JPS5929607B2 - Salt water-resistant olefin polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to olefin polymer compositions that exhibit excellent salt water resistance when laminated to metals.

BACKGROUND ART Conventionally, in order to protect the surface of water-conducting steel pipes and the like from corrosion, methods of coating the metal surface with a corrosion-resistant resin such as polyolefin have been studied. Polyolefins do not have polarity on their surfaces, so they cannot adhere firmly to metal surfaces.
It is not possible to apply a coating that can withstand practical use. In order to solve this drawback, measures have been taken to introduce polar groups, such as carboxyl groups or carboxylic acid anhydride groups, into the resin. By this measure, it is possible to achieve a strong adhesion of polyolefin to the metal surface, but the water peeling resistance, especially salt water peeling resistance, which is an even more important practical requirement, has been achieved to a sufficient level. do not. Therefore, in order to solve this drawback, a measure is often taken to apply a primer having affinity to both the metal and the polyolefin to the metal surface. This primer treatment results in an additional process, which leads to a decrease in productivity and an increase in product prices.

The inventors of the present invention have arrived at the present invention as a result of intensive studies aimed at creating an olefin polymer composition that exhibits sufficient salt water stripping resistance without applying any treatment such as a primer to the metal surface.

The first invention of the present invention is (a) a modified polyolefin grafted with a compound selected from (1) an olefin polymer fluoride, (11) an unsaturated aliphatic carboxylic acid or its derivative; 100 parts by weight of any hydrophilic olefin polymer selected from the group consisting of a composition of one or more of (1) to (110) and another olefin polymer, and ( b) A salt water-releasable olefin polymer composition comprising 0.1 to 5 parts by weight of a halogen-containing olefin polymer, and the second invention relates to (a) (1) an olefin polymer oxide; A modified polyolefin grafted with a compound selected from unsaturated aliphatic carboxylic acids or derivatives thereof, (Ii) a copolymer of an olefin and an acid compound, and Qv) 1 of (1) to (111) above.
100 parts by weight of any hydrophilic olefin polymer selected from the group consisting of the above and other olefin polymers, (b) 0.1 to 5 parts by weight of a halogen-containing olefin polymer, and (c). The present invention relates to a salt water strippable olefin polymer composition comprising 0.05 to 5 parts by weight of a divalent metal halogen-containing compound.

The hydrophilic olefin polymer as component (a) is, for example, an olefin polymer oxide obtained by contacting the (1) olefin polymer with oxygen or an oxygen-containing gas in an aqueous dispersion state, an organic solvent solution, or a molten state. ,
(;i) a modified polyolefin grafted with a compound selected from unsaturated aliphatic carboxylic acids or derivatives thereof (hereinafter referred to as acid compounds), (1j1) a copolymer with an olefinic acid compound, and ●ψ the above ( 1) or (1)
Any composition of one or more of 11) and another olefin polymer may be used.

In the case of (1) to (111), the oxidation is usually 0.5 to 150 to -KOH/9, preferably 5 to 140η-KOH/9 on the basis of monovalent carboxylic acid units.
9. It is preferably selected to be 0.5 to 30 η-KOH/9 based on units of dihydric carboxylic acid or its anhydride. Also(
In the case of v), the acid value of the composition is usually 2 x 10-3 to 15T9-KOH/9, preferably 0.5 to 1
The composition may be prepared so that it becomes 0Tf19-KOH/9.

In addition to the hydrophilic olefin polymer, the olefin polymer composition of the present invention contains a halogen-containing olefin polymer as an essential component, and compositions containing a halogen-containing divalent metal compound in addition to these are even more superior. It exhibits excellent salt water resistance and peelability.

To prepare the composition of the present invention, 100 parts by weight of the hydrophilic polymer and 0% of the halogen-containing olefinic polymer are usually added.
．． 1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, and optionally a halogen-containing compound of a divalent metal, usually 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight.
．． If 0 parts by weight is used, normal salt water peeling resistance can be sufficiently achieved.

In the present invention, the compound C (acid-based compound) selected from unsaturated aliphatic carboxylic acids or derivatives thereof that may be used to produce a hydrophilic olefin polymer refers to free acids, their acid anhydrides, and acid halides. , acid amides, imides, partial esters and salts, and partial hydrolysates thereof, and these may coexist within the same molecule.

