JP2020093406A - Decorative sheet - Google Patents

Abstract

To provide a decorative sheet capable of enhancing content percentage of a recycled resin, high in brightness, less in unevenness of color tone, capable of suppressing reduction of strength or reduction of surface appearance, and further capable of suppressing reduction of adhesiveness.SOLUTION: A decorative sheet has a first resin component containing a first layer containing a recycled PET-based resin derived from a PET bottle of 70 mass% or more, and a white pigment, a second layer having a second resin component arranged by layering in one surface side of the first layer, and containing a virgin resin of 70 mass% or more, and the white pigment, and having a thickness in a range of 25 μm to 75 μm, and a third resin composition arranged by layering in another surface side of the first layer and containing the virgin resin of 80 mass% or more, in which the white pigment is 5 pts.mass or less based on 100 pts.mass of the third resin component.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet.

As a decorative sheet used for the surface layer of wall materials, floor materials, fittings (doors, doors, etc.), furniture, sinks, vanities, etc., polyvinyl chloride sheets were once the mainstream. BACKGROUND ART In recent years, with increasing concern about environmental issues, as a decorative sheet, a sheet mainly composed of polyolefin such as polyethylene or a sheet mainly composed of polyester such as polyethylene terephthalate (hereinafter also referred to as “PET”) has become mainstream. ing. Further, there is a strong demand for the development of a decorative sheet using a recycled resin made of waste plastic.
However, the recycled resin is often colored in various colors, and the decorative sheet using the recycled resin is likely to have color variations.

The followings have been proposed as a decorative sheet using a recycled resin and suppressing color variations.
(1) A decorative sheet obtained by laminating a recycled polyvinyl chloride sheet and a new polyvinyl chloride sheet having a colored layer (see Patent Document 1).
(2) A decorative sheet containing a coloring pigment in an amount of 0.1 to 30% by mass based on a polyester composed of 3 to 70% by mass of recycled polyester and 30 to 97% by mass of virgin polyester (see Patent Document 2).
However, in the decorative sheets of (1) and (2), it is necessary to increase the proportion of the virgin resin (new resin) raw material in order to suppress the color variation, and the proportion of the recycled resin is low.

The following sheets have been proposed as sheets containing a high proportion of recycled resin.
(3) Recycled PET/recycled polyethylene/compatibilizer/blue pigment=a decorative plate in which a resin layer (corresponding to a decorative sheet) with a mass ratio of 85/15/5/1 is laminated on the surface of a steel plate (paragraph of Patent Document 3) See [0148]).
(4) A recycled plastic sheet in which 100 parts by mass of recycled PET is blended with 3 to 10 parts by mass of a specific binder and 2 to 5 parts by mass of a modifier made of titanium oxide (see Patent Document 4).

JP-A-56-080417 Japanese Patent Laid-Open No. 11-130877 JP, 2009-030062, A JP, 2002-348448, A

The resin layer in the decorative board disclosed in Patent Document 3 is colored blue in order to suppress color variation due to the recycled resin. Therefore, in the case of a compound such as the resin layer in the decorative board of Patent Document 3, it is limited to low lightness colors such as dark blue, black, and gray that are difficult to discriminate in color variation due to recycled resin, and white, It is difficult to adopt a color with high lightness such as a light color.

The recycled plastic sheet disclosed in Patent Document 4 is premised on being used as a filler for a cooling tower, and titanium oxide is added in a small amount as a modifier for imparting weather resistance. When such a recycled plastic sheet containing a small amount of titanium oxide is used as a decorative sheet, it cannot be used as a decorative sheet because it has a low lightness and thus has a high lightness such as white and light colors. Further, the other side of the sheet is transparent, and the concealing property as a decorative sheet is insufficient. Further, there is a large variation in color between raw material lots and each sheet location, and it is difficult to obtain a uniform color tone.

Further, as disclosed in Patent Document 3 and Patent Document 4, a decorative board or a recycled plastic sheet having a high content ratio of recycled resin has a problem that fine foreign matters and impurities contained in the recycled resin raw material are mixed with solvents or chemicals (acid, When exposed to a base, it tends to become a starting point of cracks, which causes a decrease in the aesthetics and strength of the decorative sheet.

Further, the decorative plate and the recycled plastic sheet having a higher content ratio of the recycled resin as disclosed in Patent Document 3 and Patent Document 4 have been a cause of the recycled resin lowering the adhesion to the wall surface.

