JPH07118471A - Aqueous dispersion of ethylene-based acetate-based copolymer saponified material and its use - Google Patents

Abstract

PURPOSE:To obtain an aqueous dispersion of a saponified material of an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) having excellent storage stability for many hours, film-forming properties at a low temperature and transparency and to provide a laminate coated with the aqueous dispersion. CONSTITUTION:This aqueous dispersion of a saponified material of an ethylene- vinyl acetate copolymer uses a saponified material of an ethylene-vinyl acetate copolymer having <=60mol% ethylene content and >=90mol% saponification degree and a melting point (Tm) satisfying the formula -209-1.46Et+3.31Sv< Tm<-109-1.46Et+3.31Sv. ((Tm: melting point ( deg.C) by differential scanning calorimeter. Et: ethylene content (mol%). Sv: degree of saponification (mol%)). A laminate is obtained by coating the aqueous dispersion (mol%).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous dispersion of a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) and a laminate thereof.

[0002]

2. Description of the Related Art Generally, it is known that a film produced from EVOH as a raw material has excellent transparency and luster, and also has excellent oil resistance, chemical resistance, and gas barrier property. . In particular, the gas barrier property is outstanding as compared with other resin films, and the oxygen permeability is extremely small, so that it is very useful as a food packaging material.

As a method of using the EVOH, EVOH is used.
A method of melting and molding into a molded product such as a bottle or a film, and a method of coating a molded product made of another resin with an EVOH liquid to improve the physical properties of the molded product are carried out. Among these, there are merits and demerits in terms of usage depending on the purpose and application, but in the case of the coating method, an EVOH film can be easily formed even on a molded product having a complicated shape, and a thin film Can also be formed,
It is economically advantageous.

Therefore, an EVOH solution prepared by dissolving EVOH in a mixed solvent such as a water-alcohol system or an EVOH aqueous dispersion prepared by dispersing EVOH in water is used. However, the EVOH solution has a problem in coating property because the solution viscosity increases remarkably as the concentration of EVOH increases. Therefore, in reality, a dilute solution must be used.

In this respect, when an aqueous dispersion of EVOH is used as a coating liquid, the above-mentioned concerns do not occur and the coatability is excellent. However, it is not always easy to obtain a dispersion liquid of EVOH, and various measures are required. For example, a method of adding water and alcohol to EVOH, heating and dissolving the mixture, and then adding a surfactant to remove the alcohol (special feature (Japanese Patent Laid-Open No. 54-78748), a method of adding water, alcohol and a surfactant to EVOH, heating and dissolving, and then removing alcohol under forced high speed stirring (JP-A-54-54).
No. 101844) and EVOH, a hydrophilic solvent and a surfactant are added, and a solution obtained by heating and dissolving is emulsified and dispersed in a precipitant, and then the dispersion is aggregated at a pH of 5.5 or less, and the residue is filtered to obtain a medium residue. Method of mixing and redispersion (JP-A-56-
No. 61430) is known.

However, the present inventors have made a detailed study on the matters disclosed in the above-mentioned publication, and found that they are Japanese Patent Laid-Open No. 54-7.
According to Japanese Patent No. 8748, when the concentration of the dispersion liquid is increased, the viscosity becomes high and the subsequent processability, coatability, uniform film forming property, etc. are deteriorated, and it is difficult to increase the concentration. In Japanese Patent Laid-Open No. 54-101844, similar to the above, there are problems such as an increase in viscosity accompanied by an increase in concentration, poor leaving stability of emulsion and poor transparency after film formation.
In Japanese Patent Publication No. 430, in addition to the increase in viscosity due to the increase in concentration as described above, there is a problem that the dispersion liquid manufacturing process is complicated.

In order to solve the above-mentioned problems, the inventors of the present invention have tried to solve the problem of EVOH during the production process of EVOH dispersion liquid.
A method was proposed in which the water-alcohol mixed solvent in (3) above was cooled to deposit EVOH fine particles, and then the resin component was concentrated by centrifugation (Japanese Patent Laid-Open No. 5-179001).

[0008]

However, according to the method disclosed in Japanese Patent Laid-Open No. 5-179001, it is true that the EVO
An EVOH dispersion having a low viscosity even in a high H concentration region and having excellent leaving stability was obtained, but sufficient leaving stability for a long time, film-forming property at a low temperature, and a good film. There is still room for improvement because the transparency etc. for giving the above are still insufficient.

