JP3172559B2 - Matte film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a matte film for matte wallpaper and a matte film having excellent stain resistance.

[0002]

2. Description of the Related Art Ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) is excellent in chemical resistance, stain resistance, and bleeding prevention of a plasticizer, and is used for wallpaper or decorative board (hereinafter referred to as PVC) made of polyvinyl chloride resin. It is used by attaching a film to the surface of PVC leather or the like. But,
EVOH films have a high glossiness, and are used in applications such as wallpaper and leather, which are required to be matted because of their low surface reflection, and are subjected to thermocompression bonding with a matting roll to perform matting. However, when the pressure is not sufficiently applied, there is a problem that the gloss of the EVOH surface is not erased.
Is required. Conventionally, methods such as sandblasting, surface treatment with chemicals, polymer blending, and etching have been proposed as methods for matting the film.However, these methods require long processing steps and long processing times, resulting in high costs. And the film-forming property is reduced.

[0003] On the other hand, a method of blending an inorganic filler is also known, but the following disadvantages have been pointed out in a conventional resin film blended with an inorganic filler. The JP 60-195129 discloses there is description about stain resistance film a blend of talc acrylic resin, but has the following problems. In other words, PVC wallpaper is easily contaminated with tobacco smoke, hand stains, graffiti, pigments of various foods, etc.In response to these problems, a stain-resistant wallpaper obtained by laminating an acrylic resin film on the PVC wallpaper is known. Although these wallpapers are superior in stain resistance as compared with non-laminated PVC wallpaper, they are not perfect, and have a drawback that the tendency is increased especially when a long period of time has passed after lamination. Further, the acrylic resin film is inferior in chemical resistance and particularly easily susceptible to esters, ketones, aromatic compounds, and the like. Therefore, it is necessary to pay attention to dirt wiping, which is not satisfactory.

Japanese Unexamined Patent Publication (Kokai) No. 60-135225 proposes a matting film in which talc is blended with an acrylic resin, but the matting effect is insufficient.
It has the problems described above.

[0005] By the way, JP-A-60-224542 Patent Publication No.
Broadcast, JP-A-60-239233, JP-Sho 62-1
Etc. The 5265 JP are known stain-resistant wallpaper, laminated with EVOH film PVC wallpaper, although excellent in chemical resistance and stain resistance, description of matting function by the inclusion of inorganic filler There is no. In addition, EVOH containing an inorganic filler is disclosed in
1822 JP, is a known disclosed as a composition in JP 61-242841 and JP 62-143980 discloses a technique related to films having a smudge resistant and matte function as shown in the present invention The idea is not disclosed.

[0006]

As described above, it was difficult to obtain a film excellent in stain resistance and excellent in matting effect by the prior art. Accordingly, an object of the present invention is to provide a matte film for wallpaper and wallpaper having excellent stain resistance and sufficient matting effect.

[0007]

The above object is achieved by providing a film comprising a resin composition of EVOH and an inorganic filler and having a surface glossiness of a certain value or less. That is, the present invention is a matte film for wallpaper comprising a layer of a resin composition comprising 50 to 99% by weight of EVOH and 50 to 1% by weight of an inorganic filler, and having a surface gloss of at least one side of 60% or less.

Hereinafter, the present invention will be described specifically. EVOH, which is one of the components forming the film of the present invention, is a saponified ethylene-vinyl ester copolymer, and preferably has an ethylene content of 20 to 60 mol%,
Preferably it is 25 to 60 mol%. Ethylene content of 2
If it is less than 0 mol%, the water resistance and the moisture resistance will be reduced, the stress cracking resistance will be reduced, and it will be difficult to maintain good melt processing characteristics. On the other hand, if it is more than 60 mol%, the water resistance and moisture resistance are improved, but the oil resistance is poor, and the oily contaminants easily penetrate, and the stain resistance is poor. The saponification degree of the vinyl ester component needs to be 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more. If the saponification degree is less than 90 mol%, the thermal stability is deteriorated, there is a disadvantage that gels and bumps are liable to be generated at the time of melt processing, and the oil resistance is also lowered, and it becomes impossible to maintain the original properties of EVOH. It becomes difficult to enjoy the effect. Here, as the vinyl ester, vinyl acetate is mentioned as a typical example, but other vinyl esters, for example, lower or higher fatty acid vinyl esters (vinyl propionate, vinyl piperate, etc.) can be used. The vinyl ester may be used alone or in combination of two or more.

