JP2018087348A - Room temperature-curable composition, sealant, and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a room temperature-curable composition that can use various crosslink components, e.g., oxime, amide, aminoxy, acetic acid type; a sealant composed of the room temperature-curable composition; and an article bonded or sealed with a cured product of the room temperature-curable composition.SOLUTION: A room temperature-curable composition contains (a) a polyoxyalkylene compound which has at least one reactive silicon group in one molecule, at a molecular chain terminal, and of which the main chain is a polyoxyalkylene polymer, (b) (b-1) a hydrolyzable organosilicon compound having two alkoxy silyl-vinylene groups on the same silicon atom and/or a partial hydrolytic condensate thereof, and/or (b-2) a hydrolyzable organosilane having one methyl, vinyl or phenyl group in one molecule, and also having two or more hydrolyzable groups, and having no amino group, excluding (b-1) component and/or a partial hydrolytic condensate thereof, and (c) a curing catalyst.SELECTED DRAWING: None

Description

  In the present invention, a reactive silicon group having a hydroxyl group bonded to a silicon atom (that is, a silanol group) as a silicon group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). A room temperature containing a polyoxyalkylene compound as a main agent (base polymer) containing at the molecular chain ends (especially at both ends of the molecular chain) and the main chain being a polyoxyalkylene polymer The present invention relates to a curable composition, and in particular, a room temperature curable composition containing an organosilicon compound having a hydrolyzable silyl group in the molecule as a curing agent (crosslinking agent), a sealing material comprising the room temperature curable composition, And an article bonded and / or sealed with a cured product of the room temperature curable composition.

  A reactive silicon group, particularly a reactive silicon group having a silanol group, is hydrolyzed and condensed in the presence of moisture. The polymer having a reactive silicon group is crosslinked and cured in the presence of moisture and can be used as a curable composition. Among these polymers, those whose main skeleton is polyoxyalkylene are generally known as modified silicones. The curable composition using this is liquid at room temperature (23 ° C. ± 10 ° C.), has a characteristic of becoming a rubber elastic body upon curing, and is widely used for architectural sealants and the like.

  It is desirable that these have an appropriate speed at the time of curing, and the rubber-like cured product desirably has a large elongation property as a surface non-adhesive property and a tensile physical property and rubber elasticity rich in flexibility. Many proposals have been made on a method for producing an organic polymer having a reactive silicon group in the molecule, and it has already been industrially produced. For example, it is an organic polymer (trade name: MS polymer) manufactured and sold by Kaneka Co., Ltd., having a main chain of polyoxypropylene and a dimethoxysilyl group bonded to the terminal.

Although this organic polymer has an appropriate curing rate at the time of curing, it is industrially limited to a polymer having a dimethoxysilyl group at the end, and an organic polymer having a silanol group at the end is used. Absent. Therefore, the type of composition that cures by condensation crosslinking is limited to reactive groups at the end of the polymer. Therefore, other than alkoxy type curing agents, for example, condensation curable compositions using oxime, amide, aminoxy, and acetic acid types may not be cured sufficiently, limiting the development of compositions that take advantage of various properties. In order to achieve high elongation of the rubber sheet, it was necessary to partially extend the chain length of the organic polymer with siloxane.
In addition, the following literature is mentioned as a prior art relevant to this invention.

Japanese Patent No. 4034716 JP 2010-209205 A

  The present invention has been made in view of the above circumstances, and an organic compound having at least one hydroxyl group or hydrolyzable group bonded to a silicon atom at a molecular chain terminal as a reactive silyl group that can be crosslinked by forming a siloxane bond. A room temperature curable composition (so-called silicon-containing RTV composition, particularly a modified silicone) in which various crosslinking components such as oxime, amide, aminoxy, and acetic acid types can be used in a curable composition containing a polymer as a main component. The object is to provide an RTV composition), a sealing material comprising the room temperature curable composition, and an article bonded or sealed with a cured product of the room temperature curable composition.

  As a result of intensive studies to achieve the above object, the present inventors have made molecular chain ends (particularly, molecular molecules) with a partial structure of at least one, preferably two or more reactive silicon groups in one molecule. A terminal silanol group-containing polyoxyalkylene compound having a structure represented by the following structural formula (1), which is contained at both ends of the chain) and the main chain is a polyoxyalkylene polymer. By using it as a main agent (base polymer) of (so-called silicon-containing RTV composition, in particular, modified silicone RTV composition), an organic polymer having a terminal alkoxysilyl group is used as the main agent (base polymer). Therefore, when the functional group (hydrolyzable group) of the cross-linking agent is limited only to an alkoxy group that can undergo a condensation reaction with the alkoxy group of the base polymer In comparison, various curing agents (such as organosilicon compounds containing hydrolyzable groups such as oximes, amides, aminoxys, acetic acid (acetoxy groups), alcohols (alkoxy groups)) as well as alkoxy groups are used as crosslinking components. It is theoretically possible to provide room temperature curable compositions of various curing reaction (condensation reaction) types (especially modified silicone RTV compositions), and the organic polymer is partially chained with siloxane. The present inventors have found that the rubber sheet can be highly elongated without including a step of extending the length, and have made the present invention.

［式中、Ｒ¹、Ｒ²はそれぞれ同一若しくは異なってもよく、非置換又は置換の炭素数１〜２０の１価炭化水素基、水素原子、又は（Ｒ³）₃Ｓｉ−Ｏ−（式中、Ｒ³は炭素数１〜２０の１価炭化水素基であり、３個のＲ³は同一であってもよく、異なっていてもよい。）で表されるトリオルガノシロキシ基である。ｎは２以上の整数である。ｍは１以上の整数である。ｐ、ｑは１以上の整数である。Ｚは主鎖のポリオキシアルキレン系重合体である。破線は結合手である。］
（ｂ）下記（ｂ−１）成分及び／又は（ｂ−２）成分： ０．１〜３０質量部、
（ｂ−１）下記一般式（２）で示される同一ケイ素原子上に２つのアルコキシシリル−ビニレン基（アルコキシシリル−エテニレン基）を有する加水分解性有機ケイ素化合物及び／又はその部分加水分解縮合物

（式中、Ｒ⁴は互いに独立に、非置換若しくは置換の、炭素数１〜２０の１価炭化水素基であり、Ｒ⁵は炭素数１〜２０の非置換若しくは置換アルキル基、又は炭素数３〜２０の非置換若しくは置換シクロアルキル基である。ａは１〜３の整数である。）
（ｂ−２）１分子中に１個のメチル基、ビニル基又はフェニル基を有し、かつ少なくとも２個の加水分解性基を有し、かつアミノ基を有さない、（ｂ−１）成分を除く加水分解性オルガノシラン及び／又はその部分加水分解縮合物
（ｃ）硬化触媒： ０．０１〜２０質量部
を含有する室温硬化性組成物。
［２］
（ａ）ポリオキシアルキレン系化合物が、下記一般式（３）で表されるものである［１］に記載の室温硬化性組成物。

