JPS62115078A - Primer - Google Patents

Abstract

PURPOSE:To ensure easy operation of bonding, coating, printing or the like and at the same time to improve workability, by using a primer comprised of a particular fluorine compd. and an organometallic compd. as active components. CONSTITUTION:A primer comprised of one or more of the fluorine org. compd. of the rational formulas which will be described below and an organometallic compd. as active components. The rational formulae include Rf-CH2OH and formulae I and II, Rf-CHO and hydrate or alcohol adduct of Rf-CHO, and formula III and hydrate or alcohol adduct of the formula III. In the formulae, Rf is 1-12C fluorinated alkyl or aryl; R1 and R2 are each fluorinated or unfluorinated 1-12C alkyl or aryl; R3 is a fluorinated or unfluorinated 1-12C alkyl or acetylacetone group. The org. group of the organometallic compd. is pref. a 3C or higher hydrocarbon group in view of treating effect and hazardness. Examples of the metal include typical metals listed in the periodic table, transition metals, metalloids, and phosphorus.

Description

Detailed Description of the Invention (a) Object of the invention "Field of industrial application" The present invention relates to a primer (undercoat) K used in adhesion, painting, printing, etc. This product is related to a primer that firmly adheres highly crystallized resin, which is difficult to coat, paint, or print, and makes it possible to coat or print easily and well.It is a so-called engineering plastic. It is widely used in various carpentry fields including the automobile industry and electrical equipment industry, which widely use polyacetal resin, polyamideimide resin, etc.

``Prior Art'' Highly crystallized resins, such as polyacetal resin, polyamide, or polyvinylidene chloride, have poor affinity and cannot be strongly bonded or coated or printed well using conventional methods. There wasn't.

Therefore, in order to improve the workability of these resins in adhesion, painting, printing, etc., methods have been proposed to improve the adhesion of the surfaces of these resins.

For example, dichromic acid treatment or a satinizing method in which heat treatment is performed in a liquid composition consisting of p-)luenesulfonic acid, a small amount of clay mineral, and an organic solvent, and an improved method thereof (Japanese Patent Application Laid-Open No. 60-11112)
181134) are known.

"Problems to be Solved by the Invention" Highly crystallized resins have a strong cohesive force and poor affinity with individual molecules, so it is difficult to adhere well, paint, or print using conventional methods. Conventionally, the above-mentioned processing methods have been proposed to solve these problems, but these methods have problems such as requiring special equipment and complicated processing operations.

Under these circumstances, the inventors of the present invention have developed a primer that can be easily applied by adhesion, painting, or printing, and have good workability, and have made extensive research efforts to solve the above problems. The inventors discovered that a primer containing an organometallic compound and a specific fluorine-based organic compound as active ingredients could achieve the intended purpose, and completed the present invention.

(B) Structure of the Invention "Means for Solving the Problem" The present inventors have discovered that, as described above, when an organometallic compound and a specific fluorine-based organic compound are used as a primer, highly crystallized resins can be firmly bonded. The present invention was completed by discovering that it can be easily coated, painted, and printed.

That is, the present invention relates to a primer characterized in that the active ingredients include one or more fluorine-based organic compounds represented by the following formula and an organometallic compound.

(2) FLt -CHO, Rr-CHO hydrate or alcohol adduct call adduct, where Rr is a fluorinated alkyl group or aryl group with 1 to 120 carbon atoms, and R1 and R2 are 1 to 120 carbon atoms
Fluorinated or non-fluorinated alkyl group or aryl group, R8 has 1 to 120 carbon atoms, fluorinated or non-fluorinated alkyl group or acetylacetone group 0 Organometallic compound The organometallic compound used in the present invention is an organic group. It is a compound in which a metal is bonded to a metal, and it can be used in the present invention regardless of its type, structure, etc.

Examples of the organic group in the organometallic compound include alkyl, alkenyl, alkoxy, aryl, acetylacetonyl, acetyloxy, cyclohexyl, etc., and hydrocarbon groups with a VCC of 3 or higher are preferable from the viewpoint of treatment effects and risks. In addition to the typical metals, transition metals, and metalloids shown in the periodic table, it also includes phosphorus.

Examples of organometallic compounds include the following.

■ M-0-)t (where M is a metal element and R is an organic group;
A metal alcoholade with the structure (the same applies below).

