JP2711613B2 - Room temperature curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a room temperature curable composition containing a silane-modified alkylene oxide polymer as a main component.

[0002]

2. Description of the Related Art Various types of room temperature curable compositions containing a silane-modified alkylene oxide polymer as a main component are already known (for example, Japanese Patent Publication No. Sho 61-1858).
No. 2, No. 61-29379, No. 61-18569,
Nos. 60-57393, 61-36008, 62
Each of these compositions forms a siloxane bond and crosslinks in the presence of moisture to form a cured product. Room temperature curable compositions containing as a main component an alkylene oxide polymer having a silanol group introduced at the molecular terminal are also known (for example, JP-B-57-52368 and JP-B-58-1).
No. 0430, No. 59-9579, No. 61-5482
No. 63-52059), these compositions contain a silane compound having at least two hydrolyzable groups, and form a siloxane bond by crosslinking in the presence of moisture. And cure. The room temperature curable composition described above is mainly used as a building sealing material.For example, when used as a joint sealing material, an external force is applied due to environmental conditions such as temperature change, earthquake, vibration, and wind. In order to maintain the waterproof function even in the case of curing, it is required that the physical properties after curing have a low modulus and a large elongation.

[0003]

However, the above-mentioned room-temperature curable composition has a drawback that the surface curability is poor when used as a sealing material for buildings, and as a result, the composition has an adhesive property on the surface of the cured product. There are problems such as the feeling remaining forever and the decrease in the surface strength of the cured product. Accordingly, an object of the present invention is to provide a room temperature curable composition containing, as a main component, a silane-modified alkylene oxide polymer having improved curing properties.

[0004]

According to the present invention SUMMARY OF], (A) a main chain _{-CH 2 CH 2 O-, -CH 2} CH (C
_{H 3) O -, - CH} 2 CH (C 2 H 5) O- and -
At least one selected from the group consisting of (CH ₂ ) ₄ O—
Consisting of different kinds of alkyleneoxy units, and having the following general formula (1) at the terminal :

Embedded image Wherein R is a hydrogen atom or a lower alkyl group;
R ^{1 to} R ⁴ may be the same or different and are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, and R ⁵ may be the same or different and may be an unsubstituted or substituted monovalent hydrocarbon group. R ⁶ is an alkylene group
And at least one selected from the group consisting of
A species of a divalent organic group, a is an integer of 1 to 3,
Even a group represented by the small without silane-modified alkylene oxide polymer having one closed, and is provided at room temperature curable composition comprising, (B) a curing catalyst.

(A) Silane-modified alkylene oxide polymer In the composition of the present invention, a silane-modified alkylene oxide polymer used as a main material is represented by the above-mentioned general formula (1) in a main chain composed of alkyleneoxy units. At least one unit to be bonded. Alkyleneoxy units constituting Here _{backbone, -CH 2 CH 2 O -,} - CH 2 CH (CH 3) O -, -
_{CH 2 CH (C 2 H 5} ) O -, - (CH 2) 4 O- der
Ri, of course, may be these are combined two or more to constitute a main chain. In the present invention, in particular _-CH 2 CH
It is desirable that the main chain is composed of (CH ₃ ) O—. Further, the silane-modified alkylene oxide polymer may contain, for example, a unit other than the above-described alkyleneoxy unit and the unit represented by the general formula (1) in a range of 3 mol% or less. However, such a unit must not have an atomic group that inhibits a reaction for introducing the unit represented by the general formula (1) into a molecule, and a suitable example thereof is It is as follows.

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In the above general formula (1), R is a hydrogen atom or a lower alkyl group. As the lower alkyl group, those having 4 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group are exemplified. Examples can be given. Most preferred as R is a hydrogen atom. Also R ¹ ~
R ⁴ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; a cyclohexyl group An alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a benzyl group and a phenylethyl group; A group substituted with a halogen atom, an alkoxy group or the like, for example, a chloromethyl group, a 3,3,3-trifluoropropyl group, a methoxyethyl group, an ethoxyethyl group;
Having 1 to 10 carbon atoms, particularly 1
To 6 are preferred. In the present invention, R ¹ and R ² are most preferably a hydrogen atom, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom, an alkyl group or an alkoxy-substituted alkyl group. .

