JP2002096422A - Multi-layer resin oriented film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-layer resin oriented film suitable for a mono- material wall paper having good printing and embossing properties, eliminating backing paper such as natural paper or pressure sensitive adhesive processing, having similar applicability as a conventional wall paper, and having a good recycle property. SOLUTION: The multi-layer resin oriented film comprises a printable top surface layer (A) and a back surface layer (B) laminated on the back face of the top surface layer (A). The top surface layer (A) contains a thermoplastic resin including an olefinic thermoplastic elastomer having a melting point of 160 deg.C or higher and an inorganic fine powder and/or an organic filler. The back surface layer (B) contains a thermoplastic resin including an olefinic thermoplastic elastomer having a melting point of 160 deg.C or higher and a surface- treated inorganic fine powder and/or an organic filler and having a liquid water absorbing capacity of 6 to 25 ml/m2 as measured by 'Japan TAPPI No.51-87'.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention is excellent in printability and embossability, does not require backing of natural paper or the like unlike conventional wallpaper, and is directly adhered to a wall with a water-soluble adhesive without wrinkles. The present invention relates to a stretched multilayer resin film which is capable of being recycled and has excellent recyclability after peeling.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin (PVC) has been used as a resin film used for architectural decoration materials (especially wallpaper).
In many cases, a calendered film or a paste-foamed material mainly composed of is used. Wallpapers using these PVC resins have problems of chlorine gas generated at the time of disposal or fire, and problems of environmental pollution such as indoor pollution due to bleeding of a plasticizer. In order to solve these problems, development of a wallpaper film using a polyolefin, a paste foaming method using a polyolefin resin, and the like have been recently performed. Recently, from the viewpoint of resource saving,
Many methods of recycling wallpaper have been proposed. But,
Conventional papers such as PVC wallpaper and polyolefin wallpaper use a backing material such as natural paper, and it is difficult to separate the resin material from the backing material (natural paper) when peeled off. For this reason, most of the waste wallpapers are landfilled and not currently recycled.

[0003] In order to use as a wallpaper, conventionally, backing of various materials has been performed on the back surface, in the case of tack paper type wallpaper, a coating treatment such as an adhesive has been performed, or when directly pasting on a wall or wood plywood, Adhesive (glue) coating is performed.
However, it has been pointed out that these methods have poor adhesiveness (strength) with adhesives and pressure-sensitive adhesives and poor drying properties. To solve these problems, natural paper is generally used as a backing material. However, when the wallpaper is replaced, the used wallpaper that has been removed cannot be recycled as it is because the composition of the resin material and the backing material (natural paper) of the replaced wallpaper are different.
For this reason, when recycling, it is necessary to separate the resin material and the backing paper. Similarly, in the case of a tack paper wallpaper coated with a pressure-sensitive adhesive containing a synthetic resin as a main component on the back surface,
It is difficult to separate the pressure-sensitive adhesive from the resin material.
For this reason, a large amount of the pressure-sensitive adhesive is peeled off in the attached state, and the resin material undergoes thermal decomposition at the time of recycling to generate foreign substances, or the flow characteristics of the resin are significantly changed,
At present, it is a big problem in quality.

Recently, in order to solve this problem, a method of separating a wallpaper resin material from a backing material (natural paper) has been proposed. For example, a backing paper is provided with a coating layer containing a water-soluble polymer and a PVC resin-based or vinyl acetate-based synthetic binder as main components, and is a wallpaper in which a PVC resin is laminated thereon. A method of separating PVC and backing paper by immersion and stirring (Japanese Unexamined Patent Publication No. 6-173)
No. 200) and a method of laminating a PET film, a PP film, or the like between a backing material and a foamed gelled PVC base material (JP-A-11-293600). However, in any of the methods, since the number of steps for separating the backing paper increases, there are problems such as an increase in cost required for recycling and a reduction in quality of the recycled resin material, and the method has not been put to practical use. For this reason, most of the stripped wallpaper is still disposed of by landfill or incineration.

[0005] In addition, there has been proposed a material for a polyolefin-based wallpaper which does not require a backing material. However, when affixing to a wall surface such as a PVC-based wallpaper using a backing paper, drying of the adhesive is required. There is a problem in workability at the time of construction such as being slow and wrinkling at the time of pasting.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve these problems of the prior art. That is, the present invention has excellent printability and embossability, does not require backing paper such as natural paper or pressure-sensitive adhesive processing, has the same workability as conventional wallpaper, and has excellent recyclability. The object was to provide a multilayer resin stretched film suitable for a monomaterial wallpaper.

[0007]

Means for Solving the Problems As a result of intensive studies, the present invention provides a multilayer stretched resin film containing an olefin-based thermoplastic elastomer having a specific melting point, thereby achieving the object of the present invention. It has been found that a film having the above characteristics is imparted, and the present invention has been completed.

[0008] That is, the present invention relates to a method for producing a printable surface layer (A) containing a thermoplastic resin containing an olefin-based thermoplastic elastomer having a melting point of 160 ° C. or higher, an inorganic fine powder and / or an organic filler. Containing a thermoplastic resin containing an olefin-based thermoplastic elastomer having a temperature of 160 ° C. or higher, a surface-treated inorganic fine powder, and / or an organic filler, “Japan TAPPI No.
51-87 "is 6-25.
The present invention provides a stretched multilayer resin film in which a back layer (B) having a thickness of ml / m ² is laminated.

