JPH0649816B2 - Interior material - Google Patents

Description

Detailed Description of the Invention A. TECHNICAL FIELD The present invention relates to an interior material using a matte film.

B. Prior art Saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVOH
Is excellent in chemical resistance, stain resistance, and bleeding prevention of a plasticizer, and is used by being film-coated on the surface of interior materials such as PVC wallpaper and PVC leather. However, in applications such as wallpaper and PVC leather, which have high glossiness such as EVOH film and require matteness, matting treatment is performed by thermocompression bonding with a matting roll. However, in the case where sufficient pressure cannot be applied, there is a problem that the gloss of the EVOH surface is not erased, and matted EVOH is required. As a conventional method of delustering the film, (1) sandblasting,
Known are (2) a surface treatment method using a chemical agent, (3) a method of blending a powdered inorganic substance, and the like. However, these methods have drawbacks such as high cost and poor film forming property. In particular, the method of blending the powdered inorganic substance (3) has a drawback that matte is not sufficient, and if the blending ratio of the powdered inorganic substance is increased to achieve sufficient matte, the film cannot be formed due to holes. Have

Furthermore, a technique of a resin composition obtained by blending EVOH and a carboxylic acid-modified olefin resin is disclosed in JP-A-55-131033.
However, the technique of the matte film is not disclosed. Moreover, when these techniques are used as they are, a matte film is not easily obtained. Also, Japanese Utility Model Publication No. 61-2652 describes a technique of a film obtained by blending EVOH and a carboxylic acid-modified olefin resin, but the blend composition is different from that of the present invention and is not a technique of matte film.

C. DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention provides an interior material in which the surface thereof is coated with a film which is improved in conventional moldability and has a sufficient matting effect.

D. Means for Solving the Problems The present invention is an interior material in which (A) EVOH is blended with (B) a carboxylic acid-modified polyethylene resin and a matte film having a gloss of 60% or less is coated on the surface.

E. More Detailed Description of the Invention EVOH of the present invention is a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, preferably 25 to 60 mol%.
It is 55 mol% and the degree of saponification of the vinyl acetate component of the copolymer is 90% or more. If the ethylene content is less than 20 mol%, the performance of the film such as water resistance and hot water resistance deteriorates. When the ethylene content is more than 60 mol% or the saponification degree is less than 90%, when the obtained film is laminated on polyvinyl chloride containing a plasticizer and used for wallpaper, etc., the plasticizer is prevented from bleeding. Performance, etc. will decrease. It is free to use comonomer components other than ethylene and vinyl acetate components in this EVOH within a range that does not impair the object of the present invention.

Next, the carboxylic acid-modified polyethylene resin used in the present invention is a polyethylene resin to which an α, β unsaturated carboxylic acid or the carboxylic acid anhydride is added or grafted. Further, the α, β unsaturated carboxylic acid or the carboxylic acid anhydride content (addition amount or graft amount) is 0.0005 to 0.
It is 5 mol%, preferably 0.001 to 0.4 mol%. If it is less than 0.0005 mol%, the dispersibility becomes poor upon blending with EVOH, and the effect of delustering the film is poor, whereas if it exceeds 0.5 mol%, the viscosity during the blending operation is large and the film-forming property becomes poor. The blending ratio of (A) EVOH and (B) carboxylic acid-modified polyethylene resin is (A) 95 to 50% by weight,
(B) A blend of 5 to 50% by weight exhibits the effect of the present invention. More preferable ranges are (A) 92 to 55% by weight, (B) 8 to
45% by weight. If the component (B) is less than 5% by weight, the glossiness is not satisfied. When it exceeds 50% by weight, (A) does not exist in the form of sea and (B) does not exist in the form of island in the film E
The original performance of VOH is deteriorated, and there are drawbacks such as holes in the film.

Next, in the present invention, the melt index (2160) of (A) EVOH and (B) carboxylic acid-modified polyethylene resin is used.
Measured at 190 ° C under g load: However, if the melting point is near 190 ° C or exceeds 190 ° C, it is measured at multiple temperatures above the melting point under 2160g load, and the reciprocal of the absolute temperature is plotted on the horizontal axis as the melt temperature on a semilog graph. Plot the index on the vertical axis,
When MIA and MIB are values extruded to ℃,
It is preferable to select so as to satisfy (1) to (3).

0.1 ≦ MIA ≦ 15 (1) 0.01 ≦ MIB ≦ 10 (2) 1.5 ≦ MIA / MIB ≦ 100 (3) Preferably, the following formula (4)- The range is (6).

0.1 ≦ MIA ≦ 15 ………… (4) 0.01 ≦ MIB ≦ 7.5 ………… (5) 2 ≦ MIA / MIB ≦ 80 ………… (6) Especially, the optimum range of MIA / MIB is 3 ≦ MIA / MIB ≦ 80.

