JPS6017306B2 - Vinylidene chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinylidene chloride drum resin composition that has excellent heat resistance, light resistance, and gas barrier properties, and has extremely low amounts of substances that migrate to the contents, and is suitable for producing transparent molded products. It is something.

Originally, vinylidene chloride polymer exhibits a highly crystalline state due to the regularity and symmetry of its structure, and has such strong cohesive force that almost no solvent can be found to dissolve it.

For this reason, it has a high melting temperature, and in addition, because of its chemical properties that make it easy to dehydrochloride, it must be said that it is virtually impossible to ripen vinylidene chloride polymer as it is because it suffers from severe thermal deterioration. Today, vinylidene chloride-based resin molded products manufactured industrially are made by copolymerizing small amounts of monomers such as vinyl chloride with the aim of partially disrupting the regularity of the polymer structure. A commonly used method is to add additives such as additives and heat stabilizers.
Adding a plasticizer to vinylidene chloride resin not only improves processing properties, but also increases the flexibility and flexibility of the resulting molded product.
This can be said to be an extremely effective method in terms of imparting flexibility and flexibility and improving impact resistance.

On the other hand, the use of additives such as plasticizers that are liquid at the temperature at which the molded product is used or stored tends to deteriorate the gas barrier properties, which are an excellent feature of vinylidene chloride resin molded products. Therefore, although the amount of plasticizer used is kept to the minimum required amount depending on the purpose and application, the gas barrier function is still unavoidable, and the current Pinichloride-based resin molded products It is difficult to say that the resin fully exhibits its excellent properties. In order to compensate for this drawback, attempts have been made to add rubbery substances such as butadiene copolymers and ethylene-vinyl acetate copolymers to vinylidene chloride resins in place of plasticizers or part of them. However, these copolymers do not have as much plasticizing ability as plasticizers, and when used as a substitute for plasticizers or as a supplement to plasticizers, they must be used in large quantities. need to be added. However, these rubbery substances do not have as good compatibility with vinylidene chloride resins as plasticizers do, and if they are mixed in large amounts, the transparency of the molded product will be impaired. More specifically, although the use of butadiene copolymers improves the impact resistance of molded products, butadiene copolymers have poor melt flowability at the molding temperature of pinylidene chloride resins. Not only does it have poor plasticizing ability, but the double bonds inside it are damaged, causing significant photodeterioration of the molded product and extremely reducing its commercial value. The use of ethylene-vinyl acetate copolymer poses no problems as far as light resistance is concerned, but copolymers with a large ethylene ratio are not compatible with vinylidene chloride-based resins, and in extreme cases , phase separation with vinylidene chloride may also occur. When the proportion of pinyl acetate in the ethylene-vinyl acetate copolymer increases to about 4% by weight, the compatibility with vinylidene chloride resin is improved, but even so, vinylidene chloride resin molded products containing it are improved. When oily foods and watery foods are packaged and heat-treated,
The molded product becomes devitrified, and as a result, it suffers from severe disadvantages, such as being restricted in its field of use. Moreover, its impact strength is 4.0 mm lower than that of those containing ethylene-vinyl acetate copolymers with a high ethylene ratio. Another improvement means is to use an ethylene-vinyl ester-vinyl chloride terpolymer (Japanese Patent Publication No. 47-1166
No. 3). This terpolymer is used in place of a plasticizer or a part thereof to provide a vinylidene chloride resin composition for molding that has excellent transparency, gas barrier properties, impact resistance, and non-extractability. That is. In fact, the vinylidene chloride resin composition containing this terpolymer almost satisfied the above four qualities; however,
The obtained molded product lacks photostability and heat resistance, and exhibits a blackish color tone. The present invention provides a vinylidene chloride resin composition for molding that has extremely excellent gas barrier properties and excellent heat resistance and light resistance without losing transparency, which is a desirable property of vinylidene chloride resins. The present inventor has discovered that a composition obtained by adding a chlorinated ethylene-vinyl ester copolymer to a pinylidene chloride resin is suitable for this purpose. Ta.

Chlorinated ethylene-vinyl ester copolymers are known to be useful as modifiers for adhesives containing polyamides and chlorinated ethylene-vinyl ester copolymers (US Pat. No. 3,464,94).