In the present invention, as the EVOH, an ethylene content of 20 to 60 mol%, a saponification degree of 90 mol% or more, and a vinylsilane content of 0.0001 to 0.5 mol%
Can be used satisfactorily for the purposes of the present invention. The olefinically unsaturated monomers containing silicon, as disclosed in JP 61-290046 discloses such a conventionally known monomer can be used. For example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, vinyl triacetoxy silane, vinyl tripropionyloxy silane and the like can be mentioned. The silicon content is selected according to each purpose, but is preferably in the range of 0.0001 to 0.5 mol%, particularly preferably 0.001 to 0.1 mol%.

Also, the melt index (A) of EVOH
The value measured under the conditions of a temperature of 190 ° C. and a load of 2160 g according to STM D1238 65T; hereinafter referred to as MI) is not particularly limited, but is 0.1 to 50 g / 10 min. Further, the EVOH referred to in the present invention may be modified with a small amount of a copolymerizable monomer as long as the object of the present invention is not hindered. Examples of the modifying monomer include propylene, 1-butene, 1-hexene, and 4-hexene. Methyl-1-pentene, acrylic acid ester, methacrylic acid ester, maleic acid, phthalic acid, itaconic acid, higher fatty acid vinyl ester, alkyl vinyl ether, N-vinylpyrrolidone, N-normal butoxymethyl acrylamide, N-
Examples thereof include (2-dimethylaminoethyl) methacrylamides or quaternary compounds thereof, and N-vinylimidazole or quaternary compounds thereof.

Next, an inorganic filler which is another component forming the film of the present invention will be described. As the inorganic filler, those having a whiteness of 80 or more as measured by a reflectance measurement using a Kett photovoltaic whiteness meter are desirable, and the weight average flake diameter is a particle diameter of “film thickness × 0.8” μ or less. is important. The whiteness is desirably 80 or more from the viewpoint of the hue of the film film made of the resin composition. For the weight average flake diameter, if the film thickness is larger than “film thickness × 0.8” μ, the blendability and blending with EVOH The film formability of the resin composition obtained by the above becomes poor. Here, the thickness of the film of the present invention is not particularly limited, but is preferably 8 μm to 60 μm, and more preferably 10 μm to 40 μm. That is, the weight average flake diameter depends on the thickness of the film, but is preferably 6 μm or less,
More preferably, it is 4 μm or less. The lower limit is not particularly limited. Note that the weight average flake diameter of the inorganic filler described above shows that there is almost no difference between the value of the raw material inorganic filler before being mixed with EVOH and the value of the inorganic filler present in the film made of the resin composition. Confirmed by scanning electron microscope. Therefore, in the present invention, the weight average flake diameter of the inorganic filler means the value of the inorganic filler before kneading in the EVOH or the value of the inorganic filler present in the film made of the resin composition.

In the present invention, the weight-average flake diameter is defined as a powder (here, an inorganic filler) is classified with a micro sieve or a sieve having various openings, and the result is expressed as Ro.
The value is plotted on a sin-Ramlar diagram and corresponds to the aperture L50 of a microsieve or sieve through which 50% by weight of the total weight of the powder used for measurement passes. That is, the weight average flake diameter L of the powder is (I) or (I
I) Defined by equation. L = L ₅₀ (in the case of micro sheave) (I) L = 2 ^1/2 · L ₅₀ (in the case of sieve) (II)

Here, a portion having a large particle size in the powder is classified by a sieve, and a portion having a small particle size is classified by a microsieve. In the present invention, examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, clay, kaolin, sericite, glass flake, mica, clay minerals such as smectite and balm curite, and the like. Talc and mica are suitable in terms of uniform mixing with EVOH and film forming properties of the resin composition. These inorganic fillers may be used alone or in combination of two or more. These inorganic fillers can be used as they are,
If necessary, those surface-treated with a surfactant, a silane coupling agent or the like can also be used.

In the resin composition of the present invention, EVOH is 50 to 99% by weight, and the inorganic filler is 50 to 1% by weight, particularly 40 to 2% by weight, especially 30 to 3% by weight. Is selected from the range. When the amount of the inorganic filler exceeds 50% by weight, fluidity at the time of melting,
The moldability and strength of the blend are reduced, the film forming property is also reduced, and if less than 1% by weight, the modifying effect is not sufficient.

