JPS61176634A - Primer - Google Patents

Abstract

PURPOSE:A primer having improved shelf stability, showing specific effects without causing variability and reduction when alpha-cyanoacrylate is applied to a nonpolar or highly crystallized resin, comprising an organometallic compound as an active ingredient, having a controlled water content. CONSTITUTION:A primer comprising an organometallic compound as an active ingredient, having <=500ppm water content. Calcium acetylacetonate, zinc acetylacetonate, dioctyltin dilaurate, isodecyl phosphite, etc. are used as the organometallic compound. Control of water content is carried out by regulating water content in a raw material and an organic solvent used during production (in dehumidified chamber). Preferably 0.5-10mm granular desiccant is added to the primer and used. The concentration of the organometallic compound in the primer is preferably 0.001-1wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Purpose of the invention ``Field of industrial application'' The primer of the present invention can be used to cure materials such as non-polar or highly crystallized resins that were conventionally difficult to adhere to, paint, or print. - good adhesion using cyanoacrylate;
It is also used to paint or print on such materials, and is widely used in the automobile industry, electrical equipment industry, etc., which widely use non-polar or highly crystallized resins such as polyolefins as raw materials. It is used in the field.

``Prior art'' Non-polar or highly crystallized resins, including polyolefins such as polyethylene fluoroethylene, polyethylene terephthalate, polyacetal, and nylon, as well as soft PvC films containing large amounts of plasticizers, etc. These are all materials that are 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 normal methods. .

Several proposals have already been made to improve the adhesive properties of these materials, such as flame treatment, corona discharge treatment, plasma jet treatment, dichromate treatment, etc. in the case of polyolefin resins. A method of generating polar groups such as carbonyl groups on the surface of the resin, 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
, 57-Also, improved resins containing solid rubber, unsaturated carboxylic acids or derivatives thereof, and radical generators, and containing propylene/styrene/butadiene block copolymers and inorganic fillers as essential components have also been proposed. .

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 alcoholade or aluminum chelate salt as an active ingredient. (
% Application No. 58-87761, No. 59-59367).

"Problems to be Solved by the Invention" The primer proposed by the present inventors has extremely excellent functions to achieve the intended purpose, but in actual use, the following problems arise. It turned out that there were some problems.

In other words, there are problems such as differences in performance as a primer even though the same materials are used, or that the performance of primers that had sufficient performance at the time of preparation deteriorates during storage or use. I found out.

The present inventors completed the present invention after conducting studies to solve the problems of the above-mentioned primers proposed by the present inventors.

(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.

In other words, the aA of the present invention is used when applying α-nanoacg V-) to non-polar or highly crystallized resins, contains an organic metal compound as an active ingredient, and has a water content of 500pp.
This invention relates to a primer characterized in that it is less than or equal to m.

In the present invention, applying α-cyanoacrylate to a non-polar or highly crystallized resin means bonding the resin of Nana et al. using α-cyanoacrylate, or applying α-cyanoacrylate (mainly a hardened film). This refers to use as an undercoat for paint or printing ink in painting or printing of these resins.

0 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. Showa 58
-87761 and 59-59567 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, acetyloquine, cyclohexyl, etc. In view of danger, hydrocarbon groups of 03 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 carboxylic acid salts having a structure of 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 a structure of M-R(7). A more preferred compound is a complex salt of a metal alcoholade o'o-c dicarbonyl represented by the structure M-O-H. In addition, for specific compounds,
Lithium acetylacetone, sodium acetylacetone, magnesium acetylacetone, titanyl acetylacetone, iron acetylacetone (1), palladium acetylacetone, indium acetylaceton, tri-n-octadecyl borate, sodium linoleate, magnesium stearate, aluminum stearate, aluminum acetate, aluminum fluoride A , [Jl[aluminum thiodiglycolate, calcium stearate, ferric stearate, ferrocene dimethyldithiocarbamate steel, zinc stearate, 2-ethylhexylzinc, zinc tartrate, stannous acetate, di-n-butyltin dimaleate , di-n-butyltin oxide, triphenyltin acetate, barium stearate, lead stearate, diptyl phosphate, 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-5ec-butoxydiisopropylate, aluminum trisacetylacetonate, aluminum mono-acetylacetonate bisethyl acetoacetate, aluminum ethyl acetate. Acetate diisopropylate, aluminum trisethylacetoacetate, aluminum oleyl acetoacetate diisopropylate, acetylacetone manganese (11), acetylacetone cobalt (1), acetylacetone nickel, acetylacetone zinc, acetylacetone zirconium, tetofugtyltitanate, tetraisopropyltitanate, dibutyltin di Particularly preferred compounds are acetate, tri-n-butyltin oxide, tin 2-ethylhexanoate, AY45-021 (trade name of a silicon compound manufactured by Resilicon ■), and trisisodecyl phosphite.

