JPH0138412B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a primer for thermoplastic polycondensation resins.

More specifically, 1,3,5-oxadiazine-
Coating of thermoplastic resin molded products and films containing isocyanate having a 2,4,6-trione ring (hereinafter simply referred to as oxadiazinetrione ring or trione ring), or adhesion of molded products and films together Or it relates to a primer useful for adhering molded products, films, and other dissimilar materials.

Conventionally, when painting or adhering thermoplastic polycondensation resin molded products such as nylon and polyethylene terephthalate or their films, various primers have been used to improve the adhesion of paints and adhesives to the base material and prevent peeling. It is proposed to use

Known examples of such primers include organic silane compounds, organic titanium compounds, polyethyleneimine compounds, isocyanate compounds, epoxy compounds, and acrylic compounds. However, in many cases, its effects are only manifested in combination with specific paints and adhesives, and the effects are not necessarily satisfactory.

An object of the present invention is to provide a primer for thermoplastic polycondensation resins that provides excellent adhesion and peeling resistance.

That is, the present invention provides 1,3,5, which is obtained by blowing carbon dioxide gas of an isocyanate compound in the presence of a tertiary phosphine at a reaction temperature of -70 to 150°C and reacting for 30 minutes to 10 hours. - A primer for thermoplastic polycondensation resin containing an isocyanate having an oxadiazine-2,4,6-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 an isocyanate group in the molecule, and such a compound is an isocyanate compound and carbon dioxide. It can be produced by reaction with Examples of the raw material isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, ω,ω'-diisocyanatodipropyl ether, 2,6-diisocyanatocaproic acid ester, 1,6,1-tripropyl ether, Isocyanatoundecane, bis(isocyanatomethyl)cyclohexane, bis(isocyanatoethyl)cyclohexane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, bis(4-isocyanatocyclohexyl)methane, xylene Aliphatic, alicyclic, and araliphatic polyisocyanates such as diisocyanate and bis(2-isocyanatoethyl)benzene are used. These polyisocyanates may be used alone or in mixtures with one another. Also, monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, ω
- Chlorhexyl isocyanate, cyclohexyl isocyanate, cyclohexylmethyl isocyanate, benzyl isocyanate, phenylethyl isocyanate, etc. can be mixed and used in the reaction. Dimers and trimers of the above polyisocyanates can also be used. The reaction between the isocyanate compound and carbon dioxide is carried out in the presence of a catalyst, and tertiary phosphines are particularly effective as the catalyst. The reaction is generally carried out by blowing carbon dioxide gas into the reaction system of the isocyanate compound and the catalyst. The reaction temperature is usually -70
~150°C, particularly -20~70°C is preferred. Such a reaction usually yields a mixture of isocyanates having one to several oxadiazinetrione rings. The reaction takes about 30 minutes, depending on the amount of catalyst.
Finished in 10 hours. After the reaction, carbon dioxide from the final reaction was removed while blowing nitrogen gas under heating, and
The terminally reacted isocyanate compound can be removed by conventional methods such as distillation and extraction. After the reaction, it is usually best to add various compounds to completely stop the progress of the reaction and to preserve the product stably. , ester derivatives, phenols, peroxides, sulfur, polysulfides, metal sulfides, halogens, and the like can be used.

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

In addition, when producing an isocyanate having an oxadiazinetrione ring from polyisocyanate and carbon dioxide, it is necessary to prepare the polyisocyanate and a polyol compound (e.g., ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylol) in advance. Propane, polyether polyol, polyester polyol, acrylic polyol, epoxy polyol,
Adducts with terminal NCO groups obtained by reacting polyhydroxypolyolefins, etc.) or polyamine compounds (e.g., ethylene diamine, hexamethylene diamine, phenylene diamine, polyether polyamines, polyamide polyamines, etc.) such that the NCO groups are in excess. can be used as polyisocyanate.

Furthermore, it is also possible to use an isocyanate having an oxadiazinetrione ring obtained by the reaction of polyisocyanate and carbon dioxide gas, which is adducted with the above active hydrogen-containing compound. Such an adduct can serve as a primer component that has even better adhesion between the paint or adhesive and the substrate and peeling resistance.

Among the isocyanates having an oxadiazinetrione ring of the present invention as described above, hexamethylene diisocyanate, 1-isocyanato-3
-Those derived from isocyanatomethyl-3,5,5-trimethylcyclohexane or bis(isocyanatomethyl)cyclohexane have low viscosity and good coating properties on thermoplastic polycondensation resin substrates, especially in terms of adhesion. Because of its excellent properties, it is an excellent primer component of the present invention.

