JPS59124921A - Primer for metal - Google Patents

Abstract

PURPOSE:A primer for metals capable of providing excellent adhesion and peeling resistance, containing an isocyanate having an oxadiazinetrione ring. CONSTITUTION:A primer useful for painting the surface of a metal or bonding metals together or a metal to another material, containing an isocyanate having a 1,3,5-oxadiazine-2,4,6-trione ring (e.g., a compound derived from hexamethylene diisocyanate). It can provide excellent adhesion and peeling resistance.

Description

[Detailed description of the invention] The present invention relates to a primer for gold 1,.1.

More specifically, 1,3.5-oxadiazine-2,4,
6-) Useful for coating metal surfaces, adhesion between metals, or adhesion between metals and other materials, containing incyanate having a ion ring (hereinafter simply referred to as oxadiazinetrione ring or trimono ring) Regarding primer.

In general, various types of resin adhesives are used to bond metals together or metals and other materials. In order to improve adhesion and prevent peeling, methods have been proposed in which the adhesive surface of metal and painted surface are treated with various primers. Known examples of such primers include organic silane compounds, organic titanium compounds, polyethyleneimine compounds, incyanate compounds, epoxy compounds, acrylic compounds, and epoxy/phenol compounds. However, in many cases, its effects are only manifested in combination with specific adhesives or paints, and the effects are not necessarily satisfactory.

An object of the present invention is to provide a metal primer that provides excellent adhesion and peeling resistance.

That is, the present invention provides 1,3,5-oxadiazine-21
This is a metal primer containing an isocyanate having a 4,6-trione ring.

The isocyanate having an oxadiazinetrione ring used as a primer component of the present invention means a compound having both an oxadiazinetrione ring and isocyanate group in the molecule, and such a compound is a combination of isocyanate and carbon dioxide. It can be produced by the reaction of Examples of the raw material incyanate include tetromethylene diisocyanate, hexamethylene diisocyanate, ω,
d-diisocyanatodipropylethe/V, 2.6-diisocyanatocaproic acid ester/L', 1,6.11-
Triisocyanatoundecane, bis(isocyanatomethyl)cyclohexane, bis(isocyanatoethyl/L/
)cyclohexane, 1-isocyanato-3-isocyanatomethyl-3,5,5=)limethylcyclohegythane, bis(4-isocyanatocyclohexy/l/)methane, xylylene diisocyanate, his(2- Aliphatic, alicyclic, and araliphatic polyisocyanates such as isocyanatoethyl/L/)benzene are used. These polyisocyanates can be used alone or in mixtures with one another. monoisocyanates, eg ethyl isocyanate, n-butyl isocyanate.

It can be used in the reaction by mixing with benzyl isocyanate, phenylethyl isocyanate, etc.

In addition, dimers and sankei forms of the above polyisocyanates can also be used. The reaction between polyisocyanate and carbon dioxide is carried out in the presence of a catalyst.
class phosphines, arsenic compounds.

Hydroquinones can be used, and tertiary phosphines are particularly effective. The reaction is generally carried out by blowing carbon dioxide gas into the reaction system of isocyanate and catalyst. J wide temperature is usually -70 to 150tE, especially -
20-70°C is preferred. Through such a reaction, one to several oxadiazinetrione rings (usually 2-
5) A mixture of isocyanates is obtained. The reaction is completed in about 30 minutes to 10 hours, depending on the amount of catalyst.

Reaction wave Unreacted carbon dioxide is removed by heating and blowing nitrogen gas, and unreacted isocyanate is removed by distillation.
It can be removed by conventional methods such as extraction. After the reaction, it is usually best to add various compounds such as tFA to completely stop the progress of the reaction and to preserve the product stably. , esthetics/I/derivatives, phenols, peroxides,
Sulfur, polysulfide, metal sulfide, halogen, etc. can be used.

The isocyanate having an oxadiazinetrione ring is usually a mixture of isocyanates having 1 to 3 trione rings, and this mixture is one of them! It can also be used as a primer component in the present invention. Moreover, this primer component may contain unreacted isocyanate.

In addition, fJ: 'J
To prepare, prepare in advance polyisocyanate and polyol compounds (e.g., ethylene glycol, propison glycol, 1+4-polybutylene glycol, glycerin, trimethylolpropane, polyether polyol).
, polyester polyol.

acrylic polyol-μ, epoxy polyol, polyhydroxy polyolefin, etc.) or polyamine compounds (
For example, an adduct having a terminal NCO group obtained by redundantly reacting ethylenediamine, Can be used.

As the primer component of the present invention, an isocyanate having an oxadiazinetrione ring obtained by the reaction of polyisocyanate and carbon dioxide gas is adducted with a compound having an active hydrogen as described above. can. When such adducts are used as primers, they exhibit even better adhesion to metals.

