JP2002241706A - Plastic adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plastic adhesive composition in a semisolid state as exhibited by moderately hydrated clay, having properties of being readily plastically deformable, rapidly curing and firmly bonding to the surface of an adherend and having effective sealing effects. SOLUTION: This plastic adhesive composition comprises a clayey substance and an acrylic ester monomer or further contains an organic peroxide catalyst and a polymerization accelerator. The clayey substance is a bentonitic or micaceous substance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an environment-friendly plastic adhesive composition which is easily cured at room temperature.

[0002]

2. Description of the Related Art Conventionally, clay minerals such as natural clays and synthetic clays have been used as local seals and emergency seal materials by utilizing the property of exhibiting plasticity by appropriately containing water. However, these have problems such as weak adhesion to the adherend, weak sealing effect, and easy peeling. In addition, although ordinary adhesives can be expected to have strong adhesive strength, they do not have plasticity, so that favorable workability, such as the above-mentioned viscous mineral, cannot be obtained. Improvement is desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a favorable workability, that is, a plasticity that is easily deformable by kneading with a hand or the like in a semi-solid state, as shown by a clay mineral containing a suitable amount of water, Further, the present invention aims to provide a plastic adhesive composition which is firmly adhered to an adherend surface, can exhibit an effective sealing effect, has a characteristic of being easily cured even at ordinary temperature, and is environmentally friendly. I have.

[0004]

Means for Solving the Problems The present invention is a plastic adhesive composition containing a clay material and an acrylate monomer, and a plastic adhesive composition containing an organic peroxide catalyst. A plastic adhesive composition containing a polymerization accelerator that promotes decomposition of an organic peroxide catalyst and promotes radical polymerization, and contains an acrylate monomer, an organic peroxide catalyst, and a clay material. A plastic adhesive composition A, and a plastic adhesive composition B containing a clay-based substance and a polymerization accelerator that promotes the decomposition of an acrylate monomer and an organic peroxide to promote radical polymerization. A plastic adhesive composition comprising an acrylonitrile-butadiene elastomer, wherein the clay material is a bentonite material. Are those, clay-based material is a thermoplastic adhesive composition is a mica-based material, promoting the degradation of the acrylic ester-based monomer and an organic peroxide-based catalyst,
Around a plastic adhesive composition B containing a polymerization accelerator for promoting radical polymerization and a clay-based substance, a plastic adhesive composition A containing an acrylate-based monomer, an organic peroxide-based catalyst and a clay-based substance And a plastic adhesive composition formed by an extrusion method.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The clay-based material used in the present invention is:
It is a basic component for causing the adhesive composition to exhibit a characteristic (plasticity) that can be easily plastically deformed, such as a clay mineral containing a moderate amount of water. Therefore, the clay-based material used in the present invention has a large specific surface area, does not react with an adhesive component, and is not limited to an organic or inorganic material as long as it does not inhibit the performance of the adhesive. A clay mineral having a large specific surface area, such as bentonite powder and mica powder, or a powder made of a substance having a layered structure is a particularly preferable material.

The clay-based material of the present invention may be used alone or as a mixture of two or more. In addition, even if a filler (a general filler) having a specific surface area smaller than that of a clay-based material and not exhibiting the above-described specific properties as in the case of a clay-based material alone is used in combination with a clay-based material. good.

When only such a general filler is used, a liquid substance having a high viscosity or thixotropic properties or a putty-like adhesive composition can be obtained. Like using a substance,
A plastic adhesive composition having specific plasticity cannot be obtained.

Here, the plasticity, which indicates the basic characteristics of the plastic adhesive composition of the present invention, is described in a dictionary of powder engineering terms (Showa 5).
Published by the editor of the Powder Engineering Society of Japan for 6 years, "If a solid is placed under appropriate conditions, it does not behave as an ideal rigid or elastic body against external forces even if it is below its melting point, and it is continuous without breaking. It is a property that can be deformed mechanically and permanently, and in the case of metals and synthetic resins, its plasticity can be changed by the temperature, and in the case of clay and flour dough, its plasticity can be changed by the water content. "
In particular, the properties of the plastic adhesive composition of the present invention mean the plasticity obtained in the case of clay in this description.

The acrylate monomers used in the present invention include acrylate monomers and methacrylate monomers. Specifically, methyl acrylate, acrylate, propyl acrylate, butyl acrylate, methacrylate Methyl, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate , 3-chloro-2-hydroxypropyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate and the like, but are not limited thereto.