The present invention has been made to solve the above drawbacks, and its object is to have excellent stability in leaving for a long time and low temperature film-forming property, and good transparency and oxygen barrier property. The present invention is to provide a dispersion of EVOH capable of giving a proper coating.

[0010]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that the ethylene content is 60 mol% or less, the saponification degree is 90 mol% or more, and the melting point (Tm The present invention finds that an aqueous dispersion of an ethylene-vinyl acetate copolymer saponified product using an ethylene-vinyl acetate copolymer saponified product satisfying the following formula can achieve the above-mentioned object. Was completed. -209-1.46Et + 3.31Sv <Tm <-10
9-1.46Et + 3.31Sv Tm: melting point (° C) by differential scanning calorimeter Et: ethylene content (mol%) Sv: degree of saponification (mol%)

The present invention is most characterized in that the EVOH specified above, which is different from the conventional EVOH, is used, and the effects of the present invention such as storage stability and transparency can be obtained by the aqueous dispersion of EVOH. Is. Such EVOH
Other than that, the effect of the present invention cannot be obtained. Hereinafter, the present invention will be specifically described.

The EVOH used in the present invention has an ethylene content of 60 mol% or less, preferably 20 to 60 mol%, more preferably 25 to 55 mol%, and a saponification degree of the vinyl acetate component of 90 mol% or more, preferably It must be 95 mol% or more. When the ethylene content is less than 20 mol%, the gas barrier property at high humidity is deteriorated, while when it exceeds 60 mol%, sufficient gas barrier property cannot be obtained, and when the saponification degree is less than 90 mol%, the gas barrier property is not obtained. Resistance and moisture resistance are reduced.

Further, in the present invention, the melting point (Tm) determined from the peak temperature of the EVOH measured by a differential scanning calorimeter (DSC) is the ethylene content (Et mol%) and the saponification degree (Sv mol). %) Is the greatest feature to use EVOH in the range satisfying the following formula. -209-1.46Et + 3.31Sv <Tm <-10
9-1.46 Et + 3.31 Sv

When the Tm value is smaller than the above range, the gas barrier property against oxygen and the like is deteriorated, and when the Tm value is larger than the above range, the stability of the dispersion liquid is deteriorated, solidification occurs at room temperature, and the film forming property is insufficient. Therefore, the transparency is lowered and the gas barrier property is provided, so that the object of the present invention cannot be achieved. That is, T of the EVOH
As long as the m value is within the above range, the effects of the present invention that are excellent in leaving stability, transparency and the like of such an aqueous dispersion of EVOH can be obtained. The effects of the present invention cannot be obtained except for such EVOH.

EVOH as defined in the present invention is generally not commercially available. That is, in the conventional EVOH, the melting point is higher than the melting point of the present invention regardless of the ethylene content or the saponification degree, and the use of EVOH having such a high melting point brings about the effect of the present invention. I can't get it. Further, the EVOH is a small amount of propylene, isobutene, α-octene, α-dodecene, α-octadecene and other α-olefins, unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides, amides, etc. A comonomer such as an anhydride, an unsaturated sulfonic acid or a salt thereof may be contained as a copolymer component.

There are any methods for obtaining EVOH satisfying the above Tm value, and the degree of polymerization may be controlled during the polymerization or saponification of EVOH, or the distribution of the degree of saponification may be taken into consideration. Practically, it is advantageous to treat EVOH obtained by a usual industrial production method with a peroxide or the like. Hereinafter, such a method will be described in detail.

