JPH0471709B2 - - Google Patents

Description

[Detailed description of the invention]

A. Field of Industrial Application The present invention relates to a faded film laminate, particularly to a faded polyvinyl chloride (PVC) wallpaper. B Prior art Saponified ethylene-vinyl acetate copolymer (hereinafter referred to as
EVOH) has excellent chemical resistance, stain resistance, and plasticizer bleed prevention properties, and is used as a film attached to surfaces such as PVC wallpaper and PVC leather.
However, EVOH film has a high gloss level, and for applications such as wallpaper and leather that require erasing, the film is heat-pressed using an erasing roll to perform the erasing process.
However, there is a problem that the gloss of the EVOH surface cannot be erased with highly foamed PVC wallpaper, etc., where sufficient pressure is not applied.
Matte EVOH is required. Conventionally known methods for eliminating film lint include (1) a sandblasting method, (2) a surface treatment method using chemicals, and (3) a method of blending powdered inorganic substances.
However, these methods have drawbacks such as high cost and poor film formation properties. Especially(3)
The method of blending powdered inorganic substances has the drawback that the erasure is not sufficient, and when the blending ratio of the powdered inorganic substances is increased to achieve sufficient erasure, holes are formed in the film, making it impossible to form a film. . Furthermore, the technology for creating a resin composition that is a blend of EVOH and carboxylic acid-modified olefin resin was published in Japanese Patent Application Laid-Open No.
Although it is described in No. 131033, the technique of erasing film is not disclosed. Furthermore, if these techniques are used as they are, pine films cannot be easily obtained. Also, Jitsukō 61-2652
The issue describes a film technology that blends EVOH and carboxylic acid-modified olefin resin, but the blend composition is different from the present invention, and it is neither a pine film technology nor a PVC laminate. C. Problems to be Solved by the Invention The present invention aims to improve the conventional poor moldability and to provide a sufficient fade-out effect. D. Means for Solving the Problems The present invention consists of laminating an erasable film with a gloss level of 60% or less, which is a blend of (A) EVOH and (B) carboxylic acid-modified polyethylene resin, on a polyvinyl chloride base material, particularly on a vinyl chloride wallpaper. It is something. The EVOH of the present invention is a saponified ethylene-vinyl acetate copolymer with an ethylene content of 20 to 60 mol%.
It is preferably 25 to 55 mol%, and the degree of saponification of the vinyl acetate component of the copolymer is 90 mol% or more. If the ethylene content is less than 20 mol%, the film's performance such as water resistance and hot water resistance will deteriorate. In addition, if the ethylene content exceeds 60 mol% or the saponification degree is less than 90 mol%, when the obtained film is laminated to polyvinyl chloride containing a plasticizer and used for wallpaper, etc., the bleed of the plasticizer may occur. Prevention performance etc. deteriorates. This EVOH contains ethylene,
Comonomer components other than the vinyl acetate component may be used freely within the range that does not impede the object of the present invention. Next, the carboxylic acid-modified polyethylene resin used in the present invention is a polyethylene resin to which α, β unsaturated carboxylic acid or the carboxylic acid anhydride is added or grafted. Further, the content (addition amount or grafting amount) of the α,β unsaturated carboxylic acid or the carboxylic acid anhydride is 0.0005 to 0.5 mol%, preferably 0.001 to 0.4 mol%. If it is less than 0.0005 mol%, the dispersibility will be poor when blended with EVOH, and the film erasing effect will be poor.
If it exceeds 0.5 mol%, the viscosity increases during the blending operation and film forming properties deteriorate. The blending ratio of (A) EVOH and (B) carboxylic acid-modified polyethylene resin is (A) 95
-50% by weight, (B) 5-50% by weight blend exhibits the effects of the present invention. More preferred ranges are (A) 92 to 55% by weight and (B) 8 to 45% by weight. If component (B) is less than 5% by weight, the gloss level will not be satisfied. If it exceeds 50% by weight, (A) will not exist in a sea-like manner and (B) will not exist in an island-like manner in the film, and the original performance of EVOH will deteriorate.
