JPS62121671A - Primer in container - Google Patents

Abstract

PURPOSE:To always develop excellent adhesive capacity in a proper amount, by receiving a primer containing an organometal compound capable of being adhered to a specific resin as an effective component in a container and impreganting a coating part with said primer prior to coating. CONSTITUTION:A primer in a container is used in adapting alpha-cyanoacrylate to a non-polar or highly crystallized resin and the primer contains an organometal compound containing an org. group represented, for example, by a 3C or more hydrocarbon group as an effective component. The container to be used consists of a main body container 1 receiving the primer and a coating part 2 impregnated with said primer. Both of them are assembled by screw threading through a packing 3 and the primer is penetrated in the porous body or felt of the coating part 2 from an occluding body 11 to be brought to a desired wet state and subjected to coating.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Object of the invention [Field of industrial application] The present invention relates to a primer packaged in a container. In particular, the primer of the present invention can be suitably used to successfully adhere materials such as non-polar or highly crystallized resins, which were conventionally difficult to adhere, apply, and print using α-cyanoacrylate. It is suitable for use as an undercoat for coating or printing on such materials, and is widely used in the automobile industry, where non-polar or highly crystallized resins such as polyolefins are widely used as raw materials. It is used in a wide variety of industrial fields, including the electrical equipment industry, and even in general households.

[Conventional technology]

Non-polar or highly crystallized resins, such as polyolefins such as polyethylene, polypropylene, polybutene, and polyfluoroethylene, polyethylene tereftate, polyacetal, and nylon, as well as soft PVC films containing large amounts of plasticizers, etc. ,
All of these materials are difficult to bond, paint, and print, and conventional methods do not allow for good adhesion of these resins.
These resin surfaces cannot be well coated or printed.

Some proposals have already been made to improve the adhesion properties of these materials; for example, in the case of polyolefin resins, flame treatment, corrosive discharge treatment, plasma treatment, dichromate treatment, etc. A method of generating a polar group such as a carbonyl group on the surface of the resin by treatment,
Also known is a method of treating the resin with a primer prepared by dissolving chlorinated polyethylene, chlorinated polypropylene, fatty acid-modified acrylic alkyd resin, etc. in an organic solvent (JP-A-52-98062, JP-A-52-98062).
No. 141328, No. 57-119929).

In addition, solid rubbers, unsaturated compounds, [1-carboxylic acids or derivatives thereof and radicals], and improved resins containing propylene/styrene/butadiene block copolymers and inorganic fillers as essential components are also available ( It is proposed.

As a result of intensive research efforts aimed at developing something superior to these conventional techniques, the present inventors discovered a primer containing an organic metal compound such as aluminum alcoholade or aluminum chelate salt as an active ingredient, and proposed the following first. (Patent Application No. 58-87761, No. 59-59367)
issue).

This primer has an extremely excellent function in achieving the intended purpose.

[Problem that the invention seeks to solve]

The primer proposed by the present inventors is extremely excellent, but as revealed in the specification of Japanese Patent Application No. 59-59367, the treatment effect varies greatly depending on the amount of primer applied, and the amount of application is not appropriate. This has disadvantages in terms of reliability, such as the adhesive strength varying or becoming low in some cases.

The present inventor aims to solve the above-mentioned problems and provide a technique that allows a primer with excellent functionality to be applied in an appropriate amount at all times, thereby fully demonstrating the excellent performance of the primer. It is something.

(B) Structure of the invention [Means for solving the problems and their effects] The container-packed primer of the present invention is used when applying α-cyanoacrylate to a non-polar or highly crystallized resin. A primer containing an organometallic compound as an active ingredient is housed in a container that has a main body for accommodating the primer and an application area moistened by the primer contained in the main body. .

According to the present invention, since the primer is wetted in the application area, it is possible to apply the primer through this application area, and in this case, the primer is applied only when the application area is wet. The application amount is regulated depending on the wet state, so that the appropriate amount is always applied.

Hereinafter, the configuration of the present invention will be explained in more detail.

(Organometallic Compound) The organometallic compound in the present invention is a compound in which an organic group and a metal are bonded. Any such material can be used in the present invention regardless of its structure or the like. Specifically, the present inventors have filed Japanese Patent Application No. 5 El-87761, No. 59-5936.
The method proposed in No. 7 can also be used in the present invention.