Ethylene content of 60 mol% or less, saponification
And the melting point (Tm) of the above formula is -109-
Higher than the value calculated from 1.46Et + 3.31Sv
Those with a high melting point (for example, ethylene content
When the amount of saponification is 38 mol% and the degree of saponification is 99.6 mol%,
The value is 164.5 ° C, higher than that, for example, the melting point is 1.
Water at 73 ° C and lower alcohol (eg ethyl)
Alcohol, methyl alcohol, iso-propyl al
Cole, n-propyl alcohol, t-butyl alcohol
Mixed solvent (water / alcohol = 9/1 to 1/9)
(Weight ratio)) or dimethyl sulfoxide (DMS
O), N, N-dimethylformamide (DMF), etc.
Dissolve in solvent. The EVOH concentration is 1 to 50 weight.
% Is appropriate. Hydrogen peroxide (usually 35 wt.
% Aqueous solution) to EVOH / EVOH / hydrogen peroxide water
(35% by weight aqueous solution) = 1 / 0.03 to 1/3 (weight
Ratio), 40-90 ° C. under stirring, 1-
The treatment is performed for 50 hours, preferably 1 to 20 hours. Also, if
In some cases, a metal catalyst (CuC) is used to adjust the reaction rate.
l ₂, CuSO_Four, MoO₃, FeSO_Four, TiCl_Four, S
eO₂Etc.) from 1 to 5000 ppm per solution, preferably
It is preferable to add about 10 to 3000 ppm.
Also, water at this time, alcohol solvent, EVOH, peroxide water
The order of adding the elements is not limited to the above order.
Of course, it is also possible to charge the above-mentioned compounds all at once. place
At the end of the process, the viscosity of the solution at the start is
One point is that the value drops below about 10%.

The EVOH solution thus obtained is preferably added with an enzyme such as catalase to decompose and remove residual hydrogen peroxide. The method for removing the residual hydrogen peroxide is not limited to the above method, and a known removal method can be adopted as long as the effect of the present invention is not impaired. The desired EVOH is obtained by removing water, alcohol or a solvent such as DMSO or DMF from the solution by a known method using a fluidized bed drier, a gas stream drier, a freeze drier or the like. Depending on the type of the subsequent aqueous dispersion production method, the EVOH solution can be directly used in the production step of the aqueous dispersion without removing the solvent such as water and alcohol.

Next, the obtained EVOH is used as an aqueous dispersion, but in the present invention, the method for producing the dispersion is not limited, and JP-A-54-78748 is used.
JP-A-54-101844, JP-A-56
Although conventionally known methods such as JP-A-61430 and JP-A-5-179001 are appropriately adopted, it is preferable to use the centrifugal separation method because of the fact that fine particles can be obtained and the concentration operation is easy. The method according to Kaihei 5-179001 is particularly preferable.

That is, (1) the EVOH of the present invention has 1 carbon atom
~ 4 heating and dissolving in a mixed solvent of alcohol and water, (2) cooling the obtained solution to precipitate the EVOH, (3) concentrating the dispersion containing the precipitated EVOH by centrifugation From the step of (4) adding an aliphatic ketone and a dispersion stabilizer to the obtained concentrate to obtain a stable dispersion, and (5) removing the aliphatic ketone and alcohol from the obtained dispersion. The following method for producing an aqueous dispersion of EVOH markedly exhibits the effects of the present invention. A more specific manufacturing method is as follows.

The alcohol used in the step (1) has 1 to 4 carbon atoms, and is methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, t. Examples thereof include one or more mixed alcohols such as butyl alcohol, and industrially, methyl alcohol and iso-propyl alcohol are preferable from the viewpoints of cost and removability.

The mixing ratio of water and alcohol is not particularly limited, but the weight ratio of water / alcohol = 9/1 to 1/9 is preferable, and water / alcohol = 7/3 to 3 is more preferable.
/ 7. If the mixing ratio is out of this range, the solubility of EVOH decreases, so that it becomes difficult to prepare a homogeneous EVOH solution, and a dispersion of good quality cannot be obtained. A preferable range of the melting temperature is 50 to 120 ° C. The amount of EVOH with respect to the water-alcohol mixed solvent is 50 to 12
Solubility at 0 ° C can be added. At this time, the EVOH concentration is 1% by weight or more and less than 20% by weight, which takes into consideration the solubility in a water-alcohol mixed solvent and the stability of the solution, and is preferably 1 to 15% by weight.

The EVOH solution is prepared according to known procedures. That is, EV is added to the above water-alcohol mixed solvent.
OH mixed, turbine type under heating at 50-120 ° C,
Rotation speed 1 using a stirrer equipped with a ribbon type stirring blade
Mix and stir under the condition of 0 to 1000 rpm to prepare a solution of EVOH.

Step (2) The EVOH solution obtained in Step (1) is cooled and EVOH
Precipitate fine particles to form a dispersion. That is, step (1)
By lowering the temperature of the EVOH solution (above the critical melting temperature of EVOH) to below the critical melting temperature of EVOH, EVOH fine particles are deposited by utilizing the difference in solubility due to the temperature difference. The cooling temperature of this process is EVOH
Considering the precipitation effect of fine particles, it is usually preferable to set the temperature to 40 ° C. or lower.