In a preferred embodiment of the present invention, the thermoplastic resin is a mixture of an olefin-based resin and an olefin-based thermoplastic elastomer.
It preferably contains 0 parts by weight. The amount of the olefin-based thermoplastic elastomer contained in the back layer (B) is preferably larger than the amount of the olefin-based thermoplastic elastomer contained in the surface layer (A). In addition, the surface of the inorganic fine powder and / or the organic filler used for the back layer (B) has at least one selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an antistatic agent. Preferably, it is processed in one.

The average contact angle of the back surface layer (B) with water is 1
The porosity of the stretched multilayer resin film is preferably 10 to 60%. Further, it is preferable that the porosity of the back surface layer (B) is larger than the porosity of the surface layer (A). The multilayer resin stretched film preferably has a film density of 0.4 to 1 g / cm ³ . The multilayer resin stretched film is preferably manufactured by laminating the surface layer (A) and the back surface layer (B) and then stretching. The surface layer (A) and the back surface layer (B) are subjected to an oxidation treatment. Are preferred.

It is preferable that the surface layer (A) is further subjected to embossing after printing. In particular, it is preferable that a water-soluble adhesive can be directly applied to the back surface layer (B), and the application can be performed by sticking to a wall or the like. The water-soluble adhesive used for the back layer (B) preferably contains at least one selected from starch, polyacrylic acid, polyacrylamide, polyethylene oxide, polyvinyl alcohol, carboxymethylcellulose, and polyvinylamide. In this specification, “to” indicates a range including numerical values described before and after it as a minimum value and a maximum value, respectively.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the stretched multilayer resin film of the present invention will be described in detail. The multilayer resin stretched film of the present invention has a surface layer (A) and a back layer (B). The surface layer (A) and the back layer (B) contain a thermoplastic resin and an inorganic fine powder and / or an organic filler. The surface layer (A) and the back layer (B) contain an olefin-based thermoplastic elastomer having a melting point of 160 ° C. or higher as a thermoplastic resin.

Structure of Surface Layer (A) Surface Layer (A) Constituting the Multilayer Stretched Film of the Present Invention
Is a surface on which various types of printing can be performed, and thereafter, processing such as embossing can be performed. By performing such treatment, the stretched multilayer resin film of the present invention can be usefully applied as wallpaper or the like. Depending on the use of such a multilayer resin stretched film, the surface layer (A) is suitable for high-definition printing by various printing methods, and adheres to the ink to prevent the ink from falling off during the embossing performed thereafter. It can be configured to have strength.

The type and composition of the thermoplastic resin used for the surface layer (A) are not particularly limited as long as the thermoplastic resin contains an olefinic thermoplastic elastomer having a melting point of 160 ° C. or higher. An olefin resin is preferably used as the other resin. Specifically, ethylene,
A homopolymer of an α-olefin having 2 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 3-methyl-1-pentene; and Examples of 2 to 5 copolymers of these α-olefins are given. The copolymer may be a random copolymer or a block copolymer. Specifically, the density is 0.
89 to 0.97 g / cm ³ , melt flow rate (19
Branched polyethylene, linear polyethylene having a melt flow rate (230 ° C., 2.16 kg load) of 0.2 to 20 g / min.
10 minutes propylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, propylene / 4-
Methyl-1-pentene copolymer, propylene-3-methyl-1-pentene copolymer, poly (1-butene), poly (4-methyl-1-pentene), propylene / ethylene-3-methyl-1-pentene And copolymers.

Of these, propylene homopolymer, propylene / ethylene random copolymer, and high-density polyethylene are preferred because they are inexpensive and have good moldability. In order to make the porosity of the back layer (B) larger than the porosity of the surface layer (A), a high-density polyethylene or a propylene / ethylene random copolymer is used for the surface layer (A). Is particularly preferred.

As the olefin thermoplastic elastomer used for the surface layer (A), it is preferable to use a composite thermoplastic elastomer composed of an olefin elastomer and an olefin resin. Particularly, the following three types can be mentioned as preferable examples. A simple blend of an olefin elastomer as a soft segment and an olefin as a hard segment. A compound obtained by partially cross-linking or polymerizing an olefin-based elastomer and an olefin-based resin. A product obtained by cross-linking an olefin-based elastomer and dispersing it in an olefin-based resin. Examples of the olefin elastomer include an ethylene rubber represented by EPDM. Examples of the olefin-based resin include polyethylene and propylene-based resins.

The melting point (DSC peak temperature) of the olefin-based thermoplastic elastomer is determined by the embossability of the surface layer (A), the film rigidity required for application to the wall surface, and the flexibility to absorb the unevenness of the wall surface after application. 160 ° C. or higher, in order to impart
More preferably, it is 180 ° C. When the melting point of the olefin-based thermoplastic elastomer is less than 160 ° C., when a water-soluble adhesive is applied to the back surface layer (B) at the time of application to a wall surface, the film tends to wrinkle, and the workability tends to deteriorate. . In addition, a flame retardant, an antioxidant, a dispersant, a fungicide, an antibacterial agent, an ultraviolet stabilizer, and the like can be added to the olefin-based thermoplastic elastomer and the thermoplastic resin as necessary.

