JPS6330348B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a primer (undercoat) used when adhering a non-polar or highly crystallized resin, or painting or printing the resin using α-cyanoacrylate. The purpose of the present invention is to use α-cyanoacrylate to successfully adhere materials such as non-polar or highly crystallized resins, which have traditionally been difficult to adhere, paint, or print, or to apply coatings to such materials. Another object of the present invention is to provide a primer that can be used to perform printing etc. satisfactorily. Non-polar or highly crystallized resins, such as polyolefins such as polyethylene, polypropylene, polybutene, and polyfluoroethylene, polyethylene terephthalate, polyacetal, and nylon, as well as soft PVC films that contain large amounts of plasticizers, etc. It is a material that is difficult to adhere to, paint, and print on, and it is not possible to adhere these resins well or to paint or print on these resin surfaces using ordinary methods. Conventionally, in order to improve the adhesion properties of these materials, for example, polyethylene and polypropylene are subjected to oxidation treatments such as flame treatment, corona discharge treatment, radiation treatment, and dichromate and sulfate treatments to remove carbonyl groups, etc. Surface treatment methods have been proposed to generate polar groups on the surfaces of these materials. Furthermore, for resins such as polyfluoroethylene that cannot be surface oxidized, special chemical treatments such as lithium paper treatment, alkali heat treatment in a helium stream, and ammonia solution treatment of metallic sodium have been proposed. However, these treatment methods require special equipment, are complicated to work with, and cannot uniformly treat objects with complex shapes.
Moreover, it has drawbacks such as high costs. Various proposals have also been made regarding primers, and according to JP-A No. 52-98062, No. 56-141328, and No. 57-119929, chlorinated polyethylene, chlorinated polypropylene, or fatty acid-modified acrylated alkyd resin is dissolved in an organic solvent. A primer has been proposed that will cause the oxidation. However, according to JP-A No. 58-8734, although these primers have good adhesion to polyolefin, they have poor adhesion to top coat paints.
Another problem is that even if the top coat and polyolefin exhibit good adhesion, the interlayer adhesion deteriorates due to repeated heating and cooling cycles. Furthermore, according to JP-A-54-124048, JP-A-54-124049, and JP-A-124095, a modified polyolefin in which a solid rubber, an unsaturated carboxylic acid or a derivative thereof, and a radical generator are blended into a polyolefin base material is proposed. According to No. 57-38827, these methods leave unreacted unsaturated carboxylic acids, radical generators, etc., which have an undesirable effect on the adhesion of the coating film. Furthermore, JP-A No. 54-124050, No. 55-34270, No. 55-
According to 84271, an improved resin containing a propylene/styrene/butadiene block copolymer and an inorganic filler as essential components has been proposed, but this method also suffers from poor weather resistance in non-coated areas and due to filler formulation. There seem to be various problems, including drawbacks such as low-temperature brittleness.
If non-polar or highly crystallized resins such as polyolefins are properly adhered or painted or printed on the surface of these resins, the excellent physical properties of polyolefins can be utilized, and weight reduction and non-rustness can be achieved as an alternative to metal materials. It has many merits such as cost reduction and cost reduction, and its contribution to various fields such as the automobile industry and the electrical equipment industry is thought to be significant. In view of these circumstances, the present inventors have made extensive research efforts to develop a surface treatment method that is simple and speedy compared to these conventional techniques. They developed a primer that enables printing, and have now completed the present invention. That is, the present invention relates to a primer consisting of an organometallic compound (excluding aluminum alcoholate and aluminum chelate compounds) for applying α-cyanoacrylate to a nonpolar or highly crystallized resin. 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. The primer of the present invention is made of an organometallic compound, and an organometallic compound 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. Examples of the organic group in the organometallic compound include alkyl, alkenyl, alkoxy, aryl, acetylacetonyl, acetyloxy, cyclohexyl, etc., and hydrocarbon groups of C ₃ or more are particularly preferred from the viewpoint of treatment effects and risks. are typical metals shown in the periodic table such as tin, aluminum, magnesium, calcium, and sodium, and transition metals such as iron, titanium, zinc, and nickel. Examples of organometallic compounds include the following. A metal alcoholate having the structure M-O-R (where M is a metal element and R is an organic group; the same applies hereinafter). Specific examples include organic titanium compounds such as tetrabutyl titanate and tetraisopropyl titanate, triisobutoxygallium, and tetrabutyl zirconate.

