiloxane R ² R ¹² SiO ₍ R ¹² SiO) _m SiR ₁₂ R having ^a viscosity of 50 to 10,000,000 mPa·s at 23° C., represented by the following formula (1 ₎ : ² (1)
(wherein each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, R ² represents an alkenyl group, and m is Represents an integer from 1 to 10,000.)
(ii) Organopolysiloxane represented by the following average formula (2) (R ¹³ SiO _1/2 ) _p (R ² _a R ¹³ _-a SiO _1/2 ) _q (SiO _4/2 ) _r ( ₂ )
(wherein each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, R ² represents an alkenyl group, p, q and r represents a number that satisfies p>0, q>0, r>0 and (p+q+r)=1, and a represents 1 or 2.)
(B) an organohydrogenpolysiloxane represented by the following average formula (3);
(H _b R ¹³ _-b SiO _1/2 ) _s (R ¹³ SiO _1/2 ) _{2 - s} (HR ¹¹ SiO _2/2 ) _t (R ¹² _{SiO 2/2 ) u} (3)
(Wherein, each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, b represents 1 or 2, s, t and u represents a number that satisfies 0≦s≦2, 2≦s+t, 2≦t+u≦800, and 0.05≦t/(t+u)≦0.5.)
(C) a hydrosilylation reaction catalyst, and (D) a silane compound or siloxane compound having one or more addition-reactive carbon-carbon unsaturated bonds in one molecule and a trialkoxysilyl group: (A) Containing 0.05 to 5 parts by mass per 100 parts by mass of the total of component and (B), the alkenyl group in component (A) and the addition-reactive carbon-carbon unsaturated bond in component (D) addition-curable silicone adhesive composition, wherein the ratio of the total number of Si—H groups including Si—H groups in component (B) to the total number of
2. The silicone adhesive composition of 1, wherein the component (D) is a silane compound or a siloxane compound represented by the following formula (4);
R ³ --(Me ₂ SiO) _v --Si(OR ¹ ) ₃ (4)
(In the formula, each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, and v is an integer satisfying 0 ≤ v ≤ 4. and R ³ represents an olefin group having a terminal alkenyl structure and having 6 or more carbon atoms when v=0, and a vinyl group when v=1 to 4.)
3. (E) an adhesion promoter (excluding the above (D) component) containing 0.05 to 10 parts by mass with respect to the total 100 parts by mass of the (A) component and the (B) component; ) The ratio of the total number of Si—H groups in the components (B) and (E) to the total number of addition reactive carbon-carbon unsaturated bonds in the component (D) and the alkenyl groups in the component is 0 .8 to 1.5 silicone adhesive composition of 1 or 2;
4. A two-component addition-curable silicone adhesive composition comprising a first component containing the components (A) and (C) and not containing the component (B); The addition-curable silicone adhesive composition of any one of 1 to 3, comprising a second agent containing component (B) and not containing component (C);
5. Provided is an article having an adhesive layer formed by curing the addition-curable silicone adhesive composition of any one of 1 to 4.

Since the addition-curable silicone adhesive composition of the present invention cures and adheres to substrates even at room temperature, it does not require a heating furnace or accompanying exhaust equipment. In addition, since it is excellent in resistance to foaming and deterioration in adhesiveness over time, further improvement in mass productivity and yield can be expected.
The addition-curable silicone adhesive composition of the present invention having such properties can be used as a general-purpose adhesive in a wide range of fields such as automotive applications and electrical and electronic applications, as well as sealing materials, gasket materials, coating materials and potting materials. can also be used as

The present invention will be specifically described below.
[1] Component (A) The organopolysiloxane of component (A) in the addition-curable silicone adhesive composition of the present invention has (i) a viscosity at 23° C. of 50 to 10, represented by the following formula (1): 000,000 mPa·s linear organopolysiloxane and (ii) at least one of organopolysiloxane represented by the following average formula (2).

