JPH01166951A - Laminated body - Google Patents

Abstract

PURPOSE:To improve moldability and obtain a sufficient mat effect, by a method wherein a mat film of predetermined glossiness obtained by blending carboxylic acid modified polyethylene resin with EVOH is laminated to vinyl chloride wall paper. CONSTITUTION:EVOH is of a saponified matter of an ethylene-vinyl acetate copolymer, whose ethylene content is 20-60mol.%, which is preferably 25-55mol.% and a saponification degree of an ingredient of vinyl acetate of the copolymer is 90% or more. Carboxylic acid modified polyethylene resin is obtained by adding or grafting alpha, beta unsaturated carboxylic acid or an anhydride of the said carboxylic acid to polyethylene resin. As for a compounding ratio between the EVOH 2 and carboxylic modified polyethylene resin 1, blending of 95-50wt.% of the former and 5-50wt.% of the latter display a suitable effect. When melt indexes of the EVOH and carboxylic acid modified polyethylene resin are made respectively MIA and MIB, the most suitable range of MIA/MIB is 3<=MIA/MIB<=80. With this construction, the target mat film whose glossiness is 60% or lower can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION A. INDUSTRIAL APPLICATION The present invention relates to matte film laminates, particularly matte polyvinyl chloride (salt) wallpaper.

"Ran-Nira J" L-niproethylene-vinyl acetate copolymer saponified product (hereinafter referred to as EVOH)
) has excellent chemical resistance, stain resistance, and plasticizer bleed prevention properties, and is used as a film attached to the surfaces of PVC wallpaper, PVC leather, etc. However, the EνOH film has a high level of gloss, and for applications such as wallpaper and leather that require a matte finish, it is heat-pressed using a matte roll to perform the matte treatment. However, there is a problem that the gloss of the EVOH surface cannot be erased in highly foamed PVC wallpaper or the like where sufficient pressure is not applied, and matte EVOH is required. Conventional methods for removing gloss from film include (1) sandblasting method, (
2) A surface treatment method using chemicals, and (3) a method of blending powdered inorganic substances are known.

However, these methods have drawbacks such as high cost and poor film formation properties. In particular, the method (3) of blending powdered inorganic substances does not provide sufficient matteness, and if the blending ratio of powdered inorganic substances is increased to achieve sufficient matteness, there are holes in the film, which prevents film formation. have.

Furthermore, the technology of a resin composition blending Eν0)1 and a carboxylic acid-modified olefin resin was disclosed in Japanese Patent Application Laid-Open No. 55-4
31033, but it does not disclose the matte film technology, and if these techniques are used as they are, it is not easy to obtain a matte film. is EVOH
h', which describes a film technology blending a carboxylic acid-modified olefin resin, has a blend composition different from that of the present invention, and is neither a matte film technology nor a PVC laminate.

C1L! ga ゛ −. The present invention aims to improve the conventional poor moldability and to provide a sufficient matting effect.

D5 A method for solving the problem The present invention is a matte film with a gloss level of 60% or less, which is a blend of (A) EVOH and (B) carboxylic acid-modified polyethylene resin, and is laminated on a polyvinyl chloride base material, especially PVC wallpaper. It is something.

61 More detailed description of the present invention β The EVOH of the present invention is a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%, and a copolymer of vinyl acetate. The degree of saponification of the components is 9e% or more. Ethylene content is 2
If it is less than 0 mol%, the performance of the film, such as water resistance and hot water resistance, will deteriorate. In addition, if the ethylene content exceeds 60 mol% or the degree of saponification is less than 90%, when the obtained film is laminated on polyvinyl chloride containing a plasticizer and used for wallpaper, etc., the bleeding of the plasticizer may be prevented. Performance etc. will deteriorate. It is free to use comonomer components other than ethylene and vinyl acetate components in this EVOH within a 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. In addition, the content (addition amount or grafting amount) of α, β unsaturated carboxylic acid or the carboxylic acid anhydride is o, ooo
s~0.5 mol%, preferably o,oot~0.4 mol%
There is. If it is less than o,ooos mol%, the dispersibility will be poor when blended with EVOH, and the film will have poor matting effect.On the other hand, if it is more than 0.5 mol%, the viscosity will increase during blending, and the film forming property will be poor. Deteriorate. (A)EV
The blending ratio of OH and (B) carboxylic acid-modified polyethylene resin is (A) 95 to 50% by weight, (B) 5 to 50% by weight.
Blends exhibit the effects of the present invention. More preferred ranges are (A292-55% by weight, (B) 8-45% by weight).