The present invention has been made in view of the above-mentioned circumstances, and it is possible to increase the content ratio of the recycled resin, and the brightness is high, the unevenness of the color tone is small, and the strength and the appearance of the surface are deteriorated. (EN) Provided is a decorative sheet that can be suppressed and can further prevent a decrease in adhesiveness.

The present invention has the following aspects.
<1> A first resin component containing a recycled PET resin derived from a PET bottle in an amount of 70% by mass or more and a first layer containing a white pigment, and a virgin resin which is arranged so as to overlap one surface side of the first layer. A second layer containing 70% by mass or more of a second resin component and a white pigment and having a thickness in the range of 25 μm or more and 75 μm or less, and a second layer of the first layer, the virgin resin. A decorative sheet having a third resin component containing 80% by mass or more of the white pigment and 5 parts by mass or less of the white pigment based on 100 parts by mass of the third resin component.
<2> The white pigment included in the first layer is in the range of 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the first resin component, and the white pigment included in the second layer. Is 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the second resin component, The decorative sheet according to <1>.
<3> The decorative sheet according to <1> or <2>, wherein the second resin component further contains the recycled PET resin in an amount of 30% by mass or less.
<4> The decorative sheet according to any one of <1> to <3>, wherein the third resin component further contains the recycled PET resin in a range of 5% by mass or less.
<5> The decorative sheet according to any one of <1> to <4>, wherein L* in the CIE 1976 L*a*b* color space is 92 or more on the surface side of the second layer.

According to the present invention, it is possible to increase the content ratio of the recycled resin, and the brightness is high, the unevenness of the color tone is small, it is possible to suppress the deterioration of the strength and the appearance of the surface, and further the deterioration of the adhesiveness. It is possible to provide a decorative sheet capable of preventing the above.

It is sectional drawing which shows the layer structure of the decorative sheet of one Embodiment of this invention.

The following definitions of terms apply throughout the specification and claims.
"L*" is JIS Z 8781-4:2013 "Colorimetry-Part 4: CIE 1976.
L*a*b* color space” (corresponding international standard ISO 11664-4:2008).
“A*” and “b*” are defined in JIS Z 8781-4:2013 “Colorimetry-Part 4: CIE 1976 L*a*b* color space” (corresponding international standard ISO 11664-4:2008). These are the color coordinates that are used.
"-" showing a numerical range means including the numerical value described before and after that as a lower limit and an upper limit.

Hereinafter, a decorative sheet according to an embodiment of the present invention will be described. The following embodiments are specifically described in order to better understand the gist of the invention, and do not limit the invention unless otherwise specified.

<Cosmetic sheet>
FIG. 1 is a cross-sectional view showing a layer structure of a decorative sheet according to an embodiment of the present invention.
The decorative sheet 10 of the present embodiment is formed by overlapping the first layer 11, the second layer 12 formed on the one surface 11a side of the first layer 11, and the other surface 11b side of the first layer 11 on the other surface 11b side. It has a multi-layer structure including the third layer 13. In this embodiment, in the decorative sheet 10, the third layer 13 side is attached to the wall surface W, for example, via the adhesive layer 14, and the second layer 12 side is exposed to the outside.

(First layer)
The first layer 11 contains at least a first resin component containing 70% by mass or more of recycled PET resin derived from a PET bottle, and a white pigment. In addition, the 1st layer 11 WHEREIN: In the range which does not impair the effect of this invention, components other than a 1st resin component and a white pigment (henceforth "other components (1st layer)" are described hereafter). May be included.

"First resin component (first layer)"
The first resin component contains 70% by mass or more of recycled PET resin derived from a PET bottle. The first resin component contains a resin other than the recycled PET resin (hereinafter, also referred to as “other resin (first layer)”) in the range of, for example, 30% by mass or less, preferably 10% by mass or less. You may stay.

It is also preferable that the recycled PET resin is contained in an amount of 25% by mass or more based on the total mass of the decorative sheet 10. If the recycled PET resin is less than 25% by mass, the ratio of the virgin resin contained in the second layer 12 described later becomes relatively large, and the significance of using the recycled PET resin as an environmental measure decreases.

The recycled PET resin is a recycled resin derived from PET bottles, and is preferably a crushed PET bottle because it is inexpensive and easily available. The recycled PET resin may include a crushed product such as a label (including printing/adhesive, etc.) attached to the PET bottle, a cap, and the like, as long as the effects of the present invention are not impaired.

For example, in Japan, in order to prevent deterioration of the quality of reused products, the designated PET bottles should be used as a PET single substance (substances other than PET main material are added or combined, etc. It is defined that it is not colored (excluding white due to crystallization of the mouth plug part). Therefore, currently, colored PET bottles are not produced in Japan, and it is requested to change colored PET bottles produced in Japan for Japan to non-colored PET bottles (http://www. petbottle-rec.gr.jp/qanda/sec13.html).