Step (3) The centrifugal separation method used in this step is a method of separating two liquid phases or a liquid phase and a solid phase by the difference in density by utilizing centrifugal force. Is a method using. That is, the dispersion liquid in which EVOH fine particles have been precipitated by the cooling in the step (2) is subjected to solid-liquid separation by a centrifugal sedimentation separator such as a screw decanter type or a cylindrical type to remove the supernatant liquid and EV
An OH concentrate is obtained.

It is essential that the EVOH concentration after the concentration is 20% by weight or more. If the concentration is less than 20% by weight, it takes time to remove alcohol in the step (5) and the stability is lowered. The upper limit is not particularly limited, but the concentration by the centrifugation method in this step is about 40% by weight. A preferred range is 20 to 35% by weight.

Step (4) Aliphatic ketone is added to the EVOH concentrate obtained in Step (3).
A dispersion stabilizer is added to stabilize the dispersion of EVOH fine particles in the concentrated liquid. That is, the aliphatic ketone remains as an anti-agglomeration agent, thereby preventing alcohol swelling of the EVOH fine particles, and the dispersion stabilizer is effective for imparting surface activity and protective colloidal property, and secondary aggregation and blocking of the fine particles ( Gelation), and it is possible to produce a dispersion liquid of EVOH having stable dispersibility.

As the aliphatic ketone used in this step, acetone and methyl ethyl ketone are preferably used. The amount used is preferably 100 to 2000 parts, more preferably 250 to 1500 parts, based on 100 parts of EVOH. If the amount of the aliphatic ketone added exceeds the above range, it takes time to remove the solvent in the step (5).
The stability of the VOH dispersion becomes poor.

As the dispersion stabilizer, usual anionic and nonionic surfactants are used. Specifically, the anionic surfactants include sodium vinyl sulfonate, sodium dodecylbenzene sulfonate, sodium lauryl sulfonate, and the like. As the nonionic type, there are polyoxyethylene type polyoxyethylene lauryl ether, polyoxyethylene nonylphenol ether, polyoxyethylene sorbitan monooleate, polyoxypropylene type and polyoxyethylene-polyoxypropylene copolymer type. . The amount of the surfactant used is such that it can be emulsified and dispersed, and does not impair the characteristics of the coating film of the EVOH dispersion, which is 0.
The range of 1 to 10 parts is preferable.

It is also advantageous to use a protective colloid agent as the dispersion stabilizer, and polyvinyl alcohol, partially saponified polyvinyl alcohol, polyvinyl alcohol derivatives, modified polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose and hydroxypropyl cellulose, poly Examples thereof include sodium acrylate, polyacrylic acid amide, polyvinylpyrrolidone and the like. The amount used is preferably in the range of 0.1 to 10 parts based on 100 parts of EVOH for the same reason as for the surfactant. The surfactant and protective colloid agent are preferably added as an aqueous solution of 1 to 20% by weight.

The aliphatic ketone and the dispersion stabilizer may be added to the EVOH concentrate with stirring, and any stirrer may be used. The order of addition is not particularly limited, but it is more efficient to add the aliphatic ketone first and then add the dispersion stabilizer, so that the dispersion liquid can be formed. In this step, since a considerably large amount of aliphatic ketone and water as a dispersion stabilizer solvent are systematically added, the concentration of the concentrated EVOH dispersion liquid once drops, but both step (3) and this step are final. It is essential to obtain a stable aqueous dispersion.

Also in this step, if necessary, it is possible to add an anti-blocking agent or a film-forming auxiliary agent in order to prevent sticking when a film is formed. In this case, examples of the anti-blocking agent include inorganic powders such as silica and talc, and examples of the film forming aid include polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin. The usage is EVOH1
The inorganic powder is appropriately selected from the range of 0.01 to 10 parts, and the film-forming aid is suitably selected from the range of 5 to 100 parts, relative to 00 parts.

Step (5) An aqueous dispersion having an EVOH concentration of 5 to 50% by weight, preferably 10 to 40% by weight, in which a solvent such as an aliphatic ketone and an alcohol is removed from the above EVOH dispersion and water is used as a main component of the medium. Get the liquid. That is, the EVOH dispersion is stirred under reduced pressure (30 to 100 mmHg) and / or under heating (40
To 80 ° C.), all or part of the aliphatic ketone and alcohol in the dispersion is removed to reduce the alcohol content in the aqueous medium to 5% by weight or less. Further, it is desirable to remove all of the aliphatic ketone, but even if a small amount remains, the effect of the present invention is not impaired.