If component (B) is less than 5% by weight, the gloss level will not be satisfied, and if it exceeds 50% by weight, (A) will not exist latently and (B) will not exist in the form of islands in the film, impairing the original performance of EVOH. This may cause problems such as holes in the film.

Next, in producing the matte film used in the present invention, for example, (A) EVOHl (B) the melt index (216
When MIA and MIS (measured at 190° C. under 0g load) are selected to satisfy the following formulas (1) to (3), a matting film with a target glossiness of 60% or less can be obtained. Can be done.

0.1≦MIA≦15 (1)0.01
≦ MIB ≦ TO (2) C5 ≦ MIA/MIB ≦ TOO (3) Preferably, it is within the iiF range of the following formulas (4) to (6).

01≦MIA≦I5 (4)001≦
MIB ≦7.5 (5)2
≦ MIA/MIB ≦80 (6) Especially for MI8, the maximum M range of MIB is 3≦ MIA/MI
B≦80.

Outside the range of formulas (1) to (3) above, the desired matte film cannot 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 an anhydride of the carboxylic acid, such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, etc. Examples of the acid include itaconic acid, maleic anhydride, and itaconic anhydride. Among these, maleic anhydride and itaconic anhydride are 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 in which polyethylene is graft-polymerized with an α,β-unsaturated carboxylic acid or the carboxylic acid anhydride is preferred.

Methods for blending EVOH and carboxylic acid-modified polyethylene resin in the present invention include melt blending using an axle or twin screw extruder. It is preferable to form the blend into a film after it has been pelletized. If the blend is formed into a film as it is without being pelletized, the blend may be poorly dispersed and the desired matte film may not be obtained. During this blending, other additives may be added as long as the object of the present invention is not impaired. Examples of such additives include antioxidants, ultraviolet absorbers, lubricants, etc. The film of the present invention can be obtained by adding the above blend to the conventional T-die method or inflation method. When obtaining a film by the T-die method, it is an important condition to rapidly cool the extruded film.

If it is slowly cooled, the gloss will increase and it will be unsatisfactory as an erasable film. Here, quenching means making the air gap of the die as small as possible and rapidly cooling it with a cast roll using an air slit or electrostatic application.

In the film used in the present invention, (A) EVOH exists latently and (B) carboxylic acid-modified polyethylene resin exists in the form of islands, which are thought to contribute to the matte appearance. If (A) is latent (B) is not island-like, then E
In the present invention, latent (dispersion medium component) and island-like (dispersed component) mean that the dispersion component is in the form of particles or a thin film. They are scattered throughout the film, and are not continuous over one surface like a laminated film, nor are they lumpy and penetrating both sides of the film.

The gloss of the film used in the present invention must be 60% or less, preferably 50% or less, and optimally 40%.
It is as follows. If it is 60% or more, it is insufficient as an erasable film. Here, glossiness refers to angle 7 using a Murakami gloss meter.
This is the average value of values measured at five arbitrary locations measured at 0 degrees.

Furthermore, the degree of unevenness of the film used in the present invention is 3 to 3.
It needs to be 15μ, preferably 4 to 12μ. If it is less than 3 μm, the film will not be matte enough, and if it is more than 15 μm, holes will easily form in the film. The method for evaluating the degree of unevenness is as follows.

