JP4745905B2 - Two-component acrylic adhesive for inorganic materials for civil engineering and construction - Google Patents

Description

The present invention relates to a two-component acrylic adhesive excellent in adhesion and curability to civil engineering and building inorganic materials such as cement products and clay products.

  A (meth) acrylic monomer (in the present invention, (meth) acrylic represents acrylic or methacrylic), an agent A containing an organic peroxide, a (meth) acrylic monomer, and the organic peroxide A two-part acrylic adhesive comprising a B liquid containing a reducing agent that forms a redox catalyst system cures in a short time at room temperature and exhibits excellent adhesive strength, as well as in a stoichiometric sense. It is characterized by the fact that strict metering and mixing of the two liquids is unnecessary and handling is easy.

  However, although the two-component acrylic adhesive exhibits excellent adhesion for bonding a hard material such as a metal material, there is a problem that the strength is insufficient due to poor curing depending on the adherend. For example, in the case where the adherend is an inorganic material such as a cement product or a clay product, there is a problem in that it is difficult to cure due to the influence of a radical polymerization inhibitor in the inorganic material, resulting in poor curing.

  As a method for solving such a problem, for example, Patent Document 1 discloses curing containing di (meth) acrylate having a specific bisphenol skeleton, dicyclopentenyloxyalkylene (meth) acrylate, and hydroxyalkyl (meth) acrylate. It is described that the use of a functional resin composition can solve the curing inhibition by an alkaline compound such as calcium hydroxide contained in concrete.

  In addition, as a method for imparting adhesion performance to an inorganic material by adopting or selecting a specific redox catalyst system, for example, Patent Document 2 discloses a two-part acrylic system using an organic peroxide and a vanadium compound as a redox catalyst system. Patent Document 3 describes that a polymerizable (meth) acrylic monomer and an organic peroxide improve adhesion to inorganic materials such as cement products and clay products by coexisting an α-hydroxycarbonyl compound in the adhesive. And a primer mainly composed of a condensate of an aldehyde and an amine and a soluble vanadium compound, and at least one of the main agent and the primer is selected from acidic phosphorus compounds, organic carboxylic acids and organic sulfonic acids. The main agent-primer acrylic adhesive containing one or more compounds is only a metal material. Not, it is described that exhibits excellent adhesion performance relative to asbestos slates.

  On the other hand, in Patent Document 4, the first solution contains a polymerizable acrylate or methacrylate material and a free radical polymerization initiator as essential components, and the second solution contains a polymerizable acrylate or methacrylate material and a transition metal salt. A two-component solventless adhesive composition having an agent system as an essential component is disclosed, and it is described that it is extremely effective to add a hydrazine derivative, particularly 1-acetyl-2-phenylhydrazine, to the first liquid. ing. Therefore, it is considered that the redox catalyst system containing the hydrazine derivative described in Patent Document 4 can be applied to the adhesion of the inorganic material, referring to the redox catalyst system described in the examples, that is, as an organic peroxide in the first liquid. Cumene hydroperoxide, 1-acetyl-2-phenylhydrazine as a hydrazine derivative, and copper (II) acetylacetonate, a copper compound similar to copper octenoate as a transition metal compound, in the second liquid When tested with a two-component acrylic adhesive, sufficient adhesive strength was not obtained for civil engineering and architectural inorganic materials.

Japanese Patent Laid-Open No. 11-106453 JP-A-11-1663 Japanese Patent Laid-Open No. 6-80937 JP 59-4667 A

  An object of the present invention is to provide a two-component acrylic adhesive having excellent adhesion and curability to civil engineering and building inorganic materials such as cement products and clay products.

  As a result of intensive studies on a redox catalyst system using a hydrazine derivative to solve the above problems, the present inventors have found that when a cobalt compound is used as an organic peroxide, a specific phenylhydrazine derivative and a transition metal compound, The present inventors have found that a two-component acrylic adhesive excellent in adhesiveness, adhesion and curability can be obtained even for civil engineering and architectural inorganic materials such as clay products.

That is, the present invention
(1) A agent comprising one or more phenylhydrazine derivatives selected from polymerizable (meth) acrylic monomers, organic peroxides, β-acetylphenylhydrazine, β-formylphenylhydrazine, and β-trifluoroacetylphenylhydrazine A two-component acrylic adhesive for inorganic materials for civil engineering / architecture, comprising a polymerizable (meth) acrylic monomer and a B agent comprising a cobalt salt of a carboxylic acid .
Is to provide.

The two-component acrylic adhesive of the present invention contains a polymerization inhibitor such as a cement product or a clay product by adopting a redox catalyst system comprising an organic peroxide, a specific phenylhydrazine derivative, and a cobalt salt of carboxylic acid. It has become possible to provide a two-part acrylic adhesive having excellent work efficiency because it has excellent adhesion, adhesion and curability to the material and is cured in a short time.

