JP4438937B2 - Room temperature curable organopolysiloxane composition - Google Patents

Description

  The present invention relates to a room temperature curable organopolysiloxane composition, and particularly to a room temperature curable organopolysiloxane composition that is excellent in storage stability and resin adhesion and has a very low odor (particularly silane odor). .

  Conventionally, various types of room temperature curable organopolysiloxane compositions that cure at room temperature by contact with moisture in the air are known, and among them, those that cure by releasing alcohol are metals. Since it does not corrode, it is mainly used for sealing, bonding, and coating of electrical and electronic equipment. A representative example of this alcohol type is JP-B-39-27643 (Patent Document 1), which discloses a composition comprising a hydroxyl-terminated organopolysiloxane, an alkoxysilane, and an organic titanium compound. . JP-A-55-43119 (Patent Document 2) discloses a composition comprising an alkoxysilyl end-capped organopolysiloxane, an alkoxysilane and an alkoxytitanium. Recently, Japanese Patent Publication No. 7-39547 (Patent Document 3) discloses a composition having excellent storage stability in a sealed state, and Japanese Patent Application Laid-Open No. 11-338090 (Patent Document 4) provides adhesion durability. There are disclosures of superior compositions.

Japanese Examined Patent Publication No. 39-27643 Japanese Patent Laid-Open No. 55-43119 Japanese Examined Patent Publication No. 7-39547 JP 11-338090 A

However, JP-B-39-27643 (Patent Document 1), JP 55-43119 (Patent Document 2) has a problem in storage stability, JP equitable 7-39547 (Patent Document 3) In Japanese Patent Application Laid-Open No. 11-338090 (Patent Document 4), there is a problem in resin adhesion, and when a low boiling point alkoxysilane is used, an unpleasant odor due to a silane odor has been confirmed.

  The present invention provides a room temperature curable organopolysiloxane composition that eliminates the above-mentioned drawbacks, has excellent storage stability and resin adhesion, has a low odor (particularly silane odor), and does not become uncomfortable during use. Is the purpose.

As a result of intensive studies to achieve the above object, the present inventors have found that organopolysiloxane represented by the following general formula (1 ), colloidal calcium carbonate whose surface is treated with a fatty acid, and paraffin-based treatment on the surface Heavy calcium carbonate treated with an agent, an alkoxysilane compound having an average of two or more hydrolyzable groups bonded to silicon atoms in one molecule and a boiling point of 150 ° C. or higher at normal pressure and / or its This object was achieved by using a partially hydrolyzed product, an organoxytitanium having at least two organoxy groups in the molecule in which tertiary carbon atoms are bonded to oxygen atoms.

（式中、Ｒはメチル基又はエチル基であり、Ｒ¹は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であり、Ｘは１０以上の整数である。Ｙは炭素原子数１〜５のアルキレン基であり、Ｎは独立に０又は１の整数である。）
で示されるオルガノポリシロキサン １００質量部、
（Ｂ）表面が脂肪酸で処理されたコロイド質炭酸カルシウム ５０〜１５０質量部、
（Ｃ）表面がパラフィン系の処理剤で処理された平均粒径が０．７〜２．５μｍである重質炭酸カルシウム １０〜５０質量部、
（Ｄ）ケイ素原子に結合した加水分解性基を１分子中に平均２個以上有し、かつ常圧での沸点が１５０℃以上であるアルコキシシラン化合物、その部分加水分解物又はこれらの混合物 ０．１〜２０質量部、
（Ｅ）下記一般式（４）

（式中、Ｒ³は酸素原子に結合する炭素原子が３級である炭素原子数４〜１０の３級炭化水素基であり、Ｒ⁴は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であるが、３級炭素原子を有さない。ａは０〜２の整数である。）
で示されるオルガノキシチタン １〜１５質量部、
（Ｆ）シランカップリング剤 ０〜１０質量部
を必須成分としてなる、保存安定性、樹脂接着性に優れ、かつ臭気（特にシラン臭）が著しく少ない樹脂との接着用の室温硬化性オルガノポリシロキサン組成物を提供するものである。 Therefore, the present invention
(A) The following general formula (1)

