JPS62119276A - Primer - Google Patents

Abstract

PURPOSE:To provide a primer containing an acrylic resin, an epoxy resin and an organic silicon compound or an organic aluminum compound, giving improved adhesivity between a fluorine-containing resin and a substrate and applicable by a simple coating method. CONSTITUTION:The objective primer can be produced by compounding (A) an acrylic resin [e.g. ethyl (meth)acrylate resin], (B) an epoxy resin (preferably bisphenol A epoxy resin) and (C) an organic silicon compound (e.g. aminomethyltriethoxysilane) or an organic aluminum compound (e.g. aluminum monoacetylacetonate). The weight ratios A/B and C/(A+B) are preferably 10/90-90/10 and 0.5/100-10/100, respectively.

Description

Detailed Description of the Invention (a) Purpose of the invention "Field of industrial application" The present invention relates to a primer (undercoat) used when applying paint, adhesive, etc. to the surface of an article (hereinafter referred to as a base material). In particular, vinyl fluoride resin (hereinafter referred to as PVF)
It is used when applying powder coatings made of fluorine-containing resins such as polyvinylidene fluoride resin (hereinafter referred to as PVDF) to base materials, and when laminating films made of these resins onto base materials. This primer relates to a primer that is effective for forming a fluorine-containing resin coating layer that can exhibit excellent adhesion to resin base materials, and is used in the electrical equipment industry and automobile industry that apply PVF and PVDF to their products. It is widely used in the precision equipment industry, chemical industry, etc.

"Conventional technology" In various industrial fields, the corrosion resistance of various raw materials is attracting particular attention as an important matter related to extending the lifespan and improving reliability of products. The application of polymeric materials with excellent corrosion resistance to products is being actively studied in conjunction with weight reduction.

Among them, VF and PVDF have a lower melting point than fluorine-based polymers and have the advantage of being easier to process and mold, and also have electrical conversion functions that conventional polymers do not have. Since it is a polymer with an extremely wide range of uses, it has been widely studied.

However, fluororesins have poor surface activity and weak adhesion to other substrates (and are difficult to bond or bond with different materials, so they are used on a variety of substrates such as glass, metals, and plastics). Chromic acid compounds (for example, U.S. Pat. No. 25621
17, No. 2562118, No. 1267266, Japanese Patent Publication No. 59-33628), phosphoric acid compounds (e.g.
7-12331. 50-8829, 5O-9635
) has been proposed, and a method of adding a surfactant, an amine compound, etc. to the above inorganic acid compound has also been proposed. However, it has drawbacks such as the need for waste liquid treatment.

Additionally, special treatments such as corona discharge and flame treatment are applied to the fluororesin or base material surface to improve adhesion, but these methods complicate the process and require special techniques. It has the following disadvantages.

As mentioned above, conventional methods have many disadvantages in achieving the purpose of improving the adhesion between PVF and PVDF and other base materials, and do not fully utilize the general-purpose characteristics of PVF and PVDF. .

"Problems to be Solved by the Invention" The present invention solves the problems of the conventional techniques used when applying the above-mentioned PVF' and PVDF to other base materials. ■ Does not require complicated pre-treatment ■ - No need for mixing due to molding ■ Significantly improves the adhesion between the base material and f) VF and PVDF (text) Structure of the invention ``Solving the problem The present inventors have made extensive studies to solve the above problems and obtain an excellent primer, and have completed the present invention by discovering that a primer containing certain components satisfies them.

That is, the present invention relates to a primer characterized by containing an acrylic resin, an epoxy resin, and an organosilicon compound or an organoaluminum compound as active ingredients.

0 Acrylic resin The acrylic resin in the present invention is one obtained by polymerizing esters of acrylics, etc., for example, as described in Encyclopedia of Polimer Science and Technology
mer 5science and Technology
), Voll, P246.

Esters of acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylate. Examples include lauryl acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and dimethylaminomethyl (meth)acrylate. Preferred (meth)acrylic esters constituting the acrylic resin in the present invention are methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.

The acrylic resin in the present invention includes a resin obtained by polymerizing a (meth)acrylic acid ester and a polymerizable monomer copolymerizable therewith, as described above, but it also includes a large amount of an M monomer. Acrylic resins cannot be used if they have been used to impair the properties of the acrylic resin. The amount of polymerizable monomer that can be used may be determined by taking into consideration the types of (meth)acrylic acid ester and polymerizable monomer used, the type of substrate to be applied, etc.

