JP2007161999A - Addition curing silicone composition for cipg yielding cured product with excellent compression set characteristics and method of reducing compression set of cured product from the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an addition curing silicone composition for CIPG which yields a cured product with particularly excellent compression set characteristics, and exhibits excellent storage stability, curing stability (the curability after storage) and adhesion; and to provide a method of reducing compression set of a cured product containing the composition. <P>SOLUTION: The addition curing silicone composition for CIPG comprises (A) 100 parts by mass of an organopolysiloxane containing at least two alkenyl groups bonded to a silicon atom in one molecule thereof; (B) an organohydrogenpolysiloxane in a sufficient quantity to provide from 0.4 to 10.0 moles of hydrogen atoms bonded to a silicon atom in this component (B) for every 1 mole of alkenyl groups bonded to silicon atoms within the entire composition; (C) an effective quantity of a platinum group metal-based catalyst; (D) a curing retarder; and (E) an inorganic acid-receiving agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention provides a cured product particularly excellent in compression set characteristics, and an addition-curable silicone composition for CIPG (Cured In Place Gasket) that is suitably used for sealing electronic parts and structural parts, and the composition of the composition The present invention relates to a method for reducing compression set of a cured product.

  In order to apply liquid silicone rubber having excellent heat resistance, environmental resistance and workability as a material for CIPG, studies have been made for improving the compression set characteristics of curable silicone resins. For example, an addition curable silicone rubber composition containing alkyl titanate (Patent Document 1), an addition curable silicone rubber composition containing cerium hydroxide (Patent Document 2), and a curing containing a salt of a cationic organic nitrogen compound Type silicone rubber composition (Patent Document 3) and the like are known. Conventionally, curable silicone adhesive compositions for sealing electronic parts and structural parts have been studied and put on the market.

  However, these compositions have problems in developing stable compression set characteristics, and are compatible with techniques for obtaining adhesion to some parts and one-pack technologies (storability improving techniques). Is difficult. In particular, alkyl titanate and cerium hydroxide promote the deterioration of hydrogen siloxane, which is a cross-linking agent, and salts of cationic organic nitrogen compounds cause deactivation of platinum group metal compounds, which are curing catalysts. May adversely affect the curability of the mold silicone composition.

Therefore, it has been desired to develop a material that gives a cured product having excellent compression set characteristics and also has excellent workability and, if desired, adhesion.
Japanese Patent No. 3537845 Japanese Patent No. 2680174 Japanese Patent Laid-Open No. 11-246766

  The present invention has been made in view of the above circumstances, and provides a cured product that is particularly excellent in compression set characteristics, and is an additive for CIPG that is excellent in storage stability, curing stability (curability after storage) and, if desired, adhesiveness. It is an object of the present invention to provide a curable silicone composition and a method for reducing compression set of a cured product of the composition.

As a result of intensive studies to achieve the above object, the present inventor found that the acid component remaining after the synthesis of the organohydrogenpolysiloxane and mixed into the addition-curable silicone composition is a permanent compression of the cured product of the composition. It was found that the distortion characteristics are adversely affected. Organohydrogenpolysiloxanes are generally synthesized using acids such as sulfuric acid or sulfonic acids (for example, methanesulfonic acid) and are neutralized during the production process. And removal is difficult. The present inventor has found that capturing an acid component with an inorganic acid acceptor in an addition-curable silicone composition is an effective means for improving the compression set characteristics of the cured product, and It has been reached. That is, the present invention
(A) The following average composition formula (1):
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, R ² is independently an alkenyl group, a is a number from 1.0 to 2.2, b is a number from 0.0001 to 0.5, where a + b is a number from 1.5 to 2.7.)
100 parts by mass of an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule,
(B) The following average composition formula (2):
R ³ _c H _d SiO _{(4-cd) / 2} (2)
Wherein R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, c is a number from 0.7 to 2.1, d is a number from 0.001 to 1.2, However, c + d is a number from 0.8 to 3.0.)
The amount of hydrogen atoms bonded to silicon atoms in the component (B) is 0.4 to 10.0 mol per 1 mol of alkenyl groups bonded to silicon atoms in the whole composition,
(C) an effective amount of a platinum group metal catalyst,
There is provided an addition curable silicone composition for CIPG, comprising (D) a curing control agent, and (E) an inorganic acid acceptor.
Secondly, the present invention is a method for reducing compression set of a cured product of an addition-curable silicone composition containing the components (A) to (D),
There is provided a method comprising preparing a composition containing the components (A) to (E), and curing the composition containing the components (A) to (E) at room temperature or under heating. .
In one embodiment of the method, the composition containing the components (A) to (E) is typically added to the addition-curable silicone composition containing the components (A) to (D). It is prepared by blending (E).
Thirdly, the present invention provides a cured product obtained by curing the composition.
Fourthly, the present invention provides a sealing material comprising the composition.
Fifth, the present invention is a method of sealing a substrate with a cured product of the composition,
Applying the composition to the substrate; and sealing the substrate with the cured product by curing the composition to form the cured product on the substrate. provide. Examples of the substrate include electronic parts and structural parts.

