JPH038675B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a caulking composition, and more particularly to a caulking composition that is used for filling joints and repairing cracks in building components on wet surfaces or underwater, and particularly has excellent adhesiveness and flexibility. Conventionally, epoxy resins have been widely used in various fields such as various paints, adhesives, and caulking materials because of their excellent chemical resistance, adhesive properties, and electrical properties. However, when it comes to caulking materials that cure in water or on wet surfaces and have sufficient adhesion, for example, caulking materials made of polybutadiene-modified epoxy resin and polyamide amine (Japanese Unexamined Patent Publication No. 58-119)
25324 Publication) etc. are used in the civil engineering field for adhesion and filling of concrete, but because of their insufficient flexibility, they cannot follow the deformation of members due to changes in humidity, wind pressure, earthquakes, and mechanical vibrations, resulting in cracks and cracks. There was a practical problem in that it peeled off. In view of these problems, the present invention aims to provide a caulking material composition with excellent adhesiveness and flexibility for filling joints and repairing cracks in building materials on wet surfaces and underwater. Used as a caulking material. As a result of intensive research to achieve the above object, the present inventors have found that epoxy resins containing epoxy resins (A) obtained by reacting long-chain dibasic acids and epoxy resins
(B) is a poorly water-soluble amine and/or amide (C)
It was discovered that a caulking composition containing a specific amount of a thixotropy agent (D) and a thixotropy agent (D) improves adhesiveness and flexibility when filling joints and repairing cracks in building components underwater or on wet surfaces.The present invention was thus achieved. did. That is, the present invention provides a compound represented by the general formula HOOC-( _CH2 ) ₅ -R-( _CH2 ) ₅ -COOH (wherein R is an alkylene group or alkenylene group having 2 to 8 carbon atoms in the straight chain portion). 100 parts by weight of an epoxy resin (B) containing at least 50% by weight of an epoxy resin (A) obtained by reacting a long-chain dibasic acid with an epoxy resin having at least two epoxy groups in the molecule; An adhesive composition comprising 4 to 430 parts by weight of a poorly water-soluble amine and/or amide (C) and 10 to 160 parts by weight of a thixotropy imparting agent (D). The long-chain dibasic acid used in the present invention has the general formula: HOOC-(CH ₂ ) ₅ -R-(CH ₂ ) ₅ -COOH (where R is an alkylene with 2 to 8 carbon atoms in the linear part). or alkenylene group), and specifically as a saturated linear dibasic acid, for example, R is -(CH ₂ ) ₄ -, -(CH ₂ ) ₈ -, As a saturated branched dibasic acid, for example, R is

【formula】

[Formula] As an unsaturated linear dibasic acid, for example, R is -CH ₂ -CH=CH-CH ₂ -, -CH ₂ -CH=CH(CH ₂ ) ₂ -CH=CH-CH ₂ -, As an unsaturated branched dibasic acid. For example, if R is

