JPH1060130A - Colored film of olefinic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative film suitable as a surface decorative material for furniture, domestic electric appliances, building materials and the like and composed mainly of an olefinic resin use of which has hitherto been avoided due to poor moldability. SOLUTION: This colored film of an olefinic resin is a 0.03 to 0.2mm-thick film comprising an olefinic resin, wherein the opacity defined by the following formula is 0.5 to 3: Opacity = log1/T (wherein T (transmittance)=/I0 wherein I0 represents incident light and I represents transmitted light) and at least one pigment, selected from among carbon black, polyazo brown, quinacridone magenta, perylene red, polyazo red, pyrrole red, isoindoline yellow, polyazo yellow, and titanium yellow, and titanium oxide, is contained. Pref., a 0.03 to 0.2 mm-thick, substantially transparent, olefinic resin film, which contains an ultraviolet absorber and a hindered amine compd. and has a total light transmittance at 555nm of not less than 70%, is laminated on the front surface side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic film made of an olefin resin used as a surface decorative material for furniture, home appliances, building materials and the like.

[0002]

BACKGROUND ART Conventionally, as a so-called decorative film as described above, a vinyl chloride resin (hereinafter, referred to as PVC) film is mainly used. However, there is a concern that the PVC film generates HCl gas at the time of incineration or combustion, and there is a movement to remove PVC from the viewpoint of environmental protection.

[0003] In order to solve this problem, olefin-based resins have attracted attention as a substitute for PVC. However, as is well known, olefin-based resins are generally inferior in processability to PVC, so that it is difficult to produce the decorative film having excellent design properties at low cost, and it is difficult to use decorative materials in recent years. It has been shunned to this day as a product that does not meet the marketability required for highly productive products.

On the other hand, lead, hexavalent chromium, cadmium and the like are used as pigments for coloring the film, without concern for promoting thermal deterioration of the film (that is, resin constituting the film) and with little progress of discoloration deterioration. Heavy metal-based compounds, such as However, heavy metal compounds including lead, hexavalent chromium, cadmium, etc.
Various environmental issues are of concern.

[0005]

An object of the present invention is to solve the above-mentioned problems of a PVC film and the environmental problems derived from pigments for coloring the film in the above-mentioned circumstances. An object of the present invention is to provide a cosmetic film that can be used.

[0006]

SUMMARY OF THE INVENTION In order to achieve the above object, the present inventors dared to use (a) an olefin resin which has been shunned to date. (B) In addition, when the olefin resin is used as a constituent resin, heavy metals such as lead, hexavalent chromium, cadmium and the like can be produced without difficulty. Inorganic pigments that do not contain, or specific organic pigments,
With the knowledge that it can be used effectively as a colorant without the disadvantages such as deterioration of the constituent resins or fading or discoloration of the colored film (that is, it can improve the hue stability of the film), It led to the proposal of the invention.

That is, the film of the present invention is a colored film made of an olefin resin having a thickness of 0.03 to 0.2 mm and a hiding degree represented by the following formula of 0.5 to 3, It is characterized by containing one or more pigments selected from carbon black, polyazo brown, quinacridone magenta, perylene red, polyazo red, pyrrole red, isoindolinone yellow, polyazo yellow and titanium yellow, and titanium oxide.

[0008]

## EQU2 ## Hiding degree = log1 / T (where T (transmittance) = I / Io Io is incident light, I is transmitted light)

The olefin resin in the present invention includes polyethylene; polypropylene; ethylene-vinyl acetate copolymer resin; ethylene-acrylic copolymer resin such as ethylene-methyl acrylate copolymer resin;
A propylene copolymer resin or the like can be used. Above all, isotactic homo, random or block polypropylene having hardness suitable as a cosmetic film is suitable.

However, when the above-mentioned isotactic polypropylene is used as an olefin resin, the softening temperature range in which an embossed pattern can be provided is narrow, and the post-embossability of the obtained film is poor. Therefore, it is desirable to blend polyethylene, especially low-density polyethylene, in order to improve post-embossing suitability. If the proportion of the polyethylene blend is too small, the blending effect will not appear,
If the amount is too large, the amount of isotactic polypropylene is relatively too small to obtain a suitable hardness as a cosmetic film, so that 100 parts by weight of isotactic polypropylene is not added to polyethylene (preferably low density polyethylene). 10) to 300 parts by weight, preferably 30 to 200 parts by weight, are suitable.

The above-mentioned film can be produced by means such as a T-die extrusion method, a calendering method, an inflation method and the like, and the production method is not particularly limited. In order to improve the properties, it is preferable to blend syndiotactic polypropylene with the above-mentioned isotactic polypropylene. If the blend ratio of the syndiotactic polypropylene is too small, the blending effect is not exhibited, and if it is too large, the amount of the isotactic polypropylene is relatively too small, so that a suitable hardness as a cosmetic film can be obtained. Therefore, 5-200 parts by weight of syndiotactic polypropylene is suitable for 100 parts by weight of isotactic polypropylene.