_R2R12SiO ^{( R12SiO )} _{m SiR12R2} ^{( 1} ₎
(R ¹³ SiO _1/2 ) _p (R ² _a R ¹³ _-a SiO _1/2 ) _q (SiO _4/2 ) _r ( ₂ )

In the above formulas, each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, and R ² represents an alkenyl group.
The monovalent hydrocarbon group for R ¹ is not particularly limited as long as it does not have an addition-reactive carbon-carbon unsaturated bond, and may be linear, branched or cyclic. are preferred, those having 1 to 10 carbon atoms are more preferred, and those having 1 to 5 carbon atoms are even more preferred.
Specific examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and n-hexyl groups; cyclic alkyl groups such as cyclohexyl groups; phenyl and tolyl groups. aryl groups such as benzyl; and aralkyl groups such as benzyl and phenylethyl groups.
Further, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as F, Cl, and Br, cyano groups, etc. Specific examples of such groups include Halogen-substituted hydrocarbon groups such as 3,3,3-trifluoropropyl group; cyano-substituted hydrocarbon groups such as 2-cyanoethyl group;
Among these, in both Formula (1) and Formula (2), R ¹ is preferably a methyl group from the viewpoint of heat resistance.

The alkenyl group represented by R ² is not particularly limited and may be linear, branched or cyclic, but preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. are more preferred, and those having 2 to 6 carbon atoms are even more preferred.
Specific examples thereof include vinyl, allyl, butenyl, pentenyl and hexenyl groups, and vinyl groups are preferred.

In the above formula (1), m represents an integer of 1 to 10,000, preferably an integer of 100 to 1,000. If m is 0, it is likely to volatilize in an atmospheric pressure environment or a reduced pressure environment during defoaming. It becomes difficult to mix uniformly.
In the above formula (2), p, q, and r represent numbers satisfying p>0, q>0, r>0 and (p+q+r)=1, and a represents 1 or 2.

The viscosity of component (i) at 23° C. is 50 to 10,000,000 mPa·s, preferably 1,000 to 100,000 mPa·s. If the viscosity is less than 50 mPa·s, it is likely to volatilize in an atmospheric pressure environment or a reduced pressure environment during defoaming. It becomes difficult to mix uniformly with the ingredients of In addition, the viscosity is a measured value using a rotational viscometer.
In addition, the component (i) preferably has a weight average molecular weight (Mw) of 500 to 500,000 in terms of standard polystyrene measured by GPC (gel permeation chromatography) using a THF solvent, preferably 1,000 to 100, 000 is more preferred.

Component (i) is preferably an organopolysiloxane represented by the following formula (1-1).
ViMe ₂ SiO(SiMe ₂ O) _m SiMe ₂ Vi (1-1)
(In the formula, Me means a methyl group, Vi means a vinyl group (the same applies hereinafter). m has the same meaning as above.)
Specific examples of component (i) include, but are not limited to, organopolysiloxanes represented by the following formulas.
_{ViMe2SiO ( Me2SiO} ) _{530SiMe2Vi
ViMe2SiO ( Me2SiO} ) _430SiMe2Vi
In addition, (i) component may be used individually by 1 type, or may be used in combination of 2 or more type.

The ratio (p+q)/r of M units to Q units in component (ii) is preferably 0.3 to 2.0, more preferably 0.5 to 1.0.
The weight average molecular weight of component (ii) is preferably 1,000 to 50,000, more preferably 2,000 to 10,000.

As the component (ii), those represented by the following average formula are preferable.
(Me3SiO1/ ₂ ) _p ( _{ViMe2SiO1 /2 ) q} ( _SiO4/2 ) _r
(Wherein, p, q and r have the same meanings as above.)
Specific examples of component (ii) include, but are not limited to, organopolysiloxanes represented by the following average formula.
(Me3SiO1/ ₂ ) _0.39 ( _{ViMe2SiO1 /2 ) 0.07} ( _SiO4/2 ) _0.54
(In the formula, Me and Vi have the same meanings as above.)
In addition, (ii) component may be used individually by 1 type, or may be used in combination of 2 or more type.

