JPH09100408A - Room temperature curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a room temperature-curable composition having delustered surface after the curing without deteriorating physical properties of a sealing material. SOLUTION: This room temperature-curable composition is composed of 100 pts.wt. a polymer comprising propylene oxide as a principal chain, having a curable and hydrolyzable silyl group having 6,000-30,000 number-average molecular weight and 0.1-20 pts.wt. at least one kind selected from the group of an amine compound, an amide compound, a fatty acid, an alcohol and a fatty ester, each having 10-200 deg.C melting point. Furthermore, 2-30 pts.wt. filler having 10-80μm average granular diameter can be contained in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a room temperature curable composition.

[0002]

2. Description of the Related Art Room temperature curable compositions are used as sealants and adhesives for joints on outer walls. Examples of the room temperature curable composition that cures into a rubber by reacting with moisture in the atmosphere include a polysulfide composition, a urethane composition, and a silicon composition. But these are
Various physical properties such as heat resistance and adhesiveness, handleability, price, etc. are not satisfactory, and there is a demand for a high-performance and inexpensive room-temperature curable composition.

Japanese Patent Publication No. 61-18582 discloses an oxypropylene polymer having a hydrolyzable silyl group at the end as a room temperature curable composition having high performance and low cost. This oxypropylene polymer has a molecular weight of 6300 to 15000 obtained by chain extension of polyoxypropylene glycol, and after introducing an ether type allyl olefin group at the terminal, it is converted into the following general formula (I) in the presence of a Group VIII transition metal. It is obtained by reacting with a hydrosilicon compound represented by

[0004]

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In the formula, R ¹ , R ² and R ³ are the same or different and each represents a hydrocarbon group, a halogenated hydrocarbon group, a halogen atom, an alkoxy group, an acyloxy group or a ketoximate group. However, at least one of R ¹ , R ² and R ³ represents a halogen atom, an alkoxy group, an acyloxy group or a ketoximate group.

Further, it is required that the room temperature curable composition used as a sealing material, an adhesive or the like does not give an uncomfortable feeling, so that it is in an excessively glossy state, that is, a so-called "shine" does not appear. To be done. Conventionally, the demand for matting has been met by using a matting paint, adding a filler having a relatively large particle diameter, or adding a porous material.

Examples of such fillers and porous materials are glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, silas balloons having an average particle size of 10 to 80 μm. , Glass balloons, silica balloons, saran balloons, acrylic balloons and the like.

However, the use of a matte coating leads to an increase in the number of processes and an increase in cost, and when a filler or a porous material is added, the tensile properties are deteriorated and it has sufficient physical properties as a sealing material. It has a defect that it is difficult to obtain a product. Therefore, in order to shorten the process and reduce the cost, a matt sealing material is currently required.

[0009]

SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide a room temperature curable composition having a matte surface after curing without deteriorating the physical properties of the sealing material.

[0010]

The room temperature curable composition according to claim 1 (hereinafter, the invention according to claim 1 is referred to as the invention 1) has a number average molecular weight of 6,000 to 30,000 and is crosslinkable. 100 parts by weight of a polymer having a main chain of propylene oxide having a certain hydrolyzable silyl group at the end, and a melting point of 10 to 2
An amine compound having a temperature of 00 ° C, an amide compound having a melting point of 10 to 200 ° C, a fatty acid having a melting point of 10 to 200 ° C,
It is characterized by comprising 0.1 to 20 parts by weight of one or more compounds selected from the group consisting of an alcohol having a melting point of 10 to 200 ° C. and a fatty acid ester having a melting point of 10 to 200 ° C.

The polymer used in the present invention 1 is a polymer whose main chain is propylene oxide. Examples of the polymer of propylene oxide include those having a repeating unit represented by -RO- (wherein R represents a propylene group), and a monomer other than propylene oxide, for example, acrylic acid. Ester type, vinyl acetate, styrene,
A vinyl monomer such as acrylonitrile may be copolymerized.

The number average molecular weight of the polymer used in the present invention 1 is 6,000 to 30,000. If it is less than 6,000, the elongation after curing will be small, and if it exceeds 30,000, the viscosity will be high and the workability will be problematic, so it is limited to the above range.

