JPS6169879A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. having excellent dispersion stability and workability and forming an adhesive layer with excellent water resistance and water-resistant adhesion, prepd. by adding a fibrous hydrated magnesium silicate clay mineral to a base resin for adhesive. CONSTITUTION:The compsn. is prepd. by adding 0.1-20pts.wt. fibrous hydrated magnesium silicate clay mineral having a particle diameter of 0.001-0.1mum (e.g. sepiolite), 0.1-100pts.wt. filler (e.g. carbon black), hardener (e.g. triethyleneamine), antiseptic for resin, plasticizer, curing accelerator, solvent, etc. to 100pts.wt. base resin for adhesive (e.g. epoxy resin). EFFECT:Bonded products which cause neither peeling-off at joint even when immersed in water for a long time nor lowering of strength are obtained. USE:Bonding of automobile parts, electric and electronic components, civil engineering structure, building, household articles, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] More specifically, the present invention relates to an adhesive composition having excellent water resistance.

[Jubei technology and problems]

Automobiles, electrical/electronic products, civil engineering/buildings.

BACKGROUND ART Medical equipment, household goods, etc., or bonded parts thereof require not only adhesive strength but also durability. especially,
In environments where adhesives are used in environments where there are substances that hinder the adhesion of adhesives, such as water and steam, there is a high demand for adhesives with excellent water resistance, and efforts are being made to develop adhesives that can prevent water from entering from outside. Ta.

As a method to solve these conventional problems, there is a method of adding a silane coupling agent to the adhesive, or a method of applying the silane coupling agent as a brimer to the surface of the adherend such as a metal surface. Magazine 16.318 (1
980)).

However, this method has disadvantages in that it requires more processing steps and is economically expensive because the Relane coupling agent itself is expensive.

[Problem of the present invention]

The present invention solves these problems and provides an adhesive composition with excellent water resistance that can prevent water from entering from the outside.

[Structure and operation of the invention]

That is, the adhesive composition of the present invention is characterized in that it contains 0.1 to 20 parts by weight of a fibrous hydrated magnesium silicate clay mineral per 100 parts by weight of the adhesive resin.

The adhesive resin used in the present invention is one that is used as a resin used in conventional adhesives, as long as it mixes well with the fibrous hydrated magnesium silicate clay mineral and can be appropriately dispersed. .

Select an appropriate one by considering the purpose of use and conditions.

Specific examples include phenol resin, melamine resin,
Isobutyne-maleic anhydride copolymer.

Thermosetting resins such as urea resin, resorcinol resin, furan resin, saturated or unsaturated polyester resin, acrylic copolymer resin, polyurethane resin, silicone resin, aminoalkyd resin, polyvinyl acetate hepal, polyvinyl alcohol /L/ (ball, PTA).

Examples include thermoplastic resins such as nylon resin, polyvinyl chloride, polyvinylp, chiller A/, polyacrylic acid ester, and nitrocellulose. These resins.

For example, in the case of polyvinyl to phosphor, it is made water-soluble by selecting the degree of saponification and degree of polymerization, and in the case of isobutyne-maleic acid copolymer, it is made water-soluble by adding an alkali. In addition, suitable curing agents, etc. 9 For example, triethylamine for epoxy resins.

Adhesive strength to adherends can be changed by adding appropriate amounts of triethylenetethumine, diamine diamide, etc.

In addition, fibrous hydrated magnesium silicate clay minerals (hereinafter referred to as
The common name for clay minerals is mountain clay minerals.
untain cork) + mountain wood (M
It is a mineral called mountain wood), mountain leather Q/IDuntainleachar), etc. It is a mineral whose main component is hydrated magnesium silicate and has a highly reactive hydroxyl group on its surface. Note that a part of magnesium may be substituted with aluminum, iron, sodium, nickel, etc.

Specifically, sepiolite, which has hydrated magnesium silicate as its main component, Attapulgite, which has hydrated magnesium aluminum silicate as its main component, and palygorskite,
Examples include O-grinite (Lough J 1nite) and sepiolite (Meers-chaum), and one type or a mixture of two or more of these is used.

