JPH07119256B2 - Method for producing hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is applied to various uses such as inks, adhesives, coating agents, paints, various types of primers such as polypropylene moldings, or fibers treating agents. The present invention relates to a method for producing a chlorinated ethylene-vinyl acetate-based copolymer used.

[Conventional technology]

Generally, ethylene-vinyl acetate copolymer (abbreviated as EVA) is chlorinated by uniformly dissolving it in an organic solvent such as carbon tetrachloride that is not itself chlorinated and chlorinated (in the present invention, Cl-EVA) is obtained.

As another method for obtaining Cl-EVA, there is an example in which chlorination is performed under UV irradiation in order to increase the reaction rate or to keep the reaction temperature of the entire system low. (Japanese Patent Publication Sho 58-2099
0, JP-A-48-4797, JP-B-47-46203) Cl-EVA obtained by chlorination in a non-aqueous system as described above is Cl-E containing a chlorine group or an acetoxy group in the polymer molecule.
Although it is VA, no hydroxyl group is contained in the Cl-EVA molecule.

At present, Cl-EVA is widely used for primers such as polypropylene resin molded products, paints, ink compositions, and fibers.

All of these uses result from good adhesion to nonpolar polymers such as polypropylene resins, excellent heat resistance, weather resistance, and chemical resistance.

[Problems to be Solved by the Invention]

As described above, Cl-EVA, which has excellent properties, has OH in the molecule.
Since it does not have a reactive functional group such as group, NH group, or COOH group, it is impossible to carry out a crosslinking reaction, and also for organic or inorganic substances such as pigments or fillers for inks or paints. There was a natural limit to affinity and dispersibility.

Therefore, conventional Cl-EVA has been improved in coating hardness and sprayability by blending with other resins such as aromatic petroleum resins.

However, since these are all mixed systems, when exposed to energy such as ultraviolet rays for a long period of time, the plasticizer and the like are released and the coating film becomes brittle, and eventually cracks are likely to occur and the surface protection function tends to be lost. The present invention focuses on the above-mentioned point, and Cl-EVA
By improving the affinity with other inorganic materials or organic materials by containing a hydroxyl group in the molecule, at the same time it has a reactive functional group, for example, by reacting with isocyanate high polyurethane-based Cl-EVA A new copolymer that allows the development of polymer materials that enable any design in molecular design. Cl containing a hydroxyl group in the molecule.
-The purpose is to provide a manufacturing method of EVA.

[Means for Solving the Problems]

The present invention is a method for producing a hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer by performing a saponification reaction simultaneously with chlorination reaction of EVA or the like in the presence of a chlorine-based organic solvent and water, and in the molecule thus obtained. A hydroxyl group characterized by using a chlorinated ethylene-vinyl acetate copolymer containing a hydroxyl group for an ink, an adhesive, a coating, a paint, a primer such as a polypropylene molding product, or a fiber treating agent. The present invention relates to a method for producing a chlorinated ethylene-vinyl acetate copolymer.

The EVA used in the present invention is a copolymer of ethylene and vinyl acetate, and has 95 to 5% by weight of ethylene component and 5 to 95% by weight of vinyl acetate component based on 100% by weight of EVA. The chlorine content of the obtained Cl-EVA was chlorinated to 5 to 50% by weight, and at the same time, the degree of saponification was saponified to 0.1 to 95% by weight.

The hydroxyl group-containing Cl-EVA of the present invention includes hydroxyl group-containing chlorinated ethylene-vinyl acetate, hydrolyzable ethylene-based polymers such as ethylene-vinyl acetate-terpolymer such as carbon monoxide copolymer, and partially saponified EVA. included. The content of vinyl acetate (or comonomer contained in the present invention) is set to 5 to 95% by weight as described above. When it is less than 5%, the property is close to that of polyethylene. Is less, it is difficult to achieve the object of the present invention, conversely, when the vinyl acetate content exceeds 95%, the property of polyvinyl acetate becomes stronger, and for example, the adhesion to polypropylene resin becomes poor. Become.

〔Example〕

 Next, the present invention will be described with reference to examples.