A 1,3-dicarbonyl complex salt represented by the structure of [Formula]. Specifically, lithium acetylacetone, beryllium acetylacetone, sodium acetylacetone, magnesium acetylacetone,
Acetylacetone calcium, acetylacetone titanyl, acetylacetone strontium, acetylacetone barium, acetylacetone thallium, acetylacetone vanadyl, acetylacetone manganese (), acetylacetone iron (), acetylacetone thorium, acetylacetone chromium (), acetylacetone rhodium, acetylacetone cobalt (), acetylacetone cobalt (), acetylacetone Nickel, copper acetylacetone,
There are acetylacetone complex salts such as acetylacetone zinc, acetylacetone zirconium, acetylacetone palladium, acetylacetone indium, acetylacetone tin () salt, and acetylacetone molybdenum, and complex salts such as acetoacetate, trifluoroacetylacetone, and benzoylacetone.

A carboxylic acid salt represented by the structure of [Formula]. Specifically, magnesium stearate, aluminum stearate, calcium stearate, ferric stearate, zinc stearate, barium stearate, lead stearate,
Potassium stearate, copper stearate, manganese stearate, nickel stearate, nickel naphthenate, cobalt naphthenate, manganese naphthenate, magnesium naphthenate, zinc naphthenate, magnesium palmitate, cadmium palmitate, cobalt palmitate, linoleic acid Sodium, sodium laurate, barium oleate, aluminum laurate, aluminum oleate, potassium oleate, aluminum acetate, stannous acetate,
These include tin 2-ethylhexanoate, aluminum formoacetate, zinc tartrate, and basic aluminum thiodiglycolate. A metal having a hydrocarbon group represented by the structure M-R. Specifically, 2-ethylhexylzinc, hecasadecyllithium, n-hexyl sodium,
Alkyl metals such as hexadecyl potassium, tri-n-octylaluminum, n-propylethyl lead, isobutylisoamylzinc, dibutyltin diacetate, di-n-butyltin dimaleate, di-n-butyltin dioxide, triphenyltin acetate, Examples include organic tin compounds such as tri-n-butyltin oxide, dioctyltin dilaurate, tributyltin acetate, tributyltin chloride, tetraamyltin, diallyltin dichloride, and ferrocene, titanocene dichloride, and nitrogenosene. Other organometallic compounds represented by M-X-R (where X is a heteroatom) Specifically, metal thioalcoholates such as n-dodecylmercaptopotassium salt, aluminum tributoxide, and 2-ethylhexane monothioic acid tin, thiodicarboxylic acid salts such as zinc 2-ethylhexane dithioate, nickel dimethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldiocarbamate, dithiocarbamates such as zinc diethyldithiocarbamate, and sulfonic acids such as nickel benzenesulfonate. salts, phosphates such as vanadium dibutyl sphosphate, and zinc 2-mercaptobenzothiazole. For the present invention, preferred compounds are compounds classified as carboxylates of and metals having a hydrocarbon group, and more preferred compounds are compounds classified as metal alcoholates of and complex salts of 1,3-dicarbonyl. be. Specific compounds include acetylacetone lithium, acetylacetone sodium, acetylacetone magnesium, acetylacetone titanyl, acetylacetone iron (), acetylacetone palladium,
Indium acetylacetone, sodium linoleate, magnesium stearate, aluminum stearate, aluminum acetate, aluminum laurate, basic aluminum thiodiglycolate, calcium stearate, ferric stearate, ferrocene, copper dimethyldithiocarbamate, zinc stearate, Preferred compounds include 2-ethylhexylzinc, zinc tartrate, stannous acetate, di-n-butyltin dimaleate, di-n-butyltin oxide, triphenyltin acetate, barium stearate, and lead stearate; calcium acetylacetone; Zinc acetylacetone, potassium oleate, nickel naphthenate, dioctyltin dilaurate are more preferred compounds, and manganese acetylacetone (), cobalt acetylacetone (), nickel acetylacetone, zinc acetylacetone, zirconium acetylacetone, tetrabutyl titanate, tetraisopropyl titanate, dibutyltin dilaurate Acetate, tri-n-butyltin oxide, and tin 2-ethylhexanoate are particularly preferred compounds. The primer made of the organometallic compound of the present invention is used by applying α-cyanoacrylate when adhering non-polar or highly crystallized resin, or when painting or printing the resin. As will be described later, it is desirable to control the coating thickness during use in order to fully exhibit the effects of the present invention, and therefore it is desirable to use it as a solution. Organic solvents used to make solutions include:
It is desirable that the organic solvent be a general organic solvent that can completely dissolve or disperse the organometallic compound, have appropriate volatility, and be easily available industrially. In addition, the solvent is preferably one that can sufficiently wet the surface of the resin such as polyolefin in order to make the primer work more efficiently, and for this purpose, the surface tension of the organic solvent must be equal to the critical surface tension γ It is more desirable to select and use a smaller one. The following table shows typical values of surface tension and critical surface tension that can be used as a reference when selecting the solvent to be used.