  The addition curable silicone composition for CIPG of the present invention gives a cured product (silicone rubber elastic body) particularly excellent in compression set characteristics, and also has excellent storage stability, curing stability and, if desired, adhesion. It can be suitably used for sealing electronic parts and structural parts.

  Hereinafter, the present invention will be described in detail. In the present specification, the viscosity is a value at 25 ° C.

[(A) component]
(A) component is the following average composition formula (1):
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, R ² is independently an alkenyl group, a is a number from 1.0 to 2.2, b is a number from 0.0001 to 0.5, where a + b is a number from 1.5 to 2.7.)
And an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule. This alkenyl group may be bonded to the silicon atom at the end of the molecular chain, or bonded to the silicon atom at the non-terminal end of the molecular chain (that is, in the middle of the molecular chain). A linear diorganopolysiloxane bonded to at least silicon atoms at both ends of the molecular chain may be preferable. The component (A) can be used alone or in combination of two or more. The molecular structure of the component (A) is not particularly limited and may be any of linear, branched, cyclic and network, but usually the main chain is a dimethylsiloxane unit, a vinylmethylsiloxane unit, a diphenylsiloxane unit. , Consisting of repeating diorganosiloxane units such as methylphenylsiloxane units, both ends of which are trimethylsiloxy group, vinyldimethylsiloxy group, divinylmethylsiloxy group, trivinylsiloxy group, vinyldiphenylsiloxy group, phenyldimethylsiloxy group, vinylmethyl A linear diorganopolysiloxane blocked with a triorganosiloxy group such as a phenylsiloxy group is preferred. The component (A) may be a polymer composed of a single siloxane unit or a copolymer composed of two or more siloxane units. Preferably, a is 1.5 to 2.0, b is 0.001 to 0.2, a + b is a positive number of 1.9 to 2.1, more preferably, a is 1.8 to 2.0, b is 0.001 to 0.1, and a + b is a positive number of 1.95 to 2.04.

Examples of R ¹ include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group; and a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; or a part or all of hydrogen atoms of these hydrocarbon groups are fluorine atoms, Groups substituted with a chlorine atom, a nitrile group, etc., for example, a trifluoropropyl group, a chloromethyl group, a cyanoethyl group and the like can be mentioned. R ¹ may be the same or different from each other. Among the components (A), those in which all R ¹ are methyl groups are preferred from the viewpoint of chemical stability and ease of synthesis. In this case, a part of the methyl group may be substituted with a phenyl group or a trifluoropropyl group as necessary.

Examples of R ² include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, and a pentenyl group. R ² is preferably a vinyl group or an allyl group. Among the components (A), those in which all of R ² are vinyl groups are most preferable from the viewpoint of easy synthesis and chemical stability.