Thus, the EVOH aqueous dispersion of the present invention can be obtained, which can be commercialized as it is, or can be adjusted in concentration by adding an appropriate amount of water. In any case, as the final product, the solid content (EV
OH) concentration is 5 to 50% by weight, preferably 10 to 40
A wt% aqueous dispersion can be produced. The aqueous dispersion has a Brookfield viscosity of 5 to 5000 (cps / 20) even when the solid content is as high as 5 to 50% by weight.
(° C) and low viscosity, and is extremely excellent in coatability. or,
Even when the aqueous dispersion is stored or transported for a long period of time, there is no trouble such as thickening, gelation and coagulation and it is very stable. The aqueous dispersion has excellent low temperature film-forming properties,
A good coating film is formed even at a low temperature of about 0 ° C., and the coating film has excellent gas barrier properties and transparency.

In the present invention, a substrate can be coated with the above aqueous dispersion, and when the aqueous dispersion is coated on the substrate, the solid content concentration in the aqueous dispersion is not particularly limited. Considering the coating properties on various base materials and the storage stability, etc., about 10 to 40% by weight is desirable.

The substrate to which the EVOH is applied in the present invention is not particularly limited, and a stretched or unstretched film, sheet, hollow container or paper of various plastics such as polyethylene, polypropylene, polyester, polystyrene, polyvinyl chloride and nylon. , Cellophane, cellulose, cellulose acetate, natural rubber, synthetic rubber,
Examples include metals. The thickness of the base material is 10 to 100.
About 0 μ is suitable.

Further, as a method for applying such an aqueous dispersion, a roller coating method such as a Meyer bar, a gravure and a reverse roll method, a spray coating method,
Any known method such as a dip coating method can be applied. Thus, a transparent coating film is formed,
The film thickness is 0.1 to 100 μ, preferably 0.5 to 10 μm.
μ is practical. If it is 0.1 μm or less, it is difficult to exhibit a sufficient gas barrier property, while if it is 100 μm or more, it is difficult to control the film thickness. It is also possible to form a moisture-proof layer on the coating film, if necessary, by coating a vinylidene chloride resin, a vinyl chloride-vinyl acetate copolymer, or the like.

The coating film of the aqueous dispersion of the present invention has excellent adhesiveness to various substrates, and it is needless to say that it can be applied without an anchor coat, but polyurethane is used for the purpose of further improving the adhesiveness. Anchor coating agents such as polyester, polyethyleneimine, etc. may be used together.

The layered product coated with the aqueous dispersion of the present invention is useful for various applications such as packaging of foods, beverages, medicines, medicines, electrical parts, machine parts and the like, containers, heating pipes, wallpaper, etc. Is.

[0040]

According to the present invention, in addition to the coatability, the aqueous dispersion of the novel EVOH having a specific melting point is excellent in the stability for standing for a long time, the low-temperature film-forming property, and the transparency. It can be used as a laminate by laminating it with a substrate.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "part" and "%" are based on weight unless otherwise specified. Example 1 To a mixed solvent of 22 parts of water and 35 parts of alcohol, 30 parts of EVOH (ethylene content 30 mol%, saponification degree 99.5 mol%, melting point 187 ° C.) was added and stirred at 70-80 ° C. for about 2 hours. Then, a transparent solution was prepared. Next, 13 parts of hydrogen peroxide solution (35% aqueous solution) and 50 parts of iron sulfate heptahydrate were added to the solution.
After adding ppm and reacting at 80 ° C for about 4 hours under stirring, the mixture was cooled to 40 ° C and further catalase was added to 3000 ppm.
30% by removing residual hydrogen peroxide
EVOH solution was obtained. The EVOH solution was heated at 100 ° C. for 9
It was dried under the condition of 0 minutes to obtain solid EVOH. The EV
The ethylene content of EVOH in the OH solution is 30 mol%,
The saponification degree was 99.5 mol%, and the melting point Tm was 148 ° C. as measured by DSC. This Tm value satisfied 77 ° C <Tm <177 ° C specified in the present application.