Example 1 For the OH group-containing Cl-EVA of the present invention, 75 g of the raw material EVA was used as a chlorine-resistant solvent such as carbon tetrachloride or a solvent such as perchlorene or trichlene.
After dissolving in 600 g, add 75 ml of water and blow chlorine gas evenly or non-uniformly until the chlorine content becomes 5 to 50% by weight, then chlorinate and remove residual unreacted chlorine with air or nitrogen. In order to vaporize it, blow steam of 0.5 to 5 kg / cm ² G to expel the solvent and then pelletize it with a desolventizer, or replace the chlorine-based solvent with a general-purpose solvent such as toluene or xylene to form a uniform solution can get. Further, the solvent is removed to obtain 103 g of the hydroxyl group-containing Cl-EVA of the present invention. The yield was 99% based on EVA.

The above chlorine-based reaction can be carried out at 80 to 150 ° C, preferably 90 to 120 ° C. If the temperature is too low, the chlorination reaction rate and the saponification reaction rate will decrease, while if the temperature is too high, the chlorination and saponification reaction rates will increase, and in some cases, once chlorinated. It is preferable to keep the temperature within the above-mentioned appropriate temperature range because the polymer causes dehydrochlorination due to local heating and becomes black.

Note that it is necessary to gradually blow chlorine gas and not to increase the amount of chlorine gas in order to avoid dehydrochlorination due to local heating.

The characteristics of the hydroxyl group-containing chlorinated ethylene acetic acid copolymer obtained by the method of the present invention are mainly due to the introduced hydroxyl group. The characteristics of Cl-EVA obtained in the absence of water and the hydroxyl group-containing Cl-EVA obtained by the above method of the present invention are compared below.

(1) Infrared absorption characteristic (IR) In FIG. 1, FIG. 3, FIG. 5 and FIG.
An IR chart of Cl-EVA (hereinafter referred to as a polymer of the present invention) is shown in FIGS. 2 and 4 in which a hydroxyl group-free Cl-EVA (conventional Cl-EVA) obtained by a conventional non-aqueous reaction is used. of
IR chart was shown.

From FIGS. 1, 3, 5, and 6, the polymers of the present invention show absorption of OH groups at 3200 to 3600 cm ⁻¹ .
On the other hand, no absorption of OH group is observed in the conventional comparative substance of Cl-EVA.

Further, in Table 1, the properties of the IR measurement sample were compared for the polymer of the present invention and the comparative substance, (conventional Cl-EVA).

Note to Table-1: 1) to 5) 1) The saponification method was used.

2) ▲ ▼ was obtained by a light scattering method, and ▲ ▼ was obtained by an osmotic pressure method.

3) Chloroform was used as a mobile phase, and measurement was performed by gel permeation chromatography (GPC). Column is Shodex GPC AC-80
4,803,802.5 (trade name) was used in combination. Calibration curves are standard polystyrene ▲ ▼ = 233,000, 92,600, 19,00
It was prepared using 0, 9,000, 2,100 and 800.

4) According to JIS K-6730, 0.2-0.5 g of chlorinated EVA was precisely weighed and dissolved in 100 ml of xylene, then 60 ml of 0.2N-NaOH methanol solution was added to completely hydrolyze the water layer / The oil layer is separated, 30 ml of 0.4N-HCl aqueous solution is added, and free acetic acid content is quantified.

5) A cast film was prepared by re-dissolving a polymer obtained by precipitating a polymer from a dilute triene solution of the polymer in a large amount of methanol, and then drying the polymer.

6) Melt flow rate The melt flow rate (MFR) of OH-containing Cl-EVA of the present invention is A
It was measured based on STM-D-1238-57T. The measurement results are shown in Table-1.

If the melt flow rate is 1 g / 10 minutes or less, the solubility in organic solvents will be poor, and if it is 500 g / 10 minutes or more, the molecular weight will be too small to be practically used as an adhesive or coating agent.

(2) Hydroxyl value As is clear from Table 1, the comparative substances (conventional Cl-EVA) all have a hydroxyl value of 0, whereas the polymer of the present invention has a hydroxyl value of 20.
It can be seen that it has a hydroxyl value of ˜72 KOH mg / g.