  The viscosity of organopolysiloxane (A) is preferably in the range of 10 to 500,000 mPa · s, more preferably in the range of 50 to 500,000 mPa · s. When the viscosity is within this range, it is preferable in the following points. Before curing, the viscosity of the composition can be kept low enough to ensure sufficient workability. Since the cured product can be sufficiently prevented from becoming brittle after curing, the cured product can be more easily deformed along with the deformation of the substrate. In addition, as (A) component, as long as the viscosity after mixing is in the said range, you may use it combining 2 or more types of organopolysiloxane.

[(B) component]
The component (B) has the following average composition formula (2):
R ³ _c H _d SiO _{(4-cd) / 2} (2)
Wherein R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, c is a number from 0.7 to 2.1, d is a number from 0.001 to 1.2, However, c + d is a number from 0.8 to 3.0.)
It is organohydrogen polysiloxane shown by these. Preferably, c is a positive number of 0.9 to 2.0, d is 0.01 to 1.0, and c + d is 1.0 to 2.5. Component (B) can be used alone or in combination of two or more. In the presence of the platinum group metal catalyst of the component (C), the component (B) reacts with an alkenyl group in the composition of the present invention, particularly an alkenyl group bonded to a silicon atom in the component (A). Acts as a cross-linking agent to give the original network structure. Therefore, the component (B) has at least 2 (usually 2 to 200), preferably 3 or more, more preferably about 3 to 100 hydrogen atoms bonded to silicon atoms in one molecule (ie, SiH group). When the component (B) is synthesized, an acid such as sulfuric acid or sulfonic acid (for example, methanesulfonic acid) is generally used.

The molecular structure of the component (B) is not particularly limited, and may be any of linear, branched, cyclic and three-dimensional network. The component (B) is a siloxane unit having at least one silicon-hydrogen bond (for example, (H) (R ³ ) ₂ SiO _1/2 unit, (H) (R ³ ) SiO _2/2 unit, ( H) Even a polymer composed only of SiO _3/2 units), such siloxane units, triorganosiloxane units ((R ³ ) ₃ SiO _1/2 units), diorganosiloxane units ((R ³ ) ₂ SiO _2/2 Unit), monoorganosiloxane units ((R ³ ) SiO _3/2 units) and SiO _4/2 units, or a copolymer with two or more types. The degree of polymerization of component (B) (or the number of silicon atoms in one molecule) is not particularly limited, but the number of silicon atoms is usually from the standpoint of compatibility with component (A) and ease of synthesis. A degree of polymerization of 2 to 300, preferably 3 to 200, particularly 4 to 150 is suitable.

Examples of R ³ include the monovalent hydrocarbon groups exemplified for R ¹ . R ³ may be the same or different from each other. Among the components (B), those in which all R ³ are methyl groups are preferable from the viewpoint of easy synthesis and chemical stability. In this case, a part of the methyl group may be substituted with a phenyl group or a trifluoropropyl group as necessary.

Examples of the (B) component organohydrogenpolysiloxane include, for example, the (B) component organohydrogenpolysiloxane, for example, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenyl. Silane, 1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, trimethyl at both ends Siloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, both ends dimethylhydrogensiloxy group-blocked Dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both ends Trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methyl siloxane-dimethylsiloxane-methylphenylsiloxane copolymers, (CH _{3) 2} HSiO _1/2 units and (CH _{3) 3} SiO _1/2 units Copolymers comprising SiO _4/2 units, (CH ₃₎ consists of ₂ HSiO _1/2 units and SiO _4/2 units, copolymers composed, (CH _{3) 2} HSiO _1/2 units and SiO _4/2 A copolymer composed of a unit and (C ₆ H ₅ ) ₃ SiO _1/2 unit, and in each of these exemplified compounds, a part of the methyl group is replaced with another alkyl group such as an ethyl group or a provir group, Those substituted with a halogen-substituted alkyl group such as 3-trifluoropropyl group or an aryl group such as phenyl group, etc.

（これらの式中、Ｌは２〜１０の整数）
などが挙げられる。

(In these formulas, L is an integer of 2 to 10)
Etc.

