JPH0374695B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Purpose of the invention ``Industrial application field'' The primer of the present invention uses α-cyanoacrylate to improve materials such as non-polar or highly crystallized resins, which were conventionally difficult to adhere, paint, and print. It is used in the automobile industry and electrical equipment industry where non-polar or highly crystallized resins such as polyolefin are widely used as raw materials. It is widely used in various fields including. "Prior Art" Soft PVC containing non-polar or highly crystallized resins, such as polyolefins such as polyethylene, polypropylene, polybutene and polyfluoroethylene, polyethylene terephthalate, polyacetal and nylon, as well as large amounts of plasticizers. Films and other materials are materials that are difficult to adhere, paint, and print on, and it is not possible to adhere these resins well or apply paint or prints on these resin surfaces using normal methods. It is. Several proposals have already been made to improve the adhesion properties of these materials. For example, in the case of polyolefin resins, treatments such as flame treatment, corona discharge treatment, plasma jet treatment, or dichromate treatment have been proposed. A method of treating the resin with a primer prepared by dissolving chlorinated polyethylene, chlorinated polypropylene, fatty acid-modified acrylated alkyd resin, etc. in an organic solvent, etc. There is. (Unexamined Japanese Patent Publication No. 52-98062, No. 56-141328, No. 56-141328, No.
57-119929) Improved resins have also been proposed that contain solid rubber, unsaturated carboxylic acids or derivatives thereof, and radical generators, and that contain propylene/styrene/butadiene block copolymers and inorganic fillers as essential components. As a result of intensive research efforts aimed at developing a method superior to these methods, the present inventors have proposed a primer containing an organic metal compound such as aluminum alcoholate or aluminum chelate salt as an active ingredient. (Special application 1987-87761,
59-59367). "Problems to be Solved by the Invention" The primer proposed by the present inventors has an extremely excellent function in achieving the intended purpose, but it has the following problems in actual use. It turned out that there were some problems. In other words, since the primer has no viscosity, especially when used as a solution, it is difficult to store in aluminum tubes or glass bottles, and it requires ingenuity to apply it evenly in a thin film without causing dripping, resulting in poor application workability. There is a problem with this. Furthermore, the performance of the primer, such as adhesive strength, varies depending on the coating thickness, so unless the coating thickness is kept within a certain value, the performance such as adhesive strength will not be constant, especially when applied thickly. , the primer layer becomes a brittle layer and cannot improve adhesion,
On the contrary, it also has the problem that it can sometimes be harmful. The present inventors continued studies to solve various problems with the above-mentioned primers proposed by the present inventors and completed the present invention. (b) Structure of the invention "Means for solving the problems" The present inventors completed the present invention by discovering that the problems of the primer described above can be solved by adding an organic polymer. It is. That is, the present invention relates to a primer that is used when applying α-cyanoacrylate to a non-polar or highly crystallized resin, and is characterized in that it contains an organometallic compound and an organic polymer as active ingredients. It is something. In the present invention, applying α-cyanoacrylate to non-polar or highly crystallized resins means using α-cyanoacrylate to adhere those resins, or applying α-cyanoacrylate (mainly a hardened film) to those resins. It means use as an undercoat for paint or printing ink in painting or printing, etc. Γ Organometallic Compound The organometallic compound in the present invention is a compound in which an organic group and a metal are bonded, and it can be used in the present invention regardless of its type, structure, etc. The methods proposed in Sho 58-87761 and Sho 59-59367 can also be used in the present invention. As described in the specification of the above application, the organic groups in the organometallic compound in the present invention include alkyl, alkenyl, alkoxy,
Aryl, acetylacetonyl, acetyloxy,
Examples include cyclohexyl, and hydrocarbon groups of C ₃ or more are particularly preferred from the viewpoint of treatment effects and risks.Metals include typical metals, transition metals, and metalloids shown in the periodic table, as well as phosphorus. Preferred compounds for the present invention are

[Formula] (where M is a metal element, R is an organic group; the same applies hereinafter) It is a compound classified as a metal having a carboxylate salt shown in the structure and a hydrocarbon group shown in the structure M-R. Preferred compounds are M-O-
A metal alcoholate represented by the structure R and