A 20 cm x 20 cm film was sampled, and the thickness was measured at 9 locations at regular intervals using a thickness measuring device (Sagi).
-nOm! 'la company DIAL INDICAT
The weight of the sampling film was measured, and the density of the sampling film was determined by the buoyancy method using a mixed solvent of toluene and carbon tetrachloride. Measure the density.

The thickness of the film is calculated from this weight and density (L
The thickness of the film of the present invention is not particularly limited, but is preferably 10 to 50 μm. If it exceeds 50 μm, it will be disadvantageous for the rapid cooling operation during film formation. Furthermore, when a Fa layer is applied to polyvinyl chloride wallpaper, a problem arises in that the layer becomes hard. By laminating the thus obtained matte 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 refers to polyvinyl chloride,
It means a copolymer of vinyl chloride and other monomers that can be copolymerized with vinyl chloride (for example, vinyl acetate, acrylic ester, etc.), and polyvinyl chloride base materials include polyvinyl chloride wallpaper, polyvinyl chloride leather, We offer PVC desk mats, PVC clear cases, and more.

In the present invention, when the above-mentioned matte film is laminated to a plasticized polyvinyl chloride base material containing a plasticizer (for example, a film or sheet used for wallpaper), it exhibits a remarkable effect. Polyvinyl chloride wallpaper often contains a plasticizer, and in that case, the content of plasticizer is often 15 to 20% of the total weight.Here, the plasticizer is: Plasticizers that are liquid at 20°C, such as dibutyl phthalate, di-2-ethylhexyl phthalate, di-isooctyl phthalate, di-iso-decyl phthalate, di-decyl phthalate, di-nonyl phthalate, di-lauryl phthalate, butyl These include phthalate plasticizers such as benzyl phthalate, phosphate plasticizers such as tricresyl phosphate, triglythyl phosphate, and triethylhexyl phosphate, and chlorine-containing plasticizers such as chlorinated paraffin. Plasticizers, such as dicyclohexyl phthalate, phthalate plasticizers such as phthalic acid diesters whose alcohol has 13 or more carbon atoms, polyhydric alcohol plasticizers such as dipentaerythritol fatty acids and esters, trioctyl melitate, etc. There are trimellitic acid plasticizers, etc. The ethylene content is 60 mol% or less and the saponification degree is 90% or more, preferably 95%.
The above EVOH exhibits plasticizer resistance and plasticizer migration resistance.Among these plasticizers, the former (a plasticizer that is liquid at 20°C) is a plasticizer that has remarkable migration property. Even very significant migration of these plasticizers can be prevented.

In particular, EVO having an ethylene content of 55 mol% or less, more preferably 50 mol% or less, and 25 mol% or more
) I has very satisfactory properties and virtually no water permeability to plasticizers.

As the ethylene content increases, the plasticizer permeation resistance gradually decreases, and when the content exceeds 60 mol%, the migration of plasticizer 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 20 mol% ungrooved region, and for example, due to the use of rags, etc., simple This is not suitable because it damages the surface when cleaning contamination caused by external factors.

In the present invention, wallpaper is typically made by coating or rolling laminating vinyl chloride on the surface of flame-retardant paper and then foaming it. If a foam with a foaming ratio of 2 or more is used in the present invention, the 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.

Example 1, Control Example 1, ethylene content 38 mol%, saponification degree 99.4 mol%,
92% EVOH pellet with a melt index of 3.8 g/10 min (190°C, weighted 24600), modified with maleic acid (modification rate 0.09 mol%), melt index i, OQ/10 min (190°C, weighted) 8% high-density polyethylene resin pellets (under 2160g conditions) were blended into pellets using a twin-screw extruder. This blend pellet was formed into a film using a T-die extruder using an air slit while being rapidly cooled to obtain a 30 μm film. The glossiness of this film was 42%, and the unevenness was 4.1μ. When a cross section of the film of Example 1 was dyed with an iodine solution that only stains EVOH and observed under a microscope, it was confirmed that carboxylic acid-modified polyethylene resin existed in the form of islands in a sea of EVOH. A schematic diagram of the TO (width direction) cross section of this film is shown in Figure 1, and a schematic diagram of the 140 (machine direction) cross section is shown in Figure 2. This film was coated with a urethane adhesive, and then di-2-ethyl was coated. Xyl phthalate 3
It was laminated and embossed on foamed PVC wallpaper containing 0% (foaming ratio: 5 times). This laminate was matte 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/1 (
1 (under conditions of 190°C and 2160 g load) modified with 97% EvOH heret and maleic acid (denaturation rate 0.09 mol%)
), melt index +, O (1/10 min (190℃
, under a load of 2160 g) was blended in a twin-screw extruder and pelletized.