The film comprising the resin composition of the present invention preferably has a structure in which the inorganic filler does not aggregate in EVOH and has a well-dispersed structure. This feature can be determined by observation with a scanning electron microscope.

Next, a method for obtaining the resin composition in the present invention will be described. In the present invention, the EVOH and the inorganic filler may be blended with E.
First, a method of melt-kneading at a temperature higher than the melting point of VOH (melt-kneading method) is mentioned.
The pellets and the inorganic filler are mixed in a conventional mixer, for example, a Henschel mixer or a super mixer, or the inorganic filler is mixed with the EVOH melt to form a master, which is used as a powder or pellet of EVOH. , And then kneading the mixture above the melting point of EVOH. Without mixing EVOH and the inorganic filler in advance as described above,
H and the inorganic filler can also be directly introduced into the kneader and kneaded. Continuous kneaders such as a continuous intensive mixer and a kneading-type twin-screw extruder (same direction or different direction) are used as kneaders for obtaining a composition having a high degree of dispersion without agglomerates of inorganic fillers. However, a batch-type kneader such as a Banbury mixer, an intensive mixer, or a pressure kneader can also be used.

Among them, the most preferable one for the purpose of the present invention is a continuous intensive mixer. Commercially available models include FCM manufactured by Farrel, CIM manufactured by Japan Steel Works, Ltd., KCM, NCM, LCM, ACM manufactured by Kobe Steel Works, Ltd., and the like. In fact, there is a single screw extruder under these kneaders,
An apparatus that simultaneously performs extrusion pelletization is desirable. Also, a twin-screw kneading extruder having a kneading disk or a kneading rotor, for example, TEX of Japan Steel Works, Ltd.
ZSK manufactured by Werner & Pfleiderer, TEM manufactured by Toshiba Machine Co., Ltd., and PCM manufactured by Ikegai Steel Co., Ltd. are also used for the purpose of kneading in the present invention.

In such a melt-kneading method, if gels or lumps are generated during the kneading and pelletizing operation, it is not preferable at the time of film forming. Therefore, it is necessary to seal the hopper port with nitrogen or extrude at as low a temperature as possible. preferable.

Another method for obtaining the resin composition is E
This is a method (solvent method) in which VOH and an inorganic filler are blended using an EVOH solvent such as a methyl alcohol / water or n-propyl alcohol / water system. The order of compounding is to add an inorganic filler to a solution in which EVOH is dissolved, or vice versa.
Either a method of adding and dissolving VOH or a method of simultaneously adding VOH may be used. After blending, Japanese patent 72
The method disclosed in US Pat. No. 5,520, which separates EVOH mixed with an inorganic filler by precipitation in a strand shape, is preferably used. After the precipitation and isolation, if necessary, treatment such as water washing and acid treatment is performed by a known method, and then drying is performed. In addition, according to the solvent method, an inorganic filler may be added in a saponification process step before obtaining EVOH.

The resin composition of the present invention can be formed by melt-extrusion of resin composition pellets by a T-die or a ring die from an extruder using a screw or plunger. In this case, the resin composition has high hygroscopicity, and when the moisture content is 0.5% or more, if extrusion molding is carried out as it is, foaming occurs and a good film cannot be obtained. To obtain a good film that does not foam, the water content is preferably 0.25
Preferably, the resin composition is dried at 90 to 120 ° C., and then the dried pellet is supplied to an extruder from a hopper purged with nitrogen. The extrusion molding temperature needs to be determined according to the melting point of EVOH of the resin composition. The melting point of EVOH largely depends on its ethylene content and degree of saponification. The melting point of EVOH increases as the ethylene content decreases and the degree of saponification increases, but the molding temperature is 20 to 120 ° C. below the melting point.
A high temperature setting, preferably 30-70 ° C. If the molding temperature is too low, the melting of the resin composition becomes non-uniform, resulting in the formation of lumps, and the melt viscosity is increased to increase the load on the screw, which is not preferable. On the other hand, if the molding temperature is too high, the thermal stability of EVOH of the resin composition decreases,
It is not preferable because it causes gelation due to thermal deterioration and a reduction in extrusion operation time due to generation of kogation at the screw portion. The melt of the resin composition is melt-extruded with the above-described T die or ring die, and subsequently cooled with a cooling roll or a cooling ring to obtain a film having a surface glossiness of 60% or less according to the present invention. The cooling temperature is 40 ~
The temperature is 100 ° C, preferably 50 to 95 ° C. The film after cooling may be subjected to heat treatment.