For PET bottles distributed in Japan, details are specified in the "Voluntary Design Guidelines for Designated PET Bottles" established by the PET Bottle Recycling Promotion Council under the guidance of the government (http://www.petbottle). -Rec.gr.jp/guideline/jisyu.html).

These voluntary design guidelines refer to PET bottles (designated PET bottles) used by the PET Bottle Recycling Promotion Council for designated display products (soft drinks, milk drinks, alcoholic beverages, specific seasonings) prescribed by the Law for Promotion of Effective Utilization of Resources. It specifies the bottles, labels (including printing/adhesives, etc.), caps, etc. to be used in order to provide containers with excellent reusability including post-use reprocessing and hygiene.

As a matter of course, the members (groups and companies) of the PET Bottle Recycling Promotion Council will comply with the voluntary design guidelines, and when non-members also manufacture, import, and sell drinks, alcoholic beverages, and specific seasonings with designated PET bottles, Alternatively, when manufacturing and importing designated PET bottles and associated packaging materials, if they are sold and used in Japan, it is necessary to comply with voluntary design guidelines.

Therefore, most PET bottles distributed in Japan are non-colored, and recycled PET resins derived from PET bottles are almost transparent.
Although the recycled PET resin is almost transparent, it is yellowish black (the value of b* in the CIE 1976 L*a*b* color space is high, due to the heat history received during the thermoforming process and the mixture of labels and the like. L* value tends to be low). Therefore, until now, it has been hesitant to use the recycled PET resin as a material for a white or light colored decorative sheet having high brightness.

In the present invention, as will be described later, the second layer 12 that is exposed to the outside is formed so as to overlap with the first layer 11, and the second layer 12 contains a second resin component mainly composed of a virgin resin. Thus, recycled PET resin can be used as a constituent material of the decorative sheet 10 having a high white color or a light color without worrying about a decrease in brightness.

The crystallization temperature of the recycled PET resin is preferably 145°C or lower, more preferably 120 to 145°C, and further preferably 125 to 140°C.
The crystallization temperature of the regenerated PET resin is measured by using a thermal analyzer (differential scanning calorimeter (DSC) etc.).

The intrinsic viscosity (IV value) of the recycled PET resin is, for example, preferably 0.60 or more, more preferably 0.65 to 0.85, further preferably 0.70 to 0.83. If the intrinsic viscosity (IV value) of the recycled PET resin is less than the lower limit of the above range, the melt viscosity may decrease when the pigment is added, which may cause a problem in extrusion moldability. When the intrinsic viscosity (IV value) of the recycled PET resin exceeds the upper limit value of the above range, the viscosity is high and the extrusion moldability may be problematic.
The intrinsic viscosity (IV value) of the recycled PET resin is measured by the test method described in JIS K 7390:2003.

The b* in the CIE 1976 L*a*b* color space of the recycled PET resin is preferably 9 or less, more preferably -6 to 8, and further preferably 0 to 7.
The b* of the recycled PET resin is measured by the test method described in JIS K 7390:2003.
The L* of the recycled PET resin in the CIE 1976 L*a*b* color space is preferably 65 or more, more preferably 68 or more, and further preferably 70 or more. When L* of the recycled PET resin is at least the lower limit value of the above range, it is easy to manufacture the white or light colored decorative sheet 10 having high brightness.

The other resin (first layer) contained in the first resin component is a resin used in a masterbatch containing a white pigment, added for the purpose of suppressing the color variation of the decorative sheet, improving the characteristics of the decorative sheet, etc. And the like. Specific examples of other resins include virgin PET-based resins, recycled resins other than recycled PET-based resins (excluding polyvinyl chloride), virgin resins other than virgin PET-based resins (excluding polyvinyl chloride), and the like. Be done.

"White pigment (first layer)"
Examples of the white pigment of the first layer 11 include titanium oxide, zinc oxide, calcium carbonate, magnesium oxide and lithobon. Titanium oxide is preferable as the white pigment because of its high hiding power.
Examples of titanium oxide include rutile type titanium oxide and anatase type titanium oxide, and rutile type titanium oxide is preferable from the viewpoint of low activity as a catalyst.