The above-mentioned polymer is, for example, disclosed in JP-A-3-725.
It is obtained by using the method disclosed in Japanese Patent No. 27. That is, in the presence of a complex metal cyanide complex catalyst, for example, propylene oxide is subjected to ring-opening addition polymerization to an initiator such as a polyhydric alcohol, and then the hydroxyl group at the molecular end is converted to an unsaturated group, and further unsaturated. It is obtained by reacting a hydrosilicon compound having a hydrolyzable group with the group.

Examples of the crosslinkable hydrolyzable silyl group include silyl groups represented by the following general formula (II).

[0015]

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In the formula, R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrocarbon group or a hydrolyzable group. However,
At least one of R ⁴ , R ⁵ and R ⁶ represents a hydrolyzable group.

It is preferable that one of R ⁴ , R ⁵ and R ⁶ is a hydrocarbon group because the reactivity can be easily controlled. The hydrolyzable group is preferably an alkoxy group because it has a good balance of reactivity. More preferably, it is a methoxy group.

The amine compound, amide compound, fatty acid, alcohol or fatty acid ester used in the present invention 1 has a melting point of 10 to 200 ° C. When the melting point is less than 10 ° C., the composition obtained easily leaches out, and when used as a sealing material, the base material is contaminated.
When the temperature exceeds 200 ° C., which causes stains, it becomes difficult to mix with the above polymer, and melting at a high temperature or a large amount of solvent is required at the time of mixing, so the range is limited. The melting point of the amine compound, amide compound, fatty acid, alcohol, or fatty acid ester is preferably 20 to 140.
° C.

An amine compound having a melting point of 10 to 200 ° C., an amide compound having a melting point of 10 to 200 ° C.,
Fatty acids having the melting point of 10 to 200 ° C., the melting point of 1
Alcohol having a temperature of 0 to 200 ° C. and the melting point of 10
The content of one or more compounds selected from the group consisting of fatty acid esters having a temperature of up to 200 ° C is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer. The content is
If the amount is less than 0.1 parts by weight, the matting effect cannot be obtained and 2
If the amount exceeds 0 parts by weight, the adhesiveness will deteriorate, so the content is limited to the above range.

Examples of the amine compound having a melting point of 10 to 200 ° C. include laurylamine (melting point 25
° C), stearylamine (melting point 50 ° C), tribenzylamine (melting point 90 ° C), diphenylamine (melting point 53)
C.), m-phenylenediamine (melting point: 63.degree. C.) and the like.

Examples of the amide compound having a melting point of 10 to 200 ° C. include lauric acid amide (melting point 86
℃), oleic acid amide (melting point 73 ° C), erucic acid amide (melting point 82 ° C), ricinoleic acid amide (melting point 65)
℃), N-stearyl stearic acid amide (melting point 94
℃), N-stearyl oleic acid amide (melting point 67
℃), N-oleyl stearic acid amide (melting point 74
℃), N-stearyl erucic acid amide (melting point 74 ℃),
Examples thereof include N-oleylpalmitic acid amide (melting point 69 ° C.), lauric acid diethanolamide, palmitic acid diethanolamide, myristic acid diethanolamide, and capric acid diethanolamide.

The fatty acids having a melting point of 10 to 200 ° C. are, for example, lauric acid (melting point 44 ° C.), tridecylic acid (melting point 45.5 ° C.), myristic acid (melting point 58.
° C), pentadecyl acid (melting point 54 ° C), palmitic acid (melting point 64 ° C), heptadecyl acid (melting point 61 ° C), stearic acid (melting point 72 ° C), nonadecanoic acid (melting point 69)
℃), arachidic acid (melting point 77 ℃), behenic acid (melting point 82
℃), lignoceric acid (melting point 84 ℃), cerotic acid (melting point 87.9 ℃), heptacosanoic acid (melting point 82 ℃), montanic acid (melting point 89 ℃), melicinic acid (melting point 94 ℃), laxeric acid (melting point 96) ℃) and the like.