These clay minerals are aggregates of long fibers having a quadrilateral cross section of about 0.01 to 0.17 zm, and the aggregates have many holes in the length direction of the fibers. There is.

In addition, the clay mineral itself absorbs a large amount of water.

It has the property of adsorption.

The clay mineral may be used in the form of a powder, a single grain, or a plate, but it is preferably crushed to the extent that the pores of the clay mineral remain, and the diameter thereof is 0.002 to 0.11 t.
It is more preferable to have a length of about 0.1 to several μm.

If it is within this range, the surface area of the clay mineral is large, so the number of active sites on the surface increases, so the characteristics of the clay mineral can be further utilized, and the clay mineral can be incorporated into adhesive resin. It can be uniformly dispersed and contributes to the reinforcing effect of adhesive compositions.

The adhesive composition of the present invention is made by mixing and dispersing the clay mineral in powder form in these adhesive resins.

When mixing, use a pole mill, a sand grinder,
It is necessary to mix the clay mineral into the adhesive resin until it is sufficiently dispersed using a RoV-mixer or the like.

Note that the clay mineral may be prepared in advance in the form of fibers with a diameter of about O,OO2 to 0.1 pm and a length of about 0.1 to @μm, and mixed into the adhesive resin. Alternatively, it may be made into the above-mentioned fibrous state during the process of mixing and dispersing it in the adhesive resin. This clay mineral is usually made by crushing it directly from a mine using a crusher or other pulverizer.

The particles of this pulverized product have a size of 0.5 to 200 μm.

The clay mineral used in the present invention has a fiber shape that is different from the above-mentioned general particles and is finer, loosened finely, and has a large diameter/length ratio.

Here, the amount of the clay mineral to be mixed may be such that it imparts appropriate thixotropy to the adhesive composition and exhibits sufficient water resistance when used as an adhesive.

In the present invention, 01 to 100 parts by weight of adhesive resin are used.
It is 20 parts by weight. When the mixing amount is within this range, the water resistance of the obtained adhesive O and the water resistant adhesion to the adherend can be improved without impairing the advantages of the adhesive.

The mixing amount is set within this range when the mixing amount is less than 0.1 parts by weight.

The water resistance and water resistant adhesion of the adhesive cannot be obtained sufficiently, and
If the amount exceeds 0 parts by weight, the viscosity of the composition will be high, the coating workability will be reduced, and the flexibility and tackiness of the adhesive after bonding will be reduced. Among these, it is more preferable that the amount is 3 to 15 parts by weight, and the above-mentioned effects can be further exhibited.

The adhesive composition according to the present invention can be produced either in a state in which the clay mineral is appropriately dispersed and solidified in the adhesive resin as described above, or in a state in which the clay mineral is properly dispersed and solidified in the adhesive resin, or it is made to have an appropriate viscosity by adding an appropriate solvent. It may be one that is easy to apply.

In this case, the solvent may be appropriately added to the adhesive composition and mixed, or the clay mineral may be mixed and dispersed in the mixture after being mixed with the adhesive resin in advance. Moreover, the clay can be adjusted by further adding a solvent as appropriate thereafter.

In addition, the solvent used is one that stabilizes the adhesive composition, and specifically, in addition to water, xylene is used.

Organic solvents include ethylene glycol monobutyl to ether, isopropyl alcohol, and methyl ethyl ketone.

Also, a filler for imparting appropriate viscosity, adhesive strength, etc. to this adhesive composition! A curing agent, a resin preservative, a plasticizer, a curing accelerator, etc. for solidifying the M fat can be added as appropriate.

For example, fillers that are commonly used in adhesives can be used; specific examples include carbon black,
Inorganic fillers such as silica powder, μsium carbonate, clay aluminum powder, and organic fillers such as short fiber nylon (length about 5 mm) and polypropylene powder.

It also contains vegetable fibers such as pulp. Mixing these fillers improves the smoothness and viscosity of the adhesive composition.