[Table] Concentration of organometallic compounds when made into solutions
It is preferably 0.001 to 10% by weight. This is because, as will be described later, the organometallic compound applied to the surface of the base material can best exhibit the desired effect of the present invention when applied to a thickness close to that of a monomolecular film. If it is 0.001%, it will be easier to achieve the purpose, and as the concentration increases, the film of the organometallic compound will become thicker in proportion, and if it becomes too thick, the layer will become fragile. . The α-cyanoacrylate in the present invention is represented by the following general formula. R in the above formula is an alkyl group, alkenyl,
Includes cyclohexyl, aryl, and alkoxyalkyl groups, specifically 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 in the present invention, these commercially available adhesives are directly used as α-cyanoacrylates. You can also use Commercially available cyanoacrylate adhesives are based on α-cyanoacrylate, and are made into adhesives by blending various components, such as those shown below, as desired. (1) Stabilizers (2) Thickeners (3) Modifiers (4) Coloring agents, etc. Stabilizers are used to improve the storage stability of cyanoacrylate adhesives, and are usually used as anionic polymerization inhibitors. Sulfur dioxide, aromatic sulfonic acids, sultones, etc. are used, and as radical polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, etc. are used. Thickeners are originally based on α-cyanoacrylate, which is a low viscosity liquid with a few cp.
It is used to thicken this into a viscous liquid of several tens to several thousand cp depending on the purpose, and is used by dissolving polymethyl methacrylate, acrylic rubber, cellulose derivatives, etc., for example. Modifiers are blended to improve impact resistance, heat resistance, etc., which are disadvantages of cyanoacrylate adhesives. Maleic anhydride and its derivatives are used. In addition, in order to make it possible to bond porous wood materials containing acidic sap, which have traditionally been considered difficult to bond, a crown compound as disclosed in Japanese Patent Publication No. 55-2238 has been used. be. Furthermore, tricresyl phosphate, dioctyl phthalate, dimethyl sebacate, or the like may be added as a plasticizer to impart flexibility to the adhesive layer after curing. Coloring agents are used to color adhesives in order to make it easier to identify adhesive locations.
Acidic salts of basic dyes as shown in Japanese Patent No. 37260 may be blended. In addition, for the purpose of imparting a fragrance to the adhesive, a fragrance such as an ester derivative disclosed in Japanese Patent Application Laid-Open No. 53-58541, for example, may be added. Further, in the present invention, α-cyanoacrylate diluted with a specific organic solvent can also be used. Suitable organic solvents include toluene, butyl acetate, or methyl chloroform, which are compatible with α-cyanoacrylate and do not impair stability, and these solvents do not contain water or other impurities. is preferred. When using the primer of the present invention for adhering non-polar or highly crystallized resins, the application method is as follows: When adhering a combination of non-polar or highly crystallized resin materials as adherends, both of them may be used. When the surface is also non-polar or a combination of a highly crystallized resin and a polar material, it is possible to immerse only the former surface in a primer solution for a few seconds, apply it with a brush, spray it, etc., and apply the primer in this way. By air-drying the adherend to remove the solvent, it is possible to obtain an adherend that adheres well with α-cyanoacrylate. The adherend made of a non-polar or highly crystallized resin coated with the primer of the present invention in this way is
The adhesive is bonded by conventional means using α-cyanoacrylate, and the resulting bonded body has excellent adhesive strength. Other methods include coating the surface of the adherend with a mixture of α-cyanoacrylate and an organometallic compound, or diluting a solution with an organic solvent if necessary, or using a two-liquid discharge type coating machine. α