It is a 1,3-dicarbonyl complex salt represented by the structure of [Formula]. In addition, for specific compounds,
Lithium acetylacetone, sodium acetylaceton, magnesium acetylacetone, titanyl acetylaceton, iron acetylacetone (), palladium acetylacetone, indium acetylaceton, tri-n-octadecyl borate, sodium linoleate, magnesium stearate, aluminum stearate, aluminum acetate, aluminum laurate, Basic aluminum thiodiglycolate, calcium stearate, ferric stearate, copper ferrocene dimethyldithiocarbamate, zinc stearate, 2-
Ethylhexylzinc, zinc tartrate, stannous acetate, di-n-butyltin dimaleate, di-n-
Butyltin oxide, triphenyltin acetate, barium stearate, lead stearate, dibutyl phosphite, tridecyl phosphate, trioleyl phosphate are preferred compounds, calcium acetylacetone, zinc acetylacetone, potassium oleate, nickel naphthenate, dioctyl Tin dilaurate is a more preferred compound;
Aluminum trisisopropylate, aluminum-mono-sec-butoxydiisopropylate,
Aluminum trisacetylacetonate, aluminum mono-acetylacetonate bisethylacetoacetate, aluminum ethyl acetoacetate diisopropylate, aluminum tris ethyl acetoacetate, aluminum oleyl acetoacetate diisopropylate, acetylacetone manganese (), acetylacetone cobalt (), acetylacetone Nickel, zinc acetylacetone, zirconium acetylacetone, tetrabutyl titanate, tetraisopropyl titanate, dibutyltin diacetate, tri-n-butyltin oxide, tin 2-ethylhexanoate, AY43-021 (trade name of silicon compound manufactured by Toray Silicon Co., Ltd.) , trisisodecyl phosphite is a particularly preferred compound. ΓOrganic polymer Examples of the organic polymer used in the present invention include various commonly known polymers, and the primer of the present invention is used after being dispersed or dissolved in an organic solvent. Therefore, polymers soluble in organic solvents are preferred for the present invention. Specific examples of the organic polymer used in the present invention include olefin copolymers such as ethylene/vinyl acetate copolymer, ethylene/acrylic acid ester copolymer, α-olefin/maleic acid copolymer, and chlorine copolymer. Chlorinated off-line polymers such as chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene/propylene copolymer, chlorinated ethylene/vinyl acetate copolymer; polyvinyl chloride, polyvinyl acetate, poly(meth)acrylic acid ester, Vinyl polymers such as polyvinyl ether, vinyl chloride/vinylidene chloride copolymer; polychloroprene,
These include synthetic rubbers such as NBR, SBR, and chlorinated rubber. Among the various organic polymers mentioned above, preferred for achieving the purpose of the present invention are chlorinated olefin polymers, which are chlorides of polymers or copolymers such as propylene or ethylene; Rubber; Olefin copolymer which is a copolymer of propylene or ethylene; Methyl methacrylate/chloroprene copolymer; particularly preferred are chlorinated polypropylene and methyl methacrylate/chloroprene copolymer. Γ Non-polar or highly crystallized resin Non-polar or highly crystallized resins for which the primer of the present invention is used include olefinic polymers represented by polyethylene, polypropylene, polybutene, and polymethylpentene, and talc,
Composites containing alumina, mica, glass fibers, etc., polyethylene terephthalate, polyacetal, polyurethane, silicone rubber, soft PVC, etc., but the primer of the present invention works most effectively when used with olefin polymers. It is. Γα-cyanoacrylate The primer of the present invention is used as a primer for α-cyanoacrylate.
-Cyanoacrylate is represented by the following general formula. R in the above formula includes alkyl, alkenyl, cyclohexyl, aryl, and alkoxyalkyl groups, and specifically includes methyl, ethyl, n-propyl, n-butyl, isobutyl, n
-pentyl, allyl, cyclohexyl, benzyl, methoxypropyl groups, etc. These α-cyanoacrylates are the main components of commercially available cyanoacrylate-based instant adhesives, and the primer according to the present invention uses these commercially available adhesives as they are. It can also be used as a primer when used as an acrylate. Furthermore, the primer of the present invention is compatible with α-cyanoacrylate and is effective as a primer for α-cyanoacrylate diluted with an organic solvent such as toluene, butyl acetate or methyl chloroform without impairing its stability. It is something. Γ Usage method As stated in the application specification, the primer of the present invention is suitable for use when a layer of an organometallic compound formed on the surface of a non-polar or highly crystallized resin has a certain thickness. Therefore, when using the primer of the present invention as a primer for α-cyanoacrylate applied to non-polar or highly crystallized resins, it is best to dissolve or disperse it in an organic solvent. preferable.
The organic solvent used is a general organic solvent that can completely dissolve or disperse the above-mentioned organometallic compound and organic polymer, has appropriate volatility, and is industrially easy to use. It is desirable that it be available at In addition, in order to apply the primer more efficiently, the solvent is preferably one that can sufficiently wet the surface of the resin such as polyolefin, and for this purpose, the surface tension of the organic solvent must be equal to the critical surface tension of the resin. It is more desirable to select and use one with a value smaller than γ _C. Specific examples of solvents include 1,1,2-
trichloro-1,1,2-trifluoroethane,
ethanol, acetone, ethyl acetate, 1,1,1
-Trichloroethane, tetrahydrofuran, 1,
These include 4-dioxane and toluene, and these may be used alone or in combination of two or more. The concentration of the organometallic compound in the primer solution when used as a solution is most effective when the organometallic compound used as the primer is formed on the resin surface in the form of a thin film, preferably a monomolecular film. Therefore, it is preferably 0.001 to 10% by weight. If the concentration is less than 0.001% by weight, it will be difficult to form a layer of the organometallic compound in the form of a thin film or monolayer;