The content of the white pigment in the first layer 11 is 5 to 15 parts by mass with respect to 100 parts by mass of the first resin component, preferably 7 to 13 parts by mass, and more preferably 9 to 12 parts by mass. By including a white pigment in the first layer 11, which is a lower layer of the second layer 12 described later, the lightness of the decorative sheet 10 is reduced due to color transmission even if the thickness of the second layer 12 exposed to the outside is reduced. Can be prevented. When the content of the white pigment is at least the lower limit value of the above range, a white or light colored decorative sheet 10 with high lightness and little color variation between raw material lots or sheet locations can be obtained. When the content of the white pigment is equal to or less than the upper limit value of the above range, abnormal extrusion behavior (abnormal width due to decrease in melt viscosity, etc.) is suppressed, and moldability in manufacturing the decorative sheet 10 is good.

"Other ingredients (first layer)"
Other components of the first layer 11 include pigments other than white pigments, compatibilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, storage stabilizers, lubricants, fillers and the like.
The content of the other components is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less with respect to 100 parts by mass of the first resin component.

(Second layer)
The second layer 12 contains at least a second resin component containing 70% by mass or more of a virgin resin (new resin) and a white pigment. In addition, the 2nd layer 12 WHEREIN: In the range which does not impair the effect of this invention, components other than a 2nd resin component and a white pigment (henceforth the "other component (2nd layer)" are described hereafter). May be included.

"Second resin component (second layer)"
The second resin component contains 70 mass% or more of virgin resin. The second resin component may contain a resin other than the virgin resin (hereinafter, also referred to as “other resin (second layer)”) in an amount of 30% by mass or less, preferably 10% by mass or less. ..

The virgin resin is a resin newly produced from a resin raw material containing almost no impurities, and from the viewpoint of improving the bondability to the first layer 11, it is a copolymer (PET) containing ethylene glycol and terephthalic acid as main monomers. , PET-G), polycarbonate, polyacrylic acid polymers are preferred.

In the decorative sheet 10, by including 70% by mass or more of a virgin resin as the second resin component of the second layer 12 that covers the first layer 11, the lightness of the second layer 12 exposed to the outside can be adjusted by the recycled PET system. The brightness of the first layer containing 70% by mass or more of resin can be increased. As a result, even the decorative sheet 10 using the recycled PET resin having a mass of 25% or more of the total resin components of the decorative sheet 10 can maintain high lightness in appearance.

Examples of the other resin contained in the second resin component include a resin used for a masterbatch containing a white pigment, a resin added for the purpose of suppressing the color variation of the decorative sheet, improving the characteristics of the decorative sheet, and the like. Can be mentioned. Specific examples of other resins include virgin resins other than virgin PET resins (excluding polyvinyl chloride), recycled PET resins, recycled resins other than recycled PET resins (excluding polyvinyl chloride), and the like. Be done. For example, as the other resin contained in the second resin component, recycled PET resin can be contained in the range of 30% by mass or less.

"White pigment (second layer)"
As with the first layer 11, examples of the white pigment of the second layer 12 include titanium oxide, zinc oxide, calcium carbonate, magnesium oxide, lithobon, and the like. Titanium oxide is preferable as the white pigment because of its high hiding power.
Examples of titanium oxide include rutile type titanium oxide and anatase type titanium oxide, and rutile type titanium oxide is preferable from the viewpoint of low activity as a catalyst.
The white pigment of the second layer 12 may be the same as the white resin of the first layer 11 or may be different from each other.

The content of the white pigment in the second layer 12 is 5 to 15 parts by mass, preferably 7 to 13 parts by mass, and more preferably 9 to 12 parts by mass with respect to 100 parts by mass of the second resin component. When the content of the white pigment is at least the lower limit value of the above range, a white or light colored decorative sheet 10 with high lightness and little color variation between raw material lots or sheet locations can be obtained. When the content of the white pigment is equal to or less than the upper limit value of the above range, abnormal extrusion behavior (abnormal width due to decrease in melt viscosity, etc.) is suppressed, and moldability in manufacturing the decorative sheet 10 is good.

"Other ingredients (second layer)"
Other components of the second layer 12 include pigments other than white pigments, compatibilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, storage stabilizers, lubricants, fillers and the like.
The content of the other components is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less with respect to 100 parts by mass of the second resin component.

The thickness of the second layer 12 having the composition as described above covers the first layer 11 containing recycled PET resin in an amount of 70% by mass or more in order to prevent penetration into the first layer 11 having low chemical resistance and solvent resistance. It is desirable to have a certain thickness or more.
The thickness range of the second layer 12 is, for example, 25 to 75 μm, preferably 25 to 40 μm.

