JPS6363758A - Primer - Google Patents

Abstract

PURPOSE:To obtain a primer which can enhance the adhesion of resins by a short-time treatment at a low temp., irrespective of the types of substrates, by blending a bisphenol A type epoxy resin with methylolphenol ether and a specified organosilicon compd. CONSTITUTION:This primer comprises a bisphenol A type epoxy resin (a), a methylolphenol ether (b) and an organosilicon compd. (c) having aminoalkyl and alkoxy groups as active ingredients. The three components are used in a weight ratio of a:b:c of pref. 98:1:1-40:30:30. The primer has excellent adhesion to substrates (e.g., metals, glass, ceramics, etc.) coated with adhesives, paints composed of polyamide resins or polyester resins in particular.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Purpose of the invention "Field of industrial application" The present invention is directed to the application of paints made of various resins to the surface of articles (hereinafter referred to as base materials) made of metals, glass, ceramics, plastics, etc. , primer (undercoat) K used when applying adhesives, paints made of various resins, etc.
It is possible to provide a primer that has excellent adhesion and durability to base materials such as adhesives. - In particular, the primer of the present invention is made of polyamide resin or polyester rA
It can exhibit excellent adhesion to base materials such as paints and adhesives made of oil, and the excellent properties of these resins include corrosion resistance, electrical insulation, and abrasion resistance. It is widely used in various industries, including the electrical equipment industry, electronic equipment industry, and machine industry that want to utilize it.

"Prior Art" Resins such as polyamide resin and polyester resin are widely used in various industrial fields.
When paints, adhesives, etc. containing these components are highly adhering to the base material, and durability is strongly required, a primer is used in conjunction with the primer. There is a need for something that can maintain this quality under harsh conditions. There is also a need for a primer whose performance does not vary due to variations in conditions such as drying time and time, and differences in film thickness, drying method, adhesion method, etc.

Conventionally, for example, a mixture of an epoxy resin and a phenol resin has been used as these primers, and there have been problems such as insufficient durability. Furthermore, in Japanese Patent Publication No. 61-14186, a precondensate of epoxy resin and phenol resin has been proposed, but this also has problems such as differences in performance due to variations in the material and insufficient adhesion. It has drawbacks.

As mentioned above, the primers that have been provided in the past provide sufficient adhesion and durability between the base material and the resin when resins such as polyamide resins and polyester resins are used under harsh conditions in various industrial fields. Not only does it not improve the performance of the primer, but it also has the drawback of requiring steps such as heating during primer production to cause condensation after application.Furthermore, it requires severe heating after application of the primer, and This method has drawbacks such as variation in effectiveness as a primer due to variations in resin fusion conditions.

``Problems to be Solved by the Invention'' The present invention solves the problems of conventional primers used when applying the above resin to a base material, and solves the problems during primer production and treatment. For example, a primer that can be produced at low cost without requiring any special process was sought. This was done in search of a primer that can improve the adhesion of resins regardless of the aft of the base material with a short treatment time.

(B) Structure of the Invention "Means for Solving the Problems" The present inventors have made extensive studies to obtain an excellent primer that solves the above problems, and have found that a primer made of specific components satisfies them. They discovered this and completed the present invention.

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

◎Resin There are various resins to which the primer according to the present invention can be applied, including nylon 6.6-6.6.
-12.11 and 12 and other primers of the present invention exhibit better effects on nylon resins and copolymers thereof, so-called polyamide resins such as compounds condensed with dimer acid and ethylenediamine, and adipic acid,
Polybasic acids such as terephthalic acid, isophthalic acid, and sepatic acid, ethylene glycol, 1゜4-butanediol, 1
．． It is a polyester resin obtained by condensation polymerization of polyvalent accols such as 6-hexanediol and neopentyl glycol according to the desired physical properties.In addition, ethylene-vinyl acetate copolymer, saponified resins of these, and polyvinyl Examples include butyral, polyurethane resin, and epoxy resin. Further, depending on the purpose, the primer of the present invention can be applied to a mixture of these or to a product to which an appropriate amount of additives such as a pigment or an antistatic agent is added.