In the present invention, one of the above-mentioned olefin-based thermoplastic elastomers may be selected and used alone, or two or more thereof may be selected and used in combination. Further, the amount of the olefin-based thermoplastic elastomer contained in the surface layer (A) is preferably smaller than the amount of the olefin-based thermoplastic elastomer contained in the back surface layer (B). Conversely, when the content is increased, the amount of vacancies in the surface layer (A) tends to be larger than that in the back layer (B), which may cause problems in recyclability, printability of the surface layer, and surface strength.

The mixing ratio of the mixture of the olefin resin and the olefin thermoplastic elastomer is as follows.
The olefin-based thermoplastic elastomer is preferably 10 to 100 parts by weight with respect to 00 parts by weight, and 20 to 8 parts by weight.
More preferably, it is 0 parts by weight.

The surface layer (A) uses an inorganic fine powder and / or an organic filler. The type of the inorganic fine powder is not particularly limited, but heavy calcium carbonate, light calcium carbonate, clay, talc, having an average particle diameter of 0.1 to 3 μm,
Preferred examples include titanium oxide, barium sulfate, zinc oxide, magnesium oxide, diatomaceous earth, and silicon oxide. Among them, light or heavy calcium carbonate, clay,
Diatomaceous earth and titanium oxide are preferred because they have good and inexpensive formation of voids generated by stretch molding.

Although the type of the organic filler is not particularly limited, it is preferable to select a resin different from the thermoplastic resin as the main component having an average particle diameter of 0.1 to 3 μm after dispersion. For example, when the thermoplastic resin film is an olefin resin film, as the organic filler,
Polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-
6,6, cyclic olefin A homopolymer of a cyclic olefin, a copolymer of a cyclic olefin and ethylene, etc., having a melting point of 12
0 ° C to 300 ° C, or glass transition temperature of 120 ° C to
Those having a temperature of 280 ° C. can be mentioned. When compounding and kneading these organic fillers in the olefin resin, a dispersant, an antioxidant, an ultraviolet stabilizer,
It is desirable to add a compatibilizer or the like. In particular, since the compatibilizing agent determines the particle form of the organic filler, it is important to select the amount and type of the compatibilizing agent.

It is desirable to select an inorganic fine powder or an organic filler having a small content of coarse particles exceeding 44 μm in order to prevent white spots during printing. In particular, by using an inorganic fine powder or an organic filler having an average particle diameter smaller than that of the inorganic fine powder or the organic filler used for the back layer (B) for the surface layer (A), pores generated by stretching can be reduced by the back layer (B). ) Can be reduced as much as possible. By doing so, the surface strength can be improved and high-definition printing can be performed.
This can eliminate defects such as surface peeling when used as wallpaper, and in embossing,
Since the embossing at a lower temperature becomes possible, the productivity is improved. For the surface layer (A), one of the above-mentioned inorganic fine powder and organic filler may be selected and used alone, or two or more may be selected and used in combination. . When using two or more types in combination,
You may mix and use an inorganic fine powder and an organic filler.

In the surface layer (A), a mixture of an olefin resin and an olefin thermoplastic elastomer is used.
It is particularly preferred that 10% to 60% by weight of an inorganic fine powder and / or an organic filler having an average particle diameter of 0.1 to 3 μm is contained in the weight%. When the content of the inorganic fine powder and / or the organic filler is less than 10% by weight, the adhesiveness of the ink tends to deteriorate. On the other hand, when the content exceeds 60% by weight, uniform stretching becomes difficult, and the surface of the film obtained by stretching tends to be blurred, which tends to lack practicality. The average particle diameter of the inorganic fine powder and / or the organic filler is 0.
When the thickness is less than 1 μm, secondary aggregation occurs due to poor dispersion in the thermoplastic resin, surface protrusions increase, and high-definition printing tends to be impossible. On the other hand, if it exceeds 3 μm, the surface smoothness tends to decrease, and high-definition printing tends to be impossible as described above.

When the multilayer resin stretched film of the present invention is applied as wallpaper, or when it is desired to suppress the deterioration over time of the material strength as a durable material and the printing ink adhesive strength after the application, the surface layer (A) is protected from oxidation. It is desirable to add an agent, an ultraviolet stabilizer, titanium oxide and the like.

Structure of back layer (B) Back layer (B) constituting the multilayer resin stretched film of the present invention
Can be embossed with a three-dimensional effect, applied with a water-soluble adhesive, and directly applied to a wall or the like. By performing such treatment, the stretched multilayer resin film of the present invention can be usefully applied as wallpaper or the like. Depending on the application of such a multilayer resin stretched film, the back surface layer (B) may have embossing suitability and workability such as drying property and adhesiveness of the adhesive when a water-soluble adhesive is applied. Can be configured.

The type of the thermoplastic resin and the thermoplastic elastomer used for the back layer (B) is as follows.
And the same as those described above. Back layer (B)
The thermoplastic resin and the thermoplastic elastomer used for the surface layer (A) may be the same as or different from those used for the surface layer (A). As the thermoplastic resin of the back layer (B), it is particularly preferable to use a propylene homopolymer in order to make the porosity of the back layer (B) larger than the porosity of the surface layer (A). The mixture ratio of the mixture of the olefin-based resin and the olefin-based thermoplastic elastomer is preferably the same as that of the surface layer (A) from the viewpoint of workability. In order to prevent the deterioration of the stretched multilayer resin film over time as a durable material, it is desirable to add an antioxidant, an ultraviolet stabilizer and the like to the back surface layer (B). Further, a flame retardant or the like may be added as necessary.

