JP5842831B2 - Room temperature curable organopolysiloxane composition and structure - Google Patents

Description

  The present invention relates to a room temperature curable organopolysiloxane composition, and in particular, it comprises two components, a main agent composition and a curing agent composition, which are mixed at the room temperature to produce a rubber-like elastic body. The present invention relates to a polysiloxane composition and a structure using the composition.

  Condensation-reactive organopolysiloxane compositions that cure at room temperature to produce rubbery elastic bodies are widely used as elastic adhesives, coating materials, electrical insulating sealing materials, and as building sealing materials in the electrical and electronic industries. ing. Among these, a one-component type (one-packaging type) room temperature curable organopolysiloxane that undergoes a curing reaction by contact with moisture in the air weighs a base polymer, a crosslinking agent, a catalyst, etc. immediately before use. However, there is a drawback that the curing rate is slow and the deep part curability is poor.

  On the other hand, the two-component room temperature curable organopolysiloxane composition has a high curing rate and excellent deep part curability. This composition is prepared by dividing into a main component comprising a polydiorganosiloxane having a hydroxyl group and / or an alkoxy group at the molecular end and an inorganic filler, and a crosslinking component. It is used as a so-called multi-packaging room temperature curable composition that is stored in separate containers and mixed at the time of use (for example, Patent Documents 1 to 3: JP-A-07-133430, JP-A-11- No. 209620 and Japanese Patent No. 4987218).

  In such a two-component room temperature curable organopolysiloxane composition, the crosslinking component is composed only of a crosslinking agent and a curing catalyst in terms of storage stability. For this reason, the blending ratio of the cross-linking component to the main component is extremely reduced to 1 to 3% by mass, and variations during measurement and poor mixing are likely to occur. In particular, in mixing using an automatic mixing / discharging machine, the mixing ratio of the main component and the cross-linking component is required to be an integer ratio of about 100: 10 or more from a practical viewpoint. In the conventional two-component room temperature curable organopolysiloxane composition composed only of the agent and the curing catalyst, it has been difficult to measure and mix without variation.

  When metering / mixing using an automatic mixing and dispensing machine, the same polymer as the base polymer (silanol group-terminated polydiorganosiloxane) blended in the main component is used to increase the blending ratio of the cross-linking component. It is conceivable to dilute the crosslinking agent by adding it to the crosslinking component as an extender, but not only does the storage stability deteriorate due to the coexistence of the polymer, the crosslinking agent and the catalyst, but such a polymer is Because of their poor compatibility, there was a problem that they were separated and could not be uniformly dispersed.

  In recent years, when a polymer having an aryl group or an aralkyl group introduced into a main chain in a main chain as in Patent Document 3 is used, compatibility with a cross-linking agent can be well dispersed uniformly, so that deep curability, uniformity of curing, Proposals have been made to improve the mixing ratio of the main component and the crosslinking component so as to be appropriately adjusted according to the use of an automatic mixing / discharging machine or the like without deteriorating characteristics such as storage stability. However, when the proposed composition is a non-fluid liquid, it is non-fluid immediately after mixing the component (A) and the component (B), but if the mixing time is long or the residence time is from the mixing to the construction time. When the length is long, fluidity is developed, and there is a problem that sealing failure and design properties are deteriorated. In addition, since it is necessary to introduce an aryl group or an aralkyl group into the main chain, monomers and oligomers necessary for introducing them are mixed as impurities and cannot be completely removed. In the electronic industry, there has been a concern that electrical failures such as contact failures are likely to occur. In addition, since a monomer for introducing an aryl group or an aralkyl group is relatively expensive, the resulting polymer is also expensive and has a low cost competitiveness.

Japanese Patent Laid-Open No. 07-133430 JP-A-11-209620 Japanese Patent No. 4987218

  The present invention has been made in order to solve these problems, and is a two-component room temperature curable organo compound that is less expensive and can maintain non-fluidity even when the mixing time and the residence time from mixing to construction are long. It is to provide a polysiloxane composition, especially with excellent properties such as deep-curing property, uniformity of curing, and storage stability, and the mixing ratio of the main component and the cross-linking component is suitable for use in automatic mixing dispensers and the like. Another object of the present invention is to provide a room temperature curable organopolysiloxane composition that can be appropriately adjusted together and a structure using the composition.