O epoxy resin The bisphenol A type epoxy resin used in the present invention is made from bisphenol A and epichlorohydrin. It is preferably about 8,800 to 5,000. Examples of these include Epicoat 1001, 1002, 1004, and 1007 manufactured by Yuka Shell Epoxy ■, which are commercially available products.
1009 etc. can be given.

◎ Methylol phenol ether The methylol phenol ether in the present invention is made by reacting phenol represented by the following structural formula with formalin rough phenol and an equimolar amount of an alkaline catalyst at low temperature to create a salt of mono-, di-, or trimethylol phenol. Compounds that are etherified by adding alkyl, alkenyl or aralkyl halides, etc. to undergo a desalting reaction, and specifically include methylolphenol ether, methylolphenol methyl ether, methylolphenol benzyl ether, methylolphenol glycidyl ether, etc. The phenolic resin is described in pages 56 to 58 of "Phenol Resin (Nikkan Kogyo Shimbun Series)", and it is preferable to use the method disclosed in Japanese Patent Publication No. 34-2642. The etherification of the hydroxyl group is preferably carried out after methylolization of the phenol in order to maintain the activity of the ortho or para position of the benzene nucleus.

Further, a product in which a portion of the condensation reaction is carried out using an appropriate amount of an acid catalyst can also be applied to the present invention.

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

◎ Organosilicon compound The organosilicon compound having an aminoalkyl group and an alkoxy group is preferably an organosilicon compound having an aminoalkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. ethoxysilane,
Aminoalkyltrialkoxysilanes having one aminoalkyl group and three alkoxy groups such as r-amino/7' lobiltriethoxysilane, r7minoprobyltriethoxysilane; N-(β-aminoethyl)amine N-(aminoalkyl)aminoalkyltrialkoxysilane having an N-(aminoalkyl)aminoalkyl group and 6 alkoxy groups such as methyltrimethoxysilane, N-(β-7minoethyl)aminemethyltriethoxyrane; amino Aminoalkyldialkoxysilane having an aminoalkyl group and two alkoxy groups such as methylmethyljethoxysilane and γ-aminopropylmethyljethoxysilane; having an N-(aminoalkyl)aminoalkyl group and two alkoxy groups N-(β-aminoethyl)
-r-aminopropylmethyljethoxysilane, etc., and those having two or more alkoxy groups are more preferred for the present invention.

◎ Preparation method The primer of the present invention contains a bisphenol A type epoxy resin, methylolphenol ether, and an organosilicon compound having an aminoalkyl group and an alkoxy group as active ingredients, and is in the form of a powder made of these ingredients. Alternatively, it can be used in liquid form, etc.
It is desirable to dissolve or disperse it in an organic solvent and use it in the form of a solution or dispersion.

The organic solvent used to form a solution or dispersion may be one that can completely dissolve or disperse the above-mentioned compounds, such as benzene, toluene, bovine silane, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone. , methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, diacetone alcohol, cellosolve acetate, etc., or a mixture thereof.

The primer solution is obtained by dissolving or dispersing the components constituting the primer of the present invention in the above-mentioned solvent, and after blending each component in the solvent, it is preferably dissolved at room temperature or under heating.
Stir and dissolve for 5 to 120 minutes at 0 to 100°C.

In addition, the solid content concentration in the solution is preferably adjusted to a range of about 6 to 40 inches, and more optimally adjusted to about 5 to 30 inches, and can be selected as appropriate 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 may be too small to produce a sufficient effect, or the amount of attached components may be too large.
There is a risk that the coating will become thick and form a single fragile layer.

98/1/1 to 40 by weight ratio of metal and organosilicon compound
/l O/30 range is preferred, more preferably 96/2/l
A range of 2 to 60/20/20 is preferred. If it is outside the above range, it is not preferable because good adhesion between the resin and the base material, which is the object of the present invention, may not be obtained or liquid stability may be impaired.