The back layer (B) uses an inorganic fine powder and / or an organic filler. Examples of the inorganic fine powder and the organic filler include those similar to those described in the surface layer (A). The inorganic fine powder and / or organic filler used for the back layer (B) may be the same as or different from those used for the front layer (A).

It is particularly preferable to use a surface-treated inorganic fine powder for the back layer (B). Examples of the surface-treated inorganic fine powder include a water-soluble anionic surfactant, a cationic surfactant, and a nonionic surfactant having an average molecular weight of 1,000 to 150,000 during wet grinding of heavy calcium carbonate. Surfactant treated, anionic antistatic, cationic antistatic, or nonionic antistatic treated during wet milling, further surfactant treatment and organic antistatic treatment Is processed in two stages. The liquid absorption volume of the obtained multilayer resin stretched film measured by “Japan TAPPI No. 51-87” is set in a preferable range (6 to 25 ml).
/ M ² ) and a hydrophilic surface having an average contact angle with water within a preferred range (10 to 50 °), a surfactant and an organic charge are added to fine powder having an average particle size of 0.5 to 10 μm. It is preferable to use a fine powder obtained by treating the inhibitor in two stages.

In order to keep the porosity of the stretched multilayer resin film in a preferable range (10 to 60%), the compounding amount of the inorganic fine powder and / or the organic filler in the back layer (B) is 30.
７０70% by weight, preferably 35-65% by weight
Is more preferable.

"Japan TAPPI No. 51-
87 ”is 25 ml / m ^2.
Or the contact angle with water is less than 10 °,
When a water-soluble adhesive is used, the adhesive component itself tends to permeate too much into the interior because the water absorption rate is too high. For this reason, a large amount of adhesive is required to be applied, which tends to increase the production cost. In addition, the adhesive tends to dry before being applied to the wall, making the installation difficult. On the other hand, if the liquid absorption volume is less than 6 ml / m ² or the average contact angle with water exceeds 50 °, on the contrary, the water absorption rate becomes slow and the drying property of the adhesive becomes slow. The installed wallpaper itself tends to rise from the wall and the workability is reduced. In addition, since the penetration of the adhesive component itself into the film is small, the adhesiveness between the adhesive and the stretched multilayer resin film tends to decrease.

The back layer (B) is composed of 30 to 70% by weight of a mixture of an olefin resin and an olefin thermoplastic elastomer, and a surface-treated inorganic fine powder having an average particle size of 0.5 to 10 μm and / or an organic fine powder. 70 to 30 filler
It is preferred that the content be contained by weight. The content of the inorganic fine powder and / or the organic filler is less than 30% by weight, or the average particle size of the inorganic fine powder and / or the organic filler is 0.5 μm.
If it is less than m, since the generation of vacancies is reduced,
There is a tendency that the embossing aptitude (embossing) is poor. In addition, the concealability of the wallpaper itself is insufficient, the background of the wall is visible, and the unevenness of the wall is conspicuous, so that the flicking property is insufficient and the sense of quality tends to be lost. Furthermore, there is a tendency that high water absorption capacity cannot be obtained. On the other hand, when the amount of the inorganic fine powder and / or the organic filler is more than 70% by weight or the average particle diameter is 10 μm or more, uniform stretching becomes difficult, and the film obtained by stretching tends to cause film blur.

Other Layers The stretched multilayer resin film of the present invention may have other layers as long as it has a surface layer (A) and a back layer (B) satisfying the conditions of the present invention. For example, one or more intermediate layers (C) may be provided between the surface layer (A) and the back layer (B). This intermediate layer (C) preferably has the same porosity as the back layer (B) from the viewpoint of embossability.

The thickness of the stretched multilayer resin film of the present invention is 3
0 to 500 μm, preferably 80 to 400 μm
m is more preferable. In addition, by laminating using various adhesives, one having a thickness of 1 mm can also be obtained. The ratio of the thickness of the surface layer (A) to the thickness of the back layer (B) [(A) / (B)] is [(1-7) / (9-3)]. It is preferable in terms of workability and emboss return. The thickness ratio of the back layer (B) is 3
If the ratio is less than a certain value, the embossing becomes poor, and the absorption of the water-soluble adhesive is insufficient, and the drying property of the adhesive tends to be poor. When the intermediate layer (C) is provided, it is preferable that the thickness of the intermediate layer (C) is included in the thickness ratio of the back surface layer (B).

Production and Processing of Stretched Multilayer Resin Film The stretched multilayer resin film of the present invention can be produced by combining various methods known to those skilled in the art. The stretched multilayer resin film produced by any method is included in the scope of the present invention as long as it satisfies the conditions described in claim 1.

For example, the surface layer (A) and the back layer (B)
May be produced by separately stretching and then laminating, or the surface layer (A) and the back layer (B)
May be manufactured by laminating and then collectively stretching. When having an intermediate layer (C), 3
The layers may be separately stretched and then laminated, or may be laminated and then stretched together, or after the surface layer (A) and the intermediate layer (C) are laminated and stretched, It may be manufactured by laminating a stretched or unstretched back layer (B). These methods can be appropriately combined.