  As a result of intensive studies in order to achieve the above object, the present inventors, in a two-component room temperature curable organopolysiloxane composition comprising (A) a main agent composition and (B) a curable composition, (B) By using a side-chain polyether-modified organopolysiloxane that is in a liquid state at 30 ° C. as a plasticizer and compatibilizer for component (B), even if the residence time from the mixing time to the construction is long It has been found that a composition capable of maintaining fluidity can be obtained.

（式中、ｍ及びｎは１以上１００以下の整数である。Ｘは独立に炭素数１〜１０の非置換又は置換一価炭化水素基であり、Ｙは下記一般式（２）で表されるポリエーテル基である。）
−Ｒ（Ｃ_pＨ_2pＯ）_qＲ （２）
（式中、Ｒは独立に炭素数１〜１０の非置換又は置換一価炭化水素基であり、ｐは１以上１０以下の整数である。ｑは１以上５０以下の整数であり、ｑが２以上の場合、ｐは互いに同一又は異種であってもよい。）
を、前記（ａ１）成分１００質量部に対して１〜４０質量部と、
（ｂ３）硬化触媒を、前記（ａ１）成分１００質量部に対して０．００１〜１０質量部
を含有し、前記（Ａ）主剤組成物と前記（Ｂ）硬化剤組成物とは、１００：３〜１００：２０の質量比で配合されることを特徴とする２成分型の室温硬化性オルガノポリシロキサン組成物。
請求項２：
（ａ２）成分の表面処理された無機充填剤がコロイド質炭酸カルシウム又は煙霧質シリカであり、表面未処理の無機充填剤が重質炭酸カルシウムである請求項１記載の２成分型の室温硬化性オルガノポリシロキサン組成物。
請求項３：
（ａ２）成分として、表面処理された無機充填剤５／５５〜４０／５５質量％と表面未処理の無機充填剤５０／５５〜１５／５５質量％とを併用した（但し、両者の合計１００質量％）請求項１又は２記載の２成分型の室温硬化性オルガノポリシロキサン組成物。
請求項４：
請求項１、２又は３記載の２成分型の室温硬化性オルガノポリシロキサン組成物にてシール又は接着された構造体。 Accordingly, the present invention provides the following room temperature curable organopolysiloxane composition and structure.
Claim 1:
A two-component room temperature curable organopolysiloxane composition comprising (A) a main agent composition and (B) a curing agent composition, which are prepared and stored separately,
The (A) main agent composition is:
(A1) 100 parts by mass of an organopolysiloxane having a hydroxyl group or an alkoxy group at the molecular end,
(A2) containing 3 to 200 parts by mass of an inorganic filler formed by using a surface-treated inorganic filler and a surface-untreated inorganic filler in combination ;
The (B) curing agent composition is:
(B1) An organosilicon compound and / or a silane coupling agent having three or more hydrolyzable groups as silicon functional groups in one molecule, or a partial hydrolyzate thereof, the hydroxyl group or alkoxy of the component (a1) An amount of 2 to 25 hydrolyzable groups per group;
(B2) a polyether-modified organopolysiloxane represented by the following general formula (1) and liquid at 30 ° C.

(In the formula, m and n are integers of 1 to 100. X is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and Y is represented by the following general formula (2). Polyether group.)
_{-R (C p H 2p O)} q R (2)
(In the formula, R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 1 to 10, q is an integer of 1 to 50, and q is In the case of 2 or more, p may be the same or different from each other.)
1 to 40 parts by mass with respect to 100 parts by mass of the component (a1),
(B3) The curing catalyst contains 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (a1) , and the (A) main agent composition and the (B) curing agent composition are 100: 3-100: RTV organopolysiloxane compositions of two-component, wherein that you are blended with 20 weight ratio.
Claim 2:
The two-component room-temperature curing property according to claim 1, wherein the surface-treated inorganic filler of component (a2) is colloidal calcium carbonate or fumed silica, and the untreated inorganic filler is heavy calcium carbonate. Organopolysiloxane composition.
Claim 3:
As the component (a2), the surface-treated inorganic filler 5/55 to 40/55% by mass and the surface untreated inorganic filler 50/55 to 15/55% by mass were used in combination (provided that the total of both was 100 A two-component room temperature curable organopolysiloxane composition according to claim 1 or 2.
Claim 4:
A structure sealed or bonded with the two-component room temperature curable organopolysiloxane composition according to claim 1, 2 or 3 .

