JPH07258489A - Composition, film and laminated product - Google Patents

Abstract

PURPOSE:To provide a composition containing a specific saponified ethylene- vinyl ester copolymer, a PE resin modified with a carboxylic acid and an in organic filler, having a stain-proofing function and giving a matte film resistant to losing the matte appearance by heating. CONSTITUTION:This composition contains (A) 40-90wt.% (preferably 60-85wt.%) of a saponified ethylene-vinyl ester copolymer having an ethylene content of 20-65mol% and a degree of saponification of the vinyl ester component of >=90mol%, (B) 5-30wt.% (preferably 5-25wt.%) of a PE resin modified with a carboxylic acid and (C) 5-30wt.% (preferably 5-25wt.%) of an inorganic filler (preferably tale or mica). The matte film produced by laminating a layer of the composition has a surface glossiness of <=50% (preferably <=40%) on at least one surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition, an inexpensive matte film which is less likely to lose its matt when heated, and a laminate having the composition layer.

[0002]

2. Description of the Related Art Conventionally, wallpaper containing a polyvinyl chloride resin layer is known. However, wallpaper containing these polyvinyl chloride resin layers, decorative sheets used for ceiling materials, wall materials, floor materials, etc. for general households, restaurants, factories, trains, automobiles, etc.
PVC steel sheets used for furniture and office machines (hereinafter collectively referred to as wallpaper) are easily contaminated with cigarette smoke, hand dust, graffiti, and pigments in various foods. Further, the plasticizer for polyvinyl chloride resin bleeds on the surface of wallpaper.
There is a problem that dust adheres to the bleeding plasticizer, and the wallpaper is more likely to be stained. Also Japanese sweets and insect repellent,
Various matte films have been used as substitutes for Japanese paper in packaging of soap and the like, but improvement in gas barrier properties is required due to lack of gas barrier properties.

As disclosed in JP-A-58-23973, there is known a stain resistant wallpaper in which an acrylic resin film is laminated on a vinyl chloride wallpaper. However, although these wallpaper are excellent in stain resistance as compared with non-laminated PVC wallpaper, it is difficult to say that they are perfect, and there is a problem that the tendency becomes large especially when a long time has passed after lamination. Further, the acrylic resin film is inferior in chemical resistance and is particularly apt to be attacked by esters, ketones, aromatic compounds and the like, so that it is necessary to pay attention to wiping off stains, which is not satisfactory.

JP-A-60-135225 and JP-A-60-195129 describe a matte film in which talc is blended with an acrylic resin, but the matting effect is insufficient, and the problems mentioned above are also present. There is.

As disclosed in Japanese Utility Model Publication No. 59-172797, a stain resistant wallpaper is known in which a film of a saponified ethylene-vinyl ester copolymer (hereinafter referred to as EVOH) is laminated on a vinyl chloride wallpaper. There is. This wallpaper is
It has excellent chemical resistance and plasticizer barrier properties, and is more resistant to stains than non-laminated PVC wallpaper. Furthermore E
The VOH film has a relatively small electric resistance and is less likely to be charged with static electricity, and therefore has an advantage that dust is not easily attached to the surface of the wallpaper. However, EVOH has a high surface gloss, and even if it is embossed, it has a high gloss. Therefore, an EVOH-based matted film is required.

JP-A-60-224542 and JP-A-60-224542
In JP-A-239233, JP-A-60-242053 and JP-A-62-15265, EVOH is also excellent in blocking the plasticizer for polyvinyl chloride resin, and EVOH is a plasticizer for polyvinyl chloride resin. It is described that the contamination resistance can be improved by using it for blocking. However, even in the above-mentioned Japanese Laid-Open Patent Publication, there is no description about a matted film.

JP-B-51-21822, JP-A-61-
No. 242841 and JP-A No. 62-143980 describe a blend of EVOH and an inorganic filler, but do not describe a stain resistance and a matted film.