A preferred production method is to laminate the surface layer (A) and the back layer (B), and if there is an intermediate layer (C), the surface layer (A), the intermediate layer (C), and the back layer (B). The process includes a step of stretching at a time later. Compared to the case of separately stretching and laminating, it is simpler and the cost is lower. In addition, it is easier to control the holes formed in the surface layer (A) and the back layer (B).

Various known methods can be used for stretching. Specific examples of the stretching method include inter-roll stretching using a peripheral speed difference between roll groups, and clip stretching using a tenter oven. Among them, uniaxial roll stretching is preferable because the stretching ratio can be arbitrarily adjusted and the size and number of pores formed can be controlled. In addition, since the resin is stretched and oriented in the flow direction of the film, it is possible to obtain a multilayer resin stretched film having a higher tensile strength and less dimensional change due to tension during printing and processing as compared with a non-stretched film. Such a multilayer stretched resin film is extremely useful for wallpaper.

The stretching ratio is not particularly limited, and is appropriately selected depending on the purpose and the characteristics of the thermoplastic resin used. For example, when a propylene homopolymer or a copolymer thereof is used as the thermoplastic resin, the ratio is 1.2 to 12 times, preferably 2 to 7 times. Although the stretching temperature is not particularly limited, the stretching is preferably performed at a temperature lower by 5 ° C. or more (preferably 10 ° C. or more) than the melting point of the resin used for the back layer (B).
If the temperature is not lower than 5 ° C, the sheet sticks to the roll surface in stretching between rolls, and a sticking pattern tends to appear on the stretched film surface. In addition, since the occurrence of cracks due to pores in the back surface layer (B) is reduced, the water absorption capacity becomes poor. When the water-soluble adhesive is directly applied to a wall, the water-soluble adhesive tends to be poorly dried, and the workability tends to be greatly reduced. The stretched multilayer resin film of the present invention can be subjected to a heat treatment at a high temperature, if necessary.

The stretched multilayer resin stretched film after stretching has fine pores. The porosity of the stretched multilayer resin film of the present invention is preferably from 10 to 60%, more preferably from 15 to 50%. In addition, the porosity in the present specification indicates that the porosity in a region observed by an electron microscope photograph is obtained from an area ratio using an image analyzer (Model: Luzex IID, manufactured by Nireco Co., Ltd.).

If the porosity of the stretched multilayer resin film is less than 10%, the water absorption capacity when a water-soluble adhesive is used tends to be insufficient. If the porosity is more than 60%, the water absorption capacity is too large, and a large amount of the adhesive is required to penetrate into the layer. The porosity of the back layer (B) is preferably larger than the porosity of the front layer (A). If the porosity of the surface layer (A) is larger, problems may occur in terms of recyclability, printability of the surface layer, and surface strength.

The multilayer resin stretched film of the present invention has a density of
0.4 to 1 g / cm ³ , preferably 0.45 to 1 g / cm ^3.
More preferably, it is で 0.95 g / cm ³ . The multilayer resin stretched film of the present invention is particularly preferably a film having white opaque pores.

The stretched multilayer resin film of the present invention may be used as it is, or may be used by being laminated on another thermoplastic film or the like. For example, another thermoplastic resin film can be laminated on the surface layer (A) of the multilayer resin stretched film of the present invention. Examples of the film to be laminated include a transparent or opaque film such as a polyester film, a polyamide film, and a polyolefin film.

Further, in order to improve the printability, the surface layer may be subjected to various oxidation treatments, or may be coated with an antistatic agent, an anchor coating agent, a waterproofing agent and the like. Further, it is preferable to perform various oxidation treatments on the back surface layer in order to improve the hydrophilicity and the adhesiveness with the water-soluble adhesive. Examples of the method of the oxidation treatment include a corona discharge treatment, a plasma treatment, a flame treatment, a glow discharge treatment, and an ozone treatment, and the corona discharge treatment and the flame treatment are preferable.

The stretched multilayer resin film of the present invention is particularly useful for wallpaper and decorative paper for decorative plywood, but is also useful for flooring materials, interior materials of automobiles, tack-labeled tack labels, and the like.

The surface of the stretched multilayer resin film of the present invention can be printed according to the purpose of use. The type and method of printing are not particularly limited. For example, printing can be performed by using known printing means such as gravure printing using an ink in which a pigment is dispersed in a known vehicle, aqueous flexo, silk screen, UV offset rotary printing, and the like. In addition, printing can be performed by metal deposition, gloss printing, mat printing, or the like. The pattern to be printed can be appropriately selected from natural products such as stones, wood, lattices, polka dots, and floral designs, abstract designs, characters, and the like.

The multilayer resin stretched film of the present invention can be embossed. Embossing is generally performed after printing, but printing may be further performed after embossing. The embossing can be performed, for example, by using a known various press such as a lithographic press or a roll embossing machine or an embossing machine to form the embossed plate unevenness by heat or pressure. The roll embossing method is a method of shaping an uneven shape of a cylindrical embossing plate on a target material by hot pressure. The hot pressing is performed by heating the resin used for the surface layer (A) of the multilayer resin stretched film between the heat deformation temperature and the melting temperature, and pressing the embossing plate against the surface of the multilayer resin stretched film. After shaping, cooling is performed to fix the shape. As the heating method, for example, a method such as infrared irradiation, hot air blowing, conduction heat from a heating roller, dielectric heating, or the like is used. In addition, embossing can be performed at the same time as film formation either before or after stretching without using an embossing machine.