  According to the two-component room temperature curable organopolysiloxane composition of the present invention, it is cheaper and can maintain non-flowability even when the mixing time and the residence time from mixing to construction are long, and the main component and the crosslinked The blending ratio with the components can be appropriately adjusted according to the use of an automatic mixing / discharging machine or the like. Furthermore, it is excellent in various properties such as deep part curability, uniformity of curing, and storage stability.

Hereinafter, embodiments of the room temperature curable organopolysiloxane composition of the present invention will be described.
The present invention is a two-component room temperature curable organopolysiloxane composition obtained by blending a main agent composition comprising the component (A) and a curing agent composition comprising the component (B).
The main agent composition as component (A) is:
(A1) an organopolysiloxane having a hydroxyl group or an alkoxy group at the molecular end;
(A2) composed of an inorganic filler,
The curing agent composition as component (B)
(B1) an organosilicon compound and / or a silane coupling agent having three or more hydrolyzable groups as silicon functional groups in one molecule, or a partial hydrolyzate thereof;
(B2) a side-chain polyether-modified organopolysiloxane that has a lower viscosity than the component (a1) and is liquid at 30 ° C .;
(B3) contains a curing catalyst.

(A) The organopolysiloxane having a hydroxyl group or an alkoxy group at the molecular terminal constituting the main agent composition is usually used as a base polymer of a condensation type silicone rubber that can be cured at room temperature.
(A1) The organic group directly bonded to the silicon atom of the component is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; an alkenyl group such as a vinyl group or an allyl group; Aryl groups such as 2-phenylethyl and aralkyl groups such as 2-phenylpropyl; and monovalent substituted carbons such as chloromethyl, β-cyanoethyl and 3,3,3-trifluoropropyl A hydrogen group and the like are exemplified, but a methyl group, a vinyl group or a phenyl group is preferable because synthesis is easy, and a methyl group which is advantageous in terms of cost is more preferable among them.
In addition, a hydroxyl group or an alkoxy group is selected as the molecular end of (a1). In the case of an alkoxy group, a methoxy group, an ethoxy group, an isopropoxy group, and the like are exemplified. Among these, a hydroxyl group or a methoxy group is preferable, and a hydroxyl group is particularly preferable.

  The organopolysiloxane preferably has a viscosity at 23 ° C. of 100 to 500,000 mPa · s, particularly 500 to 100,000 mPa · s. In the present invention, the viscosity is a value measured with a rotational viscometer. If the viscosity is less than 100 mPa · s, the mechanical properties of the rubber-like elastic body after curing tend to be insufficient, and conversely if it exceeds 500,000 mPa · s, the viscosity further increases when a filler or the like described later is blended. Therefore, poor mixing with the component (B) and ejection properties are deteriorated. A particularly preferable range is 700 to 50,000 mPa · s.

(A) The main component composition (a2) inorganic filler is blended with the main component composition (A) for the purpose of imparting mechanical strength and hardness to the rubber elastic body after curing, Known inorganic fillers can be used. For example, silica powder such as fumed silica, precipitated silica, diatomaceous earth, heavy calcium carbonate, colloidal calcium carbonate, titanium oxide, carbon black, aluminum hydroxide, aluminum oxide, zinc carbonate, zinc oxide, etc. These may be used alone or in combination of two or more. Among these, use of heavy calcium carbonate, colloidal calcium carbonate, fumed silica, precipitated silica, aluminum hydroxide, aluminum oxide, zinc carbonate, and zinc oxide is desirable.
Moreover, it is not limited about the surface treatment of these inorganic fillers. In the case of surface treatment, organic silicon compounds such as dichlorodimethylsilane, chlorotrimethylsilane, dimethylpolysiloxane, octamethylcyclotetrasiloxane, hexamethyldisilazane, fatty acids, resin acids, sulfonic acids, paraffins, etc. are exemplified. Is done.

  (A2) As for the compounding quantity of an inorganic filler, 1-500 mass parts is preferable with respect to 100 mass parts of (a1) component, Furthermore, 3-200 mass parts is more preferable. (A2) When the blending amount of the inorganic filler is less than 1 part by mass, the resulting cured product has insufficient mechanical strength. Conversely, when it exceeds 500 parts by mass, the viscosity of the component (A) is too high and mixed. Is difficult, and a uniform composition cannot be obtained.