When the ranges of the above formulas (1) to (3) are satisfied, a desired matte film for surface coating of a suitable interior material can be obtained.

The carboxylic acid component of the carboxylic acid-modified polyethylene resin used in the present invention is an α, β-unsaturated carboxylic acid having 3 to 10 carbon atoms or the carboxylic acid anhydride, such as acrylic acid, methacrylic acid, ethacrylic acid, and maleic acid. Examples thereof include acids, itaconic acid, maleic anhydride, and itaconic anhydride. Of these, maleic anhydride and itaconic anhydride are preferable. The polyethylene resin includes high density polyethylene, low density polyethylene, and linear low density polyethylene.

The method for producing the carboxylic acid-modified polyethylene resin used in the present invention is not particularly limited, but a method of graft-polymerizing an α, β-unsaturated carboxylic acid or the carboxylic acid anhydride onto polyethylene is preferable.

The blending method of the EVOH and the carboxylic acid-modified polyethylene resin in the present invention includes a method such as melt blending with a single-screw or twin-screw extruder. The blend is preferably pelletized once and then formed into a film. When the film is formed as it is without being pelletized, the dispersion of the blend is poor, and the desired matte film for surface coating of the interior material may not be obtained. During this blending, other additives may be added within the range not impairing the object of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers and lubricants. The film used in the present invention is obtained by melt-forming the above-mentioned blend by a usual T-die method or an inflation method. For example, when the film is obtained by the T-die method, rapid cooling of the extruded film is a suitable condition.
When slowly cooled, the glossiness increases and the matte film becomes unsatisfactory. Here, the term "quick cooling" means that the die air gap is made as small as possible, and the extruded film is cooled by air slit, air chamber or electrostatic application, for example, adjusted to 60 ° C or lower, preferably 60 to 30 ° C. It is to cool rapidly by bringing it into close contact with the cast roll.

Next, in the film used in the present invention, (A) EVOH is present in the form of sea and (B) the carboxylic acid-modified polyethylene resin is present in the form of islands, and it is considered that this contributes to delustering. If (A) is not sea-like and (B) is island-like, EV
The original surface properties of OH are impaired, and defects such as holes are formed during film formation. In the present invention, the sea-like (dispersion medium component) and the island-like (dispersion component) are dispersion components dispersed in a granular or thin film form, and are not continuous on one surface like a laminated film but are in a lump form on the front and back of the film. It is not something that penetrates.

The glossiness of at least one side of the film used in the present invention is 60.
% Or less is necessary, preferably 50% or less, and optimally 40% or less. If it exceeds 60%, it is insufficient as a matte film for surface coating of interior materials such as wallpaper and vinyl chloride leather. Here, the glossiness is the average value of the values measured at any 5 points measured with a Murakami glossmeter at an angle of 75 degrees.

Furthermore, the unevenness of the film used in the present invention is 3 to 15 μm.
And it is preferably 4 to 12 μ. Three
If it is less than μ, it is not enough as a matte film for coating the surface of the interior material, and if it exceeds 15 μ, holes are likely to be formed in the film. The method for evaluating the degree of unevenness is as follows.

A 20 cm x 20 cm film is sampled and the thickness is measured at appropriate intervals at nine locations. Thickness measuring device (DIAL INDICA manufactured by Saginomiya)
TOR MODERU LCM-0101) and measure the average value (L1)
And In addition, the weight of the sampling film is measured,
Moreover, the density of the sampling film is measured by a buoyancy method using a mixed solvent of toluene and carbon tetrachloride. Calculate the film thickness from this weight and density (L2)
And When the unevenness degree is ΔL, it is expressed by the following equation.

ΔL = (L1) − (L2) The thickness of the film used in the present invention is not particularly limited, but is preferably 10 to 50 μm. If it exceeds 50 μ, it is disadvantageous for the rapid cooling operation during film formation.

By laminating this film on the surface of the interior material, especially on the surface of the wallpaper made of polyvinyl chloride containing a plasticizer, it is possible to prevent bleeding of the plasticizer and to impart a sense of high-grade lusterlessness. .

The present invention will be further described with reference to examples. Unless otherwise specified,% in the examples means% by weight.

F. Examples Example 1, Control Example 1 Ethylene content 38 mol%, saponification degree 99.4 mol%, melt index 3.8 g / 10 min (190 ° C., load 2160 g conditions)
92% EVOH pellets, maleic anhydride modified (modification rate 0.09 mol%), melt index 1.0 g / 10 minutes (190
8% of high-density polyethylene resin pellets (under conditions of temperature and load of 2160 g) were blended by a twin-screw extruder and pelletized.