Further, R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group, and specific examples include the same groups as the monovalent hydrocarbon groups described above for R ^{1 to} R ^4. . In the present invention, most preferable examples of R ⁵ include an alkyl group, an alkenyl group and an aryl group. The R ⁶ is I divalent organic radical der, main styrene group, an ethylene group, a propylene group, methylethylene group, tetramethylene group, alkylene groups such as a hexamethylene group,
An arylene group such as a phenylene group and a tolylene group , and most preferably an alkylene group having 1 to 3 carbon atoms. A is an integer of 1 to 3, and as understood from the numerical value of a, the unit represented by the general formula (1) includes -Si
The (OR) _a group is always contained, and this group acts as a crosslinkable group in the presence of moisture to cause a hydrolysis-polycondensation reaction to form a cured product.

In the present invention, specific examples of the unit represented by the general formula (1) are not limited thereto, but are as follows.

Embedded image [In the above formula, Ph represents a phenyl group. ]

In the above-mentioned silane-modified alkylene oxide polymer, the number of units represented by the general formula (1) is at least 1, especially 2 to 3, in one molecule. Thereby, the curability is improved.
The molecular chain form of the silane-modified alkylene oxide polymer may be any of linear, branched, cyclic or a combination thereof, and the molecular weight is not particularly limited. It is preferably in the range of 000 to 12,000.

Further, the silane-modified alkylene oxide polymer has an alkylene oxide polymer having a molecular chain terminal blocked with an amino group-containing organic group, and a compound represented by the following general formula (2):

Embedded image [Wherein R ^{1 to} R ⁶ and a are as defined above], and are synthesized by reacting with a silane compound corresponding to the unit of the general formula (1). That is, the amino group at the molecular end of the alkylene oxide polymer reacts with the α, β-unsaturated carboxyl group in the silane compound to form a unit represented by the general formula (1) into the alkylene oxide polymer chain. Will be introduced. The reaction can be performed in the absence of a solvent, or can be performed using a suitable organic solvent such as toluene or xylene. In the reaction, HgCl ₂ , Hg (OAc) ₂ , RhCl ₃ , T
It can also be carried out using a catalyst such as 1 (OAc) ₃ . It is desirable to use the silane compound such that the α, β-unsaturated carboxyl group in the silane compound is 1 to 10 times the mole of the amino group. The reaction temperature is between 0 and
It is preferable that the temperature be in the range of 150 ° C.

Here, specific examples of the amino group-containing organic group at the molecular chain terminal of the alkylene oxide polymer include, for example, —OCH ₂ CH ₂ NH ₂ , —OCH ₂ CH (CH ₃ ) N
_{H 2, -OCH 2 CH 2 NH} (CH 3), - OOC-C
_{2 H 4 -CONH-C 2 H} 4 -NH 2, -OOC-C 2
H ₄ can be exemplified _{-CONH-C 2} H 4 -NH ₂ or the like. Two or more of these may be bonded to the molecular terminal of the alkylene oxide polymer.
The blocking of the molecular end of the alkylene oxide polymer with the amino group-containing organic group is carried out, for example, by halogenating the hydroxy group of the hydroxy-containing alkylene oxide polymer with PBr ₅ or the like and then reacting with ammonia or the like. be able to.

(B) Curing Catalyst As the curing catalyst, for example, those similar to those used for a silicone resin composition which cures in the presence of moisture,
For example, a tin-based catalyst, a titanium-based catalyst, or the like can be used. Specific examples of the tin-based catalyst include tin naphthenate, tin caprylate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltindiolate, diphenyltin diacetate, dibityltin oxide, dibutyltin dimethoxide, and dibutylbis (tributyltin). Ethoxysiloxy) tin, dibutyltin benzylmalate and the like. Specific examples of the titanium-based catalyst include titanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrabis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium and titanium isopropoxyoctylene glycol. Acid esters and titanium chelate compounds can be mentioned. The amount of these curing catalysts used may be a so-called catalyst amount,
For example, it is used in an amount of 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, per 100 parts by weight of the component (A).

In order to increase the activity of the curing catalyst,
A basic compound can be used in combination as an auxiliary. Suitable examples of such basic compounds include octylamine,
Amines such as laurylamine, imidazoline, tetrahydropyrimidine, 1,8-diazabicyclo (5,4,
0) Examples thereof include guanidyl group-containing silanes or siloxane compounds such as undecene-7 and guanidinepropyltris (trimethylsiloxy) silane, and partially hydrolyzed products thereof. These are generally used in an amount of 0.1 to 10 parts by weight, especially 0.5 to 100 parts by weight of the component (A).
It is used in a proportion of up to 5 parts by weight.