Specifically, organic titanium compounds such as aluminum isopropylate and sopropyl titanate, boric acid compounds such as tri-butyl borate, triphenyl borate, tri-octadecyl borate, and motuptyl dimethyl borate, and trios of phosphates. Phosphate esters such as leil, tridecyl phosphate, digtyl phosphite, trisisodecyl phosphite, di-2-ethylhexyl phosphite, tridecyl phosphite,
and tetraoctyl silicate triisobutoxygallium, tetrabutyl zirconate, etc.

Carbonyl complex salt. Specifically, aluminum trisacetylacetonate, aluminum mono-acetylacetonate bisethylacetoacetate, aluminum ethyl acetoacetate diisopropylate, aluminum trisethylacetoacetate, aluminum oleyl acetoacetate diisopropylate, lithium acetylacetonate, beryllium acetylacetone, Sodium acetylacetone, indium acetylaceton, calcium acetylacetone, titanyl acetylaceton, strontium acetylacetone, barium acetylaceton, thallium acetylaceton, vanadyl acetylacetone, manganese (I) acetylacetone, iron (1) acetylaceton, thorium acetylaceton, indium acetylaceton (1), idium acetylaceton, acetylacetone cobalt (1), acetylacetone cobalt (I), acetylacetone nickel, acetylacetone copper, acetylacetone zinc, acetylacetone zirconium, acetylacetonomiradium, acetylacetone indium, acetylacetone tin (I)
V) salts, acetylacetone complex salts such as molybdenum acetylacetone, and complex salts such as acetoacetate, trifluoroacetylacetone, and benzoylacetone.

■ Carboxylate salt represented by the structure M-0-C-R.

Specifically, magnesium stearate, aluminum stearate, calcium stearate, ferric stearate, zinc stearate, barium stearate, lead stearate, potassium stearate, copper stearate, manganese stearate, nickel stearate, Nickel naphthenate, cobalt naphthenate, manganese naphthenate, magnesium nanthenate, zinc naphthenate, magnesium palmitate, cadmium palmitate, cobalt palmitate, sodium linoleate, sodium laurate, barium oleate, aluminum laurate, oleic acid aluminum, potassium oleate,
Aluminum acetate, stannous acetate, tin 2-ethylhexanoate, aluminum formacetate, zinc tartrate,
There is basic aluminum thiodiglycolate.

■ A metal having a hydrocarbon group represented by the structure MR.

Specifically, 2-ethylhexylzinc, hexadecyl lithium, n-hexyl sodium, hexadecyl potassium, n-) IJ octyl aluminum, n-'propylethyl lead, tri-n-pentylantimony, tri-n-
Alkyl metals such as tethylantemon, isobutylisoamylzinc, dibutyltin diacetate, di-n-butyltin dimaleate, di-n-butyltin dioxide, triphenyltin acetate, tri-n-butyltin oxide, dioctyltin dilaurate, tributyltin acetate, tributyltin Organic tin compounds such as chloride, tetraamyltin, diallyltin dichloride, methylvinyldichlorosilane, octadecyldimethyl[:3+)rimethoxysilyl)propyl]ammonium chloride (AY43-021: trade name manufactured by Toray Silicon ■), ferrocene, titanocene dichloride,
Examples include Nirakerocene.

■ Other organometallic compounds represented by M-X-R (where X is a heteroatom) Specifically, n-dodecylmercaptopotassium salt, metal thioalcolade such as aluminum trithiobutoxide, 2-ethylhexane thiodicarboxylic acid salts such as tin monothioate, zinc 2-ethylhexane dithioate, nickel dimethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, zinc dietherdithiocarpamate, and nickel benzenesulfonate. sulfonates such as, phosphates such as diptylvanadium phosphate, and zinc 2-mercaptobenzothiazole.

For the present invention, preferred compounds are compounds classified as carboxylic acid salts in (1) and metals having a hydrocarbon group in (2), and compounds classified as metal alcoholades in (1) and 1,3-dicarbonyl complex salts in (2) are preferred compounds. This is a more preferred compound. Specific compounds include aluminum oleyl acetoacetate diisopropylate, aluminum mono-cropoxy diisoglobilate, aluminum ethyl acetoacetate diisopropylate, aluminum isopropylate, zinc acetylacetone, cobalt acetylacetone, nickel acetylacetone,
- Isopropyl titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bistributyltin oxide.

AY43-021. Preferred compounds include calcium naphthenate, magnesium naphthenate, cobalt naphthenate, tin octylate, and manganese acetylacetone (
1), acetylacetone zirconium, tetrabutyl titanate, isobrobyl triisostearoyl tetanoate, tetraingropyrubis(dioctyl phosphite) titanate, dibutyltin diacetate, di2-ethylhexyltin dilaurate, nickel naphthenate, trisisodecylhof Particularly preferred compounds include phite and the like.