（式中、Ｒ¹、Ｒ²、ｎ、ｍ、ｐ、ｑ、Ｚは上記と同じである。）
［３］
上記式（３）中のＺが、下記一般式（４）で示されるものである［２］に記載の室温硬化性組成物。

（式中、Ｒ⁶は２価炭化水素基であり、ｒは１以上の整数である。破線は結合手である。）
［４］
（ａ）ポリオキシアルキレン系化合物が、直鎖状構造である［１］〜［３］のいずれかに記載の室温硬化性組成物。
［５］
（ａ）ポリオキシアルキレン系化合物の分子量が、２００〜５０，０００である［１］〜［４］のいずれかに記載の室温硬化性組成物。
［６］
更に、（ａ）成分１００質量部に対して、
（ｄ）充填剤： ３〜１，０００質量部、及び／又は
（ｅ）接着促進剤： ０．１〜３０質量部
を含有するものである［１］〜［５］のいずれかに記載の室温硬化性組成物。
［７］
更に、（ａ）成分１００質量部に対して、
（ｆ）可塑剤として、下記一般式（５）で表されるオルガノポリシロキサン： ０．１〜１００質量部

（式中、Ｒ⁷は互いに独立に、非置換若しくは置換の、炭素数１〜２０の脂肪族不飽和結合を含有しない１価炭化水素基であり、ｂは該オルガノポリシロキサンの２３℃における粘度が１．５〜１，０００，０００ｍＰａ・ｓとなる数である。）
を含有するものである［１］〜［６］のいずれかに記載の室温硬化性組成物。
［８］
［１］〜［７］のいずれかに記載の室温硬化性組成物からなるシーリング材。
［９］
［１］〜［７］のいずれかに記載の室温硬化性組成物の硬化物で接着及び／又はシールした物品。 That is, the present invention provides the following room temperature curable composition, sealing material, article and the like.
[1]
(A) Poly having a structure represented by the following structural formula (1), wherein at least one reactive silicon group is contained in one molecule at the molecular chain terminal and the main chain is a polyoxyalkylene polymer. Oxyalkylene compound: 100 parts by mass,

[Wherein, R ¹ and R ² may be the same or different and each is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or (R ³ ) ₃ Si—O— (formula R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ³ may be the same or different. n is an integer of 2 or more. m is an integer of 1 or more. p and q are integers of 1 or more. Z is a main chain polyoxyalkylene polymer. A broken line is a bond. ]
(B) The following (b-1) component and / or (b-2) component: 0.1-30 mass parts,
(B-1) Hydrolyzable organosilicon compound having two alkoxysilyl-vinylene groups (alkoxysilyl-ethenylene group) on the same silicon atom represented by the following general formula (2) and / or a partial hydrolysis condensate thereof

(In the formula, R ⁴ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. 3 to 20 unsubstituted or substituted cycloalkyl groups, a is an integer of 1 to 3)
(B-2) having one methyl group, vinyl group or phenyl group in one molecule, having at least two hydrolyzable groups, and having no amino group, (b-1) Hydrolyzable organosilane excluding components and / or partially hydrolyzed condensate thereof (c) Curing catalyst: A room temperature curable composition containing 0.01 to 20 parts by mass.
[2]
(A) The room temperature curable composition according to [1], wherein the polyoxyalkylene compound is represented by the following general formula (3).

(In the formula, R ¹ , R ² , n, m, p, q, and Z are the same as above.)
[3]
The room temperature curable composition according to [2], wherein Z in the formula (3) is represented by the following general formula (4).

(In the formula, R ⁶ is a divalent hydrocarbon group and r is an integer of 1 or more. The broken line is a bond.)
[4]
(A) The room temperature curable composition according to any one of [1] to [3], wherein the polyoxyalkylene compound has a linear structure.
[5]
(A) The room temperature curable composition in any one of [1]-[4] whose molecular weight of a polyoxyalkylene type compound is 200-50,000.
[6]
Furthermore, with respect to 100 parts by mass of component (a),
(D) Filler: 3 to 1,000 parts by mass, and / or (e) Adhesion promoter: 0.1 to 30 parts by mass [1] to [5] Room temperature curable composition.
[7]
Furthermore, with respect to 100 parts by mass of component (a),
(F) Organopolysiloxane represented by the following general formula (5) as a plasticizer: 0.1 to 100 parts by mass

(In the formula, R ⁷ independently of each other is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 20 carbon atoms, and b is the viscosity of the organopolysiloxane at 23 ° C. Is a number from 1.5 to 1,000,000 mPa · s.)
The room temperature-curable composition according to any one of [1] to [6].
[8]
A sealing material comprising the room temperature curable composition according to any one of [1] to [7].
[9]
An article adhered and / or sealed with a cured product of the room temperature curable composition according to any one of [1] to [7].

  In the room temperature curable composition of the present invention, a terminal silanol group-containing polyoxyalkylene compound is used as a main component (base polymer) of the room temperature curable composition, so that various curing agents (oxime, amide, aminoxy, acetic acid ( It is possible to use an organosilicon compound containing a hydrolyzable group such as an acetoxy group or an alcohol (alkoxy group) as a crosslinking component, and it is possible to provide a room temperature curable composition utilizing various characteristics. It becomes. Thereby, the room temperature curable composition excellent in curability can be supplied, and it can be widely used for sealants in which characteristics of various types of crosslinking components are expressed. Furthermore, by using the room temperature curable composition of the present invention, the rubber sheet can be highly elongated.

  Hereinafter, the present invention will be described in more detail.

［式中、Ｒ¹、Ｒ²はそれぞれ同一若しくは異なってもよく、非置換又は置換の炭素数１〜２０の１価炭化水素基、水素原子、又は（Ｒ³）₃Ｓｉ−Ｏ−（式中、Ｒ³は炭素数１〜２０の１価炭化水素基であり、３個のＲ³は同一であってもよく、異なっていてもよい。）で表されるトリオルガノシロキシ基である。ｎは２以上の整数である。ｍは１以上の整数である。ｐ、ｑは１以上の整数である。Ｚは主鎖のポリオキシアルキレン系重合体である。破線は結合手である。］ (A) Component: Terminal Silanol Group-Containing Polyoxyalkylene Compound The component (a) according to the present invention is a main component (base polymer) of the room temperature curable composition of the present invention, and is a terminal silanol group-containing polyoxyalkylene. A compound containing at least one reactive silicon group in one molecule, preferably two or more reactive silicon groups as a partial structure at the end of the molecular chain (particularly at both ends of the molecular chain), A terminal silanol group-containing polyoxyalkylene compound having a structure represented by the following structural formula (1), which is an oxyalkylene polymer.

[Wherein, R ¹ and R ² may be the same or different and each is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or (R ³ ) ₃ Si—O— (formula R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ³ may be the same or different. n is an integer of 2 or more. m is an integer of 1 or more. p and q are integers of 1 or more. Z is a main chain polyoxyalkylene polymer. A broken line is a bond. ]

  When the number of silanol group-containing reactive silicon groups represented by the structural formula (1) contained in one molecule is less than 1 on average, the curability of the composition containing this as a main ingredient is insufficient. In addition, if the amount of the reactive group is too large, the network structure becomes too dense, and the resulting cured product may not exhibit good mechanical properties. Therefore, the number of silanol group-containing reactive silicon groups contained in one molecule is 1 or more, preferably 1.1 to 4, more preferably 2 to 4, and still more preferably 2 (for example, One at each end of the molecular chain).