As the component (A), the compounding ratio when the component (i) and the component (ii) are used in combination is not particularly limited, but [(i) component]/[(ii) component] (mass ratio ) is preferably 0.3 to 10, more preferably 0.5 to 3.
The viscosity of the mixture of components (i) and (ii) at 23° C. is preferably 1 to 100,000 mPa·s, more preferably 5 to 10,000 mPa·s. If the viscosity is within this range, fluidity is high and handling is easy.
In addition, since the component (ii) may become solid at 23° C., it may be used by dissolving it in the component (i).

[2] Component (B) Component (B) in the addition-curable silicone adhesive composition of the present invention is an organohydrogenpolysiloxane represented by the following average formula (3).
(H _b R ¹³ _-b SiO _1/2 ) _s (R ¹³ SiO _1/2 ) _{2 - s} (HR ¹¹ SiO _2/2 ) _t (R ¹² _{SiO 2/2 ) u} (3)

Examples of the monovalent hydrocarbon group for R ¹ in formula (3) include the same groups as those exemplified for the component (A) above, but a methyl group is preferred.
b represents 1 or 2, preferably 1;
s is a number that satisfies 0≤s≤2, preferably 2.
Although s+t is 2 or more, 3 or more is preferable.
t and u are numbers satisfying 2≦t+u≦800, but preferably numbers satisfying 2≦t+u≦300. Further, t/(t+u) is a number that satisfies 0.05≦t/(t+u)≦0.5, but preferably a number that satisfies 0.15≦t/(t+u)≦0.3.

In the above formula (3), when t+u is less than 2, three-dimensional cross-linking cannot be formed, or the silicone cured product is very soft and low in strength, and satisfactory rubber physical properties cannot be obtained, and t+u exceeds 800. As a result, the component (B) becomes highly viscous, making it difficult to uniformly mix it with the other components. Also, if t/(t+u) is less than 0.05, the cured silicone product will be very soft and low in strength, and satisfactory rubber physical properties cannot be obtained.

The kinematic viscosity of component (B) at 25° C. is not particularly limited, but is preferably 0.5 to 20,000 mm ² /s, more preferably 1 to 500 mm ² /s. Here, the kinematic viscosity is a value measured using a Canon Fenske viscometer.
The weight average molecular weight of component (B) is preferably 600 to 60,000, more preferably 1,000 to 10,000.
Specific examples of component (B) include, but are not limited to, organohydrogenpolysiloxanes represented by the following average formula.
In addition, (B) component may be used individually by 1 type, or may be used in combination of 2 or more type.

（左式において、シロキサン単位の配列順は任意である。）

(In the left formula, the siloxane units can be arranged in any order.)

The blending amount of component (B) is preferably 1 to 200 parts by mass, more preferably 2 to 50 parts by mass, per 100 parts by mass of component (A). With such a blending amount, sufficient hardness and strength can be obtained when the silicone adhesive composition is cured.
Also, the number of all Si—H groups including Si—H groups in component (B) with respect to the number of alkenyl groups in component (A) and component (D) described later (number of Si—H groups in component (B) number, or when the (E) component described later is included, the ratio of the total number of Si—H groups in the (B) component and the Si—H groups in the (E) component) is [Si—H group]/ [Alkenyl group and addition reactive carbon-carbon unsaturated bond]=0.8 to 1.5, preferably 1 to 1.3. Within such a range, good curability can be obtained, and foaming during curing can be suppressed.