  First, the civil engineering and architectural inorganic materials in the present invention are asbestos cement board, mortar, calcium silicate board, concrete, cement products of materials using other cement as raw materials, tiles, bricks, tiles, sanitary ware, earthen pipes, etc. Means clay products. In particular, it is preferable to apply the two-component acrylic adhesive of the present invention to cement products such as asbestos cement board and concrete. In the present invention, for civil engineering / architectural inorganic materials, it goes without saying that civil engineering / architectural inorganic materials are used, but one is for civil engineering / architectural inorganic materials and the other is for metal, wood, plastic and other dissimilar materials. Of course, use for bonding is also included.

  In the present invention, the polymerizable (meth) acrylic monomer which is the main agent used in both the A agent and the B agent includes (meth) acrylic acid, (meth) acrylic acid alkyl ester, phenoxyethyl (meth) acrylate, and cyclohexyl (meth). Acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester, poly (meth) acrylate of polyhydric alcohol, epoxy (meth) acrylate obtained by addition reaction of (meth) acrylic acid to epoxy resin, Di (meth) acrylates of alkylene oxide adducts of bisphenol A or bisphenol S such as urethane poly (meth) acrylate, polyester (meth) acrylate, or 2,2-bis [4- (methacryloxyethoxy) phenyl] propane Etc., and they are alone or used in combination of two or more.

  Moreover, the organic peroxide as a polymerization initiator mix | blended in A agent is hydroperoxides, such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide. Peroxyesters such as t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxide decanoate, etc. can be used alone or in combination of two or more thereof. Hydroperoxides are particularly preferable from the viewpoint of curing in a short time, which is one of the characteristics. The compounding amount of the organic peroxide is preferably 1 to 10 parts by weight, and more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the polymerizable (meth) acrylic monomer blended in the agent A.

The phenylhydrazine derivative blended in the agent A is one or more phenylhydrazine derivatives selected from β-acetylphenylhydrazine, β-formylphenylhydrazine, and β-trifluoroacetylphenylhydrazine.

  The blending amount of the phenylhydrazine derivative is selected from a range in which both the curing speed and the storage stability are compatible, and specifically 0.05 to 100 parts by weight of the polymerizable (meth) acrylic monomer blended in the agent A. -5 parts by weight is preferable, and 0.1-2 parts by weight is more preferable.

Moreover, as cobalt salt of carboxylic acid mix | blended in B agent, organic acids, such as cobalt acetate, cobalt benzoate, cobalt citrate, cobalt naphthenate, cobalt stearate, cobalt oleate, cobalt 2-ethylhexanoate These cobalt salts are used, and these may be used alone or in combination of two or more. The amount of the carboxylic acid cobalt salt is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymerizable (meth) acrylic monomer blended in the B agent in consideration of the curing speed, storage stability, and the like. Furthermore, 0.5-3 weight part is preferable.

  In addition, in the present invention, the agent A and / or agent B for the purpose of adjusting the viscosity and improving the flexibility of the cured product, further, polymethyl methacrylate, polyvinyl butyral, acrylonitrile-styrene copolymer (AS resin), Thermoplastic resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), methacrylate ester-butadiene-styrene copolymer (MBS resin), methacrylate ester-butadiene-acrylonitrile-styrene copolymer (MBAS resin), Styrene-butadiene rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), chloroprene rubber (CR), nitrile rubber (NBR), chlorinated rubber, acrylic rubber, epichlorohydrin rubber, liquid polybutadiene, terminal acrylic Degeneration Liquid polybutadiene, liquid rubber such as liquid acrylonitrile-butadiene copolymer, crystalline silica powder, fused silica powder, spherical silica powder, silica powder such as fumed silica, silica sand, carbon black, wollastonite, clay, mica , Magnesium oxide, iron oxide, titanium oxide, bentonite, lead chromate, nickel slag, aluminum hydroxide, spherical alumina powder, stainless steel powder, silicon carbide powder, silicon nitride powder, boron nitride powder, talc powder, carbonic acid Inorganic fillers such as calcium powder, glass beads, shirasu balloon, aluminum powder, and titanium powder can be appropriately blended.

  For the purpose of improving long-term storage stability at room temperature, p-benzoquinone, 2,6-di-t-butyl-4-methylphenol, 2,2-methylenebis (4-methyl-6-t-butylphenol) 1,4-naphthoquinone, hydroquinone, hydroquinone monomethyl ether, ethylenediaminetetraacetic acid tetrasodium, oxalic acid and other radical polymerization inhibitors, and coloring dyes and pigments can be blended.