Other Ingredients A silane compound having a hydrolyzable group or a hydrolyzate thereof can be added to the composition of the present invention from the viewpoints of ease of production, storage stability when uncured, and the like. . Specific examples thereof include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, and tetramethoxysilane, methyltri (methylethylketoxime) silane,
Methyltripropenyloxysilane, methyltriacetoxysilane, organosilanes in which the methyl group of these silane compounds is changed to a vinyl group, a phenyl group, and a trifluoropropyl group, and a hydrolyzate of these are exemplified. Particularly preferred are alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane and tetramethoxysilane, and partial hydrolysates thereof.

The room-temperature-curable composition of the present invention may contain various additives conventionally used in this type of composition. For example, for the purpose of reinforcing or increasing the amount of the filler, a filler can be added as necessary. Such fillers include fumed silica, calcined silica,
Fine powdered silica such as precipitated silica, pulverized silica, and fused silica powder; metal oxides such as diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, and magnesium oxide; metal carbonates such as calcium carbonate, magnesium carbonate, and zinc carbonate Salts; metal hydroxides such as cerium hydroxide and aluminum hydroxide; and glass fibers, glass wool, carbon black, fine powdered mica, asbestos, and the like; and those obtained by subjecting their surfaces to hydrophobic treatment with silane or the like. .
Other additives include thixotropic agents such as polyethylene glycol and derivatives thereof; pigments; dyes; antioxidants; antioxidants; antistatic agents; flame retardants such as antimony oxide and paraffin chloride; boron nitride; Such as thermal conductivity improvers, plasticizers, anti-sagging agents,
Examples include a stain inhibitor, a preservative, a bactericide, a fungicide, and an adhesion-imparting agent. Particularly as an adhesion-imparting agent,
Organosilicon compounds having a reactive organic group such as an amino group, an epoxy group or a mercapto group are suitable. Additives other than the components (A) and (B) used as necessary are used in amounts that do not impair the object of the present invention of improving curability.

Room Temperature Curable Resin Composition The composition of the present invention is easily prepared by uniformly mixing the above-mentioned components, and is easily cured at room temperature in the presence of moisture to produce a rubber elastic material. To form a cured product. This composition comprises a building sealant, a coating agent,
It is useful as a sealant for electric and electronic parts, a potting agent, and a surface treatment agent for fibers. In order to apply this composition to a suitable substrate, it may be used by diluting it with a hydrocarbon solvent such as toluene, xylene or petroleum ether, or a solvent such as ketones or esters.

[0017]

EXAMPLES Synthesis Example 1 Polypropylene glycol having a molecular chain terminal of -OC
The one having a molecular weight of 11,000 blocked with H ₂ CH ₂ NH ₂ is used. Γ-dehydrated by heating under reflux to a toluene solution of the polypropylene glycol (100 g).
(Acroxypropyl) trimethoxysilane (10 g)
Was added and reacted at 120 ° C. for 4 hours. After the reaction,
By removing volatile components in the reaction solution under reduced pressure under heating, a viscous liquid (109 g) having a transparent feeling was obtained (yield: 99%). The molecular weight of the obtained product was 12,000. The acryloyl group of γ- (acroxypropyl) trimethoxysilane was stoichiometrically added to the amino group at the end of polypropylene glycol by NMR analysis, IR analysis, and analysis of the amount of Si—OCH ₃ groups by alkali decomposition. It was confirmed that the binding was performed.

Synthesis Example 2 Synthesis Example 1 was the same as Synthesis Example 1 except that γ- (methacryloxypropyl) trimethoxysilane (11 g) was used instead of γ- (acryloxypropyl) trimethoxysilane (10 g). Similarly, a transparent viscous liquid (109 g) was obtained (99% yield). The molecular weight of the obtained product was 12,000. The same analysis as in Synthesis Example 1 confirmed that the methacryloyl group of γ- (methacryloxypropyl) trimethoxysilane was bonded to the amino group at the end of polypropylene glycol in a stoichiometric manner.

Synthesis Example 3 The terminal of the molecular chain is blocked with --OCH ₂ CH (CH ₃ ) NH ₂ and the main chain has the following formula (3)

Embedded image A transparent viscous liquid (108 g) was obtained in the same manner as in Synthesis Example 1 except that polypropylene glycol having a molecular weight of 11,000 and having three units represented by the following formula was used (yield: 98%). The molecular weight of the product obtained is 12,000
It was 0. Further, by the same analysis as in Synthesis Example 1, γ-
It was confirmed that the acryloyl group of (acryloxypropyl) trimethoxysilane was bonded to the amino group at the end of the polypropylene glycol in a stoichiometric manner.