◎ How to use The primer of the present invention is preferably used as a primer solution dissolved or dispersed in a solvent with good stability and solubility as in I above, but various base materials for the primer solution can be used. As for the application method, general methods such as coating in a solution, brush application, application with various coaters, spray application, etc. can be used, and the base material to be applied is , each 1 metal 1-4 For example, iron, steel and their metals such as zinc, nickel, tin,
Copper cadmium plated, chromate or phosphoric acid treated, glass,
Preferably, it is made of ceramic or the like and has a cleaned surface.

After applying the primer of the present invention to a base material by the above method, coating, laminating,
It can be applied by methods such as spraying, electrostatic coating, and fluidized dipping, and can be bonded or brought into close contact by applying the temperature and pressure necessary for the resin to form a uniform layer.

At this time, the primer of the present invention applied to the base material can be dried at room temperature or under heat as long as it is completely dry, preferably at around 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 are applied onto the primer-coated base material and heated to form a broken resin film, thereby achieving the eroded adhesion between the base tube and the resin, which is the object of the present invention. Preferably, the primer thickness is 0.5 to 1
0μ, the resin fusion conditions are higher than the melting point of the resin @summer, and the time for complete melting is usually 30 to 40 seconds or more.

The heating method is not particularly limited, but conventional methods such as open heating, infrared rays, high frequency heating, and heat pressing can be used.

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

Also, regarding durability, it is not a normal phenolic resin,
It contains so-called phenol ether, in which the highly polar phenolic water group is etherified and made hydrophobic, and organosilicon compounds and epoxy resins are presumed to be present due to moisture in the air.

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

0 Example 1 Bisphenol A type epoxy resin (Epicoat 1007 manufactured by Yuka Shell Epoxy ■: molecular weight 2900) 10.
ti part, 2 parts by weight of methylolphenol allyl ether, aminomethyl) 60 parts by weight of acetone, 20 parts by weight of toluene, and 50 parts by weight of methyl cellosolve were added to 0.11 parts by weight of IJ ethoxysilane, and the mixture was stirred and dissolved at room temperature. The solution (referred to as Primer 1) was applied to the substrates shown in Table 1 and dried for 10 minutes at room temperature.

Next, nylon 11 (manufactured by Nippon Rilsan ■, nylon 11: melting point: 190°C) and nylon 6/6-6 were placed on the base material.
/12 copolymer (manufactured by Nippon Rilsan ■: Platamide H-
105a point (approx. 130°C) powder was spread at 505'/m',
Using the same base material, 2k
g/cyt under the conditions shown in Table 1, and after being left at room temperature for 24 hours or more,
The test piece was run on a tensile tester at a speed of 0xm/min to determine the T-break strength. Further, after adhesion, the T-peel strength was determined by the same method after being left for 300 hours at 50° C. and 95% humidity. The results are shown in Table 1.

0 Example 2 In Example 1, the coating resin was pressure-adhered to a polyester resin (manufactured by Toagosei Kagaku Kogyo ■: PE5110, melting point: 110°C) under the conditions shown in the second coating, and the initial T-Foil 9 strength was The results obtained using the same method as in Example 1, except that , are shown in the second column.

Comparative Example 1 In Example 1.2, the brimer was not used, and the results of determining the T-bond strength are shown in Table 2.

0 Example 3 The ratios of epoxy resin, methylolphenol allyl ether and amine methyltriethoxysilane were changed, and a brimer was prepared using the same formulation as in Example 1, and applied to a cold rolled steel plate of 0.3 m t x 100 H x 25 fl. The resin was fused under the predetermined conditions shown in the third coating, and the following was determined in the same manner as in the examples. Example 4 Epoxy resin (Epicor) 1009: Molecular weight 575
0: Yuka Shell Epoxy ■), methylolphenol methyl ether, γ-aminopropyltriethoxysilane, and nylon 11 as the resin, but using the same method as in Example 1 to measure T-bond strength. is shown in the fourth garment.

(c) Effects of the Invention As is clear from the above examples, the primer of the present invention makes it possible to significantly improve the adhesion between the base material and the resin compared to a base material that does not use primer. , an extremely effective and simple method for improving durability, enables low-cost manufacturing and coating, and enables the application of various resins to various industrial materials under harsh conditions. In particular, it has the excellent effect of opening up new fields of application for polyamide/polyester resins.

Claims (1)

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