In order to prevent variations in the quality and properties of primers containing O-water organometallic compounds and deterioration of quality during use or storage, it is necessary to keep the water content in the primers at a certain level, that is, 500 ppm or less. However, the above-mentioned problems could only be solved by maintaining the water content below so op pm.

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, or the combination of organic species.

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.

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 preferable to take measures to prevent the moisture content from exceeding 500 ppm even after a long period of time.

Prevent moisture absorption of primer during storage. For example, the container may be made of a non-moisture-permeable material such as a glass container, a metal container, or a plastic container with a layer of polyvinylidene chloride, but moisture absorption is unavoidable during use. Since it is undesirable to limit the container material to a specific material, a desiccant or adsorbent should be added to the primer to reduce the moisture content in the primer by 5% due to moisture absorption.
00 ppmf: It is preferable not to exceed it.

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 making them coexist, 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 desiccant agents, such as phosphorus pentoxide,
Activated alumina, anhydrous sulfuric acid, magnesium oxide, calcium oxide, calcium chloride, magnesium sulfate, diatomaceous earth, anhydrous zinc chloride, anhydrous sulfuric acid steel (I), silica gel, silica alumina, etc. Also, as an adsorbent, Molecuiera sheep is used. , activated carbon, etc., but it is preferable that those used in combination with the primer satisfy the following conditions.

(1) Solid (1) Neutral or nearly neutral (110) Something that does not chemically react with the primer (between 110 and 110)
(V) Those that do not inhibit the primer function. Therefore, desiccants or adsorbents that are preferably used in combination with the primer include activated alumina, magnesium oxide,
Examples include magnesium sulfate, diatomaceous earth, and alkaline alumina, and more preferred are silica gel and molecular sheep.

The desiccant or adsorbent used in combination with the primer preferably has a granular shape, and the particle size is Q, 5 to 10 mm.
A range of degrees is particularly preferred. 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 used in combination with a desiccant or adsorbent, the amount used is Oα-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. It is something.

N CH,=C OOR In the above formula, R includes alkyl, alkenyl, cyclohexV/I/, aryl, and alkoxyalkyl groups, and specifically, methyl, ethyl, n-propyl, n-butyl, isobutyl. , n-pentyl, allyl, cyclohexyl, benzyl, methoxypropyl 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 can be used directly from such commercially available adhesives. - It can also be used as a primer when used as a cyanoacrylate.

Furthermore, the primer of the present invention is compatible with α-cyanoacrylate and contains toluene, which does not impair its stability.
It is also effective as a primer for α-cyanoacrylate diluted with an organic solvent such as butyl acetate or methyl chloroform.

Non-polar or highly crystallized resins Non-polar or highly crystallized resins used with the primer of the present invention include olefin polymers represented by polyethylene, polypropylene, polypuden, and polymethylpentene, and talc, alumina, Composites containing mica and glass fiber, polyethylene terephthalate, polyacetal, polyurethane, silicone rubber, soft PVC, etc., but the primer of the present invention works most effectively when used with olefin polymers. .

O 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 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 off-line polymers such as chlorinated polypropylene, chlorinated ethylene/propylene copolymer, chlorinated ethylene/vinyl acetate copolymer: polyvinyl chloride, polyvinyl acetate, poly(meth)acrylic acid ester, polyvinyl ether , vinyl polymers such as vinyl chloride/vinylidene chloride copolymer; synthetic rubbers such as polychloroprene, NBRlSBR, 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 an organic polymer is used in combination, the amount to be added in the primer solution varies depending on the type of organic polymer, but is in the range of o, i to 20! Its
It is preferable that If this concentration is less than 0.1%, it will have little effect on improving coatability (20"iL'ji
If it exceeds k%, it will interfere with the function of the organometallic compound which plays the main role as a primer, reducing its effectiveness as a primer. In addition, the addition of the organic polymer is such that the viscosity of the primer solution is 2 to 5000c.
It is preferable to determine the type and amount so that the temperature falls within the range of p/25°C.