In the above formula (1), R ^1, R ² may be the same or different, monovalent hydrocarbon radical unsubstituted carbon atoms or a substituted 1-20, hydrogen atom, or (R ^{₃₎ 3} Si-O -(Wherein R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ³ may be the same or different). It is. The unsubstituted or substituted monovalent hydrocarbon group for R ¹ and R ² has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably about 1 to 8 carbon atoms, and may be the same or different. An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are preferable. . Moreover, as monovalent hydrocarbon group of R < ³ >, it is C1-C20, Preferably it is 1-10, More preferably, it is about 1-8, and it may be the same or different, and it is C1-C20. It is preferably an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

Specific examples of R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, and heptyl group. Alkyl groups such as octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group; cyclopentyl group, cyclohexyl group, etc. A cycloalkyl group; an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, and a hexenyl group; an aryl such as a phenyl group, a tolyl group, a xylyl group, and an α-, β-naphthyl group Group: benzyl group, 2-phenylethyl group, 3-phenylpropyl group, etc. Aralkyl groups; groups in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as F, Cl, Br, or cyano groups, such as 3-chloropropyl groups, 3, 3, 3 Examples thereof include -trifluoropropyl group, 2-cyanoethyl group, etc .; hydrogen atom; triorganosiloxy group such as trimethylsiloxy group, triethylsiloxy group, triphenylsiloxy group, and the like.
Among these, as R ¹ , a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group and a phenyl group are particularly preferable from the viewpoint of availability, productivity, and cost. R ² is preferably a hydrogen atom.
Examples of R ³ are the same as those exemplified for the monovalent hydrocarbon groups of R ¹ and R ² above. R ³ is preferably a methyl group, an ethyl group, or a phenyl group.

Moreover, in said formula (1), n is an integer greater than or equal to 2, m is an integer greater than or equal to 1, Preferably, n is an integer of 2-8, m is an integer of 1-8, More preferably, n is an integer of 2 to 4, and m is an integer of 2 to 4.
Furthermore, in said formula (1), p is an integer greater than or equal to 1, q is an integer greater than or equal to 1, Preferably, p is an integer of 1-8, q is an integer of 1-100, More preferably , P is an integer of 1 to 3, q is an integer of 1 to 50, and more preferably, p is 1 or 2, q is an integer of 1 to 10, especially 1 to 5, particularly 1 to 3. It is an integer.

The main chain skeleton of the polyoxyalkylene compound that is an organic polymer containing at least one silanol group-containing reactive silicon group in one molecule is a repeating unit represented by the following general formula (6) (for example, It preferably has an oxyalkylene group or the like.
—R ⁶ —O— (6)
(In the formula, R ⁶ is a divalent hydrocarbon group.)

R ⁶ is not particularly limited as long as it is a divalent hydrocarbon group (particularly an aliphatic divalent hydrocarbon group), but a linear or branched alkylene group having 1 to 14 carbon atoms is preferable. More preferably, it is a C2-C4 linear or branched alkylene group.

It is not particularly restricted but includes the repeating unit represented by the above formula (6), for _{example, -CH 2 O -, - CH} 2 CH 2 O -, - CH 2 CH 2 CH 2 O -, - CH 2 CH (CH _{3) O -, - CH 2} CH (CH 2 CH 3) O -, - CH 2 C (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 , etc. and the like oxyalkylene group O- etc. Can do.

The main chain skeleton of the oxyalkylene polymer may be composed of one type of repeating units represented by the above formula (6), or may be composed of two or more types of repeating units. In particular, when used in a sealant or the like, a polymer containing propylene oxide (—CH ₂ CH (CH ₃ ) O—) as a main component is preferable.

（式中、Ｒ⁶は上記と同じであり、好ましくは炭素数１〜１４の直鎖又は分岐鎖のアルキレン基であり、より好ましくは炭素数２〜４の直鎖又は分岐鎖のアルキレン基である。ｒは１以上、好ましくは２０〜５００、より好ましくは４０〜２００、更に好ましくは５０〜１６０の整数である。破線は結合手である。） In the above formula (1), Z is a main chain polyoxyalkylene polymer having a repeating unit represented by the above formula (6), and the one represented by the following general formula (4). It can be illustrated.

(In the formula, R ⁶ is the same as described above, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. R is 1 or more, preferably 20 to 500, more preferably 40 to 200, still more preferably 50 to 160. The broken line is a bond.)

  Further, the polyoxyalkylene compound which is a terminal silanol group-containing organic polymer according to the present invention preferably has a viscosity at 23 ° C. of 10 to 100,000 mPa · s, more preferably 50 to 50,000 mPa · s, Particularly preferred is 100 to 10,000 mPa · s. When the viscosity of the polyoxyalkylene compound that is the terminal silanol group-containing organic polymer is 10 mPa · s or more, it is easy to obtain a coating film having excellent physical and mechanical strength, and 100,000 mPa · If it is s or less, the viscosity of the composition does not become too high, and workability during use is good, which is preferable. Here, the viscosity is a numerical value obtained by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.).

The polyoxyalkylene compound as the terminal silanol group-containing organic polymer may be linear or branched, but is preferably linear, and its molecular weight is 200. About 50,000 is preferable. More preferably, it is 1,000-20,000.
Here, the molecular weight or the degree of polymerization (the number of repeating oxyalkylene units) is, for example, a number average molecular weight (or number average degree of polymerization) in terms of polystyrene in gel permeation chromatography (GPC) analysis using tetrahydrofuran (THF) or the like as a developing solvent. Etc. (hereinafter the same).

In the present invention, the polyoxyalkylene compound (polyoxyalkylene structure) is “linear” means that the divalent oxyalkylene groups which are repeating units constituting the polyoxyalkylene structure are linear. Each oxyalkylene group itself may be linear or branched (eg, a propyleneoxy group such as —CH ₂ CH (CH ₃ ) O—). May be.

（式中、Ｒ¹、Ｒ²、ｎ、ｍ、ｐ、ｑ、Ｚは上記と同じである。） Examples of such polyoxyalkylene compounds include those represented by the following general formula (3).

(In the formula, R ¹ , R ² , n, m, p, q, and Z are the same as above.)

（式中、ｍ１はｍと同じであり、ｒ１はｒと同じであり、ｐ１はｐと同じであり、ｑ１はｑと同じである。） As a polyoxyalkylene type compound represented by Formula (3), what is shown below can be illustrated, for example.

(In the formula, m1 is the same as m, r1 is the same as r, p1 is the same as p, and q1 is the same as q.)

  The above polyoxyalkylene compounds that are terminal silanol group-containing organic polymers may be used alone or in combination of two or more.

（式中、Ｒ¹、Ｚ、ｐ、ｍは上記と同じであり、ｓは０以上、好ましくは０〜８、より好ましくは０〜２の整数である。） <Method for producing terminal silanol group-containing polyoxyalkylene compound>
The novel polyoxyalkylene compound which is a terminal silanol group-containing organic polymer which is an embodiment of the present invention is, for example, as a first step, in which both ends of a molecular chain represented by the following general formula (7) are alkenyl groups. A bifunctional organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom (Si-H group) at both ends of a molecular chain represented by the following general formula (8) on a blocked polyoxyalkylene polymer (silicon compound) ) Is subjected to hydrosilylation addition reaction to link the alkenyl group-blocked polyoxyalkylene polymers at the beginning of the molecular chain to extend the chain length, and in the second stage, the chain length-extended alkenyl at both ends of the molecular chain A base-blocked polyoxyalkylene polymer and a hydrogen atom (Si-H group) bonded to a silicon atom at one end of a molecular chain represented by the following general formula (9) A two-stage hydrosilylation addition reaction in which an organosilane or organopolysiloxane compound (silicon compound) having a hydroxyl group (silanol group) bonded to a silicon atom at the other end is further subjected to a hydrosilylation addition reaction It can be easily produced by reaction.