【formula】

etc. can be mentioned. These dibasic acids are 1
One species may be used alone, or two or more species may be used in combination. The epoxy resin to be reacted with the long-chain dibasic acid in the present invention includes those having at least two epoxy groups in the molecule, such as bisphenol type epoxy resins and hydrogenated products thereof, cycloaliphatic epoxy resins, phenols, or cresols. General-purpose epoxy resins such as novolac type epoxy resin, phthalate glycidyl ester type epoxy resin, dimer acid type epoxy resin, and polyglycol type epoxy resin can be mentioned. These epoxy resins may be used alone or in combination.
You may use more than one species together. The general formula of the epoxy resin (A) having at least two epoxy groups obtained by reacting the long-chain dibasic acid obtained in this way with a general-purpose epoxy resin, and the compound that is an example of the epoxy resin (A). Chemical structural formula (epoxy resin (A)
-1 to 6) are shown in Table 2 below. In the present invention, the epoxy resin (A) having at least two epoxy groups in the molecule obtained by reacting the long-chain dibasic acid with the epoxy resin is used as the epoxy resin (B) in the caulking material composition. At least 50 of the ingredients
Contain at least % by weight. As the epoxy resin (B) component, the epoxy resin (A) may be used alone or in combination of two or more types, or the epoxy resin (A) and the above-mentioned general-purpose epoxy resins may be used in combination.
In any case, epoxy resin (A) is epoxy resin
It is necessary that the component (B) contains 50% by weight or more, and if the content of the epoxy resin (A) is less than 50% by weight, high adhesion and flexibility in water or on wet surfaces cannot be obtained. The caulking material composition of the present invention is made of epoxy resin.
It can be obtained by blending (B) with a specific amount of a poorly water-soluble amine and/or amide ((C) and a thixotropy imparting agent (D). It is blended in a proportion of 4 to 430 parts by weight per 100 parts by weight of (B).If the blending amount is less than 4 parts by weight, curing will be insufficient;
If more than 430 parts by weight is blended, unreacted curing agent will remain and both will lower the cohesive force of the adhesive, resulting in lower adhesive strength and lower water resistance, which is not preferable. In the present invention, the poorly water-soluble amine and/or amide (C) refers to aromatic amines that are poorly soluble in water and have the ability to replace water molecules, polyalkylene polyamines, polyamides, amide polyamines, NBR-modified amines, etc. for use in epoxy resins. One or more types of curing agents are used. Specifically, as an aromatic amine, m-
Phenylene diamine, 4,4'-methylene dianiline, etc., polyamides made from linoleic acid dimer and ethylene diamine, polyamides made from linoleic acid dimer and diethylene triamine, etc., tall oil and triethylenetetramine as amide polyamines. Amidopolyamine from and,
Examples include amide polyamines made from ricinoleic acid and triethylenetetramine, dibutylaminopropylamine, bis(hexamethylene)triamine, etc. as polyalkyl polyamines, and reactants of carboxylated NBR and N-aminopiperazine as NBR-modified amines. Ru. In the present invention, an ordinary room temperature curing agent can also be used together with the poorly water-soluble amine and/or amide (C). Examples of these room temperature curing agents include aliphatic polyamines, amine adducts, tertiary amines, and modified polymercaptans. For example, aliphatic polyamines include triethylenetetramine and dimethylaminopropylamine, amine adducts include diethylenetriamine and bisphenol A type epoxy resin adducts, triethylenetetramine and ethylene oxide adducts, and tertiary amines include 2,4,6 -Tris(dimethylaminomethyl)phenol, benzyldimethylamine, and modified polymercaptans include trimercaptomethyltrioxane and the like. As mentioned above, the caulking material composition of the present invention can be obtained by blending a specific amount of a poorly water-soluble amine and/or amide (C) into an epoxy resin (B), and further blending a thixotropy imparting agent (D). It will be done. The thixotropy imparting agent (D) is blended in an amount of 10 to 160 parts by weight per 100 parts by weight of the epoxy resin (B). If the amount is less than 10 parts by weight, sufficient thixotropy will not be obtained, resulting in sagging from the applied area, making it difficult to function as a joint filling and crack repair material, and if more than 160 parts by weight is added, the viscosity will increase. This causes significant difficulty in construction workability, and both are unfavorable. The thixotropy imparting agent (D) in the present invention includes inorganic magnesium montmorillonite, colloidal silica, asbestos powder, slate powder, light calcium carbonate, carbon black, etc.
Examples of organic materials include hydrogenated castor oil and polyethylene. These thixotropy imparting agents may be used alone, or
Two or more types may be used in combination. The caulking material composition of the present invention may contain appropriate amounts of extenders, reinforcing agents, fillers, application materials, etc., as required. Examples of these include coal tar, glass fiber, asbestos fiber, carbon fiber, cellulose, polyethylene powder, quartz powder, mica, alumina, kaolin, magnesia, silica, titanium dioxide, Portland cement, iron oxide, aluminum powder, etc. There are many methods available, and any of them can be used effectively depending on the purpose. Furthermore, the caulking material composition in the present invention is
A silane coupling agent can be mixed in for the purpose of increasing its adhesion. For example, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane Examples include silane, γ-mercaptopropyltrimethoxysilane, and the like. Hereinafter, the present invention will be specifically explained based on Examples and Comparative Examples. Note that all formulation values in Table 1 are parts by weight. Examples 1 to 12 and Comparative Examples 1 to 3 The compositions shown in the column of main component in Table 1 were mixed on a paint mill to prepare a main component. Similarly, the formulation shown in the column of curing agent components in Table 1 was mixed on a paint mill to obtain a curing agent. A caulking material composition was obtained by mixing this base agent and a curing agent. In addition, the general formula of the epoxy resin (A) obtained by reacting a long chain dibasic acid and an epoxy resin, and the epoxy resins (A)-1 to 6 listed in Table 1 used in Examples and Comparative Examples
The chemical structural formula of is shown in Table 2. Table 1 shows the properties (hardness, elongation, 180° peel, bending strength and slump) of the caulking composition thus obtained. Note that these characteristics were measured as shown below. (1) Hardness: A caulking composition was injected into a mold with a diameter of 50 mm and a thickness of 10 mm, and after hardening at 20°C for one week, it was measured using a Shore's Durometer Type D. (2) Elongation: Inject the caulking composition into a 1 mm x 150 mm x 150 mm mold, cure at 20℃ for 1 week, punch out with a JIS No. 3 dumbbell, and then use a tensile tester equipped with an elongation measurement method using a TV camera. The measurement was carried out at 20°C and at a tensile speed of 500 mm/min. (3) 180° Peel: Immediately after taking out a 10 mm x 25 mm x 80 mm mortar with a weight ratio of Portland cement and silica sand of 1:1 at 20°C for one day, apply a caulking composition to a thickness of 3 mm. A plain woven cloth was layered on top of this, cured at 20℃ for one week, and then tested using the above tensile tester.
Measurements were made at a peel rate of 50 mm/min at °C. Note that (material failure) in Table 1 represents material failure of mortar. (4) Bending strength: Similar to the measurement of beer at 180°, a caulking composition was applied to the bottom of a mortar with dimensions of 40 mm x 40 mm x 80 mm that was immersed in water, adhered to the bottom surfaces, and cured at 20°C for one week. 10 minutes at 20℃ using Shimadzu Autograph IS-5000.
A three-point bending test was performed at a compression rate of mm/min.
The method was based on JISK7203-1982 bending test method for hard plastics. Note that (material failure) in Table 1 represents material failure of mortar. (5) Slump; using caulking material composition
A slump test was conducted on JISA5751-1975 oil-based caulking materials for construction. In the slump results in Table 1, slump within 3 mm is marked as 〇.
Those with slump exceeding 3 mm were marked as ×.

