JP3071632B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a secondary mold having excellent moldability.
The present invention relates to a laminate obtained by laminating an axially oriented copolymerized polyester film on a polyvinyl chloride substrate, and more particularly to a laminate having extremely excellent stain resistance when used for wallpaper.

[0002]

2. Description of the Related Art Inorganic materials and organic materials have conventionally been used as surface finishing materials for house walls. Recently, so-called wallpaper has been often used as the surface of indoor walls. Wallpaper materials are also diversified, but the drawbacks of wallpaper are generally that they are easily stained, and that once they get dirty, they cannot be easily cleaned.

[0003] In particular, polyvinyl chloride is widely used as a sheet or film in the field of wallpaper and the like because of its excellent physical properties, good moldability and low cost. However, since most polyvinyl chloride is used as a composition containing a plasticizer,
When using polyvinyl chloride film as wallpaper,
There are drawbacks such as that the surface is easily stained and it is difficult to remove the stain, or that the plasticizer migrates to the surface and contaminates the surface of the wallpaper.

There are various methods for solving such problems, such as a method of treating the surface of a polyvinyl chloride film with a synthetic resin composition for preventing migration of a plasticizer, and a method of blending a component for preventing contamination into the polyvinyl chloride film. It has been suggested that the flexibility of the polyvinyl chloride substrate is impaired,
It has drawbacks such as insufficient pollution control effect and uneconomical effect.

For example, a method of surface treatment with a polyacrylate solution has the advantage that it can be carried out by a simple method such as gravure coating or doctor coating, but cannot completely stop the transfer of the plasticizer. Further, a method of laminating an acrylonitrile copolymer film (Japanese Patent Laid-Open No. Sho 59-20663) or an ethylene / vinyl alcohol copolymer film (Japanese Patent Publication No. Hei 4-71709) on a polyvinyl chloride base material is based on the method of laminating a plasticizer. Although contamination due to migration can be prevented, stain resistance (ease of adhesion of oil-based stains such as magic ink and shoe ink, and ease of removal of the attached stains) is not sufficient.

Furthermore, a method of laminating an acrylic resin film provided with an active energy ray-curable coating film (Japanese Patent Publication No.
-3381) can prevent migration of the plasticizer to the surface,
Although the stain resistance to oily stains is good, the degree of squeezing (the degree of shaping, hereinafter referred to as “formability”) when the laminate is subjected to unevenness such as embossing due to the provision of a curable coating film ) May be insufficient or the curable coating film may be partially peeled off. Further, in order to sufficiently prevent the migration of the plasticizer, it is necessary to apply a thick coating film, which is not only economical but also not economical.

On the other hand, polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as “PET”) have excellent properties such as heat resistance, weather resistance and chemical resistance. Although it has good stain resistance to dirt, the conventional method of laminating a polyester film on the surface of a polyvinyl chloride base material has a drawback that molding processability during embossing is poor.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the drawbacks of the prior art, prevent bleeding of the plasticizer contained in a polyvinyl chloride base material onto the surface, and provide stain resistance and moldability. It is to provide a good laminate.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to develop a laminate having no problem when used as the above-mentioned wallpaper, and as a result, have reached the present invention.

That is, the present invention has a melting point of 210 to 245.
℃ copolyester, thickness is 5-40μm
Is a laminate obtained by laminating the biaxially oriented copolymerized polyester film on at least one surface of a polyvinyl chloride base material.

The copolyester referred to in the present invention is a saturated polyester composed of a dicarboxylic acid component and a diol component, a copolyester having a melting point in the range of 210 to 245 ° C., and a particularly preferable example is copolyethylene terephthalate. It can be mentioned as.

The dicarboxylic acid component includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decane dicarboxylic acid; An alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid can be exemplified. Examples of the diol component include aliphatic diols such as ethylene glycol, butane diol, and hexane diol; branched glycols such as neopentyl glycol; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol; An alicyclic diol such as methanol can be exemplified. These can be used as components of a copolyester having a melting point in the range of 210 to 245 ° C.