The resin composition of the present invention contains other thermoplastic resins, fillers, plasticizers, lubricants, desiccants, antioxidants, heat stabilizers, ultraviolet absorbers as long as the object of the present invention is not impaired. , Coloring agents and the like can be freely added.
In particular, it is preferable to add one or two kinds of hydrotalcite-based compounds, metal salts of higher fatty acids such as calcium stearate, magnesium acetate, hinder phenol-based, and hinderamine-based heat stabilizers as a measure to prevent gelation. is there.

Next, what is important in the present invention is that at least one surface of the film obtained from the above composition has a surface gloss of 60% or less. . It is preferably at most 50%, more preferably at most 40%. If it is 60% or more, it is insufficient as a matte film. Here, the glossiness is an average value of values measured at arbitrary five points measured at an angle of 70 degrees with a Murakami glossmeter. A film having such a glossiness can be obtained using the above composition, for example, by employing the method described above.

The film of the present invention can be used in a laminated state with a wallpaper base material, particularly a wallpaper base material containing a polyvinyl chloride resin layer, so that the effect can be more exerted. In particular, when a polyvinyl chloride base material containing a plasticizer is used as the polyvinyl chloride base material, bleeding of the plasticizer onto the surface can be prevented by the film of the present invention. When laminated to a wallpaper substrate, the film of the present invention is in the outermost layer and has a gloss of 6
It is best if no more than 0% of the surface is on the outer surface. The method of lamination is not particularly limited, but includes, for example, a dry lamination method. The adhesive for dry lamination is not particularly limited as long as the interlayer adhesion is sufficient.

Thus, the present inventionMatte film for wallpaper
Has a stain-resistant function and matte effect even for long-term use
Have enough,Matte film for wallpaperVery useful as
It is. Hereinafter, the present invention will be described more specifically with reference to Examples.
However, the present invention is not limited by this.
Absent. Parts mean parts by weight.

[0025]

Example 1 90 parts of EVOH having an ethylene content of 31 mol%, a saponification degree of a vinyl acetate component of 99.5 mol%, an MI of 1.6 g / 10 min, a weight average flake diameter of 1.5 μm, Whiteness 95
Was premixed in a Hensiel mixer, followed by high-speed mixing to obtain a mixture. Continued inner diameter 30
mm mixing chamber, having two stages of mixing rotors, kneading and extruding pellets using a two-stage twin-screw different-direction continuous extruder having a deaeration mechanism between the two rotors and a single-screw extruder connected thereto By carrying out the reaction, pellets of the EVOH resin composition were obtained. The pellet was made substantially anhydrous, and the melting point Tm was measured (heating rate: 10 ° C./min) using Mettler DSC30. Table 1 shows the results.

After drying the pellets at 105 ° C. (water content was 0.2%), an extruder having a 40 mm diameter full flight screw and a 500 mm width coat hanger die (temperature 230 ° C.) Surface temperature 90 ° C
Was formed using a casting roll (cooling roll) of Example 1 to obtain a non-stretched film of the composition having a thickness of 15 μm.
The glossiness of this film was 22%, and it was a film having excellent matting properties. When the cross section of this film was observed with a scanning electron microscope, the talc was not aggregated and the dispersibility of the talc was good.

Using a gravure coater for this film,
Urethane adhesive Adcoat A having a solid content of 20% by weight
D-335A and a curing agent Cat-10 (Toyo Morton Co., Ltd., mixing ratio: 17: 1) were coated to a coating amount of 2 g / m ² (based on solid content), and dried at 70 ° C. for 4 minutes. The polyvinyl chloride resin wallpaper (PVC wallpaper, polyvinyl chloride resin is a plasticizer (diphthalate)) obtained by laminating the coated surface of the film coated with the adhesive and flame-retardant paper thus obtained.
2-ethylhexyl) is combined with 100 parts by weight of polyvinyl chloride resin (including 55 parts by weight) of polyvinyl chloride resin, and pressure-bonded with a hot embossing roll (130 ° C.) to obtain wallpaper having a stain resistance function and the like. Was. After standing at room temperature for one month, the polyvinyl chloride resin layer destroyed the wallpaper, and the adhesive strength was sufficient.