(In the formula, R ¹ , Z, p and m are the same as above, and s is an integer of 0 or more, preferably 0 to 8, more preferably 0 to 2.)

Specific examples of the polyoxyalkylene polymer in which both ends of the molecular chain represented by the above formula (7) are blocked with an alkenyl group include, for example, the following structural formula (where r is the same as above): Examples thereof include, but are not limited to, polyoxyalkylene polymers having both ends blocked with alkenyl groups.

Specific examples of the silicon compound represented by the above formula (8) include, for example, those represented by the following structural formula (wherein p is the same as above and Ph represents a phenyl group). However, it is not limited thereto, and any silicon compound containing Si—H groups at both ends of the molecular chain can be used.

Specific examples of the silicon compound represented by the above formula (9) include, but are not limited to, those represented by the following structural formula (where Ph represents a phenyl group). Alternatively, any silicon compound containing a Si—H group at one end of the molecular chain and a Si—OH group at the other end can be used.

  The molecular weight (particularly the number average molecular weight) of the polyoxyalkylene polymer represented by the above formula (7) is usually 2,000 to 20,000, preferably 3,000 to 15,000, more preferably. What is necessary is just about 4,000-8,500. When the molecular weight of the polyoxyalkylene polymer represented by the formula (7) is too small, the physical properties of the cured product after curing are not sufficient, and when it is too large, the viscosity is remarkably increased and workability is deteriorated. The curability of the product may be reduced.

  As described above, the above polyoxyalkylene polymer is linked to the polyoxyalkylene polymer having alkenyl groups at both ends by hydrosilylation addition reaction of silicon compounds having hydrogen atoms bonded to silicon atoms at both ends. To prepare a polymer having an alkenyl group at both ends with an extended chain length, wherein the remaining alkenyl group has a hydrogen atom bonded to a silicon atom at one end and a silicon atom at the other end. It can be easily produced by a two-step reaction by addition reaction of a silicon compound having a hydroxyl group bonded to to a hydrosilylation reaction.

  The polyoxyalkylene polymer represented by the above formula (7) and the silicon compound represented by the above formula (8) are reacted so that the polyoxyalkylene polymer represented by the above formula (7) becomes an excessive amount. The reaction ratio is 1.0: 0.1 to 1.0: 0 in terms of the molar ratio of the alkenyl group in formula (7) to the Si—H group in formula (8). .95, particularly 1.0: 0.3 to 1.0: 0.8 is preferable. If the amount of the silicon compound represented by the formula (8) is too small, the chain length of the organic polymer may not be sufficiently extended. If the amount is too large, the viscosity increases and the workability deteriorates, and the alkenyl group that can be reacted in the next reaction. In some cases, sufficient physical properties of the final cured product cannot be obtained.

  Further, a polyoxyalkylene polymer blocked with an alkenyl group at both ends of a molecular chain obtained by reacting a polyoxyalkylene polymer represented by the above formula (7) with a silicon compound represented by the above formula (8) to extend the chain length; The reaction ratio with the silicon compound represented by the above formula (9) is the molar ratio of the alkenyl group in the polyoxyalkylene polymer with the chain length extended to the Si—H group in the formula (9). 0.8: 1.0 to 1.5: 1.0, particularly 0.9: 1.0 to 1.1: 1.0 is preferable. If the amount of the silicon compound represented by the formula (9) is too small, the cured product after curing may not be completely cured and sufficient rubber properties may not be obtained. It may be difficult to obtain elasticity and may be disadvantageous in terms of cost.

Examples of the addition reaction catalyst used when adding the silicon compound include platinum group metal catalysts such as platinum, palladium, rhodium, and ruthenium, with platinum being particularly preferred. Examples of the platinum-based material include platinum black, alumina, silica, or the like supported on solid platinum, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefin, or platinum and vinyl. Examples include complexes with siloxane.
These platinum group metal catalysts may be used in a so-called catalyst amount, for example, 0.1 to 1,000 ppm, particularly 0.5 to 100 ppm in terms of platinum group metal with respect to the silicon compound. It is preferable.

  These reactions are preferably carried out at a temperature of 50 to 120 ° C., particularly 60 to 100 ° C. for 0.5 to 12 hours, particularly 1 to 6 hours, respectively, and can be carried out without using a solvent. An appropriate solvent such as toluene or xylene may be used if necessary as long as the addition reaction is not adversely affected.

  These reactions are represented by the following formula [1] when, for example, a polyoxyalkylene polymer in which both ends of the molecular chain are blocked with alkenyl groups is used, and allyl group-blocked polypropylene at both ends of the molecular chain is used. .

（式中、Ｒ¹は前記の通りであり、ｐ２、ｑ２、ｍ２はそれぞれ１以上の整数である。ｒ２は２０以上の整数である。）

(In the formula, R ¹ is as described above, and p2, q2, and m2 are each an integer of 1 or more. R2 is an integer of 20 or more.)

(B) Component: Hydrolyzable organosilane and / or its partially hydrolyzed condensate The component (b) according to the present invention acts as a curing agent (crosslinking agent) component in the room temperature curable composition of the present invention. Yes, and consists of component (b-1) and / or component (b-2) described below. If the room temperature curable composition of the present invention does not have at least one of the component (b-1) or the component (b-2), an excellent cured product cannot be obtained.

  The component (b-1) is a hydrolyzable organosilicon compound (hydrolyzable organosilane) having two alkoxysilyl-vinylene groups (alkoxysilyl-ethenylene groups) on the same silicon atom represented by the following general formula (2) And / or a partial hydrolysis condensate thereof. In the present invention, the partially hydrolyzed condensate is a product obtained by partially hydrolyzing and condensing the hydrolyzable organosilane, and has at least 2, preferably 3 or more residual hydrolyzable groups in the molecule. Meaning an organosiloxane oligomer.

（式中、Ｒ⁴は互いに独立に、非置換若しくは置換の、炭素数１〜２０の１価炭化水素基であり、Ｒ⁵は炭素数１〜２０の非置換若しくは置換アルキル基、又は炭素数３〜２０の非置換若しくは置換シクロアルキル基である。ａは１〜３の整数である。）

(In the formula, R ⁴ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. 3 to 20 unsubstituted or substituted cycloalkyl groups, a is an integer of 1 to 3)

Here, in the above formula (2), the unsubstituted or substituted monovalent hydrocarbon group for R ⁴ has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably about 1 to 8 carbon atoms. Or may be different, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl Group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; Aryl groups such as phenyl group, tolyl group, xylyl group, α-, β-naphthyl group; benzyl group, 2-phenyl group An aralkyl group such as a ruethyl group or a 3-phenylpropyl group; and a group in which some or all of the hydrogen atoms of these groups are substituted with a halogen atom such as F, Cl or Br or a cyano group, such as 3 Examples include -chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group and the like. Among these, a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group and a phenyl group are particularly preferable from the viewpoint of availability, productivity, and cost.