  In the present invention, (B) the curing agent composition (b1) an organosilicon compound and / or silane coupling agent having three or more hydrolyzable groups as silicon functional groups in one molecule, or a part thereof The hydrolyzate acts as a crosslinking agent and an adhesion aid for the component (a1) described above, hydrolyzes with moisture in the air, and easily becomes a hydroxyl group (silanol group) or an alkoxy group of the component (a1). A cured product is formed by a condensation reaction, and adhesion to the substrate is imparted.

Examples of the hydrolyzable group possessed by the component (b1) include alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group and butoxy group; alkoxyalkoxy groups such as methoxyethoxy group; amide group and the like.
Examples of the group bonded to the silicon atom other than the hydrolyzable group include an unsubstituted or substituted monovalent hydrocarbon group similar to the organic group directly bonded to the silicon atom in the component (a1). From the viewpoint of crosslinking speed, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms and a phenyl group are preferable. Among them, an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 3 carbon atoms are preferable. More preferred.

  Specific examples of such component (b1) include tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, ethylorthosilicate, propylorthosilicate, aminopropyltrimethoxysilane. And alkoxysilanes such as aminopropyltriethoxysilane and partially hydrolyzed condensates thereof.

  Moreover, as a silane coupling agent used here, a (meth) acryl silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, a mercapto silane coupling agent etc. are illustrated, Specifically, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltri Ethoxy Down, 3-chloropropyl triethoxy silane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, and the like.

  The amount of component (b1) is adjusted so that the number of hydrolyzable groups can be 2 to 25 with respect to one hydroxyl group or alkoxy group of component (a1). When the blending amount of the component (b1) is less than this range, crosslinking is not sufficiently performed and a cured product having sufficient hardness cannot be obtained. On the other hand, when blending exceeding this range, the deep part curability is inferior and disadvantageous in cost, and mechanical properties after curing may be deteriorated.

  In the present invention, the component (b2) constituting the (B) curing agent composition together with the component (b1) is excellent in the component (b1) and the component (b3) described later in the (B) curing agent composition. The mixing ratio of the main component composition (A) and the curing agent composition (B) is adjusted to a mixing ratio suitable for metering / mixing such as an automatic mixing / discharging machine. In addition, in the case of a non-flowable composition, when mixed with the component (A), in addition to serving as a plasticizer for imparting appropriate flexibility to the cured product cured after mixing with the component (A), It is an essential component for the present composition, which makes it possible to maintain non-flowability even when the residence time from mixing to construction is long.

（式中、ｍ及びｎは１以上１００以下の整数である。また、Ｘは炭素数１〜１０、好ましくは１〜６の非置換又は置換一価炭化水素基であり、Ｙは下記一般式（２）で表されるポリエーテル基である。なお、ポリエーテル基及び炭素数１〜１０、好ましくは１〜６の非置換又は置換一価炭化水素基は互いに同一又は異種であってもよい。）
−Ｒ（Ｃ_pＨ_2pＯ）_qＲ （２）
（式中、Ｒは独立に炭素数１〜１０の非置換又は置換一価炭化水素基であり、ｐは１以上１０以下の整数である。また、ｑは１以上５０以下の整数であり、ｑが２以上の場合、ｐは互いに同一又は異種であってもよい。） As the component (b2), a polyether-modified organopolysiloxane represented by the following general formula (1) and liquid at 30 ° C. is used.

(In the formula, m and n are integers of 1 or more and 100 or less. X is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and Y is the following general formula. The polyether group and the polyether group and the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms may be the same or different from each other. .)
_{-R (C p H 2p O)} q R (2)
(In the formula, R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 1 to 10, and q is an integer of 1 to 50, When q is 2 or more, p may be the same or different from each other.)

  Here, X in the component (b2) is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 alkyl groups such as a methyl group, an ethyl group, and a propyl group, and a vinyl group. , An alkenyl group such as an allyl group, and an aryl group such as a phenyl group are selected. Moreover, Y which (b2) component has is a polyether group represented by the said General formula (2), R is a C1-C10, Preferably it is a 1-6 unsubstituted or substituted monovalent hydrocarbon group. Yes, an alkyl group such as methyl, ethyl or propyl is selected. Q is an integer of 1 to 50, and among these, q is preferably an integer of 2 to 25. When q is 2 or more, the p value in the formula (2) may have different integer units. When q exceeds 50, the viscosity of the side chain polyether-modified organopolysiloxane cannot be used because it is too high or solidified, and the compatibility with the components (b1) and (b3) also decreases.