JP-A-64-74252 and JP-A-1-
No. 166951 describes a laminate of a matt film made of EVOH and a carboxylic acid-modified polyethylene resin (hereinafter abbreviated as CMPE) and polyvinyl chloride. However, both EVOH and CMPE are expensive, and an inexpensive matted film is desired. Further, there is a drawback that the matte tends to return during heating for embossing.

[0009]

As described above, there is a strong demand for an inexpensive matted film, especially wallpaper, which has a stain-preventing function and is less likely to lose its matte when heated. As a substitute for Japanese paper, a matted film having a good gas barrier property is required.

The present invention was conceived in order to solve the above-mentioned drawbacks of the prior art, and has a barrier property of a plasticizer for polyvinyl chloride resin, a stain prevention function, and the like. An object of the present invention is to obtain an inexpensive matt film which is less likely to lose its matt upon heating, and a matt film which has a good gas barrier property as a substitute for wallpaper, especially wallpaper and Japanese paper.

[0011]

[Means for Solving the Problems] The above objects are 40 to 90% by weight of EVOH having an ethylene content of 20 to 65% by mole, a saponification degree of a vinyl ester component of 90% by mole or more, and CMPE.
It is achieved by providing a composition consisting of 5 to 30% by weight and an inorganic filler of 5 to 30% by weight, and a matted film using the composition. Also provided are a laminate in which the matted film is laminated on at least one surface of a base material such as a polyvinyl chloride resin layer containing a plasticizer, particularly the outermost layer, and a packaging material in which the mat film is laminated with various base materials. To be achieved.

In the present invention, EVOH has an ethylene content of 20 to 65 mol%, preferably 25 to 60.
Those having a mol% and a saponification degree of the vinyl ester component of 90 mol% or more, preferably 95 mol% or more are suitably used. If the ethylene content is less than 20 mol%, the water resistance is poor, and if it exceeds 65 mol%, the oil resistance and the gas barrier property are poor, and oily pollutants easily permeate, which is unfavorable. The degree of saponification of the vinyl ester component is 90
Even if it is less than mol%, the oil resistance and gas barrier properties are inferior,
Oily pollutants are easily penetrated and the stain resistance is also poor, which is not preferable. As a vinyl ester used as a raw material for EVOH, vinyl acetate is preferable from the economical viewpoint. This E
Comonomer components other than ethylene and vinyl ester can be used in VOH within a range that does not impair the object of the present invention.

EVOH may be a composition of two or more kinds of EVOH having different ethylene contents, degrees of saponification and degrees of polymerization, and boric acid, an antioxidant, and
You may blend thermoplastic resins, such as a slip agent, a coloring agent, a deodorant, an antibacterial agent, polyamide, and polyolefin.

In the present invention, CMPE is a polyethylene resin obtained by graft-polymerizing an α, β-unsaturated carboxylic acid or the carboxylic acid anhydride. Also, α, β-
The unsaturated carboxylic acid or the carboxylic anhydride content (grafting amount) is 0.0005 to 0.5 mol%, preferably 0.001 to 0.4 mol%. 0.0005 mol%
If it is less than 0.5%, the dispersibility becomes poor at the time of blending with EVOH, the matte effect of the film is poor, and if it exceeds 0.5 mol%, the viscosity during the blending operation is large and the film forming property becomes poor. Although it is desirable that all polyethylene resins are graft-modified with α, β-unsaturated carboxylic acid or the carboxylic acid anhydride, it is a blend of a high-concentration carboxylic acid-modified seed polymer and an unmodified polymer. The graft amount may be within the above range. Examples of the α, β-unsaturated carboxylic acid or the carboxylic acid anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride, with maleic anhydride being preferred. Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, with high-density polyethylene being preferred.

