JPS6017383B2 - Method for producing surface-treated vinyl alcohol polymer film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a vinyl alcohol polymer film surface treated with an ionomer resin.

Vinyl alcohol polymer films such as polyvinyl alcohol films have poor slip properties and are prone to blocking when stacked or rolled, so the film surface is coated with inorganic or organic fine powder, silicon dioxide, titanium dioxide,
A suitable example is to attach clay or starch silicone coated powder, but if enough powder is attached to improve slip properties and blocking resistance, heat sealability and adhesive sealing properties can be improved. In addition to having the disadvantage of compromising one's sexuality,
The adhering fine powder easily falls off, not only interfering with the subsequent bag making and printing processes and contaminating the work environment, but also contaminating the contents (textile products, etc.) that are packed into the bags after bag making. arise.

In addition, a method of coating with a polystyrene emulsion has been proposed instead of powder, but the film forming temperature is high, the improvement effect on slip property and blocking resistance is not necessarily sufficient, and furthermore, it is difficult to use a vinyl alcohol polymer film. There is also a risk that the excellent gloss and transparency that it possesses may be diminished. The present invention completely solves the above-mentioned problems of the conventional method, and produces a surface-treated vinyl alcohol polymer film by applying an ionomer resin emulsion to the surface of the vinyl alcohol polymer film and drying it. It is characterized by:

By employing the method of the present invention, the following excellent effects can be achieved.

01 Low static friction and good slip properties.

This property means that the winding of the film proceeds smoothly, the winding appearance is beautiful, and the bags are easy to align during bag making, which is a great practical advantage. ■ Since transparency is not impaired, the excellent gloss and transparency inherent in vinyl alcohol polymer film can be utilized as is.

'31 Almost no shedding occurs even when swept with a cloth.

Therefore, the bag making process and printing process are smooth, the working environment is not contaminated, and the contents packed in the bag are not contaminated. [4}
Excellent blocking resistance.・Even when stacking a large number of films or bags, or winding the film on a winder, the films do not overlap or block. Shows sufficient blocking resistance even at high temperatures and high humidity. [51
Does not impair heat sealability.

Even with ordinary commercially available products, if the amount of dusting or coating is increased, the slip properties and anti-blocking properties will improve accordingly, but the heat sealing properties will drastically decrease and the product will eventually lose its practicality. However, in the present invention, although the slip property and blocking resistance are significantly improved,
Heat-sealability is hardly impaired. [6] Does not impair adhesive sealing properties.

For the same reason as stated in [5} above, in the present invention, the sealing performance by glue is hardly impaired. [7}
Since there is little curling of the film after coating, workability in the subsequent bag making process and printing process is good.

The vinyl alcohol polymer in the present invention refers to a partially or completely saponified product of a vinyl ester polymer or copolymer, or a subsequently modified product. For example, [a' polyvinyl alcohol obtained by saponifying about 50 to 100 mol% of polyvinyl acetate, 'b] mainly composed of pinyl acetate, and other copolymerizable monomers such as olefins (ethylene, propylene, Q-butene, Q-octene, Q-dodecene,
Q-octadecene, etc.), unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, etc.) or their esters or salts, unsaturated polycarboxylic acids (maleic acid,
fumaric acid, itaconic acid, etc.) or their partial or complete esters or salts or anhydrides), unsaturated sulfonic acids (
(ethylene sulfonic acid, allyl sulfonic acid, methalylsulfonic acid, etc.) or their salts, amides (acrylamide, methacrylamide, etc.), nitriles (acrylonitrile, methacrylonitrile, etc.), vinyl efful, vinyl ketoso, vinyl chloride, etc. A polymer in which part or all of the vinyl acetate component of the polymer is saponified (the proportion of other copolymerizable monomers is 50 mol% or less, especially 20 mol% or less. However, when ethylene is used as a comonomer, the ethylene content is It may be about 95 mol% at most.
), 'c--The above [a}, {b' is acetalized, urethanized, phosphoric acid esterified, cyanoethylated, or modified after vinyl monomer is grafted.
Such vinyl alcohol polymer films include not only flat films, but also cylindrical films and sheets, as well as hollow fibrous materials, bottle-shaped or box-shaped containers, and the like.