0 Epoxy resin In the present invention, the epoxy resin refers to at least 1 epoxy resin in one molecule.
It refers to a known compound having 1 or more oxirane groups, and is a general bisphenol A type and Fi epoxy resin represented by the following structural formula, Y: alkyl group or 1 glycidylamine type epoxy resin, such as R, , R, :
Novolak epoxy resins such as alkylene groups, aralkylene groups, cycloalkylene groups, etc., for example, R: alkyl groups, aralkyl groups, etc. can be applied. Compounds having an oxirane group other than those listed above can also be mentioned.

For the present invention, as the epoxy resin, bisphenol A type epoxy resins that better exhibit the desired effects of the present invention are preferred.

OOrganosilicon compounds and organoaluminum compounds Specific examples of organosilicon compounds in the present invention include aminemethyltriethoxysilane, γ-aminopropyltriethoxysilane, r-aminoisobutyltrimethoxysilane, N-(β-aminoethyl ) Preferred compounds include those having one or more aminoalkyl groups and alkoxy groups, such as aminemethyltrimethoxysilane, aminomethylmethyljethoxysilane, and N-(β-aminoethyl)-γ-aminepropylmethyldimethoxysilane. . In addition, compounds having one or more oxirane groups in the molecule, such as r-glycidoxypurvyltrimethoxysilane and r-glycidoxyglovylmethyldimethoxysilane, are also effective organosilicon compounds in the present invention. .

Examples of the organoaluminum compound in the present invention include carboxylic acid salts having a structure of an organic group such as alkoxy or acetylacetonyl (the same applies hereinafter), and compounds having a hydrocarbon group having a structure of AJ-R. Preferred compounds are aluminum alcoholade and rubonru complex salts having the structure Al-0-R. Specific examples of these compounds include aluminum trisisopropyleate, aluminum tris-acetonate, aluminum mono-acetylacetonate, bisethylacetoacetate, aluminum acetylacetonate, and the like.

O Preparation Method The primer of the present invention exhibits its effectiveness even more when the layer consisting of an acrylic resin, an epoxy resin, and an organosilicon compound or an organoaluminum compound has a certain thickness. When applying this primer to various base materials, especially when using it as a primer for PVF and PVDF, it can be used in powder or liquid form, but it can be dissolved or dispersed in an organic solvent and used as a solution or dispersion. It is preferable to use

The organic solvent used may be one that can completely dissolve or disperse the above composition, such as ebuluene, xylene, benzene, ethyl acetate, butyl acetate, acetone,
Methyl ethyl ketone, cyclohexanone, methanol,
Solvents include ethanol, inglobil alcohol, diacetone alcohol, cellosolve acetate, etc., or a mixture thereof.

The primer solution is obtained by completely dissolving or dispersing the components constituting the primer of the present invention in the above solvent, and after mixing each component in the solvent, stirring, preferably 4
It is created by heating to 0 to 50°C.

In addition, the solid content concentration in the solution is preferably adjusted within the range of about 3 to 40 inches, and more optimally adjusted to about 5 to 30 inches. It can be formed. Outside this range, the amount of the necessary components deposited on the substrate may be too small (sufficient effect may not be achieved or the amount deposited may be too large), resulting in a thick coating and the formation of a brittle layer.

The blending ratio of each component in the present invention is acrylic resin (hereinafter referred to as component A)/epoxy resin (hereinafter referred to as component B).
component) is preferably 3/97 to 97/3 in weight ratio, more preferably 10,790 to 90/10.
When component/B component is outside the above range, it is difficult to obtain good adhesion between PVF and PVDF and the base material, which is the objective of the present invention.

Further, the blending ratio C/(A-1-B) of the organosilicon compound or aluminum compound (hereinafter referred to as component C) is preferably 0.2/100 to 25/100 in terms of weight ratio, and more preferably 0.5/ It is 100 to 10/100. If the ratio is less than 0.2/100, PVF and P
If the adhesion between vDF and the base material becomes poor and exceeds 25/100, it is unfavorable in terms of cost and liquid stability.

How to use the primer of the present invention, as described above, is preferably used as a primer solution dissolved or dispersed in a solvent with good stability and solubility.How to apply the primer solution to various base materials. For this, general methods for applying paints, etc., such as dipping in a solution, brushing, coating with various coaters, and spray coating, can be used. Preferably, the base material is made of a material having a heat resistance temperature higher than the melting point, such as metal base materials such as iron, steel, aluminum, nickel, titanium, and zinc, and ceramic product base materials such as glass ceramics and ceramics. These substrates do not require special pretreatment such as blast treatment, alkali or acid cleaning, etc., but preferably have a cleaned surface.