According to Japanese Patent Publication No. 42-16420, it is also known to be useful as a reinforcing agent for improving the impact resistance of hard vinyl chloride resins. The fact that the chlorinated ethylene-vinyl ester copolymer can improve various properties of vinylidene chloride resins, which are essentially different from these polymers or resins in terms of chemical and physical properties, is that This is completely unexpected. Furthermore, this is completely surprising considering the fact that ethylene-vinyl ester-vinyl chloride copolymers containing chlorine atoms in the polymer molecule are insufficient for improving vinylidene chloride resins. According to the present invention, parts by weight of a vinylidene chloride resin 10 made of a copolymer of 75 to 95% by weight of vinylidene chloride and 26 to 5% by weight of a polymerizable monomer; Pinyl ester content is 10 to 4% by weight (based on non-chlorinated copolymer)
3 to 6 parts by weight of a chlorinated ethylene-pinylester copolymer having a chlorine content of 3 to 55% by weight (based on the chlorinated copolymer); Provided is a vinylidene chloride resin composition comprising:

The chlorinated ethylene-vinyl ester copolymer used in the present invention is obtained by chlorinating an ethylene-vinyl ester copolymer by a conventional method.

The ethylene-vinyl ester copolymer referred to in the present invention is
It refers to a copolymer of ethylene and vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, or a mixture of these pinylesters, and ethylene-vinyl acetate copolymer is particularly preferred because it can be obtained at low cost.

Depending on the vinyl ester content in the ethylene-vinyl ester copolymer, the copolymer's thermal stability, melt viscosity, or compatibility with the vinylidene chloride resin composition differs, but the copolymer can be used in the present invention. The ethylene-vinyl ester copolymer preferably contains vinyl ester in an amount of 1% by weight or more and 4% by weight or less.

When the vinyl ester content is 1% by weight, the compatibility with the vinylidene chloride resin is improved by chlorination, but it is not sufficient and it is impossible to obtain a transparent molded product within a practical range. An ethylene-vinyl ester copolymer containing more than 4% by weight of vinyl ester has some stickiness in itself, and if left for a long time, a phenomenon of mutual blocking is observed. If it is chlorinated, the stickiness will be further promoted,
It becomes extremely difficult to handle it, and when it is mixed with vinylidene chloride resin, it must be mixed in the form of a solution, which limits the means available and unavoidable drawbacks include increased costs. The ethylene-vinyl ester copolymer used in the present invention has a melt index (melt index: AS) of usually 0.1 to 1000, preferably 1 to 500.
TMD-1238). The chlorine content of chlorinated ethylene-vinyl ester copolymer is 3
~55% by weight is suitable. Chlorinated ethylene-vinyl ester copolymers with a chlorine content of more than 55% by weight have high rigidity, lose plasticizing ability, and are susceptible to thermal decomposition, so they cannot be mixed with vinylidene chloride resin and molded. This becomes difficult unless a considerable amount of plasticizer is used in combination. On the other hand, a slight effect is observed even with a chlorine content of 3% by weight;
Considering the cost required for chlorination, less than 3% by weight is not very practical. Furthermore, according to the present invention, in order to provide excellent transparency to a transparent molded article, it is found that it is preferable to satisfy the following formula, where the pinyester content is X% by weight and the chlorine content is Y% by weight. Issued: -0
．． 7×131SYS-X+80 (1) The chlorinated ethylene-vinyl ester copolymer used in the present invention has a structure essentially different from that of the ethylene-vinyl ester-vinyl chloride terpolymer. was confirmed.

Figure 1 shows the NMR spectrum of an example of chlorinated ethylene-vinyl acetate copolymer (Example 11), and Figure 2 shows the
NM of ethylene-vinyl acetate-vinyl chloride terpolymer
The R spectrum is shown. In FIG. 2, there is a strong absorption by the proton of the methylene group of the vinyl chloride repeating unit at the 6=1.8 position, whereas in FIG. 1, the absorption near the same position is much smaller. The reason why the chlorinated ethylene-vinyl ester copolymer provides improvements that cannot be obtained with the ethylene-vinyl ester-vinyl chloride copolymer is thought to be due to the structural differences between the two copolymers. It will be done. That is, when an ethylene-vinyl ester-pinyl chloride terpolymer is obtained, for example, by radical copolymerization, the composition of the resulting polymer is determined by the abundance ratio of each monomer at the moment of polymerization and the amount of each monomer. Since it is determined by the reactivity ratio between monomers, even in the case of ethylene-vinyl ester-vinyl chloride terpolymer, each monomer has a distribution along the polymer main chain that conforms to statistical rules. However, the distribution contains consecutive head-to-tail bonds of vinyl chloride with a high probability. If dehydrochlorination occurs at the end of this vinyl chloride chain part due to heat or light, the dehydrochloride will propagate one after another to the adjacent saddle parts starting from that point. It is thought that a so-called zipper reaction occurs, and the generated polyene structure becomes the source of color development of the resin. On the other hand, the chlorinated ethylene-vinyl ester copolymer referred to in the present invention is a post-chlorinated ethylene-vinyl ester copolymer, so hydrogen and hydrogen are added to random positions in the copolymer. Chlorine is distributed in a substituted form. Therefore, there are few structures in which vinyl chloride is continuous in the polymer chain of the chlorinated copolymer, and this means that the vinylidene chloride resin composition to which the chlorinated ethylene vinyl ester copolymer is added is This may be the reason for the more stable behavior towards light. The term "pinylidene chloride resin" as used in the present invention refers to a copolymer of vinylidene chloride and other copolymer monomers whose main component is vinylidene chloride. Contains ~9% Pini IJden chloride.