Examples of the alcohol having a melting point of 10 to 200 ° C. include cetyl alcohol (melting point 49
° C), heptadecyl alcohol (melting point 54 ° C), stearyl alcohol (melting point 60 ° C), nonadecyl alcohol (melting point 63 ° C), eicosyl alcohol (65.5).
C.), ceryl alcohol (melting point 79.degree. C.), melysyl alcohol (melting point 86.5.degree. C.) and the like.

Examples of the fatty acid ester having a melting point of 10 to 200 ° C. include butyl stearate (melting point 2
3 ° C), stearic acid monoglyceride (melting point 58 ° C),
Pentaerythritol tetrastearate (melting point 65
℃), stearyl stearate (melting point 55 ℃) and the like.

The amine compound, amide compound, fatty acid, alcohol or fatty acid ester used in the first invention is preferably an amine compound having a melting point of 20 to 140 ° C., an amide compound having a melting point of 20 to 140 ° C. Etc.

If necessary, a curing catalyst such as a silanol condensation catalyst may be added to the room temperature curable composition of the present invention 1. Examples of the silanol condensation catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin carboxylates such as tin naphthenate; Reaction product of dibutyltin oxide and phthalic acid ester; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminumethylacetoacetate; zirconium tetraacetylacetonate Chelate compounds such as titanium tetraacetylacetonate; lead octylate; other acidic catalysts and basic catalysts known as silanol condensation catalysts. It is. These may be used alone or in combination of two or more.

The room temperature curable composition of the present invention 1 requires various additives such as physical property modifiers for improving tensile properties, fillers, reinforcing materials, plasticizers, colorants, antioxidants, flame retardants and the like. You may add according to.

Examples of the physical property modifier for improving the tensile properties and the like include, for example, a silicon compound having one silanol group in one molecule, and a silicon compound which is hydrolyzed to form a compound having one silanol group in one molecule. Examples include various silane coupling agents such as compounds.

Examples of the filler include calcium carbonate, magnesium carbonate, hydrous silicic acid, silicic acid anhydride, calcium silicate, silica, titanium dioxide, clay, talc, carbon black and the like. These may be used alone or in combination of two or more.

Examples of the plasticizers include phosphoric acid esters such as tributyl phosphate and tricresyl phosphate; phthalic acid esters such as dioctyl phthalate; fatty acid monobasic acid esters such as glycerin monooleate; dibutyl adipate; Examples thereof include fatty acid dibasic acid esters such as dioctyl adipate. These may be used alone or in combination of two or more. Addition of the above plasticizer further enhances the elongation property after curing and enables a lower modulus.

A room temperature curable composition obtained by further adding to the room temperature curable composition of the present invention 1 a pigment; an ultraviolet absorber; an antioxidant; a flame retardant; various solvents such as toluene and alcohol. May be modified.

A room temperature curable composition according to claim 2 (hereinafter,
The invention according to claim 2 is referred to as present invention 2), wherein the room temperature curable composition of the present invention 1 further comprises 2 to 30 parts by weight of a filler having an average particle size of 10 to 80 μm.

When the average particle size of the filler used in the present invention 2 is small, the matting effect is small, and when it is large, the elongation after curing of the composition is small.
Limited to μm.

In the present invention 2, the content of the above-mentioned filler is limited to 2 to 30 parts by weight, preferably, since the matting effect decreases as the content decreases, and the elongation after curing of the composition decreases as the content increases. 5 to 15 parts by weight.

The filler used in the present invention 2 is not particularly limited as long as it has the above-mentioned average particle diameter, but for example, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads. , Porous silica, shirasu balloon, glass balloon, silica balloon, saran balloon, acrylic balloon and the like. Among these, glass balloons are particularly preferable because the decrease in elongation after curing of the composition is small.

