JPH0412736B2 - - 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 represented by 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, resin acid-modified acrylated alkyd resin, etc. in an organic solvent. and so on. (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, there may be differences in performance as a primer even though the same materials are used, or there may be problems in which primers that had sufficient performance at the time of preparation deteriorate in performance during storage or use. I found it. The present inventors continued their studies to solve the problems of 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 have discovered that the problems with the primers are caused by the water present in the primers, and that it is necessary to control the water content in the primers. The present invention was completed by discovering that the above-mentioned problems could be solved. That is, the present invention is used when applying α-cyanoacrylate to a non-polar or highly crystallized resin, which uses an organic metal compound as an active ingredient and suppresses moisture content to 500 ppm or less using a desiccant or adsorbent. The present invention relates to a primer characterized in that: 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. Γorganometallic compound The organometallic compound in the present invention is a compound in which an organic group and a metal are bonded, and its type,
It can be used in the present invention regardless of structure etc., and specifically, the present inventors have disclosed Japanese Patent Application Nos. 58-87761 and 59-59.
The method proposed in No. 59367 can also be used in the present invention. As stated 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, cyclohexyl, etc. In terms of properties, hydrocarbon groups of C3 or _higher are particularly preferred, and the 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 and R is an organic group; the same applies hereinafter) and M-
It is a compound classified as a metal having a hydrocarbon group represented by the structure R, and more preferable compounds are metal alcoholates represented by the structure M-O-R and