These usually contain 60 to 95 parts by weight of vinyl chloride IJden and 4
It can be produced by copolymerizing 0 to 5 parts by weight of other polymer monomers by a conventional method. Other polymer monomers mentioned here include, for example, pinyl chloride or acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate. , or methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate,
methacrylic acid esters such as stearyl methacrylate, or unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or maleic acid monoesters such as monomethyl maleate, monobutyl maleate, or acrylic acid amides; Acrylonitrile, methacrylonitrile, styrene, orthomethylstyrene, ethylene, fluoride.

Lopyrene, isobutylene, butadiene, divinylbenzene, 1,4-dibutylene glycol dimethacrylate,
Alternatively, vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, and higher alkyl vinyl ethers such as pinylate laurate and vinyl stearate may be mentioned. Two or more kinds of these polymerizable monomers may be used. Furthermore, polymerization by a normal method here refers to suspension polymerization, emulsion polymerization, solution polymerization, etc.
Any method generally used for the polymerization of vinylidene chloride may be used, or a method in which monomer groups or specific monomers are added stepwise or continuously during the polymerization. It's okay.

The degree of polymerization of the obtained copolymer is 0.5 to 2.0 as measured by an Ubbelod viscometer. &． p. s. Preferably 0.8-1
．． &． p. s. (in 2% o-dichlorobenzene, 120
℃). Vinyl chloride resins and vinylidene chloride resins are completely different types.

Therefore, it is an important requirement that the vinyl chloride resin of the present invention contains at least 75% by weight of vinylidene chloride. Even in a copolymer of vinylidene chloride and vinyl chloride, the crystalline state of the polymer differs depending on its composition ratio, and therefore its properties, such as compatibility with solvents and rheological properties, change as the composition ratio changes. Onaka changes. The following is known about the relationship between composition ratio and crystal structure. The crystal form of a copolymer with a vinylidene chloride mole fraction of 0.560 or more is the same as that of a vinylidene chloride polymer, and the crystal form of a copolymer with a vinylidene chloride mole fraction of 0.145 or less is: It is the same as that of vinyl chloride polymer. Copolymers with compositions in between have no crystalline structure. Also,
In a copolymer having a vinylidene chloride mole fraction of 0.560 or more, the degree of crystallinity decreases as the vinylidene chloride mole fraction decreases. (J.POLYMERSCI.
, A2 1749 (1964)) Furthermore, unlike vinylidene chloride polymers, vinyl chloride polymers are not symmetrically attached to chlorine on the main chain, and the movement of the polymer segments is restricted, making it difficult to use them industrially. The atactic vinyl chloride polymers used do not form crystals. Due to this difference in crystallinity, not only do they not interact with each other, but their behavior with solvents and plasticizers is also different.
It is 0. The difference in composition between vinylidene chloride and vinyl chloride, and the resulting difference in crystalline state, also makes a difference in the gas barrier building.

These differences have been discussed in detail in the literature [for example, "Vinychloride Redenta Resin" by Toyohisa Sonoda (Nikkan Kogyo Shimbun)
; PolymerPreprint 8, p. 137,
1967 etc.] The mixing ratio of the chlorinated ethylene-vinyl ester copolymer to the vinylidene chloride resin is:
A suitable amount is 3 to 60 parts by weight per 10 parts by weight of the pinylidene chloride resin. When the amount of the chlorinated ethylene-vinyl ester copolymer used exceeds 6 parts by weight, the resulting molded article has a decreased tensile strength, and handling at high temperatures is particularly problematic. In addition, if the amount of chlorinated ethylene-pinylester copolymer used is less than 3 parts by weight, it will be necessary to use a considerable amount of plasticizer from the viewpoint of processability and molded product quality. , the gas barrier properties of the molded product will not be much different from those of ordinary molded products, and the characteristics of the present invention will be lost. o To mix the chlorinated ethylene-vinyl ester copolymer with the pinylidene chloride resin, mix the chlorinated ethylene-vinyl ester copolymer in pellet or powder form, or use its solvent. There is a method of mixing by adding and then removing the solvent, but another method is to dissolve the chlorinated ethylene-vinylester copolymer in pinylidene chloride monomer and other polymerizable monomers, One method may be to subsequently polymerize the vinylidene chloride copolymer and the chlorinated ethylene-vinyl ester copolymer to uniformly disperse them.