  The amount of component (B) added is the amount of silicon in component (B) per mole of alkenyl groups bonded to silicon atoms in the entire composition (particularly alkenyl groups bonded to silicon atoms in component (A)). The amount of hydrogen atoms bonded to the atoms is 0.4 to 10.0 mol, preferably 1.2 to 5.0 mol. When the amount of the hydrogen atom is less than 0.4 mol, the resulting composition tends to be insufficiently cured, and it is difficult to obtain a cured product having a required strength. If the amount of hydrogen atoms is more than 10.0 mol, the resulting composition may foam during curing, or the physical properties of the cured product may change over time.

[Component (C)]
The platinum group metal catalyst of component (C) has the effect of promoting the addition reaction (hydrosilylation reaction) between the alkenyl group-containing organopolysiloxane of component (A) and the organohydrogenpolysiloxane of component (B). Have. Component (C) can be used alone or in combination of two or more. As the component (C), a known hydrosilylation reaction catalyst can be used. Specific examples thereof include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and olefins, aldehydes, vinyl siloxanes, acetylene alcohols, rhodium, and the like.

  When it is necessary to keep chlorine ions from mixing into the composition of the present invention, a platinum group metal catalyst that does not substantially contain chlorine ions can be used. Specific examples thereof include zero-valent platinum complexes having a chlorine ion of 5 ppm or less. More specifically, for example, vinylsiloxane-platinum complexes described in US Pat. Nos. 3,715,334, 3,775,452, 3,814,730 and the like can be mentioned.

  The amount of component (C) added may be an effective amount as a hydrosilylation reaction catalyst, but can be appropriately increased or decreased depending on the desired curing rate. Usually, the amount added is such that the amount of platinum group metal atoms is within the range of 0.1 to 2,000 ppm, preferably 1 to 200 ppm, based on the weight of the total composition.

[Component (D)]
Component (D) is a curing control agent, and is added to adjust the curing time of the composition of the present invention and to put the composition into practical use. Component (D) can be used alone or in combination of two or more. Examples of the component (D) include conventionally known curing control agents. Specific examples thereof include vinyl group-containing organopolysiloxanes such as vinylcyclotetrasiloxane; triallyl isocyanurate; alkyl maleates such as diallyl maleate. Acetyl; acetylene alcohol compounds; hydroperoxides such as ketone peroxide (Permec N: manufactured by NOF Corporation); N, N, N ′, N′-tetramethylethylenediamine; benzotriazole; or combinations thereof Can be mentioned. Of these, acetylene alcohol compounds are preferred.

Examples of the acetylene alcohol compound include acetylene alcohol and silane-modified products and siloxane-modified products thereof.
As the acetylene alcohol, those in which an ethynyl group and a hydroxyl group are bonded to the same carbon atom are particularly preferable. Specific examples thereof include the following compounds.

  The silane-modified product and the siloxane-modified product of acetylene alcohol are compounds in which the hydroxyl group of acetylene alcohol is silylated with, for example, alkoxysilane or alkoxysiloxane, respectively, and converted to a Si—O—C bond. Specific examples thereof include the following compounds.

（式中、ｎは０〜５０の整数であり、ｍは１〜５０、好ましくは３〜５０の整数である。）

(In the formula, n is an integer of 0 to 50, and m is an integer of 1 to 50, preferably 3 to 50.)

  The addition amount of the component (D) may be a necessary amount corresponding to the desired curing time, and can be appropriately increased or decreased. For example, 0.0001 to 10 parts by mass, preferably 0.01 to 100 parts by mass per 100 parts by mass of the component (A). 1 part by mass.

[(E) component]
The component (E) is an inorganic acid acceptor and is added to adsorb and neutralize the acid component remaining after the synthesis of the organohydrogenpolysiloxane of the component (B) and mixed in the composition of the present invention. Curing of the addition-curable silicone composition containing the components (A) to (D) by preparing a composition containing the components (A) to (E) and curing the composition at room temperature or under heating. The compression set of an object can be reduced effectively. Component (E) can be used alone or in combination of two or more.