These monomers may be used alone, but it is more preferable to use two or more of them in combination in order to obtain desirable properties as a plastic adhesive.

Further, a polymerizable vinyl monomer other than these acrylate monomers may be used in combination.

Further, the plastic adhesive composition of the present invention can remarkably improve the properties of the plastic adhesive by simultaneously containing an acrylate monomer and an elastomer component. preferable.

The type of the elastomer component can be arbitrarily selected, but a particularly preferred elastomer component is an acritonitrile-butadiene elastomer.

The organic peroxide catalyst used in the present invention can be arbitrarily selected from those exhibiting the function of a so-called radical polymerization initiator. For example, benzoyl peroxide, methyl ester ketone hydroperoxide, t-butyl hydroperoxide, di-t-butyl hydroperoxide, dicumyl peroxide, cumene hydroperoxide and paramenthane hydroperoxide are typical examples. But are not limited to these.

Examples of the polymerization accelerator used in the present invention that promotes decomposition of the organic peroxide catalyst and promotes radical polymerization include metal soaps such as cobalt naphthenate, dimethyl-P-toluidine, diethyl- P-toluidine,
Representative examples include diethylhydroxy-P-toluidine, isopropanol-P-toluidine or thioamide compounds such as thiourea, acetylthiourea, tetramethylthiourea, ethylenethiourea, or mercaptobenzimidazole, but are not limited thereto. is not.

The adhesive composition A of the present invention containing an acrylate monomer, an organic peroxide catalyst and a clay material, and promotes decomposition of the acrylate monomer and the organic peroxide catalyst. A plastic adhesive composition composed of two components, an adhesive composition B containing a polymerization accelerator that promotes radical polymerization and a clay-based material, can be referred to as a two-component main component type adhesive.

In the two-part adhesive of the present invention, at least one of the A agent and the B agent contains an acrylonitrile-butadiene elastomer (NBR), and the other components are optionally contained in the A agent and / or the B agent. The two-agent type is a particularly preferred composition system in the present invention.

The two-part adhesive composition of the present invention can be easily cured at room temperature or at a low temperature outdoors in winter by sufficiently mixing the two agents A and B by appropriately selecting and combining the compositions. be able to.

The present inventors have developed a plastic adhesive composition containing an acrylate monomer, an organic peroxide catalyst, and a clay material, and promote the decomposition of an acrylate monomer and an organic peroxide catalyst. A and B two-agent type adhesive compositions comprising a polymerization accelerator for promoting radical polymerization and a plastic adhesive composition B containing a clay-based adhesive composition, are in contact with each other simply without being stirred. It has been found that a structure can be obtained in which only an extremely thin film is formed at the interface, the whole is not cured, and the whole is cured only when strongly stirred and mixed.

The present inventors have argued that when composition B is exposed to air for a long time, air curing partially starts, but by arranging composition B as the core of composition A of the present invention, It was found that the air curability of the composition B can be prevented.

That is, in the two-agent main component type plastic adhesive composition of the present invention, a composition B containing a polymerization accelerator which promotes decomposition of an acrylate monomer and an organic peroxide catalyst to promote radical polymerization. A composition containing an acrylate monomer and an organic peroxide catalyst
Found that the storage stability of the obtained plastic adhesive composition is remarkably improved.

Further, the present inventors have found that a molded article having such a constitution can be easily obtained by a co-extrusion molding method in which the plastic adhesive compositions A and B of the present invention are simultaneously extruded and molded. Was.

When the thermoplastic adhesive composition of the present invention is extruded, paraffin, mineral oil, silicone oil, etc. may be used on the surface of composition A or B as a separating agent and a molding aid for composition A and composition B. Found that a good molded product can be obtained by molding in the presence of

[0024]

The present invention relates to a plastic adhesive composition containing an acrylate monomer, an organic peroxide catalyst, a polymerization accelerator, and a clay material.

The plastic adhesive composition of the present invention can be obtained by filling a liquid composition containing an acrylate monomer with a clay mineral such as bentonite powder or mica powder, or by adding a clay mineral such as bentonite powder or mica powder. When the clay mineral is impregnated with a liquid composition containing an acrylate monomer, the resulting adhesive composition is a composition exhibiting the plasticity unique to the present invention, similar to clay containing a moderate amount of water. Becomes

The plasticity peculiar to the plastic adhesive composition of the present invention means that it is soft, does not stick to fingers and has any thickness as compared with the case where a general filler is used. It can be extended and easily plastically deforms.