  (B2) As for the compounding quantity of a component, 1-40 mass parts is preferable with respect to 100 mass parts of above-described (a1) components, Furthermore, 1-20 mass parts is more preferable. If the blending amount is less than 1 part by mass, blending with the component (A) becomes difficult, and all effects characteristic of the present composition are lost. On the other hand, if it exceeds 40 parts by mass, the physical properties of the rubber after curing may be lowered or bleeding may occur on the surface.

Component (b3) is a curing catalyst for forming a crosslinked structure by reacting the hydroxyl group or alkoxy group of component (a1) with the hydrolyzable group of component (b1) in the presence of moisture.
Such curing catalysts include iron octoate, manganese octoate, zinc octoate, tin naphthate, tin caprylate, tin oleate, carboxylic acid metal salts; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin Organotin compounds such as diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dioctyltin dilaurate, dioctyltin diversate; tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, 1,3 -Alkoxy titaniums such as propoxy titanium bis (ethyl acetyl acetate); aluminum tris acetylacetonate, aluminum tris Organoaluminum such as tylacetoacetate, diisopropoxyaluminum ethylacetoacetate, triethoxyaluminum; organozirconium such as zirconium tetraacetylacetonate, tetraisopropoxyzirconium tetrabutoxyzirconium, tributoxyzirconium acetylacetonate, tributoxyzirconium stearate Illustrative are organic bismuth compounds such as compounds, bismuth tris (2-ethylhexanoate) or bismuth tris (neodecanoate). Organotin compounds, alkoxy titaniums, and organic bismuth compounds are preferred because they have a large catalytic ability in the presence of a trace amount, and among them, organotin compounds are particularly preferred.

  The amount of component (b3) is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, per 100 parts by mass of component (a1). If it is less than 0.001 part by mass, it does not sufficiently act as a curing catalyst, and not only does it take a long time to cure, but also deep part curability deteriorates. On the other hand, when the amount exceeds 10 parts by mass, the curability after mixing is too fast, making it impossible to perform the work or causing a decrease in adhesiveness, which is disadvantageous in terms of cost.

  The room temperature curable organopolysiloxane composition of the present invention comprises (A) a main agent composition containing the above-described (a1) component and (a2) inorganic filler, and (b1) component and (b2) component which are crosslinking agents. And (b3) a curing catalyst composition containing (B3) a curing catalyst, and prepared separately, and stored separately in a state where moisture is blocked. In use, (A) the main agent composition and (B) the curing agent composition are mixed at an appropriate blending ratio and exposed to moisture in the air, so that a condensation reaction occurs and cures at room temperature. A cured product having rubber-like elasticity is obtained.

  The composition of the present invention further includes a pigment for coloring, a viscosity modifier for improving the extrusion workability, an ultraviolet absorber, a fungicide, a heat resistance improver, a flame retardant, etc., depending on the purpose. Various additives may be added. These additives are usually added and mixed in the (A) main agent composition.

According to the present invention, a structure sealed or bonded with the organopolysiloxane composition is provided. Examples of such a structure include a building and an electric / electronic component.
Further, examples of sealing or bonding include sealing materials, potting materials, coating materials, adhesives, and on-site molded gaskets.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, all the parts in an Example represent a mass part, and physical-property values, such as a viscosity which is not described in particular, show the value in 23 degreeC measured with the rotational viscometer.