- It is also possible to adopt a method of simultaneously discharging a solution of cyanoacrylate and an organometallic compound to simultaneously apply the primer and adhesive and bond them. However, when the mixing method is employed, sufficient care must be taken when handling to avoid contamination with foreign substances such as moisture, amines, and alcohols, as α-cyanoacrylate has the unique property of exhibiting strong anionic activity. For painting or printing on non-polar or highly crystallized resins, apply a primer using the method described above on the base material surface made of those resins, and then apply α-cyanoacrylate on top of it to form a film of the polymer. By doing so, the base material becomes a base material with good suitability for painting and printing, so it can be coated on that surface by conventional means, and the base material painted or printed in this way becomes a coating with excellent performance. Or it can be a printed substrate, ie a non-polar or highly crystallized resin. The method of applying the primer of the present invention when painting or printing is almost the same as when applying the adhesive, but the excellent effects in painting or printing are produced by the following steps, which will be explained below. The process is a preferred method for painting or printing. First, as a first step, a primer prepared by dissolving an organometallic compound in an organic solvent is applied to the surface of the base material to be painted or printed. The above primer can be applied to the surface of the substrate by the usual brushing, dipping, or spraying methods, and the open time after treatment is usually 5 to 60 minutes at room temperature. Depending on the work process, it can take several days. As the second step, α-cyanoacrylate is applied onto the base material coated with the above primer,
- forming a film of cyanoacrylate polymer; The α-cyanoacrylate can be applied by a brushing method using a brush treated with an acid in advance, a dipping method, a spraying method, or the like. However, when using the spray method, it is preferable to use a diluted solution of α-cyanoacrylate in an organic solvent to prevent problems with nozzle clogging. Furthermore, when using a commercially available cyanoacrylate adhesive as α-cyanoacrylate, it is preferable to use one that is commercially available as a low viscosity grade. The substrate coated with α-cyanoacrylate is left at room temperature for 12 hours or more to form a thin layer of α-cyanoacrylate polymer on its surface. The film thickness of the α-cyanoacrylate polymer is not particularly limited, but it should be
It is preferable to set it to about 50μ. By the method described above, the base material coated with the primer and α-cyanoacrylate is coated with a general paint or printed with a printing ink. There are various types of paints or printing inks, and there are various classification methods, but the following are listed based on the vehicle resin component. Rosin derivatives, nitrocellulose resins, vinyl resins, acrylic resins, polyester resins, polyamide resins, polyurethane resins, phenolic resins, epoxy resins, aminoalkyd resins, melamine resins, UV-curable acrylic oligomers, etc. However, although any of these can be applied to the present invention, the following are more suitable for use in polyolefins:
Paints or printing inks based on polyurethane resins, epoxy resins, alkyd resins, etc. are particularly preferred. Furthermore, since there is a limit to the heat resistance of the base resin, especially polyolefin, the baking paint preferably has a baking temperature of 90° C. or lower. The paint application method can be done by conventional methods such as brushing, bar coater method, roller method or spray method, while the printing method can be done by conventional methods such as silk screen printing method, gravure printing method or flexo printing method. This can be done using the following method. The primer made of the organometallic compound of the present invention can be used to adhere a non-polar or highly crystallized resin using α-cyanoacrylate, or to paint or print on the resin using α-cyanoacrylate and a paint or printing ink, etc. Although the reason for improving the ability of organic metal compounds is unknown, as shown in the table below, it depends on the type of organometallic compound, but it is most effective when applied very thinly, that is, when applied at 0.001 to 1 g/ ^m2 . The effect is noticeable.