The unsubstituted alkyl group for R ⁵ has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, more preferably about 1 to 4 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl Group, octadecyl group, nonadecyl group, eicosyl group and the like. As an unsubstituted cycloalkyl group, it is C3-C20, Preferably it is 4-8, More preferably, it is about 5-6, and a cyclopentyl group, a cyclohexyl group, etc. are mentioned. In addition, some or all of the hydrogen atoms of these alkyl groups and cycloalkyl groups may be substituted with halogen atoms such as F, Cl, Br, cyano groups, etc., for example, 3-chloropropyl Group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group and the like. Among these, R ⁵ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of hydrolyzability.

The hydrolyzable organosilicon compound represented by the general formula (2) of the component (b-1) is mainly used as a curing agent. In General formula (2), a is an integer of 1-3 independently for every silicon atom, However, 2 or 3 is preferable from a sclerosing | hardenable point. In particular, those having an alkoxy group such as three methoxy groups as two alkoxysilyl-vinylene groups on the same silicon atom in the molecule (that is, those having a total of six alkoxy groups in the molecule) Since there are two trifunctional alkoxysilane sites in one molecule, it is useful as a curing agent (crosslinking agent) for dealcohol-modified silicone (room temperature curable composition).
Below, the synthesis example of (b-1) component is shown.

<Production of hydrolyzable organosilicon compound having two alkoxysilyl-vinylene groups on the same silicon atom>
The hydrolyzable organosilicon compound having two alkoxysilyl-vinylene groups (alkoxysilyl-ethenylene groups) of the component (b-1) on the same silicon atom is, for example, an organo having two ethynyl groups on the same silicon atom. Silane and two alkoxyhydrosilanes can be easily produced by addition reaction by hydrosilylation reaction. This reaction formula is represented, for example, by the following formula [2].

（式中、Ｒ⁴、Ｒ⁵、ａは前記一般式（２）の通りである。）

(In the formula, R ⁴ , R ⁵ and a are the same as those in the general formula (2).)

  Examples of the addition reaction catalyst used when adding alkoxyhydrosilane include platinum group metal catalysts such as platinum, palladium, rhodium, and ruthenium, with platinum being particularly preferred. Examples of the platinum-based material include platinum black, alumina, silica, or the like supported on solid platinum, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefin, or platinum and vinylsiloxane. And the like can be exemplified. The amount of platinum used may be a so-called catalytic amount, for example, the total mass of silanes (total mass of organosilane having two ethynyl groups on the same silicon atom and alkoxyhydrosilane) of the platinum group metal. It can be used in an amount of 0.1 to 1,000 ppm, particularly 0.5 to 100 ppm in terms of mass.

  This reaction is generally preferably carried out at a temperature of 50 to 120 ° C., particularly 60 to 100 ° C., for 0.5 to 12 hours, particularly 1 to 6 hours, and can be carried out without using a solvent. As long as the addition reaction is not adversely affected, an appropriate solvent such as toluene or xylene can be used if necessary.

  In the addition reaction of alkoxyhydrosilane to the acetylene group (ethynyl group), for example, a geometric isomer represented by the following reaction formula [3] (that is, a mixture of E and Z forms) is generated. In this case, the generation of E form (trans form) is highly selective and more active, but the alkoxysilyl-vinylene group-containing hydrolyzable organoas component (b-1) of the present invention. Even if a small amount of Z form (cis form) coexists as silane, it does not adversely affect its characteristics, and therefore it can be used as a mixture of geometric isomers without separating them.

（式中、破線は結合手である。）

(In the formula, the broken line is a bond.)

Specific examples of the hydrolyzable organosilicon compound having two alkoxysilyl-vinylene groups on the same silicon atom represented by the formula (2) include those represented by the following structural formula. (B-1) A component can be used individually by 1 type or in combination of 2 or more types.

  The component (b-2) has any one of a methyl group, a vinyl group, and a phenyl group in one molecule, and has at least 2, preferably 3 hydrolyzable groups, and an amino group. It is a hydrolyzable organosilane other than the component (b-1) and / or a partially hydrolyzed condensate thereof having no group, and is used as a crosslinking agent.

  Here, as the hydrolyzable group, the methoxy group, the ethoxy group, the propoxy group, the isopropoxy group, the butoxy group, the isobutoxy group, the tert-butoxy group, etc. Preferably it is C2-C40, such as a C1-C4 alkoxy group, a methoxymethoxy group, a methoxyethoxy group, Preferably it is C2-C10, More preferably, it is a C2-C4 alkoxy alkoxy group, vinyloxy group, An alkenyloxy group, a dimethyl ketoxime group, a diethyl ketoxime group, a methyl ethyl ketoxime group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, such as an allyloxy group, a propenoxy group, and an isopropenoxy group Such as C3-C20, preferably C3-C10, more preferably C3-C6 Oxime group, 2 to 20 carbon atoms such as acetoxy group, preferably having from 2 to 10 carbon atoms, more preferably the like acyloxy group having 2 to 5 carbon atoms.

  Specific examples of the component (b-2) include methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, methyltris (methoxyethoxy) silane, and vinyltris (methoxyethoxy). Silane, methyl tripropenoxy silane, vinyl triisopropenoxy silane, phenyl triisopropenoxy silane, methyl triacetoxy silane, vinyl triacetoxy silane and the like, and partial hydrolysis condensates thereof (b-2) The component is not limited to these. These can be used singly or in combination of two or more.

The hydrolyzable organosilicon compound of component (b) and / or its partial hydrolysis condensate (that is, the total amount of component (b-1) and component (b-2)) is polyoxyalkylene of component (a). 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the polymer, 0.1 mass If the amount is less than parts, sufficient crosslinking cannot be obtained, and it is difficult to obtain a composition having the desired rubber elasticity. If the amount exceeds 30 parts by weight, the mechanical properties of the obtained rubber properties are lowered, which is further disadvantageous economically. Will occur.
In addition, as (b) component which is a hardening | curing agent (crosslinking agent) in the room temperature curable composition of this invention, you may use said (b-1) component or (b-2) component each independently, Further, the component (b-1) and the component (b-2) may be used in combination. The use ratio when the component (b-1) and the component (b-2) are used in combination is, for example, the mass ratio of the component (b-1) to the component (b-2), 99: 1 to 1:99, Preferably it is 90: 10-10: 90, More preferably, it is about 70: 30-30: 70, More preferably, it can be set as about 60: 40-40: 60.

Component (c): curing catalyst (non-metallic organic catalyst and / or metallic catalyst)
Component (c) is a curing catalyst (non-metallic organic catalyst and / or metallic catalyst), and acts to accelerate the curing of the room temperature curable composition of the present invention.