In the present invention, the inorganic filler is Ke.
tt Whiteness is 80 by reflectance measurement by photoelectric whiteness meter
The above is preferable, and the weight average flake diameter is preferably “film thickness × 0.8” μm or less. The whiteness is 80 in terms of the hue of the matte film.
The above is preferable, and if the weight average flake diameter exceeds “film thickness × 0.8” μm, the blendability with EVOH and the film-forming property of the matted film obtained by blending deteriorate. That is, the weight average flake diameter depends on the film thickness, but is preferably 6 μm or less, and more preferably 4 μm or less. The lower limit value is not particularly limited. The weight average flake diameter of the above-mentioned inorganic filler was confirmed by a scanning electron microscope to be almost the same as the value of the raw material inorganic filler before being mixed with EVOH and the value of the inorganic filler present in the matte film. In the present invention, the weight average flake diameter of the inorganic filler means the weight average flake diameter of the raw inorganic filler before being mixed with EVOH, or the weight average flake diameter of the inorganic filler present in the matted film. .

In the present invention, the weight average flake diameter is
The inorganic filler was classified with a micro sieve or a sieve having various openings, the results were plotted on a Rosin-Rammlar diagram, and 50 of the total weight of the inorganic filler used for measurement was plotted.
Micro sieve or sieve opening through which% passes L ↓ 50
Is a value corresponding to. That is, the weight average flake diameter L of the inorganic filler is defined by the formula (I) or (II). L = L ↓ 50 (for microsieve) (I) L = 20 ↑ 1/2 * L ↓ 50 (for sieve) (II)

Here, the part of the inorganic filler having a large particle size is classified by a sieve, and the part of the inorganic particle having a small particle size is classified by a microsieve. As the inorganic filler in the present invention, calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, clay, kaolin, sericite, glass flakes,
Examples include viscous minerals such as mica, smectite and vermiculite. Of these, EV is talc and mica.
It is preferable in terms of uniform mixing with OH and film forming property of a matted film. These inorganic fillers may be used alone or in combination of two or more. Also, these inorganic fillers may be used as they are,
If necessary, those surface-treated with a surfactant or a silane coupling agent can be used.

The blending ratio of EVOH, CMPE and inorganic filler is 40 to 90% by weight of EVOH and 5 to 30 of CMPE.
% By weight, 5-30% by weight of inorganic filler, preferably E
VOH is 60 to 85% by weight, CMPE is 5 to 25% by weight, and inorganic filler is 5 to 25% by weight. 30 inorganic fillers
If the content exceeds 5% by weight, pinholes are likely to occur in the matte film when deep embossing is applied, and if the content of the inorganic filler is less than 5% by weight, matte tends to return during heating such as high temperature embossing or heat sealing, Also, the matte film tends to be expensive. If the CMPE exceeds 30% by weight, the stain resistance is poor and the gas barrier property is also poor. When the CMPE is less than 5% by weight, pinholes are easily generated in the matte film when deep embossing is applied, and the matte property is not sufficient. EVOH and CMPE
Melt index (temperature 190 ℃, load 2.16k
Measured according to ASTM D 1238 under conditions of g: However, for those with a melting point of around 190 ° C or above 190 ° C, under a load of 2.16 kg, at a plurality of temperatures above the melting point, the absolute temperature of one logarithmic graph is measured. When the reciprocal number is plotted on the horizontal axis and the melt index is plotted on the vertical axis, and the values obtained by externally bending at 190 ° C. are MIa and MIb, respectively, 3 ≦ MIa / MI
When b ≦ 80, a better matted film can be obtained.

In the present invention, EVOH, CMPE and the inorganic filler are melt-blended by a method of pre-blending using a twin-screw extruder, a Brabender plastograph or the like, or by directly feeding them to various molding machines. Then, a method of molding while kneading with a molding machine, once preparing high-concentration master pellets with an extruder,
There is a method of melt-extruding a product diluted to about 1/30. In order to disperse the inorganic filler more uniformly, metal soaps such as sodium stearate, magnesium stearate and zinc stearate, and dispersion aids such as ethylene bis fatty acid amide and polyethylene wax may be added. Further, an antioxidant and an ultraviolet absorber may be added. There is no particular limitation on the order of blending, and EVO
H, CMPE and inorganic filler may be blended at the same time, EVOH and CMPE may be blended first, then inorganic filler may be blended therewith, EVOH and inorganic filler may be blended first, and CMPE may be blended therewith. Alternatively, CMPE and the inorganic filler may be first blended and EVOH may be blended therein.