[Table] However, * indicates base metal failure.
The values in the above table are based on a polypropylene plate (thickness 2 mm) as the adherend, acetylacetone zirconium as the primer (used as a methyl chloroform solution of various concentrations), and an α-cyanoacrylate adhesive (Aron Alpha #201 as the α-cyanoacrylate). (trade name, manufactured by Toagosei Kagaku Kogyo Co., Ltd.), and the differences in the expression of tensile shear strength of the bonded area were determined depending on the amount of primer applied. The adhesive was cured for one day at 23°C and 60% RH. From the above results, it was found that the primer is most effective when applied in a state close to a monomolecular layer, and since it has the structure of an organometallic compound, that is, a polar segment and a non-polar segment, the present invention It is presumed that the effect is expressed by the following mechanism. That is, the organometallic compound of the present invention has a non-polar or highly crystallized resin surface and an α-cyanoacrylate layer (monomer or hardened polymer film layer).
The group exists in a state close to a monomolecular film between the resin layer and the α-cyanoacrylate layer, and the lipophilic group and the polar group are arranged in an orderly manner. It is presumed that it acts as a binder between the α-cyanoacrylate layer and the α-cyanoacrylate layer, thereby exerting the effects of the present invention. Therefore, in order to better express the effects of the present invention, it is necessary to consider the combination of the metal element and organic group constituting the organometallic compound, that is, the type of the organometallic compound, and the material of the adherend or base material. The organometallic compound to be used, its concentration, application amount, etc. must be determined. As for the coating amount, as shown in the table above, it goes without saying that good results will not be obtained unless it is so small that the primer layer cannot completely cover the surface to be bonded, painted, or printed. If the primer layer is too thick and the thickness far exceeds a monomolecular layer, the layer itself will become a fragile 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 . By strongly bonding the non-polar or highly crystallized resin and α-cyanoacrylate through an organometallic compound, the adhesion of the resin is strengthened by α-cyanoacrylate, and a film of α-cyanoacrylate polymer is formed. is firmly adhered to the surface of the resin, and can be easily painted or printed with commonly used paints or printing inks without causing any problems. The excellent effects obtained by the present invention were achieved for the first time by a combination of α-cyanoacrylate, an organometallic compound, and a non-polar or highly crystallized resin, which could not be achieved by conventional polyolefins such as polyethylene. When bonding, organic titanium compounds have been considered as primers or surface treatments, but in those cases, epoxy, urethane, rubber, or acrylic adhesives have been used as adhesives. Therefore, no excellent effects were observed, and the effects of the present invention cannot be predicted from these results, and the effects produced by the present invention are so excellent that those skilled in the art cannot predict them. Naturally, the desired effect of the present invention is achieved only when the base material is non-polar or highly crystallized resin, and is not applicable to other base materials such as metal, wood, etc. This does not occur in ceramics, etc. The primer of the present invention is effective for nonpolar or highly crystallized resins such as polyethylene terephthalate, polyacetal, nylon, etc., and is particularly effective for polyolefins. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1, Comparative Example 1 The following primers, adherends, and α-cyanoacrylates were used. 1 Primer (1) Acetylacetone zirconium reagent 1st class (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (2) Acetylacetone manganese () reagent 1st grade (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (3) Acetylacetone nickel reagent 1st class (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.2 g of each of the above compounds was dissolved in 99.8 g of a first grade toluene reagent (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a primer solution. 2 Adherent material (1) Polyethylene plate (25 x 100 x 2 mm) (2) Polypropylene plate (25 x 100 x 2 mm) (3) Polyb template (25 x 100 x 2 mm) 3 α-cyanoacrylate Aron Alpha #201 (cyano Acrylate adhesive (trade name manufactured by Toagosei Kagaku Kogyo Co., Ltd.) Apply the above primer solution to both sides of the test piece with a brush, let it air dry for about 10 minutes, and then apply α to one side.
- Cyanoacrylate was applied, both sides were brought together, a pressing load of 0.1 Kgf/cm ² was applied, and the product was cured for 24 hours. The tensile shear adhesive strength was measured using a Strograph W type tester at a tensile speed of 20 in accordance with JISK6861-1977.
Measured in mm/min. As a comparative example, the adhesive strength was measured in the same manner as in the example except that the adhesive was bonded without using a primer. These results are shown in Table 1.

