JP3457050B2 - Saponified ethylene-vinyl acetate copolymer solution and its use - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solution of a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH), and more specifically, an EV having excellent adhesiveness to a substrate.
It relates to an OH solution and its coating laminate.

[0002]

2. Description of the Related Art A film obtained from EVOH has excellent transparency and oxygen barrier property and is useful as various packaging materials for foods, medical products, industrial chemicals, etc., or as a composite material laminated with plastic film, paper or metal foil. is there. Although an EVOH film can be formed by any method, it is possible to form a film having a relatively small film thickness, and a film having a complicated shape such as a hollow container can be easily formed. The solution coating method, in which a solution of EVOH dissolved in a solvent is applied to a substrate, has attracted attention because of its ability to form a resin and a coating operation with a relatively simple apparatus.

In such a method, flame treatment, corona treatment, anchor coat treatment, primer treatment and the like have been conventionally performed on the surface of the base material in order to improve the adhesion to the base material. Polyurethane compounds and polyester-isocyanate compounds are preferably used as agents. However, when the above anchor coat treatment is performed, the process becomes long and the treatment agent and treatment device are required, which leads to an increase in cost. To solve this drawback, JP-A-4-8745 proposes blending a polyoxazoline compound with EVOH.

Further, when performing the solution coating method,
The storage stability and the storage stability of the EVOH solution become problems, and EVOH precipitates are deposited, which may cause disadvantages such as re-dissolution at high temperature during use. As a solution to this problem, JP-A-2-47144 discloses that boric acid is added to an EVOH solution.

Further, the applicant of the present invention also discloses in Japanese Patent Laid-Open No. 5-295119.
In the publication, it is proposed that the use of an EVOH solution having a specific melting point improves the leaving stability, the adhesion to a substrate, the transparency of a coating film, and the like.

[0006]

However, when the inventors of the present invention examined the technique disclosed in JP-A-4-87745 in detail, the stability of the EVOH solution and the transparency of the coating film after molding were investigated. Etc. were found to be insufficient. or,
The technique disclosed in Japanese Patent Application Laid-Open No. 2-47144 is intended to improve the stability of the EVOH solution, and improvement of the adhesiveness to the substrate is not considered, and it is still insufficient.

Also in Japanese Patent Laid-Open No. 5-29119,
Use of only an EVOH solution having a specific melting point can be adopted when a polar polymer such as a polyester film is used as a base material, but when a nonpolar polymer such as a polyolefin is used as a base material, it is still more in terms of adhesiveness. It is not satisfactory, and it is expected to develop an EVOH solution which is excellent in oxygen barrier property, transparency of coating film, and stability in leaving, and also excellent in adhesiveness to a substrate such as polyolefin. It's a reality.

[0008]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to achieve such an object, the ethylene content is 20 to 60 mol%, the saponification degree is 90 mol% or more, and the melting point ( Tm) satisfies the following formula (I): saponified ethylene-vinyl acetate copolymer, borax, and water with 1 to 1 carbon atoms.
No. 4 mixed solvent of lower alcohol, and the amount of borax is 0.01 to 20 parts by weight based on 100 parts of saponified ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer. The present invention has been completed by finding the fact that a solution can achieve the above-mentioned object. -209-1.46Et + 3.31Sv <Tm <-109-1.46Et + 3.31Sv ... (I) Tm: Melting point (degreeC) by a differential scanning calorimeter Et: Ethylene content (mol%) Sv: Degree of saponification (mol%)

In the present invention, the specific melting point (T
The greatest feature is that borax is added to the EVOH solution having m), and such a combination provides the effect of the present invention that the adhesiveness to a substrate far exceeding that of the prior art is exhibited. is there. The effects of the present invention cannot be obtained with EVOH other than the above. Hereinafter, the present invention will be specifically described.

The EVOH used in the present invention has an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%,
More preferably, it should be 27 to 50 mol% and the saponification degree of the vinyl acetate component should be 90 mol% or more, preferably 95 mol% or more. When the ethylene content is less than 20 mol%, the gas barrier property at high humidity is lowered, while when it exceeds 60 mol%, sufficient gas barrier properties and coating properties such as printability are deteriorated. If the saponification degree is less than 90 mol%, the gas barrier property and the moisture resistance will be deteriorated.