With such a thickness range, the low-brightness first layer 11 containing the recycled PET resin is transparent through the second layer 12 of the decorative sheet 10 that is exposed to the outside, and the decorative sheet 10 has a bright external appearance. Is prevented from decreasing. Further, if the second layer 12 is too thick, the proportion of the recycled PET resin used in the entire decorative sheet 10 decreases, and the significance of using the recycled PET resin decreases.

(Third layer)
The third layer 13 contains at least a third resin component containing 80 mass% or more of a virgin resin (new resin). The third layer 13 may further contain a white pigment in an amount of 5 parts by mass or less with respect to 100 parts by mass of the third resin component. Furthermore, the third layer 13 is a component other than the third resin component and/or the white pigment optionally contained (hereinafter, referred to as “other component (third layer)”, as long as the effect of the present invention is not impaired. ].) may be included.

"Third resin component (third layer)"
The third resin component contains 80 mass% or more of virgin resin. The third resin component contains a resin other than the virgin resin (hereinafter, also referred to as “other resin (third layer)”) in a range of, for example, 20 mass% or less, preferably 10 mass% or less. Good.

The virgin resin is a resin that is newly manufactured from a resin raw material that contains almost no impurities. From the viewpoint of improving the bondability to the first layer 11 and the adhesiveness to the wall surface W via the adhesive layer 14, ethylene glycol is used. And a copolymer containing terephthalic acid as a main monomer (PET, PET-G), a polycarbonate, and a polyacrylic acid polymer are preferable.
The virgin resin used for the third layer 13 may be the same as the virgin resin used for the second layer 12, or different types of virgin resin may be used.

In the decorative sheet 10, by including 80 mass% or more of a virgin resin as the third resin component of the third layer 13 that covers the first layer 11, the decorative sheet 10 forms a surface to be adhered to the wall surface W. The adhesion of the layer 13 to the wall surface W is improved. Further, by not containing the white pigment or limiting the content to 5 parts by mass or less with respect to 100 parts by mass of the third resin component, it is possible to prevent the adhesiveness from being lowered due to the dispersant contained in the white pigment.

Other resins included in the third resin component include virgin resins other than virgin PET-based resins (excluding polyvinyl chloride), recycled PET-based resins, and recycled resins other than recycled PET-based resins (excluding polyvinyl chloride). ) And the like. For example, as the other resin contained in the third resin component, recycled PET resin can be contained in the range of 20% by mass or less.

"White pigment (third layer)"
It is preferable that the white pigment of the third layer 13 is not included, but when it is included, titanium oxide, zinc oxide, calcium carbonate, magnesium oxide, lithobon, or the like can be used as in the case of the first layer 11. Titanium oxide is preferable as the white pigment because of its high hiding power.
Examples of titanium oxide include rutile type titanium oxide and anatase type titanium oxide, and rutile type titanium oxide is preferable from the viewpoint of low activity as a catalyst.
The white pigment of the third layer 13 may be the same as the white resin of the first layer 11 or the second layer 12, or may be different from each other.

"Other ingredients (third layer)"
Other components of the third layer 13 include pigments other than white pigments, compatibilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, storage stabilizers, lubricants, fillers and the like.
The content of the other components is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less, relative to 100 parts by mass of the third resin component.

The thickness of the third layer 13 having the above composition is to cover the first layer 11 containing recycled PET resin in an amount of 70% by mass or more and prevent penetration into the third layer 13 having low chemical resistance and solvent resistance. It is desirable to have a certain thickness or more.
The thickness range of the third layer 13 is, for example, 15 to 70 μm, preferably 25 to 40 μm.

When the thickness is within such a range, a decrease in adhesiveness caused by the dispersant in the pigment contained in the recycled PET resin of the first layer 11 penetrating to the adhesive layer 14 side of the third layer 13 and bleeding out is prevented. Can be prevented.
Further, if the third layer 13 is too thick, the proportion of the recycled PET resin used in the entire decorative sheet 10 decreases, and the significance of using the recycled PET resin decreases.

(Overall makeup sheet structure)
The total thickness of the decorative sheet 10 including the first layer 11, the second layer 12, and the third layer 13 as described above is preferably 0.1 to 0.5 mm, more preferably 0.2 to 0.4 mm. .. When the thickness of the decorative sheet 10 is at least the lower limit value of the above range, the mechanical strength and the hiding power of the decorative sheet 10 can be easily increased. When the thickness of the decorative sheet 10 is less than or equal to the upper limit value of the above range, the three-dimensional processability and flexibility of the decorative sheet 10 are good.