Depending on the application, it is possible to mix and use additives such as plasticizers, heat stabilizers, light stabilizers, and thickeners, but the composition and molded products thereof with excellent gas barrier properties, which are the characteristics of the present invention, can be used in combination. In view of the purpose of obtaining the desired product, the total amount of these additions is preferably 1 part by weight or less per 100 parts by weight of the vinylidene chloride resin and 3 to 6 parts by weight of the chlorinated ethylene-pinylester copolymer.

The resin composition of the present invention can be used for films, sheets, tubes,
It is particularly suitable for manufacturing transparent molded products of various shapes such as bottles.

One of its advantages is that it provides excellent gas barrier properties, making it possible to produce molded articles that are extremely useful as packaging materials for various substances. Another advantage is that the superior moldability allows the amount of additives such as plasticizers to be reduced, thereby reducing the migration of these additives into the packaged contents. Furthermore, in order to have excellent heat resistance and light resistance, the composition of the present invention contains a large amount of heat stabilizer and light stabilizer as in the case of the conventional composition of ethylene-vinyl ester-vinyl chloride and vinylidene chloride resin. etc. is not required. Addition of heat stabilizers such as epoxidized vegetable oil reduces gas barrier properties, and addition of triazole-based, benzophene-based, or salicylic acid-based light stabilizers is preferred from food hygiene standpoints when applied to food packaging. do not have. Furthermore, molded articles produced from the compositions of the present invention have excellent color tone. FIG. 3 shows the relationship between brightness and oxygen permeability coefficient by comparing the composition of the present invention and a conventional composition of ethylene-vinyl ester-vinyl chloride and vinylidene chloride resin. This clearly shows that the composition of the present invention has an excellent gas barrier effect. Hereinafter, the present invention will be explained in more detail with reference to Examples.

Note that parts and % in Examples and Comparative Examples represent parts by weight and % by weight, respectively. Example 1 78 parts of vinylidene chloride, 22 parts of vinyl chloride, 2
0.5 part of acetyl tributyl citrate solution in which 0% diisopropyl peroxydicarbonate was dissolved was mixed and suspension polymerization was carried out by a conventional method to obtain a pinylidene chloride copolymer.

The pinylidene chloride content is 88.2% and the viscosity is 1.0
$. p. s. (2% o-dichlorobenzene solution, 120
oo). A separable four-necked glass flask with a capacity of 2 is equipped with a cooling device and a cooling tube, and E1 is placed inside it.
vax40 (ethylene monovinyl acetate copolymer manufactured by DuPont, vinyl acetate amount 40%) 100 ml, azobisisobutyronitrile 29 ml, carbon tetrachloride 700 ml, 75 ml
The mixture was uniformly dissolved while raising the temperature to

After reaching 75°C, chlorine gas was continuously blown into the reactor, and the reaction was carried out at that temperature for 4 hours.

Heating and blowing of chlorine gas were stopped, and nitrogen gas was bubbled in to create dissolved chlorine. As a result of chlorine analysis, the chlorine content of chlorinated E1vax40 after removing the solvent was 3.9.
%Met. 100 g of this chlorinated product was dissolved in chloroform, mixed with vinylidene chloride copolymer lk9, and then the chloroform was removed by evaporation. This composition,
An unstretched parison and a blown film were obtained by extrusion using a conventional method using a screw extruder having a die diameter of 1.5 inches and L/D=12. Comparative Example 1 For a part of the vinylidene chloride copolymer obtained in Example 1,
The following plasticizers were mixed to give a final composition of 3.0% tributyl citrate, 3.5% dibutyl sebatate, and 1.7% epoxidized soybean oil.

This composition was extruded in the same manner as in Example 1 to obtain an unstretched parison and a blown film. Example 2 Example 1, except that lauroyl peroxide 2 was used instead of azobisisobutyronitrile 2.
Chlorination was carried out in exactly the same manner.

The chlorine content of the obtained chlorinated E1vax40 was 7.7%
Met. This chlorinated product 1002 and the chlorinated vinylidene copolymer lk9 of Example 1 were mixed in the same manner as in Example 1 to obtain a stretched parison and a blown film.