The proportion of the copolymer depends on the type of the copolymer, but the resulting polymer melting point is in the range of 210 to 245 ° C., preferably 215 to 240 ° C., more preferably 220 to 235 ° C. If the melting point of the polymer is less than 210 ° C., the heat resistance is inferior, so that it cannot withstand heating during printing or the like. On the other hand, if the melting point of the polymer exceeds 245 ° C., the crystallinity of the polymer is too large, and the formability such as drawing is impaired.

Here, the melting point of polyester is measured by Du.
Pont Instruments 910 DSC
And determining a melting peak at a heating rate of 20 ° C./min. In addition, the sample amount is about 20 mg.

The copolyester of the present invention preferably contains inert particles in order to improve the workability during film formation or handling of the laminate. Examples of the inert particles include, for example, , Kaolin, alumina, titanium oxide, calcium carbonate and the like, or a fine particle made of a polymer having good heat resistance such as a silicone resin and a cross-linked polystyrene.

The copolymerized polyester in the present invention is not limited by the production method. For example, a method of subjecting terephthalic acid, ethylene glycol and a copolymer component to an esterification reaction and then subjecting the resulting reaction product to a polycondensation reaction to form a copolymerized polyester, or a transesterification reaction of dimethyl terephthalate, ethylene glycol and a copolymer component. And then subjecting the resulting reaction product to a polycondensation reaction to form a copolymerized polyester.

In the production of the copolymerized polyester, if necessary, other additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, and an antistatic agent can be added. As such antioxidants, for example, hindered phenol compounds, hindered amine compounds, sulfur atom-containing ester compounds, and the like, and when absorbing ultraviolet light, for example, benzophenone compounds, benzotriazole compounds,
Sasylate compounds and the like can be mentioned.

The polyester film of the present invention is obtained by melting the copolymerized polyester added with the above-mentioned additives such as a lubricant during the polycondensation reaction or at the time of film formation and discharging it from a die to form a film. What has been biaxially stretched and heat-set is preferably used.

Further, the polyester film of the present invention comprises:
It can be manufactured using a conventionally known film forming method. For example, the copolymerized polyester is melted into a sheet, quenched to form an unstretched film, heated by roll heating, infrared heating, or the like, and stretched in the machine direction to obtain a vertically stretched film. The stretching in the longitudinal direction is preferably performed by utilizing the peripheral speed difference between two or more rolls. The stretching temperature is preferably a temperature higher than the glass transition point (hereinafter sometimes referred to as “Tg”) of the copolymerized polyester, and more preferably 20 to 40 ° C. higher than Tg. The stretching ratio in the machine direction is preferably 2.5 times or more and 4.0 times or less, and more preferably 2.8 times or more and 3.9 times or less, although it depends on the required characteristics of the intended use. When the stretching ratio is 2.5 times or less, unevenness of the thickness of the film becomes worse, and it is difficult to obtain a good film.

The longitudinally stretched film is preferably stretched in the transverse direction, and then subjected to heat setting and heat relaxation in order to obtain a biaxially oriented film. These processes are preferably performed while the film is running. Can be. The stretching in the transverse direction is preferably started at a temperature 20 ° C. higher than the glass transition point of the copolymerized polyester, and the melting point of the polyester (hereinafter referred to as “T
m ") in some cases while raising the temperature to a temperature lower by 120 to 30 ° C. The stretching start temperature is preferably (Tg + 40) ° C. or lower. For example, in the case of polyethylene terephthalate obtained by copolymerizing 12% by mole of isophthalic acid, the temperature is preferably in the temperature range of 73 to 113 ° C. The maximum stretching temperature is 100 to 4 from Tm.
Preferably, the temperature is 0 ° C. lower.