O Fluorine-based organic compound The fluorine-based organic compound used in the present invention is represented by the following formula, and is a chain or cyclic hydrocarbon hydrogen atom having a polar group such as a hydroxyl group or a carbonyl group in the molecule. is a compound in which part or all of is substituted with fluorine atoms.

(2) Rt-CHO, Rt-CHO hydrate or alcohol adduct call adduct, where Rt is a fluorinated alkyl group or aryl group with 1 to 120 carbon atoms, R and R7 are 1 to 120 carbon atoms
Fluorinated or non-fluorinated alkyl group or aryl group, R5 has 1 to 120 carbon atoms, fluorinated or non-fluorinated alkyl group or acetylacetone group Specific examples of these compounds include the following: Can be mentioned.

2, 2.2. - trifluoroethanol, 2.2.3.
6-titrafluoroglopanol, 2.2.3.3.3
- Pentafluoroglopanol, 2.2.5.3.4.
4.4-Hebutafluorobutanol, 2.2.3.3.
4.4,5°5.5-nonafluoropentanol, 1.
1.1-3 Refluorinproper tool, 1.
i, 1.3.3.3-hexafluoroisopropanol, octafluoro(8)-butanol, perfluoro tert-butanol, hexafluoro tert-butanol, 2-)! Fluoromethylpropanol 2.1
-chloro-1,1,3,5,5-pentafluoro-2-
Proper tools! 1.3,4.4.4-pentafluorobutanol-2,3,3,4,5,5,5-hexafluoro-2-methylpentanol-2,2,2,3,3,
4,4゜5.5-octafluoro-1-pentanol,
2, 2.3.3.4.4.5.5.6.6.7. Otsu 8.
8.8-Pentadecafluorooctano-1, trifluoroacetaldehyde, trifluoroacetaldehyde hydrate, pentafluorobenzaldehyde, 2, 2.
5.3.4.4-Hexafluoro-1,5-bentanediol, pentafluorobenzyl alcohol, 1.1.
1-trifluoroacetone, hexafluoroacetone,
Hexafluoroacetone hydrate, trifluoromethyl trichloromethyl ketone, pentafluoroethyl ethyl ketone, pentafluorophenyl methyl ketone, methylhebutafluoropropyl ketone, hexafluoro-2-phenylisoglobanol, hexafluoro-2-(p −
) ril) inpropatol, 1÷pentafluorophenyl) ethanol, thecafluorodiphenylmethanol,
trifluoroacetaldehyde ethyl hemiacetal,
Heptafluoro-n-butyraldehyde ethyl hemiacetal, trifluoroacetaldehyde trifluoroethyl hemiacetal, hexafluoroacetylacetone, sym-dichlorotetrafluoroacetone, sym-
Dichlorotetrafluoroacetone hydrate.

Among these compounds, preferred compounds for the present invention are:
A substance that dissolves or disperses the organometallic compound and has appropriate volatility, and further has properties that allow it to penetrate into the highly crystallized resin to be coated or to dissolve the resin. It is preferable to have the following.

O combination ratio The effect of the primer of the present invention is mainly caused by the organometallic compound, as described later, and when the organometallic compound is formed on the resin surface in the form of a thin film or a monomolecular film, the effect of the present invention increases. is fully demonstrated,
The amount of organometallic compound in the primer is preferably 0.001 to 10% by weight, more preferably 0.001% by weight.
~1 fold f1%. If this concentration is less than α001% by weight, it is difficult to form a layer of the organometallic compound in the form of a thin film or a monomolecular film! If the amount exceeds 10% by weight, the layer tends to become too thick and becomes a brittle layer, reducing the effectiveness of the primer. .

0 Other additives The primer of the present invention contains the above-mentioned organometallic compound and a fluorine-based organic compound as active ingredients, and can sufficiently exhibit the desired effects of the present invention by itself. However, as a primer, Organic solvents and organic polymers can be added to improve the coating properties.

The solvent is preferably one that can completely dissolve or disperse the organometallic compound and the fluorine-based organic compound, has appropriate volatility, and can sufficiently wet the surface of the resin. .

Specific examples of solvents include 1.1.2-) IJ dichloro 1.1.2-) U fluoroethane, ethanol, acetone, ethyl acetate, i, 1.1-1 lychloroethane, tetrahydrofuran, 1,4-dioxane. , toluene, etc., and these may be used alone or in combination of two or more.