Example 3 Using the same reaction apparatus as Example 1, temperature 750q○, E1
In the evening, chlorine gas was continuously blown into a homogeneous solution of 700% carbon tetrachloride for 2 hours to cause a chlorination reaction.

And all the while, photographic lighting (Toshiba Photo Reflector Lamp Daylight Color Flood 100V50
0W) was irradiated from outside the reaction vessel. Obtained E1va
The chlorine content of the x4 enriched product was 15.6%.

100 kg of this chlorinated product and 1 kg of the vinylidene chloride copolymer of Example 1 were mixed in the same manner as in Example 1 to obtain an unstretched parison and a blown film.

Example 4 E1vax4 was irradiated with light using the same method and under the same conditions as Example 3.
0300 evening, carbon tetrachloride 1500 chlorine gas was given to me 2 times in a row.
In addition to this, 2 tons of lauroyl peroxide was added before the start of the reaction, 7 hours after the start of the reaction, and 1 hour after the start of the reaction, for a total of 6 tons.

The chlorine content of the obtained chlorinated product was 27.0%.

100 g of this chlorinated product and the vinylidene chloride copolymer lk9 of Example 1 were mixed in the same manner as in Example 1 to obtain an unstretched parison and a blown film. Comparative Example 2 E1vax40100 was dissolved in chloroform and mixed with the vinylidene chloride copolymer lk9 of Example 1.

After removing chloroform, an unstretched parison and a blown film were obtained in the same manner as in Example 1. Comparative Example 3 Under light irradiation as in Example 4, E1vax
40,100 pm, carbon tetrachloride 1,500', temperature 75°C
Chlorine gas was blown in for 100 hours.

However, 28 tons of lauroyl peroxide was added before the start of the reaction and twice every 7 hours after the start of the reaction, for a total of 14 times. The chlorine content of the obtained chlorinated product was 44.5%.
Met.

As in Example 1, 100 g of the chlorinated compound was dissolved in chloroform and mixed with the pinylidene chloride copolymer lk9 of Example 1, and after removing the chloroform, an unstretched parison and a blown film were obtained. Comparative Example 4 Chlorination was carried out in the same manner as in Example 1 except that azobisisobutyronitrile 2 was not used.

The chlorine content of the enriched E1vax4 obtained was 2.8
%Met.

In the same manner as in Example 1, 100 g of the chlorinated compound was dissolved in chloroform and mixed with the vinylidene chloride copolymer lk9 of Example 1, and after removing the chloroform, an unstretched parison and a blown film were obtained.

Example 5 E1vax40300 was dissolved in carbon tetrachloride 1500, and chlorine gas was blown into the solution at 75q0 for 1 hour.

The chlorine content of the obtained chlorinated product was 10.5%.
Dissolve 200 parts of this E1vax40 chloride in vinylidene chloride, divide it into 100 parts each into two glass ampoules, and add 78 parts of vinylidene chloride, 22 parts of pinyl chloride, and 0.1 part of diisopropyl peroxydicarbonate. , acetyltributyl citrate 0.4 part, hydroxypropyl methylcellulose 0.4 part, water 14 Ikarigun, E1v
I prepared two bottles of ax40 chloride 2 anchors.

These were fed for 4 hours at 37o0 in the first stage, and at 483 in the second stage.
Polymerization was carried out at 0 for 2 anchor hours, for a total of 6 anchor hours. 2 pieces total 10
A composition of 45 days was obtained.

An unstretched parison and a blown film were obtained from this composition in the same manner as in Example 1.

Regarding the unstretched parisons and blown films obtained in Comparative Examples 1 to 4 and Examples 1 to 5 above, the rigidity,
The amount of n-hebutane extracted and the oxygen permeability coefficient were measured, and the color tone and transparency were evaluated.

The results are summarized in Table 1. Table 1 Notes: 1) Chlorine content of 1vax40 chloride per day
Based on NGER's oxygen flask combustion method.

2) By a method according to ASTM DI043-51,
Measured at 20℃, the sample shape is as follows: Length
36 Inside the desk 10 Thickness 0.50-0.85 Pig shape factor
53) The volume ratio of n-hebutane to film is 400
Extraction was carried out at 60° C. for 30 minutes, and the weight of the film after drying was measured and expressed as a weight loss rate relative to the weight before extraction.

4) Modern Ontrol, Inc. Manufactured by O
Regarding the rigidity, which was measured using an XTRANIOO type oxygen permeability measuring device according to the method described in the instruction manual at a measurement temperature of 20°C, all of the examples were better than Comparative Example 2, Comparative Example 3, or Comparative Example 4. It can be said that it is small and almost equivalent to Comparative Example 1.