[Table] *marked Base material failure Tensile shear adhesive strength is the average value of three test pieces.
Example 2, Comparative Example 2 The following primers, adherends, and α-cyanoacrylates were used. 1 Primer (1) Di-n-butyltin diacetate reagent grade 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) (2) Ferric stearate reagent grade 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3 g of the above compound A primer solution was prepared by dissolving it in 99.7 g of methyl chloroform industrial grade (manufactured by Toagosei Chemical Industry Co., Ltd.). 2 Adherent material (1) Polyacetal plate (25 x 100 x 3 mm) (2) Polyurethane plate (25 x 100 x 3 mm) (3) EPT plate (25 x 100 x 3 mm) 3 α-cyanoacrylate Aron Alpha #221 (cyano Acrylate adhesive (trade name, manufactured by Toagosei Kagaku Kogyo Co., Ltd.) The adhesion method and the measurement method for tensile shear adhesive strength were carried out in the same manner as in Example 1. Also, comparative example 2
The adhesive strength was measured in the same manner as in Example 2 except that the adhesive was bonded without using a primer. These results are shown in Table 2.

[Table] *marked Base material failure Tensile shear adhesive strength is measured using 3 test pieces
The average value is shown.
Example 3, Comparative Example 3 The following primers, adherends, and α-cyanoacrylates were used. 1 Primer (1) Acetylacetone cobalt () reagent 1st class (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (2) Acetylacetone zinc reagent 1st class (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.5% of the above compound was added to 1.2.2-trichlor, 1.1.2
Solution 2 dissolved in 99.5 g of industrial grade trifluoroethane (manufactured by Daikin Industries, Ltd.) Adherent material Teflon film 25 x 100 x 0.1 mm 3 α-cyanoacrylate Aron Alpha #221F (cyanoacrylate adhesive Toagosei Chemical Co., Ltd.) (trade name, manufactured by Kogyo Co., Ltd.) The adhesion method and the measurement method for tensile shear adhesive strength were carried out in the same manner as in Example 1. Furthermore, as Comparative Example 3, adhesive strength was measured in the same manner as in Example 3 except that the adhesive was bonded without using a primer. These results are shown in Table 3.

[Table] *marked Base material failure Tensile shear adhesive strength is measured using 3 test pieces
The average of
Example 4, Comparative Examples 4 to 5 The following primers, adherends, and α-cyanoacrylates were used. 1 Primer (1) Tetraisopropyl titanate (2) Tetrabutyl titanate 0.5 g of each of the above compounds was dissolved in 99.5 g of methyl chloroform industrial grade (above) to prepare a primer solution. 2 Adherent material (1) Polyprene plate (25 x 100 x 2 mm) 3 α-Cyanoacrylate Aron Alpha #201 (above) Adhered in the same manner as in Example 1, measured the tensile shear adhesive strength, and reported the results. 4. Table 4 also shows the tensile shear adhesive strength when a two-component epoxy adhesive (commercially available) was used as Comparative Example 4, and when no primer was used as Comparative Example 5.