Even when these organic solvents are used in combination, it is better to avoid the amount of the organometallic compound in the primer falling outside the above range, and it is also preferable to avoid the amount of the fluorine-based organic compound being less than 20 parts by weight. The amount of the compound is 2
0! If it is less than i1, the effect as a primer becomes inferior, presumably because the formation of a layer of the organometallic compound on the resin surface is inhibited.

Organic polymers improve coating properties by imparting viscosity to the primer, and include ethylene/vinyl acetate copolymer, ethylene/acrylic acid ester, chlorinated polyethylene, polyvinyl acetate, and poly(meth)acrylic acid. A polymer such as an ester is selected and used depending on the type and amount of the fluorine-based organic compound and the organic solvent.

0 Target Resin The primer of the present invention 9 can be applied to various resins, but the intended effects of the present invention can be fully exerted especially when applied to highly crystallized resins.

Specifically, the highly crystallized resin referred to in the present invention is the following resin.

These are polyacetal, polyamide, polyimide, polyamideimide, polyethylene terephthalate, polybutylene terephthalate, polytetrafluoroethylene, polyvinylidene chloride, polyethylene, polypropylene, polyphenylene sulfite, polysulfone, polyphenylene oxide, polyarylate, and polyetherke.

O Adhesives, Paints and Printing Inks The primer of the present invention is useful for adhesion of resins, especially highly crystallized resins,
It is used when painting or printing,
Various types of adhesives, paints, or printing inks can be used for adhering, painting, or printing the resin coated with the primer of the present invention.

As the adhesive, for example, cyanoacrylate adhesive, epoxy adhesive, polyester adhesive, acrylic adhesive, urethane adhesive, chloroprene adhesive, etc. can be applied.

There are various paints and printing inks that can be applied.
The following are classified according to the cicle resin components:

Rosin derivatives, nitrocellulose resins, vinyl resins, acrylic resins, polyester resins, polyamide resins, polyurethane resins, phenolic resins, epoxy resins, aminoalkyd resins, melamine resins,
Curable acrylic oligomers can be applied, but more suitable ones are polyurethane resins,
Examples include epoxy resin-based, alkyd resin-based paints, and printing inks.

In any case, when a thermosetting type is used, it is preferable to use one with a curing temperature of 90° C. or lower, since there is a limit to the heat resistance of the base resin.

0 How to use The primer of the present invention is composed of an organometallic compound, a fluorine-based organic compound, a solvent added as desired, and an organic polymer. These components are mixed and uniformly dispersed or dissolved. It can be constructed by

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

The resin coated with the primer is air-dried at room temperature and the solvent is removed to form a single layer of primer on the surface.

A resin having a single layer of primer can be firmly bonded to itself or to other materials using the above-mentioned adhesive, and can similarly be easily coated with paint or printing ink on its surface using conventional methods. can be painted or printed.

Alternatively, a diluted solution of an organic solvent such as toluene or ethyl acetate that does not impair the stability of α-cyanoacrylate or the same compound, such as toluene or ethyl acetate, is applied onto the primer layer using a brush that has been previously treated with an acid, or by dipping. This is a preferable method because it is possible to take the sample out and leave it at room temperature to form a thin layer of α-cyanoacrylate polymer before painting or printing, and a finish with good adhesion can be obtained.

In order to better demonstrate the effects of the primer of the present invention, it is necessary to consider the type of target resin, especially the highly crystallized resin, the type of organometallic compound and fluorine-based organic compound to be used, the combination ratio, and the application rate. The amount etc. must be determined.

Regarding the amount of coating, as described later, the thickness of the primer layer has a large effect on the effect, so it is preferable to apply the organic metal compound in an amount of 0.001 to 1 g/m', and more preferably. is 0.01~0.1,!
It is to apply so that it becomes i'/rrl.

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

In other words, the organometallic compound, which is a component of the primer of the present invention, has both polar and non-polar groups in its molecular structure and has a compulsory function, and when this primer is applied to a resin, it has an affinity for the resin. Due to the strong synergistic action of the fluorine-based compound, the resin and the non-polar groups of the organometallic compound coated in a thin film form a strong bond, and the polar groups of the organometallic compound are oriented upward on the surface of the resin. is activated. When an adhesive, paint, or printing ink having a polar group is applied to the resin surface activated in this way, a strong bond is formed by secondary bonds and hydrogen bonds, which are not susceptible to 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.