The plasticity specific to the plastic adhesive composition of the present invention is such that the clay-based material has a specific layered molecular structure, and the powder having such a molecular structure is an acrylate-based monomer component. This is presumed to be due to the property of retaining the liquid component containing in a special form.

On the other hand, when a clay-based substance is not used and instead a large amount of a general filler such as calcium carbonate powder or fine powder of silica fume is filled, it is obtained. The adhesive composition can be obtained from a thixotropic liquid to an ultrahigh-viscosity state, and further to a putty-like or lump-like shape. There is such a sticky property (adhesiveness) as to be adhered to, and when crushed, there is a property that it cannot be stretched to a certain thickness or less. No specific plasticity is obtained.

In addition, the ordinary two-part adhesive containing no clay-based material starts curing from the contacted part immediately after the two parts come into contact, and becomes a partially cured product.

However, when the plastic adhesive composition containing the clay-based material of the present invention is brought into contact with the two components, simply contacting them only forms a thin cured film at the interface, and the curing is not achieved. The composition may not progress further.

Further, the plastic adhesive composition B containing a polymerization accelerator has an air-curing property, and when it comes into contact with air during storage, it has a property of curing to form a cured product. It was found that such a property was lost when the composition was covered with a composition A containing peroxide with the core as a core.

From these two findings, when composition B is used as a core and extruded into a shape covered by composition A,
The adhesive composition comprising the A agent and the B agent is stably present at room temperature, and is easily mixed when mixed with a finger or the like, and easily when pressed against a seal portion of an adherend or a crack in concrete or the like. It has been found that a characteristic plastic adhesive composition which cures and adheres is obtained.

As described above, according to the present invention, the adhesive property and the weakness of the sealing force, which are the drawbacks of clay, are remarkably improved, and at the same time, it has the unique plasticity which conventional adhesives do not have. Also, it is possible to provide a plastic adhesive composition which is extremely useful in the industrial field.

Hereinafter, the present invention will be described more specifically with reference to examples.

EXAMPLES Example 1 As a polymerizable vinyl monomer containing an organic peroxide,
Commercially available Hard Rock IIDK-530LVA (acrylic two-pack main agent type adhesive for injection manufactured by Denki Kagaku Kogyo) 100
g of a plastic adhesive composition containing 144 g of bentonite (super clay) as a clay-based substance and 4 g of pigment titanium white as a general filler, and containing an organic peroxide-based catalyst and a clay-based substance. The product A was obtained.

Next, a commercially available Hard Rock II is used as an adhesive composition containing a polymerization accelerator for accelerating radical polymerization.
DK-530LVB (Acrylic 2 manufactured by Denki Kagaku Kogyo Co., Ltd.)
100 g of liquid base type injection adhesive) was used, and 148 g of bentonite (Super Clay manufactured by Toyshun Yoko Co., Ltd.) was added and mixed as a clay-based substance, and a polymerization accelerator for promoting radical polymerization and a clay-based substance were added. A plastic adhesive composition B was obtained.

In an atmosphere at an ambient temperature of 25 ° C., using cracked concrete as an adherend, take approximately the same amount of compositions A and B, knead them with a finger, and then concrete When pressed against the cracked part, it adhered and cured after 30 minutes. After curing in a room at room temperature for one day, a compressive stress was applied to the cracked portion of the concrete of the cracked adherend, and a destructive test was performed.

As a result, the cracks in the concrete of the adherend were securely bonded and bonded, and the base material concrete was broken.

Composition B was used as a core (cylinder having a diameter of about 10 mm), which was covered with composition A. The composition B and composition A were coextruded into a cylinder having a diameter of about 14 mm. The obtained cylindrical plastic adhesive composition was sealed with a polyethylene film and stored.

After storing for one month in a constant temperature room at 20 ° C., the thermoplastic adhesive composition sealed and stored with a polyethylene film is kneaded with a finger in an atmosphere at an ambient temperature of 25 ° C. The plastic adhesive composition kneaded with the finger was pressed against a cracked portion of concrete as an adherend when pressed out of the film and adhered to the cracked portion of the concrete, and cured 30 minutes later. After curing for one day, a compressive stress was applied to the cracked portion of the concrete to perform a destructive test. As a result, it was confirmed that the base material concrete was destroyed and the cracked portion of the concrete was securely bonded by the cured thermoplastic adhesive composition.