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). %) EVOH in a range satisfying the following formula (I) is defined. -209-1.46Et + 3.31Sv <Tm <-109-1.46Et + 3.31Sv ... (I)

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 solution is deteriorated and the solution is solidified at room temperature or has an adhesive force to the substrate. And the object of the present invention cannot be achieved. That is, if the Tm value of the EVOH is within the above range, the EVOH
The EVOH solution obtained by the combination of borax and borax is excellent in gas barrier properties, transparency, leaving stability, etc., and
The effect peculiar to the present invention that the adhesiveness with the base material such as polyolefin is excellent can be obtained. The effects of the present invention cannot be obtained except for such EVOH.

EVOH as defined in this invention is generally not commercially available. That is, ordinary E commercially available
The melting point of VOH is higher than the melting point of the present invention regardless of the ethylene content or saponification degree, and the effect of the present invention cannot be obtained by using EVOH having such a high melting point. Further, the EVOH contains a smaller amount of propylene, isobutene, α-octene, α-dodecene, α.
-Containing an α-olefin such as octadecene, an unsaturated carboxylic acid or a salt thereof, a partial alkyl ester, a complete alkyl ester, a nitrile, an amide, an anhydride, a comonomer such as an unsaturated sulfonic acid or a salt thereof as a copolymer component It doesn't matter.

In the present invention, the solvent for EVOH is 10 to 90% by weight of water and 90 to 10% by weight of a lower alcohol having 1 to 4 carbon atoms, particularly at least one of propyl alcohol or butyl alcohol, methyl alcohol and ethyl alcohol. % Mixture is used. The amount of water is 10
-90 wt%, preferably 30-70 wt%, 1
If it is 0% by weight or less or 90% by weight or more, it is difficult to obtain a uniform solution and the coating film becomes opaque.

Examples of the propyl alcohol of the alcohol component include n-propyl alcohol and iso-propyl alcohol, and examples of the butyl alcohol include n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol. , Iso-propyl alcohol is preferably used.

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.

The ethylene content is 20 to 60 mol%, the saponification degree is 90 mol% or more, and the melting point (Tm) is -109 of the above formula.
Those having a melting point higher than the value calculated from −1.46Et + 3.31Sv (for example, when the ethylene content is 38 mol% and the saponification degree is 99.6 mol%, the value of the above formula is 165 0.2 ° C., which has a melting point of 173 ° C. or higher, is dissolved in the mixed solvent of water and lower alcohol. The EVOH concentration is suitably 1 to 50% by weight, preferably 10 to 40% by weight. Hydrogen peroxide (usually 35% by weight aqueous solution) was added to the solution, and EVOH / hydrogen peroxide solution (35% by weight aqueous solution) was added to EVOH.
Add to be 1 / 0.03 to 1/3 (weight ratio),
40 to 90 ° C. under stirring for 1 to 50 hours, preferably 1 to
Process for 20 hours. In some cases, metal catalysts (CuCl ₂ , CuSO ₄ , Mo in order to adjust the reaction rate are used.
_{O 3, FeSO 4, TiCl 4} , SeO 2 and the like) solution per 1 to 5000 ppm, preferably 10~3000ppm
It is preferable to add to some extent. The order of adding water, alcohol, EVOH, and hydrogen peroxide at this time is not limited to the above order. Of course, it is also possible to charge the above-mentioned compounds all at once. At the end of the treatment, the point at which the viscosity of the solution at the time of start was about 10% of the initial viscosity or less
I will use this as a guide.

The EVOH solution thus obtained can be blended with borax as it is to form the EVOH solution of the present invention, but it is preferable to add an enzyme such as catalase to decompose and remove the 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. Alternatively, the solution may be replaced with a solvent and dissolved in a mixed solvent of water and alcohol specified in the present invention to prepare an arbitrary solution. Alternatively, the target solid EVO can be obtained by removing the solvent of water and alcohol from the solution by a known method such as a fluidized bed dryer, a flash dryer, and a freeze dryer.
You can also get H.

In the present invention, EVOH obtained as described above
Or EVOH solution, borax, water and carbon number 1-4
Is mixed with a mixed solvent of lower alcohol of 0.01 to 2 parts by weight with respect to 100 parts by weight of EVOH.
The amount is 0 parts by weight, preferably 0.02 to 5.00 parts by weight, and more preferably 0.04 to 1.00 parts by weight. If the blending amount of such borax is less than 0.01 parts by weight, the adhesive force to the substrate will be insufficient, while if it exceeds 20 parts by weight, the solution will gel and coating will be difficult, and the effect of the present invention will not be obtained. . The mixed solvent of water and the lower alcohol having 1 to 4 carbon atoms is the mixed solvent as described above. The order of mixing EVOH, borax, and mixed solvent is not particularly limited, and batch charging,
A borax is added to a solution in which EVOH is dissolved in a mixed solvent, EVOH is added later, or the like is appropriately selected.