Further, a method of dispersing an inorganic filler in a solution of EVOH or a method of dissolving EVOH in a dispersion liquid of an inorganic filler and removing a solvent may be followed by blending with CMPE. EVOH by dispersing the inorganic filler in the ethylene-vinyl ester copolymer solution, then saponifying and removing the solvent
And CMPE may be blended therewith, or an inorganic filler may be dispersed during the polymerization of the ethylene-vinyl ester copolymer. Furthermore, a method of dispersing an inorganic filler in a solution of CMPE, or a method of dispersing C in an inorganic filler dispersion liquid
You may melt | dissolve MPE, remove a solvent, and then blend with EVOH.

The thickness of the matte film of the present invention is not particularly limited, but is preferably 10 to 40 μm, and 10 to 3
0 μm is more preferable. When the thickness of this composition layer is, for example, less than 10 μm when laminated with a polyvinyl chloride resin layer, pinholes are easily generated in the matte film during embossing, and the plasticizer blocking property in the polyvinyl chloride resin layer is high. Is preferable, and if it exceeds 40 μm, the cost becomes high.

In the present invention, the matte film has a surface gloss of at least 50% on one side, preferably 45% or less.
Below, it is important that it is more preferably 40% or less. When the surface glossiness exceeds 50%, it is insufficient as a matte film. Here, the glossiness is an average value of arbitrary 5 points measured at an angle of 75 degrees with a Murakami glossiness meter.

The matted film of the present invention can be obtained by a melt extrusion method such as a T-die method or an inflation method. When obtaining a film by the T-die method, for example, rapid cooling of the extruded film is an important condition.
When gradually cooled, the glossiness becomes large and the matte film becomes unsatisfactory. Here, the rapid cooling means that the air gap of the die is made as small as possible and the air is rapidly cooled by the cast roll by the air slit. In the present invention, the composition layer (matted film layer) is effectively used as a laminate with another resin. Examples of the other resin layer include polyvinyl chloride resin, particularly polyvinyl chloride resin containing a plasticizer, polyolefin (polyethylene, polypropylene, etc.), polystyrene, polyester, polyamide and the like. The laminated body is obtained by dry laminating, heat laminating, and polysand laminating. Further, a method of extrusion laminating the composition of the present invention to another resin film,
Alternatively, the composition of the present invention and another resin may be coextruded to form a laminate.

In the present invention, a typical example of the use is one in which the composition layer of the present invention is laminated on a wallpaper containing a polyvinyl chloride resin layer containing a plasticizer. Here, wallpaper means wallpaper (flame-retardant paper, non-woven fabric, glass fiber,
On a support made of asbestos paper, etc., polyvinyl chloride resin, plasticizer, if necessary, a composition prepared by mixing a pigment, a filler, a stabilizer, etc. is laminated by a calendar method, a coating method, etc., Furthermore, these laminates are printed, and by adding a foaming agent, polyvinyl chloride resin is foamed 1.5 to 15 times in the final product), decorative sheets (thin paper). Printed decorative board, which is laminated on a support made of plywood, particle board, etc.), decorative gypsum board, PVC steel plate,
It is a generic term for PVC non-combustible boards and PVC decorative boards.

In the present invention, the plasticizer for polyvinyl chloride resin is liquid at 20 ° C., and is 20 to 7 relative to the total weight.
5% by weight is contained. Examples of the plasticizer which is liquid at 20 ° C. include dibutyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, didecyl phthalate, dinonyl phthalate, butyllauryl phthalate, dilauryl phthalate, butyl phthalate. There are phthalic acid ester-based plasticizers such as benzyl, phosphate ester-based plasticizers such as tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, and chlorine-containing plasticizers such as chlorinated paraffin.