As described in the specification of the above-mentioned application, examples of the organic group in the organometallic compound of the present invention include alkyl, alkenyl, alkoxy, aryl, acetylacetonyl, acetyloxy, cyclohexyl, etc. Hydrocarbon groups having 3 or more carbon atoms 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 and the like.

Preferred compounds for the present invention are carboxylic acid salts having the structure M-0-C-R (where M is a metal element and R is an organic group; the same applies hereinafter), and a hydrocarbon group having the structure M-R. It is a compound classified as a metal.

More preferred compounds are metal alcoholades represented by the structure M--H and 1,3-dicarbonyl complex salts represented by the structure.

Specific compounds include acedelacetone lithium,
Acetylacetone sodium, acetylacetone magnesium, acetylacetone titanyl, acetylacetone 1~
iron (■), palladium acetylacetone, indium acetylacetonate, 1-IJ-n-octadecyl borate, sodium linoleate, magnesium stearate, aluminum stearate, aluminum acetate, aluminum laurate, basic aluminum thiosyglycolate, stear Calcium phosphate, ferric stearate, copper ferrocene dimethyldithiocarbamate, zinc stearate, zinc 2-ethylhexyl, zinc tartrate, stannous acetate, di-n-butyltin dimaleate, di-n
-butyltin oxide, triphenyltin acetate,
Barium stearate, lead stearate, dibutyl phosphite, tridecyl phosphate, and trioleyl phosphate are preferred compounds, and calcium acetylacetone, zinc acetylacetone, potassium oleate, nickel naphthenate, and dibutyltin diacetate are more preferred compounds. , aluminum trisisopropylate, aluminum mono-5ec-butoxydiisopropylate,
Aluminum tris acetylacetonate, aluminum mono-acetylacetonate bis ethyl acetoacetate, aluminum ethyl acetoacetate diisopropylate, aluminum tris ethyl acetoacetate, 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, octadecyldimethyl C3-()IJmethodi1-cysilyl)propylummonium chloride (AY4 3-0 2 1: A particularly preferred compound is trisisodecyl phosphite (trade name, manufactured by Toray Silicon Co., Ltd.).

(Water in Primer) In order to prevent variations in quality and characteristics of primers containing organometallic compounds as active ingredients, and to prevent quality deterioration during use or storage, the amount of water in the primer should be kept at a certain level, that is, 500 ppm or less. It is preferable to do so. By maintaining the water content at 500 ppm or less, the above problems can be effectively solved.

In order to suppress the water content in the primer to 500 ppm or less, it is desirable to control the water 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 preferable to carry out the production in a dehumidified room or to use moisture-proof equipment.

Also, even if there is no moisture in the primer immediately after manufacturing,
The primer may absorb moisture from the air during use or storage, and the moisture content in the primer may exceed 500 ppm over a long period of time. Moisture content is 500ppm
It is preferable to take measures to ensure that the amount is not exceeded.

Measures to prevent moisture absorption of the primer during storage or use include containers made of moisture-impermeable materials, such as glass containers, metal containers, or plastic containers with a layer of polyvinylidene chloride. However, in the present invention, since a container is used that has a main body part that stores the primer during use and an application part that can be wetted by the primer in the main body part, it is easy to absorb moisture during use. An adsorbent is present (for example, as described later, a desiccant may be located at the bottom or inner peripheral wall of the main body portion),
Due to this moisture absorption, the moisture in the primer is 500pI.
) m is preferably not exceeded.

For example, in carrying out the present invention, the desiccant or adsorbent can be stored in a container, particularly inside the main body portion or in the lid, by creating a space for the desiccant or the like. Alternatively, as will be described later, the desiccant or adsorbent may be placed on the bottom or inner peripheral wall of the main body, or it may be directly dispersed or coexisted in the primer.

By such means, it is possible to remove moisture absorption and also moisture caused by raw materials, and the moisture content is always 500 p.
The primer can have a p m or less.