It is a 1,3-dicarbonyl complex salt represented by the structure of [Formula]. Specific compounds include lithium acetylacetone, sodium acetylaceton, magnesium acetylaceton, titanyl acetylacetone, iron acetylacetonate (), 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, zinc 2-ethylhexyl, zinc tartrate, stannous acetate, -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, dioctyltin dilaurate are more preferred compounds, aluminum trisisopropylate,
Aluminum mono-sec-butoxy diisopropylate, aluminum trisacetylacetonate, aluminum mono-acetylacetonate bisethylacetoacetate, aluminum ethyl acetoacetate diisopropylate, aluminum trisethylacetoacetate, aluminum oleyl acetoacetate diisopropylate, Acetylacetone manganese (), acetylacetone cobalt (), acetylacetone nickel, acetylacetone zinc, acetylacetone zirconium, tetrabutyl titanate, tetraisopropyl titanate, dibutyltin diacetate, tri-n-butyltin oxide, tin 2-ethylhexanoate, AY43-021 (Toray) Particularly preferred compounds are silicone compound (trade name) manufactured by Silicon Co., Ltd. and trisisodecyl phosphite. Γ Water In order to prevent variations in the quality and properties of primers containing organometallic compounds as active ingredients, as well as deterioration of quality during use or storage, the amount of water in the primer must be kept at a certain level, i.e.
It is necessary to keep the water content below 500 ppm, and the above problems can only be solved by maintaining the water content below 500 ppm. In order to suppress the moisture content in the primer to 500 ppm or less, it is desirable to control the moisture content in the organic metal compound as a raw material, the organic solvent used in combination, and the organic polymer. Furthermore, when producing a primer using these raw materials, it is also preferable to carry out the production in a dehumidified room or to use moisture-proof equipment. However, even if there is no moisture in the primer immediately after manufacture, it will absorb moisture from the air during use or storage, and over a long period of time, the moisture content in the primer will exceed 500 ppm, reducing the performance of the primer. Therefore, it is necessary to take measures to ensure that the moisture content does not exceed 500 ppm even after a long period of time. To prevent the primer from absorbing moisture during storage, the container may be made of a moisture-impermeable material, such as a glass container, a metal container, or a plastic container with a layer of polyvinylidene chloride. Moisture absorption during use is unavoidable, and it is undesirable to limit the container material to a specific one. Therefore, the present inventors made the primer coexist with a desiccant or adsorbent, and the moisture content in the primer was reduced to 500 ppm due to moisture absorption. This was done so as not to exceed. The desiccant or adsorbent can be stored in a space inside the container or on the lid so that it does not come into contact with the primer, but a simple method is to add a solid desiccant or adsorbent to the primer solution. There is a method of coexisting with the primer, and by such a method, it is possible to remove moisture absorption and also moisture caused by the raw materials, and it is possible to obtain a primer with a moisture content of 500 ppm or less at all times. There are various desiccants, such as phosphorus pentoxide, activated alumina, anhydrous calcium sulfate, magnesium oxide, calcium oxide, calcium chloride, magnesium sulfate, diatomaceous earth, anhydrous zinc chloride, anhydrous copper sulfate, silica gel,
There are silica alumina, etc., and adsorbents include molecular sieve, activated carbon, etc.
It is preferable that the primer used in combination with the primer satisfies the following conditions. () Solid () Neutral or nearly neutral () Does not chemically react with the primer () Does not dissolve in the primer () Does not inhibit the primer function Therefore, it can be used in combination with the primer. Preferred desiccants or adsorbents include activated alumina, magnesium oxide, magnesium sulfate, diatomaceous earth, silica alumina, and more preferred are silica gel and molecular sieve. The desiccant or adsorbent used in the primer is preferably in the form of granules, and the particle size is
Particularly preferred is a thickness in the range of about 0.5 to 10 mm.
If the particle size is less than this, it will become dispersed in the primer and will flow out when the primer is used and adhere to the treated surface, which is undesirable.On the other hand, if the particle size is too large, the volume will become large, which is also undesirable from the viewpoint of the product form. Appropriate. When a desiccant or adsorbent is used in combination, the amount to be used may be determined by taking into consideration the expected amount of moisture absorption and the moisture absorption capacity of the desiccant or adsorbent. Γα-Cyanoacrylate The primer of the present invention is used as a primer for α-cyanoacrylate, and α-cyanoacrylate is represented by the following general formula. R in the above formula is alkyl, alkenyl,
Includes cyclohexyl, aryl, and alkoxyalkyl groups, and specific examples include methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, allyl, cyclohexyl, benzyl, and methoxypropyl groups. 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 Non-polar or highly crystallized resin The non-polar or highly crystallized resin used with the primer of the present invention includes olefinic polymers represented by polyethylene, polypropylene, polybutene, and polymethylbentene, as well as talc, alumina, Composites containing mica and glass fibers, polyethylene terephthalate, polyacetal, polyurethane, silicone rubber, soft PVC, etc., but the primer of the present invention works most effectively when used with olefin polymers. . Γ Organic polymer The primer of the present invention can be used in combination with various commonly known organic polymers.
Thereby, coating properties etc. can be improved. As for the organic polymer, it is preferable to use the primer of the present invention by dispersing or dissolving it in an organic solvent. This is the preferred method for using the primer. Specific examples of organic polymers that can be used in combination include olefin copolymers such as ethylene/vinyl acetate copolymer, ethylene/acrylic acid ester copolymer, α-olefin/maleic acid copolymer, and chlorinated polyethylene. , chlorinated olefin polymers such as chlorinated polypropylene, chlorinated ethylene/propylene copolymer, chlorinated ethylene/vinyl acetate copolymer: polyvinyl chloride,
Vinyl polymers such as polyvinyl acetate, poly(meth)acrylic acid ester, polyvinyl ether, and vinyl chloride/vinylidene chloride copolymers; synthetic rubbers such as polychloroprene, NBR, SBR, and chlorinated rubber; Among the various organic polymers mentioned above, more preferred are chlorinated olefin polymers which are chlorides of polymers or copolymers of propylene or ethylene, etc. Chlorinated rubber: Copolymers of propylene or ethylene, etc. Olefin copolymer as a polymer: methyl methacrylate/chloroprene copolymer, and particularly preferred are chlorinated polypropylene and methyl methacrylate/chloroprene copolymer. When using an organic polymer in combination, the amount added depends on the type of organic polymer, but it should be added in the primer solution.
It is preferably 0.1 to 20% by weight. If this concentration is less than 0.1% by weight, it will have little effect on improving coating properties, and 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 the effectiveness as a primer will decrease. decrease. In addition, the addition of the organic polymer will cause the viscosity of the primer solution to be between 2 and 2.
It is preferable to determine the type and amount so that the temperature is within the range of 5000 cp/25°C. Γ Usage method As stated in the application specification, the primer of the present invention is suitable for use when the layer of an organometallic compound formed on the surface of a non-polar or highly crystallized resin has a certain thickness. Therefore, the primer of the present invention can be applied to non-polar or highly crystallized resin.
When used as a cyanoacrylate primer, it is preferably dissolved or dispersed in an organic solvent. The organic solvent used is a general organic solvent that can completely dissolve or disperse the above-mentioned organometallic compound, has appropriate volatility, and is easily available industrially. It is desirable that there be. In addition, the solvent is preferably one that can sufficiently wet the surface of the resin such as polyolefin in order to apply the primer more efficiently.
For this purpose, it is more desirable to select and use an organic solvent whose surface tension is smaller than the critical surface tension γc of these resins. Specific examples of the solvent include 1,1,2-trichloro-1,1,2-trifluoroethane, ethanol, acetone, ethyl acetate, 1,1,1-trichloroethane, tetrahydrofuran, 1,4-dioxane, toluene. etc., 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, more preferably
It is 0.001 to 1% 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 monomolecular film, and if it exceeds 10% by weight, the layer will likely become too thick. , a thicker layer becomes a brittle layer, reducing its effectiveness as a primer. 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. The non-polar or highly crystallized resin on which the primer layer is formed can be firmly adhered to each other or to other materials by α-cyanoacrylate. A thin layer of α-cyanoacrylate polymer is formed by applying a diluted solution with an organic solvent such as toluene or ethyl acetate that does not impair the properties using a brush that has been treated with an acid in advance, or by dipping it and leaving it at room temperature. After that, painting can be carried out using a common paint by a roller method, a spray method, or the like. Further, for printing, after performing the same processing, printing can be performed using a general printing ink by a silk screen printing method, a gravure printing method, or the like. In order to better exhibit the effects of the primer of the present invention, the type of organometallic compound to be used, its concentration, application amount, etc. must be determined by considering the type of non-polar or highly crystallized resin. Regarding the amount of coating, it is natural that if it is too small and the organometallic compound cannot completely cover the resin surface, the result will not be good, and if it is too large, the organometallic compound layer will be far more than a thin film. If the thickness exceeds , the layer itself becomes a brittle layer and the effect of the present invention will not be exhibited, so the coating amount of the organometallic compound is preferably 0.001 to 1 g/ ^m2 is 0.01
A preferred method for using the present invention is to apply the coating at a concentration of ~0.1 g/m ² . "Function" The primer of the present invention does not have the same characteristics as the primers previously proposed by the present inventors in Japanese Patent Application Nos. 58-87761 and 59-59367, but does not have the same properties as the primers during storage and use. The problem of deterioration of properties due to drying is solved in one fell swoop by suppressing the moisture content in the primer to 500ppm or less.
This is because the presence of water prevents deterioration due to hydrolysis reactions of organometallic compounds, and when the primer is applied to non-polar or highly crystallized resins, the water in the primer is scattered on the surface of those resins.
This is presumed to be due to eliminating the need to prevent the formation of a primer layer. The present invention provides an excellent primer that has the effect of maximizing the primer effect of the organometallic compound by suppressing the water content to 500 ppm or less. "Example" The present invention will be specifically described below with reference to Examples and Comparative Examples. Example 1, Comparative Example 1 The following three types of primers were prepared. A: 1%-monosec-butoxyaluminum diisopropylate in toluene solution B: 1%-ethylacetoacetate aluminum diisopropylate in ethyl acetate solution C: 1%-aluminum tris(ethylacetoacetate) in methylchloroform solution In a container Using a 100 c.c. polyethylene bottle, the primers were placed in the bottles, and 5 wt % of each of silica gel blue particles (manufactured by Hayashi Junyaku Co., Ltd.) as a solid desiccant was added to the primers. Storage conditions were 25°C and 90 to 100% RH, and moisture analysis and primer performance tests were conducted at predetermined intervals. The test method was as follows. (1) Moisture analysis Karl Fischer analysis method Analyzer AQUACOUNTER AQ-1
Made by HIRANUMA (2) Primer performance test Compliant with JIS K6861-1977 Test piece (polypropylene plate 25 x
Wipe both sides of the (100 x 2 mm) with a primer-impregnated cloth for about 5 minutes, then apply Aron Alpha #201 to one side.
Apply (cyanoacrylate adhesive manufactured by Toagosei Kagaku Kogyo Co., Ltd.) and press both sides together with a clamping force of 0.1 kg.
f/cm ³ was added to adhere and cure for 24 hours. The tensile shear adhesive strength of the adhesive was measured using a Strograph W type tester (manufactured by Toyo Seiki Co., Ltd.) at a tensile speed of 20.
Measured in mm/sec. Further, as Comparative Example 1, a similar test was conducted on a sample without silica gel added. These results are shown in Table 1.