These films may be subjected to heat treatment, uniaxial or double stretching treatment, lamination treatment with other materials, etc. Ionomer resin emulsion is a metal ion-containing resin obtained by reacting a copolymer of Q-olefin such as ethylene with an unsaturated acid having a carboxyl group, such as acrylic acid or methacrylic acid, with an ionic metal compound. It is called an emulsion, and the metal ions include alkali metal ions,
Examples include alkali metal ions, iron group element ions, zinc group element ions, copper ions, tin ions, bell ions, and aluminum ions.

Ionomer resin emulsions are marketed, for example, by Asahi Dow Co., Ltd. as Kari Corporen Latex and by Mitsui Polychemical Co., Ltd. as Imilan. The coating amount of ionomer resin emulsion is 0.0 net.
It is effective from around 0.001 m/m, but usually 0.001
~0.2 evening/, preferably 0.005-0.05 evening/
It is desirable to select the desired effect so that if the amount applied is too small, the desired effect will not be achieved sufficiently, while if the amount applied is too large, gloss, transparency, heat sealability, and adhesive sealability will be impaired. become.

During application, a vinyl alcohol polymer can be added to the ionomer-resin emulsion as a shedding preventive agent in the form of a powder, an aqueous solution, or an emulsion.

The blending amount of the vinyl alcohol polymer with respect to the ionomer resin is up to about 50% by weight at most, and is usually selected from the range of 10 to 30% by weight. In addition, ionomer resin emulsions contain silicone resins and fluororesins to improve slip properties, silicon dioxide, colloidal silica, aluminum oxide, titanium dioxide, and other additives to improve blocking resistance, antifoaming agents, and other additives. can be blended as needed.

The film may be coated on one side or both sides, and may be applied not only to the entire surface but also to a part of the film. Application can be carried out by any method such as roll coating, brush coating, dipping, curtain flow coating, doctor knife coating, and spray coating. Drying may be performed at room temperature or under heating. A reduced pressure drying method is also appropriately employed. Next, the method of the present invention will be further explained with reference to Examples.

Hereinafter, "parts" and "%" are expressed on a weight basis unless otherwise specified. Example 1 Degree of polymerization 17
00 An aqueous solution with a polyvinyl alcohol concentration of 20% was prepared by heating and dissolving 10 parts of polyvinyl alcohol with a degree of saponification of 99.5 mol% and 10 parts of glycerin in water. Thirty French films were produced.

This film was heat-treated at a temperature of 120 to 150 oo to obtain a key-soluble film. One side of this film was coated with an ionomer resin emulsion (Corpolene Latex L-4000 manufactured by Asahi Dow Co., Ltd.) diluted with water at a film speed of 20 m/min using a 60 mesh roll to reduce the resin content.
．． 5%) was roll coated at a rate of 4.8 coats/hr, and then dried at a roll surface temperature of 80o0.

The amount of coat was 0.015 evening/after on the internet. The properties of the film thus obtained are shown in Table 1. Control example 1 Raw material film of Example 1 (uncoated) Comparative example 2 A 0.5% aqueous suspension of colloidal silica (average particle size 18 h) was applied to the raw material film of Example 1 and dried. The applied amount was 0.015 yen/pillow film.

Control Example 3 In Control Example 2, the amount of colloidal silica applied was 0.03.
Evening/when used as a pillow.

Control example 4 The raw material film of Example 1 was coated with an aqueous dispersion of polystyrene (
The film was coated with a film with a concentration of 0.5% and an average particle size of 0.1 μm, and the dry coating amount was 0.015 μm/m in net.

The results of the above Control Examples 1 to 4 are also shown in Table 1.

Table 1 (Note) The static friction angle is measured using a slide tester manufactured by Toyo Seiki Co., Ltd. at 20°C and 85% RH.

The haze value is measured using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.

The shedding property was determined by visually evaluating the degree of shedding when the film was swept 50 degrees with a black cloth, and was evaluated on a 9-point scale, with no shedding at all being grade 0, and commercially available Pinilon film being grade 8. Blocking resistance was determined by testing the sample at 30°C and 80% RH under K24.
After leaving it for a while to reach equilibrium moisture, under the same conditions KIO
The size of ten toga. A large number of samples were stacked and left under a load of 1.0× for 24 hours, and then the state of adhesion was determined. A: No adhesion at all B: Slight adhesion is observed, but usable C: Adhesive, plate-like object, unusable Heat sealability: Use burn roller, lower blade 100
℃, pressure 1.0 & dust, 0.5 seconds were fixed conditions, and the upper blade temperature was changed at three points to seal, and the adhesive strength was measured using a 1800 bow eye.