Further, in order to improve the impact resistance of the film, the above-mentioned isotactic polypropylene or a blend thereof with polyethylene or syndiotactic polypropylene is mixed with ethylene-propylene rubber, water-added SBR, It is desirable to incorporate a rubber component such as polybutene. The mixing ratio of the rubber component varies depending on the desired impact strength, and cannot be unconditionally determined.
In the film of the present invention, the olefin resin 100
The amount may be appropriately selected from the range of 10 to 200 parts by weight based on the desired impact strength.

In the present invention, carbon black, polyazo brown, quinacridone magenta, perylene red, polyazo red, pyrrole red, isoindolinone yellow, polyazo yellow, One or more pigments selected from titanium yellow and titanium oxide are used.

The above-mentioned inorganic titanium oxide, titanium yellow and carbon black are also organic polyazo brown, quinacridone magenta, perylene red, polyazo red, pyrrole red, isoindolinone yellow,
Polyazo yellow also has no fear of deteriorating the film of the present invention composed of an olefin-based resin, and also has excellent light resistance and weather resistance, so that the film of the present invention is less likely to be discolored or discolored, The hue stability of the film of the present invention can be made extremely excellent.

The titanium oxide may be of rutile type or anatase type which is generally used as a normal white pigment called titanium white, but from the viewpoint of light resistance and weather resistance, it is rutile type. Is preferred.

In the film of the present invention, carbon black, polyazo brown, quinacridone magenta, perylene red, polyazo red, pyrrole red, isoindolinone yellow, polyazo yellow, titanium yellow are used in accordance with the desired color hue for the film. One or more types are appropriately selected and blended from the group consisting of, and titanium oxide is blended together with these pigments as an essential pigment.

The compounding amount of these pigments is appropriately selected according to the desired hue and the required degree of hiding, but the compounding amount of titanium oxide is 100% by weight of the olefin resin for the following reasons. The amount is preferably 0.5 to 30 parts by weight based on parts. If the titanium oxide is less than 0.5 parts by weight, the degree of hiding of the film represented by the above formula becomes insufficient, and if it is more than 30 parts by weight, the processability of the olefin-based resin composition containing the titanium oxide is reduced. Getting worse. In particular, when the hardness is high and the thickness is thin, as in the case of a cosmetic film, the deterioration of the processability becomes remarkable. That is,
When the film of the present invention is produced by a calendering method, the film ends are cut off after rolling with calender rolls.If the amount of titanium oxide is too large, the film is particularly high in hardness and thin in thickness. In this case, the cut portion (so-called "ear cut") is likely to occur during the cutting operation, and if the ear cut occurs, the cutting operation cannot be continued, resulting in extremely low work efficiency. Further, when the film of the present invention is manufactured by an extrusion method, if the blending amount of titanium oxide or iron oxide is too large, the droplets of the composition adhere to the lip portion of the extrusion die in a so-called “eye stain” shape. Such a phenomenon often occurs that the droplets fall on the film immediately after extrusion and contaminate the surface state (referred to as "eye stain" of the film).

Each of the above pigments may be directly mixed with the olefin resin as a pigment. In particular, when the amount of the pigment added is small, not only a desired color cannot be obtained due to a slight difference in the amount, It is desirable to use one that has been diluted with an olefin-based resin in advance (that is, a diluted pigment) because color blur is likely to occur and hue stability is lacking. As the olefin resin for dilution at this time, one having excellent compatibility with the olefin resin used in the film of the present invention (particularly preferably the same kind of resin)
When the above-mentioned blend is used as the olefin resin, an olefin resin having a melting point equal to or lower than the melting point of the olefin resin having the highest melting point in each olefin resin to be blended is used. Is desirable in order to easily and surely obtain a uniform mixed state.

The degree of dilution is such that the concentration of each pigment in each of the diluted pigments is 1 to 70 wt%.
From the dilution ranges within the above ranges, those having an appropriate dilution are selected and used according to the desired blending amounts of the above-mentioned pigments.

In the film of the present invention, in addition to the above components, if necessary, an antistatic agent, an antioxidant, a light stabilizer, a lubricant, an ultraviolet absorber, the above-described lead and hexavalent chromium Additives such as coloring agents other than heavy metal compounds including cadmium and the like may be blended.

The above film of the present invention has a thickness of 0.03 to 0.2 for practical reasons as a cosmetic film.
It is important that the degree of concealment represented by the above formula in mm is 0.5 to 3.