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[Table] As shown in Table 1, Examples 1 to 12, which are caulking material compositions of the present invention, have high flexibility and
It has excellent peel strength and bending strength, and also shows little slump in the slump test, indicating that it has thixotropy. On the other hand, in Comparative Example 1 in which no thixotropy imparting agent was added, slump occurred and sufficient thixotropy could not be obtained. Furthermore, Comparative Example 2 in which a general-purpose epoxy resin was used alone had high hardness, low elongation, and poor peel strength. Furthermore, Comparative Example 3 using another general-purpose epoxy resin had low elongation and poor peel strength. As explained above, an epoxy resin (B) containing a specific range of an epoxy resin (A) obtained by reacting a long-chain dibasic acid with an epoxy resin having at least two epoxy groups in the molecule has a poorly water-soluble amine and/or amide (C) and thixotropic agent (D)
The caulking material composition of the present invention, which is made by adding a specific amount of Because it uses a substitutable amine and/or amide, it cures well in water or on a wet surface, and it also reacts with a long-chain dibasic acid and an epoxy resin that has at least two epoxy groups in the molecule. Because it uses the obtained epoxy resin (A), it has excellent underwater adhesion and flexibility. Therefore, the composition of the present invention can be used as a caulking material used for filling joints and repairing cracks in building components, and can also be used as a sealing material, caulking material, and adhesive used in civil engineering and marine engineering.

Claims (1)

[Claims] 1 Represented by the general formula HOOC-(CH ₂ ) ₅ -R-(CH ₂ ) ₅ -COOH (wherein R is an alkylene group or alkenylene group having 2 to 8 carbon atoms in the straight chain portion) 100 parts by weight of an epoxy resin (B) containing at least 50% by weight of an epoxy resin (A) obtained by reacting a long-chain dibasic acid with an epoxy resin having at least two epoxy groups in the molecule; , 4 to 430 parts by weight of a poorly water-soluble amine and/or amide (C), and 10 to 160 parts by weight of a thixotropy imparting agent (D).