This blend pellet was formed into a film using a T-die extruder while rapidly cooling using an air slit to obtain a 28μ film. The glossiness of this film was 75%, and the unevenness was 2.2μ. This film was coated with a urethane adhesive and 30% di-2-ethylhexyl phthalate was added.
It was laminated and embossed on the foamed PVC wallpaper (expansion ratio: 5 times). This laminate was glossy and had a poor appearance.

Example 2, Control Example 2, ethylene content 44 mol%, saponification degree 99.4 mol%,
55% EVOH pellet with melt index 5.0g/Nomin (190℃, weighted 2160g under Q), itaconic acid modification (denaturation rate o, oos mol%), melt index 0.2o/10min (190℃, Weighted 2160
45% low-density polyethylene (under 100 g conditions) was blended and pelletized using a single-screw extruder. This blend pellet was formed into a film using a T-die extruder while rapidly cooling using an air slit to obtain a 25μ film. The glossiness of this film was 18%, and the unevenness was 1.5μ. When the cross section of Manako's film was observed under a microscope in the same manner as in Example 1, it was found that the carboxylic acid-modified polyethylene resin
It was confirmed that it exists in the form of an island in the OH sea.

Coat this film with urethane adhesive and
- This product is laminated and embossed on foamed PVC wallpaper containing 45% ethylhexyl phthalate (foaming ratio: 6x).
'111 had no such defects and had a good appearance.

As a control example 2, ethylene content was 44 mol%, saponification degree was 99.4 mol%, and melt index was 5.0 g710.
min (190°C, 12160g added) of EVOH
Heret 45% and itaconic acid modification (denaturation rate 0.005
mol%), melt index 0.2Q710 min (19
Low-density polyethylene 5 (0°C, 2160g load condition)
5% were blended and pelletized in a -screw extruder. This blend pellet was extruded into a T-die, blended, and formed into a film while being rapidly cooled using an extruder using an air slit to obtain a 25 μm film. This film had holes and was defective. In addition, the cross section of this film is shown in Example 1.
When similarly observed under a microscope, it was confirmed that the carboxylic acid-modified polyethylene resin did not exist in the form of islands in the sea of EVOH.

Example 3, Control Example 3, ethylene content 52 mol%, saponification degree 95.5 mol%,
Melt index 8.7Q/10 minutes (190℃, 2160g load condition) EVOH belay door 5% and maleic acid modification (modification rate 0.01 mol%), melt index 0.2G/10 minutes (190℃, A film was formed in the same manner as in Example 1 except that 25% high-density polyethylene under a load of 2160 g was used to obtain a 45 μm film.

The glossiness of this film was 28%, and the unevenness was 6.7μ. Furthermore, when the cross section of this film was observed under a microscope in the same manner as in Example 1, it was found that the carboxylic acid-modified polyethylene resin was
It was confirmed that it exists like an island in the sea of VOH. 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 was matte and had a good appearance.