In the present invention, the method for laminating the matted film is not particularly limited. Actual exploitation 59-17279
No. 7, a method using a urethane adhesive, JP-A-60-224542 and JP-A-60-239233.
As described in JP-A No. 60-242053 and JP-A-60-242053, a method of using a mixture of a modified product of a copolymer of vinyl acetate and vinyl chloride and a urethane-based adhesive is exemplified. Alternatively, the composition and a thermoplastic resin capable of adhering to both polyvinyl chloride and the composition may be coextruded, and the obtained film may be laminated.

The laminate of the present invention thus obtained is
Even when used for a long period of time, there is no change in the laminate strength, the stain-preventing function is maintained, and matteness does not return when heated, which makes it very useful as wallpaper.

Another typical example of the use of the present invention is to use the composition layer of the present invention as an alternative to Japanese paper having a gas barrier property and laminate it with another resin. As described above, the laminating method includes a method of co-extruding the composition and another resin, a method of extrusion laminating the composition to another film, a method of dry laminating another film and a matted film, and a matted film. A known method such as a method of extrusion laminating another resin can be adopted. The laminate obtained in this manner is cheaper than the laminate obtained by laminating Japanese paper and a gas barrier film. Washi alternatives include Japanese sweets, bean sweets, delicacies,
Examples include food such as bonito flakes, insect repellents, and chemicals such as soap.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[0030]

【Example】

Example 1 EVOH7 having an ethylene content of 33 mol%, a saponification degree of a vinyl acetate component of 99.5 mol%, and an MI of 5.5 g / 10 min.
5 parts by weight, 15 parts by weight of maleic anhydride graft-modified high-density polyethylene with MI 0.3 g / 10 min, 10 parts by weight of talc powder having a weight average flake diameter of 1.5 μm and whiteness of 95, and a twin screw extruder of 30 mmφ Using 220
Blend pelletized at ° C. 2 the blended pellets
0 mmφ single screw extruder (extrusion temperature 220 ° C,
L / D = 20) was used to obtain a matted film (gloss 18%) having an air gap of 0.5 mm and a cast roll temperature of 60 ° C. and a thickness of 15 μm. A gravure coater was used for this film, and a urethane adhesive Adcoat AD-335A having a solid content concentration of 20% by weight and a curing agent Cat-10 were used.
(Toyo Morton Co., Ltd., mixing ratio 17: 1) coating amount 2
g / m ↑ 2 (based on solid content) Coat to 70 ℃
After drying for 4 minutes with a gravure coater, MPR-TM (manufactured by Nisshin Chemical Co., Ltd.), which is a modified product of a copolymer of vinyl acetate and vinyl chloride dissolved in a solid content concentration of 18% by weight, is used. The coating amount was 2 g / m 2 (solid content basis), and the coating was dried at 70 ° C. for 1 minute.

On the other hand, 100 parts by weight of the paper, 100 parts by weight of polyvinyl chloride resin and 5 parts by weight of the filler are added to the flame-retardant paper for backing impregnated with 24 parts by weight of the guanidine sulfamate flame retardant.
0 parts by weight, plasticizer (di-2-ethylhexyl phthalate) 55 parts by weight, pigment 20 parts by weight, flame retardant 3 parts by weight, stabilizer 2 parts by weight, foaming agent 2 parts by weight, and binazine (organic arsenic antibacterial agent). ) After laminating 2 parts by weight of the formulation, the vinyl chloride was foamed to obtain a vinyl chloride wallpaper.

An adhesive surface coated on the matte film,
Combine the polyvinyl chloride resin surfaces laminated on the paper, 150 ℃
It was pressed with a hot embossing roll and simultaneously embossed to obtain a wallpaper with a stain prevention function. There was no matte return during embossing, and it retained a good appearance.