When the stretched multilayer resin film of the present invention is used as a decorative plywood, the design can be improved by wiping after embossing and filling the recess with wiping ink. In particular, it is suitable for reproducing the appearance of the conduit portion of the wood grain.

In addition to the wiping, a surface protective layer made of a transparent resin layer can be formed on the outermost layer.
The surface protective layer has a function of protecting the surface layer and imparting a three-dimensional effect to a design such as a pattern or emboss of the lower layer. Therefore, the surface protective layer is particularly useful when the stretched multilayer resin film of the present invention is used as a decorative board or wallpaper.
The surface protective layer can be formed by coating or bonding. In order to further improve the surface properties, it is preferable to use a colorless transparent or colored transparent resin having excellent surface properties such as weather resistance, abrasion resistance, and stain resistance. Preferred as such a resin are, for example, two-component curable resins such as various acrylates, polyesters and the like, ionizing radiation curable resins, polyurethanes and unsaturated polyesters, fluororesins, polysiloxane resins and the like. The surface protective layer may contain known antibacterial agents, antifungal agents, fragrances and the like.

Application of Multilayer Stretched Resin Film The back surface of the multilayer stretched resin film of the present invention is directly coated with an adhesive so that it can be used for wood wall materials, gypsum boards, various composite materials (resin decorative boards, wood plywood, etc.) and the like. It can be used by directly bonding to a metal plate such as an iron plate or an aluminum plate. Therefore, when the stretched multilayer resin film of the present invention is used for wallpaper or the like, it is not necessary to back the backing material (natural paper or the like) on the back surface. For this reason, when the stretched multilayer resin film of the present invention is used for wallpaper or the like, the backing material (natural paper or the like) is mixed with the recycled material when the unnecessary wallpaper is peeled off from the wall after construction and the wallpaper is recycled. Therefore, it is possible to recycle mono-material materials.

The adhesive used for laminating the stretched multilayer resin film of the present invention is not particularly limited, and a water-soluble adhesive, a hydrated carbon-based adhesive, a synthetic resin-based adhesive, or the like can be used. The adhesive may be either a solvent-based adhesive or a water-soluble adhesive, but it is preferable to use a water-soluble adhesive from the viewpoint of workability and safety (poisoning due to solvent scattering, fire, etc.).

The water-soluble adhesive has a property of dissolving or swelling in water. Examples of the protein-based adhesive include gelatin, glue, casein and the like. Examples of the hydrated carbon-based adhesive include starch and its derivatives, and cellulose derivatives such as hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose (CMC), and viscose. Other examples include arabic rubber and tragacanth rubber.

Examples of the synthetic resin adhesive include polyvinyl alcohol, polyvinyl ether, polyvinyl pyrrolidone and the like. Other examples include polyacrylamide, polyethylene oxide, polyvinylamide, water-soluble polyurethane, polyacrylic acid-based resins and salts thereof, and further, as an adhesive, emulsification of vinyl acetate, acrylic acid ester, ethylene vinyl acetate, vinyl chloride, etc. Emulsion adhesives obtained by polymerization are exemplified.

Among them, as a water-soluble adhesive used for laminating the multilayer resin stretched film of the present invention to a wall or the like, starch and its derivatives, polyacrylic acid, polyacrylamide, polyethylene oxide, poly (ethylene oxide), polyacrylic acid, polyacrylamide, polyethylene Vinyl alcohol, carboxymethyl cellulose (CMC), and polyvinyl amide are preferred, and starch and its derivatives are more preferred.

[0054]

EXAMPLES The characteristics of the present invention will be described more specifically with reference to examples, comparative examples and test examples. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples are
Changes can be made as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples described below. The materials used in the following examples and comparative examples are summarized in Tables 1 and 2. In addition, MFR in a table | surface means a melt flow rate.

[0055]

[Table 1]

[0056]

[Table 2]

(Examples 1 to 6 and Comparative Examples 1 and 2) According to the following procedures, a multilayer resin stretched film of the present invention (Examples 1 to 6) and a comparative multilayer resin stretched film (Comparative Examples 1 and 2) Was manufactured, and wallpaper was manufactured using these. Comparative Example 1 is the same as the multilayer resin stretched film of Example 2 in JP-A-11-348192. Table 3
4 to 4 collectively show the types and amounts of materials used in the production of each film, the stretching conditions, and the states of the produced films.

Formulations [A] and [B] were prepared by mixing the olefinic resin, elastomer and fine powder. Examples 3 and 4 and Comparative Example 1
Then, the blend [C] was also prepared by mixing the olefin resin, the elastomer and the fine powder. When only the compound [A] and the compound [B] were prepared, each was melt-kneaded by two extruders set at 250 ° C., and the two compounds were laminated and extruded in a die. Then, the mixture was cooled to 70 ° C. by a cooling device to obtain a two-layer unstretched sheet. When Formulation [A], Formulation [B] and Formulation [C] were prepared, these formulations were set at 250 ° C.
Each of the extruders was melt-kneaded, and the mixture [A] was blended on the front side of the blend [C] and the blend [B] was blended on the back side in a die.
Were extruded and cooled to 70 ° C. by a cooling device to obtain a three-layer unstretched sheet.