Workability, reinforcing properties, etc. can be improved.

The amount of the filler to be mixed may be an amount that provides the above-mentioned effects and does not inhibit the intended function of the adhesive, but is usually 0.1 parts by weight per 100 parts by weight of the adhesive resin. ~1
00 parts by weight.

Further, as the curing agent, those normally used for adhesives can be used, and the curing agent is appropriately selected according to the functional groups possessed by the adhesive resin. For example, for epoxy resins, O curing agents such as triethylamine, triethylenetetramine, and dicyandiamide are used.

The hardness of the resin after curing, the adhesive strength to the adherend, etc. can be changed.

The adhesive composition according to the present invention can be applied to or during application by a well-known application process, for example.

Manual transfer methods such as brush painting or robe transfer methods.

The adhesive is applied using methods such as contact pressure using a pole point, spraying using a nozzle type, and gravity applying method, and then heated or dried as required to adhere and attach to the tray.

The adhesive layer at the joint obtained from the buccal surface has the clay mineral uniformly dispersed in the form of fibers, and has excellent water resistance and water-resistant adhesion. That is.

Even if the bonded product is immersed in water for a long time, the bonded portion will not peel off, and there will be no decrease in the tensile strength of the bonded portion.

The reason why the adhesive layer of the 9M#' bonded part has such excellent water resistance and water resistant adhesion is that the adhesive layer has excellent water resistance and water resistant adhesion, although the mechanism is not yet clear.

Since the fibrous clay mineral is uniformly dispersed in the adhesive layer, it prevents moisture from penetrating into the adhesive layer.At the same time, the fibrous clay mineral has a reinforcing effect on the adhesive layer. This seems to be to prevent swelling, deformation, etc. of the resin.

〔Effect of the invention〕

The adhesive composition of the present invention has excellent dispersion stability and workability because the clay mineral in the form of fibers is uniformly dispersed and has appropriate thixotropy. Further, the adhesive layer of the bonded portion obtained by applying the adhesive to the adhered object has excellent water resistance and water resistant adhesion.

〔Example〕

Hereinafter, one aspect of the present invention will be explained in detail.

Example 1 As an adhesive resin, a mixture of a commercially available Epivia type epoxy resin, a urethane modified resin, and an NBR modified resin in a ratio of 40:35 to 25 was prepared.

To 100 parts by weight of this resin, Turkish Seviolite powder having a particle size in the range of 100 to 200 meshes was added in the amount shown in Table 1 and dispersed until the particle size was less than a three-roll mill.

next. To this mixture, 18 parts by weight of dicyandiamide and 70 parts by weight of aluminum powder were added to 100 parts by weight of the resin.
Adhesive compositions according to the present invention containing 5 parts by weight of kaolin and soft calcium carbonate were obtained (sample numbers 1 to 7).

The obtained adhesive composition was applied to an SPCC mild steel plate (25X100X0.8a) that had been degreased with thinner and petroleum benzene
The adhesive thickness is o.m) from the longitudinal end to the 10fi+ position. 5ff, and on top of that, 8PCO mild steel plates of the same shape were overlapped in the longitudinal direction and glued. It was cured at 180° C. for 20 minutes to obtain a test specimen.

Next, these test pieces were placed in warm water at 40°C for 10 days, and
days, 30 days. Each was immersed, and then a tensile shear test was conducted in an atmosphere at 20°C.

The number of tests in each test was three for each adhesive. This is the result obtained.

Shown in Table 1. Note that the values in Table 1 are the average of three tests.

For comparison purposes. Adhesive compositions (sample numbers C1 to C5) that do not contain the clay mineral or contain an excessive amount of the clay mineral and have the same composition as those described above (sample numbers C1 to C5) are prepared, and adhesives similar to those described above are prepared. A performance evaluation test was conducted.The results are also shown in Table 1.

In addition, in the table, PHB. What is Per Handred Re?
Sin means the ratio of additive added to 100 parts of the resin.

