JPH0613677B2 - Primer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Purpose of the invention "Industrial field of application" The present invention relates to a coating material made of various resins on the surface of an article (hereinafter referred to as "base material") made of metal, glass, ceramics, plastics or the like. , A primer (undercoating agent) used when applying an adhesive, etc.
It is possible to provide a primer that has excellent adhesion and durability to a substrate such as an adhesive. In particular, the primer of the present invention is capable of exerting an excellent effect on adhesion to a substrate such as a coating material and an adhesive made of a polyamide resin or a polyester resin, and has excellent properties of these resins, that is, corrosion resistance. It is widely used in various industries including the electric equipment industry, the electronic equipment industry, and the machine industry, which try to utilize the characteristics such as electric insulation and abrasion resistance.

“Prior Art” Resins such as polyamide resin and polyester resin are widely used in various industrial fields.
A paint or adhesive containing them as a component is highly adhered to a base material, and when durability is strongly required, a primer is used in combination, and as a primer, the adhesion between the base material and the resin is improved, and What is needed to maintain it under harsh conditions is required. There is also a demand for a primer whose performance does not fluctuate due to changes in conditions such as temperature and time and differences in film thickness, drying method, bonding method and the like.

Conventionally, for example, a mixture of an epoxy resin and a phenol resin has been used as these primers, but there are problems that the construction requires a long time at a high temperature and sufficient durability cannot be obtained. In addition, Japanese Patent Publication No. 61-14186 proposes a precondensate of an epoxy resin and a phenol resin, but it also has drawbacks such as a difference in performance due to changes in construction conditions and a lack of sufficient adhesion. Have

As described above, the primer that has been conventionally provided has sufficient adhesion and durability between the base material and the resin when the resin such as polyamide resin and polyester resin is used under severe conditions in various industrial fields. Not only does it not improve, but also has the drawback of requiring a step such as heating for condensation after coating during primer production, and further requires harsh heating after primer coating, heating after coating, It has a defect that the effect as a primer varies due to the variation of resin fusion conditions.

"Problems to be Solved by the Invention" The present invention solves the problems of the conventional primer used when applying the above-mentioned resin to a substrate, and at the time of manufacturing the primer and treating the primer. It was designed to find a primer that can be produced at low cost without requiring a special process, does not require harsh conditions, is stable because the primer effect does not change due to changes in temperature conditions, and especially at low temperatures and short times. The purpose is to find a primer that can improve the adhesion of resin regardless of the type of the substrate in the treatment.

(B) Structure of the Invention "Means for Solving Problems" The inventors of the present invention have diligently studied in order to obtain an excellent primer that solves the above problems, and that a primer composed of a specific component satisfies them. The present invention has been completed by finding out the above.

That is, the present invention relates to a primer characterized by using a bisphenol A type epoxy resin, a methylolphenol ether and an organosilicon compound having an aminoalkyl group and an alkoxy group as active ingredients.

◎ Resin The resin to which the primer according to the present invention is applied includes various resins, and the one in which the effect of the primer of the present invention is better expressed is nylon 6, 6-6,
Nylon resins such as 6-12, 11 and 12 and copolymers thereof, so-called polyamide resins such as compounds obtained by condensing dimer acid and ethylenediamine, and polybasic acids such as adipic acid, terephthalic acid, isophthalic acid and sebacic acid. And a polyhydric alcohol such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. according to the desired physical properties, which is a polyester resin obtained by combination condensation polymerization. Examples thereof include vinyl acetate copolymers and saponified resins thereof, polyvinyl butyral, polyurethane resins and epoxy resins. Further, depending on the purpose, the primer of the present invention can be applied to a mixture of these and a material to which an additive such as a pigment or an antistatic agent is added in an appropriate amount.

◎ Epoxy resin The bisphenol A-type epoxy resin used in the present invention is made from bisphenol A and epichlorohydrin, and the bisphenol A-type epoxy resin that better expresses the effects aimed at by the present invention has an average molecular weight of It is preferably about 800 to 5000. Examples of them include, for example, Epicoat 1001, 1002, 1004, 1007, 1 manufactured by Yuka Shell Epoxy Co., Ltd., which is a commercially available product.
009 etc. can be given.