(3) Nuclear magnetic resonance (proton NMR) NM of the novel polymer of the present invention (Table-1 substance No. 4)
The R chart is shown in FIG. Polymers of the invention, Table-
The No. 1 and No. 3 NMR charts of No. 1 are basically the same as those of FIG. 7 except that the area ratio of each peak is different. The solvent is
CDCl ₃ was used and benzene was used as an internal standard.

(4) Solvent / Solubility Property The SP value of the solvent in the form of comparing the novel polymers 1 and 2 (Table 1) of the present invention with corresponding comparative substances (conventional Cl-EVA) (1) and (2) ( Solubility parameters) ([delta] h, [delta] p) are used for the results, and the results are shown in Tables 2 and 3 and FIGS. 8 to 11. (Measurement method) 50 mg of polymer (dry) and 1.0 g of solvent were sealed in an ampoule, allowed to swell overnight, and then left in an oil bath at 130 ° C for 1 hour, then 1 hour after reaching 100 ° C. , 1 at 25 ℃
Whether it was dissolved or insoluble at each temperature was judged based on the transparency of the ampoule liquid after being kept at a constant temperature of 10 ° C. for 1 hour using a refrigerator. It can be seen from FIGS. 8 to 10 that the polymer of the present invention has a slightly higher dissolution region of δp than the comparative substance (conventional Cl-EVA).

This is due to the effect of OH incorporated in the polymer. Polymers shown in FIG. 8, FIG. 9, FIG. 10, and FIG.
Solvent = 5 (weight) / 100 (weight).

[Effects of the Invention] The effects of the present invention are summarized as follows.

(I) The OH group-containing Cl-EVA of the present invention makes good use of the good resistance to dissolution due to the contained OH groups, and thus has a good affinity with, for example, automobile paints such as automobile bumper primers and inorganic pigments containing OH groups. It can be widely used for ink compositions, paints, various primers and fiber treatments, etc., which have excellent color development due to their properties.

(Ii) Adhesive Properties Table 4 shows the adhesive properties of the OH group-containing Cl-EVA of the present invention.

According to Table-4, the OH group-containing Cl-EVA of the present invention has an adhesion to OPP, O
It can be seen that the PP / OPP peel strength is superior to that of the conventional Cl-EVA used as a comparative substance.

(Method) Adhesion to OPP: Biaxially oriented polypropylene film (OPP)
(Thickness 60μ; manufactured by TOYOBO Co., Ltd.) was coated with a toluene solution of the polymer, and was forcibly dried with warm air at 80 ° C for 30 minutes, and then 1
Make a notch in the width of 0.5 cm for the air-dried coating film and peel it off 5 times with cellophane tape made by Nichiban Co., Ltd.
The number of times it has peeled off is displayed. This test is carried out on 5 wells and the average value is taken.

Peel strength: 130 ° C, 1Kg against the above dry coating film
After heat-sealing at / cm ² G for 1 second, the material was aged at room temperature for 1 hour, cut into a width of 0.9 cm, and the peel strength per 1 cm was determined.

[Brief description of drawings]

1, 3, 5, and 6 are IR charts of the novel polymer of the present invention, FIGS. 2 and 4 are IR charts of conventional Cl-EVA, and FIG. 7 is a novel chart of the present invention. The NMR chart of the polymer, FIG. 8 and FIG. 10 show the solubility of the novel polymer of the present invention. FIG. 9 and FIG.
It is a figure of (delta) p- (delta) h which shows the solubility of Cl-EVA.

Claims (3)

[Claims] 1. A hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer characterized in that an ethylene-vinyl acetate copolymer is subjected to a saponification reaction simultaneously with a chlorination reaction in the presence of a chlorine-based organic solvent and water. Manufacturing method. 2. An ethylene vinyl acetate-based copolymer having an ethylene component of 95 to 5 wt% and a vinyl acetate component of 5 to 95 wt% in the ethylene vinyl acetate-based copolymer is used. Hydrochloric acid-containing chlorinated ethylene described
A method for producing a vinyl acetate copolymer. 3. The hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer produced according to claim 1 for use in inks, adhesives, coating agents, paints, polypropylene, etc., or fibers. The method for producing a hydroxyl group-containing chlorinated ethylene-vinyl acetate copolymer according to claim 1, which is used as a treating agent.