(same as below).

Example 2.

As a resin for adhesives.゛Methyl methacrylate 300 it
parts, 50 parts by weight of methacrylic acid-2-hydroxyethyl/l/l, and 40 parts by weight of methacrylic acid. Acrylonitrile p-
A mixture of 80 parts by weight of butadiene copolymer was prepared by stirring and dissolving it at 60°C. Next, to 100 parts by weight of this resin, the amount of Seviolite powder from Spain with a particle size of 200 mesh or less as shown in Table 2 was added. The particle size of sepiolite powder is reduced to 0.2μm by heating roller at 60℃.
Disperse and mix uniformly until the following is achieved, and after cooling, add to the mixture.

5 parts by weight of ethylene thiourea were added to 100 parts by weight of the resin, and the mixture was stirred and mixed using a Pk crusher to obtain an adhesive composition A according to the present invention.

Next, as an adhesive resin, methyl methacrylate/l/4
00 parts by weight of methacrylic acid-2-hydroxyethyloxyethyl chloride-butadiene copolymer (90 parts by weight) were stirred and dissolved at t-60°C, and this mixed resin 1 was dissolved.
00 parts by weight contains 200 me,shi.

Sepiolite powder from Spain with the following particle size was used as a second
Add the amount shown in the table, disperse and mix in the same manner as above, and after cooling, add 35 parts by weight of cumene hydroperoxide to 100 parts by weight of the resin, stir and mix with a crusher, and Adhesive composition B according to the present invention was obtained.

These adhesive compositions A and Bt- obtained were applied to a 5rcc mild steel plate (25
1 from the longitudinal end of X10[)Xo, 8 ml)
The adhesive layer was applied to a thickness of 0.25 m1K up to 1 il. Next, the two pieces were overlapped and adhered so that the areas coated with the adhesive composition overlapped, but the areas coated with the bracket did not face each other, and a test sample piece was obtained.

Next, for these test pieces, 5il! The same adhesive performance evaluation test as in Example 1 was conducted. The results are shown in Table 2.

For comparison, compositions similar to the above-mentioned adhesive compositions A and B were prepared, except that they did not contain the clay mineral, and the same adhesive performance evaluation test as above was conducted. The results are also shown in Table 2.

However, the number of tests in each test is 3 points for each adhesive, and the values in the table 91 indicate the average of the 3 test points.

Example 3 First, 60 parts by weight of urea and 200 parts by weight of 30% formalin were mixed, neutralized to 9P)II7 with sodium hydroxide, and the mixture was heated to boiling and refluxed for 10 minutes. 0.3 parts by weight of formic acid was added to this reaction mixture, and the mixture was heated and boiled again to obtain an adhesive resin.

Next, 100% of the resin was added to 100N of urea.
Add a dispersion mixture of American attapulgite powder in the amount shown in Table 6 and 5 times the amount of water as shown in Table 6. .2/ Mixed and dispersed until it became less than blood.

Furthermore, 1.5 parts by weight of ammonium sulfate, 30 parts by weight of fl-recrylic alcohol, and 10 parts by weight of walnut powder were added to the mixture, and mixed and pulverized for a long time using a jigger. Then, an adhesive composition according to the present invention was obtained.

A test piece similar to that in Example 1 was prepared using the obtained adhesive composition, and an adhesive performance evaluation test was conducted in the same manner as in Example 1. The results are shown in Table 3.

For comparison, we prepared an adhesive composition that did not contain the clay mineral and had the same composition as above except that the clay mineral was mixed in an excessive amount, and conducted the same adhesive performance evaluation test. I did this. The results are also shown in Table 3.

Claims (2)

[Claims] (1) An adhesive composition comprising 0.1 to 20 parts by weight of a fibrous hydrated magnesium silicate clay mineral per 100 parts by weight of an adhesive resin. (2) The adhesive composition according to claim (1), wherein the fibrous hydrated magnesium silicate clay mineral is fibrous with a diameter of 0.002 to 0.1 μm.