There are various drying agents used at this time, such as I'i, phosphorus oxide, activated alumina, anhydrous Calcilla sulfate J1, magnesium oxide, calcium oxide, calcium chloride, magnesium sulfate, Examples include diatomaceous earth, anhydrous zinc chloride, anhydrous copper sulfate (■), silica gel, silica alumina, and adsorbents such as molecular sieve and activated carbon. The material used in contact with the primer is preferably one that satisfies the following conditions.

(1) Solid (II) Neutral or nearly neutral (III) Non-chemically reactive with the primer (IV) Non-dissolved in the primer (V) Non-interfering with the primer function Preferred desiccants or adsorbents include activated alumina, magnesium oxide, magnesium sulfate, diatomaceous earth, silica alumina, and more preferred are silica gel and molecular sieves.

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.

(Container) The container used in the present invention has a main body portion that accommodates the primer and an application portion that can be wetted by the primer. For example, a container having a main container 1 and an applicator 2 as illustrated in FIG. 1 can be used. The example shown in FIG. 1 consists of a main body part 1, an occlusion body 11 therein, an applicator part 2, a panning 1-3, a middle part 5, and a cap 6. An occlusion body 11 that absorbs primer and stores dirt is housed in the main body part 1. The tip of the main body part 1 becomes a protruding part 12. This protruding part 12 has a threaded part 1 on the outside.
2'. On the other hand, the application section 2 is arranged inside the middle MS. The inner peripheral surface of the inner lid 5 is a threaded portion 51, which is screwed into the threaded portion 12' of the main body portion to be assembled. A banking 3 is interposed between the inner lid 5 and the main body portion 1.

The desiccant is shown by the broken line in Figure 1! It may be arranged so that it is provided at the bottom of the main container 1, which is the part shown in FIG.

Although various shapes and materials can be used for each part, those shown in Table 1 below are particularly suitable for use in the present invention due to their usage. Preferably, it does not contain.

In addition, in order to moisten the primer, the application part should be selected from porous materials, laminates, felt, and other materials used in general writing instruments (felt ben, etc.), depending on the wet state and the application of the container. Configuration example Also, as shown in FIG. 2, a camp 4 has a porous coating section 2 in a hollow main body container 1 made of soft plastic or the like.
It is also possible to use a container covered with a primer, wet the primer in the main container 1 to the application section 2, and apply the primer through the application section 2.

(α-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.

N CH2=C OOR In the above formula, R includes alkyl, alkenyl, cyclohexyl, aryol, and alkoxyalkyl groups, and specifically, methyl, ethyl, n-propyl, n
-butyl, isobutyl, n-pentyl, allyl, cyclohexyl, hensyl, methoxypropyl groups, and the like.

These α-cyanoacrylates are the main components of commercially available cyanoacrylate-based instant adhesives, and the primer according to the present invention uses α-cyanoacrylate as is from these commercially available adhesives. It can also be used as a primer when used as a primer.

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.

(Non-polar or highly crystallized resin) Examples of the non-polar or highly crystallized resin for which the primer of the present invention is used include polyethylene, polypropylene,
These include olefin polymers such as polybutene and polymethylpentene, composites made by blending these with talc, alumina, mica, glass fiber, etc., as well as polyethylene terephthalate, polyacetal, polyurethane, silicone rubber, and soft PVC.

The primer of the present invention works most effectively when used with olefin polymers.

(Organic Polymer) Various commonly known organic polymers can be used in combination with the primer of the present invention, thereby improving coating properties and the like. 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 a preferable method for using the primer.

Specific examples of organic polymers that can be used in combination include olefin polymers such as ethylene/vinyl acetate copolymer, ethylene/acrylic acid ester copolymer, α-olefin/maleic acid copolymer, and chlorinated ethylene/maleic acid copolymer. Chlorinated off-line polymers such as propylene copolymers, chlorinated ethylene/vinyl acetate copolymers, polyvinyl chloride, polyvinyl acetate, poly(meth)acrylates, polyvinyl ethers, vinyl chloride/vinylidene chloride copolymers and synthetic rubbers such as polychloroprene, NBRXSBR, 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, chlorinated rubber, and copolymers of propylene or ethylene. The polymers include olefin copolymers and methyl methacrylate-1/cobropyrene copolymers, and particularly preferred are chlorinated polypropylene and methyl methacrylate-1/chloroprene copolymers.