The sealability was determined by using a calcium bromide (35% concentration) water-containing methanol adhesive, and measuring the adhesive strength at 1800 tensile strength 5 hours after applying the adhesive.

Curl property was determined by heating a sample of 10 degrees horizontally and 20 degrees vertically at 20℃.
It was hung under conditions of 65% RH, and the curled area was expressed as a percentage after being left for 24 hours. In addition, when the experiment was conducted in the same manner as in Control Example 2 or 3 J except that a silicon oxide characteristic powder with a particle size of 1 French or more was used instead of colloidal silica, the transparency of the film was impaired, it was easy to fall off, and the sealability was poor. The results were also slightly inferior to those using colloidal silica. Example 2 Instead of roll-coating the ionomer resin emulsion with 4.8 sonotor, an ionomer resin emulsion (Corpolene Latex L-40 manufactured by Asahi Dow Co., Ltd.) was used.
(resin content: 40%)
An experiment was carried out under the same conditions as in Example 1, except that a mixture containing 0 parts of anchor was diluted with water to give a resin content of 0.5% and was roll coated at 5.67 min/hr.

The results were as follows. Static friction angle 22.00 Slip property Good haze value 1.0% Shedding property 0 class blocking resistance A Heat sealing property 27000 IOOO Yu/C 30000 1030 Yu/Ku 33000 1000 Tanohada glue sealing property 790 Yu/curl control Example 3 Medium 25-layer film formed by T-die melt extrusion method, thickness 4
The coating liquid used in Example 2 was applied to one side of a 0r saponified ethylene-pinyl acetate copolymer film (ethylene content in the copolymer: 38 mol%, degree of saponification of vinyl acetate component: 98.7 mol%). It was roll coated at a rate of 4.8 coats/hr and then dried at a roll surface temperature of 10,500.

The net coat amount was 0.011 yen/tiger. The results are shown in Table 2. Comparative Example 5 Raw material film of Example 3 Comparative Example 6 An aqueous suspension of colloidal silica (average particle size 18 hr) was applied to the raw material film of Example 3 at a rate of 0.015 m/h and dried.

Control Example 7 The raw material film of Example 7 was coated with an aqueous polystyrene dispersion (
The film was coated with a film with a concentration of 1.6% and an average particle size of 0.1 french, and the dry coating amount was about 0.011 m/m on net.

The results of Example 3 and Comparative Examples 5 to 7 are shown above in Table 2.

Table 2 Example 4 Film formed by inflation melt extrusion method 0 out of 30
On the side, one sheet of 30A thick Q-dodecene-modified polyvinyl alcohol film (copolymerization ratio of Q-dodecene 4.5
(mol%, degree of saponification of pinyl acetate component: 99.0 mol%) was cut into two sheets, the front and the back, to obtain a flat film.

Next, the coating liquid used in Example 2 was applied to one side of this film and dried, and then the remaining one side was subjected to the same treatment.
The amount of coat is 0.011 coat per side on the net.
It was a pleasure. Comparative example 8 Raw material film of Example 4 Comparative example 9 Both sides of the raw material film of Example 4 were coated with colloidal silica (
A water suspension with an average particle diameter of 15 m (15 m) was applied with a net at a rate of 0.015 m/day and dried.

Control Example 10 An aqueous polystyrene dispersion (concentration 1.6%, average particle size 0.1 mm) was applied to both sides of the raw material film of Example 4, and the net coating amount per dry side was 0.01 mm. / Final film.

The results of Example 4 and Control Examples 8 to 10 are shown in Table 3.

Claims (1)

[Claims] 1. A method for producing a surface-treated vinyl alcohol polymer film, which comprises applying an ionomer resin emulsion to the surface of the vinyl alcohol polymer film and drying it. 2. The method according to claim 1, which comprises applying a mixture of an ionomer resin emulsion and a vinyl alcohol polymer to the surface of a vinyl alcohol polymer film and drying the mixture.