Further, L* in the CIE 1976 L*a*b* color space on the surface side of the second layer 12 of the decorative sheet 10 is preferably 92 or more. Thereby, the white or light colored decorative sheet 10 having high brightness can be obtained. The L* of the decorative sheet 10 is measured based on JIS Z 8781-4:2013.

The decorative sheet 10 of the present embodiment may have a functional layer for imparting various functions as needed, as long as the effects of the present invention are not impaired. Examples of the functional layer include a coating layer for imparting stain resistance and weather resistance, a transfer layer, and a printing layer for imparting designability.
The surface shape of the second layer forming the surface of the decorative sheet 10 is not particularly limited and may be smooth or may have a shape having irregularities due to embossing or the like.

The decorative sheet 10 according to the present embodiment has, for example, a resin mixture containing a resin component, a white pigment, and the like, which form the first layer 11, the second layer 12, and the third layer 13, respectively, and is heated and melted and kneaded to form a multilayer. It is obtained by coextrusion into a sheet. For example, the resin forming the first layer 11, the resin forming the second layer 12, and the resin forming the third layer 13 are supplied to a coextrusion molding machine, and a feed block type T die is used to Coextrusion is performed at about 200° C. to form the decorative sheet 10 including the first layer 11, the second layer 12, and the third layer 13.

Alternatively, by molding the resin mixture into a sheet shape and bonding the second layer 12 to the one surface 11a side of the obtained first layer 11 and the third layer 13 to the other surface 11b side, respectively, The decorative sheet 10 is obtained.
Examples of the method for molding the resin mixture include an extrusion molding method and a calender molding method.
The decorative sheet 10 may be unstretched or stretched.

Although the decorative sheet 10 is composed of the three layers of the first layer 11, the second layer 12, and the third layer 13 in the above-described embodiment, an arbitrary functional layer is further provided between the layers. It can also be formed. Further, a transparent protective film or the like can be further formed on the surface of the second layer 12.

(Mechanism of action)
In the decorative sheet 10 of the present embodiment described above, the first resin component of the first layer 11 has the first resin component containing 70% by mass or more of the recycled PET resin derived from the PET bottle. It is more environmentally friendly than decorative sheets containing vinyl and decorative sheets with a low proportion of recycled resin in all resin components.

Then, in the decorative sheet 10 of the present embodiment, the second layer 12 having the second resin component containing 70% by mass or more of the virgin resin is arranged on the first layer 11 containing a large amount of recycled PET resin. As a result, the surface of the decorative sheet 10 that is exposed to the outside is the second layer 12, so that it is possible to maintain a high lightness in appearance and realize the decorative sheet 10 with less unevenness in color.

The second layer 12 exposed on the outer surface of the decorative sheet 10 has the second resin component containing 70% by mass or more of the virgin resin, and is caused by the base in the impurities generated when the proportion of the recycled resin is high. It is possible to realize the decorative sheet 10 in which cracks are unlikely to occur and which can prevent deterioration of the appearance of the surface and deterioration of the strength.

Further, in the decorative sheet 10 of the present embodiment, the third layer 13 having the third resin component containing 80% by mass or more of the virgin resin is provided on the first layer 11 containing a large amount of recycled PET resin. For example, in the decorative sheet 10, since the third layer 13 is adhered to the wall surface W, a decrease in the adhesiveness caused by the dispersant in the pigment bleeding out to the surface of the decorative sheet, which occurs when the proportion of recycled resin is high. Can be prevented. Therefore, it is possible to realize the decorative sheet 10 having good adhesiveness even when the decorative sheet 10 has the first layer 11 containing a large amount of recycled PET resin.

INDUSTRIAL APPLICABILITY The decorative sheet of the present invention is used as a surface layer for wall materials, floor materials, fittings (doors, doors, etc.), furniture, sinks, vanities, etc., and is preferably doors for furniture, sinks, vanities, etc. Used for the surface layer of.

Although the embodiments of the present invention have been specifically described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. The embodiments and their modifications are included in the scope of the invention and the scope thereof, and are included in the invention described in the claims and the scope of equivalents thereof.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

"Evaluation method"
・Surface color tone A CIE 1976 L*a*b* was measured using a spectrophotometer (CCM) (COLOR-7, manufactured by Kurabo Industries, Ltd.) under the conditions of a light source D65 and a viewing angle of 10° under three conditions. L*, a*, and b* in the color space were obtained, and the average value of three points was used.