After the formed unstretched sheet was heated to the stretching temperature shown in Table 4, it was stretched in the machine direction between rolls at the magnification shown in Table 4. However, in Example 4, the non-stretched sheet having the three-layer structure was heated to 130 ° C., stretched 5 times in the longitudinal direction between rolls, then heated to 155 ° C., and then stretched in the transverse direction using a tenter stretching machine. And stretched 9 times to obtain a biaxially stretched film. In Comparative Example 2, stretching was not performed. Next, a corona treatment of 50 W / m ² · min was performed on both surfaces of the obtained stretched film using an electric discharge machine (manufactured by Kasuga Electric Co., Ltd.) to obtain a multilayer resin stretched film. The porosity, total porosity, total thickness, and density of each layer of the obtained stretched multilayer resin film were as shown in Table 4.

The surface layer (A) of these multilayer resin stretched films was subjected to gravure printing of a floral pattern (ink: manufactured by Toyo Ink Co., Ltd .: trade name “CCST”), and then 100 ° C.
The embossing of the silk pattern was performed using a 0.5 mm deep embossing roll heated to obtain a wallpaper. Further, a water-soluble starch-based adhesive (manufactured by Yayoi Chemical Co., Ltd .: trade name "Lure Mild" mixed with water at a ratio of 1: 1) was used for the back layer (B) of the stretched multilayer resin film using an automatic wallpaper sizing machine. It was applied and quickly bonded to the wall of a wood plywood.

(Comparative Examples 3 and 4) In addition to the above-mentioned multilayer resin stretched film, a vinyl acetate-based adhesive (manufactured by Chuo Rika) was applied to the back layer (B) of the unstretched film having a two-layer structure obtained in Comparative Example 2. "Product name AC-500") is applied, and the basis weight is 80 g /
those stuck lined natural paper m ^2, and was prepared as Comparative Example 3. Furthermore, commercially available PVC lined with natural paper
The wallpaper was Comparative Example 4.

Gravure printing of a flower pattern (ink: trade name “CCST”, manufactured by Toyo Ink Co., Ltd.) was applied to the surface layer (A) of Comparative Example 3 and the side not backed by the natural paper of Comparative Example 4. After that, embossing of the silk pattern was performed with an embossing roll having a depth of 0.5 mm heated to 100 ° C. to obtain a wallpaper.
Further, a water-soluble starch-based adhesive (manufactured by Yayoi Chemical Co., trade name: "Lure Mild" and water mixed 1: 1) was applied to the back layer (B) of Comparative Example 3 and the backing paper side of Comparative Example 4. It was applied using an automatic wallpaper gluing machine, and was quickly bonded to the wall surface of wood plywood.

(Test Example) The following tests and evaluations were performed on the prepared multilayer stretched resin films and wallpaper.

1) Water contact angle The water contact angle of the back surface layer (B) of each of the multilayer stretched resin films prepared in Examples 1 to 6 and Comparative Examples 1 and 2 was measured using a contact angle meter (Kyowa) using ion-exchanged water. Interface Chemical Co., Ltd .: Model CA
The measurement was performed 10 times in -D), and the average value was obtained.

2) Liquid absorption capacity The liquid absorption capacity of the back layer (B) of each prepared wallpaper is
The measurement was performed in accordance with “Japan TAPPI No. 51-87” (Paper and Pulp Technology Association, Paper and Pulp Test Method No. 51-87, Brist method). That is, using a Bristow tester II manufactured by Kumagai Riki Kogyo Co., Ltd., 20 μl of a mixture of a 20: 1 red aqueous ink and ion-exchanged water was added dropwise in a non-pressurized state, and 50 (T The liquid absorption volume at ^1/2 ms) was determined.

3) Printability Adhesive tape (trade name "Cellotape", manufactured by Nichiban Co., Ltd.) is attached to the ink surface of each gravure-printed multilayer stretched resin film, and after sufficiently pressing, the adhesive tape is turned at 90 degrees. The peeling of the ink at a constant speed was determined according to the following criteria. ◎: No ink is peeled at all. ○: Material portion of the film is destroyed, but there is no practical problem. △: Almost all of the ink is peeled, but there is a practical problem with resistance when peeled. X: All the ink is peeled. No resistance when peeling, cannot be used practically

4) Suitability for Embossing The surface irregularities of each embossed wallpaper were visually judged by the following criteria (evaluation of embossing). ：: There is a three-dimensional effect and there is sharpness. Δ: There is a three-dimensional effect, but it lacks a little sharpness. No problem in practical use ×: Neither depth nor sharpness. It was not practically usable. Further, a starch-based adhesive was applied to the back layer (B) surface of each embossed wallpaper with a brush in an appropriate amount, and was adhered to the surface of the plywood so that air did not enter. Two sheets of plywood are stuck on top of each other with the wallpaper stuck on top of each other.
After pressurizing g / m ² for 3 minutes, the embossed state of the wallpaper taken out and affixed was visually judged by the following criteria (evaluation of emboss return). ：: No change ：: The three-dimensional effect is slightly reduced, but there is no practical problem. △: The three-dimensional effect is lacking, and the emboss is clearly returned.
There is a problem in practical use ×: Almost no embossing, practically unusable