Wherein R is a methyl group or an ethyl group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
100 parts by mass of an organopolysiloxane represented by
(B) co surface-treated with a fatty acid Lloyd calcium carbonate 50 to 150 parts by weight,
(C) 10-50 parts by weight of heavy calcium carbonate having an average particle size of 0.7-2.5 μm, the surface of which has been treated with a paraffinic treatment agent,
(D) An alkoxysilane compound, a partially hydrolyzed product thereof, or a mixture thereof, having an average of two or more hydrolyzable groups bonded to a silicon atom and having a boiling point of 150 ° C. or higher at normal pressure .1-20 parts by mass,
(E) The following general formula (4)

(Wherein R ³ is a tertiary hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the oxygen atom is tertiary, and R ⁴ is a substituted or unsubstituted one having 1 to 10 carbon atoms. (It is a valent hydrocarbon group but has no tertiary carbon atom. A is an integer of 0 to 2.)
1 to 15 parts by mass of organoxytitanium represented by
(F) Silane Coupling Agents Room temperature-curable organopolysiloxane for adhesion to a resin having 0 to 10 parts by mass as an essential component, excellent storage stability and resin adhesion, and extremely low odor (especially silane odor) A composition is provided.

  According to the present invention, it is possible to provide a room temperature-curable organopolysiloxane composition that is excellent in storage stability and resin adhesion, has little odor (particularly silane odor), and does not become uncomfortable during use.

（式中、Ｒはメチル基又はエチル基であり、Ｒ¹は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であり、Ｘは１０以上の整数である。Ｙは炭素原子数１〜５のアルキレン基であり、Ｎは独立に０又は１の整数である。）
で示されるオルガノポリシロキサンであることが必要である。 The component (A) used in the present invention is a base polymer of the present composition, and in order to obtain storage stability, the following general formula (1)

Wherein R is a methyl group or an ethyl group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
It is necessary that in a organopolysiloxane emissions represented.

  (A) The preferable viscosity of a component is 100-1,000,000 mPa * s on 25 degreeC conditions. This is because if it is less than 100 mPa · s, the cured elastomer may not be able to give excellent physical properties, particularly flexibility and high elongation, and if it exceeds 1,000,000 mPa · s, the composition This is because the viscosity of the product is increased, and the dischargeability during construction may be significantly reduced. Therefore, it is more preferably 5,000 to 100,000 mPa · s. This viscosity is a value measured by a rotational viscometer.

In said general formula (1 ) , R is a methyl group or an ethyl group, and a methyl group is preferable. R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group or a propyl group, or a cycloalkyl group such as a cyclohexyl group. And a group in which the hydrogen bond of these groups is partially substituted with a halogen atom, for example, 3,3,3-trifluoropropyl group, etc., methyl group, ethyl group, vinyl group, phenyl group, 3, A 3,3-trifluoropropyl group is preferred, and a methyl group is particularly preferred. The plurality of R ¹ in the general formula (1 ) may be the same group or different groups.
Y is an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group, and an ethylene group is preferable.
A polymer in which Y is an oxygen atom is also well known, but in the present invention, if Y is an oxygen atom, the storage stability is insufficient.

  The composition (B) used in the present invention is a colloidal calcium carbonate whose surface is treated with a fatty acid, and the surface (C) component is a heavy calcium carbonate treated with a paraffinic treatment agent. It is an essential component for imparting storage stability and good workability to the resin, and imparting resin adhesion and appropriate rubber properties.

  Here, the reason why the components (B) and (C) are used in combination is that good adhesion to a resin adherend (PPS, acrylic resin, etc.), which is said to be difficult to adhere only with the component (B), cannot be obtained. This is because, by adding the necessary amount of the component (C), the adhesion to these hardly-adhesive resin adherends becomes good, and an appropriate workability can be obtained. In addition, the component (C) alone not only significantly deteriorates the resin adhesiveness, but also causes the composition to fall and the workability to deteriorate.

  (B) It is essential that the surface of the component is treated with a fatty acid, and colloidal calcium carbonate treated with other treatment agents (resin acid, etc.) or colloidal calcium carbonate whose surface is untreated is used. With such a composition, the adhesiveness and workability to difficult-to-adhere resin also decrease. In addition, it is essential that the component (C) has a paraffinic surface, heavy calcium carbonate treated with other treating agents (fatty acid, resin acid, etc.), or heavy untreated surface. In the composition using quality calcium carbonate, the adhesiveness and workability with respect to difficult-to-adhere resin also decrease.