[3] Component (C) Component (C) in the addition-curable silicone adhesive composition of the present invention comprises the alkenyl group in component (A) above and addition-reactive carbon-carbon in component (D) described below. It is a hydrosilylation reaction catalyst for promoting the addition reaction between the unsaturated bond and the Si—H groups in component (B) and component (E) described later.
Specific examples thereof include simple platinum group _metals such as _{platinum (} including _{platinum black} ), _rhodium , and _{palladium ; 6.nH2O} , _{Na2PtCl6.nH2O} , _{K2PtCl4.nH2O , PtCl4.nH2O , PtCl2 , Na2HPtCl4.nH2O ( wherein n} is ₀ to platinum chloride, chloroplatinic acid and chloroplatinates such as an integer of 6, preferably 0 or 6; alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972); Complexes of platinic acid and olefins (see U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum black, palladium, etc. A platinum group metal supported on a carrier such as alumina, silica, carbon; rhodium-olefin complex; chlorotris(triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group Platinum group metal-based catalysts such as complexes with containing siloxanes are included.
In addition, (C)component may be used individually by 1 type, or may be used in combination of 2 or more type.

The amount of (C) used is not limited as long as it promotes the curing (hydrosilylation reaction) of the composition. is preferably in the range of 0.01 to 500 ppm, more preferably in the range of 0.05 to 100 ppm, and even more preferably in the range of 0.01 to 50 ppm.

[4] Component (D) Component (D) in the addition-curable silicone adhesive composition of the present invention has at least one addition-reactive carbon-carbon unsaturated bond per molecule and is a trialkoxy It is a silane compound or siloxane compound having a silyl group, and is an adhesion assistant for imparting adhesion to substrates to the addition-curable silicone adhesive composition of the present invention.
It is particularly effective for adhesion to metal, and excess Si—H groups in the composition are consumed by the hydrosilylation reaction with the addition reactive carbon-carbon unsaturated bond contained in this component, It also has the function of suppressing foaming of the cured product over time.

In the present invention, component (D) is preferably a silane compound or a siloxane compound represented by the following formula (4).
R ³ --(Me ₂ SiO) _v --Si(OR ¹ ) ₃ (4)

In formula (3), R ¹ has the same meaning as above, but is preferably a methyl group.
v is an integer satisfying 0≤v≤4; when v=0, R ³ represents an olefinic group having a terminal alkenyl structure and having 6 or more carbon atoms; when v=1 to 4, R ³ represents a vinyl group. Preferred olefinyl groups include 5-hexenyl, 6-heptenyl, 7-octenyl, 8-nonenyl and 9-decenyl groups.

Specific examples of component (D) include vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003), vinyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-1003), and 7-octenyl. trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1083), p-styryltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1403), compounds represented by the following structural formulas, and the like.
In addition, (D) component may be used individually by 1 type, or may be used in combination of 2 or more type.

Component (D) is added in an amount of 0.05 to 5 parts by mass per 100 parts by mass of components (A) and (B). If the amount added is less than 0.05 parts by mass, foaming may occur during curing and adhesion may be insufficient. As a result, satisfactory rubber physical properties may not be obtained.

[5] Component (E) To the addition-curable silicone adhesive composition of the present invention, an adhesion aid other than component (D) may be added as component (E).
Among component (E), specific examples of adhesion promoters containing siloxane bonds include γ-(glycidyloxypropyl)trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403), γ-(methacryloxy propyl)trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503), hydrolysates thereof, compounds represented by the following structural formulas, and the like.
In addition, (E) component may be used individually by 1 type, or may be used in combination of 2 or more type.

Further, specific examples of adhesion promoters that do not contain siloxane bonds include allyl glycidyl ether, vinylcyclohexene monoxide, diethyl 2-allylmalonate, diallyl bisphenol ether, allyl benzoate, diallyl phthalate, tetraallyl pyromellitic acid ester ( Fuji Film Wako Pure Chemical Industries, Ltd., TRIAM805), triallyl isocyanurate, and the like.

When component (E) is used, the amount added is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to the total of 100 parts by mass of components (A) and (B). preferable. If the blending amount of the component (E) is within the above range, appropriate adhesiveness can be imparted.