[Table] *marked Base material failure Tensile shear adhesive strength is measured using 3 test pieces
The average value is shown.
Comparative Examples 6 to 8 Adhesion was performed in the same manner as in Example 4 and Comparative Example 4.5, except that a chrome-plated steel plate (25 x 100 x 1.6 mm) was used instead of the polypropylene plate as the adherend, and the tensile shear adhesive strength was The measured results are shown in Table 5.

[Table] Example 5, Comparative Examples 9 to 11 The following materials were used for the primer, α-cyanoacrylate, paint, and base material. 1 Primer (1) Magnesium acetylacetone Reagent 1st class (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (2) Copper acetylacetone Reagent 1st class (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (3) Di-n-butyltin dimaleate Reagent 1st class ( (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (4) Aluminum oleate reagent 1st grade (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (5) Cobalt balmitate reagent 1st grade (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.1g of each of the above compounds was dissolved in 99.9gr of tetrahydrofuran reagent grade 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) to prepare a primer solution. 2 α-Cyanoacrylate 50 g of ethyl α-cyanoacrylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd.*) is uniformly dissolved in 50 g of n-butyl acetate reagent grade 1 (manufactured by Tokyo Kasei Kogyo Co., Ltd.) to form an α-cyanoacrylate solution. And so. *Contains 100ppm of sulfur dioxide gas and 500ppm of hydroquinone as stabilizers3 Paint (1) Nitrocellulose-based Lutzker enamel (blue) spray type (manufactured by Nippon Paint Co., Ltd.) (2) Acrylic resin paint (yellow) (Toagosei Chemical Industry Co., Ltd.) (3) Two-component polyurethane paint (brown) (manufactured by Chugoku Paint Co., Ltd.) 4 Base material Polypropylene plate (100 x 100 x 2 mm) First, apply a primer solution to the surface of the base material with a brush. Air dried for 10 minutes. Next, an α-cyanoacrylate solution was uniformly sprayed onto this surface using a spray gun and left at room temperature for 24 hours. Subsequently, a paint was uniformly sprayed onto this surface using a spray gun and left at room temperature for 3 days. The performance of the coating is determined after room temperature and environmental exposure tests.
Evaluation was made by a grid test according to JISK5400-1979. The environmental exposure test was conducted under the following conditions. Environmental exposure conditions (1) UV/humidity cycle A cycle of UV-60°C/4 hours → steam 40°C/4 hours was repeated 25 times. Equipment: UVCON tester (manufactured by Toyo Seiki Co., Ltd.) (2) Heat resistance Heated in hot air at 80°C for 24 hours. Equipment: Lab oven (manufactured by Tabai Seisakusho Co., Ltd.) (3) Water resistance Immersed in tap water at room temperature for 24 hours. (4) Thermal shock The cycle of -20°C/1 hr → 60°C/1 hr was repeated 30 times. Apparatus: TSC-10A type (manufactured by Tabai Seisakusho Co., Ltd.) The results are shown in Table 6. The following comparative experiment was conducted to compare the performance of the coating film of Example 5. Comparative Example 9 is the same as Example 5 except that the primer and α-cyanoacrylate are not used, and Example 5 is the same as Example 5 except that the primer is not used.
Comparative Example 10 was the same as Example 5, and Comparative Example 11 was the same as Example 5 except that α-cyanoacrylate was not used. The performance of the coating films of Comparative Examples 9 to 11 is shown in Table 6 in the same manner as in Example 5.

【table】

【table】

Claims (1)

[Claims] 1 Primer consisting of organometallic compounds (excluding aluminum alcoholates and aluminum chelate compounds) for applying α-cyanoacrylates to non-polar or highly crystallized resins.