There are also disadvantages such as holes in the film. Next, in the present invention, when the melt index (measured at 190°C under a load of 2160 g) of (A) EVOH and (B) carboxylic acid-modified polyethylene resin is MIA and MIB, the following formulas (1) to ( It is important to select a film that satisfies 3), and by doing so, it is possible to obtain a matting film with a desired gloss level of 60% or less. 0.1≦MIA≦15 (1) 0.01≦MIB≦10 (2) 1.5≦MIA/MIB≦100 (3) Preferably, it is within the range of the following formulas (4) to (6). 0.1≦MIA≦15 …(4) 0.01≦MIB≦7.5 …(5) 2≦MIA/MIB≦80 …(6) In particular, the optimal range of MIA/MIB is 3≦MIA/MIB≦80. Outside the range of formulas (1) to (3) above, the desired erasable film cannot be obtained. The carboxylic acid component of the carboxylic acid-modified polyethylene resin used in the present invention is α having 3 to 10 carbon atoms,
β-unsaturated carboxylic acids or carboxylic acid anhydrides, such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride, among which maleic anhydride, Itaconic anhydride is preferred. Examples of the polyethylene resin include high density polyethylene, low density polyethylene, and linear low density polyethylene. Although there are no particular limitations on the method for producing the carboxylic acid-modified polyethylene resin used in the present invention, a method of graft polymerizing an α,β-unsaturated carboxylic acid or the carboxylic acid anhydride to polyethylene is preferred. The blending method of EVOH and carboxylic acid-modified polyethylene resin in the present invention includes a melt blending method using a single screw or twin screw extruder,
Alternatively, there is a dry blend method. During blending, other additives may be added as long as the purpose of the present invention is not impaired. Examples of such additives include antioxidants, ultraviolet absorbers, lubricants, and the like. The film of the present invention can be obtained from the above-mentioned blend by a conventional T-dye method or inflation method. For example, when obtaining a film by the T-die method, it is an important condition to rapidly cool the extruded film. When slowly cooled, the gloss increases and the film becomes unsatisfactory as an erasable film. Here, quenching means making the air gap of the die as small as possible and rapidly cooling it with an air slit or a cast roll by applying electrostatic charge. In the film used in the present invention, (A) EVOH is present in the form of a sea, and (B) the carboxylic acid polyethylene resin is present in the form of islands, and it is thought that these contribute to erasure. Unless (A) becomes ocean-like (B) becomes island-like,
The original surface properties of EVOH are impaired, and defects such as holes are created during film formation. In the present invention, sea-like (dispersion medium component) and island-like (dispersed component) means that the dispersed components are scattered in the form of particles or thin films, and are not continuous over one surface like a laminated film, but are in the form of a lump on the front and back sides of the film. It is not something that penetrates. The film used in the present invention must have a gloss level of 60% or less, preferably 50% or less, and optimally 40% or less. If it exceeds 60%, it is insufficient as an erasable film. Here, the glossiness is the average value of the values measured at five arbitrary points using a Murakami glossmeter at an angle of 75 degrees. Furthermore, the unevenness of the film used in the present invention must be 3 to 15 microns, preferably 4 to 12 microns. If it is less than 3μ, it will not be sufficient as an erasable film, and if it is more than 15μ, holes will easily form in the film. The method for evaluating the degree of unevenness is as follows. A 20cm x 20cm film was sampled, and the thickness was measured at nine locations at appropriate intervals using a thickness measuring device (Saginomiya DIAL INDICATOR).
MODERU LCM-0101) and the average value is defined as (L1). In addition, the weight of the sampling film was measured, and the density of the sampling film was measured using a mixed solvent of toluene and carbon tetrachloride.
