JPH011784A - Primer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 bond α-cyanoacrylate, which is a material such as highly crystallized resin or non-polar resin, which has been difficult to adhere to in the past. It is mainly used in the automobile industry, electrical equipment industry, and other industries where highly crystallized resins such as engineering plastics such as polyacetal or nonpolar resins such as polyolefins are widely used as raw materials. It is used in fields such as the mechanical industry.

"Prior Art" Highly crystallized resins such as engineering plastics such as polyacetal, nylon or polyethylene terephthalate, or non-polar resins such as polyethylene,
Polypropylene, polybutene, and the like are materials that are difficult to adhere, paint, and plate, and the current situation is that these resins cannot be well bonded, painted, or plated using conventional methods.

Several proposals have already been made to improve the adhesion of these resins. For example, in the case of highly crystallized resins, acid treatment with sulfuric acid, phosphoric acid, p-)luenesulfonic acid, etc. Methods such as adding inorganic fillers such as calcium carbonate and sputtering have been proposed.

(JP-A No. 56-152845, No. 57-96026, No. 60-10187<S) In the case of polyolefin, flame treatment, corona discharge, plasma jet treatment, treatment with a chlorinated polyolefin primer, and other treatments such as inorganic filler or solid A method of compounding rubber is mentioned.

The present inventors have made extensive research efforts with the aim of developing a technology superior to these methods, and as a result, we have discovered that organometallic compounds,
We discovered and proposed a primer containing a fluorine-based compound or a phosphite-based compound as an active ingredient. (Applications No. 60-253701, No. 61-4255, No. 6l - "Problems to be Solved by the Invention") The primer proposed by the present inventors has an extremely excellent function to achieve the intended purpose. The mechanism seems to be related to the force and pulling action of organometallic compounds or phosphite compounds at the interface between the resin and the adhesive. The present inventors continued their earnest research efforts in order to search for a new compound that has functionality equivalent to or higher than that of the compound.

(b) Structure of the invention "Means for solving the problem" The present inventors found that guanidine compounds among various compounds have the above-mentioned functions, and used primers containing these compounds as active ingredients. The present invention has found that highly crystallized resins or non-polar resins can be firmly bonded by doing so, and the present invention relates to a cyanoacrylate brimer characterized in that the derivatives thereof are used as active ingredients.

O-guanidine compounds In the present invention, the compounds used as the active ingredients of the primer include guanidine, biguamado, or their derivatives (
All of these are hereinafter collectively referred to as guanidine compounds), and guanidine or guar'Jyo derivatives are:
Guanizi.

Or biga ψdo. Ao, base. One part or all of hydrogen) is substituted with an alkyl group such as a methyl group, an aromatic ring such as a phenyl group or an alkylphenyl group, such as a tolyl group, or a heterocyclic ring such as a benzimidazolyl group.

Specific examples of derivatives of guanidine or guanidine include the following, and this may be because they have weak basicity compared to guanidine or guanidine, or because they have a weak basicity compared to guanidine or guanidine. It is a more preferable compound than di-, matayu, and guar-9y.

1,i,i-tetramethylguanidine, 1,3-diphenylguanidine, di-0-tolylguanidine, 1-0-
) Rilbiguaside, 2-guanidiophylum J benzimidazole.

0 Organic solvent The primer containing the guanidine compound of the present invention as an active ingredient is used as a pretreatment agent for highly crystallized or non-polar resin adhesion using α-cyanoacrylate. In order to form a homogeneous and thin film of the guanidine compound on the surface of the resin, it is preferable to use it as an organic solvent solution.

The organic solvent is preferably a general organic solvent that can completely dissolve or disperse the guanidine compound of the present invention, has appropriate volatility, and is easily available industrially.

Further, it is preferable that the organic solvent has a property that can sufficiently wet the surface of the resin, and for this purpose, it is more preferable to select and use an organic solvent whose surface tension is smaller than the critical surface tension γC of the resin. For example, regarding γC, polyacetal has a value of 40, nylon 66 has a value of 46, PET has a value of 46, and polyethylene has a value of 31, whereas organic solvents have a surface tension lower than the γC of 1, 1.2.
-Trichloro-1,λ2-trifluoroethane (19)
, ethanol (22), acetone (23), n-hexane (18), ethyl acetate (24) or toluene (28).
) etc. (all values in parentheses are surface tension).

The effect is best exhibited when the guanidine compound is formed into a thin film, preferably a monomolecular film, so α01
It is preferably 1Q w t %, more preferably 0.05 to 5 w t %. Its concentration is 0.
If it is less than 0.1 wt %, it will be difficult to form the guanidine-based compound into a thin film, and if it exceeds 10 wt %, it will become a brittle thick layer and its function as a primer will deteriorate, which is not preferable.

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. Therefore, it is preferable to use the primer of the present invention by dispersing or dissolving it in an organic solvent. This is a 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 polypropylene, chlorinated ethylene/propylene copolymer, chlorinated ethylene/acetate copolymer, etc.: polyvinyl chloride, polyvinyl acetate, poly(meth)acrylic acid Vinyl polymers such as esters, polyvinyl ethers, vinyl chloride/vinylidene chloride copolymers, and 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 an organic polymer is used in combination, the amount added is preferably 0.1 to 20% by weight in the primer solution, although it depends on the type of organic polymer. If the concentration is less than 0.1% by weight, it will have little effect on improving coatability, and if it exceeds 20% by weight, it will interfere with the function of the primer, reducing its effectiveness as a primer. In addition, the addition of the organic polymer is such that the viscosity when used as a primer solution is 2 to 5.0.
It is preferable to determine the type and amount so that the temperature is within the range of 0.00 cp/25°C.