Further, in the present invention, in addition to EVOH, borax and mixed solvent, trimethylolpropane, triphenylmethane triisocyanate, ethylene diisocyanate, 1,4-butane diisocyanate, 1,6-
Isocyanate compounds such as hexane diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, 2,4- and 2,6-tolylene diisocyanate, methylene diphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, xylene diisocyanate; formaldehyde, acetaldehyde , Mono-aldehydes such as propionaldehyde, butyraldehyde and glyoxylic acid; dialdehydes such as glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, maleindialdehyde and phthalaldehyde; polyhydric aldehydes such as starch; hexa Methylenetetramine, ethylenediamine, trimethylenediamine phenylenediene Diamines such as Min; N- methylol urea, dimethylol urea, alkylated methylol urea, N- methylol melanin, methylol compounds such as alkylated methylolmelamine melanin; epichlorohydrin,
Epoxy compounds such as propylene oxide, styrene oxide, cyclohexene oxide, cyclopentene oxide; at least one selected from dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid 0.1 to 20
It is also possible to mix in about wt%, which shows the effect of the present invention.

The thus-obtained EVOH solution of the present invention is applied to a substrate. The concentration of the EVOH solution is not particularly limited, but the EVOH solution can be applied to various types of substrates and the stability of leaving it to stand. Considering this, 1 to 50% by weight, preferably 10 to 4
0% by weight, more preferably about 20 to 30% by weight is desirable.

In the present invention, the substrate to which the EVOH is applied 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.

According to the present invention, the EVOH coating film and the base material can be firmly adhered to each other at the time of coating without subjecting the base material to the anchor coating treatment as in the prior art. As a coating method at this time, a roller coating method such as a Meyer bar, a gravure and a reverse roll method, a spray coating method, a dip coating method or any other known method can be applied. Then, after the EVOH solution is applied to the base material, it is dried by a known method. For example, the drying temperature is 30 to 150 ° C., preferably 70 to 120.
It may be heated at a temperature of about C for about 3 seconds to 5 minutes. Although the volatile components in the coating film, that is, water and alcohol are removed by such drying, it is usually performed until the volatile components become 2% by weight or less.

Thus, a transparent coating film of EVOH is formed, but the film thickness is practically about 0.5 to 500 μm, preferably about 1 to 100 μm. If it is less than 0.5μ, it is difficult to exhibit sufficient gas barrier properties, while 500
If it is more than μ, it becomes 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 EVOH solution of the present invention has excellent adhesion to various substrates, and it is naturally possible to apply it without an anchor coat, but for the purpose of further improving the adhesiveness. Anchor coat agents such as polyurethane, polyester and polyethyleneimine may be used together.

Laminates obtained by coating various substrates with an EVOH solution are 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. Typical layer thickness of packaging materials and containers with high practicality is 10 to 100
0μ base material (polyester, polyethylene, etc.) / EVOH (volatile content 0.5 to 5% by weight) having a film thickness of 0.5 to 500μ, or 0.5 to 3μ film thickness on the EVOH layer having the above structure. A vinylidene chloride resin layer or a vinyl chloride-vinyl acetate copolymer layer is provided to some extent.
The shape may be any shape such as a film shape, a sheet shape, a hollow bottle and a tube.

[0027]

The present invention uses an EVOH solution consisting of EVOH having a specific melting point, borax, and a water-alcohol mixed solvent.
In addition to having excellent gas barrier properties, it also has very good adhesion to various substrates such as polyolefins.

[0028]

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. Examples 1 to 4 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 the temperature was adjusted to about 2 at 70 to 80 ° C. Stir for hours to prepare a clear solution. 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.
The residual hydrogen peroxide was removed to finally prepare a 20% EVOH solution, and borax as shown in Table 2 was added thereto to obtain an EVOH solution of the present invention. The ethylene content of EVOH in the EVOH solution was 30 mol%, the saponification degree was 99.5 mol%, and the melting point Tm was measured by DSC.
It was 148 degreeC when measured by. This Tm value satisfied 77 ° C <Tm <177 ° C specified in the present application.