Measure the density using the buoyancy method. The thickness of the film calculated from this weight and density is (L2), and the unevenness is ΔL, which is expressed by the following formula. ΔL=(L1)−
(L2) The thickness of the film of the present invention is not particularly limited, but
It is preferably 10-50μ. If it exceeds 50μ, it will be disadvantageous to the rapid cooling operation during film formation. Furthermore, when laminated to polyvinyl chloride wallpaper, the laminate becomes stiff. By laminating the thus obtained erasable film of the present invention on a polyvinyl chloride base material, especially wallpaper or leather made of polyvinyl chloride containing a plasticizer, it is possible to prevent the bleeding of the plasticizer and to achieve gloss. It can give a sense of luxury that has disappeared. In the present invention, polyvinyl chloride means polyvinyl chloride, a copolymer of vinyl chloride and other monomers that can be copolymerized with it (e.g., vinyl acetate, acrylic ester, etc.), and polyvinyl chloride group Examples of materials include polyvinyl chloride wallpaper, polyvinyl chloride leather, polyvinyl chloride desk mat, and polyvinyl chloride clear case. In the present invention, when the above-mentioned erasable film is laminated on a plasticized polyvinyl chloride base material containing a plasticizer (for example, a film or sheet used for wallpaper), it exhibits a remarkable effect. Let me explain the points. Polyvinyl chloride wallpapers often contain plasticizers, in which case the content of plasticizers is often 15-20% based on the total weight. Here, the plasticizer is a plasticizer that is liquid at 20°C, such as dibutyl phthalate, di-2-ethylhexyl phthalate, di-isioctyl phthalate, di-isodecyl phthalate, di-decyl phthalate, di-nonyl phthalate, di- - Phthalate plasticizers such as lauryl phthalate and butylbenzyl phthalate, tricresyl phosphate,
There are phosphate plasticizers such as tri-butyl phosphate and tri-ethylhexyl phosphate, chlorine-containing plasticizers such as chlorinated paraffin, and plasticizers that are solid at room temperature, such as dicyclohexyl phthalate and alcohols with a large number of carbon atoms. Phthalate plasticizers such as phthalate diesters of 13 or more,
Examples include polyhydric alcohol plasticizers such as dipentaerythritol fatty acid ester, and trimellitic acid plasticizers such as trioctyl trimellitate. EVOH having an ethylene content of 60 mol % or less and a saponification degree of 90 mol % or more, preferably 95 mol % or more exhibits plasticizer resistance and plasticizer migration resistance. Among these plasticizers, the former (a plasticizer that is liquid at 20° C.) is a plasticizer that exhibits remarkable migration, but the EVOH can also prevent extremely significant migration of these plasticizers. In particular, the ethylene content is 55 mol% or less, more preferably 50 mol%
EVOH in the area below and 25 mol% or more is
It has very satisfactory properties and exhibits virtually no plasticizer permeability. As the ethylene content increases, the plasticizer permeation resistance gradually decreases, and when the content exceeds 60 mol%, plasticizer migration to the surface is gradually observed when laminated to a flexible polyvinyl chloride sheet or film. As a result, stain resistance also decreases. On the other hand, as the ethylene content decreases, properties such as plasticizer permeability improve further, but water resistance becomes poor in the region of less than 20 mol%. This is not suitable because it damages the surface when cleaning the contamination caused by the cause. In the present invention, wallpaper is typically a flame-retardant paper coated with vinyl chloride or rolled and laminated and then foamed. If a foam having a foaming ratio of 2 or more is used in the present invention, the elimination effect of the present invention will be more pronounced. More preferably, the foaming ratio is 3 or more. The present invention will be further explained below with reference to Examples. % in the examples indicates weight % unless otherwise specified. E Example Example 1, Control Example 1, EVOH 92% with ethylene content 38 mol%, saponification degree 99.4 mol%, melt index 3.8 g/10 minutes (190°C, load 2160 g conditions), maleic anhydride 8% high density polyethylene resin with a content (grafting amount) of 0.09 mol% and a melt index of 1.0 g/10 minutes (190°C, load 2160 g) was blended in a twin-screw extruder and pelletized. The blend pellets were formed into a film using a T-die extruder while being rapidly cooled using an air slit to obtain a 30μ film. The gloss level of this film is 42%, and the unevenness is
It was 4.1μ. EVOH the cross section of the film of Example 1
When dyed with an iodine solution that only stains the resin and observed under a microscope, the carboxylic acid-modified polyethylene resin is EVOH.
It has been confirmed that there are islands in the ocean. A schematic diagram of the TD (width direction) cross section of this film is shown in FIG. 1, and a schematic diagram of the MD (machine direction) cross section is shown in FIG. This film was coated with a urethane adhesive and laminated to foamed PVC wallpaper (expansion ratio: 5 times) containing 30% di-2-ethylhexyl phthalate and embossed. This laminate had no seams and had a good appearance. As a control example 1, the ethylene content was 38 mol%, the degree of saponification was 99.4 mol%, and the melt index was 3.8 g/
EVOH97% for 10 minutes (190℃, load 2160g)
and 3% high-density polyethylene resin with a maleic anhydride content (graft amount) of 0.09 mol% and a melt index of 1.0 g/10 minutes (190°C, load 2160 g).
were blended and pelletized using a twin-screw extruder. This blend pellet was rapidly cooled using a T-die extruder using an air slit to form a film to form a film of 28 μm.