As a control example 3, EvO ■ Hellet 75% with ethylene content of 44 mol%, degree of saponification of 99.4 mol%, melt index of 5.0 g for 710 minutes (190° C., load of 2160 g), and melt index of 0.2. A film was formed in the same manner as in Example 1, except that 25% high-density polyethylene (190° C., under a load of 2160 g) was used to obtain a 45 μm film. This film had a streaky pattern in the machine direction and had a poor appearance. Further, the glossiness was 85% and the unevenness was 3.1μ. Furthermore, when the cross section of this film was observed using the mv&mirror as in Example 1, it was observed that there were places where the polyethylene resin existed in layers in the EVOH sea, and places where the polyethylene resin was in the form of large lumps. This film was coated with a urethane adhesive and di-2-ethylhexyl phthalate 35
% foamed PVC wallpaper (foaming ratio: 3 times) and embossed. This laminate was glossy and had a poor appearance.

Example 4, Control Example 4, EvOH Hellet 75% ethylene content 275%, saponification degree 99.5 mol%, melt index 1.3 g 710 minutes (190 ° C., load 2160 g conditions),
Maleic acid modification (modification rate 0.01 mol%), melt index 0.4 g/10 min (190°C, weighted 2160
A film was formed in the same manner as in Example 1, except that 25% of low-density polyethylene was used (under the conditions of 3.g and 30 μm) to obtain a 30 μm film. 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 was matte and had a good appearance.

As a control example 4, the ethylene content was 27.5 mol%, the degree of saponification was 994 mol%1, and the melt index was 1.3 g/1.
0 minutes at 190°C and a load of 2160g), EVOH
Pellets 75% and maleic acid modification (denaturation rate 0.01 mol%) melt index 0.4g/10min (190℃
A film was formed in the same manner as in Example 1, except that 25% poly-10-pyrene was used (under a load of 2160 g).
A film of μ was obtained. This film had a streaky pattern in the machine direction and had a poor appearance. Also, the gloss level is 814
%Met.

Example 5 Ethylene content 31.5%, saponification degree 99.5 mol%,
Melt index 1.0g 710 minutes (190'C1 load 2160g condition), lz-/door 5 to EVOH
% and linear low density polyethylene modified with maleic acid (denaturation rate 0.01 mol%), melt index y, 0.4 g/10 min (190°C, load 2160 g conditions).
A film was formed in the same manner as in Example 1 except that 5% was used, and a 32μ film was obtained. In addition, a foamed PVC wallpaper fabric layer 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 linear low-density polyethylene modified with maleic acid (modification rate 0.01 mol%) and melt index 2.0 g/10 minutes was used.
A 3μ film and a foamed PVC wallpaper fabric layer were obtained.

Example 6 A film was formed 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 0.1 g/10 min was used.
A 33μ film and foamed PVC wallpaper laminate was obtained.

Example 7 Ethylene content 31.3%, saponification degree 99.6 mol%,
A film was formed in the same manner as in Example 6 except that two EvOH foils with a melt index of 7.5 g/10 minutes were used to obtain a 30 μm film and a foamed PVC wallpaper fit layer.

Control example 6 EVOH with ethylene content 315%, saponification degree 99.5 mol%, melt index +2.0 g / 1 G min.
Example 1 except that 75% pellets and 25% linear low density polyethylene modified with maleic acid (modification rate 0.01 mol%) and melt index 0.1 g/10 min were used.
A film was formed in the same manner as above to obtain a 30μ film and a foamed PVC wallpaper laminate.

Glossiness of the films obtained in Examples 5 to 7 and Control Examples 5 to 6,
Table 1 shows the degree of unevenness and appearance evaluation of the foamed PVC wallpaper laminate.

According to the present invention, a PVC wallpaper laminate with excellent matteness 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 schematic TD concave cross section of the film obtained in Example 1, and FIG. 2 shows a schematic MD concave cross section. 1-m-carboxylic acid modified polyethylene 2--- EVOH

Claims (2)

[Claims] (1) Ethylene content 20-60 mol%, saponification degree 90%
The above saponified ethylene-vinyl acetate copolymer (A) 9
5 to 50% by weight and carboxylic acid-modified polyethylene resin (
B) A laminate obtained by laminating a matte film containing 5 to 50% by weight and having a surface gloss of 60% or less on a polyvinyl chloride base material. (2) The laminate according to claim 1, which has a surface gloss of 40% or less.