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. Such solvents include
Ketones such as acetone, methyl ethyl ketone, aromatic hydrocarbons such as toluene, xylene, halogenated saturated or unsaturated hydrocarbons such as methylene chloride, trichloromethane, trichloroethane, trichloroethylene, or e.g. Ethyl acetate,
Aliphatic esters such as butyl acetate are used. When used as a solution, the concentration of the isocyanate component having an oxadiazinetrione ring is preferably 0.1 to 50% by weight.

The primer of the present invention may be further added with a viscosity modifier, a filler, a dispersion stabilizer, etc., if necessary.

Adhesives that can be used in combination with the primer of the present invention include any type of adhesive that has been conventionally used as a paint or adhesive for thermoplastic polycondensation resins, especially nylon and polyethylene terephthalate. Examples thereof include epoxy resin-based, polyurethane-based, and polyolefin-based paints and adhesives. Among these, the primer of the present invention is a polyolefin adhesive [a hot melt adhesive based on an ethylene-vinyl acetate copolymer (vinyl acetate content: 5 to 50% by weight) and its saponified product or a carboxyl modified product thereof] , Takemelt series Takemelt M-203, Takemelt M-207 manufactured by Takeda Pharmaceutical Co., Ltd.] is particularly useful.

Thermoplastic polycondensation resins to which the primer of the present invention is applied include, for example, polyamide (so-called nylon), polyethylene terephthalate, polycarbonate, and other resins, which are widely used as films or molded products. The primer of the present invention can be widely used for adhesion between films or molded products, for adhesion of films or molded products with different materials, and for coating these molded products.

When adhering or painting a polycondensation resin using the primer of the present invention, the primer composition is first applied to the surface of the resin to be adhered or painted, and is usually dried at room temperature. The primer of the present invention does not lose its effectiveness as a primer even if it is left for a while after drying. This point is one of the advantages when compared with conventional isocyanate-based 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 is 0.5g/ ^m2 to 100 as primer solid content.
g/ ^m2 . Then, paint is applied on the primer coating film formed by the above operation, or an adhesive is applied, and a similarly primer-treated grease or other different material is overlaid to complete the adhesion.

The material treated with the primer of the invention is
It exhibits excellent adhesive strength after adhesion and provides a coating film that does not peel off after painting.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but these are not intended to limit the present invention in any way.

Reference example 1 841g of hexamethylene diisocyanate at 40℃
While blowing carbon dioxide gas, 1.8 g of tri-n-butylphosphine was added, and the reaction was carried out for 6 hours while stirring. Stop the supply of carbon dioxide gas and remove the sulfur powder.
0.3 g was added, stirred for 30 minutes, and then 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
It has an NCO content of 4.78meq/g, an oxadiazinetrione content of 2.77meq/g, and a residual monomer amount of 0.4
%.

Reference Example 2 3.0 g of tri-n-butylphosphine was added to 971 g of 1,3-bis(isocyanatomethyl)cyclohexane at 10°C while blowing carbon dioxide gas, and the reaction was carried out for 5 hours while stirring. Replace the carbon dioxide supply with nitrogen and add 3.8g of benzoyl peroxide to 80
Stir for a minute. 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 product has an NCO content of 4.35 meq/g, an oxadiazinetrione content of 2.22 meq/g, and a residual monomer content of 0.8%.

Reference example 3 1,3-bis(isocyanatomethyl)cyclohexane 194g and tri-n-butylphosphine 2.0g
A reaction was carried out for 8 hours in the same manner as in Reference Example 2 using
The reaction was stopped using 2.6 g of benzoyl peroxide.
The product was dissolved in 100 ml of toluene, 500 ml of n-hexane was added thereto, and the solution was thoroughly shaken to remove the solvent layer. After repeating this extraction operation three times in total, butyl acetate was added to the extraction residue to reduce the nonvolatile content to 85%.
% solution. The NCO content of this thing is
2.60meq/g, oxadiazinetrione content is
It is 2.27meq/g.

Reference Example 4 40% of trimethylbenzylammonium hydroxide dissolved in 4 g of butyl acetate in 194 g of 1,3-bis(isocyanatomethyl)cyclohexane
Add 0.04 g of methanol solution and react at room temperature for 3 hours with stirring. The reaction is stopped by adding 0.2 g of benzoyl chloride. The NCO content of the product has decreased to 39.0% (43.2% before reaction), and the infrared absorption spectrum shows absorption at 1690 cm ^-1 , indicating that isocyanurate has been produced. To this was added 1.4 g of tri-n-butylphosphine while blowing carbon dioxide gas at 20°C, and the mixture was allowed to react for 4 hours with stirring. After replacing the carbon dioxide 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%
It is. This infrared absorption spectrum and NMR
The spectrum shows that a product containing both oxadiazinetrione and isocyanurate rings is obtained.