Among the isocyanates having an oxadiazinetrione ring of the present invention as described above, hexamethylene diisocyanate, 1-incyanato-3-incyanatomethyl-3,5,5-1-limethylcyclohexane or bis(incyanato-3-incyanatomethyl-3,5,5-1-limethylcyclohexane) are preferred. A primer derived from (anatomethyl)cyclohexane is an excellent primer component for the present invention because it has low viscosity, good coatability to metal substrates, and particularly excellent adhesion.

In a preferred embodiment of the present invention, a primer is used in which an isocyanate having an oxadiazinetrione ring is dissolved in an inert solvent.

Examples of such solvents include ketones such as acetone and methyl ethyl ketone, aromatic aqueous compounds such as toluene and xylene, and halogenated solvents such as methylene chloride, trichloromethane, trichloroethane, and trichloroethylene. saturated or unsaturated J, Q hydrogen chloride,!, or for example vinegar ``
Ethyl.

rll; Fatty acid esters such as butyl) etc. are used. When used as a solution, the C degree of the isocyanate component having an oxadiazinetrione ring is 01 to 0.
Preferably, it is 50% by weight.

The primer of the present invention may further contain a viscosity modifier, if necessary.
Adding fillers, dispersion stabilizers, etc. will not make any difference.

Adhesives and paints that can be used in combination with the primer of the present invention may be of any type as long as they have been conventionally used as adhesives or paints for metals, such as epoxy resins, Examples include polyurethane-based and polyolefin-based adhesives and paints.

Among these, the primer of the present invention uses a polyolefin adhesive (ethylene-vinyl acetate copolymer (vinyl acetate content: 5 to 50% by weight) and its saponified product or its carboxy tLy'lJ form as base 7. Hot melt adhesive (Takemelt ■ series; Takemelt ■M
-204, Takemelt [F] M-301 Takeda Pharmaceutical Co., Ltd. (
+n5)) is particularly useful in combination with

The primers of the present invention can be applied to iron, copper,
There are aluminum, lead, etc., and it can be widely applied when painting the surfaces of these metals, adhering these metals together, or adhering these metals to different materials.

Paint metal using the primer of the invention.

When adhering, the primer composition is applied to the metal surface to be coated and bonded, and dried at room temperature. Even if the primer of the present invention is allowed to stand for a while after drying, its usefulness as a primer does not deteriorate. This point is one of the advantages when compared with conventional isocyanate yarn primers.

For this coating method, a conventional coating method such as a dipping method, a spraying method, a brushing method, etc. can be appropriately adopted. The coating amount of the primer of the present invention is approximately Q, 5 B as the solid content of the primer.
It can be applied to adhesive and painted surfaces at a rate of 7m2 to 100g/m2. Then, paint or adhesive is applied on the primer coating film formed by the above operation, and metal or other different materials that have been similarly treated with the primer are overlaid to complete the painting and adhesion.

Materials primed with the 1 primer of the present invention exhibit excellent adhesion strength after bonding and are easily peeled off after coating.
: A coating film free of blemishes is obtained.

Hereinafter, the present invention will be explained in more detail by showing examples and a comparative example, but these are not intended to limit the present invention in any way.

Reference example/ While blowing carbon dioxide gas into 841g of hexamethylene diisocyanate at 40℃)! 1.8 g of J-n-butylphosphine was added, and the reaction was carried out for 6 hours with stirring.

Stop the supply of carbon dioxide gas, add 0.3g of sulfur powder, and
After stirring for 0 minutes, the mixture was cooled.

When the raw material was removed from this material using a thin film evaporator, 255 g of a pale yellow, slightly viscous liquid was obtained. This thing is no good
It has an O content of 4.78 meq/g, an oxadiazinetrione content of 2.77 meq/g, and a residual monomer amount of 0.4%.

Reference example λ 1,3-bis(incyanatomethyl)cyclohexane 9
To 71 g, 30 g of tri-n-butylphosphine was added while blowing carbon dioxide gas at 1, and the reaction was carried out for 5 hours while stirring. The supply of carbon dioxide gas was replaced with nitrogen, and 3.8 g of tri-n-butylphosphine was added. The mixture was added and stirred for 80 minutes. When the raw material was removed by evaporation of the product using a thin film evaporator, 280 g of a pale yellow viscous liquid was obtained. This one has an NGO content of 4.35 meq/g and an oxadiazinetrione content of 2.
It was 22 meq/g, and the residual amount of upper glutinous acid was 0.8%.

Reference Example 3 1.3-Bis(isocyanatomethy)V) 40% methanol/L of trimethylbenzylammonium hydroxide dissolved in 4 g of butyl acetate in 194 g of cyclohexane
/Add 4g of common liquid o0 and leave it at room temperature for 3 hours F+! Allow to react while stirring. The reaction is stopped by adding 0.2 g of benzoino chloride. NC○containing H'( of the product is 390%(
(432%) before the reaction, and the infrared absorption spectrum shows absorption at 1690C, l11', indicating that isocyanatomethy is produced. To this was added 1.4 g'ffi of tri-n-butylphosphine while blowing 1 charcoal gas at 20° C., and the mixture was allowed to react for 4 hours while stirring. After replacing the major acid gas supply with nitrogen, 1.2 g of dimethyl sulfate was added to stop the reaction. The NCO content of the product is 25.9%. The infrared absorption spectrum and NMR nuvector show that a product containing both an oxadiazinetrione ring and an isocyanate ring is obtained.