  The component (E) is preferably one that does not liberate the captured acid component even at a high temperature. Examples of this purpose include inorganic acid adsorbents and basic inorganic fillers. Examples of the inorganic acid adsorbent include Kyoword series such as Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.), IXE series such as IXE600 (manufactured by Toagosei Co., Ltd.), and the like. Examples of the basic inorganic filler include alkaline earth metal carbonates and alkali metal carbonates. Among these basic inorganic fillers, alkaline earth metal carbonates are preferred in view of the influence on other properties of the composition of the present invention. Among these carbonates, carbonic acid carbonate is preferred because of its availability. Calcium and zinc carbonate are useful. Since the component (E) can be added to the composition without impairing the storage stability and curing stability of the composition of the present invention, the composition is distributed as a one-component composition containing the component (E). Can be made. There is no particular limitation on the timing of mixing the component (E) with the components (A) to (D). For example, the components (A) to (E) may be mixed simultaneously, the component (E) may be added to the mixture of the components (A) to (D), and the components (A) to (D) ) The component (E) may be added to any one of the components, or to any two or three mixtures, and then the remaining components may be added.

  The addition amount of the component (E) is not particularly limited, but an appropriate amount is selected in consideration of the effects on the effect of the composition of the present invention and the physical properties of the cured product. Specifically, for example, 0.01 to 50 parts by mass, preferably 0.1 to 30 parts by mass, per 100 parts by mass of component (A).

[Other ingredients]
An adhesiveness imparting agent such as alkoxysilane can also be added to the composition of the present invention. This adhesion-imparting agent is a component that gives the composition of the present invention excellent self-adhesiveness to various substrates such as metals and organic resins. Examples of this adhesion-imparting agent include alkenyl groups such as vinyl groups. Silane having at least one, preferably two or more functional groups selected from the group consisting of: (meth) acryloxy group, hydrosilyl group (SiH group), epoxy group, alkoxy group, carbonyl group, and phenyl group Organosilicon compounds such as cyclic or linear siloxanes having 2 to 30 atoms, preferably about 4 to 20 atoms, and (mono, di or tri) alkoxysilyl modified products of triallyl isocyanurate or (parts thereof) ) Hydrolyzed condensate (that is, silicone-modified triallyl isocyanurate).

  This adhesiveness imparting agent can be used alone or in combination of two or more, and is usually 15 parts by weight or less (that is, 0 to 15 parts by weight) with respect to 100 parts by weight of component (A), Preferably 0.01 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight can be blended, and there is no particular limitation as long as the effect of the composition is not impaired, but the adhesion-imparting agent is in the molecule. In the case of having one having a hydrosilyl group (SiH group), a hydrogen atom bonded to the silicon atom in the component (B) with respect to 1 mol of the alkenyl group bonded to the silicon atom in the component (A) ( It is preferable to mix the adhesion-imparting agent in an amount such that the total molar ratio between the SiH group) and the hydrogen atom bonded to the silicon atom in the adhesion-imparting agent (SiH group) is 0.4 to 10, particularly 1.2 to 5.0. .

  Specific examples of the adhesion-imparting agent include the following compounds. Here, Me represents a methyl group.

上記の接着性付与剤により、該組成物は、自己接着性を有し、基材への密着性が向上する。この場合、被着体の材質に特に限定はなく、その例としては、ガラス、ステンレス、アルミニウム等の金属やＰＢＴ、ＰＰＳ、ナイロン、ＡＢＳ等の熱可塑性樹脂などが挙げられる。

With the above-described adhesion-imparting agent, the composition has self-adhesiveness, and adhesion to the substrate is improved. In this case, the material of the adherend is not particularly limited, and examples thereof include metals such as glass, stainless steel, and aluminum, and thermoplastic resins such as PBT, PPS, nylon, and ABS.

  In addition, the composition of the present invention includes a reinforcing silica filler in an amount that does not interfere with its effect, a non-reinforcing filler such as quartz powder and diatomaceous earth, an inorganic pigment such as cobalt blue, a colorant such as an organic dye, and an oxidation agent. Heat resistance and flame retardancy improvers such as cerium, bengara, titanium oxide, and carbon black can also be added. Furthermore, for the purpose of improving the conductive stability, carbon black, graphite, or the like having a powder, whisker, or developed structure may be added to the composition of the present invention.