Preparation of such an aqueous dispersion of EVOH
The following steps (1) to (5) were performed.Process (1)  Iso-propyl alcohol 45 to 10 parts of the above EVOH
Part and 45 parts of water are added to add a turbine type stirring blade stirrer
Mix at a rotation speed of 500 rpm at 80 ° C for about 2 hours.
Dissolve 10% EVOH in water-alcohol with combined stirring.
I made a liquid.Process (2) The EVOH solution of step (1) is placed in a thermostat at 5 ° C for 24 hours.
Let it stand for a while and deposit EVOH fine particles to form fine particles.
A child dispersion liquid was obtained.

Step (3) After returning the dispersion liquid to room temperature, it was transferred to a centrifuge and centrifuged for 30 minutes at a rotation speed of 7,000 rpm, and then the supernatant was removed to obtain 40 parts of 25% EVOH concentrate. Got Step (4) Next, 50 parts of acetone was added to the concentrated solution, and the mixture was stirred for about 5 minutes with the same stirrer as in step (1). Thereafter, 0.5 part of a surfactant (sodium laurylate) and 0.2 part of a protective colloid agent (partially saponified polyvinyl alcohol having a polymerization degree of 500 and a saponification degree of 88 mol%) are added, and the mixture is further stirred for 20 minutes. A stable EVOH dispersion was obtained. The surfactant and the protective colloid agent were each used as a 5% aqueous solution.

Step (5) The EVOH dispersion liquid obtained in the step (4) was transferred to an evaporator, and while being heated to 60 ° C., the pressure was gradually reduced to 30 m.
Solvent removal in the dispersion was performed at mHg for about 2 hours. Thereafter, water was added to adjust the concentration to obtain an EVOH aqueous dispersion having a concentration of 20%. The content of iso-propyl alcohol in the aqueous dispersion was 3% in the aqueous medium, and the content of acetone was 0.

Next, drawn polypropylene (thickness 20 μ)
Then, the EVOH aqueous dispersion was coated with a bar coater and dried at 100 ° C. for minutes to obtain a laminate having an EVOH film thickness of 3 μm. EVOH thus obtained
The following physical properties of the aqueous dispersion and its laminate were measured.

(Viscosity) EV obtained by B-type viscometer
The viscosity of the OH aqueous dispersion at 20 ° C. was measured. (Stability upon standing) 100 ml of the obtained EVOH aqueous dispersion
Transfer to a 100 ml graduated cylinder and place at 24 ° C for 24 hours.
After a lapse of time, the amount of the separated transparent liquid was measured. Separately EVOH aqueous dispersion (100 g in a 200 ml beaker) 2
After 1 week at 0 ° C., the redispersibility when stirring at 60 rpm × 5 minutes was examined. Stability was evaluated based on the following criteria.

(Low-temperature film-forming property) A stretched polypropylene (thickness 20 μm) was coated with the obtained EVOH dispersion liquid to a thickness of 3 μm by a bar coater and dried for 3 minutes to obtain a transparent coating film. The lowest temperature was measured and the low temperature film-forming property was evaluated.

(Oxygen Barrier Property) Oxygen permeability when a stretched polypropylene (thickness 20 μm) was coated with an EVOH aqueous dispersion with a thickness 3 μm was measured at 20 ° C. and 65% RH (cc / m ² · atm · 24hr). (Transparency) The haze value was evaluated by a haze meter.

Examples 2 to 4 EVOH (raw material) shown in Table 1 was used to obtain EVOH of the present invention having the Tm value shown in Table 1 as in Example 1. In Example 4, cupric chloride was used instead of iron sulfate heptahydrate. Next, according to Example 1, an aqueous dispersion of EVOH was obtained (in Example 2, an aqueous dispersion having a concentration of 30% was obtained), and further a laminate thereof was obtained. The same measurements as in Example 1 were carried out on these EVOH aqueous dispersions and their laminates.

Comparative Example 1 Commercially available EVOH (ethylene content 30 mol%, saponification degree 99.5 mol%, melting point 187 ° C., 77 as in Example 1)
C. <Tm <177.degree. C., the melting point of which is out of the regulation of the present application) 30 parts were added to 35 parts of water and 35 parts of alcohol, and an EVOH aqueous dispersion and its laminate were obtained in the same manner as in Example 1. . The same measurements as in Example 1 were carried out on these EVOH aqueous dispersions and their laminates.