This blend pellet was extruded by a T-die extruder onto a cast roll adjusted to 40 ° C, and at the same time, air was blown onto the film surface on the side opposite to the cast roll side from the air slit to form a film on the film while rapidly cooling it. I got a film. The film has a gloss of 42% and an unevenness of 4.
It was 1μ. When the cross section of the film of Example 1 was dyed with an iodine solution that stains only EVOH and observed under a microscope, it was confirmed that the carboxylic acid-modified polyethylene resin was present in the EVOH sea in an island shape. TD of this film
A schematic view of the cross section (width direction) is shown in FIG. 1 in MD (machine direction).
A schematic view of the cross section is shown in FIG.

As Comparative Example 1, ethylene content 38 mol%, saponification degree 9
9.4 mol%, melt index 3.8 g / 10 minutes (190 ° C,
97% EVOH pellets under a load of 2160 g and maleic anhydride modified (modification rate 0.09 mol%), melt index
3 g of high-density polyethylene of 1.0 g / 10 minutes (under conditions of 190 ° C. and load of 2160 g) was blended by a twin-screw extruder and pelletized. This blend pellet was formed into a film on the film under the same conditions as in Example 1 to obtain a 28 μm film. The glossiness of this film was 75% and the roughness was 2.2μ.

Example 2, Comparative Example 2 Ethylene content 44 mol%, saponification degree 99.4 mol%, melt index 5.0 g / 10 min (190 ° C., load 2160 g conditions)
55% EVOH pellets and modified with itaconic acid (modification rate of 0.
005 mol%), melt index 0.2 g / 10 min (190
45% of low-density polyethylene (under conditions of temperature and load of 2160 g) was blended by a single-screw extruder and pelletized. This blend pellet was formed into a film on the film under the same conditions as in Example 1 to obtain a film of 25 μm. The glossiness of this film was 18% and the roughness was 7.5μ. When the cross section of this film was observed with a microscope as in Example 1, it was confirmed that the carboxylic acid-modified polyethylene resin was present in the EVOH sea in the form of islands.

As Comparative Example 2, ethylene content 44 mol%, saponification degree 9
9.4 mol%, melt index 5.0 g / 10 minutes (190 ° C,
Uniaxially screened with 45% EVOH pellets (under a load of 2160 g), 55% low density polyethylene with itaconic acid modification (modification rate 0.005 mol%), melt index 0.2 g / 10 min (190 ° C, under a load of 2160 g). It was blended in an extruder and pelletized. This blend pellet was formed into a film on the film under the same conditions as in Example 1 to obtain a film of 25 μm. This film had holes and was defective. When the cross section of this film was observed with a microscope in the same manner as in Example 1, it was confirmed that the carboxylic acid-modified polyethylene resin did not exist in the EVOH sea like islands.

Example 3, Control Example 3 52 mol% ethylene content, 95.5 mol% saponification degree, melt index 8.7 g / 10 min (190 ° C., load 2160 g conditions)
75% EVOH pellets and maleic acid modified (modification rate 0.01
Mol%), melt index 0.2 g / 10 min (190 ° C., load 2160 g) 25% high-density polyethylene was used, except that a film was formed on the film in the same manner as in Example 1 to obtain a film of 45 μm. . The gloss of this film is 28%, and the unevenness is 6.7.
It was μ. When the cross section of this film was observed with a microscope as in Example 1, it was confirmed that the carboxylic acid-modified polyethylene resin was present in the EVOH sea in the form of islands.

As Comparative Example 3, ethylene content 44 mol%, saponification degree 9
9.4 mol%, melt index 5.0 g / 10 minutes (190 ° C,
Example 1 except that 75% of EVOH pellets (under a load of 2160 g) and 25% of high-density polyethylene of a melt index of 0.2 g / 10 min (190 ° C., under a load of 2160 g) were used.
A film was formed on the film in the same manner as, to obtain a film of 45 μm. This film had a streak pattern in the machine direction and had a poor appearance. The glossiness was 85% and the unevenness was 3.1μ. Further, when the cross section of this film was observed with a microscope in the same manner as in Example 1, a portion where the polyethylene resin was layered in the sea of EVOH and a portion where the polyethylene resin was formed into a large lump were observed.

Example 4, Control Example 4 Ethylene content 27.5%, saponification degree 99.5 mol%, melt index 1.3 g / 10 min (190 ° C., load 2160 g conditions)
Of 75% EVOH pellets and maleic acid modified (modification rate
0.01 mol%), melt index 0.4 g / 10 min (190
A film was formed on the film in the same manner as in Example 1 except that 25% of low-density polyethylene (under conditions of temperature and load of 2160 g) was used, and
I got a film. The glossiness of this film was 22%. The irregularity was 10.8μ.

