JPH0139683B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to primer compositions, and more particularly to primer compositions that are effective in promoting the adhesion of polyolefin materials to adherends. Generally, polyolefins such as polyethylene and polypropylene are said to be difficult to bond materials. Conventionally, when bonding such difficult-to-bond materials, a method has been adopted in which the surface to be bonded is subjected to corona discharge treatment or acid treatment to modify the surface and then apply the adhesive, but this method requires a lot of labor and materials during the bonding process. Problems include increased costs. On the other hand, a method of achieving adhesive bonding by improving the adhesive strength of the adhesive after solidification has also been put into practical use. However, with this adhesive force method, there is a problem in durability in the case of a structure in which external stress is applied to the bonding interface, and the current situation is that the use of the structure is limited and the applications thereof are restricted. The inventors of the present invention have carried out extensive research in order to resolve these problems and ensure effective adhesion of polyolefin materials to ensure a range of applications.As a result, the inventors of the present invention applied a primer containing specific components to the adhesive surface in advance. It was discovered that the workability and cost increase would be alleviated compared to conventional surface modification treatment, and the adhesion of the adhesive would be dramatically improved, achieving the desired purpose. I've reached it. That is, the present invention comprises a chlorinated polymer, an amine compound having at least one alkoxysilyl group and at least one primary amino group and/or secondary amino group in one molecule, and at least one alkoxysilyl group in one molecule; The present invention provides a primer composition comprising a reaction product obtained by dehydrating a carbonyl compound having a carbonyl group and an organic solvent. Examples of the chlorinated polymer used in the present invention include chlorinated isoprene-based synthetic rubber, chlorinated homopolymers or copolymers of olefins (ethylene, propylene, etc.), and homopolymers of butadiene, styrene, etc. Alternatively, chlorinated copolymers may be mentioned, and one or two of these may be used.
A mixture of more than one species is ready for use. Usually chlorination rate
A chlorination ratio of 20 to 50% is preferred, and a chlorinated olefin homopolymer having a chlorination ratio of 20 to 40% is particularly effective. Such a chlorinated polymer suppresses the phenomenon of repelling on the adhered surface due to volatilization of the solvent after application of the primer, and functions as a primer film forming agent that is uniform over the entire surface. It may be selected within the range of ~20% by weight. In this range, application of the primer composition,
A uniform primer film can be formed after drying. The component used in the present invention is a reaction product obtained by dehydrating the above-mentioned amine compound and carbonyl compound. As the above amine compound, for example, the formula: [In the formula, R ¹ and R ² are the same or different alkyl groups having 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, and butyl), and R 3 is an alkyl group having 1 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms.
4 is a divalent hydrocarbon group (e.g. methylene, ethylene, propylene and butylene), Z is hydrogen or an aminoalkyl group having 1 to 4 carbon atoms (e.g. aminomethyl, aminoethyl, aminopropyl and aminobutyl), and m is 0, 1 or 2] (hereinafter referred to as compound []) are preferred, and specific examples include N-(β-aminoethyl)aminomethyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-
Aminopropyltriethoxysilane, N-(β-
(aminoethyl)-γ-aminopropylmethyldimethoxysilane and the like. Other preferred examples of the above amine compounds include:
Excess amount and formula of the above compound []: [In the formula, R ¹ , R ² , R ³ and m have the same meanings as above.
G is a glycidoxy group or an epoxycyclohexyl group] Examples include reaction products with epoxyalkylalkoxysilane compounds (hereinafter referred to as compounds []) shown in the following. This reaction may usually be carried out in a suitable organic solvent with heating and stirring at a ratio of 0.9 mol or less (preferably 0.1 to 0.6 mol) of compound [] to 1 mol of compound []. The above compound []
Specific examples include γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy Examples include silane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, and the like. On the other hand, examples of the carbonyl compound include acetaldehyde, propionaldehyde, n-
Aldehydes such as butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, benzaldehyde, cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, trimethylcyclohexanone, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketones, aliphatic ketones such as diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, and the formula: R ⁴ −CO−CH ₂ −CO−R ⁵ [] [wherein R ⁴ and R ⁵ are the same or different alkyl groups having 1 to 16 carbon atoms (e.g. methyl, ethyl, propyl, butyl, heptyl, hexyl,
octyl, nonyl, decyl, undecyl, hexadecyl, etc.), an aryl group having 6 to 12 carbon atoms (such as phenyl, tolyl, naphthyl, etc.), or an alkoxy group having 1 to 4 carbon atoms (such as methoxy, ethoxy, propoxy, and butoxy). Examples include β-dicarbonyl compounds (acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, methylethyl malonate, dibenzoylmethane, etc.). Among these, β- having an active methylene group
Dicarbonyl compounds [ ] are particularly preferred. The dehydration reaction between the amine compound and the carbonyl compound may be carried out in accordance with a conventional dehydration condensation reaction between an amine and an aldehyde or ketone, and is carried out, for example, in the presence of a water absorbing agent or while distilling off water under heating to reflux. More specifically, a carbonyl compound in a stoichiometrically equivalent or excessive amount of the amine compound (however, in the case of a β-dicarbonyl compound, one of the two carbonyl groups is reacted) is mixed with toluene, In a suitable organic solvent such as xylene or benzene, a water absorbing agent such as a molecular sieve or anhydrous magnesium sulfate is added, and the reaction is carried out at room temperature or under heating while stirring. The reaction product of the amine compound and the carbonyl compound resulting from this dehydration reaction can be used alone or as a mixture of two or more. Since the reaction products of these components are hydrolyzed by moisture in the air or humidity and moisture on the surface of the adherend, the alkoxysilyl group contributes to the adhesion promoting effect, and the primary amino group and/or secondary amino group It is thought that the group accelerates the curing reaction of the adhesive and further acts as a crosslinking agent. The amount to be blended may normally be selected within the range of 0.1 to 5% by weight, preferably 1.0 to 4% by weight, based on the total amount of the primer composition. As a result, the adhesion of the primer composition to the adherend and the compatibility with the adhesive become good, and the adhesion is efficiently improved. The organic solvent used in the present invention is as follows:
Any substance may be used as long as it does not become cloudy or precipitate relative to the ingredients, such as hydrocarbons (benzene, toluene, xylene, methylene chloride, perchloren, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) , ester systems (ethyl acetate, butyl acetate, isobutyl acetate, etc.), and ether systems (ethyl ether, tetrahydrofuran, dioxane, butyl cellosolve, etc.), and one or a mixture of two or more of these can be appropriately selected and used. Serve. The primer composition according to the present invention is prepared by blending the above-mentioned essential components in predetermined proportions and mixing them all at once, but appropriate amounts of ordinary components may be blended as necessary. For example, if a water absorbing agent such as molecular sieve is added at 1 to 5% by weight, it will suppress the hydrolysis reaction of the components.
It is advantageous in terms of stability as it does not change in quality during the standing period, and if dyes and pigments are added, it becomes easy to confirm whether it has been applied. The composition of the present invention having the above structure is applied to the surface of the adherend by a conventional method (for example, brush coating, spray coating).
A primer film is formed by drying at room temperature or at a temperature of 60 to 100°C.
The adherend material is not limited to polyolefin materials.
For example, various inorganic materials are also included. In addition, as the adhesive applied after the primer coating, any known adhesive may be used, but in particular, if a reaction-curable urethane resin adhesive, acrylic resin adhesive, or epoxy resin adhesive is used, The effect of increasing the adhesive force is noticeable. Hereinafter, the present invention will be described in more detail with reference to Production Examples and Examples (including examples for comparison). The manufacturing examples show the manufacturing of the components.
In the example sentences, "parts" means "parts by weight." Production Example 1 150 parts of dehydrated toluene, 22.2 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 15 parts of molecular sieve as a water absorbing agent were added to a reaction tank purged with dry nitrogen gas, and the mixture was heated to room temperature. Gradually add 20 parts of acetylacetone while stirring.
After the addition was completed, the reaction was continued for 4 hours at room temperature with stirring. After the reaction is completed, the water absorbing agent is removed by suction to obtain a reaction product toluene solution. This solution has an active ingredient content of 22%
and stored in a dry state. Production example 2 22.1 parts of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane
7.03 parts (molar ratio, 1:3) is added to 150 parts of dehydrated toluene, and the mixture is heated and reacted at 50° C. for several hours with stirring to obtain a mixture containing aminoalkoxysilane having unreacted amino groups and imino groups. 15 parts of molecular sieves are added to 179.13 parts of the above mixture, and 26 parts of ethyl acetoacetate is added dropwise thereto at room temperature while stirring. The mixture is stirred at room temperature for 6 hours to react, and a toluene solution of the reaction product is obtained. This solution has an active ingredient content of 25%. Production Examples 3 to 9 A toluene solution containing the components is obtained under the same conditions and operations as in Production Example 1 or 2, except that the amine compound and carbonyl compound in the numbers shown in Table 1 are used as the reaction components.