Reference example 5 194 g of 1,3-bis(isocyanatomethyl)cyclohexane and 11.8 g of 1,6-hexanediol
React at 80°C for 3 hours with stirring. later 30
Cool to ℃, add 0.8 g of triethylphosphine while passing carbon dioxide gas, and react for 6 hours. When the supply of carbon dioxide gas was stopped and the reaction was stopped by adding 0.6 g of ethyl bromoacetate, the NCO content of the product was 21.7%.
It is. The infrared absorption spectrum and
The NMR spectrum shows that a product with a urethane bond and an oxadiazinetrione ring is obtained.

Example 1 3 g of the isocyanate component having an oxadiazinetrione ring obtained in Reference Example 1 was added to 97% ethyl acetate.
g to obtain a primer solution.

The primer solution was applied with a brush to the adhesion surface of each of two nylon 6 films each having a thickness of 50 μm, and dried at room temperature. Between these coated surfaces,
A modified polyolefin hot-melt adhesive (Takemelt M-207, manufactured by Takeda Pharmaceutical Co., Ltd.) was sandwiched in a sandwich shape and bonded under contact pressure at 120° C. for 10 minutes.

When the 180° peel strength of the thus obtained adhesive test piece was measured according to the JISK6854 test method, it was found that 10
Above Kg/cm, the 6 nylon film itself was destroyed.

As a comparative example, an adhesive test piece was prepared in the same manner using a nylon 6 film not coated with the primer solution, and when the 180° peel strength was measured, only a value of 1.0 kgcm was obtained.

Furthermore, as a comparative example, instead of the isocyanate component of the above primer, TDI (Takenate 80,
A primer solution similar to the above was obtained using a primer solution (manufactured by Takeda Pharmaceutical Co., Ltd.). This primer solution was applied onto a 6-nylon film using the method described above to prepare an adhesive test piece. When its 180° peel strength was measured, a value of only 3.5 kg/cm was obtained.

Example 2 2 g of the diisocyanate component having an oxadiazinetrione ring obtained in Reference Example 3 was dissolved in 98 g of methyl ethyl ketone to obtain a primer solution.

The above primer solution was applied with a brush to the adhesive surface of each of two polyethylene terephthalate (hereinafter abbreviated as PET) films having a thickness of 50 μm, and was dried at room temperature. A modified polyolefin hot melt adhesive (Takemelt M
-203 (manufactured by Takeda Pharmaceutical Co., Ltd.) was sandwiched in the shape of a sandwich sandwich and adhered with contact pressure at 160°C for 3 minutes.

When the 180° peel strength of the thus obtained adhesive test piece was measured according to the JISK6854 test method, it was found to be 10.5
The value in kg/cm is shown.

As a comparative example, an adhesive test piece was prepared using the same procedure from a 50μ thick PET film without the above primer solution applied, and the 180° peel strength was measured, and a value of only 2.0 kg/cm was obtained. .

Example 3 2.5 g of the isocyanate component having an oxadiazinetrione ring obtained in Reference Example 4 was added to ethyl acetate.
A primer solution was obtained by dissolving 97.5g of the primer.

Apply the above primer solution with a brush to the adhesive surface of two 2.0 mm thick (width 25 mm, length 100 mm) polycarbonate adhesive test plates (manufactured by Japan Test Panel Industry Co., Ltd.) and dry at room temperature. I let it happen. A modified polyolefin hot melt adhesive (Takemelt M-207 Takeda Pharmaceutical Co., Ltd.) is placed between the coated surfaces.
A film of 50 μm thickness (manufactured by J.D. Co., Ltd.) was sandwiched in a sandwich shape and pressed at 120° C. for 3 minutes at a pressure of 8 kg/cm ² .

When the tensile shear adhesive strength of this adhesive test piece was measured according to the JIS K6850 test method, it showed a value of 45 kg/cm ² .

As a comparative example, an adhesive test piece was prepared in the same manner without applying the primer solution, and the tensile shear adhesive strength was measured, and the value was 20 Kg/cm ² .

Claims (1)

[Claims] 1 In the presence of tertiary phosphines, the reaction temperature -
1,3,5-oxadiazine-2, obtained by blowing carbon dioxide gas from an isocyanate compound at 70 to 150°C and reacting for 30 minutes to 10 hours.
A primer for thermoplastic polycondensation resin containing an isocyanate having a 4,6-trione ring.