・Basic resistance 2.5 cm square absorbent cotton containing 10% NaOH aqueous solution is placed on a 10 cm square decorative sheet sample and allowed to stand for 24 hours at 23°C and 50% humidity. Place. After that, the absorbent cotton was removed, the surface was washed with water and dried for 24 hours, and the presence or absence of cracks on the sample of the decorative sheet was observed.
After the production of the (initial) decorative sheet, the above-mentioned basicity evaluation was carried out using a sample of the decorative sheet cut into 10 cm squares.
(After aging) A sample of the decorative sheet cut into 10 cm squares was stored for 14 days in a thermo-hygrostat set to a temperature of 45° C. and a humidity of 95%, and then the above-mentioned evaluation of basicity was performed.

-Adhesiveness After the sample of the decorative sheet was stored in a constant temperature and high humidity tank set at a temperature of 45°C and a humidity of 95% for 14 days, Shinko Bond TA435 was applied to the particle board, and the sample of the decorative sheet was stored for 24 hours after pressure bonding, The sample of the decorative sheet is peeled off under each temperature condition (0°C, -10°C, -20°C). The wood adhering to the back surface of the peeled decorative sheet sample was observed, and the percentage of the adhering area of the wood to the sample area of the decorative sheet was defined as the wood fracture rate (%).
Wood fracture rate 100% to 80%... Evaluation A
Wood fracture rate 80% to 50%... Evaluation B
Wood part breakage rate 50% to 0% ... Evaluation C
If the evaluation is A, it is considered that sufficient adhesion is obtained.

(Example 1)
First layer:
Recycled PET-based resin A resin mixture prepared by adding a masterbatch (including titanium oxide and virgin A-PET resin) to “Alimpet” (recycled plastic bottle recovered from Italy) manufactured by ALIPLAST was used.
Table 1 shows the content of the white pigment with respect to the resin component.
Second layer:
PET-G resin (virgin resin) A resin mixture obtained by adding a master batch (including titanium oxide and virgin PET-G) to "K2012" manufactured by SK Chemicals was used.
Table 1 shows the content of the white pigment with respect to the resin component.
Third layer:
PET-G resin (virgin resin) "K2012" manufactured by SK Chemicals was used.
The above raw materials were extruded from a T-die at 265° C. by a co-extrusion method using a three-kind three-layer extruder and cast on a cooling roll at 40° C. to obtain the second layer/first layer/third layer. Sheets having a layer thickness of 250 μm of 33 μm/184 μm/33 μm respectively were obtained.

(Example 2)
Except for changing the virgin resin of the second layer, the resin component of the masterbatch of the second layer, and the virgin resin of the third layer from PET-G resin to PET resin (A-PET) "CR8816" manufactured by Kajun Co., Ltd. A decorative sheet of Example 2 was obtained in the same manner as in Example 1.

(Example 3)
The second layer of virgin resin, the second layer of masterbatch resin component, and the third layer of virgin resin are PET-G resin, polymethyl methacrylate resin (PMMA1) made by Asahi Kasei "Delpet (registered trademark) 60N". A decorative sheet of Example 3 was obtained in the same manner as in Example 1, except that the decorative sheet was changed to ".

(Example 4)
The second layer of virgin resin, the second layer of masterbatch resin component, and the third layer of virgin resin are made of PET-G resin, polymethylmethacrylate resin (PMMA2) manufactured by Mitsubishi Chemical Corporation "Acrypet (registered trademark)". A decorative sheet of Example 4 was obtained in the same manner as in Example 1 except that the decorative sheet was changed to IRS204”.

(Example 5)
A decorative sheet of Example 5 was obtained in the same manner as in Example 1, except that the thickness of each of the second layer/first layer/third layer was changed to 25 μm/184 μm/33 μm and the layer thickness was changed to 242 μm.

(Examples 6, 8, and 11)
The thickness of each layer of the second layer/first layer/third layer, the ratio (% by mass) of the recycled PET resin and the virgin resin, and the content of the white pigment to the resin component were changed as shown in Table 2. In the same manner as in Example 1, the decorative sheets of Examples 6, 8 and 11 were obtained.

(Examples 7, 9, 10)
Example 7, except that the ratio (mass %) of the recycled PET resin and virgin resin in each of the second layer/first layer/third layer was changed as shown in Table 2, Example 7, 9, 10 decorative sheets were obtained.

(Comparative Example 1)
The decorative sheet of Comparative Example 1 was obtained by extruding only the first layer using recycled resin without providing the second layer and the third layer of Example 1.
The obtained decorative sheet had a low lightness due to the coloring of the recycled resin, and in the evaluation of the basic resistance, the recycled resin was exposed to the base to cause cracks, and the adhesive strength to wood was also compared with those in Examples 1 to 11. weak.