[6] Component (F) The photocurable silicone adhesive composition of the present invention may be thickened or gelled prior to heat curing, such as when the composition is prepared or when the composition is applied to a substrate. For the purpose of controlling the reactivity of the hydrosilylation reaction catalyst so as not to cause the (F) reaction control agent may be added as necessary.
Specific examples of reaction control agents include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl cyclohexanol, ethynylmethyldecylcarbinol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and the like can be mentioned, and these may be used alone or in combination of two or more.
Among these, 1-ethynylcyclohexanol, ethynylmethyldecylcarbinol, and 3-methyl-1-butyn-3-ol are preferred.

When component (F) is used, the amount added is preferably 0.01 to 2.0 parts by mass, preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of components (A) and (B) combined. part is more preferred. Within such a range, the effect of reaction control is sufficiently exhibited.

[7] Other Components In addition to components (A) to (F) above, the addition-curable silicone adhesive composition of the present invention may contain other components as exemplified below, as long as the objects of the present invention are not compromised. You may
Other components include, for example, thixotropic agents such as fumed silica; reinforcing agents such as fumed silica and crystalline silica; heat resistance improvers such as metal oxides and metal hydroxides; light stabilizers; thermal conductivity-enhancing fillers such as alumina and crystalline silica; and viscosity modifiers such as non-reactive silicone oils having no reactive functional groups.

The addition-curable silicone adhesive composition of the present invention is prepared by mixing the above components (A) to (D), optional components (E) and (F), and other components by a known method. can be prepared by
As a preferred embodiment, the first agent comprising (A) component, (C) component and optionally other components, and the (A) component, (B) component and optionally other components comprising the first agent It is a two-part composition in which two parts are prepared separately and the first part and the second part are mixed before use. In addition, there may be a component commonly used in the first agent and the second agent. Storage stability can be further ensured by making the composition into such a two-pack type.

The mixing ratio of the first agent and the second agent at the time of use is determined based on the formulation design of the above components, and any mixing ratio can be set so that the silicone adhesive composition of the present invention is obtained after mixing. In particular, from the viewpoint of ease of mixing, the mixing ratio (volume ratio) of the first agent and the second agent is preferably set in the range of the first agent: the second agent = 10: 1 to 1: 10. It is more preferable to set the ratio of the first agent to the second agent in the range of 2:1 to 1:2.

Mixing of the first agent and the second agent may be carried out by weighing the respective liquids and then mixing them with a mixer or the like. It may be mechanically fed from and mixed in a mixer.
Examples of packaging containers include resin double cartridges manufactured by MIX-PAC, resin cartridges manufactured by Shirouma Science, and resin syringes manufactured by Musashi Engineering. Examples of the dispenser include a Heishinsotsu Co., Ltd. Heno dispenser, a Musashi Engineering Co., Ltd. two-liquid mixing type dispenser, and a Naka Liquid Control Co., Ltd. two-liquid mixing type dispenser.

The addition-curable silicone adhesive composition of the present invention cures and adheres to substrates even at room temperature (5 to 35° C.), so it does not require a heating furnace or associated exhaust equipment.
The composition of the present invention can also be cured by heating, and this method is effective when it is desired to improve mass productivity. At this time, a sufficient effect can be obtained even with a small device for local heating.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the following examples, the viscosity is the value at 23°C measured with a rotational viscometer, and the kinematic viscosity is the value at 23°C using a Canon-Fenske viscometer. Moreover, the weight average molecular weight is a standard polystyrene conversion value obtained by GPC measurement using a THF solvent.

[Examples 1 to 3, Comparative Examples 1 and 2]
A two-component silicone adhesive composition was prepared by mixing the following components at the compounding ratio shown in Table 1. Specifically, (Ai-2) and (A-ii) are first mixed, and (Ai-1), (C), and fumed silica are mixed and defoamed in the resulting mixture. The first agent, (Ai-1), (Ai-2), (B), (D), (E), (F), and fumed silica are mixed and defoamed. Each agent was prepared.