Next, the corona-treated surface of the stretched polypropylene film (thickness 20 μ) is coated with the EVOH solution by an applicator coating method, and the temperature is set to 100 ° C.
And dried for 3 minutes to obtain a laminate having an EVOH film thickness of 3 μm. The following physical properties of the EVOH solution thus obtained and the laminate thereof were measured.

(Stability under standing) The obtained EVOH solution was added to 2
The sample was left in a thermostatic chamber at 0 ° C., and the number of days until EVOH started to gel was examined. (Transparency) The haze value by a haze meter was evaluated (%).

(Interlayer Adhesion) Cellophane tape was attached to the surface of EVOH, and the cellophane tape and polypropylene film were pulled to measure the adhesion (g / 15 mm). Thirty
The tensile speed is 0 mm / min. (Oxygen barrier property) Stretched polypropylene (20μ thick)
The oxygen permeability when EVOH solution was coated to a thickness of 3μ was measured at 20 ° C. and 65% RH (cc / m ² · atm ·
24hr).

Examples 5 to 7 EVOH (raw material) having an ethylene content of 30 mol%, a saponification degree of 99.4 mol% and a melting point of 188 ° C. was used in Example 1 except that the reaction time was changed to 20 hours. 20% as well
Was prepared, and then borax was added in an amount as shown in Table 2 to obtain an EVOH solution of the present invention and a laminate thereof. The same measurements as in Example 1 were performed on these EVOH solutions and the laminate thereof. The EV in the EVOH solution
OH has an ethylene content of 30 mol% and a saponification degree of 99.4.
Mol%, melting point Tm measured by DSC 14
It was 8 ° C. This Tm value is 76 ° C <Tm <
It satisfied 176 ° C.

Example 8 A 30% EVOH solution was prepared in the same manner as in Example 1 except that EVOH (raw material) having an ethylene content of 40 mol%, a saponification degree of 99.9 mol% and a melting point of 171 ° C. was used. Then, 1.00 part of borax was added to 100 parts of EVOH to obtain an EVOH solution of the present invention and a laminate thereof. The same measurement as in Example 1 was performed on the obtained EVOH solution and its laminate. The ethylene content of EVOH in the EVOH solution was 40 mol% and the saponification degree was 99.9 mol%.
The melting point Tm was 139 ° C. when measured by DSC. This Tm value is 63 ° C <Tm <163 defined in the present application.
It satisfied the temperature of ° C.

Comparative Example 1 Commercially available EVOH (ethylene content 30 mol%, saponification degree 99.5 mol%, melting point 188 ° C., 77 as in Example 1)
℃ <Tm <177 ℃, the melting point is outside the specification of the present application) 20 parts to water 40 parts, alcohol 40 parts, 70
Stir for about 2 hours at ~ 80 ° C, clear EV with 20% concentration
An OH solution was prepared, and 0.30 part of borax was added to 100 parts of EVOH to obtain an EVOH solution and a laminate thereof. The same measurement as in Example 1 was performed on the obtained EVOH solution and its laminate.

Comparative Example 2 An EVOH solution and its laminate were obtained in the same manner as in Example 1 except that borax was not added. The same measurement as in Example 1 was performed on the obtained EVOH solution and its laminate.

Comparative Example 3 In Example 1, EVOH (ethylene content 30 mol%, saponification degree 99.6 mol%, melting point 188 ° C.) was used,
Perform the same procedure except that iron sulfate heptahydrate was not used.
An EVOH solution having an m value of 180 ° C. was obtained. The Tm value is outside the range of 77 ° C <Tm <177 ° C specified in the present application. The E
Boron sand was added to a VOH solution (20% concentration) in an amount of 0.30 part based on EVOH to obtain an EVOH solution and a laminate thereof. The same measurement as in Example 1 was performed on the obtained EVOH solution and its laminate.

Comparative Example 4 In Example 1, 30 parts of EVOH (ethylene content 30 mol%, saponification degree 99.5 mol%, melting point 187 ° C.),
35 parts of alcohol (0 part of water), 35 parts of hydrogen peroxide (35% aqueous solution), 3000 ppm of iron sulfate heptahydrate, reaction time was 10 hours, and the same procedure was followed to prepare an EVOH solution having a Tm value of 60 ° C. Obtained. This Tm value is 77 ° C specified in the present application.
It is outside the range of <Tm <177 ° C. The EVOH solution (2
Boron sand (0% concentration) was added to EVOH in an amount of 0.30 part to obtain an EVOH solution and a laminate thereof. EV obtained
The same measurement as in Example 1 was performed on the OH solution and its laminate.