Reference example 22 g of the isocyanate component having an oxadiazinetrione ring obtained in Reference example
35 g of 100 g of Toluene, 50 gal of toluene, and 3 L of dibutyltin dilaurate were reacted for 3 hours at 70 tE with stirring to obtain an NGO content of 0.76 meq/g and an oxadiazinetrione content of 0.6 meq/g. An adduct having g was obtained.

The infrared absorption spectrum and NMR spectrum of this product revealed that a product having a urethane bond and an oxadiazinetrione ring was obtained.

Example/Reference Example 5 g of the incyanate component having an oxadiazinetrione ring obtained in Reference Example Z was dissolved in 95 g of 1Ii2 ethyl acetate to obtain a primer bath liquid. The above primer solution was applied with a brush onto the adhesion surface of each of two copper foils having a thickness of 35 μm, and dried for 30 minutes at room temperature. Between the coated surfaces, apply modified polyolefin hot melt 412 adhesive (Takemel 09M-2, 04i Takeda Pharmaceutical Co., Ltd. ((1)
) was sandwiched and pressed using a heated press at 160 tons for 10 minutes at 100 kq7 cJ (gauge pressure). Using the adhesive test piece obtained in this way, a 1800 peel test was conducted according to JIS K6854 Test Q;4 method, and the result was 26.0 kg/1nch.
Indicates the adhesive strength of /c.

As a comparative example, the above primer solution was not applied to the cloth. '
Using +'+, create an adhesive sample in the same manner as 1.
80° 1] 1.11 When the strength was measured, it was 3.3
Only the value of kq/1nch could be T'4.

Ratio (as an example, instead of the isocyanate component of the above primer, TD Engineering (Takenate ■80.Takeda) j'14
An adhesive test piece was prepared in exactly the same manner except that a primer solution prepared using Shinko A4 (manufactured by i'ti) was used, and the 180° peel strength was measured.
Only the value of ch was obtained.

Example Reference Example 2.5 g of the isocyanate component having an oxadiazinetrione ring obtained in λ was mixed with 97 g of methyl ethyl ketone.
A primer solution was obtained by dissolving 5 g of the primer.

The above primer solution was applied with a brush to the adhesion surface of each of two degreased aluminum plates having a thickness of 0.2 nm, and was dried at room temperature for 20 minutes. 100 µm of modified polyolefin hot melt adhesive (Takemel M-301; Takeda Shohin Kogyo Co., Ltd.)
M J
I made it 'ir'j.

Using this adhesive test piece, a 180° peel 1: aff test was performed according to the JIS K6854 smell test method, and the result was 35 k
The adhesive strength was greater than g/1 nch, and the aluminum material was destroyed.

Example 3 7 g of the isocyanate component having an oxadiazinetrione ring obtained in Reference Example 3 was mixed with 93 g of methylene chloride.
Dissolve the primer bath.

The primer I4 solution was applied with a brush to the adhesion surface of each of two 1.6 mm thick iron plates (cold-rolled plates) and dried for 10 minutes at room temperature. During this application, a modified polyolefin pot melt adhesive (Takemel ■
M, -204 Takeda Pharmaceutical yarn (4→ made; thickness 100i
□ This adhesion test 1. Pull the moxibustion piece according to the JIS K6850 wiping method to create a long shear groove. When I measured the strength, it was 170kg7
cm2 value, and the failure state was cohesive failure.

Oxadiazinetrione 1,1 obtained by 19E elliptical experiment 191
A primer solution was obtained by dissolving 5 g of the adduct with ethyl acetate in 95 g of ethyl acetate.

Adhesive surface of cross-linked polyethylene plate with thickness l+n+n and thickness 1. , Apply the above primer 7d solution with a brush to the adhesive surface of 1 roll (cold-rolled steel plate) of 6 nm iron, and apply it at room temperature for 30 minutes.
Let dry for a minute. Apply a modified polyolefin hotme/reto adhesive (Takemel M-2) to 111 on this coated surface.
04 Takeda Pharmaceutical Co., Ltd. (manufactured by T'13) 100μ thick film was sandwiched and heated at 15L for 15 minutes.
It was crimped with contact pressure.

This adhesive test piece was J, T S K 68547ft,
! The peel strength of 1800 mm was determined according to the above method and showed an edge of 2151 g/1 nch.

As a comparative example, a piece for jTF, 7A test river was made in the same manner as above except that the above primer and no cloth material were used, and its 180°f, lI its': 'L bow/λ
Sa7<, n1i11%7 where 11.5 k'
,! / Indicates the value of 1nch.

Claims (1)

[Claims] 1. A metal primer comprising an isocyanate having a 3.5-oxadiazine-2,4,6-trione door.