For example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, mexaconic acid, citraconic acid, itaconic acid, 3-cyclohexenecarboxylic acid, 4-cyclohexenedicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, maleoyl Examples include chloride, maleimide, monomethyl maleate, sodium acrylate, calcium acrylate, zinc acrylate, potassium methacrylate, calcium methacrylate, zinc methacrylate, dipotassium maleate, zinc maleate, and partial hydrolysates thereof. In the present invention, the olefin polymers include ethylene, propylene, 1-butene, 4-methyl-1-benzene, 1-
Homopolymers and copolymers of 1-olefins, usually containing 2 to 10 carbon atoms, such as hexene, 1-octene, 1-decene, etc., such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl- 1-benzene, ethylene-propylene copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer, ethylene-4-methyl-1-benzene copolymer, 4-methyl-
1-benzene-1-decene copolymers, copolymers of the above-mentioned 1-olefins and small amounts of diolefins, such as ethylene-butadiene copolymers and propylene-butadiene copolymers alone, and their various homopolymers and The composition is a combination of two or more selected from various copolymers, and may be crystalline or amorphous.

Wax-like materials are not suitable for adhesion evaluation based on tensile strength, but sufficient effects are recognized by other evaluation methods. In these crystalline polyolefins, polyethylene has an intrinsic viscosity (g) of a decalin solution at 135°C, usually 0.5 to 5.0, preferably 0.7 to 3.0, an X-ray crystallinity of 60 to 85%, and a density of 0. .90 to 0.979
/Mll is preferably 0.92 to 0.969/ml.

This polyethylene may be a copolymer containing 1-olefin units such as propylene units, 1-butene units, butazinine units, etc. in addition to ethylene units. limited Polypropylene is a fucarin solution at 135° C. (g) Usually 0.5 to 10, preferably 1.0 to 4.0, X-ray crystallinity usually 50 to 60%, density 0.90 to 0.929/
ml, and for copolymers with ethylene, the ethylene unit content is usually 8m01% or less.

Halogen-containing olefin polymers, particularly useful chlorine-containing olefin polymers include, for example, chlorine-containing polyethylene, chlorine-containing polypropylene, chlorine-containing polymers of ethylene-propylene, chlorine-containing copolymers of ethylene-1-butene, and ethylene propylene. Chlorine-containing copolymers of one non-conjugated diene, such as chlorine-containing copolymers of ethylene-propylene-dicyclopentazine, ethylene-propylene-
Various chlorine-containing polymers can be mentioned, such as a chlorine-containing copolymer of ethylidenenorbornene and a chlorine-containing copolymer of ethylene-propylene-1,5-hexadiene.

These chlorine-containing polymers may be a composition of two or more types. Further, the method of introducing chlorine atoms may be any of the following methods: chlorinating the polymer, grafting vinyl chloride or the like onto the polymer, or polymerizing using a chlorine-containing monomer. The range of various polymers will be explained next. Examples of the chlorine-containing polyethylene include those having a chlorine content of usually 10 wt% or more, preferably 30 to 70 wt%.
The chlorination method may be an aqueous suspension method or an organic solvent dissolution method. As such chlorine-containing polyethylene, Osaka Soda (
Examples include Daisolak 8 manufactured by Daiso Corporation, Elasuren (trademark) manufactured by Showa Denko K.K., and Superchron (trademark) manufactured by Sanyo Kokusaku Pulp Co., Ltd. The chlorine-containing polypropylene usually has a chlorine content of 10 wt% or more, preferably 25 wt% or more.
Or 70wt? I can list the following.

The chlorination method may be an aqueous suspension method or an organic solvent dissolution method.
As the raw material polypropylene, any polypropylene from amorphous to highly crystalline can be used, but polypropylene with low crystallinity is preferred. Examples of such chlorine-containing polypropylene include Hardren (trademark) manufactured by Toyo Kasei Kogyo Co., Ltd. and Superclone (trademark) manufactured by Sanyo Kokusaku Pulp Co., Ltd. The term chlorine-containing compounds of divalent metals is a comprehensive concept, and includes not only dichlorides but also their hydrates, oxychlorides, complexes and complexes of chlorides and hydroxides, and their hydrates. , complexes of chlorides and oxides, their hydrates, double chlorides, complex chlorides, and their hydrates, and other compounds containing a bond between a divalent metal and chlorine.

Preferred are dichlorides and their hydrates. The mechanism by which these chlorine compounds contribute to improving salt water peeling resistance is not clear, but when they are blended with components (a) and (b) and melt-molded, they generate components such as hydrogen chloride. It is assumed that a suitable treatment is applied to the metal surface.