Next, the present invention will be described in more detail with reference to examples. In the following examples and comparative examples, parts represent parts by weight, and gelation time, set time, surface curability, and adhesive strength (tensile shear strength, compression shear strength) as performance evaluation items. ) Was measured under the following conditions.
<Gelification time>
In an atmosphere of 23 ° C. and 50% RH, 0.5 g of each of agent A and agent B was weighed into a polyethylene container, and the time until gel formation was measured starting from the time of mixing for 10 seconds to be the gelation time .
<Surface hardening>
Using a cold-rolled steel sheet having a thickness of 1.6 mm, a width of 25 mm, and a length of 100 mm as a test piece in an atmosphere of 23 ° C. and 50% RH, the surface of the test piece is 12 mm in length so that the length of the overlapping portion is 12 mm. An equal amount mixture of agent A and agent B was applied to the surface, and the surface condition of the adhesive protruding after curing for 24 hours under the same conditions was visually observed and evaluated according to the following criteria.
○ Completely cured.
△ The inside is hardened, but the surface is slightly sticky.
X The protruding adhesive was not cured and was sticky.

<Adhesive strength>
In an atmosphere of 23 ° C. and 50% RH, apply equal amounts of agent A and agent B to one of the test pieces, and bond and fix the test pieces so that they are rubbed together. Later, the measurement was performed under the following conditions.
[Tensile shear strength]
Using the test piece shown below, the length of the polymerization part was set to 12 mm, and the measurement was performed according to JIS K6850.
Cold rolled steel sheet: thickness 1.6mm, width 25mm, length 100mm
Asbestos-cement board: 3mm thick, 25mm wide, 100mm long
Calcium silicate plate: 6mm thick, 25mm wide, 100mm long
Tile: Thickness 4mm, width 25mm, length 100mm (bonds the ungrounded ground)
Lauan plywood: thickness 2.5mm, width 25mm, length 100mm
[Compressive shear strength]
A mortar test piece having a thickness of 10 mm, a width of 25 mm, and a length of 30 mm as a test piece (prepared in accordance with JIS R5201 and polished with water-resistant abrasive paper # 150 defined in JIS R6253 to remove fragile and powdered materials. The sample was washed with water and dried at 23 ° C. and 50% for 24 hours or more.), And the length of the polymerization part was 25 mm, and the measurement was performed according to JIS K6852.

[Preparation of each adhesive]
Table 1 shows the composition (Nos. 1 to 5) of the prepared agent A. These A agents were stable for more than half a year at 23 ° C. in a state where 100 g of polyethylene was filled in a 100 ml polyethylene container.

  Next, Table 2 shows the prepared agent B (Nos. 1 to 3). These B agents were stable at 23 ° C. for more than half a year in a state where 100 g was filled in a 100 ml polyethylene container.

Examples 1-3, Comparative Examples 1-8
The A and B agents shown in Tables 1 and 2 were combined to make a two-component acrylic adhesive, and the adhesive performance was evaluated. The results are shown in Table 4.

From the results in Table 3, No. 1 containing the phenylhydrazine derivative of the present invention was blended. No. 1 to No. 3 using a cobalt salt of carboxylic acid . The two-component acrylic adhesive according to Examples 1 to 3 combined with the B agent of 1 showed excellent values for the gelation time, surface curability, and adhesive strength for cement products and clay products. On the other hand, the two-part acrylic adhesive of Comparative Example 1 using an aliphatic hydrazine derivative and Comparative Example 2 containing no hydrazine derivative is hardened but takes a long time to gel. It did not adhere to calcium silicate plates and tiles at all. Moreover, the compressive shear strength with respect to the mortar was not sufficient.

In addition, the two-part acrylic adhesives of Comparative Examples 3 to 5 using copper (II) acetylacetonate (redox catalyst system similar to copper octenoate of Patent Document 4) are similarly applied to cement products and clay products. Did not adhere.
Furthermore, the two-component acrylic adhesives of Comparative Examples 6-8 using vanadyl acetylacetonate , which was effective for bonding inorganic materials in Patent Documents 2 and 3, showed excellent adhesion performance for tiles, Although the gelation time was short and the surface curability was good, the adhesive strength to asbestos cement board, calcium silicate board and mortar was low and lacked practicality.

  According to the present invention, a two-component acrylic adhesive having a high curing speed and a high adhesive strength is provided for an inorganic material for civil engineering / architecture. For example, an asbestos-cement board used for an inorganic material for civil engineering / architecture. , Mortar, calcium silicate board, concrete, other cement products made of cement as raw materials, tiles, bricks, tiles, sanitary ware, clay products such as sanitary ware, clay pipes, etc. Reliable construction in time has become possible.

Claims (1)

Polymeric (meth) acrylic monomer, organic peroxide, β-acetylphenylhydrazine, β-formylphenylhydrazine, A-agent comprising one or more phenylhydrazine derivatives selected from β-trifluoroacetylphenylhydrazine and polymerizable A two-component acrylic adhesive for inorganic materials for civil engineering and construction, comprising a (meth) acrylic monomer and a B agent comprising a cobalt salt of a carboxylic acid .