Comparative Example 1 350 g of calcium carbonate (400 N manufactured by Toyo Powder Co., Ltd.) was mixed in the same manner as in Example 1 in place of the clay-based substance of Example 1 in 100 g of Hard Rock IIDK-530LVA and 100 g of LVB. When calcium carbonate was used as a general filler in place of the clay-based material, the adhesive composition obtained when using 350 g or more of calcium carbonate became flaky. Also, add 300 calcium carbonate
The composition used is self-flowing, does not exhibit the specific plasticity of a clay-based material, has poor shape retention, and is soon collapsed and deformed even when molded into a certain shape. Was.

Comparative Example 2 As a polymerizable vinyl monomer containing an organic peroxide,
Commercially available Hard Rock IIDK-530LVA (acrylic two-pack main agent type injection adhesive manufactured by Denki Kagaku Kogyo) 100
g of the mixture, 144 g of calcium carbonate as a general filler and 4 g of titanium pigment white were added and mixed, and an adhesive composition GA containing an organic peroxide-based catalyst and a general filler was used.
I got

Next, a commercially available Hard Rock II as an adhesive composition containing a polymerization accelerator for accelerating radical polymerization is used.
DK-530LVB (Acrylic 2 manufactured by Denki Kagaku Kogyo Co., Ltd.)
100 g of liquid main agent type injection adhesive), and 148 g of calcium carbonate as a general filler were added thereto and mixed.
An adhesive composition GB containing a polymerization accelerator for promoting radical polymerization and a general filler was obtained.

The composition GB was used as a core (a cylinder having a diameter of about 10 mm), which was covered with the composition GA. The composition GB and the composition GA were coextruded into a cylinder having a diameter of about 14 mm.
After sealing the obtained columnar plastic adhesive composition with a polyethylene film and storing it in a constant temperature room at 20 ° C. for one month, the sealed thermoplastic adhesive composition is partially solidified by touching with a finger. It was recognized that. Further, when taken out of the package, a hardened mass was formed on the surface of the composition B.

[0044]

Industrial Applicability The present invention has a favorable workability, that is, a plastic workability that can be easily plastically deformed by kneading with a hand or the like, as shown by a clay mineral containing a suitable amount of water, that is, it has plasticity and Provided is an environment-friendly plastic adhesive composition having a feature of firmly adhering to a surface, exhibiting an effective sealing effect, and being easily cured even at room temperature.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H017 AA03 AA27 AA31 AB01 AB07 AC17 AD05 AD06 AE03 4J040 CA072 FA141 FA151 GA03 GA05 GA11 HA356 HB41 HC06 HC23 HD08 HD43 KA02 LA06 MA06

Claims (9)

[Claims] 1. A plastic adhesive composition containing a clay-based material and an acrylate-based monomer. 2. The method according to claim 1, further comprising an organic peroxide catalyst.
Plastic adhesive composition as described 3. The plastic adhesive composition according to claim 1, further comprising a polymerization accelerator that promotes decomposition of the organic peroxide catalyst and promotes radical polymerization. 4. A plastic adhesive composition A containing an acrylate-based monomer, an organic peroxide-based catalyst and a clay-based material, and promotes the decomposition of an acrylate-based monomer and an organic peroxide to form radical polymerization. Adhesive composition consisting of two components, a polymerization accelerator for accelerating the reaction and a plastic adhesive composition B containing a clay-based material 5. The plastic adhesive composition according to claim 1, which contains an acrylonitrile-butadiene elastomer. 6. The plastic adhesive composition according to claim 1, wherein the clay-based material is a bentonite-based material. 7. The plastic adhesive composition according to claim 1, wherein the clay-based material is a mica-based material. 8. Acrylic acid is added around a plastic adhesive composition B containing a polymerization accelerator and a clay-based substance, which promotes decomposition of an acrylate-based monomer and an organic peroxide-based catalyst and promotes radical polymerization. The plastic adhesive composition according to any one of claims 1 to 7, which is coated with a plastic adhesive composition A containing an ester monomer, an organic peroxide catalyst, and a clay material. 9. The molding according to claim 8, wherein the molding is performed by an extrusion molding method.
Plastic adhesive composition as described