[Example 1]
Colloidal calcium carbonate whose surface is treated with fatty acid on 45 parts of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 1,000 mPa · s (hydroxyl content: about 0.101 mmol / g) (a1-1) (Product name: Shiraka Hana CC-R, manufactured by Shiraishi Calcium Co., Ltd.) (a2-1) 40 parts and untreated heavy calcium carbonate (Product name: Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd.) (a2 -2) 15 parts were added and kneaded under reduced pressure using a planetary mixer to obtain a uniform (A) main agent composition.
Side chain polyether-modified organopolysiloxane having a viscosity of 130 mPa · s blocked with methyl groups (trade name; KF-6011, manufactured by Shin-Etsu Chemical Co., Ltd.) (b2-1) 0.5 part of methoxysilane (alkoxy group content about 22.0 mmol / g) (b1-1) and tetra-n-propyl orthosilicate (alkoxy group content about 15.2 mmol / g) (b1-2) 0 0.5 parts, 1.95 parts of 3-aminopropyltrimethoxysilane (alkoxy group content of about 13.6 mmol / g) (b1-3) and 0.05 part of dioctyltin diversate (b3) By mixing, a (B) curing agent composition was prepared.
To 100 parts of the component (A), 10 parts of the component (B) were added, mixed for 10 minutes under vacuum conditions, and various evaluations were performed.

[Example 2]
Colloidal calcium carbonate whose surface is treated with fatty acid on 45 parts of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 1,000 mPa · s (hydroxyl content: about 0.101 mmol / g) (a1-1) (Product name: Shiraka Hana CC-R, manufactured by Shiraishi Calcium Co., Ltd.) (a2-1) 40 parts and untreated heavy calcium carbonate (Product name: Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd.) (a2 -2) 15 parts were added and kneaded under reduced pressure using a planetary mixer to obtain a uniform (A) main agent composition.
Side chain polyether-modified organopolysiloxane having a viscosity of 130 mPa · s blocked with methyl groups (trade name; KF-6011, manufactured by Shin-Etsu Chemical Co., Ltd.) (b2-1) in 2.1 parts, 0.15 part of methyltrimethoxysilane (alkoxy group content about 22.0 mmol / g) (b1-1) and tetra-n-propyl orthosilicate (alkoxy group content about 15.2 mmol / g) (b1-2) ) 0.15 part, 3-aminopropyltrimethoxysilane (alkoxy group content of about 13.6 mmol / g) (b1-3) 0.585 part, dioctyltin diversate (b3) 0.015 part In addition, it mixed and the (B) hardening | curing agent composition was prepared.
To 100 parts of the component (A), 3 parts of the component (B) were added, mixed for 10 minutes under vacuum conditions, and various evaluations were performed.

[Example 3]
Colloidal calcium carbonate whose surface is treated with fatty acid on 45 parts of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 1,000 mPa · s (hydroxyl content: about 0.101 mmol / g) (a1-1) (Product name: Shiraka Hana CC-R, manufactured by Shiraishi Calcium Co., Ltd.) (a2-1) 40 parts and untreated heavy calcium carbonate (Product name: Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd.) (a2 -2) 15 parts were added and kneaded under reduced pressure using a planetary mixer to obtain a uniform (A) main agent composition.
Side chain polyether-modified organopolysiloxane having a viscosity of 130 mPa · s blocked with methyl groups (trade name; KF-6011, manufactured by Shin-Etsu Chemical Co., Ltd.) (b2-1) 1.0 part of methoxysilane (alkoxy group content about 22.0 mmol / g) (b1-1) and tetra-n-propyl orthosilicate (alkoxy group content about 15.2 mmol / g) (b1-2) 1 0.0 part, 3.9 parts of 3-aminopropyltrimethoxysilane (alkoxy group content of about 13.6 mmol / g) (b1-3) and 0.10 parts of dioctyltin diversate (b3) By mixing, a (B) curing agent composition was prepared.
To 100 parts of the component (A), 20 parts of the component (B) were added, mixed for 10 minutes under vacuum conditions, and various evaluations were performed.

[Example 4]
A fume having a surface treated with dichlorodimethylsilane on 45 parts of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 1,000 mPa · s (hydroxyl content: about 0.101 mmol / g) (a1-1) Silica (trade name: Aerosil R-972, manufactured by Nippon Aerosil Co., Ltd.) (a2-3) and surface-untreated heavy calcium carbonate (trade name: Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd.) ( a2-2) 50 parts was added and kneaded under reduced pressure using a planetary mixer to obtain a uniform (A) main agent composition.
Side chain polyether-modified organopolysiloxane having a viscosity of 920 mPa · s blocked with methyl groups (trade name; KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) (b2-2) 0.5 part of methoxysilane (alkoxy group content about 22.0 mmol / g) (b1-1) and tetra-n-propyl orthosilicate (alkoxy group content about 15.2 mmol / g) (b1-2) 0 0.5 parts, 1.95 parts of 3-aminopropyltrimethoxysilane (alkoxy group content of about 13.6 mmol / g) (b1-3) and 0.05 part of dioctyltin diversate (b3) By mixing, a (B) curing agent composition was prepared.
To 100 parts of the component (A), 10 parts of the component (B) were added, mixed for 10 minutes under vacuum conditions, and various evaluations were performed.