In order to investigate the stain prevention function, E of the wallpaper is used.
Oily red ink (Mitsubishi Marker made by Mitsubishi Pencil Co., Ltd.) and soy sauce (Kikkoman dark mouth made by Kikkoman Co., Ltd.) were applied to the VOH surface in a size of 2 cm × 2 cm, and wiped off with gauze with benzine 24 hours later. No trace was left on the surface, and even if wiped off with gauze moistened with a neutral detergent, no trace was left on soy sauce, and the surface was not damaged by water, and it had sufficient water resistance. It was confirmed that the stain prevention function was complete, as shown in Table 1.

Comparative Example 1 In Example 1, 30 parts by weight of EVOH and 35 parts of CMPE were used.
The procedure was carried out in the same manner as in Example 1 except that the amount of talc was changed to 35 parts by weight and the amount of talc was changed to 35 parts by weight.

Comparative Example 2 The procedure of Example 1 was repeated, except that CMPE was replaced by ordinary high-density polyethylene that was not modified with carboxylic acid. The evaluation after that was interrupted.

Comparative Example 3 The procedure of Example 1 was repeated except that the talc powder having a weight-average flake diameter of 12 μm and a whiteness of 95 was used, but the pinholes were too frequent to form a good film. The subsequent evaluation was interrupted.

Comparative Example 4 In Example 1, 75 parts by weight of EVOH and CMPE25
The procedure was carried out in the same manner as in Example 1 except that parts by weight and talc were changed to 0 parts by weight. The matte film had a gloss of 22% and good stain resistance, but when it was pressed by a hot embossing roll at 150 ° C. and simultaneously embossed, a matte return was observed.

Example 2 EVOH 8 having an ethylene content of 44 mol%, a saponification degree of a vinyl acetate component of 99.5 mol% and an MI of 1.6 g / 10 min.
0 parts by weight, 10 parts by weight of high density polyethylene grafted with maleic anhydride of 0.3 g / 10 min MI, 10 parts by weight of a talc powder having a weight average flake diameter of 1.5 μm and a whiteness of 95 were mixed with a twin screw extruder. Blend pelletized at 220 ° C. A matte film (glossiness 17%) having a thickness of 15 μm was obtained from the blended pellets at 220 ° C. using a single screw extruder.

An adhesive for dry lamination {Takelac A-385 / Takenate A-50 (manufactured by Takeda Pharmaceutical Co., Ltd.) mixed at a ratio of 6: 1} was applied to the film as a solid content of 3 g / m ↑ 2, After evaporating the solvent at 70 ° C,
A low-density polyethylene film having a thickness of 60 μm {Suzuron L S201 manufactured by Aicello Chemical Co., Ltd.} was laminated to obtain a laminated film.

Gas barrier property is 7.0 ml / m ↑ 2.2
4h • atm (Modern Controls,
Oxtran 10 / 50A type was good at 20 ° C. and 85% RH).

COMPARATIVE EXAMPLE 5 In Example 2, 70 parts by weight of EVOH and 30 parts of CMPE were used.
The procedure was carried out in the same manner as in Example 2 except that the amount of talc was changed to 0 parts by weight. The matte film had a good gloss of 18%, but had a gas barrier property of 17 ml / m ↑ 2.24.
h · atm was inferior to Example 2.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

INDUSTRIAL APPLICABILITY An inexpensive matte film and a laminate having excellent antifouling function and less likely to lose mattness upon heating are obtained, and are useful as wallpaper and as a substitute for Japanese paper requiring gas barrier properties.

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Claims (3)

[Claims] 1. Saponified ethylene-vinyl ester copolymer having an ethylene content of 20 to 65 mol%, a saponification degree of a vinyl ester component of 90 mol% or more, 40 to 90 wt%, and a carboxylic acid-modified polyethylene resin 5 to 30 wt%. And a composition comprising 5 to 30% by weight of an inorganic filler. 2. A matte film comprising the composition according to claim 1 and having a surface glossiness of 50% or less on at least one side. 3. A laminate having at least one composition layer according to claim 1.