In order to examine the barrier properties of the plasticizer for the polyvinyl chloride resin, a non-plastic polyvinyl chloride film of 6 cm × 6 cm and a thickness of 70 μm was adhered to the EVOH resin composition film surface of the wallpaper, and A 3 kg load is applied to the polyvinyl chloride film, and the test is performed at 70 ° C. for 7 days (the test under these conditions is a temperature that is difficult to experience in daily life.
If the efficacy is maintained under these conditions, it is a condition that the efficacy can be maintained at room temperature for a long period of time) .Then, the weight change of the non-plasticized polyvinyl chloride film was examined.
No increase in weight was observed, and no stickiness was observed on the EVOH resin composition film surface, and the barrier performance of the plasticizer was complete.

In order to examine the stain prevention function (stain resistance), an oil-based red ink (Mitsubishi Marker manufactured by Mitsubishi Pencil Co., Ltd.) having a size of 2 cm × 2 cm was applied to the surface of the EVOH resin composition film of the wallpaper. Lipstick (lipstick made by Shiseido Co., Ltd.), soy sauce (rich soy sauce made by Kikkoman Corp.)
Was applied, and after 24 hours, it was wiped off with gauze with benzine, but no trace was left. Even when wiped off with a gauze moistened with a neutral detergent, no trace was left in the case of lipstick and soy sauce, and sufficient water resistance was observed without damaging the surface with water. Table 1 shows the above results.

Example 2 A test was performed in the same manner as in Example 1 except that the blend ratio of EVOH and talc was changed as shown in Table 1. Table 1 shows the results.

Example 3 A test was carried out in the same manner as in Example 1 except that the EVOH used was changed as shown in Table 1. Table 1 shows the results.

Example 4 A test was carried out in the same manner as in Example 1 except that the talc used was changed as shown in Table 1. Table 1 shows the results.

Comparative Example 1 In Example 1, EVOH alone was used without blending talc, with an ethylene content of 31 mol%, a saponification degree of a vinyl acetate component of 99.5 mol%, and an MI of 1.6 g / 10 min. A test was performed in the same manner as in Example 1 except for the above. The glossiness was high, and no matting property was exhibited. Table 1 shows the results
Shown in

Comparative Examples 2-3 Tests were carried out in the same manner as in Example 1 except that the EVOH used was changed as shown in Table 1. The film appearance and stain resistance were insufficient. Table 1 shows the results.

Comparative Example 4 The same measurement as in Example 1 was carried out except that the blending ratio of EVOH and talc was changed at the ratio shown in Table 1. However, pelletization of the composition was difficult, and various evaluations could not be made. Was. Table 1 shows the results. Table 1 shows the results.

Comparative Example 5 A test was carried out in the same manner as in Example 1 except that the blend ratio of EVOH talc was changed as shown in Table 1. With a small amount of talc blend, the glossiness was high and the mattness was not developed. Table 1 shows the results.

Comparative Example 6 A test was carried out in the same manner as in Example 1 except that the talc used was changed as shown in Table 1. A through hole was generated in the film, and a film that could be used was not obtained. Table 1 shows the results.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

The matte film for wallpaper of the present invention has both excellent stain resistance and matte properties, and is particularly useful for laminating PVC wallpaper and the like.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J 5/18 B32B 27/28 C08K 7/00 C08L 23/26 C08L 29/04

Claims (6)

(57) [Claims] 1. Saponification with an ethylene content of 20 to 60 mol%
Ethylene-vinyl alcohol copolymer having a degree of 95 mol% or more and 50 to 99 wt% and a weight average flake diameter of 6 μ or less
A single-layer matte film for wallpaper having a surface glossiness of at least 60% or less, comprising a resin composition comprising 50 to 1% by weight of an inorganic filler. 2. The method of claim 1, wherein the matte film is coated on a surface.
Laminate so that the surface with a gloss of 60% or less is the outer surface
Multilayer matte film for wallpaper was. 3. An ethylene-vinyl alcohol copolymer
Has a melt index of 0.1 to 50 g / 10 min.
The matte film according to claim 1 or 2. 4. A matte film and a wallpaper substrate according to claim 1, wherein the matte film has a surface gloss.
Wallpaper that is laminated so that the surface with a degree of 60% or less is the outer surface . 5. The wallpaper substrate includes a polyvinyl chloride resin layer.
The wallpaper according to claim 4. 6. An ethylene-vinyl alcohol copolymer
And inorganic filler are kneaded with a twin-screw extruder and then pelletized
And the obtained pellet is formed into a film by an extruder.
2. The method for producing the film according to 1.