[Comparative Example 1]
In Example 1, it prepared similarly except having remove | excluded the side chain polyether modified organopolysiloxane by which both ends were blocked with the methyl group, and various evaluation was performed on the same conditions.

[Comparative Example 2]
In Example 1, instead of the side-chain polyether-modified organopolysiloxane blocked at both ends with methyl groups, 7 parts of dimethylpolysiloxane (b2-3) having both ends blocked with methyl groups at a viscosity of 100 mPa · s were used. Other than using, it prepared similarly and performed various evaluation on the same conditions.

[Comparative Example 3]
In Example 1, 7 parts of diphenylpolysiloxane (b2-4) having both ends blocked with methyl groups and having a viscosity of 300 mPa · s instead of side chain polyether-modified organopolysiloxane blocked at both ends with methyl groups Other than using, it prepared similarly and performed various evaluation on the same conditions.

[Comparative Example 4]
Colloidal calcium carbonate whose surface is treated with fatty acid on 45 parts of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 1,000 mPa · s (hydroxyl content: about 0.101 mmol / g) (a1-1) (Product name: Shiraka Hana CC-R, manufactured by Shiraishi Calcium Co., Ltd.) (a2-1) 40 parts and untreated heavy calcium carbonate (Product name: Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd.) (a2 -2) 15 parts were added and kneaded under reduced pressure using a planetary mixer to obtain a uniform (A) main agent composition.
Side chain polyether-modified organopolysiloxane having a viscosity of 130 mPa · s blocked with methyl groups (trade name; KF-6011, manufactured by Shin-Etsu Chemical Co., Ltd.) (b2-1) 0.7 part 0.05 parts of methyltrimethoxysilane (alkoxy group content of about 22.0 mmol / g) (b1-1) and tetra-n-propyl orthosilicate (alkoxy group content of about 15.2 mmol / g) (b1-2) ) 0.05 part, 0.195 part of 3-aminopropyltrimethoxysilane (alkoxy group content of about 13.6 mmol / g) (b1-3) and 0.005 part of dioctyltin diversate (b3) In addition, it mixed and the (B) hardening | curing agent composition was prepared.
One part of the component (B) was added to 100 parts of the component (A) and mixed for 10 minutes under vacuum conditions, and various evaluations were performed.

[Comparative Example 5]
Colloidal calcium carbonate whose surface is treated with fatty acid on 45 parts of α, ω-bis-dihydroxy-dimethylpolysiloxane having a viscosity of 1,000 mPa · s (hydroxyl content: about 0.101 mmol / g) (a1-1) (Product name: Shiraka Hana CC-R, manufactured by Shiraishi Calcium Co., Ltd.) (a2-1) 40 parts and untreated heavy calcium carbonate (Product name: Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd.) (a2 -2) 15 parts were added and kneaded under reduced pressure using a planetary mixer to obtain a uniform (A) main agent composition.
Side chain polyether-modified organopolysiloxane having a viscosity of 130 mPa · s blocked with methyl groups (trade name; KF-6011, manufactured by Shin-Etsu Chemical Co., Ltd.) (b2-1) 1.5 parts of methoxysilane (alkoxy group content of about 22.0 mmol / g) (b1-1) and tetra-n-propyl orthosilicate (alkoxy group content of about 15.2 mmol / g) (b1-2) 1 5 parts, 5.85 parts of 3-aminopropyltrimethoxysilane (alkoxy group content of about 13.6 mmol / g) (b1-3) and 0.15 part of dioctyltin diversate (b3) By mixing, a (B) curing agent composition was prepared.
30 parts of the component (B) were added to 100 parts of the component (A) and mixed for 10 minutes under vacuum conditions, and various evaluations were performed.