In the film of the present invention comprising the above-mentioned components and having the above-mentioned characteristics, a pattern or a character may be printed on one side or both sides. The printing ink may be any ink that can be adhered to the olefin resin, but is preferably a urethane ink or a thermosetting ink containing no halogen from the environmental point of view described above. As a printing method using these inks, a printing method such as a screen printing method, a gravure printing method, a flexographic printing method, and an offset printing method can be adopted. Of course, prior to printing, the surface to be printed of the film of the present invention may be subjected to a corona discharge treatment or the like.

Further, in the film of the present invention, embossing can be performed, and so-called valley printing can be performed on a concave portion carved by embossing. The embossing is performed by a method of embossing at the same time when a film is produced by a T-die extruder, a calendar, or the like, or a post-embossing method of embossing in a later step after the film is produced. The embossing may be performed after the printing is performed, or may be performed before the printing. When embossing is performed prior to printing, the surface roughness (Ra) should be 1.5 μm or less in consideration of printability.
Preferably, it is applied so as to have a satin shape of 0.2 to 1.0 μm.

As described above, the surface of the film of the present invention, which has been subjected to printing or embossing as required, has a thickness of 55%.
Total light transmittance of 5 nm is 70% or more, and thickness is 0.03 to
A substantially transparent olefin-based resin film having a thickness of 0.2 mm and containing a hindered amine (light stabilizer) and an ultraviolet absorber can also be laminated. As the hindered amine, compounds as shown in Chemical formulas 1 and 2 can be used. As the ultraviolet absorber, benzophenone-based compounds,
Known UV absorbers such as benzotriazoles can be used.

[0025]

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[0026]

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The amount of hindered amine to be added to the substantially transparent olefin resin film is as follows.
The amount of the ultraviolet absorber is preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the olefin resin. By laminating this substantially transparent olefin-based resin film, it is possible to protect the printing and improve the expressiveness of a deep design, and to obtain a cosmetic film made of an olefin-based resin excellent in weather resistance. it can.

The substantially transparent olefin-based resin film can be produced by means of a T-die extrusion method, a calendar method, an inflation method or the like, as in the case of the film of the present invention described above. The lamination of the substantially transparent olefin resin film and the above-mentioned film of the present invention is performed by a method using an appropriate adhesive, a method by heat fusion, or the like. At this time, if necessary, corona discharge treatment can be used together.

One side or both sides of the substantially transparent olefin-based resin film can be subjected to printing or embossing, if necessary, similarly to the above-mentioned film of the present invention, or can be engraved by embossing. So-called valley printing can be applied to the recessed portion. This printing, embossing, or the like may be performed in advance before lamination, or may be performed after lamination. When embossing is performed prior to printing, the surface roughness (Ra) is 1.5 μm or less, preferably 0.2 to 1.0 as in the above-described film of the present invention.
It is desirable to apply it so that it has a μm satin shape.

When the lamination of the substantially transparent olefin resin film and the above-mentioned film of the present invention is carried out using an appropriate adhesive, the adhesive surface is taken into consideration in consideration of the adhesive strength. The surface on the side where
a) It is desirable that embossing is performed so as to form a satin shape of 0.2 μm or more, preferably 0.2 to 5.0 μm. However, when printing is performed after embossing on the surface on the side to be the adhesive surface, this is not limited, and as described above,
Surface roughness (Ra) 1.5 μm or less, preferably 0.2 to
It is desirable that embossing is performed so as to form a 1.0- [mu] m satin shape.

Further, in the film of the present invention, as the backing material (backing material), a transparent, translucent or opaque olefin resin film of the same type or different from the olefin resin of the above-mentioned film of the present invention is laminated. You may. The transparent, translucent or opaque olefin-based resin film as the backing material is also similar to the above-described film of the present invention or the substantially transparent olefin-based resin film, such as a T-die extrusion method, a calendar method, an inflation method, and the like. The backing material and the film of the present invention can be laminated by a method using an appropriate adhesive, a method by heat fusion, or the like.If necessary, a corona discharge treatment may be used in combination. Can also.

[0032]

【Example】

Examples 1 to 6 Using an olefin resin composition having the composition shown in Table 1, 9
In a 0 mm single screw extruder, the thickness of the embossing roll pressed on the film surface is 0.7 μm with a satin squeezed surface having a roughness of 0.7 μm at a cylinder temperature of 220 ° C. and a die temperature of 210 ° C. A .1 mm film of the invention was produced. The degree of hiding of the obtained film was measured, and the results are shown in Table 1.

[0033]

[Table 1-1]

[0034]

[Table 1-2]

Examples 7 to 9 Using an olefin resin composition having the composition shown in Table 2, using a calender at a roll temperature of 185 ° C., a surface roughness (Ra) of 0.5 μm was applied to the film surface of the embossed roll pressed.
Thus, a film of the present invention having a thickness of 0.1 mm to which a m. Measure the degree of hiding of the obtained film,
The results are shown in Table 2.