I got the film. The gloss level of this film is 75
%, and the degree of unevenness was 2.2μ. This film was coated with a urethane adhesive and laminated to foamed PVC wallpaper (expansion ratio: 5 times) containing 30% di-2-ethylhexyl phthalate and embossed. This laminate had seams and had a poor appearance. Example 2, Control Example 2, ethylene content 44 mol%, saponification degree 99.4 mol%, melt index 5.0 g/10 minutes (190°C, load 2160 g), EVOH 55%, itaconic acid content (grafted amount ) 0.005 mol%, melt index 0.2 g/10 minutes (190℃, load 2160g)
45% low density polyethylene resin was blended using a single screw extruder and pelletized. The blend pellets were formed into a film using a T-die extruder while being rapidly cooled using an air slit to obtain a 25μ film. The gloss of this film is 18% and the unevenness is 7.5μ
It was hot. Furthermore, when the cross section of this film was observed under a microscope in the same manner as in Example 1, it was confirmed that the carboxylic acid-modified polyethylene resin existed in the form of islands in the sea of EVOH. This film is coated with a urethane adhesive to create foamed PVC wallpaper containing 45% di-2-ethylhexyl phthalate (foaming ratio: 6x).
It was laminated and embossed. This laminate had no seams and had a good appearance. As a control example 2, the ethylene content was 44 mol%, the degree of saponification was 99.4 mol%, and the melt index was 5.0 g/
EVOH45% for 10 minutes (190℃, load 2160g)
and itaconic acid content (grafting amount) 0.005 mol%,
Melt index 0.2g/10 minutes (190℃, load
55% of low density polyethylene resin (2160g condition) was blended into pellets using a single screw extruder. This blended pellet was rapidly cooled using a T-die extruder using an air slit to form a film of 25 μm.
I got the film. This film had holes and was defective. In addition, the cross section of this film is shown in Example 1.
Similar observation under a microscope confirmed that there were no islands of carboxylic acid-modified polyethylene resin in the sea of EVOH. Example 3, Control Example 3, ethylene content 52 mol%, degree of saponification 95.5 mol%, melt index 8.7 g/10 minutes (190°C, load 2160 g), EVOH 75%, maleic anhydride content (grafted) A film was formed in the same manner as in Example 1, except that 25% high-density polyethylene resin with a melt index of 0.01 mol% and a melt index of 0.2 g/10 minutes (190°C, 2160 g load) was used to obtain a 45μ film. Ta. The gloss of this film is 28% and the unevenness is 6.7μ
It was hot. Furthermore, when the cross section of this film was observed under a microscope in the same manner as in Example 1, it was confirmed that the carboxylic acid-modified polyethylene resin existed in the form of islands in the sea of EVOH. This film was coated with a urethane adhesive and laminated to foamed PVC wallpaper (foaming ratio: 3 times) containing 35% di-2-ethylhexyl phthalate and embossed. This laminate had no seams and had a good appearance. As a control example 3, the ethylene content was 44 mol%, the degree of saponification was 99.4 mol%, and the melt index was 5.0 g/
EVOH75% for 10 minutes (190℃, load 2160g)
and 25% high-density polyethylene resin with a melt index of 0.2 g/10 minutes (at 190°C and a load of 2160 g).