0α-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 includes alkyl, alkenyl, cyclohexyl, aryl, and alkoxyalkyl groups, specifically methyl, ethyl, n-propyl, n
-butyl, isobutyl, n-pentyl, allyl, cyclohexyl, benzyl, methoxypropyl groups, and the like.

These α-cyanoacrylates are the main components of commercially available cyanoacrylate-based instant adhesives, and the primer of the present invention has sufficient functionality as a primer for these commercially available adhesives. be.

O Crystalline or non-polar resins Highly crystalline or non-polar resins with which the primer of the present invention may be used include polyacetals, polyamides, polyethylene terephthalate, polybutylene terephthalate, polyetheretherketone, polyethylene, polypropylene, polybutene, polymethylpentene. , silicone rubber, polyphenylene ether, etc. How to Use The primer of the present invention contains a guanidine compound as an active ingredient, and optionally an organic solvent and an organic polymer are added thereto. It can be prepared by mixing and uniformly dissolving or dispersing.

The method for applying this primer to the resin surface does not require any special operation, and can be carried out by brushing, spraying, dipping in the primer, or the like.

A primer layer is formed on the surface of the resin by air-drying the resin coated with the primer at room temperature. The resin having the primer layer can be firmly bonded to itself or to other materials using the above-mentioned α-cyanoacrylate.

In order to better exhibit the effects of this primer, the type and concentration of the guanidine compound to be treated must be determined by considering the type of resin to be treated.

Regarding the amount of application, as mentioned above, primer + m
The coating thickness of the guanidine compound has a large effect on the effect, so the coating amount of the guanidine compound should be 0.001 to 1? It is preferable to apply the coating in such a manner that the amount is 0.01 to α1?
/ ze.

"Effect" It is presumed that the primer of the present invention exerts its effect through the following mechanism.

In other words, the guanidine-based compound, which is the active ingredient of the primer of the present invention, has a coupling function that has both polar atoms and non-polar groups in its molecular structure. The nonpolar group of the compound diffuses and bonds with the resin, and the polar atoms of the guanidine compound are oriented upward on the surface of the resin, activating the resin surface. When α-cyanoacrylate having a polar group is applied to the resin surface activated in this way, strong bonding is formed by secondary bonds and hydrogen bonds, which resist intermolecular attraction.

Therefore, this strong bonding is thought to be most effective when the primer layer is formed in the form of a monomolecular film or a thin film close to it, and this has been experimentally confirmed.

"Examples" The present invention will be explained in more detail by referring to Examples and Comparative Examples below.

Example 1, Comparative Example 1 The following 48i class primer solution was prepared.

(11t t 3.3-tetra (manufactured by Tokyo Kasei Kogyo ■)
Methylguanidine in 0.3 thiacetone solution (211,3-diphenyl (Omukai Shinko Kagaku Kogyo Guanidine's 0.3 thiacetone) Toluene solution (3: 0-tolylg (Inunai Shinko Kagaku Kogyo Anidine's α6% medicinal product) (manufactured by Daien Shinko Kagaku Kogyo Guanide Co., Ltd.) Chil chloroform solution (411-0-MJ Ruby (manufactured by Daien Shinko Kagaku Kogyo Guanide Co., Ltd.) The performance test of the tanol solution primer was conducted in accordance with JIS K6861.

Test piece, Polyacetal ψ Epital F200225x100x2m Made by Mitsubishi Gas Chemical, Duracon M9002
Made by Polyplastics, Tenac 7050
Manufactured by Asahi Kasei, Delrin 500
Adhesive Aron Alpha+201 manufactured by DuPont ■ (Cyanoacrylate adhesive, manufactured by Toagosei Chemical Industry ■) Brush the primer described above on both sides of the test piece, let it air dry for about 5 minutes, and then apply the adhesive to one side. Both surfaces were overlapped, a pressing load of 01 kp f /cl/l was applied, and the product was left at room temperature for 24 hours. Tensile shear adhesive strength was measured using a Strograph W type tester at a tensile rate of 20 ml.
Measured in m.

As Comparative Example 1, a test was conducted in the same manner as in Example 1 except that no primer treatment was performed.

These results are shown in Table 1.

Table 1 Note: Breaking = base material destruction Example 2, comparative example 2 The following four types of primer solutions were prepared.

(5) Diphenylguanidine (Omukai Shinko Kagaku α)
The performance test of the 5% n-hexane solution (manufactured by Kogyo) solution primer was carried out in accordance with Example 1, except that the following test piece was used.

Test piece: Polypropylene Ichimitsui Noblen + I Do 25x100x2 tx
Made by Mitsui Toatsu Chemical ■ J 340W'
Made by Mitsui Petrochemical ■ BJ309V
, Tonen Petrochemical, X-IA
# Mitsubishi Yuka ■Table 2 Example 3, Comparative Example 3 The following six types of primer solutions were prepared.

(9) Diphenylguanidine (Omukai Shinko Chemical Q
, ethyl 2-thiacetate solution (manufactured by Kogyo ■) ton solution The performance test of the refluoroethane solution primer was carried out in accordance with Example 1, except that the following (7) was used as the test piece.

Test piece: ・EPT EP27 25X100X211+8 synthetic rubber ■PET $100 25X100X
Q, 1fl Mitsubishi Plastics Table 6 (c) Effects of the invention By using the primer of the present invention, adhesion of highly crystallized resins or non-polar resins with α-cyanoacrylate can be carried out easily and neatly. It can be used as an alternative to metal materials for engineering plastics or polyolefins, and has many advantages such as weight reduction, rust resistance, and cost reduction, and its contribution to various fields such as the automobile industry and electrical equipment industry is extremely large. It is something.

Claims (1)

[Claims] 1. A cyanoacrylate primer containing guanidine, biguanide, or a derivative thereof as an active ingredient.