◎ Methylol phenol ether The methylol phenol ether in the present invention has the following structural formula The phenol and formalin are reacted with phenol in an equimolar alkali catalyst at low temperature to form a salt of mono-, di- or trimethylolphenol, and an alkyl, alkenyl or aralkyl halide is added to this to carry out a desalting reaction ether. Specific examples thereof include methylolphenol allyl ether, methylolphenol methyl ether, methylolphenol benzyl ether, methylolphenol glycidyl ether, and the like. The method described in JP-B-34-2642 is preferable, and the etherification of the phenolic hydroxyl group is effective for the activity at the ortho or para position of the benzene nucleus. To keep Used to go after the methylol the phenol is desirable.

Also, a suitable amount of an acid catalyst which has been subjected to a partial condensation reaction can be applied to the present invention.

For the present invention, it is more preferable that R shown in the structural formula is itself reactive, such as an allyl group.

◎ Organosilicon compound As the organosilicon compound having an aminoalkyl group and an alkoxy group, an organosilicon compound having an aminoalkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 4 carbon atoms is preferable, and specifically, aminomethyltri Ethoxysilane,
Aminoalkyltrialkoxysilane having one aminoalkyl group and three alkoxy groups such as γ-aminopropyltriethoxysilane and γ-aminopropyltriethoxysilane; N- (β-aminoethyl) aminomethyltrimethoxysilane , N- (aminoalkyl) aminoalkyltrialkoxysilanes having an N- (aminoalkyl) aminoalkyl group and three alkoxy groups, such as N- (β-aminoethyl) aminomethyltriethoxysilane; aminomethylmethyldiethoxy Aminoalkyldialkoxysilane having an aminoalkyl group and two alkoxy groups such as silane and γ-aminopropylmethyldiethoxysilane; N- (β having an N- (aminoalkyl) aminoalkyl group and two alkoxy groups -Aminoethyl) -γ-amino B and the like pills methyl diethoxy silane, an alkoxy group having 2 or more is even more preferred taken present invention.

◎ Adjustment method The primer of the present invention contains a bisphenol A type epoxy resin, a methylolphenol ether and an organosilicon compound having an aminoalkyl group and an alkoxy group as active ingredients, and its form is a powder consisting of those ingredients. It is also possible to use it in liquid form,
It is desirable to dissolve or disperse in an organic solvent and use as a solution or a dispersion.

The organic solvent used in forming the solution or dispersion may be any one capable of completely dissolving or dispersing the above compound, for example, benzene, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone,
Methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, diacetone alcohol, cellosolve acetate, or the like, or a mixed solvent thereof.

The primer solution is obtained by dissolving or dispersing the components constituting the primer of the present invention in the solvent, and after mixing the components in the solvent at room temperature or under heating, preferably 4
It is prepared by stirring and dissolving at 0 to 100 ° C. for 5 to 120 minutes.

Further, the solid content concentration in the solution is preferably adjusted within the range of about 3 to 40%, and more preferably adjusted to about 5 to 30%, and is appropriately selected depending on the coating method and conditions. By doing so, a good film can be formed.

Outside this range, the amount of necessary components attached to the base material is small and sufficient effects cannot be obtained, or the amount of attachment is large,
The coating may become thick and form a brittle layer.

The blending ratio of each component in the primer of the present invention is preferably in the range of 98/1/1 to 40/30/30 by weight ratio of epoxy resin, methylolphenol ether and organic silicon compound, and further 96/2/2 to 60. / 20/2
A range of 0 is preferred. When the amount is out of the above range, it is not preferable because good adhesion between the resin and the substrate, which is the object of the present invention, cannot be obtained, or the liquid stability is impaired.

◎ Method of use The primer of the present invention is preferably used as a primer solution which is dissolved or dispersed in a solvent having good stability and solubility as described above, but to various base materials of the primer solution. As a coating method of the above, it is possible to use a general method as a coating method such as dipping in a solution, brush coating, coating with various coaters, spray coating, etc. iron,
Steel and its metals plated with zinc, nickel, tin, copper, cadmium and their chromate or phosphoric acid treatment, or glass, ceramics, etc., preferably with a cleaned surface Is desirable.

After applying the primer of the present invention to the substrate by the above method, various resins are coated in any shape, for example, in the shape of film, sheet, block, powder, coating, laminating, spraying, electrostatic coating, fluidized dipping, etc. Given by,
The resin can be adhered or adhered by the temperature and pressure required to form a uniform layer.

At this time, the primer of the present invention applied to the base material may be dried at room temperature or under heating as long as it is in a completely dried state, preferably at about 50 to 150 ° C for 5 to 10 minutes. The conditions may be appropriately selected within a range that does not adversely affect the material.