The temperature in the stretching process in the transverse direction may be continuous or stepwise (sequential), and usually the temperature is raised sequentially. For example, the transverse stretching zone of the stenter is divided into a plurality of sections along the film running direction, and the temperature is raised by flowing a heating medium at a predetermined temperature in each zone. If the stretching start temperature in the transverse direction is too low, the film breaks, which is not preferable. On the other hand, if the maximum stretching temperature is lower than (Tm-120) ° C., the heat shrinkage of the film increases, and the uniformity of physical properties in the width direction is unfavorably reduced. On the other hand, the maximum stretching temperature is (Tm-3
0) When the temperature is higher than 0 ° C., the film becomes soft, and the film is broken by disturbance or the like, which is not preferable.

The stretching ratio in the transverse direction is preferably 2.5 times or more and 4.0 times or less, and more preferably 2.8 times or more and 3.9 times or less, although it depends on the required characteristics of the intended use. Is preferred. If the ratio is 2.5 times or less, the thickness unevenness of the film becomes worse and a good film is hardly obtained. If the ratio is 4.0 times or more, breakage is liable to occur during film formation, which is not preferable.

The copolymerized polyester film of the present invention comprises:
The thickness is 5 to 40 μm, and preferably 6 to 30 μm. If the thickness is less than 5 μm, breakage or the like is likely to occur during processing, while if it exceeds 40 μm, not only is moldability during embossing deteriorated, but it is not economical.

In the present invention, polyvinyl chloride is mainly composed of polyvinyl chloride or a copolymer of vinyl chloride and another monomer copolymerizable with vinyl chloride (eg, vinyl acetate, acrylate ester, etc.). A composition that
In addition, as a polyvinyl chloride substrate, polyvinyl chloride wallpaper,
PVC leather, PVC desk mat,
The thickness is 50 to 8 in a polyvinyl chloride clear case etc.
Those having a thickness of 00 μm, particularly those having a thickness of 100 to 500 μm can be preferably exemplified.

Conventionally known methods can be used to laminate the copolymerized polyester film of the present invention (hereinafter sometimes referred to as “surface layer”) and a polyvinyl chloride substrate (hereinafter sometimes referred to as “substrate layer”). It can be used, for example, a method of extruding and bonding a polyvinyl chloride substrate heated and melted on a copolymerized polyester film and bonding the same, and bonding the polyester resin film and / or the polyvinyl chloride substrate by heating and pressing. A method in which an adhesive layer is applied in advance to an adhesive surface of a copolymerized polyester film and / or a polyvinyl chloride substrate, and then heated and pressed to adhere, a copolymerized polyester film and a polyvinyl chloride substrate A method of extruding a hot-melt adhesive layer between them and bonding by pressing, a bonding surface of a copolymerized polyester film and / or a polyvinyl chloride substrate The adhesive solution dissolved in a solvent is applied, it is possible to use a method such as crimping while removing the solvent.

After laminating a copolymerized polyester film and a polyvinyl chloride base material containing a foaming agent, the laminated body is heated to foam the polyvinyl chloride base material, and the resultant can be used as wallpaper.

When the copolymerized polyester film and the polyvinyl chloride base material are laminated using an adhesive layer, examples of the adhesive include polyurethane, phenol, furan, urea, melamine, polyester, and the like. Epoxy type, silicone type thermosetting resin, vinyl acetate, ethylene-vinyl acetate copolymer and its partial hydrolyzate, ethylene-acrylic acid copolymer, acrylic resin, thermoplastic resin such as polyamide, butadiene- Acrylonitrile rubber, neoprene and other rubber derivatives, other glue,
Examples of the adhesive include one or more of casein, natural resin, gum arabic and the like.

Of these adhesives, polyester-based adhesives are preferable, and it is preferable to use a copolymerized polyester-based adhesive together with an isocyanate-based or epoxy-based curing agent.

[0029]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The following observations were made on the obtained laminates, and each was evaluated according to the following criteria.