(A) Component:
(Ai-1) Organopolysiloxane represented by the following average formula (viscosity at 23° C.: 10,000 mPa·s)
_{ViMe2SiO ( Me2SiO} ) _530SiMe2Vi
(Ai-2) Organopolysiloxane represented by the following average formula (viscosity at 23° C.: 5,000 mPa·s)
_{ViMe2SiO ( Me2SiO} ) _430SiMe2Vi
(A-ii): Organopolysiloxane having a weight average molecular weight of 4,500 represented by the following average formula (Me ₃ SiO _1/2 ) _0.39 (ViMe ₂ SiO _1/2 ) _0.07 (SiO _4/2 ) _0.54

(B) Component:
(B-1) A dimethylsiloxane-methylhydrogensiloxane copolymer with trimethylsiloxy group-blocked dimethylsiloxane at both molecular chain ends represented by the following average formula (kinematic viscosity at 23°C: 99.0 mm ² /s, containing silicon-bonded hydrogen atoms amount = 0.0037 mol/g)

（式中、シロキサン単位の配列はランダムまたはブロックである。）

(Wherein, the arrangement of siloxane units is random or block.)

(B-2) Methylhydrogensiloxane endblocked with trimethylsiloxy groups at both molecular chain ends represented by the following average formula (viscosity at 23° C.: 4.5 mm ² /s, content of silicon-bonded hydrogen atoms=0.0145 mol/g )

(C) Component:
(C-1) Dimethylsiloxane solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 1.0% by mass)

(D) Component:
(D-1) 7-octenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1083)
(D-2) p-styryltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1403)
(D-3) Silicone oligomer represented by the following structural formula

(E) Component: Adhesive Aid (E-1) A compound represented by the following structural formula

(E-2) a compound represented by the following structural formula

Component (F): reaction control agent (F-1) ethynylmethyldecylcarbinol

Other Ingredients:
Fumed silica (Nippon Aerosil Co., Ltd., Aerosil NSX-200, specific surface area 140 m ² /g, average primary particle diameter 8 nm)

The foamability and adhesiveness of the addition-curable silicone adhesive compositions prepared in the above examples and comparative examples were evaluated by the following methods. Table 2 shows the results.
[Method for Mixing and Discharging Addition Curing Silicone Adhesive Composition]
A static nozzle (21 steps) was attached to the tip of a resin double cartridge made by MIX-PAC Co., Ltd. filled with an addition-curing silicone adhesive composition, and a cartridge gun was used to apply the first agent and the second agent at a ratio of 1:1. Discharge was performed while mixing by volume.

[Foamability test]
Using the mixing and discharging method described above, 0.3 to 0.4 g of the addition-curable silicone adhesive composition prepared in each of the above examples and comparative examples was applied onto a glass slide, and an Al plate spacer was used to attach the adhesive. The other slide glass was laminated so that the thickness was 1 mm, and the laminated product was allowed to stand in an environment of 21° C. to 25° C. and 50% RH for 24 hours to cure the addition-curable silicone adhesive composition. At that time, the presence or absence of foaming in the cured product was visually observed.
The double cartridge filled with the addition-curable silicone adhesive composition was allowed to stand in an environment with a humidity of 85% RH and a temperature of 30°C, and the period until foaming occurred in the cured product was evaluated by the observation method described above. did.

[Adhesion test]
A polybutylene terephthalate (PBT) plate and an aluminum die-cast (ADC12) plate were used as adherends, and the adhesion of the addition-curable silicone adhesive compositions prepared in the above examples and comparative examples to each was evaluated. The addition-curable silicone adhesive composition is mixed and applied onto the adherend using the mixing and discharging method described above, and allowed to stand in an environment of 21° C. to 25° C. and 50% RH for 24 hours to effect addition-curable silicone adhesion. The agent composition was cured. The resulting cured product was cut with a razor blade, and the state (peeling or adhesion) when manually pulled in a 90° direction was evaluated in an environment of 21°C to 25°C.
The double cartridge filled with the addition-curable silicone adhesive composition was stored for one week in an environment of 85% RH and 30°C humidity immediately after preparation, and then stored for 1 week in an environment of 85% RH and 30°C humidity. Adhesiveness tests were conducted after each month of storage.