Synthesis Example 4 A transparent viscous liquid (109 g) was obtained in the same manner as in Synthesis Example 2 except that the polypropylene glycol used in Synthesis Example 3 was used (yield: 99%). . The molecular weight of the obtained product was 12,000. The same analysis as in Synthesis Example 1 confirmed that the methacryloyl group of γ- (methacryloxypropyl) trimethoxysilane was bonded to the amino group at the end of polypropylene glycol in a stoichiometric manner.

[0021] Synthesis Example 5 molecular chain _{terminals, -OOC-C 6 H 4 -CONH} -C 2 H
₄ -NH ₂ group (97%), - COOH group (2%) and -
A 10,000-glycol polypropylene glycol blocked with OH groups (1%) is used. Γ- (Acroxypropyl) trimethoxysilane (20 g) was added to a toluene solution of the above polypropylene glycol (100 g), which was dehydrated by heating under reflux, and reacted at 120 ° C. for 4 hours. After the completion of the reaction, the volatile components in the reaction solution are removed under reduced pressure by heating to obtain a transparent viscous liquid (116
g) was obtained (96% yield). The molecular weight of the obtained product was 12,000. In addition, the same analysis as in Synthesis Example 1 confirmed that the acryloyl group of γ- (acroxypropyl) trimethoxysilane was bonded to the amino group at the end of polypropylene glycol in a stoichiometric manner.

[0022] Synthesis Example 6 molecular chain _{terminals, -OOC-C 2 H 4 -CONH} -C 2 H
₄ -NH ₂ group (99%), except that and Using -COOH group (1%) polypropylene glycol having a molecular weight of 10,000 blocked with in the same manner as in Synthesis Example 5, viscous liquid with a transparency ( 116 g) was obtained (96% yield). The molecular weight of the obtained product was 12,000. Also, by the same analysis as in Synthesis Example 1, γ- (acroxypropyl)
It was confirmed that the acryloyl group of trimethoxysilane was bonded to the amino group at the terminal of the polypropylene glycol in a stoichiometric manner.

Examples 1 to 6 Dioctyl phthalate (200 g) and precipitated calcium carbonate (1,000 g) were mixed with each of the polymers (800 g) obtained in Synthesis Examples 1 to 6 using a three-roll mill. A compound was prepared. To this base compound (200 g), add 5 g of methyltrimethoxysilane, 1 g of dibutyltin dilaurate, 1 g of γ-aminopropyltriethoxysilane, and 1 g of γ-guanidylpropyltrimethoxysilane. A composition was prepared. After forming this composition into a sheet having a thickness of 2 mm, the composition was allowed to stand in an atmosphere of 20 ° C. and 60% RH for 7 days, and the physical properties of the obtained cured product were measured in accordance with JIS K-6301 (the hardness was , Measured using a type A hardness spring tester). Further, JIS A-5 was prepared using this composition.
758 H-shaped blocks were created. Using glass as the adherend, curing was performed for 7 days in an environment of 23 ° C. and RH 55%, and then curing was further performed at a temperature of 30 ° C. for 7 days. The cured product was subjected to a tensile tester to measure a 50% modulus, a maximum tensile strength, and a maximum elongation. Table 1 shows the results
Shown in

[0024]

[Table 1]

[0025]

According to the present invention, the curability which is a disadvantage of the curable composition using the conventional silane-modified alkylene oxide polymer can be effectively improved. The cured product obtained from the composition of the present invention shows no tackiness on the surface and a high surface strength.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masatoshi Arai 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) References JP-A-4-89860 ( JP, A) JP-A-4-170432 (JP, A)

Claims (2)

(57) [Claims] (A) The main chain is -CH ₂ CH ₂ O-, -C
_{H 2 CH (CH 3) O} -, - CH 2 CH (C 2 H 5) O
-And- (CH ₂ ) ₄ O-.
At least one type of alkyleneoxy unit, having at the terminal the following general formula (1): Wherein, R is a hydrogen atom or a lower alkyl group, R ¹ to R ⁴ may be the same or different, a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group,, R ⁵ May be the same or different and are an unsubstituted or substituted monovalent hydrocarbon group, and R ⁶ is selected from the group consisting of an alkylene group and an arylene group
A divalent organic radical selected, a is a silane-modified alkylene oxide polymer having one closed even an integer of 1 to 3, in the group represented by small without and, (B) a curing catalyst, A room temperature curable composition comprising: 2. A cured product obtained by curing the composition according to claim 1.