When using an organic polymer in combination, the amount added depends on the type of organic polymer, but is 0.1 to 20% by weight in the brimer solution.
It is preferable that If this concentration is less than 0.1% by weight, it may be less effective in improving coating properties, and if it exceeds 20% by weight, it may interfere with the function of the organometallic compound, which plays the main role as a primer. may reduce its effectiveness as a primer. In addition,
The type and amount of the organic polymer to be added is preferably determined so that the viscosity of the brimer solution is in the range of 2 to 100 cp/25°C.

(Method of Use) As stated in the application specification, the primer of the present invention is used when the layer of an organometallic compound formed on the surface of a non-polar or highly crystallized resin has a certain thickness. 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 organometallic compound, and
It is desirable that it has appropriate volatility and is easily available industrially.

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 a smaller one. Specific examples of solvents include 1
, 1.2-trichloro-1,2,il-lifluoroethane, 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. In order to
It is preferably 0.001 to 10% by weight, more preferably 0.001 to 1% by weight. Its concentration is 0.
If it is less than 0.001% by weight, it becomes difficult to form a layer of the organometallic compound in the form of a thin film or a monomolecular film.
If it exceeds 0% by weight, the layer tends to become too thick, and the thick 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, and needs to be applied in an appropriate amount, particularly in the form of a thin film as described above.

As mentioned above, the thickness of the primer layer formed on the surface of the resin, such as non-polar or highly crystallized resin, greatly affects the treatment effect, so in order to maximize the effect of the primer according to the present invention, It is desirable to apply the primer quantitatively, easily, and with good workability in the form of a continuous thin film as much as possible. The inventors of the present invention have found that it is sufficient to use a container having an application section that is wetted by the primer in the main body and can be applied.

A resin coated with a primer using the container according to the present invention can be air-dried at room temperature to remove the solvent, thereby forming a single layer of primer on the resin surface.

In this way, non-polar or highly crystallized resins on which a single layer of primer is formed can be firmly adhered to each other or to other materials by α-cyanoacrylate. Furthermore, if necessary, a diluted solution with an organic solvent such as toluene or ethyl acetate that does not impair the stability of α-cyanoacrylate-1 or the same monomer is applied onto the layer using a brush that has been previously treated with an acid. Alternatively, by dipping and leaving at room temperature, α-
A thin layer of cyanoacrylate polymer is formed and then a common paint is applied by a roller method or a spray method. It is possible to perform one loading. 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 and its concentration should be determined by considering the type of material such as non-polar IIl or highly crystallized resin to be applied. is preferred.

Regarding the amount of coating, as clarified in the specification of Japanese Patent Application No. 51-59367, if the amount of coating is so small that the organometallic compound layer cannot completely cover the resin surface, it is good. On the other hand, if there is too much of the organometallic compound and the thickness of the organometallic compound becomes much more than a thin film, the layer will become fragile and will not be effective. The amount of organic metal compound applied is o, oot
~1g/r+? It is more preferable to apply the primer in an amount of 0.01 to 0.1 g/resistance, but if the primer is used in a container as in the present invention and the application area is moistened with the primer, the primer is applied. For example, it is possible to easily apply such an appropriate amount.

〔Example〕

The present invention will be specifically described below with reference to Examples and Comparative Examples. It should be noted that, as a matter of course, the present invention is not limited to the examples described below.

Example 1, comparison layer 〇- (Preparation of primer) The following five types of primers were prepared.

A: 1% zinc acetylacetonate in methyl chloroform B: 1% potassium oleate in methyl chloroform C: 1% cobal naphthenate in methyl chloroform D: 1% tetrabutyl titanate in methyl chloroform Solution E: 1%-trisisodecylphosphite in methyl chloride? 8? (9° (Assembling the container) In this example, as shown in Fig. 1, an eel-min type applicator was assembled. That is, an aluminum main body container (28°
Silica gel blue (particle size approx. 5″″)
Ig and occlusion body ($11 wool prismatic, 17 x 22 x 100
1111), and 25 g of each of the above primers was injected and impregnated therein. Next, the polyethylene backing was attached and the polyester was attached to complete the assembly.