[Table] Examples 1 to 16 Chlorinated polypropylene (product name "Super Chron 803M" manufactured by Sanyo Kokusaku Pulp Co., Ltd., 30% toluene solution, chlorination rate 30%), reaction product toluene solution of Production Examples 1 to 9, and ethyl acetate The number of copies shown in Table 2 is accurately weighed into a sample bottle, and these are mixed all at once to prepare a primer composition. The primer compositions of each example were subjected to the adhesive strength test described below, and the measurement results are shown in Table 2. Incidentally, an example for comparison is shown in Example 10 in which no components are blended. Test method A polypropylene plate manufactured by Mitsui Petrochemicals (registered trademark "IP305") cut into 25 mm width x 100 mm length was used as the adherend, and after degreasing it with toluene, a primer composition was applied to the adhesive surface with a brush. and dry to form a primer film. Next, a shear test piece is prepared using a two-component urethane resin adhesive (trade name "Penguin Cement #920") manufactured by Sunstar Giken Co., Ltd. as an adhesive. After curing and curing the test piece at room temperature for 3 days,
Immediately (normal), immersed in water for 7 days (water resistant)
Or, after leaving it in an oven at 80° C. for 7 days and cooling it (heat resistant), the shear adhesive strength (Kg/cm ² ) is measured using an autograph.

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Claims (1)

[Scope of Claims] 1. A chlorinated polymer, an amine compound having at least one alkoxysilyl group and at least one primary amino group and/or secondary amino group in the molecule, and at least one alkoxysilyl group in the molecule; A primer composition comprising: a reaction product obtained by dehydrating a carbonyl compound having a carbonyl group; and an organic solvent. 2. The first component in which the amine compound in the component is an aminoalkylalkoxysilane compound.
Compositions as described in Section. 3. The composition according to item 1, wherein the amine compound in the component is a reaction product of an epoxyalkylalkoxysilane compound and an excess amount of an aminoalkylalkoxysilane compound. 4 The carbonyl compound in the above component is β
- The composition according to item 1 above, which is a dicarbonyl compound.