After applying the brimer of the present invention to a substrate in the above method, PVF or PVDF can be coated, laminated, sprayed, electrostatically coated, fluidized, etc. in any form, such as a film sheet, block, powder, etc. Depending on the method, it may be applied and heated to 150-250°C to form a P V F or PVDF' film, or it may be bonded by applying a pressure of 0, 1-10 ky/cd using a hot press. I can do it.

At the time of heating, the present invention's brimer applied to the base material was heated at a temperature of 20 to 40°C.
The area has been dry for more than 10 minutes, or
It is preferable to bake at around 100° C. for 6 to 5 minutes, and it may be selected as appropriate within a range that does not adversely affect the base material.

In this way, by coating PVF and PVDF on the base material coated with brimer and heating to form PVF and PVDF films, the purpose of the present invention is to combine PVF and PVDF with the base material.
It can produce excellent adhesion with VF and PVDF.

[For production]

The mechanism of action of the primer of the present invention is not clear, but an organosilicon compound or an organoaluminium compound is adsorbed and activated on the PvF and PVDF surface, and it also has excellent adhesion to epoxy resin base materials and excellent adhesion to acrylic resin. It is presumed that excellent adhesion between the base material and the resin is produced due to the compatibility with PVF and PVDF, and the reaction between the organosilicon compound or the organoaluminum compound, the resin component, and the base material.

In addition, organosilicon compounds and organoaluminum compounds react and crosslink with resin components when they come into contact with moisture in the air after the solvent has evaporated, forming a strong film, so they have excellent heat resistance and can even be applied to metals. In this case, the anticorrosion effect also brings about the unexpectedly excellent effects of the present invention.

[Examples and comparative examples]

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

0 Example 1 Acrylic resin (Dyanal BR-7 manufactured by Mitsubishi Rayon ■)
0), 5 parts by weight of bisphenol A epoxy resin (Epicoat 1007 manufactured by Yuka Shell Epoxy ■: Molecule i29)
00) and 0.1 part by weight of γ-aminopropyltriethoxysilane, 30 parts by weight of acetone, 40 parts by weight of toluene, and 20 parts by weight of methyl cellosolve acetate were added, and the mixture was stirred and dissolved at room temperature. (referred to as Primer 1) was applied to the substrate shown in Table 1 and dried for 10 minutes at room temperature.

Then PVDF powder (Dynamft Nov
(manufactured by e1) was sprayed at 501/rrl, sandwiched between the same base materials, and bonded while stacked at 170°C for 1 minute under a pressure of 2k)/cd, and the T-peel strength was measured. did.

The results are shown in Table 9.

0 Example 2 Using PvF film (thickness 100 μm), 2 kg/
Table 9 shows the results of measuring the T-peel strength using Primer 1, adhering with a heated press at 150°C for 1 minute under cIII pressure, and using Primer 1 according to other methods as in Example-1. .

0 Example 6 Acrylic resin (manufactured by Mitsubishi Rayon ■, Paravet) 6 parts by weight, bisphenol A epoxy resin (Ebicor MOO
7) 5 parts by weight acetylacetonaluminum 0.1
Using a solution (referred to as Primer 2) in which 30 parts by weight of acetone, 40 parts by weight of toluene, and 20 parts by weight of methylcellulopacetate were added to the heavy electric part and dissolved with stirring at room temperature, the other conditions were as in Example 1. Table 2 shows the results of measuring the T-type peel strength according to 2.

Comparative Example 1 Table 9 shows the results of measuring the T-peel strength of each of the oak base materials shown in Table 1 according to the method of Examples 1 and 20 without using Primer 1.2.

Example 4 0,3 rug tX100mX501 coated with Primer 1
A galvanized chromate steel sheet of Im was heated at 150° C. for 1 minute in an open state, then subjected to a salt spray test at 35° C. for 240 hours, and the rusting status was visually determined. Table 2 shows the results.

Comparative Example 2 Under the same conditions as in Example 4, the rusting status of the primer-untreated steel plate is shown in Table 2.

Table 1 *1 Cold rolled steel plate (5pcc) 0.3mmt x 100nm x 25m*2 Galvanized colored chromate treated steel plate 0.3vmr x 1
0 0m , base material and P
It significantly improves the adhesion with VF and PVDF and can be applied using a simple method, and its effect is achieved without the need for complicated pretreatment.
It has become possible to apply VF and PVDF, and it has become possible to improve the corrosion resistance and extend the life of various raw materials and products in various industries. This has the advantage of being able to open up new fields of application.

Claims (1)

[Claims] 1. A primer characterized by containing an acrylic resin, an epoxy resin, and an organosilicon compound or an organoaluminum compound as active ingredients.