In this way, various resins can be applied onto the primer-coated substrate, heated, and excellent adhesion between the substrate and the resin, which is the object of the present invention, can be produced by forming a resin film. Preferred conditions therefor are as follows: the primer thickness is 0.5 to 10 μm, the resin fusion condition is a temperature equal to or higher than the melting point of the resin, and the time for the resin to be completely melted is usually 30.
It is heating for 40 seconds or more.

The heating method is not particularly limited, but an ordinary method such as an oven, infrared ray, high frequency, or heat press is used.

"Action" Although the mechanism of action of the primer of the present invention is not clear, the adhesion of epoxy resin and methylolphenol ether to excellent substrates and the compatibility with resins such as nylon, and especially the aminoalkyl group among organosilicon compounds It is presumed that the compound having an alkoxy group selectively activates the surface of the resin such as nylon to generate the adhesive force between the base material and the resin.

Regarding durability, it is not a normal phenol resin,
The phenolic hydroxyl group with strong polarity is etherified and contains hydrophobic, so-called phenol ether,
Further, it is presumed that the organosilicon compound and the epoxy resin cause extremely excellent water resistance, heat resistance, chemical resistance, etc. because they gradually undergo a crosslinking reaction due to the moisture in the air.

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

Example 1 Bisphenol A type epoxy resin (oiled shell epoxy
Epicoat 1007: molecular weight 2900) 10 parts by weight, methylolphenol allyl ether 2 parts by weight,
0.1 parts by weight of aminomethyltriethoxysilane,
Acetone (30 parts by weight), toluene (20 parts by weight), methyl cellosolve (50 parts by weight) were added, and the solution (referred to as Primer 1) that was stirred and dissolved at room temperature was applied to the base material shown in Table 1 and then at room temperature. It was dried for 10 minutes.

Next, nylon 11 (manufactured by Nippon Rilsan Co., Ltd.,
Nylon 11: melting point approx. 190 ° C) and nylon 6 / 6-
6/12 copolymer (manufactured by Japan Rilsan Co., Ltd .: Pratamide H-105 melting point about 130 ° C.) powder was sprinkled at 50 g / m ² and sandwiched with the same base material, and 2 kg / while being stacked.
Under pressure of cm ² , under the conditions shown in Table 1, pressure bonding,
200mm / at 25 ± 3 ℃ after left at room temperature for 24 hours or more
The tensile strength was measured by applying a tensile tester at a speed of minutes.
Further, after adhesion, the mixture was allowed to stand at 50 ° C. and 95% humidity for 300 hours, and then the T-peel strength was determined by the same method. The results are shown in Table 1.

Example 2 In Example 1, the coating resin was a polyester resin (TOA Synthetic Chemical Industry Co., Ltd .: PES110, melting point about 110 ° C.).
Table 2 shows the results of the same procedure as in Example 1 except that the initial T-peeling strength was obtained by pressure bonding under the conditions shown in Table 2.

Comparative Example 1 In Examples 1 and 2, the results of obtaining the T-peel strength without using a primer are shown in Tables 1 and 2.

Example 3 A primer was prepared by changing the ratios of epoxy resin, methylolphenol allyl ether and aminomethyltriethoxysilane, and the same formulation as in Example 1 was used to apply it to a cold-rolled steel plate 0.3 mmt × 100 mm × 25 mm. Table 3 shows the T-peel strength obtained by melting the resin under the predetermined conditions shown in Table 3 and then obtaining it in the same manner as in the examples.

Example 4 Epoxy resin (Epicoat 1009: molecular weight 3750:
(Oilized Shell Epoxy Co., Ltd.), methylolphenol methyl ether, and γ-aminopropyltriethoxysilane were used, and nylon 11 was used as the resin. The results of measuring the T-peel strength were the same as in Example 1. It is shown in Table 4.

(C) Effect of the invention As is clear from the above examples, according to the primer of the present invention, it is possible to remarkably improve the adhesive force between the base material and the resin, as compared with the base material not using the primer. It is extremely effective for improving durability and can be manufactured and applied at low cost by a simple method, and various resins can be applied to various industrial materials under harsh conditions. In particular, it has the excellent effect of being able to open up new fields of application with polyamide / polyester resins.

Claims (1)

[Claims] 1. A primer comprising a bisphenol A type epoxy resin, a methylolphenol ether and an organosilicon compound having an aminoalkyl group and an alkoxy group as active ingredients.