  As the non-metallic organic catalyst of the curing catalyst, known curing accelerators for the condensation curable organopolysiloxane composition can be used, and are not particularly limited. For example, phosphazene-containing compounds such as N, N, N ′, N ′, N ″, N ″ -hexamethyl-N ′ ″-(trimethylsilylmethyl) -phosphorimidic triamide, 3-aminopropyltriethoxysilane , N-β (aminoethyl) γ-aminopropyltrimethoxysilane and other aminoalkyl group-substituted alkoxysilanes, hexylamine, amine compounds such as dodecylamine phosphate or salts thereof, and quaternary ammonium salts such as benzyltriethylammonium acetate Dialkylhydroxylamine such as dimethylhydroxylamine, diethylhydroxylamine, tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane While silane and siloxanes containing a guanidyl group and the like, non-metal-based organic catalyst is not limited thereto. Moreover, you may use a nonmetallic organic catalyst 1 type or in mixture of 2 or more types.

  As the metal catalyst for the curing catalyst, known ones can be used as the curing accelerator for the condensation curable organopolysiloxane, and are not particularly limited. For example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dineodecanoate, alkyltin ester compounds such as di-n-butyl-dimethoxytin, tetraisopropoxytitanium, tetra-n-butoxytitanium, Titanic acid ester or titanium chelate compound such as tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetonato) titanium, titanium isopropoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc-2-ethyloctate, Arcore such as iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, aluminum isopropylate, aluminum secondary butyrate Aluminum compounds, aluminum chelate compounds such as aluminum alkyl acetate / diisopropylate, aluminum bisethyl acetoacetate / monoacetyl acetonate, bismuth (III) neodecanoate, bismuth (III) 2-ethylhexanoate, bismuth citrate (III ), Organometallic compounds such as bismuth octylate, and lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, and lithium oxalate, but the metal catalyst is not limited thereto. Moreover, you may use a metallic catalyst 1 type or in mixture of 2 or more types.

  The amount of these curing catalysts used may be a small amount of catalyst, and the amount of component (c) is 0.01 to 20 parts by weight, especially 0.05 to 100 parts by weight of component (a). 10 parts by mass is preferable, and 0.05 to 5 parts by mass is more preferable. If the amount is less than 0.01 parts by mass, good curability cannot be obtained, so that a problem that the curing rate is delayed occurs. On the contrary, if the amount exceeds 20 parts by mass, the curability of the composition is too fast, so that the allowable range of working time after application of the composition may be shortened or the mechanical properties of the resulting rubber may be reduced. is there.

(D) Component: Filler The component (d) is a filler (inorganic filler and / or organic resin filler), and is an optional component that can be blended as needed in the room temperature curable composition of the present invention. Used to give sufficient mechanical strength to the cured product formed from the composition. Known fillers can be used, for example, finely divided silica, fumed silica, precipitated silica, silica obtained by hydrophobizing these silica surfaces with an organosilicon compound, glass beads, glass balloons, Transparent resin beads, silica airgel, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, metal oxides such as fumed metal oxide, wet silica or those whose surfaces are silane-treated, quartz powder, carbon black, talc, zeolite And reinforcing agents such as bentonite, metal carbonates such as asbestos, glass fiber, carbon fiber, calcium carbonate, magnesium carbonate, zinc carbonate, glass wool, fine mica, fused silica powder, synthetic resin such as polystyrene, polyvinyl chloride, and polypropylene Powder or the like is used. Of these fillers, inorganic fillers such as silica, calcium carbonate, and zeolite are preferable, and fumed silica and calcium carbonate whose surfaces are hydrophobized are particularly preferable.

  The amount of component (d) is preferably 0 to 1,000 parts by mass, and particularly preferably 0 to 300 parts by mass, per 100 parts by mass of component (a). If it is used in an amount larger than 1,000 parts by mass, not only the viscosity of the composition increases and the workability deteriorates, but also the rubber strength after curing decreases and it becomes difficult to obtain rubber elasticity. In addition, when mix | blending (d) component, it is usually preferable to set it as 3 mass parts or more especially 5 mass parts or more. If it mix | blends, the mechanical strength of the hardened | cured material obtained can be made high enough.

(E) Component: Adhesion Promoter (e) The component is an adhesion promoter and is an optional component that can be blended as needed into the room temperature curable composition of the present invention, and is sufficient for a cured product formed from this composition. Used to give good adhesion. As the adhesion promoter (a silane coupling agent such as a functional group-containing hydrolyzable silane), known ones are preferably used, such as a vinyl silane coupling agent, a (meth) acryl silane coupling agent, an epoxy silane coupling agent, Examples include aminosilane coupling agents, mercaptosilane coupling agents, and the like, specifically, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3 -2- (Aminoethylamino) propylto Examples include limethoxysilane, γ-mercaptopropyltrimethoxysilane, isocyanate silane, and the like, and compounds in which these are partially hydrolyzed and condensed. Of the adhesion promoters, vinyl silane coupling agents such as vinyl tris (β-methoxyethoxy) silane can also function as the component (b-2).
Of these, aminosilanes such as γ-aminopropyltriethoxysilane, 3-2- (aminoethylamino) propyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl). ) Epoxy silanes such as ethyltrimethoxysilane and isocyanate silane are preferred.

  (E) It is preferable to mix | blend 0-30 mass parts with respect to 100 mass parts of said (a) component, especially 0.1-20 mass parts. When the adhesion promoter is not used with the filler or the adherend, it is not necessary to use it.

(F) Component: Various plasticizers The room temperature curable composition of the present invention may further contain (f) various plasticizers in addition to the components (a) to (e).

  Examples of the plasticizer used in the room temperature curable composition of the present invention include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and diheptyl phthalate (DHP). , Dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalate, adipine Dioctyl acid (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis (2-ethylhexyl) azelate (DOZ), sebacic acid Dibutyl (DBS) Dioctyl sebacate (DOS), dibutyl maleate (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TB20P) , Tris (2-ethylhexyl) phosphate (TOP), tri (chloroethyl) phosphate (TCEP), trisdichloropropyl phosphate (CPP), tributoxyethyl phosphate (TBXP), tris (β-chloropropyl) phosphate (TMCPP), tris There are phenyl phosphate (TPP), octyl diphenyl phosphate (ODP), acetyl triethyl citrate, tributyl acetyl citrate, and others, trimellitic acid plasticizer, polyester Tell plasticizers, chlorinated paraffins, stearic acid plasticizers, and silicone oils (non-functional organopolysiloxanes) such as dimethylpolysiloxane, recently polyoxypropylene glycols, paraffins, naphthenes, isoparaffins, etc. And petroleum-based high-boiling solvents. These may be used alone or in combination of two or more.

（式中、Ｒ⁷は互いに独立に、非置換若しくは置換の、炭素数１〜２０の脂肪族不飽和結合を含有しない１価炭化水素基であり、ｂは該オルガノポリシロキサンの２３℃における粘度が１．５〜１，０００，０００ｍＰａ・ｓとなる数である。） In addition, as said silicone oil (nonfunctional organopolysiloxane), Preferably, the organopolysiloxane represented by following General formula (5) can be used.

(In the formula, R ⁷ independently of each other is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 20 carbon atoms, and b is the viscosity of the organopolysiloxane at 23 ° C. Is a number from 1.5 to 1,000,000 mPa · s.)

In the above formula (5), R ⁷ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms that does not contain an aliphatic unsaturated bond, specifically, a methyl group Alkyl group such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl Group, aryl group such as xylyl group and naphthyl group, aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group, and part or all of hydrogen atoms of these groups are halogen atoms such as F, Cl and Br Examples thereof include chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group and the like.