5) Wallpaper workability Each multilayer resin stretched film is cut into a size of 90 cm × 180 cm, and a commercially available starch-based adhesive (“Lure” manufactured by Yayoi Chemical Co., Ltd.) Mild ") diluted 1: 1 with water was applied with an automatic wallpaper sizing machine (manufactured by Kyokuto Sanki Co., Ltd.) and quickly stuck to the wall of wood plywood. This series of workability was determined based on the following criteria. ○: Adhered continuously and neatly without sticking wrinkles △: Some sticking wrinkles occurred, it took time to stick and there was a practical problem X: Many sticking wrinkles, etc. I can not use it

6) Suitability for Recycling One month after the applied wallpaper was peeled off from the wall surface, the peeled wallpaper was crushed into chips, and then set at a temperature 60 ° C. higher than the melting point of the high melting point resin material used. ,
Remelt extrusion was performed with a twin screw extruder equipped with a 100 mesh screen pack. At this time, it was determined whether re-melt extrusion (regeneration) was possible based on clogging, smoking, discoloration, and the like of the screen pack.

Table 4 summarizes the test results of the above test examples.

[0071]

[Table 3]

[0072]

[Table 4]

[0073]

As is apparent from Table 4, the stretched multilayer resin film of the present invention is excellent in printing suitability and embossing suitability (good embossing and little return). In addition, since the multilayer resin stretched film of the present invention has a water absorbing ability of a water-soluble adhesive applied to the back surface layer (B), it can be directly adhered to a wall or the like with a water-soluble adhesive, and can be used as a backing material and a pressure-sensitive type. It does not require adhesive processing and has excellent recyclability. Therefore, the stretched multilayer resin film of the present invention can be suitably used as wallpaper or the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29L 7:00 B29L 7:00 9:00 9:00 F term (Reference) 4F100 AA01A AA01B AJ06B AJ07B AK03A AK03B AK21B AK25B AK26B AK54B AL05A AL09A AL09B BA02 BA07 CA18B CA22B CA23A CB00B DD01A DD013 DE01A DE01B DJ00A DJ00B EH46B EH463 EJ12A EJ12B EJ123 EJ37 GB08 HB31A JA04A JA04B JB16A JB16B JD15B JL01 JL16 YY00A YY00B 4F210 AA03 AA09H AA45 AB10 AB11 AB16 AG01 AG03 AG20 QC01 QC05 QG01 QG15 QG18 QW21

Claims (14)

[Claims] 1. A melting point of 160 ° C. on the back surface of a printable surface layer (A) containing a thermoplastic resin containing an olefin-based thermoplastic elastomer having a melting point of 160 ° C. or higher, an inorganic fine powder and / or an organic filler. The above-mentioned thermoplastic resin containing an olefin-based thermoplastic elastomer, containing a surface-treated inorganic fine powder and / or an organic filler, and having a liquid absorption volume of 6 to 25 ml / measured by "Japan TAPPI No. 51-87" A multilayer resin stretched film in which a back layer (B) having a m ² is laminated. 2. The thermoplastic resin is a mixture of an olefin-based resin and the olefin-based thermoplastic elastomer, and contains 10 to 100 parts by weight of the olefin-based thermoplastic elastomer based on 100 parts by weight of the olefin-based resin. 2. The multilayer resin stretched film according to item 1. 3. The stretched multilayer resin film according to claim 2, wherein the amount of the olefin-based thermoplastic elastomer contained in the back layer (B) is larger than the amount of the olefin-based thermoplastic elastomer contained in the surface layer (A). . 4. The surface of the inorganic fine powder and / or organic filler used for the back layer (B) is selected from anionic surfactants, cationic surfactants, nonionic surfactants, and antistatic agents. The stretched multilayer resin film according to any one of claims 1 to 3, which has been treated with at least one of the following. 5. The stretched multilayer resin film according to claim 1, wherein the back layer (B) has an average contact angle with water of 10 to 50 °. 6. The porosity of the multilayer resin stretched film is 10 to 10.
The multilayer resin stretched film according to any one of claims 1 to 5, which is 60%. 7. The stretched multilayer resin film according to claim 1, wherein the porosity of the back layer (B) is larger than the porosity of the surface layer (A). 8. The multilayer resin stretched film having a density of 0.4 to 0.4.
Multilayer stretched resin film according to any crab of claims 1 to 7 which is 1 g / cm ^3. 9. The multilayer resin stretched film according to claim 1, which is produced by laminating a surface layer (A) and a back surface layer (B) and then stretching. 10. The stretched multilayer resin film according to claim 1, wherein the stretching is at least uniaxial stretching. 11. The stretched multilayer resin film according to claim 1, wherein an oxidation treatment is applied to the surface layer (A) and the back layer (B). 12. The printing method according to claim 1, wherein after printing on the surface layer (A), embossing is further performed.
12. The stretched multilayer resin film according to any one of items 11 to 11. 13. The stretched multilayer resin film according to any one of claims 1 to 12, wherein a water-soluble adhesive is applied to the back surface layer (B). 14. The water-soluble adhesive is selected from the group consisting of starch, polyacrylic acid, polyacrylamide, polyethylene oxide,
14. The stretched multilayer resin film according to claim 13, comprising at least one selected from polyvinyl alcohol, carboxymethyl cellulose, and polyvinyl amide.