[Test method]
The room temperature-curable organopolysiloxane compositions (silicone rubber compositions) of the above Examples and Comparative Examples were poured into a 2 mm mold and cured at 23 ° C. and 50% RH for 3 days to obtain a rubber sheet having a thickness of 2 mm. The tack-free time (touch drying time) was measured according to the method specified in JIS A 5758, and the rubber physical properties were measured from a 2 mm thick sheet according to JIS K 6249. Further, from this composition, a shear adhesion test body having an adhesion area of 2.5 mm ² and an adhesion thickness of 1 mm was prepared using an aluminum adherend having a width of 25 mm and a length of 100 mm, and was subjected to 3 days at 23 ° C. and 50% RH. Curing and measurement were performed to confirm the shear adhesive strength and the cohesive failure rate. In the curing rate test method, a glass petri dish having an inner diameter of 10 mm was filled with a sample, and the thickness cured from the portion exposed to air after 1 day at 23 ° C. and 50% RH was measured.
The non-fluidity confirmation test includes three types of the above liquid compositions comprising a liquid composition after mixing for 10 minutes, a liquid composition after mixing for 20 minutes, and a liquid composition mixed for 10 minutes and left for 20 minutes. Was filled in an aluminum channel having a width of 20 mm, a length of 150 mm, and a depth of 10 mm, and then immediately standing vertically to measure the distance at which the liquid composition flows. The results of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 1.

  As can be seen from Table 1, the curing agent composition which is the component (B) prepared in Examples 1 to 4 has good initial uniformity and is mixed with the main agent composition which is the component (A). The non-fluidity can be maintained even when the mixing time and the residence time from mixing to construction are long. In addition, even when such a component (A) and component (B) are mixed in an appropriate ratio, they are cured at room temperature by being left in the air, the deep curability is good, and there is no variation in hardness. A cured product is obtained.

  The room temperature curable organopolysiloxane composition of the present invention comprises two components, a main agent composition as component (A) and a curing agent composition as component (B), and can be produced at low cost. ) After mixing the component (B) and the component (B), the non-fluidity can be maintained even if the mixing time and the residence time from mixing to construction are long. Furthermore, the blending ratio of these components can be appropriately adjusted according to the use of an automatic mixing / discharging machine or the like. And since a mixed composition is excellent in various characteristics, such as deep part sclerosis | hardenability and the uniformity of hardening, it is suitable as a sealing material, a potting material, a coating material, an adhesive agent, an on-site molded gasket etc.

Claims (4)

A two-component room temperature curable organopolysiloxane composition comprising (A) a main agent composition and (B) a curing agent composition, which are prepared and stored separately,
The (A) main agent composition is:
(A1) 100 parts by mass of an organopolysiloxane having a hydroxyl group or an alkoxy group at the molecular end,
(A2) containing 3 to 200 parts by mass of an inorganic filler formed by using a surface-treated inorganic filler and a surface-untreated inorganic filler in combination ;
The (B) curing agent composition is:
(B1) An organosilicon compound and / or a silane coupling agent having three or more hydrolyzable groups as silicon functional groups in one molecule, or a partial hydrolyzate thereof, the hydroxyl group or alkoxy of the component (a1) An amount of 2 to 25 hydrolyzable groups per group;
(B2) a polyether-modified organopolysiloxane represented by the following general formula (1) and liquid at 30 ° C.

(In the formula, m and n are integers of 1 to 100. X is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and Y is represented by the following general formula (2). Polyether group.)
_{-R (C p H 2p O)} q R (2)
(In the formula, R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 1 to 10, q is an integer of 1 to 50, and q is In the case of 2 or more, p may be the same or different from each other.)
1 to 40 parts by mass with respect to 100 parts by mass of the component (a1),
(B3) The curing catalyst contains 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (a1) , and the (A) main agent composition and the (B) curing agent composition are 100: 3-100: RTV organopolysiloxane compositions of two-component, wherein Rukoto formulated in 20 mass ratio. The two-component room-temperature curing property according to claim 1, wherein the surface-treated inorganic filler of component (a2) is colloidal calcium carbonate or fumed silica, and the untreated inorganic filler is heavy calcium carbonate. Organopolysiloxane composition. As the component (a2), the surface-treated inorganic filler 5/55 to 40/55% by mass and the surface untreated inorganic filler 50/55 to 15/55% by mass were used in combination (provided that the total of both was 100 A two-component room temperature curable organopolysiloxane composition according to claim 1 or 2. A structure sealed or bonded with the two-component room temperature curable organopolysiloxane composition according to claim 1 , 2 or 3 .