  In the organopolysiloxane represented by the above formula (5), the value of b indicating the number of repeating diorganosiloxane units (degree of polymerization) is usually 3 to 3,000, preferably 5 to 2,000. More preferably, it may be an integer of about 10 to 1,000.

  (F) It is preferable that the compounding quantity in the case of mix | blending a component is 0.1-100 mass parts with respect to 100 mass parts of (a) component, More preferably, it is 10-80 mass parts. When the amount of the component (f) is within the above range, it is preferable because the viscosity can be easily handled in construction without impairing the mechanical properties and flame retardancy of the room temperature curable composition of the present invention.

-Other ingredients-
In the room temperature curable composition of the present invention, in addition to the components (a) to (f), various other additives as necessary, for example, pigments such as iron oxide and titanium oxide, dyes, anti-aging agents, You may mix | blend well-known additives, such as antioxidant, an antistatic agent, an adhesion imparting agent, antiseptic | preservative, other flame retardance imparting agents, such as zinc carbonate, an antifungal agent, and an antibacterial agent. What is necessary is just to add these other additives in the quantity of the range which does not prevent the effect of this invention.

  Furthermore, the room temperature curable composition of the present invention may use an organic solvent as necessary. Examples of organic solvents include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane and isododecane, aromatic hydrocarbon compounds such as toluene and xylene, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetra Chain siloxanes such as siloxane, dodecamethylpentasiloxane, 2- (trimethylsiloxy) -1,1,1,2,3,3,3-heptamethyltrisiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, etc. And cyclic siloxane. What is necessary is just to adjust the quantity of the organic solvent suitably in the range which does not prevent the effect of this invention.

The room temperature curable composition of the present invention can be obtained by uniformly mixing the above-mentioned components and further predetermined amounts of the above-mentioned various additives in a dry atmosphere.
Specifically, the above components (a) to (c), and if necessary, the components (d) to (f) and other various additives are used to form bubbles in a state where moisture is blocked or under reduced pressure. It is preferable to prepare by mixing uniformly while removing. Although it does not specifically limit as a mixing apparatus, It is preferable to use the universal mixing stirrer (made by Dalton) connected to a vacuum pump, a planetary mixer (made by Inoue Seisakusho Co., Ltd.), etc.

  The room temperature curable composition is cured by leaving it at room temperature (23 ° C. ± 10 ° C.), and the molding method, curing conditions, and the like are known methods and conditions according to the type of the composition. can do.

  The room temperature curable composition of the present invention is easily cured at room temperature (23 ° C. ± 10 ° C.) by storing it in an airtight container in the absence of moisture, that is, blocking moisture and exposing it to moisture in the air at the time of use. To do. When cured, the room temperature curable composition of the present invention becomes a cured product having excellent flame retardancy, good adhesion to glass and painted aluminum without a primer, and excellent deformation followability. Moreover, the cured | curing material obtained has favorable rubber elasticity. Therefore, it is useful as a sealing material used for a building sealing material. The method of using the room temperature curable composition of the present invention as a sealant is not particularly limited as long as it uses a conventionally known method of using a sealant.

  Examples of the article bonded and / or sealed with the cured product of the room temperature curable composition of the present invention include articles composed of glass, various metals, and the like.

  The room temperature curable composition of the present invention thus obtained is a rubber elastic body that is rapidly cured at room temperature (23 ° C. ± 10 ° C.) by moisture in the air and has excellent heat resistance, weather resistance, and adhesion to various substrates. Form a cured product. Moreover, the room temperature curable composition of the present invention is particularly excellent in storage stability and curability, for example, after storage for 6 months, it quickly cures when exposed to the air, and has excellent physical properties as described above. Give a cured product with. Furthermore, no toxic or corrosive gases are released during curing, and no rust is produced on the surface to which this composition is applied. Also, the composition can be cured and molded to obtain various molded products.

  EXAMPLES Hereinafter, although an Example and a reference example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following specific examples, “part” means “part by mass”, and the viscosity is a value measured by a rotational viscometer at 23 ° C., and the molecular weight and degree of polymerization (of polyoxyalkylene units). The number of repetitions) is a polystyrene-equivalent number average molecular weight and number average degree of polymerization in GPC analysis using THF as a developing solvent.

[Synthesis Example 1]
<Synthesis of terminal silanol group-containing polyoxyalkylene compounds>
Into a 500 mL four-necked separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, 500 g of terminal allyl group-containing polypropylene glycol having a molecular weight of 7,400 (the functional group equivalent of the terminal allyl group is 0.160). Mol) and a platinum catalyst (vinyl siloxane complex solution of chloroplatinic acid, platinum concentration; 1% by mass) were added, and the temperature was raised to 90 ° C. with heating and stirring.
Next, when 5.36 g of 1,1,3,3-tetramethyldisiloxane (the amount of terminal Si—H functional group: 0.080 mol) was added dropwise with stirring, an exotherm was observed, and the reaction temperature was The reaction system was maintained at 90 to 95 ° C. for 6 hours.
To this, 23.9 g (terminal Si) of 1-hydroxy-octamethyltetrasiloxane (ie, 1-hydroxy-7-hydrogen-1,1,3,3,5,5,7,7-octamethyltetrasiloxane) -H functional group amount 0.080 mol) was added dropwise, the reaction temperature was 90 to 95 ° C., and this reaction system was maintained for 6 hours. After completion of the reaction, a small excess of 1-hydroxy-octamethyltetrasiloxane was removed under reduced pressure. After cooling to room temperature, filtration was performed to obtain 498 g (viscosity 28.8 Pa · s, yield 95%) of terminal silanol group-containing polypropylene glycol (polymer AA). This reaction formula is represented by the following formula [4].

（式中、ｒ’は１２７、ｑ’は１である。）

(In the formula, r ′ is 127 and q ′ is 1.)

[Synthesis Example 2]
Into a 500 mL four-necked separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, 500 g of terminal allyl group-containing polypropylene glycol having a molecular weight of 8,400 (in terms of functional group equivalent of terminal allyl group 0.112) Mol) and a platinum catalyst (vinyl siloxane complex solution of chloroplatinic acid, platinum concentration; 1% by mass) were added, and the temperature was raised to 90 ° C. with heating and stirring.
Next, when 4.45 g of 1,1,3,3-tetramethyldisiloxane (the amount of functional group of terminal Si—H is 0.067 mol) is added dropwise with stirring, an exotherm is observed, and the reaction temperature is The reaction system was maintained at 90 to 95 ° C. for 6 hours.
To this, 13.38 g of 1-hydroxy-octamethyltetrasiloxane (the functional group amount of terminal Si—H: 0.045 mol) was added dropwise, the reaction temperature was set to 90 to 95 ° C., and this reaction system was maintained for 6 hours. . After completion of the reaction, a small excess of 1-hydroxy-octamethyltetrasiloxane was removed under reduced pressure. After cooling to room temperature, the mixture was filtered to obtain 492 g of a terminal silanol group-containing polypropylene glycol (polymer BB) (viscosity 29.3 Pa · s, yield 95%).