A metal-resin laminate for evaluating the adhesive strength (measured as peel strength) and salt water resistance (measured as salt water peel width) of the laminate of the polyolefin composition of the present invention and metal is prepared as follows.

Metal plate (140 dragon x 1) with the standards and treatments described below
40mm x 1m0 was placed on the hot plate of a compression molding machine set at 200℃, approximately 289 resin was spread almost horizontally on the metal plate and preheated for 5 minutes to melt the resin, and then the pressure was 40k9. / ~ Press at G for 5 minutes and place about 1 on the metal plate.
A laminate in which a mm-thick resin layer is press-bonded is obtained. The peel strength measurement and salt water peel test of the obtained laminate are carried out as follows.

Peel strength measurement: A sample with a width of 20 mm was cut from the laminate of the steel plate (1 m 71 L thick) and a hydrophilic polyethylene layer (approximately 1 mm thick) prepared by the above method, and a peel angle of 18 mm was cut in an atmosphere of 23°C.
00, peel strength (K9/CTL
) to measure.

A sample with a width of 2071 cm was cut from the original laminate for measuring peel strength in salt water peel test.
A sample of tm was cut out, immersed in saline solution with a concentration of 3 wt%, and left at a temperature of 60°C for a predetermined time while stirring the saline solution at 1000 rpm. Salt water peeling rate (M77!/day, hereinafter abbreviated as PR).

) to evaluate. The immersion test was not continuous immersion, but a total of 8 cycles, each cycle consisting of 8 hours of immersion followed by 16 hours of standing in the air. This test is considered more severe than continuous immersion. It is a type of accelerated test in that it involves changes in temperature, changes in moisture content, changes in oxygen concentration, etc. Example 1 Hydrophilic polyethylene (acid value 0.7, density 0.969/M
2, MIlO9/10min) A composition was prepared by blending each part by weight of chlorinated polyethylene or chlorinated polypropylene listed in Table 1 to 100 parts by weight.
No. 89 was laminated on a steel plate (JIS G3l4, hub polished, degreased with xylene-acetone, 140 mL x 140 mm x 1 m) according to the above-mentioned laminate preparation method, and a specimen was cut out using the same method.

This sample was subjected to the above test to measure initial peel strength (PSO) and salt water peel rate (PR).

The results are shown in Table 1. Control Example 1 The same procedure as in Example 1 was carried out without blending chlorinated polyethylene or chlorinated polypropylene. As a result, the initial peel strength was 4.4 k9/Cml, and the salt water peel rate (PR) was 3071.
tm/day, it was found to be unusable.

The results are also shown in Table 1. Example 2 Hydrophilic polyethylene (acid value 0.7, density 0.969/M
2. MllO9/107! U7t) 100 parts by weight in Table 2
A composition was prepared by adding 0.05 part by weight of the metal chloride described above and 0.5 part by weight of chlorinated polyethylene or chlorinated polypropylene, and the rest was carried out in the same manner as in Example 1. The results are shown in Table 2.

It can be seen from the table that there is a significant synergistic effect between the metal chloride and the chlorinated polyolefin.

Claims (1)

[Scope of Claims] 1 (a) A modified polyolefin grafted with a compound selected from (i) an olefin polymer oxide, (ii) an unsaturated aliphatic carboxylic acid or a derivative thereof, (iii)
a copolymer of an olefin and an acid compound, and (iv)
100 parts by weight of any hydrophilic olefin polymer selected from the group consisting of a composition of one or more of the above (i) to (iii) and another olefin polymer, and (b) 0.0 parts by weight of a halogen-containing olefin polymer. A salt water strippable olefin polymer composition comprising 1 to 5 parts by weight. 2 (a) (i) Olefin polymer oxide, (ii) modified polyolefin grafted with a compound selected from unsaturated aliphatic carboxylic acids or derivatives thereof, (iii)
a copolymer of an olefin and an acid compound, and (iv)
100 parts by weight of any hydrophilic olefin polymer selected from the group consisting of a composition of one or more of the above (i) to (iii) and another olefin polymer, (b) 0.0 parts by weight of a halogen-containing olefin polymer. 1 to 5 parts by weight and (c
) A salt water strippable olefin polymer composition comprising 0.05 to 5 parts by weight of a divalent metal halogen-containing compound.