In other words, in order to obtain a flexible molded product that is equal to or more flexible than ordinary molded products, a chlorinated copolymer with a degree of chlorination within a certain range is required. next,
Regarding the amount of n-hebutane extracted, except for Comparative Example 1, no liquid additives such as plasticizers were added, so the extracted amount was extremely small in all cases other than Comparative Example.

Regarding the oxygen permeability coefficient, for the same reason as the amount of n-heptane extracted, the other samples had better oxygen barrier properties than Comparative Example 1. Regarding the transparency of the film, Comparative Example 3 is also good, but in the case of Comparative Example 3, the above-mentioned rigidity is 4, which is not preferable. Example 6 A series of experiments were conducted using various chlorinated ethylene-vinyl acetate copolymers with vinyl acetate and chlorine contents.

Chlorination was performed using one of the following methods. Method A: Using the same reactor as in Example 1, add 150 qo of ethylene monovinyl acetate copolymer and 1000 qo of carbon tetrachloride, heat to 50 qo, make a homogeneous solution, and then add chlorine gas to about 300 qo.
Chlorination was carried out by blowing at a flow rate of 1.5 m/min.

Meanwhile, the lamp used in Example 3 was connected to the front surface of the reactor.
Irradiated at the skin level.

Method B: 200 ml of ethylene-vinyl acetate copolymer powder,
Suspend bentonite at 1,000 ml of water, and the reaction temperature is 5 ml.
The chlorination reaction was carried out at 0 qo and a chlorine flow rate of 100/min.

Each obtained chlorinated ethylene-vinyl acetate copolymer 10
A blown film (approximately 50 mm thick) was similarly obtained by mixing the vinylidene chloride copolymer lk9 of Example 1 in the same manner as in Example 1.

Since the reaction time differs for each example, it is listed in Table 2 together with the chlorine content and cloud value of the blown film.

Table 2 Transparency (cloud value) of blown film x Inflation film obtained in Comparative Example 1 xx Cloud value; J
Cloud value according to IS K 6714K is 10% or less,
It has good transparency, and if it exceeds 10%, it appears slightly milky to the naked eye.

On the coordinates where the axis is the vinyl acetate content of the ethylene-vinyl acetate copolymer and the vertical axis is the chlorine content of the chlorinated copolymer, films with a haze value of 10% or less are shown in Table 2. Plotting the positions of white circles and other white triangles shows the results as shown in Figure 4. As is clear from Figure 4, the upper limit of the chlorine content is 55%, and the transparency of the pinylidene chloride copolymer film containing the chlorinated ethylene-vinyl acetate copolymer depends on the composition of the ethylene monovinyl acetate copolymer. In the relationship between the ratio and the chlorine content of the product obtained by chlorinating it, it can be said that it is excellent only if it satisfies the specific conditions shown by the above formula (1). Example 7 A method similar to Example 1 was used to polymerize 92% of a mixture of 85 parts of vinylidene chloride and 15 parts of pinyl chloride using 0.15% of azobisisobutyronitrile as a polymerization catalyst.
Contains vinylidene chloride with a viscosity of 1.0 order. p. s.
A vinylidene chloride-vinyl chloride copolymer (2% o-dichlorobenzene solution, 120°C) was produced.

10 of the above vinylidene chloride-vinyl chloride copolymer lk9
A blown film was obtained in the same manner as in Example 6 by mixing with the chlorinated ethylene-vinyl acetate copolymer of Experiment No. 9 of Example 6 and extrusion molding.

The cloud value of this blown film was 8.5. Example 8 By the same method as in Example 1, 85% of azobisisobutyronitrile was used as a polymerization catalyst from a mixture of 7 parts of vinylidene chloride and 3 parts of vinyl chloride.
% vinylidene chloride and a viscosity of 1.09 (in 2% o-dichlorobenzene, 120° C.), a vinylidene chloride-vinyl chloride copolymer was obtained.

Using this copolymer and the chlorinated ethylene-pinyl acetate copolymer of Experiment No. 9 of Example 6, a blown film was obtained in the same manner as in Example 7.

The cloud value of this film was 7.7. Example 9 A mixture of 93% vinylidene chloride and 7% methyl acrylate was polymerized by a conventional suspension polymerization method using 0.2% lauroyl peroxide as a catalyst, and the vinylidene chloride content was 9.
A 2.4% pinylidene chloride-methyl acrylate copolymer was prepared.