[Synthesis Example 3]
In a 500 mL four-necked separable flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 250 g of terminal allyl group-containing polypropylene glycol having a molecular weight of 7,200 (converted to functional group of terminal allyl group 0.063). Mol) and 0.5 g of a platinum catalyst (vinyl siloxane complex solution of chloroplatinic acid, platinum concentration; 1% by mass) were added, and the temperature was raised to 90 ° C. with heating and stirring.
Next, when 3.39 g of 1,1,3,3-tetramethyldisiloxane (the functional group amount of terminal Si—H is 0.050 mol) is added dropwise with stirring, an exotherm is observed and the reaction temperature is The reaction system was maintained at 90 to 95 ° C. for 6 hours.
To this, 3.76 g of 1-hydroxy-octamethyltetrasiloxane (terminal Si—H functional group amount 0.012 mol) was added dropwise, the reaction temperature was set to 90 to 95 ° C., and this reaction system was maintained for 6 hours. . After completion of the reaction, a small excess of 1-hydroxy-octamethyltetrasiloxane was removed under reduced pressure. After cooling to room temperature, the mixture was filtered to obtain 244 g of a terminal silanol group-containing polypropylene glycol (polymer CC) (viscosity 31.4 Pa · s, yield 95%).

[Example 1]
100 parts of polypropylene glycol (polymer AA) having a terminal silanol group having a viscosity of 28.8 Pa · s produced in Synthesis Example 1, 9.3 parts of bis (trimethoxysilyl-ethylene) dimethylsilane (the following structural formula), di- A composition was prepared by mixing 0.5 parts of n-butyl-dimethoxytin under moisture blocking until uniform.

[Example 2]
A composition was prepared in the same manner as in Example 1 except that 7.8 parts of vinyltrimethoxysilane was used instead of bis (trimethoxysilyl-ethylene) dimethylsilane.

[Example 3]
In Example 1, instead of bis (trimethoxysilyl-ethylene) dimethylsilane, 16.4 parts of vinyltriisopropoxysilane and dioctyltin dineodecanoate instead of di-n-butyl-dimethoxytin A composition was prepared in the same manner except that the same amount was used.

[Example 4]
In Example 1, instead of the terminal silanol group-containing polypropylene glycol (polymer AA) having a viscosity of 28.8 Pa · s produced in Synthesis Example 1, the terminal silanol group-containing polypropylene having a viscosity of 29.3 Pa · s produced in Synthesis Example 2 was used. A composition was prepared in the same manner except that 100 parts of glycol (polymer BB) was used.

[Example 5]
In Example 1, instead of the terminal silanol group-containing polypropylene glycol (polymer AA) having a viscosity of 28.8 Pa · s produced in Synthesis Example 1, the terminal silanol group-containing polypropylene having a viscosity of 31.4 Pa · s produced in Synthesis Example 3 was used. A composition was prepared in the same manner except that 100 parts of glycol (polymer CC) was used.

[Comparative Example 1]
A composition was prepared in the same manner as in Example 1, except that the same amount of Kaneka MS polymer S303H (molecular chain-end dimethoxysilyl group-blocked polyoxypropylene polymer, manufactured by Kaneka Corporation) was used instead of polymer AA. .

  Next, each composition immediately after preparation prepared in Examples 1 to 5 and Comparative Example 1 was extruded into a sheet having a thickness of 2 mm, exposed to air at 23 ° C. and 50% RH, and then the sheet was subjected to the same atmosphere. The physical properties (initial physical properties) of the cured product obtained by leaving it for 7 days were measured according to JIS K-6249. In addition, hardness was measured using the durometer A hardness meter of JIS K-6249. Table 1 shows the results.

Each cured product obtained in Examples 1 to 5 is equivalent to the conventional modified silicone rubber cured product based on Kaneka MS polymer S303H whose end is blocked with a dimethoxysilyl group as shown in Comparative Example 1. It was confirmed that the rubber physical properties (elongation and tensile strength) were satisfied. Moreover, about the hardness, it has confirmed that the hardened | cured hardened | cured material of higher hardness was obtained compared with the conventional modified silicone rubber hardened | cured material.
Therefore, by using the novel polyoxyalkylene compound having a reactive silicon group having a silanol group at the molecular chain terminal of the present invention as a base polymer of the modified silicone RTV composition, various curing agents (oxime, amide, aminoxy, Acetic acid (acetoxy group), Alcohol (alkoxy group) and other hydrolyzable organosilicon compounds) can be used as cross-linking components, which makes it possible to modify various types of curing reactions (condensation reactions). It can be expected that a silicone RTV composition will be obtained.

Claims (9)

(A) Poly having a structure represented by the following structural formula (1), wherein at least one reactive silicon group is contained in one molecule at the molecular chain terminal and the main chain is a polyoxyalkylene polymer. Oxyalkylene compound: 100 parts by mass,

[Wherein, R ¹ and R ² may be the same or different and each is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or (R ³ ) ₃ Si—O— (formula R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ³ may be the same or different. n is an integer of 2 or more. m is an integer of 1 or more. p and q are integers of 1 or more. Z is a main chain polyoxyalkylene polymer. A broken line is a bond. ]
(B) The following (b-1) component and / or (b-2) component: 0.1-30 mass parts,
(B-1) Hydrolyzable organosilicon compound having two alkoxysilyl-vinylene groups on the same silicon atom represented by the following general formula (2) and / or a partial hydrolysis condensate thereof

(In the formula, R ⁴ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. 3 to 20 unsubstituted or substituted cycloalkyl groups, a is an integer of 1 to 3)
(B-2) having one methyl group, vinyl group or phenyl group in one molecule, having at least two hydrolyzable groups, and having no amino group, (b-1) Hydrolyzable organosilane excluding components and / or partially hydrolyzed condensate thereof (c) Curing catalyst: A room temperature curable composition containing 0.01 to 20 parts by mass. The room temperature curable composition according to claim 1, wherein the (a) polyoxyalkylene compound is represented by the following general formula (3).

(In the formula, R ¹ , R ² , n, m, p, q, and Z are the same as above.) The room temperature curable composition according to claim 2, wherein Z in the formula (3) is represented by the following general formula (4).

(In the formula, R ⁶ is a divalent hydrocarbon group and r is an integer of 1 or more. The broken line is a bond.)   (A) Polyoxyalkylene type compound is a linear structure, The room temperature curable composition of any one of Claims 1-3.   (A) The molecular weight of a polyoxyalkylene type compound is 200-50,000, The room temperature curable composition of any one of Claims 1-4. Furthermore, with respect to 100 parts by mass of component (a),
(D) Filler: 3 to 1,000 parts by mass and / or (e) Adhesion promoter: 0.1 to 30 parts by mass The content according to any one of claims 1 to 5 Room temperature curable composition. Furthermore, with respect to 100 parts by mass of component (a),
(F) Organopolysiloxane represented by the following general formula (5) as a plasticizer: 0.1 to 100 parts by mass

(In the formula, R ⁷ independently of each other is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 20 carbon atoms, and b is the viscosity of the organopolysiloxane at 23 ° C. Is a number from 1.5 to 1,000,000 mPa · s.)
The room temperature-curable composition according to any one of claims 1 to 6.   The sealing material which consists of a room temperature curable composition of any one of Claims 1-7.   The article | item adhere | attached and / or sealed with the hardened | cured material of the room temperature curable composition of any one of Claims 1-7.