In this case, the colloidal calcium carbonate as the component (B) is preferably one having an average particle diameter of 0.01 to 0.1 μm, particularly 0.03 to 0.06 μm as measured by an electron microscope. The air permeability method specific surface area of the colloidal calcium carbonate is 3m ² / g or more, particularly preferably 4~7m ² / g. Examples of the fatty acid for treating the colloidal calcium carbonate include those having 10 to 20 carbon atoms, particularly 12 to 18 carbon atoms, and may be mixed fatty acids. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, but is preferably a saturated fatty acid. Specific examples include oleic acid, palmitic acid, stearic acid, and the like, and one or more of them can be used. The treatment amount is preferably 0.5 to 5% by mass, particularly 2.0 to 4.0% by mass with respect to calcium carbonate.

On the other hand, the heavy calcium carbonate as the component (C) has an average particle size of 0 . 7~2.5μm der is, also, it is preferable air permeability method specific surface area of calcium carbonate is 0.5 to 2.5 m ² / g, especially 0.8~2.0m ² / g. The paraffin-based treating agent for treating heavy calcium carbonate is not particularly limited as long as it is a linear or branched paraffin, but those having 20 to 30 carbon atoms are preferable, and one or more of these are used. Is preferred. The treatment amount is preferably 0.1 to 5% by mass, particularly 1.0 to 2.5% by mass with respect to calcium carbonate.
The surface treatment of the calcium carbonate can be performed by a known method.

  (B) and (C) component may use the calcium carbonate processed beforehand, and may process it at the time of manufacture of this composition. In order to significantly improve the storage stability of the composition, it is important that the surface treatment agent, the by-products during the treatment, the catalyst, and the like do not substantially remain in the composition. For this purpose, it is preferable to use pretreated calcium carbonate.

  (B) Although the addition amount of a component is 50-150 mass parts normally with respect to 100 mass parts of (A) component, Preferably it is 70-120 mass parts. If the amount is too large, the resin adhesiveness decreases and the viscosity of the composition increases, resulting in poor ejection properties during mixing and construction. If the amount is too small, the physical properties of the rubber after curing are degraded.

  (C) Although the addition amount of a component is 10-50 mass parts normally with respect to 100 mass parts of (A) component, Preferably it is 15-35 mass parts. If the amount is too large, the resin adhesive property and rubber physical properties are deteriorated, and the discharge property during mixing and construction is deteriorated.

  The component (D) in the present invention has an average of 2 or more, particularly 3 or more hydrolyzable groups (alkoxy groups) bonded to a silicon atom, and has a boiling point of 150 ° C. or higher at normal pressure. A certain alkoxysilane compound and / or a partial hydrolyzate thereof. The remaining group bonded to the silicon atom other than the hydrolyzable group is not particularly limited as long as it is a monovalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, Illustrative examples include alkyl groups such as propyl groups, alkenyl groups such as vinyl groups, and aryl groups such as phenyl groups. The conditions to be satisfied include a boiling point of 150 ° C. or higher at normal pressure. Strong when the boiling point is less than 150 ° C, such as methyltrimethoxysilane (bp 102 ° C), methyltriethoxysilane (bp 143 ° C), vinyltrimethoxysilane (bp 123 ° C) Odor may remain.

  Specific examples of the component (D) include tetrafunctional alkoxysilanes such as tetraethoxysilane and methyl cellosolv orthosilicate, ethyltriethoxysilane (bp 160 ° C), vinyltriethoxysilane (bp 158 ° C). ), N-butyltrimethoxysilane (bp 164.8 ° C.), propyltrimethoxysilane, phenyltrimethoxysilane (bp 130 ° C./45 mmHg), trifunctional alkoxysilane such as butyltrimethoxyethoxysilane And partially hydrolyzed condensates thereof. Even a silane having a boiling point of less than 150 ° C. can be used as long as it is a hydrolyzed dimer or trimer. These may be used alone or in combination of two or more. In addition, bifunctional alkoxysilanes such as diphenyldimethoxysilane may be additionally added in order to impart low modulus to the rubber elastic body after curing.