This copolymer and the chlorinated ethylene-vinyl acetate copolymer of Experiment No. 9 of Example 6 were mixed to obtain a blown film in the same manner as in Example 7.

The cloud value of this film was 7.1. Example 10E
300 g of VA (vinyl acetate, about 33%, 33%) was dissolved in 1850 g of carbon tetrachloride, placed in a 4-necked separable flask made of gas, and subjected to a chlorination reaction under a rope.

The reaction conditions were a chlorine gas flow rate of approximately 300 I/min and a reaction temperature of 5.
0qo, reaction time 6 hours. Obtained chlorinated EVA
The elemental analysis values are 484% carbon, 6.5% hydrogen, and 8% oxygen.
．． 7%, and chlorine 37.2%. In addition, chlorinated EVA
, 3030, reduced viscosity in cyclohexanone solvent is 0
．． It was 703d'/evening. Example 1
Three types of compositions were prepared by mixing in the same manner as above, and further adding epoxidized soybean oil as a heat stabilizer at levels of 1%, 2%, and 3%. From these, an unstretched parison and a blown film were obtained in the same manner as in Example 1. Furthermore, it is a type for measuring the color difference on the sides of a parison wound into a spiral. It was used as a color sample. The oxygen permeability coefficient measured on the film and the L value measured on the spiral sample of the unstretched parison are shown in Table 3.

Comparative example 5 Water 1.8k9 in a 5-layer Hastelloy B (nickel-molybdenum-chromium alloy) lined autoclave with hawk clothing layer.
Methyl biloxypropyl cellulose was added for 1.8 hours, acetyl tributyl citrate solution containing 20% diisopropyl peroxydicarbonate was added for 15 hours, and the atmosphere was replaced with nitrogen and evacuated. 4
80 yen, 390 yen of ethylene was charged.

Polymerization was carried out at 50°C for 4 hours.

The initial pressure of 55k9/kg dropped to 50kg' after 4 hours. The polymerization rate was 57.5%. As a result of elemental analysis, the obtained terpolymer contained 50.2% carbon, 7.3% hydrogen, 7.3% oxygen, and 36.0% chlorine, and its reduced viscosity was 0.473 d' /It was evening. This ternary copolymer 1 base and the vinylidene chloride copolymer 9 of Example 1 were mixed in the same manner as in Example 1, and epoxidized soybean oil was added at 1%, 2%, and 3%. Added at a level of %,
Three types of compositions were prepared.

From these, as in Example 10, a blown film and a parent. A color swirl sample was prepared, and the oxygen permeability coefficient and color difference L value were measured. The results are listed in Table 3 together with those of Example 10. FIG. 3 also shows the relationship between molded article lightness and oxygen permeability coefficient. A molded product made of a terpolymer and 1% epoxidized soybean oil looks particularly black;
L value is low.

As seen in Table 3, the terpolymer and 2% epoxidized soybean oil and the chlorinated VA and 1% epoxidized soybean oil have the same L value. In other words, if you bring in products of the same color and compare them, the product using a terpolymer requires about 1% more epoxidized soybean oil to be added than the product using chlorinated EVA. , the gas barrier properties will be sacrificed accordingly (see Figure 3).
. Table 3 Comparison of oxygen permeability coefficient and color tone of molded articles Oxygen permeability coefficient; Measurement temperature: 35° C. Brightness (L value); Based on Nippon Denshoku Kogyo Co., Ltd.'s face u color difference meter.

Example 11 of 30 side color reflective surfaces Example 10 EVA (about 14% vinyl acetate, MI15)
Chlorinated using the same method.

However, the reaction conditions were: after reacting at 6000 for 2 hours,
The conditions were two-stage, including precipitation and reaction at 5,000 ℃ for 4.5 hours. The elemental analysis value of chlorinated EVA is carbon 45.5
%, hydrogen 6.0%, oxygen 3.9%, and chlorine 44.2%, and its reduced viscosity was 0.693/h.

This chlorinated EVAI Etsuro and 9 parts of the pinylidene chloride copolymer of Example 1 are mixed by the same method as in Example 1,
Epoxidized soybean oil 2.5%, 5% was added.

An unstretched parison was obtained from these two types of compositions in the same manner as in Example 1, and these were further compression-molded under the following conditions to produce a 1-thickness plate. That is, first stage 50kg/
, 160℃, 1 minute, second row 200k9'c vertebrae, 160
qo, 1 minute. The above molded plate was irradiated with ultraviolet rays for 4 hours using a carbon fedometer specified in JIS-K7102.