Comparative Example 5 EVOH (ethylene content 40 mol%, saponification degree 99.9 mol%, melting point 171 ° C.) was used in Example 1,
Perform the same procedure except that iron sulfate heptahydrate was not used.
An EVOH solution having an m value of 167 ° C. was obtained. The Tm value is outside the range of 63 ° C. <Tm <163 ° C. defined in the present application. The E
Boron sand was added to a VOH solution (30% concentration) in an amount of 0.30 part with respect to EVOH to obtain an EVOH solution and a laminate thereof. The same measurement as in Example 1 was performed on the obtained EVOH solution and its laminate.

Comparative Example 6 An EVOH solution and a laminate thereof were obtained in the same manner as in Example 1 except that the content of borax was changed to 30 parts with respect to 100 parts of EVOH. The same measurement as in Example 1 was performed on the obtained EVOH solution and its laminate. Table 2 shows the measurement results of Examples and Comparative Examples.

[0040]

[Table 1] EVOH Tm value range after reaction of EVOH (raw material) Et Sv Tm value of melting point (° C) Examples 1 to 4 30 99.5 187 148 77 <Tm <177 〃 5 to 7 30 99.4 188 148 76 <Tm <176 〃 8 40 99.9 171 139 63 <Tm <163 Comparative example 1 30 99.5 188 187 77 <Tm <177 〃 2 30 99.5 187 148 77 <Tm <177 〃 3 30 99.6 188 180 77 <Tm <177 〃 4 30 99.5 187 60 77 <Tm <177 〃 5 40 99.9 171 167 63 <Tm <163 〃 6 30 99.5 187 148 77 <Tm <177 Note) Et: Ethylene content (mol%) Sv: Saponification degree (mol%) Tm: melting point by DSC (° C)

[0041]

[Table 2] Intercalation of borax Interlayer transparency Oxygen permeability Addition amount Stability Adhesive strength (parts) (days) (g / 15mm) (%) (cc / m ² · atm · 24hr) Example 1 0.01> 60 200 2.0 4.6 〃 2 0.04>60> 300 2.2 4.3 〃 3 0.08>60> 300 2.1 4.5 〃 4 0.16>60> 300 2.0 4.3 〃 5 0.30>60> 300 2.1 4.3 〃 6 0.60>60> 300 2.0 4.5 〃 7 1.00 >60> 300 2.2 6.3 〃 8 1.00>60> 300 2.0 8.1 Comparative Example 1 0.30 <2 50 2.2 3.9 〃 2 −> 60 150 2.0 5.0 〃 3 0.30 <10 55 5.2 8.3 〃 4 0.30>60> 300 5.5 45 〃 5 0.30 <10 60 6.5 8.4 〃 6 30.0 The solution gels and cannot be applied to the substrate

[0042]

Since the present invention uses an EVOH solution consisting of EVOH having a specific melting point, borax, and a mixed solvent of water-alcohol, the stability of standing for a long time, the transparency of the coating film, the gas In addition to having excellent barrier properties, it also has excellent adhesiveness to various base materials such as polyolefin, and is used as a laminate by laminating with various base materials, for example, for food-related packaging, containers, etc. be able to.

Claims (2)

(57) [Claims] 1. An ethylene content of 20 to 60 mol%,
An ethylene-vinyl acetate copolymer saponified product having a saponification degree of 90 mol% or more and a melting point (Tm) satisfying the following formula (I), borax, and a mixture of water and a lower alcohol having 1 to 4 carbon atoms. It is composed of a solvent, and the content of borax is 0.01 to 100 parts with respect to 100 parts of saponified ethylene-vinyl acetate copolymer.
20 parts by weight of a saponified solution of an ethylene-vinyl acetate copolymer. -209-1.46Et + 3.31Sv <Tm <-109-1.46Et + 3.31Sv ... (I) Tm: Melting point (degreeC) by a differential scanning calorimeter Et: Ethylene content (mol%) Sv: Degree of saponification (mol%) 2. A laminate comprising a base material coated with the saponified ethylene-vinyl acetate copolymer solution.