[Form of composition]
Since the composition of the present invention is excellent in storage stability and curing stability, it can be prepared as a one-component composition and is excellent in workability. Further, the composition of the present invention can be prepared and stored in at least two liquids as in the case of ordinary curable silicone rubber compositions, and can be cured by mixing these liquids at the time of use. . Therefore, the form of the composition of the present invention is not particularly limited. For example, it may be a one-pack type or a two-pack type, but is preferably a one-pack type from the viewpoint of workability during use.

[Use of composition]
The cured product of the composition of the present invention is excellent in compression set characteristics. Moreover, since this composition can be prepared as a one-component composition as described above, it is excellent in workability. In addition, the composition can impart adhesiveness and further improve the adhesion to the substrate, if desired. The composition is therefore particularly suitable for CIPG.

  The composition of the present invention can be cured by heating after being applied to a predetermined substrate depending on the application. The curing conditions of the composition of the present invention vary depending on the amount and are not particularly limited. The curing temperature is preferably room temperature (23 ± 3 ° C.) to 180 ° C., more preferably room temperature to 120 ° C. Usually, the curing time is about 5 to 1,000 minutes.

The composition of the present invention is useful for sealing electronic parts and structural parts. These parts use the cured product of the composition of the present invention,
Sealing the part with a method comprising: applying the composition to the part; and curing the composition to form the cured product on the part, thereby sealing the part with the cured product. be able to. As the curing conditions, those described above can be used. Examples of the electronic component include a transistor, an IC, a CPU, a memory, a sensor, and a battery. Examples of the structural component include an in-vehicle ECU, an electrical component such as a sensor, and a mobile device.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in full detail, this invention is not limited by these Examples.

[Examples 1-8 and Comparative Examples 1-6]
According to Table 1, each component was mixed and the composition was obtained. In the table, the amount of each component added is expressed in parts by mass. The following compounds were used as the components (A) to (F) in the table. Me represents a methyl group, and Vi represents a vinyl group.
(A) V-Sx
ViMe ₂ Si-O- (SiMe ₂ -O) ₅₀₀ -SiMe ₂ Vi-containing vinyl group-containing organopolysiloxane (viscosity: 10000 mPa · s)
(B) H-Sx
Hydrogenated polysiloxane represented by Me ₃ Si-O- (SiMe ₂ -O) _10- (SiMeH-O) ₃₀ -SiMe ₃ (viscosity: 70 mPa · s)
(C) Platinum catalyst Complex of platinum and 1,2-divinyl-1,1,2,2-tetramethyldisiloxane / toluene solution (platinum content: 0.5% by mass)
(D) Curing control agent Ethynyl-cyclohexanol / toluene solution (50% by mass)
(E) Inorganic acid acceptor
a. IXE (registered trademark) -600 (Toagosei)
b. IXE (registered trademark) -700 (Toagosei)
c. KYOWARD (registered trademark) 500 (Kyowa Chemical Industry)
d. Calcium carbonate
e. Zinc carbonate (F) adhesion promoter
a. The following formula:

で表わされる化合物
b. 下記式：

Compound represented by
b. The following formula:

で表わされる化合物。

A compound represented by

(viscosity)
Using a rotational viscometer RB-80H (manufactured by Toki Sangyo Co., Ltd.), the viscosity immediately after preparation (initial) and the viscosity after storage at 40 ° C. for 7 days were measured for each composition. The results are shown in Table 1.

(Hardness)
The composition immediately after preparation (initial stage) and the composition after storage for 7 days at 40 ° C. were each cured by heating at 120 ° C. for 60 minutes. The hardness of the obtained cured product was measured with a durometer type A hardness meter. The measurement results are shown in Table 1.