  (D) The compounding quantity of a component is 0.1-20 mass parts with respect to 100 mass parts of (A) component, Preferably, it is used in the range of 1-10 mass parts. If the amount is less than 0.1 parts by mass, sufficient crosslinking cannot be obtained, and it is difficult to obtain a composition having the desired rubber elasticity. If the amount exceeds 20 parts by mass, the resulting cured product has reduced mechanical properties and the odor of the composition. Gets worse.

（式中、Ｒ³は酸素原子に結合する炭素原子が３級である炭素原子数４〜１０の３級炭化水素基であり、Ｒ⁴は炭素原子数１〜１０の置換もしくは非置換の一価炭化水素基であるが、３級炭素原子を有さない。ａは０〜２の整数である。）
で示される酸素原子に結合した３級炭素原子を少なくとも２個有するオルガノキシチタンである。Ｒ⁴の炭素原子数１〜１０の一価炭化水素基としては、３級炭化水素基を有さないものであり、特に直鎖状又は１個の分岐鎖を有するアルキル基が好ましく、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等が挙げられ、炭素原子数１〜４のものが好ましい。Ｒ³は炭素原子数４〜１０の３級炭化水素基であり、ｔ−ブチル基が好ましい。上記オルガノキシチタンの具体例としては、テトラ−ｔｅｒｔ−ブトキシチタン、イソプロポキシ−トリ−ｔｅｒｔ−ブトキシチタン、ブトキシ−トリ−ｔｅｒｔ−ブトキシチタン、ジイソプロポキシ−トリ−ｔｅｒｔ−ブトキシチタンなどが例示される。 The component (E) used in the present invention is a catalyst for curing the present composition, and the following general formula (4)

(Wherein R ³ is a tertiary hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the oxygen atom is tertiary, and R ⁴ is a substituted or unsubstituted one having 1 to 10 carbon atoms. (It is a valent hydrocarbon group but has no tertiary carbon atom. A is an integer of 0 to 2.)
An organoxytitanium having at least two tertiary carbon atoms bonded to an oxygen atom represented by The monovalent hydrocarbon group having 1 to 10 carbon atoms of R ⁴ is a group having no tertiary hydrocarbon group, particularly preferably a linear or alkyl group having one branched chain, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group and the like, and those having 1 to 4 carbon atoms are preferable. R ³ is a tertiary hydrocarbon group having 4 to 10 carbon atoms, preferably a t-butyl group. Specific examples of the organoxytitanium include tetra-tert-butoxytitanium, isopropoxy-tri-tert-butoxytitanium, butoxy-tri-tert-butoxytitanium, diisopropoxy-tri-tert-butoxytitanium and the like. The

  (E) The addition amount of a component is the range of 1-15 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 3-10 mass parts. If the amount added is small, good storage stability cannot be obtained, and the time for obtaining a cured product of the present composition becomes longer. On the contrary, if the amount is too large, the surface curability is too fast, the deep portion curability is deteriorated, or the storage stability is deteriorated.

  The silane coupling agent of (F) component is a component which has an effect | action as an adhesive provision component in the room temperature curable organopolysiloxane composition of this invention. Known silane coupling agents are preferably used, and examples include (meth) acryl silane coupling agents, epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, and the like. γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, N-β- (aminoethyl) )-[Gamma] -aminopropyltrimethoxysilane, [gamma] -aminopropyltriethoxysilane, [gamma] -mercaptopropyltrimethoxysilane and the like are exemplified.

  The amount of the silane coupling agent used is 0 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). When adhering without using a silane coupling agent with a filler and an adherend, it is not necessary to use a silane coupling agent. .

The room temperature-curable organopolysiloxane composition of the present invention preferably contains (G) a non-reactive silicone oil, preferably polydimethylsiloxane having both ends blocked with trimethylsilyl groups. By blending this component, properties such as workability and thread breakage are improved, and rubber properties after curing can be adjusted.
The viscosity (25 ° C.) is preferably 5 to 50,000 mPa · s, particularly 50 to 5,000 mPa · s. It is preferable that a compounding quantity is 0-100 mass parts with respect to 100 mass parts of (A) component, especially 5-80 mass parts.