Each part of the pen-type applicator was heated at 60℃/2 in a vacuum drying dish.
It was used after being thoroughly dried for 4 hours.

(Primer Performance Test) Primers were evaluated as follows in accordance with JIS K686-1977.

Primer was applied to both sides of a polypropylene test piece (25
201 (cyanoacrylate adhesive, manufactured by Toagosei Kagaku Kogyo Co., Ltd.) was applied and overlapped, and the clamping force was 0. 1kgf
/cJ was added and cured at room temperature for 24 hours.

The tensile shear adhesive strength was measured using a Strograph W type testing machine (manufactured by Toyo Seiki Co., Ltd.) at a tensile rate of 20 dragons/fin.

As Comparative Example 1, the primer prepared above was applied with a brush to the surface of a polypropylene test piece.

The test was conducted in the same manner as in Example 1 except for the above.

These results are shown in Table 2.

In Table 2, In of the primer is indicated by the above-mentioned symbols 8 to E.

Table 2 As is clear from Table 2, the adhesive of the comparative example was 7.11^11 due to a certain amount of tensile force, but the one to which the present invention was applied showed +, l il failure 1ζl, and strong adhesion. It can be seen that this is being done.

Inuha Port I Yu” U Transportation (Preparation of primer) The following five types of primers were prepared.

F: o, s%-monosecondobutoxy AA-diisopropylate toluene 'lfl'/fftC: O, S%
-A j! -5ec-butyrate toluene solution H: 0.5% -ethylacetoacetate-1-A A'-diisopropylate toluene solution I: 0.5% -A! - Tris (acetylacetonate)
Toluene solution J: 0.5%-Aff-monoacetylacetonate bis(acetoacetate-1) toluene solution (container assembly) In this example, a container was assembled as follows, and a felt-tip applicator was used. And so. That is, silica gel blue (particle size approximately 5") Ig and an occlusion body (polyester foam cylindrical shape 20ΦX100I""
), and 15 g of each of the above primers was injected and impregnated into the container. Next, the polyethylene gasket was attached, the inner lid with the flat nylon pen-shaped applicator was screwed on, and the camp was attached to complete the assembly. Furthermore, to maintain airtightness, vinyl tape was wrapped around the fitting part of the cap to seal it. As in Example 1, each part of the applicator was sufficiently dried.

(Performance test of primer) Performance of the pen-shaped primer prepared above when stored at room temperature was measured in the same manner as in Example 1.

As Comparative Example 2, the primer prepared in Example 2 was stored in a polyethylene bottle (loOcc volume), and as a treatment method, the surface of a polypropylene test piece was coated with the same primer with a brush. The test was conducted in the same manner as in Example 1 except for the above.

These results are shown in Table 3. The types of primers are indicated by the symbols F~ and ■ as described above.

Table 3 It can be seen from Table 3, as well as from Table 2 above, that the application examples of the present invention are extremely excellent.

(c) Effects of the Invention As described above, by using the packaged primer of the present invention, relatively small-scale adhesion, painting, or printing of non-polar or highly crystallized resin with α-cyanoacrylate can be easily and speedily performed. It becomes possible to implement the method without causing variations in performance and without deterioration in performance during storage and use. Moreover, according to the present invention, relatively small-scale work such as bonding can be performed extremely easily.

As described above, according to the present invention, non-polar or highly crystallized resins such as polyolefins can be well adhered, or the surfaces of these resins can be coated or printed. It can bring many benefits such as lighter weight, less rust, and lower costs, and its contribution to various fields such as the automobile industry, electrical equipment industry, and other industries is extremely large.

[Brief explanation of drawings]

1 and 2 are schematic cross-sectional views each illustrating an embodiment of the present invention. DESCRIPTION OF SYMBOLS 1... Container body, 11... Occlusion body, 2... Application part, 3... Backing, 4.6... Cap, 5...
・Inner lid.

Claims (1)

[Claims] 1. A primer containing an organometallic compound as an active ingredient used when applying α-cyanoacrylate to a non-polar or highly crystallized resin is provided with a main body portion that accommodates the primer and a main body portion that is housed in the main body portion. A container-packed primer, characterized in that the primer is stored in a container having an application area moistened with the primer.