The black carbon temperature at that time was 40°C±2°C. Due to the irradiation, some discoloration was observed, so the degree of discoloration was measured using a color difference meter.

The results are shown in Table 4. Separately, the NM of this chlorine fine VA
The results are shown in Figure 1. Comparative Example 6 2k of n-hebutane was added to the autoclave used in Comparative Example 5.
9. 17.5 hours of an acetyl tributyl citrate solution in which 20% diisopropyl peroxydicarbonate was dissolved was added, the mixture was purged with nitrogen, the mixture was evacuated, and 72 hours of vinyl acetate, 6312 hours of vinyl chloride, and 295 hours of ethylene were charged.

Polymerization was carried out at a temperature of 5 psi for 4 hours. The initial pressure of 20 kg/kg decreased to 1.7 k9/kg after 48 hours. The polymerization rate was 47.8%. The elemental analysis values of the obtained terpolymer were as follows: carbon 46.8%, hydrogen 6.8%, oxygen 3.0%,
The chlorine content is 43.4%, and its reduced viscosity is 0.18.
It was the evening of 0. This terpolymer 1 foundation and Example 1
2.5% of epoxidized soybean oil and 5% of vinylidene chloride copolymer were mixed in the same manner as in Example 1.
% was added.

Molded plates were prepared from these two compositions in the same manner as in Example 11, and were irradiated with ultraviolet rays in the same manner. The color change due to irradiation was large, and the yellowness was measured using a color difference meter, and the results are shown in Table 4.

Separately, this terpolymer was subjected to NMR measurement, and the results are shown in FIG. Comparative Example 7 2.5% and 5% of epoxidized soybean oil were added to the vinylidene chloride copolymer used in Example 1, and a molded plate was produced in the same manner as in Example 11.

Further, ultraviolet irradiation was carried out in the same manner, but the dramatization results after irradiation for 4 songs are listed in Table 4 together with Example 11 and Comparative Example 6. Molded articles made of terpolymers have very poor light resistance and extremely high yellowness.

Rather than yellow, it should more accurately be called dark brown. On the other hand, it is clear that the molded article made of chlorinated EVA shows less discoloration due to ultraviolet irradiation and has light resistance equal to or higher than that of Comparative Example 7. As mentioned above, this difference is thought to be due to the difference in chemical structure shown in FIGS. 1 and 2. Table 4 Yellowness/browning test of molded products after UV irradiation: According to JISK7102, 4 hours, 40±2°C Yellowness: According to JISK7103

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a chart of the NMR spectrum of the chlorinated ethylene-vinyl acetate copolymer used in the present invention. FIG. 2 shows a chart of the NMR spectrum of ethylene monoacetate-vinyl chloride terpolymer. FIG. 3 shows the relationship between the oxygen permeability coefficient and brightness of molded articles made from the composition of the present invention and a composition containing ethylene-vinyl acetate-vinyl chloride. FIG. 4 shows the correlation between chlorine content and vinyl acetate content in the chlorinated ethylene-vinyl acetate copolymer passed through the composition of the present invention. Figure 1 Ticket 2 Figure 4 Figure 3

Claims (1)

[Scope of Claims] 1 (A) 100 parts by weight of a vinylidene chloride resin made of a copolymer of 75 to 95% by weight of vinylidene chloride and 25 to 5% by weight of a monomer copolymerizable therewith; B) A chlorinated ethylene-vinyl ester copolymer having a vinyl ester content of 10 to 40% by weight (based on the non-chlorinated copolymer), the chlorine content of which is 3 to 55% by weight (based on the non-chlorinated copolymer). Chlorinated ethylene-vinyl ester 3
-60 parts by weight of a vinylidene chloride resin composition. 2. The vinylidene chloride resin composition according to claim 1, wherein the vinylidene chloride resin is a copolymer of vinylidene chloride and vinyl chloride. 3. The vinylidene chloride resin composition according to claim 1 or 2, wherein the chlorinated ethylene-vinyl ester copolymer is a chlorinated ethylene-vinyl acetate copolymer. 4. The vinylidene chloride resin composition according to any one of claims 1 to 3, wherein the chlorinated ethylene-vinyl ester copolymer contains vinyl ester and chlorine in a proportion that satisfies the following relational expression: -0.7X+31≦Y≦
-X+80 [wherein, X represents the vinyl ester content (weight % based on the non-chlorinated copolymer) and Y represents the chlorine content (weight % based on the chlorinated copolymer)]. 5. A transparent molded article comprising the vinylidene chloride resin composition according to any one of claims 1 to 4. 6. The transparent molded article according to claim 5, wherein the transparent molded article is an inflation molded article.