(Compression set)
The composition immediately after preparation was cured by heating at 120 ° C. for 60 minutes to obtain a molded product having a diameter of 25 mm and a height of 12.0 mm. The height of the molded product was compressed to 9.0 mm at 110 ° C. with a compression jig, and held as it was for 100 hours, 500 hours, or 1000 hours. After 30 minutes from the end of compression, the height H of the molded product is measured, and the following formula:
(12.0-H) / (12.0-9.0) × 100
Was used to calculate compression set (%).

(Shearing adhesive strength)
The composition immediately after the preparation was sandwiched between glass plates or stainless steel plates (SUS304), and then cured by heating at 100 ° C. for 60 minutes. At that time, the adhesion area was 25 mm × 10 mm, and the thickness of the adhesion layer was 2.0 mm. The shear adhesive strength of the obtained cured product was measured by an autograph (AG-IS) manufactured by Shimadzu Corporation. The results are shown in Table 1.

（注）ＴＩＰＴ：テトライソプロポキシチタン、ＤＴＭＡ：ドデシルトリメチルアンモニウム、×：未硬化

(Note) TIPT: Tetraisopropoxytitanium, DTMA: Dodecyltrimethylammonium, x: Uncured

Claims (15)

(A) The following average composition formula (1):
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, R ² is independently an alkenyl group, a is a number from 1.0 to 2.2, b is a number from 0.0001 to 0.5, where a + b is a number from 1.5 to 2.7.)
100 parts by mass of an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule,
(B) The following average composition formula (2):
R ³ _c H _d SiO _{(4-cd) / 2} (2)
Wherein R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, c is a number from 0.7 to 2.1, d is a number from 0.001 to 1.2, However, c + d is a number from 0.8 to 3.0.)
The amount of hydrogen atoms bonded to silicon atoms in the component (B) is 0.4 to 10.0 mol per 1 mol of alkenyl groups bonded to silicon atoms in the whole composition,
(C) an effective amount of a platinum group metal catalyst,
An addition-curable silicone composition for CIPG comprising (D) a curing control agent, and (E) an inorganic acid acceptor.   The composition according to claim 1, wherein the component (E) is an inorganic acid adsorbent.   The composition according to claim 1, wherein the component (E) is a basic inorganic filler.   4. The composition according to claim 3, wherein the basic inorganic filler is an alkaline earth metal carbonate.   The composition according to claim 1 having self-adhesiveness.   The composition according to claim 1, which is a one-component type. (A) The following average composition formula (1):
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, R ² is independently an alkenyl group, a is a number from 1.0 to 2.2, b is a number from 0.0001 to 0.5, where a + b is a number from 1.5 to 2.7.)
100 parts by mass of an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule,
(B) The following average composition formula (2):
R ³ _c H _d SiO _{(4-cd) / 2} (2)
Wherein R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, c is a number from 0.7 to 2.1, d is a number from 0.001 to 1.2, However, c + d is a number from 0.8 to 3.0.)
The amount of hydrogen atoms bonded to silicon atoms in the component (B) is 0.4 to 10.0 mol per 1 mol of alkenyl groups bonded to silicon atoms in the whole composition,
(C) an effective amount of a platinum group metal catalyst, and (D) a method for reducing compression set of a cured product of an addition-curable silicone composition containing a curing controller,
Preparing a composition containing the components (A) to (D) and (E) an inorganic acid acceptor; and the composition containing the components (A) to (E) at room temperature or under heating. A method comprising curing.   The method according to claim 7, wherein the component (E) is an inorganic acid adsorbent.   The method according to claim 7, wherein the component (E) is a basic inorganic filler.   10. The method according to claim 9, wherein the basic inorganic filler is an alkaline earth metal carbonate.   The method according to claims 7 to 10, wherein the composition is self-adhesive.   12. The method according to claims 7 to 11, wherein the composition is a one-part type.   Hardened | cured material obtained by hardening the composition of Claims 1-6.   The sealing material which consists of a composition of Claims 1-6. A method of sealing a substrate with a cured product of the composition according to claim 1,
Applying the composition to the substrate and sealing the substrate with the cured product by curing the composition to form the cured product on the substrate.