If it exceeds 100%, the layer tends to become too thick, and the thick layer becomes a brittle layer, reducing its effectiveness as a primer. Further, the concentration of the organic polymer is preferably 0.1 to 20% by weight, although it depends on the type of organic polymer. If this concentration is less than 0.1% by weight, it will be difficult to express the desired effect of the present invention,
If it exceeds 20% by weight, it will interfere with the function of the organometallic compound, which plays the main role as a primer, and its effectiveness as a primer will decrease.
The type and amount of the organic polymer to be added is preferably determined so that the viscosity of the primer solution is in the range of 2 to 5000 cp/25°C. If the viscosity of the primer solution falls outside this range, it will be difficult to achieve the object of the present invention. When used as a solution, it is also possible to add a small amount of a thickener such as fumed silica to obtain a thixotropic solution. The primer of the present invention is preferably used as a primer solution dissolved or dispersed in an organic solvent as described above, but the primer solution can be applied to a non-polar or highly crystallized resin using a paint, etc. General methods such as dipping in a solution, brushing, spraying, etc. can be used to apply the primer, and the resin coated with the primer in such a manner is air-dried at room temperature to remove the solvent, and the resin surface is coated with the primer. A primer layer can be formed. In order to better express the effects of the present invention,
The type of organometallic compound and organic polymer to be used, their concentration, amount of application, etc. must be determined by considering the type of non-polar or highly crystallized resin.
Regarding the coating amount, it is natural that if it is too small and the organometallic compound layer cannot completely cover the resin surface, the result will not be good, and if it is too large, the organometallic compound layer will not form a thin film. If the thickness exceeds much, the layer itself becomes a brittle layer, and the effect of the present invention will not be achieved.
It is preferable for the present invention to apply the coating at an amount of 0.01 to 0.1 g/m ² , more preferably 0.01 to 0.1 g/m ² . "Function" The primer of the present invention is inferior to the coating workability of the primers previously proposed by the present inventors in Japanese Patent Application Nos. 58-87761 and 59-59367, and requires strict control of coating thickness. This problem was solved at once by adding an organic polymer, and this may be due to the effect of adding viscosity to the primer by adding the organic polymer, but that alone explains it. This is an impossible event. In any case, the problems of the previously proposed primers are solved by the combined use of an organic polymer, and the present invention provides a more excellent primer. "Example" The present invention will be specifically described below with reference to Examples and Comparative Examples. Example 1 0.5 parts by weight of manganese ()acetylacetonate and chlorinated polypropylene (Superchlorine)
A primer was obtained by dissolving 2 parts by weight of 106H (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) in 97.5 parts by weight of toluene. After applying this primer to a polypropylene resin test piece conforming to JISK686-1977, air drying and adhering with 2-ethylcyanoacrylate,
After curing for a day, the tensile shear strength was measured according to JISK686-1977. Furthermore, the set time was also measured using the above materials and method. The results are shown in Table 1. Examples 2 to 7 Tests similar to those in Example 1 were conducted using the organometallic compounds, organic polymers, and solvents shown in Table 1. The results are shown in Table 1. Example 8 Tetrabutyl titanate 0.5% by weight, methyl methacrylate/chloroprene copolymer (composition ratio
The viscosity of the 3% by weight toluene solution primer (25/75, molecular weight approximately 200,000) is approximately 100 cp, and it is easy to work with such as brushing, and after filling into an aluminum tube,
After folding it in four and leaving it indoors for 6 months, the weight loss and its ability as a primer were examined. There was no weight loss, the test results were the same as in Example 1, and no performance deterioration was observed. Comparative Example 1 Polypropylene resin was bonded with 2-ethylcyanoacrylate without using a primer, and the tensile shear strength was measured. The results are shown in Table 1. Comparative Example 2 The same test as in Example 1 was conducted using a solution of 2 parts by weight of chlorinated polypropylene (Superchron 106H)/98 parts by weight of toluene as a primer. The results are shown in Table 1. Comparative Example 3 Tetrabutyl titanate 3 as a primer
Example 1 using a solution of parts by weight/97 parts by weight of toluene
A similar test was conducted. The results are shown in Table 1. Comparative Example 4 The viscosity of the primer of a toluene solution containing 0.5% by weight of tetrabutyl titanate was approximately 1 cp, which made workability such as brushing difficult.When a storage test similar to Example 8 was conducted, the contents were found to be volatile. It was so intense that after 6 months it was no longer useful as a primer.

【table】

[Table] (C) Effects of the Invention By using the primer of the present invention, adhesive coating or printing of non-polar or highly crystallized resins using 2-cyanoacrylate can be done easily and quickly, and the influence of the concentration of organometallic compounds can be reduced. It is now possible to apply non-polar or highly crystallized resins such as polyolefins, or to coat or print the surfaces of these resins, making it possible to utilize the excellent physical properties of polyolefins.
It has many advantages over metal materials, such as lighter weight, less rust, and lower costs, and its contribution to various fields such as the automobile industry and the electrical equipment industry is extremely large.

Claims (1)

[Claims] 1. A primer that is used when applying α-cyanoacrylate to a nonpolar or highly crystallized resin, and is characterized in that it contains an organometallic compound and an organic polymer as active ingredients.