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

Example 1. Comparative example 1 (1) Preparation of primer The following five types of composition liquids were prepared as primers.

A: Trifluoroethanol solution of α5chi Al-diisopropylate B: 0.5%-acetylacetone Tetrafluoro-1-propatol solution of manganese (1) C: O,S%-hebutafluoro- of bistributyltin oxide 1-Butanol solution D: 0.5%-pentafluoro-1-propatur solution of gobalt naphthenate E: 0.5%-trisisodecylphosphite hexafluoro-2-propatol solution (2) Primer performance Test Compliant with JIS K 6B61-1977 Test piece: Polyacetal and nylon 625X100X3 Adhesive a: Aron Alfana 201 (cyanoacrylate adhesive manufactured by Toagosei Kagaku Kogyo Co., Ltd.) b Two-pound E set (epoxy adhesive two-component type) (Manufactured by Konishi Co., Ltd.) C Nihardlock E-510 (Modified acrylic adhesive, two-component type, manufactured by Denki Kagaku Kogyo Co., Ltd.) Wipe both sides of the test piece with a primer-impregnated cloth, air dry for about 5 minutes at room temperature, and then adhere to one side. After applying the agent, the other side was placed one on top of the other, a pressing force of 0°jkpf/al'l was applied, and the product was cured at room temperature for 24 hours.

The tensile and shear adhesive strengths were measured using a Strograph W type tester at a tensile rate of 2 On+/-.

Further, as a comparative example, a test was conducted in the same manner as in Example 1 except that the adhesive was bonded without being treated with a primer.

Example 2, comparative example 2 (1) Preparation of primer The following three composition solutions were prepared as primers.

F: 1%-ethylacetoacetate-A, g-diisopropylate 50%-hexafluoroacetylacetone 49%-11
,2-trichloro-1,2,2-)lifluoroethane G: 1 dyptyl-8 n-diacetate 50 heptafluoro-n-butyraldehyde ethyl hemiacetal 49%-methylchloroform H: 1%-diethylhexyl- 8n-laurate 5
0%-2,2,3,3,4,4,5,5-octafluoro-1-pentanol 49%-14-dioxane (2) Performance test of primer
) Example 1 except that 25X100X0.03u+ is used.
The test was conducted in the same manner. These results are shown in Table 2.

Table 2 Example 6, Comparative Example 3 (1) Preparation of primer Composition solutions A-H prepared in Example 1.2 were used.

(2) Measurement of paint film adhesion Compliant with JIS K 5400-1979 Test piece: Polyacetal, nylon 6 100X100X31111 Paint a: Nitrocellulose lacquer enamel brown (Kansai Paint Co., Ltd.) Niacrylic paint yellow (Toagosei Kagaku Kogyo Co., Ltd.) (manufactured by) C:
Synthetic resin paint blue (manufactured by Toa Paint Co., Ltd.) d: Urethane paint two-component brown (manufactured by Chugoku Paint Co., Ltd.) e: Aroni, Kusu UV
3607 Clear (manufactured by Toagosei Kagaku Kogyo Co., Ltd.) Wipe the surface of the test piece with a cloth impregnated with primer, air dry at room temperature for about 5 minutes, then apply paint to this surface with a brush and leave it at room temperature for 6 minutes.
Dry for several days (Ultraviolet light only: Uv lamp 80 W)
x 10 cm / 2' m). The adhesion of the coating film was measured using a cross-cut Serono 7 tape. These results are summarized in Table 3 (c) Effects of the Invention By using the primer of the present invention, adhesion of highly crystallized resins, which had been considered difficult in the past, or painting or printing on the resins can be easily and efficiently performed, and also firmly. It has become possible to use high-crystalline resins, so-called engineering plastics, in place of metal materials, and has many advantages such as the use of excellent physical properties, aging, rust resistance, and cost reduction. The contribution to various fields such as industry is extremely large.

Name of watch applicant Toagosei Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. A primer characterized by containing as active ingredients one or more fluorine-based organic compounds represented by the following formula and an organometallic compound. (1) R_fCH_2OH, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) R
＿f-CHO, R_f-CHO hydrate or alcohol adduct (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Hydrate or alcohol adduct However, here R_1 is Fluorinated alkyl group or aryl group having 1 to 12 carbon atoms, R_1 and R_2 have 1 to 12 carbon atoms
12 fluorinated or non-fluorinated alkyl groups or aryl groups, R_3 is a fluorinated or non-fluorinated alkyl group or acetylacetone group having 1 to 12 carbon atoms