  In addition to the components (A) to (F) described above, the room temperature curable organopolysiloxane composition of the present invention can further improve the flow characteristics before curing as necessary to form a rubber-like elastic body after curing. In order to impart necessary mechanical properties, a fine powdery inorganic filler may be added. Inorganic fillers include quartz fine powder, fumed silica, precipitated silica, fumed titanium dioxide, diatomaceous earth, aluminum hydroxide, particulate alumina, magnesia, zinc oxide, zinc carbonate and their silanes, silazanes, and low polymerization. Examples thereof include those that have been surface-treated with siloxanes and organic compounds.

  Furthermore, an organic solvent, an antifungal agent, a flame retardant, a heat resistance agent, a plasticizer, a thixotropic agent, an adhesion promoter, a curing accelerator, a pigment, and the like are added to the room temperature curable organopolysiloxane composition of the present invention. Can do.

  The room temperature-curable organopolysiloxane composition of the present invention can be obtained by mixing the components (A) to (F) and various additives as necessary while blocking moisture. The obtained composition can be used as a so-called one-packaging room temperature curable organopolysiloxane composition that is stored as it is in a closed container and is cured into a rubber-like elastic body by being exposed to moisture in the air during use.

The room temperature curable organopolysiloxane composition of the present invention is used as a sealing material for buildings, as a sealing material for electrical and electronic parts, as an adhesive or a moisture-proof coating agent, as a textile product, glass product, metal product, plastic product, etc. It can be applied to applications as a coating agent or an adhesive.
In this case, the room temperature curable organopolysiloxane composition of the present invention is suitable for adhesion to hard-to-adhere resins such as acrylic resin, polycarbonate resin, polybutylene terephthalate (PBT) resin, polystyrene, ABS resin, and vinyl chloride resin. Used effectively.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part and a viscosity shows the measured value of the measuring method with a rotational viscometer at 25 degreeC.

[Synthesis Example 1]
In a three-necked flask with an internal volume of 2 liters equipped with a thermometer, stirrer and cooler, 2500 g of α, ω-dimethylvinyl-dimethylpolysiloxane having a viscosity of 30,000 mPa · s, 400 g of toluene, and trimethoxy 11.9 g of silane and 1.0 g of 50% toluene solution of chloroplatinic acid as a catalyst were added and mixed for 9 hours at room temperature under N ₂ stream. Thereafter, the mixture was heated to 100 ° C. under a reduced pressure of 10 mmHg to distill off the diluent toluene and excess trimethoxysilane, and 2,350 g of a colorless transparent liquid having a viscosity of 40,000 mPa · s and a nonvolatile content of 99.9%. Obtained. When the obtained liquid was mixed with tetrapropyl titanate at a ratio of 100: 1 (mass ratio), it did not immediately thicken and was cured after one day. From this, it can be confirmed that methyltrimethoxysilane was added to the vinyl group at the end of the polymer. This polymer is referred to as polymer A.

[Synthesis Example 2]
Α, ω-dimethylvinyl-dimethylpolysiloxane 2 having two vinyl groups in the side chain with a viscosity of 30,000 mPa · s in a three-necked flask having an internal volume of 2 liters equipped with a thermometer, a stirrer and a condenser , 500 g, 400 g of toluene, 15 g of trimethoxysilane and 1.0 g of a 50% toluene solution of chloroplatinic acid as a catalyst were added and mixed for 9 hours at room temperature under a N ₂ stream. Thereafter, the mixture was heated to 100 ° C. under a reduced pressure of 10 mmHg to distill off the diluent toluene and excess trimethoxysilane, and 2,250 g of a colorless transparent liquid having a viscosity of 52,000 mPa · s and a non-volatile content of 99.9%. Obtained. When the obtained liquid was mixed with tetrabutyl titanate at a ratio of 100: 1 (mass ratio), it did not immediately thicken and was cured after one day. This confirms that methyltrimethoxysilane has been added to the vinyl group contained in the polymer. This polymer is referred to as polymer B.

[Example 1]
100 parts of polymer A, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC coat P-10, manufactured by Maruo Calcium Co., Ltd.) was mixed uniformly, and 9 parts of phenyltrimethoxysilane (bp 130 ° C./45 mmHg) and tetra-tert. -A composition was prepared by mixing 9 parts of butoxytitanium until uniform under moisture barrier.

[Example 2]
100 parts of polymer B, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC Coat P-10, manufactured by Maruo Calcium Co., Ltd.) were uniformly mixed, and 9 parts of phenyltrimethoxysilane and 9 parts of tetra-tert-butoxytitanium were then blocked under moisture. A composition was prepared by mixing until uniform.