[0036]

[Table 2]

Example 10 After the corona discharge treatment was applied to the surface of the film of the present invention of Examples 1 to 4 to which a satin squeezed surface having a surface roughness (Ra) of 0.7 μm was applied on the embossed roll squeezed surface. , Wood grain pattern printing was performed using black urethane ink mixed with carbon black. Then, syndiotactic polypropylene /
With respect to 100 parts by weight of low-density polyethylene (60/40), 0.2 parts by weight of hindered amine (trade name "ADK STAB LA-63" manufactured by Asahi Denka Co., Ltd.), 0.2 parts by weight of benzophenone-based ultraviolet absorber, and phenol-based antioxidant Embossing roll squeezing produced by an extruder using an olefin resin composition containing 0.2 parts by weight of an agent (trade name "ADK STAB AO-60" manufactured by Asahi Denka Co., Ltd.) and 0.005 parts by weight of phthalocyanine blue as a raw material. A 0.1 mm thick substantially transparent film (with a total light transmittance of 555 nm of 85%) in which a matte finish having a surface roughness (Ra) of 2 μm is applied to the printing surface of the pressed surface is applied to the printing surface. Lamination was performed using an adhesive to obtain a laminated film. The obtained film had very little discoloration even when irradiated with a sunshine weatherometer for 1500 hours, and was excellent in weather resistance.

Example 11 After applying a corona discharge treatment to the surface of the films of the present invention of Examples 7 to 9 to which a matte squeezed surface having a surface roughness (Ra) of 0.5 μm was applied on the embossed roll squeezed surface. , Wood grain pattern printing was performed using black urethane ink mixed with carbon black. Subsequently, isotactic homopolypropylene / isotactic random polypropylene / low density polyethylene / syndiotactic polypropylene (20
/ 30/40/10) with 100 parts by weight of hindered amine (trade name "ADK STAB LA-6" manufactured by Asahi Denka Co., Ltd.).
3 ") 0.2 parts by weight, benzophenone-based ultraviolet absorber 0.2 parts by weight, phenolic antioxidant (trade name" ADK STAB AO-60 "manufactured by Asahi Denka Co., Ltd.) 0.2 parts by weight, phthalocyanine blue 0.005 Thickness obtained by using an olefin-based resin composition to which parts by weight have been added as a raw material and having a surface roughness (Ra) of 2 μm on the back surface of the film on the embossing roll pressing surface prepared by a calender at a roll temperature of 185 ° C. 0.1 mm of substantially transparent film (555
After the above-mentioned printed surface was laminated with an adhesive, it was heated and subjected to wood grain embossing to obtain a laminated film. The obtained film had very little discoloration even when irradiated with a sunshine weatherometer for 1500 hours, and was excellent in weather resistance.

[0039]

As described above, according to the film of the present invention, the following effects can be obtained. (1) There is no concern that HCl gas is generated during incineration or combustion, and no heavy metal-based compound is used, which is preferable from the viewpoint of environmental protection. (2) A cosmetic film having excellent design properties can be manufactured at low cost, and an excellent marketability can be expected as a decorative film having high decorativeness. (3) Since it has excellent weather resistance and extremely little discoloration, it is suitable for long-term use as a cosmetic film.

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[Procedure amendment]

[Submission date] November 1, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

[0010] However, when using the above-mentioned isotactic polypropylene as the olefin resin has a narrow softening temperature range can be imparted to grain embossed, poor embossing suitability After the resulting film. Therefore, it is desirable to blend polyethylene, especially low-density polyethylene, in order to improve post-embossing suitability. If the proportion of the polyethylene blend is too small, the blending effect will not appear,
If the amount is too large, the amount of isotactic polypropylene is relatively too small to obtain a suitable hardness as a cosmetic film, so that 100 parts by weight of isotactic polypropylene is not added to polyethylene (preferably low density polyethylene). 10) to 300 parts by weight, preferably 30 to 200 parts by weight, are suitable.

Claims (2)

[Claims] An olefin resin having a thickness of 0.0
3 to 0.2 mm, concealment degree represented by the following formula is 0.5 to 3
A colored film of carbon black, polyazo brown, quinacridone magenta, perylene red, polyazo red, pyrrole red, isoindolinone yellow, polyazo yellow,
An olefin-based resin colored film comprising one or more pigments selected from titanium yellow and titanium oxide. ## EQU1 ## Opacity = log1 / T (where T (transmittance) = I / Io Io is incident light, I is transmitted light) 2. A substantially transparent olefin containing a UV absorber and a hindered amine compound on the surface side and having a total light transmittance of at least 70% at 555 nm and a thickness of 0.03 to 0.2 mm. 2. A laminated resin film.
The olefin-based resin colored film according to the above.