(1) Formability Between a flat rubber plate and an embossed silicon plate,
The laminate is sandwiched so that the surface layer is on the silicon plate side.
When embossing at 50 ° C., pressing 20 kgf / cm ² and pressing time 90 seconds, the emboss of the silicon plate is
The degree of shaping on the surface layer side of the laminate was observed, and the results were evaluated according to the following criteria. ：: The emboss is almost formed on the surface layer side of the laminate. Δ: Emboss is slightly formed on the surface layer side of the laminate. X: The emboss is hardly formed on the surface layer side of the laminate.

(2) Stain resistance After the surface layer side of the laminate was contaminated with magic ink and shoe polish, it was left at room temperature for 168 hours, removed with a neutral detergent and ethanol, and the results were evaluated according to the following criteria. . ○: Contaminants can be completely removed. Δ: Contaminants cannot be completely removed. X: Contaminants cannot be removed at all.

Examples 1-4 and Comparative Examples 1-2 Copolymerized components and copolymerized polyethylene terephthalate having a melting point shown in Table 1 were melt-extruded at the temperatures shown in Table 1 and quenched and solidified to obtain unstretched films. . Next, the unstretched film was stretched longitudinally and transversely under the conditions shown in Table 1, and then heat-set, followed by heat relaxation of 4.5% in the transverse direction to obtain a biaxially oriented film. The films obtained in Examples 1-4 and Comparative Examples 1-2 were coated with a polyester-based adhesive,
The film was laminated on a foamed PVC base material containing 30% of -ethylhexyl phthalate (foaming rate: 5 times, average thickness: 200 µm) and embossed to prepare a wallpaper. Table 1 shows the evaluation results of the obtained wallpaper. Wallpapers using the laminate of the present invention were all excellent in moldability and stain resistance. Since the laminate of Comparative Example 1 was thin, the film was broken and could not be processed into wallpaper. The wallpaper of Comparative Example 2 was excellent in stain resistance because the film thickness was large.
Moldability was poor.

The film was coated with the polyester-based adhesive by applying a coating solution prepared as described below to the surface of the polyester film to be adhered to the substrate, followed by drying by heating.

14 parts of toluene, 14 of methyl ethyl ketone
SYNOL UF-30 (manufactured by Siden Chemical Co., polyester-based adhesive: solid content concentration: 70%) in a mixed solvent consisting of 6 parts by weight and 6 parts of cyclohexanone, and Byron 20SS
(Polyester adhesive manufactured by Toyobo: solid concentration 70
%) And stirred and dissolved, and then coronate 20
30 (manufactured by Nippon Polyurethane Industry, isocyanate-based curing agent: solid content concentration: 50%) was added and blended before coating.

Comparative Example 3 Example 1 was repeated except that a biaxially oriented polyethylene terephthalate film having a film thickness of 12 μm was used instead of the copolymerized polyester film.
Wallpaper was obtained in the same manner as. Table 1 shows the evaluation results of the obtained wallpaper. The stain resistance was excellent, but the moldability was poor.

[Comparative Examples 4 and 5] Table 1 currently used
The wallpaper made of a laminate having polyvinyl chloride as a base material was evaluated in the same manner as in Example 1. All of the wallpapers had good moldability, but were poor in stain resistance.

[0037]

[Table 1]

As is clear from the results in Table 1, the wallpaper using the laminate of the present invention was excellent in moldability and stain resistance.

[0039]

The laminate obtained by laminating the copolymerized polyester film of the present invention on a polyvinyl chloride substrate has excellent moldability and stain resistance, and is extremely useful as wallpaper.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 D21H 27/20

Claims (3)

(57) [Claims] 1. A laminate comprising a biaxially oriented copolymerized polyester film having a melting point of 210 to 245 ° C. and a thickness of 5 to 40 μm laminated on at least one surface of a polyvinyl chloride base material. 2. The laminate according to claim 1, wherein an adhesive layer is provided between the polyvinyl chloride substrate and the biaxially oriented copolymerized polyester film. A wallpaper comprising the laminate according to claim 1 or 2.