Comparative Examples 2 and 3 Example 1 was repeated except that EVOH (raw material) shown in Table 1 was used and no metal catalyst was used.
EVOH having a Tm value shown in was obtained. All of these Tm values are outside the range specified in the present application. Further, an aqueous dispersion of each of the EVOH was prepared in the same manner as in Example 1 (in Example 3, an aqueous dispersion having a concentration of 30% was obtained), and a laminate thereof was prepared. The same measurements as in Example 1 were carried out on these EVOH aqueous dispersions and their laminates.

Comparative Example 4 In Example 1, 30 parts of EVOH (ethylene content 30 mol%, saponification degree 99.5 mol%, melting point 187 ° C.),
EVOH having a Tm value of 65 ° C. was obtained in the same manner except that 35 parts of hydrogen peroxide solution (35% aqueous solution), iron sulfate heptahydrate 3000 ppm, and reaction time were 10 hours. The Tm value is outside the range of 77 ° C <Tm <177 ° C specified in the present application.
Further, an aqueous dispersion of the EVOH was prepared in the same manner as in Example 1, and a laminate thereof was prepared. The same measurements as in Example 1 were carried out on these EVOH aqueous dispersions and their laminates. Table 2 shows the measurement results of Examples and Comparative Examples.

[0053]

[Table 1] Range of EVOH Tm value after reaction of EVOH (raw material) Et Sv Tm value of melting point (° C) Example 1 30 99.5 187 148 77 <Tm <177 〃 2 40 99.9 171 135 63 <Tm <163 〃 3 40 96.0 158 132 50 <Tm <150 〃 4 30 99.5 187 145 77 <Tm <177 Comparative Example 1 30 99.5 187 187 77 <Tm <177 〃 2 30 99.5 187 180 77 <Tm <177 〃 3 40 99.9 171 167 63 <Tm <163 〃 4 30 99.5 187 65 77 <Tm <177 Note) Et: Ethylene content (mol%) Sv: Degree of saponification (mol%) Tm: Melting point by DSC (° C)

[0054]

[Table 2] Viscosity Stability Stability Minimum film forming temperature Oxygen permeability Transparency (cps) (° C) (cc / m ² · atm · 24hr) (%) Example 1 580 ◎ 50 3.5 3.5 2.1 〃 2 30 ◎ 45 5.1 2.0 〃 3 135 ◎ 45 5.2 5.2 〃 4 620 ◎ 50 3.3 3.3 2.3 Comparative example 1 450 △ 105 5.5 7.3 〃 2 480 △ 95 6. 6 6.5 〃 3 20 △ 90 90 4.0 9.0 〃 4 550 ◎ 40 65 1.9

[0055]

INDUSTRIAL APPLICABILITY The present invention is a novel EV having a specific melting point.
It is an aqueous dispersion composed of OH. In addition to coating properties, it is excellent in leaving stability for a long time and low-temperature film-forming property, and the obtained film has excellent oxygen barrier property and good transparency. Further, it can be used as a laminated body by further laminating it with various base materials, for example, for food-related packaging, containers and the like.

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[Procedure amendment]

[Submission date] January 10, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

Next, a corona-treated stretched polypropylene (thickness 20 μm) was coated with such an EVOH aqueous dispersion by a bar coater and dried at 100 ° C. for minutes to obtain a laminate having an EVOH film thickness of 3 μm. It was The following physical properties of the EVOH aqueous dispersion thus obtained and the laminate thereof were measured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C09D 123/26 PEV

Claims (3)

[Claims] 1. A saponified ethylene-vinyl acetate copolymer having an ethylene content of 60 mol% or less, a saponification degree of 90 mol% or more, and a melting point (Tm) satisfying the following formula is used. An aqueous dispersion of a saponified product of an ethylene-vinyl acetate copolymer. -209-1.46Et + 3.31Sv <Tm <-10
9-1.46Et + 3.31Sv Tm: melting point (° C) by differential scanning calorimeter Et: ethylene content (mol%) Sv: degree of saponification (mol%) 2. The aqueous dispersion of saponified ethylene-vinyl acetate copolymer according to claim 1, wherein the solid content of the dispersion is 5 to 50% by weight. 3. A laminate comprising a substrate coated with an aqueous dispersion of the saponified ethylene-vinyl acetate copolymer.