Q How to use the primer of the present invention, as stated in the above specification, 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 to be 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

In addition, in order to apply the primer more efficiently, it is preferable that the solvent sufficiently wets the surface of the resin such as polyolefin. It is more desirable to select and use a solvent with a lower tensile strength.Specific examples of solvents include 1.1.2-)lichloro-1,1,2-)lifluoroethane, ethanol, acetone, ethyl acetate, 1. 1.
1-) Lichloroethane, tetrahydrofuran, 1.4-
These include 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 such that its effectiveness is best achieved 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. nt, 0.
It is preferably α00.1 to 10% by weight, more preferably α001 to 1% by weight. Its concentration is 0.
If it 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 a monomolecular film;
If the amount exceeds 0% by weight, the layer tends to become too thick, and the thick layer becomes brittle, 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 mentioned above, but the method of applying the primer solution to a nonpolar or highly crystallized resin is as follows: General methods such as dipping in a solution, brushing, spraying, etc. can be used as a coating method.Resins coated with a primer using such methods can be air-dried to remove the solvent. A single layer of primer can be formed on the surface.

The layer is pre-acid-treated with a diluted solution with an organic solvent such as toluene and ethyl acetate, which does not impair the stability of α-cyanoacrylate or the same monomer. It can be applied with a brush or dipped, taken out and left at room temperature to form a thin layer of α-cyanoacrylate polymer, and then painted using a general paint by a roller method or a spray method. can. 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 express the effects of each foam of the present invention, the type of organometallic compound to be used, its concentration, amount of application, etc. must be determined by considering the type of non-polar or highly crystallized resin. Must be. Regarding the amount of coating, it is natural that if it is too small and the organometallic compound layer cannot completely cover the resin surface, good results will not be obtained, and if it is too large, the organometallic compound layer will become thin film-like. If the thickness of the organometallic compound exceeds 0.001 to 1 g, the layer itself becomes fragile and the effect of the present invention will not be achieved. A preferred method for using the present invention is to apply the coating so that the ratio is more preferably 0.01 to a1y/- than /rrl.

"Function" The primer of the present invention was first disclosed in the patent application filed in 1983 by the present inventors.
The primers proposed in No. 87761 and No. 59-59367 have disadvantages, such as variations in properties as a primer,
The problem of deterioration of properties during storage and use can be solved at once by suppressing the amount of water in the primer to 500 ppm or less. This is due to the fact that water in the primer is prevented from scattering on the surface of non-polar or highly crystallized resins and interfering with the formation of a single layer of primer. Estimated.

By suppressing the water content to 500 ppm or less, the present invention has the effect of maximizing the effectiveness of the organometallic compound as a primer, and further integrates into an excellent primer.

"Example" The present invention will be specifically described below with reference to Examples and Comparative Examples.

Example 1. Comparative example 1 As a primer, mix the following three types.

A: Toluene solution of 1%-mono-5ec-butoxyaluminum diisopropylate B: Acetic acid-fP solution of 1%-ditylacetoacetate aluminum diisopropylate C: Methyl chloroform solution of 1m-aluminum tris(ethyl acetoacetate) A 100 cc polyethylene bottle was used as a container, and 5 wt% of each film was added to the fimer.

The storage conditions were 25° C. and 90 to 100 LsRH, and moisture analysis and primer performance tests were conducted at predetermined intervals.

The test method is as follows.

(1) Moisture analysis Karl Fischer analysis method analyzer AQUACOUNTERAQ-I HIRA
Made by NUMA (2) Primer performance test test piece compliant with JIS K6861-1977 (
Polypropylene plate e@e25x10Qx2m'm
Wipe both sides of t) with a primer-impregnated cloth for about 5 minutes, then add Aron Alfuka Q and IKtf/d to one side and adhere 2.
It was cured for 4 hours.

Measured at 20 mm/sec.

In addition, as Comparative Example 1, a similar test was conducted on a container without silica gel added.

The results of Kohori et al. are shown in Table 1.

Example 2. Comparative example 2 The following three types of composition liquids were prepared as primers.

D: Xylene solution of 0.5%-butyltin diacetate E: Butyl acetate solution of 0.5 es-tetraisopropyl titanate F: Trichlorethylene solution of α5-thiacetylacetone zirconium A 100% polyethylene bottle was used in the container, and this was used as a primer. 3 wt% of each was added.

Storage conditions are 250.90-100% kl (binding.

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 sheep. These results are shown in Table 2.

(/→ 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 speedily performed, without causing any variation in performance, and with ease of storage. Adhesion of non-polar or highly crystallized resins such as polyolefins or coating or printing on the surfaces of these resins can be performed successfully without deterioration of performance during use and during use. Therefore, the use of excellent physical properties such as 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 used when applying α-cyanoacrylate to a non-polar or highly crystallized resin, which contains an organic metal compound as an active ingredient and has a water content of 500 ppm or less.