A film of 45 μm was formed in the same manner as in Example 1 except that a film of 45 μm was used. This film had a streaky pattern in the machine direction and had a poor appearance. The gloss level was 85% and the unevenness was 3.1μ. Furthermore, when the cross section of this film was observed under a microscope in the same manner as in Example 1,
It was observed that there were places where polyethylene resin existed in layers in the EVOH sea, and places where polyethylene resin was in the form of large lumps. This film was coated with a urethane adhesive and laminated to foamed PVC wallpaper (foaming ratio: 3 times) containing 35% di-2-ethylhexyl phthalate and embossed. This laminate had seams and had a poor appearance. Example 4, Control Example 4, EVOH 75% with ethylene content 27.5 mol%, saponification degree 99.5 mol%, melt index 1.3 g/10 minutes (190°C, load 2160 g conditions), maleic anhydride content (grafted) A 30μ film was formed in the same manner as in Example 1, except that 25% of low density polyethylene resin was used (190°C, 2160g load) with a melt index of 0.01 mol% and a melt index of 0.4g/10 minutes (190°C, 2160g load). Obtained. The gloss of this film was 22%. The degree of unevenness was 10.8μ. This film was coated with a urethane adhesive and laminated to foamed PVC wallpaper (expansion ratio 5 times) containing 40% di-2-ethylhexyl phthalate and embossed. This laminate had no seams and had a good appearance. As control example 4, ethylene content was 27.5 mol%,
Saponification degree 99.4 mol%, melt index 1.3
g/10 minutes (190℃, load 2160g)
EVOH75% and maleic anhydride modification (denaturation rate 0.01)
Mol%) Melt Index 0.4g/10min (190
℃, under 2160g load condition) Polypropylene resin
A film of 30μ was obtained in the same manner as in Example 1 except that 255 was used. This film had a streaky pattern in the machine direction and had a poor appearance. Also, the gloss was 81.4%. Example 5 EVOH 75% with ethylene content 31.5 mol%, saponification degree 99.8 mol%, melt index 1.0 g/10 minutes (190°C, load 2160 g conditions), maleic acid modification (modification rate 0.01 mol%), melt index
A film was formed in the same manner as in Example 1, except that 25% of the linear low density polyethylene resin was used at 0.4 g/10 minutes (at 190° C. and under a load of 2160 g) to obtain a 32 μm film. In addition, a foamed PVC wallpaper laminate was obtained in the same manner as in Example 1. Control Example 5 A film was formed in the same manner as in Example 5, except that a linear low-density polyethylene resin with a maleic anhydride content (grafting amount) of 0.01 mol% and a melt index of 2.0 g/10 minutes was used. A foamed PVC wallpaper laminate was obtained. Example 6 A film was formed in the same manner as in Example 5 except that a linear low-density polyethylene resin with a maleic anhydride content (grafting amount) of 0.01 mol% and a melt index of 0.1 g/10 minutes was used. A foamed salt paste wallpaper laminate was obtained. Example 7 A film was formed in the same manner as in Example 6 except that EVOH with an ethylene content of 31.3 mol%, a degree of saponification of 99.6 mol%, and a melt index of 7.5 g/10 minutes was used. A wallpaper laminate was obtained. Control example 6 Ethylene content 31.5 mol%, saponification degree 99.5 mol%, melt index 12.0 g/10 minutes EVOH75
%, maleic anhydride content (grafting amount) 0.01 mol %, melt index 0.1 g/10 min linear low-density polyethylene resin was used at 25%. A film and foamed PVC wallpaper laminate were obtained. Table 1 shows the glossiness and unevenness of the films obtained in Examples 5 to 7 and Control Examples 5 to 6, and the appearance evaluation of the foamed PVC wallpaper laminate.

[Table] F Effects of the Invention According to the present invention, a PVC wallpaper laminate with excellent erasability can be obtained, and it can be used for pollution prevention purposes by taking advantage of the characteristics of EVOH.

[Brief explanation of the drawing]

FIG. 1 shows a model TD cross section of the film obtained in Example 1, and FIG. 2 shows a model MD cross section. 1... Carboxylic acid modified polyethylene resin, 2...
...EVOH.

Claims (1)

[Claims] 1. A saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more.
(A) 95-50% by weight and carboxylic acid-modified polyethylene resin (B) 5-50% by weight, melt index of (A) and (B) (measured at 190°C under a load of 2160g)
A laminate comprising a polyvinyl chloride base material laminated with an erasable film that satisfies the following formulas (1) to (3) and has a surface gloss of 60% or less, where MIA and MIB are represented by MIA and MIB. 0.1≦MIA≦15 …(1) 0.01≦MIB≦10 …(2) 1.5≦MIA/MIB≦100 …(3) 2. Claims in which the surface gloss of the erasable film is 40% or less The laminate according to item 1. 3. Wallpaper consisting of a laminate according to claim 1 or 2.