[Example 3]
100 parts of polymer A, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC Coat P-10, manufactured by Maruo Calcium Co., Ltd.) were mixed uniformly, and 9 parts of phenyltrimethoxysilane and 9 parts of isopropoxy-tri-tert-butoxytitanium were moistened. A composition was prepared by mixing under blockage until uniform.

[Example 4]
100 parts of polymer A, 45 parts of polydimethylsiloxane blocked with methyl groups at both ends with a viscosity of 100 mPa · s, 90 parts of colloidal calcium carbonate surface-treated with fatty acid (Carlex 300, manufactured by Maruo Calcium Co., Ltd.), surface treatment with paraffin 30 parts of heavy calcium carbonate (MC Coat P-10, manufactured by Maruo Calcium Co., Ltd.) were mixed uniformly, and 9 parts of phenyltrimethoxysilane and 9 parts of diisopropoxy-di-tert-butoxytitanium were added thereto. A composition was prepared by mixing under moisture block until uniform.

[Comparative Example 1]
In Example 1, colloidal calcium carbonate treated with resin acid (MT-100, manufactured by Maruo Calcium Co., Ltd.) was used instead of colloidal calcium carbonate surface-treated with fatty acid, as in Example 1. The composition was prepared by the method.

[Comparative Example 2]
In Example 1, the same method as in Example 1 was used except that heavy calcium carbonate treated with a fatty acid (Snowlite, manufactured by Maruo Calcium Co., Ltd.) was used instead of heavy calcium carbonate surface-treated with paraffin. A composition was prepared.

[Comparative Example 3]
A composition was prepared in the same manner as in Example 1 except that methyltrimethoxysilane (bp 102 ° C.) was used instead of phenyltrimethoxysilane.

[Comparative Example 4]
In Example 1, a composition was prepared in the same manner as in Example 1, except that tetraisopropoxytitanium was used instead of tetra-tert-butoxytitanium.

  The compositions of these examples and comparative examples were molded into a sheet having a thickness of 2 mm and cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH, and their rubber properties (hardness, elongation, tensile strength) ) Was measured according to JIS K6249. At that time, the smell of the composition was sniffed, and it was confirmed whether or not it felt uncomfortable. At the same time, the prepared composition is applied to a resin adherend having a thickness of 25 × 100 × 2 mm, left at room temperature to form a rubber elastic body, and then the resulting cured product is pulled to bond the adherend. The property was confirmed visually. Here, hard vinyl chloride resin, polystyrene, polycarbonate, and acrylic resin, which are relatively easy to use as building materials, were selected as the resin adherend. In the storage stability test, the uncured composition was heated in a dryer at 70 ° C. in the form of a cartridge, and then cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH. Rubber properties and adhesiveness were measured in the same manner as the composition. The results of Examples 1 to 4 are shown in Table 1, and the results of Example 1 and Comparative Example are shown in Table 2.

Claims (2)

(A) The following general formula (1)

Wherein R is a methyl group or an ethyl group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
100 parts by mass of an organopolysiloxane represented by
(B) co surface-treated with a fatty acid Lloyd calcium carbonate 50 to 150 parts by weight,
(C) 10-50 parts by weight of heavy calcium carbonate having an average particle size of 0.7-2.5 μm, the surface of which has been treated with a paraffinic treatment agent,
(D) an alkoxysilane compound, a partially hydrolyzed product thereof, or a mixture thereof, having an average of two or more hydrolyzable groups bonded to a silicon atom and having a boiling point of 150 ° C. or higher at normal pressure .1-20 parts by mass,
(E) The following general formula (4)

(In the formula, R ³ is a tertiary hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the oxygen atom is tertiary, and R ⁴ is a substituted or unsubstituted one having 1 to 10 carbon atoms. (It is a valent hydrocarbon group but has no tertiary carbon atom. A is an integer of 0 to 2.)
1 to 15 parts by mass of organoxytitanium represented by
(F) Silane coupling agent A room temperature-curable organopolysiloxane composition for adhesion to a resin , characterized by comprising 0 to 10 parts by mass as an essential component.   Furthermore, (G) non-reactive silicone oil is contained, The room temperature curable organopolysiloxane composition of Claim 1 characterized by the above-mentioned.