As Comparative Example 4, ethylene content 27.5 mol%, saponification degree
99.4 mol%, melt index 1.3 g / 10 min (190 ° C,
75% EVOH pellets under load of 2160 g) and maleic acid modified (modification rate 0.01 mol%) melt index 0.
A film was formed on the film in the same manner as in Example 1 except that 25% of polypropylene of 4 g / 10 min (190 ° C., load of 2160 g) was used to obtain a film of 30 μm. This film had a streak pattern in the machine direction and had a poor appearance. The glossiness was 81.4%.

Example 5 Ethylene content 31.5%, saponification degree 99.5 mol%, melt index 1.0 g / 10 min (190 ° C., load 2160 g)
Of 75% EVOH pellets and maleic acid modified (modification rate
0.01 mol%), melt index 0.4 g / 10 min (190
Linear low-density polyethylene at ℃ and load of 2160g)
A film was formed on the film in the same manner as in Example 1 except that 25% was used,
A 32μ film was obtained.

Control Example 5 Maleic acid modification (modification rate 0.01 mol%), melt index 2.0 g / 10 min linear low density polyethylene was used in the same manner as in Example 5 except that a film was formed into a film to obtain a 33 μ film. .

Example 6 A film having a thickness of 33 μm was obtained by forming a film on a film in the same manner as in Example 5 except that linear low density polyethylene modified with maleic acid (modification rate 0.01 mol%) and melt index of 0.1 g / 10 min was used. .

Example 7 A film having a thickness of 30 .mu.m was obtained by forming a film on a film in the same manner as in Example 6 except that EVOH pellets having an ethylene content of 31.3%, a saponification degree of 99.6 mol%, a melt index of 7.5 g / 10 min were used. It was

Control Example 6 Ethylene content 31.5%, saponification degree 99.5 mol%, melt index 12.0 g / 10 min, EVOH pellet 75%,
Maleic acid modification (modification rate 0.01 mol%), melt index 0.1 g / 10 min linear low density polyethylene was used in the same manner as in Example 1 except that 25% was used.
I got a film.

Glossiness of the films obtained in Examples 5-7 and Comparative Examples 5-6,
The unevenness is shown in Table-1.

Comparative Example 7 The blend pellets used in Example 1 were mixed with a T-die extruder.
The film was extruded onto a drum adjusted to 80 ° C. and slowly cooled to form a film on the film to obtain a film of 30 μm. The glossiness of this film was 65%, and the roughness was 2.8μ.

Comparative Example 8 In Comparative Example 7, maleic anhydride modified high-density polyethylene resin was replaced with maleic anhydride modified (modification rate 0.1 mol%), melt index 6 g / 10 min ethylene (75 wt%)-acrylic acid ethyl ester. A film of 30 μm was obtained under the same conditions as in Comparative Example 7 except that (25% by weight) copolymer was used. The gloss of this film is 68%, and the unevenness is
It was 2.7μ.

By laminating the matte film obtained in the above Examples 1 to 7 on the surface of a soft polyvinyl chloride wallpaper containing a plasticizer, a high-quality wallpaper with no bleeding of the plasticizer and a loss of gloss can be obtained. I was able to get it.

G. EFFECTS OF THE INVENTION According to the present invention, interior materials such as wallpaper and vinyl chloride leather, which have a high-definition appearance with no gloss, can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a TD cross section of a film covering the surface of the wallpaper obtained in Example 1, and FIG. 2 is a schematic view of an MD cross section. 1 ... Carboxylic acid modified polyethylene 2 ... EVOH

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 29/04 51/06 LLE 7142-4J E04F 13/00 B 9127-2E (56) References Special Kai 62-153333 (JP, A) JP 62-153332 (JP, A) JP 61-252258 (JP, A) JP 60-212444 (JP, A) JP 55-131033 ( JP, A) JP-A-52-77160 (JP, A)

Claims (2)

[Claims] 1. An ethylene content of 20 to 60 mol% and a saponification degree of 90%.
The above saponified ethylene-vinyl acetate copolymer (A) 95
The interior material is composed of 5 to 50% by weight and 5 to 50% by weight of the carboxylic acid-modified polyethylene resin (B), and has a surface coated with a matte film having a surface glossiness of 60% or less on at least one side. 2. The interior material according to claim 1, wherein the following formulas (1) to (3) are satisfied when the melt indexes of (A) and (B) are MIA and MIB. 0.1 ≦ MIA ≦ 15 ………… (1) 0.01 ≦ MIB ≦ 10 ………… (2) 1.5 ≦ MIA / MIB ≦ 100 ………… (3)