As shown in Table 2, the addition-curable silicone adhesive compositions of the present invention prepared in Examples 1 and 2 can suppress foaming during curing even after long-term storage, and adhere to substrates. It is also found to be superior in terms of sex.
On the other hand, the compositions of Comparative Examples 1 and 2, which do not contain the component (D) of the present invention, have a short storage period until foaming occurs during curing, and are inferior in adhesion to the substrate after long-term storage. I understand.

Claims (4)

(A) at least one of (i) and (ii) below;
(i) Linear organopolysiloxane R ² R ¹² SiO ₍ R ¹² SiO) _m SiR ₁₂ R having ^a viscosity of 50 to 10,000,000 mPa·s at 23° C., represented by the following formula (1 ₎ : ² (1)
(wherein each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, R ² represents an alkenyl group, and m is Represents an integer from 1 to 10,000.)
(ii) Organopolysiloxane represented by the following average formula (2) (R ¹³ SiO _1/2 ) _p (R ² _a R ¹³ _-a SiO _1/2 ) _q (SiO _4/2 ) _r ( ₂ )
(wherein each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, R ² represents an alkenyl group, p, q and r represents a number that satisfies p>0, q>0, r>0 and (p+q+r)=1, and a represents 1 or 2.)
(B) an organohydrogenpolysiloxane represented by the following average formula (3);
(H _b R ¹³ _-b SiO _1/2 ) _s (R ¹³ SiO _1/2 ) _{2 - s} (HR ¹¹ SiO _2/2 ) _t (R ¹² _{SiO 2/2 ) u} (3)
(Wherein, each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, b represents 1 or 2, s, t and u represents a number that satisfies 0≦s≦2, 2≦s+t, 2≦t+u≦800, and 0.05≦t/(t+u)≦0.5.)
(C) a hydrosilylation reaction catalyst, and (D) a silane compound or siloxane compound having one or more addition-reactive carbon-carbon unsaturated bonds in one molecule and a trialkoxysilyl group: (A) Containing 0.05 to 5 parts by mass per 100 parts by mass of the total of component and (B), the alkenyl group in component (A) and the addition-reactive carbon-carbon unsaturated bond in component (D) The ratio of the total number of Si—H groups including the Si—H groups of component (B) to the total number of is 0.8 to 1.5 ,
The (D) component is represented by the following formula (4)
R ³ --(Me ₂ SiO) _v --Si(OR ¹ ) ₃ (4)
(In the formula, each R ¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon unsaturated bond, and v is an integer satisfying 0 ≤ v ≤ 4. and R ³ represents an olefin group having a terminal alkenyl structure and having 6 or more carbon atoms when v=0, and a vinyl group when v=1 to 4.)
An addition-curable silicone adhesive composition that is a silane compound or a siloxane compound represented by (E) an adhesion promoter (excluding the above (D) component) containing 0.05 to 10 parts by mass with respect to the total 100 parts by mass of the (A) component and the (B) component; ) The ratio of the total number of Si—H groups in the components (B) and (E) to the total number of addition reactive carbon-carbon unsaturated bonds in the component (D) and the alkenyl groups in the component is 0 .8 to 1.5, the silicone adhesive composition according to claim 1 . A two-component addition-curable silicone adhesive composition comprising a first component containing the components (A) and (C) and not containing the component (B); 3. The addition-curable silicone adhesive composition according to claim 1 or 2 , comprising a second agent containing component (B) and not containing component (C). An article having an adhesive layer formed by curing the addition-curable silicone adhesive composition according to any one of claims 1 to 3 .