In the second aspect of the present invention, the average particle size is 10 to 80 μm.
By containing the filler of (1), the matting effect is further enhanced, and an amine compound having a melting point of 10 to 200 ° C, an amide compound having a melting point of 10 to 200 ° C, a fatty acid having a melting point of 10 to 200 ° C, Good elongation characteristics can be obtained by mixing one or more compounds selected from the group consisting of alcohols having a melting point of 10 to 200 ° C. and fatty acid esters having a melting point of 10 to 200 ° C. in a specific ratio. Have.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 8 and Comparative Examples 1 to 3 (raw materials used) Polymer having a hydrolyzable silyl group at the end: "Excester 2410" manufactured by Asahi Glass Co., Ltd. (molecular weight 17,000, molecular weight distribution 1. 4) Stearylamine, lauric acid amide, stearyl alcohol, palmitic acid, laurylamine-Glass balloon: "Z27" manufactured by Asahi Glass Co., Ltd., average particle size 6
0 μm ・ Calcium carbonate: Shiraishi Kogyo's "CCR" ・ Titanium oxide ・ Polypropylene glycol: Asahi Glass "Exenol 2020" ・ Vinyltrimethoxysilane ・ Aminoethylaminopropyltrimethoxysilane ・ Dibutyltin dilaurate

(Preparation of Room Temperature Curable Composition) A room temperature curable composition was prepared with the blending composition shown in parts by weight in Table 1. Specifically, the above “Excester 2410” is mixed with stearylamine, lauric acid amide, stearyl alcohol, palmitic acid or laurylamine, which is melted by heating.
And, glass balloon, calcium carbonate, titanium oxide, polypropylene glycol were uniformly mixed with a sealed stirrer, dehydrated by heating under reduced pressure at 110 ° C for 2 hours, cooled to 30 ° C, and further vinyltrimethoxysilane, aminoethylaminopropyl. Trimethoxysilane and dibutyltin dilaurate were uniformly dispersed to obtain a room temperature curable composition.

(Performance Evaluation) A mold is placed on a glass plate which has been treated so that the room temperature curable composition does not adhere thereto, and the room temperature curable composition thus obtained is carefully filled so that bubbles do not enter. Flatten the surface with a spatula, leave it for 7 days at 20 ° C. and 65% relative humidity to cure it, and cure it for 70 m.
A sample of m × 150 mm × 5 mm (height) was prepared. Using the obtained sample, the glossiness, stain resistance and elongation were evaluated by the following methods. -Glossiness: The specular gloss of 60 degrees was measured according to JIS Z 8741. -Staining property: After outdoor exposure for 3 months at Chikko Shinmachi, Sakai City, Osaka Prefecture, sensory evaluation of surface stains was performed. (Evaluation Criteria) A: Almost no stain. Δ: A little soiled and darkened. Elongation: Measured according to JIS K 6301. Table 1 shows the above evaluation results.

[0041]

[Table 1]

[0042]

Since the room temperature curable composition of the present invention 1 has the above-mentioned constitution, it does not deteriorate the physical properties of the sealing material, the surface after curing is matte, and dust and dust after the construction. It is possible to prevent the stain due to the adhesion of the adhesive, and it can be suitably used for sealing and bonding the joints of the outer wall. Invention 2
Since the room temperature curable composition of No. 1 has the above-mentioned composition, the surface after curing is particularly matt, and the physical properties (especially, elongation) of the sealing material are hardly deteriorated, and dust and dust after the construction are applied. It is possible to prevent the stain due to the adhesion of the adhesive, and it can be suitably used for sealing and bonding the joints of the outer wall.

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Claims (2)

[Claims] 1. 100 parts by weight of a polymer having a number average molecular weight of 6,000 to 30,000 and having a crosslinkable hydrolyzable silyl group at its end as a main chain of propylene oxide, and a melting point of 1
An amine compound having a temperature of 0 to 200 ° C. and a melting point of 10 to 200
An amide compound having a melting point of 10 to 200 ° C., a fatty acid having a melting point of 10 to 200 ° C., an alcohol having a melting point of 10 to 200 ° C., and
A room-temperature curable composition comprising 0.1 to 20 parts by weight of one or more compounds selected from the group consisting of fatty acid esters having a melting point of 10 to 200 ° C. 2. The room temperature curable composition according to claim 1, further comprising 2 to 30 parts by weight of a filler having an average particle size of 10 to 80 μm.