(Comparative example 2)
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that each of the second layer/first layer/third layer was changed to 17 μm/88 μm/17 μm and the layer thickness was changed to 122 μm.
Since the second layer of the obtained decorative sheet is thin, the coloring of the first layer using the recycled resin cannot be hidden. Moreover, in the evaluation of the base resistance, the base penetrated into the recycled resin of the first layer, and a crack was generated.

(Comparative example 3)
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 3 except that each of the second layer/first layer/third layer was changed to 17 μm/88 μm/17 μm and the layer thickness was changed to 122 μm.
Since the second layer of the obtained decorative sheet is thin, the coloring of the first layer using the recycled resin cannot be hidden. Moreover, in the evaluation of the base resistance, the base penetrated to the first layer, and a crack was generated.

(Comparative example 4)
A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the third layer was changed to a resin mixture in which a masterbatch (including titanium oxide and virgin PET-G) was added to PET-G resin. .. Table 3 shows the content of the white pigment with respect to the resin component.
The obtained decorative sheet had a lower adhesive strength to wood as compared with Examples 1 to 11.

(Comparative example 5)
A decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the third layer was changed to a mixture of 70% by mass of virgin resin (A-PET) and 30% by mass of recycled PET resin.
The obtained decorative sheet had a lower adhesive strength to wood as compared with Examples 1 to 11.

(Comparative example 6)
Extrusion molding was performed using only the first layer as in Comparative Example 1, but the first layer was changed to a mixture of 70% by mass of recycled PET resin and 30% by mass of virgin resin (A-PET), and the makeup of Comparative Example 6 was changed. Got the sheet.
In the evaluation of the base resistance, the obtained decorative sheet was cracked by the base, and the adhesive strength to wood was lower than that of Examples 1 to 11.

Table 1 shows the configurations and evaluation results of the samples of Examples 1 to 5, Table 2 shows the configurations and evaluation results of the samples of Examples 6 to 11, and the configurations and evaluation results of the samples of Comparative Examples 1 to 6. 3 shows each.

The decorative sheets of Examples 1 to 11 were all excellent in surface color tone, and were superior to Comparative Examples 1 to 6 in both base resistance and adhesiveness.
On the other hand, the decorative sheet obtained in Comparative Example 1 has low lightness due to the coloring of the recycled resin, cracks occur due to exposure of the recycled resin to the base, and the adhesive strength to wood is weaker than in Examples 1 to 11. ..
Further, in the decorative sheets obtained in Comparative Examples 2 and 3, since the second layer is thin, the coloring of the first layer using the recycled resin cannot be hidden. Moreover, in the evaluation of the base resistance, the base penetrated into the recycled resin of the first layer, and a crack was generated. The decorative sheet obtained in Comparative Example 4 had a lower adhesion to wood than in Examples 1 to 11. The decorative sheet obtained in Comparative Example 5 had a lower adhesion to wood than in Examples 1 to 11. In the evaluation of base resistance, the decorative sheets obtained in Comparative Example 6 were cracked by the base, and the adhesive force to wood was lower than that in Examples 1 to 11.
From the above examples, it was confirmed that the decorative sheet of the present invention has excellent surface color tone, base resistance and adhesiveness.

INDUSTRIAL APPLICABILITY The decorative sheet of the present invention is useful as a white or light colored decorative sheet which is environmentally friendly and has high brightness.

10... Decorative sheet 11... 1st layer 12... 2nd layer 13... 3rd layer W... Wall surface

Claims (5)

A first resin component containing 70% by mass or more of recycled PET resin derived from a PET bottle, and a first layer containing a white pigment,
A second layer, which is arranged on one side of the first layer and has a second resin component containing 70% by mass or more of a virgin resin, and a white pigment, and has a thickness of 25 μm or more and 75 μm or less,
It is arranged on the other surface side of the first layer and has a third resin component containing 80% by mass or more of a virgin resin, and the white pigment is 5 parts by mass or less with respect to 100 parts by mass of the third resin component. A decorative sheet characterized by being present. The white pigment contained in the first layer is in the range of 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the first resin component,
The decorative sheet according to claim 1, wherein the white pigment contained in the second layer is in a range of 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the second resin component. The decorative sheet according to claim 1, wherein the second resin component further contains the recycled PET resin in an amount of 30% by mass or less. The decorative sheet according to any one of claims 1 to 3, wherein the third resin component further contains the recycled PET resin in a range of 5% by mass or less. The decorative sheet according to any one of claims 1 to 4, wherein L* in the CIE 1976 L*a*b* color space is 92 or more on the surface side of the second layer.

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