[Table] Material breakage = Destruction of test piece Example 2, Comparative Example 2 The following three types of composition liquids were prepared as primers. D: 0.5%-butyltin diacetate xylene solution E: 0.5%-tetraisopropyl titanate butyl acetate solution F: 0.5%-acetylacetone zirconium trichlorethylene solution A 100cc polyethylene bottle was used as the container, and the above primer was placed in it. and 3 wt % of each of Molecular Sieve 3A particle size 3.2 mm (manufactured by Kishida Chemical Co., Ltd.) as an adsorbent was added to the primer. Storage conditions were 25° C. and 90 to 100% RH, and moisture analysis and primer performance tests were conducted at predetermined intervals in the same manner as in Example 1. Further, as Comparative Example 2, a similar test was conducted on a product without addition of molecular sieve. These results are shown in Table 2.

[Table] Material damage = destruction of test piece
(c) Effects of the Invention By using the primer of the present invention, adhesion, painting or printing of non-polar or highly crystallized resins with 2-cyanoacrylate can be easily and quickly done without causing any variation in performance.
In addition, it can now be carried out without deterioration of performance during storage or use, and can be applied successfully to adhesion of non-polar or highly crystallized resins such as polyolefins, or to coating or printing on the surfaces of these resins. As a result, it has many advantages such as utilizing the excellent physical properties of polyolefin, etc., being lighter than metal materials, being less rusty, and reducing costs. The degree is very large.

Claims (1)

[Claims] 1 Used when applying α-cyanoacrylate to non-polar or highly crystallized resins, containing an organometallic compound as an active ingredient, and having moisture content suppressed to 500 ppm or less using a desiccant or adsorbent. A primer featuring: