JP7310254B2 - Decorative sheet and decorative member - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet and a decorative member.

In general, steel plates, etc. are used for building interior and exterior materials such as walls, ceilings, floors, and entrance doors, as well as fittings and fittings such as window frames, doors, handrails, baseboards, rims, and malls. A decorative member is used in which a metal member, a resin member, or a wooden member is used as an adherend (base material), and a decorative sheet is adhered to the adherend. A decorative sheet used for such a decorative member may have a back coat layer formed as a back surface primer on the back surface (adhesive surface) of the decorative sheet in order to improve adhesion to the substrate (for example, Patent Document 1). .

Decorative sheets for building materials are required to have durability against high temperatures and high humidity (moisture heat resistance), especially when used for building exterior materials, bathroom wall materials, and the like, which can be exposed to high temperatures and high humidity. However, the conventional decorative sheet has a problem that the primer tends to hydrolyze in a hot and humid environment, and sufficient adhesion cannot be maintained between the decorative sheet and the substrate.
Further, for example, if the decorative sheet is stored in a roll form before being attached to the base material, the original films may adhere to each other, causing blocking. If the blocking strength increases, problems such as peeling of the ink and tearing of the original film occur when the printing roll is peeled off.

Japanese Patent No. 3147735

SUMMARY OF THE INVENTION An object of the present invention is to provide a decorative sheet which is excellent in resistance to moisture and heat and which can maintain a stable adhesive strength to suppress the occurrence of blocking.

In order to solve the above problems, one aspect of the present invention includes a base layer and a primer layer laminated on one surface of the base layer, wherein the primer layer is composed of urethane-based resin and vinyl chloride. - A main component containing a mixture with a vinyl acetate copolymer resin, and a cellulose resin and silica added to the main component, wherein the urethane-based resin is polycaprolactone polyol, polyalkylene glycol and polyisocyanate is a constituent element, the average particle size of the silica is in the range of 1 μm or more and 20 μm or less, and the amount of the silica added is 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the main component Within range .
Another aspect of the present invention includes a substrate made of a wood-based material or a metal-based material, and the decorative sheet according to the above-described aspect attached to the surface side of the substrate.

ADVANTAGE OF THE INVENTION According to one aspect of the present invention, it is possible to provide a decorative sheet that is excellent in moist heat resistance, maintains stable adhesive strength, and can suppress the occurrence of blocking.

It is a sectional view showing a decorative sheet concerning an embodiment of the present invention. FIG. 4 is a cross-sectional view showing a decorative sheet according to a modified example of the present invention;

BEST MODE FOR CARRYING OUT THE INVENTION A decorative sheet and a decorative member according to an embodiment of the present invention will be described below with reference to the drawings. The present invention is not limited to the following embodiments, and modifications such as design changes can be made based on the knowledge of those skilled in the art. included in the range of In addition, each drawing may be appropriately exaggerated to facilitate understanding. In addition, in each drawing, the "surface" refers to the surface facing the same direction as the "surface" of each layer, with one surface (surface, front surface) of the base material of the decorative sheet as a reference. The surface on the opposite side (the other surface) is called a "back surface".

(composition)
As shown in FIG. 1, the decorative member 100 according to the embodiment of the present invention includes a substrate 11 and a decorative sheet 10 attached to the surface 11a side of the substrate 11. As shown in FIG.
(substrate)
As the material of the substrate 11, for example, a wood-based material or a metal-based material can be used. As the wood-based material, for example, wood veneer, wood plywood, laminated lumber, particle board, medium-density fiberboard, and hard fiberboard can be employed. Moreover, as the metal-based material, for example, a steel plate, a brass plate, an aluminum plate, a duralumin plate, and a stainless steel plate can be adopted. For example, an adhesive layer may be provided between the substrate 11 and the decorative sheet 10 as needed.

(decorative sheet)
As shown in FIG. 1, the decorative sheet 10 according to the embodiment of the present invention includes a base layer 1, a pattern layer 2 provided on the surface 1a side of the base layer 1, and a pattern layer 2 on the surface 2a side of the pattern layer 2. The provided adhesive resin layer 3, the transparent resin layer 4 provided on the surface 3a side of the adhesive resin layer 3, the surface protective layer 5 provided on the surface 4a side of the transparent resin layer 4, and the substrate layer and a primer layer 6 provided on the back surface 1b side (an example of one surface side) of the substrate 1. The decorative sheet 10 is attached to the substrate 11 via the primer layer 6 on the back surface 1b side. A predetermined adhesive layer may be provided between the primer layer 6 and the surface 11a of the substrate 11 depending on the case.

The decorative sheet 10 has a primer layer 6 laminated on one surface of the substrate layer 1 (in FIG. 1, the back surface 1b of the substrate layer 1), and the other surface of the substrate layer 1 (in FIG. The surface 1a) of the material layer 1, the pattern layer 2, the adhesive resin layer 3, the transparent resin layer 4, and the surface protective layer 5 are laminated to form. The pattern layer 2, the adhesive resin layer 3, the transparent resin layer 4 and the surface protective layer 5 are sometimes collectively referred to as "decorative layer". In addition, in the decorative sheet 10, the configuration other than the primer layer 6 is not particularly limited. The thickness of the decorative sheet 10 is preferably 40 μm or more and 300 μm or less.

The surface 5a of the surface protective layer 5 is provided with an uneven pattern 15 formed by embossing. As the concave-convex pattern 15, for example, a pattern synchronized with the pattern of the pattern layer 2 or a pattern not synchronized with the pattern can be used. The depth of the unevenness of the uneven pattern 15 is preferably 10 μm or less from the viewpoint of anti-fouling performance, tactile performance, and the like.

(Base material layer)
As a material of the base material layer 1, for example, a polyolefin resin can be used. The polyolefin-based resin is not particularly limited, and the same thermoplastic resins used as base materials in conventional decorative sheets can be used. For example, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, Polyolefins such as ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid (ester) copolymers, ethylene-unsaturated carboxylic acid copolymer metal neutralized products (ionomers), and other olefin-based copolymer resins A resin or the like, or a mixture, copolymer, composite, laminate, or the like of two or more of these can be used.

As the polyolefin-based resin, it may be appropriately selected and used from the many types already listed according to the purpose of use of the decorative sheet 10 and the like. In particular, polypropylene-based resins, that is, homo- or copolymers containing propylene as a main component, are most suitable for general use. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, or the like may be used alone or appropriately blended, or a resin obtained by further blending them with an atactic polypropylene. Further, it may be a copolymer containing an olefinic monomer other than propylene. Examples thereof include propylene-α-olefin copolymers containing 15 mol % or more of one or more comonomers of 1,4-methylpentene-1, hexene-1 or octene-1. In addition, low-density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, styrene-butadiene copolymer, which are usually used for softening polypropylene resin Modifiers such as coalescence or hydrogenated products thereof can be added as appropriate.

Moreover, it is preferable that the base material layer 1 in this embodiment is a colored thermoplastic resin layer that is colored opaquely and has a concealing property. As a result, the base layer 1 can conceal color variations, defects, and the like on the surface of the substrate when the decorative sheet 10 and the substrate 11 are laminated to form the decorative member 100, for example. In order to make the most of the texture of the surface of the substrate 11, the substrate layer 1 is preferably a colored thermoplastic resin layer having transparency to the extent that the surface of the substrate 11 can be seen through.

(picture layer)
The pattern layer 2 is a layer for imparting a design to the decorative sheet 10 with a pattern. The pattern layer 2 is formed using printing ink, a coating agent, or the like. The printing ink or the like is not particularly limited, and the same printing ink or the like as used in the design layer of conventional decorative sheets can be used. For example, acrylic ink can be used. As the acrylic ink, for example, an ink using, as a binder resin, a two-liquid curable urethane resin obtained by blending an isocyanate curing agent in an acrylic polyol vehicle can be used. Further, other resin components may be added to the pattern layer 2 as necessary. As components other than the binder resin of the pattern layer 2, for example, coloring agents such as pigments and dyes, extender pigments, solvents, various additives such as light stabilizers, and the like can be used. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.

The method of providing the pattern layer 2 is not particularly limited, and ordinary printing methods such as gravure printing, offset printing, screen printing, flexographic printing, and ink jet printing can be used. Any pattern can be used as the pattern of the pattern layer 2. For example, a wood grain pattern, a stone pattern, a texture pattern, an abstract pattern, a geometric pattern, or a combination of two or more of these patterns can be used. can do

(Adhesive resin layer)
The method of bonding the transparent resin layer 4 to the substrate layer 1 on which the pattern layer 2 is printed is not particularly limited. Various lamination techniques such as lamination and sand lamination can be used.
The material of the adhesive resin layer 3 is not particularly limited, and can be appropriately selected from resin materials such as urethane, acrylic, acrylic silicone, fluorine, and epoxy. The adhesive resin layer 3 is formed by using an appropriate coating method such as gravure coating, micro gravure coating, comma coating, knife coating, die coating, and the like, using a material that is appropriately selected and made into an ink.

(Transparent resin layer)
The material of the transparent resin layer 4 is not particularly limited, and for example, polyolefin is preferably used. The polyolefin-based resin is not particularly limited, and the same thermoplastic resins used as base materials in conventional decorative sheets can be used. In this embodiment, the transparent resin layer 4 is formed, for example, as a transparent thermoplastic resin layer. Examples of polyolefin include polypropylene, polyethylene, polybutene, and various α-olefin copolymers (copolymers of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc.). The transparent resin layer 4 may optionally contain various additives such as ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light scattering agents, and luster modifiers. You may

The method for producing the transparent resin layer 4 is not particularly limited, and for example, a normal method such as calendar film formation or extrusion film formation can be used.

(Surface protective layer)
The surface protective layer 5 is a layer provided to provide the decorative sheet 10 with functions such as weather resistance, scratch resistance, stain resistance, and design. The material of the surface protective layer 5 is not particularly limited, and may be appropriately selected from, for example, resin materials such as urethane, acrylic, acrylic silicone, fluorine, and epoxy resins.
The surface protective layer 5 may optionally contain various additives such as ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light scattering agents and gloss modifiers. You may
The method of forming the surface protective layer 5 is not particularly limited. The surface protective layer 5 is formed by curing by a method suitable for the material, such as heat curing or ultraviolet curing.

(primer layer)
The primer layer 6 is formed by applying a primer (undercoating agent) to one surface (back surface 1b in this example) of the base material layer 1 . Moreover, the primer layer 6 formed on one surface of the base material layer 1 may be called a back surface primer.

A primer is a low-viscosity liquid with a low non-volatile content that is applied to improve the adhesion of the surface of an adherend. When the adhesive is applied on the primer layer 6, the adhesive is reapplied after the primer has dried sufficiently. The type of primer differs according to the type of adherend and adhesive.
In the present embodiment, the primer layer 6 is composed mainly of a mixture of urethane-based resin and vinyl chloride-vinyl acetate copolymer resin (hereinafter sometimes referred to as "vinyl chloride-acetate resin"). is formed including In addition, a main component represents 50 mass % or more of the whole, for example.

The urethane resin of this embodiment can be synthesized by a known technique, that is, an addition polymerization reaction between a polyol and a polyisocyanate. The terminal of the urethane resin is usually an isocyanate group blocked with a hydroxyl group or an amine. When the terminal of the urethane resin is a hydroxyl group, the primer layer 6 can be cured by adding a curing agent such as isocyanate to the main component described above.

As the urethane resin as the main component of the primer layer 6, it is preferable to use a urethane resin containing at least specific constituents, ie, polycaprolactone polyol, polyalkylene glycol and polyisocyanate. The above-mentioned urethane resin can be synthesized by a known technique, ie, addition polymerization reaction of polyol and polyisocyanate.

Polycaprolactone polyol, which constitutes the urethane resin contained in the main component of the primer layer 6 in the present embodiment, is a material obtained by ring-opening polymerization of ε-caprolactone and has an ester bond inside. For this reason, the polycaprolactone polyol in the primer layer 6 has good adhesion to the substrate 11 made of various materials and to the adhesive layer appropriately provided between the substrate 11 and the decorative sheet. It contributes to improvement of adhesion with the decorative sheet 10 . In addition, the polycaprolactone polyol described above generally has excellent hydrolysis resistance as compared with a general-purpose polyester polyol obtained by polycondensation of a dicarboxylic acid such as adipic acid and a diol.

Moreover, the polyalkylene glycol constituting the urethane resin described above in the present embodiment has a polyether structure, and is inferior in hydrolysis resistance to the above-described polycaprolactone polyol, but is excellent in flexibility. Therefore, the bending adhesion during processing is improved. By using polyalkylene glycol and polycaprolactone polyol together as constituent elements of the urethane resin used in the present embodiment, it is possible to improve durability to hydrolysis (resistance to moist heat) and workability in a high-temperature and high-humidity environment. can.
As polyalkylene glycol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be used, and polytetramethylene glycol having high hydrophobicity is preferable from the viewpoint of durability against high temperature and high humidity (resistance to moist heat).

In the present embodiment, the urethane resin described above preferably further contains neopentyl glycol as a component. Moist heat resistance is improved by containing neopentyl glycol.
The polycaprolactone polyol and polyalkylene glycol of the present embodiment can be appropriately selected from various commercially available materials, for example, from the viewpoint of the molecular weight and the number of functional groups (the number of hydroxyl groups per molecule).

In the present embodiment, the polyisocyanate constituting the urethane resin described above can be, for example, diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and hydrogenated products thereof. Diisocyanates are preferred.

The composition of the urethane resin of the present embodiment is not particularly limited, but considering the suitability of the primer layer 6 to be formed by application and various performances of the decorative sheet 10, each component of the urethane resin shown in the following structural formula Units (caprolactone unit (CL unit), alkylene glycol unit (AG unit), diisocyanate unit (I unit), neopentyl glycol unit (NPG unit), when the amounts of substances are respectively X, Y, Z, N) are as follows: It is desirable to satisfy the relational expressions (formulas 1 to 3).

3<(X+Y+Z)/N<50 (Formula 1)
0.1<X/Y<10 (Formula 2)
Z/(X+Y+Z+N)<0.5 (Formula 3)

The molecular weight of the urethane resin of the present embodiment is not particularly limited, but considering the printability of the primer layer 6 formed by normal printing and various performances of the decorative sheet 10, the weight average molecular weight (Mw) is 5,5. A range of 000 to 100,000 is preferred.

Cellulose resin is added to the mixture of urethane-based resin and vinyl chloride resin as the main component of the primer layer 6 .
As the cellulose resin, for example, a cellulose resin having an ester group, cellulose acetate, or the like can be used. In particular, among cellulose resins having an ester group, cellulose acetate butyrate (CAB) contributes to blocking resistance in the primer layer 6 . Cellulose can be natural or artificial.
The amount of the cellulose resin added is desirably in the range of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the main component. Hereinafter, the range of the addition amount of the cellulose resin mentioned here may be referred to as the appropriate range.

Furthermore, silica is added to the mixture of the urethane-based resin and the vinyl chloride resin as the main component of the primer layer 6 .
In the present embodiment, the average particle size of silica is desirably in the range of 1 μm or more and 20 μm or less.
Here, as a method for measuring the above-mentioned "average particle size", for example, it is preferable to measure using a Mastersizer 3000 measuring device manufactured by Malvern Panalytical. Moreover, the measuring instrument is not limited to this measuring instrument as long as it measures the average particle diameter with the same purpose as this measuring instrument.
The amount of silica to be added is desirably in the range of 1 part by mass or more and 15 parts by mass or less per 100 parts by mass of the main component. In the primer layer 6, adding silica to the main component described above is effective in preventing blocking during winding storage of the decorative sheet 10 and in improving adhesiveness due to an anchoring effect. Hereinafter, the ranges of the average particle size and amount of silica mentioned here may be referred to as appropriate ranges.

In addition to the cellulose resin and silica, predetermined additives may be added to the primer layer 6 in addition to the main components described above. As a predetermined additive, for example, a curing agent may be added. For example, the curing agent used for curing the urethane resin described above is not particularly limited, and polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and xylylene diisocyanate and hydrogenated products thereof, or diphenylmethane diisocyanate and its water. It can be appropriately selected from commercially available curing agents containing additives and the like.

(Uneven pattern)
The uneven pattern 15 is for imparting a three-dimensional design to the surface of the decorative sheet 10 . Any uneven shape can be used as the uneven pattern 15 . For example, it is possible to use wood vessel-like, stone-like, cloth-like, abstract pattern-like, Japanese paper-like, suede-like, leather-like, satin-like, sand-like, hairline-like, parallel straight line group, or combinations thereof. . As a method for forming the uneven pattern 15, for example, a doubling embossing method, an extrusion lamination simultaneous embossing method, or the like, which is performed before, after, or at the same time as lamination of the surface protective layer 5 on the surface 1a of the base material layer 1, is adopted. can do.

(Modification)
In the above-described embodiment, the decorative sheet 10 includes the base material layer 1, the pattern layer 2, the adhesive resin layer 3, the transparent resin layer 4, the surface protective layer 5, and the primer layer 6. Although an example is shown, other configurations can also be adopted. For example, as shown in FIG. 2, the decorative sheet 10 may be configured to include only the base material layer 1 and the primer layer 6 . That is, the decorative sheet 10 does not have to be provided with the decorative layers (the pattern layer 2, the adhesive resin layer 3, the transparent resin layer 4 and the surface protective layer 5).

As described above, the decorative sheet 10 according to the present embodiment is a decorative sheet provided with the primer layer 6 laminated on the back surface 1b (an example of one surface) of the base material layer 1, and the primer layer 6 is made of urethane. A main component containing a mixture of a base resin and a vinyl chloride-vinyl acetate copolymer resin, and a cellulose resin and silica added to the main component, and the urethane resin is polycaprolactone polyol, polyalkylene Glycol and polyisocyanate are the constituents. As a result, it is possible to provide the decorative sheet 10 that is excellent in moist heat resistance, can maintain stable adhesive strength, and can suppress the occurrence of blocking.

The cellulose resin added to the main component of the primer layer 6 is cellulose acetate butyrate, and the amount of the cellulose resin added is within the range of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the main component. Therefore, it is possible to provide the decorative sheet 10 capable of maintaining more stable adhesive strength.
In addition, the average particle size of silica added to the main component of the primer layer 6 is in the range of 1 μm to 20 μm, and the amount of silica added is in the range of 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the main component. By making it within, it becomes possible to provide the decorative sheet 10 capable of maintaining a more stable adhesive strength.

Further, the decorative member 100 according to the present embodiment includes a substrate 11 made of a wood-based material or a metal-based material, and the decorative sheet 10 according to the present embodiment, which is formed by being attached to the surface 11a side of the substrate 11. As a result, it is possible to provide the decorative member 100 that is excellent in moist heat resistance and capable of maintaining stable adhesive strength.

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
<Example 1>
One surface (surface 11a in this example) of a substrate layer 1 (thickness: 55 μm) formed of a colored polyethylene resin is subjected to corona discharge treatment, and then a pattern layer 2 made of urethane printing ink and urethane adhesive. An adhesive resin layer 3 made of an agent, a transparent resin layer 4 (thickness: 70 μm) which is a transparent thermoplastic resin layer made of polypropylene (PP), and a surface protective layer 5 mainly composed of an acrylic resin composition. , were formed in this order.
The other surface of the base material layer 1 (back surface 11b in this example) was subjected to corona discharge treatment and then coated with a primer to form a primer layer 6 (thickness: 1 μm). A decorative sheet 10 (layer thickness: 135 μm) was obtained.
In Example 1, the primer of the primer layer 6 is mainly composed of polycaprolactone polyol, polytetramethylene glycol, and neopentyl glycol as polyols, urethane resin using isophorone diisocyanate as polyisocyanate, and vinyl chloride- Formed containing a mixture with a vinyl acetate copolymer resin. Further, to the main component, 10 parts by mass of cellulose acetate butyrate (CAB) as a cellulose resin is added to 100 parts by mass of the main component, and silica particles having an average particle size of 2 μm are added to 100 parts by mass of the main component. The primer of primer layer 6 in Example 1 was obtained by adding 6 parts by mass.
After the formation of the primer layer 6, the surface of the decorative sheet 10 on the primer layer 6 side is bonded to the decorative sheet 10 with the substrate 11, which is an aluminum base, using an adhesive for building materials (No. Tape Industry Co., Ltd., No. 5211). Thus, the decorative member 100 was obtained.

<Comparative Example 1>
A decorative member 100 of Comparative Example 1 was obtained in the same manner as in Example 1, except that the vinyl chloride-vinyl acetate copolymer resin was not added to the primer layer 6 of the decorative sheet 10 .
<Comparative Example 2>
A decorative member 100 of Comparative Example 2 was obtained in the same manner as in Example 1 except that cellulose acetate butyrate was not added to the primer layer 6 of the decorative sheet 10 .
<Comparative Example 3>
A decorative member 100 of Comparative Example 3 was obtained in the same manner as in Example 1, except that the vinyl chloride-vinyl acetate copolymer and cellulose acetate butyrate (CAB) were not added to the primer layer 6 of the decorative sheet 10. rice field.
<Comparative Example 4>
A decorative member of Comparative Example 4 was obtained in the same manner as in Example 1, except that polyester polyol was used as the main component of primer layer 6 of decorative sheet 10 instead of polycaprolactone polyol.
<Comparative Example 5>
Polyester polyol is used instead of polycaprolactone polyol as the main component of the primer layer 6 of the decorative sheet 10, and the amount of cellulose resin (cellulose acetate butyrate (CAB) in this example) added is 0 with respect to 100 parts by mass of the main component. A decorative member of Comparative Example 5 was obtained in the same manner as in Example 1, except that the content was 0.5 parts by mass.
<Comparative Example 6>
The same procedure as in Example 1 was performed except that polyester polyol was used as the main component of the primer layer 6 of the decorative sheet 10 instead of polycaprolactone polyol, and the amount of the cellulose resin added was 18 parts by mass with respect to 100 parts by mass of the main component. A decorative member of Comparative Example 6 was obtained by the method.

<Evaluation>
The decorative sheets obtained in the above examples and comparative examples were evaluated for blocking resistance and wet heat resistance by the following methods. Table 1 shows the evaluation results.

(a) Blocking test (blocking resistance evaluation)
For the following examples and comparative examples, 10 decorative sheets 10 each having a size of 5 cm×5 cm were stacked with the front side (surface protective layer 5) facing up, and a load of 20 kg was applied. The blocking state when left for a week was confirmed.
Evaluation criteria ○: Can be easily peeled off with almost no resistance △: There is resistance when peeled off, but there is no problem in production

(b) Adhesion test (wet heat resistance evaluation)
The decorative members 100 of the following examples and comparative examples were left in an environment of 85° C. and 85% for 1 to 4 weeks, dried at normal temperature and normal humidity for 1 day, and then the adhesion between the substrate 11 and the decorative sheet 10 was checked. .
Here, "maintaining stable adhesive strength", which is the object of the present invention, means, for example, that the decorative member 100 is kept in an environment of temperature 85°C and humidity 85% (hereinafter referred to as "85°C 85% environment") for four weeks. After being left to stand and dried for one day at normal temperature and humidity, the standard is that the adhesion between the substrate 11 and the decorative sheet 10 is maintained.
Evaluation criteria ○: No peeling interface is formed during peeling, sheet material is broken △: Sheet material is broken while peeling interface is generated during peeling ×: Sheet is not broken during peeling, peeling interface is generated

As shown in Table 1, the decorative sheet 10 shown in Example 1 was evaluated as acceptable for both blocking resistance and moist heat resistance. On the other hand, as shown in Table 1, the decorative sheets 10 of Comparative Examples 1 to 4 included "x" in the evaluation results of at least one of the blocking resistance and the heat and humidity resistance, and it was seen that there was a problem.

Specifically, in Comparative Example 1, the main component of the primer layer 6 did not contain a vinyl chloride-vinyl acetate copolymer resin. Therefore, the decorative member 100 of Comparative Example 1 cannot maintain stable adhesive strength between the decorative sheet 10 and the substrate 11 in a high-temperature and high-humidity environment. The result of the force test was a failure "x".
In Comparative Example 2, since no cellulose resin (cellulose acetate butyrate in this example) was added to the main component of the primer layer 6, the decorative sheet 10 was not provided with sufficient blocking resistance, and the blocking test result was It became a failure "x". Furthermore, in the decorative member 100 of Comparative Example 2, the decorative sheet 10 and the substrate 11 could not maintain stable adhesive strength in a hot and humid environment. The result of the test was a failure "x".
In Comparative Example 3, the primer layer 6 did not contain the vinyl chloride-vinyl acetate copolymer resin as the main component, and furthermore, the cellulose resin was not added. Therefore, the decorative sheet 10 was not provided with sufficient anti-blocking property, and the result of the blocking test was "NG". Furthermore, the decorative member 100 of Comparative Example 3 was unable to maintain stable adhesive strength between the decorative sheet 10 and the substrate 11 in a hot and humid environment. The result of the test was a failure "x".
Further, in the decorative sheet of Comparative Example 4, polyester polyol was used instead of polycaprolactone polyol as a component of the urethane resin as the main component of the primer layer 6 . Therefore, the decorative member 100 of Comparative Example 4 could not maintain a stable adhesive strength between the decorative sheet 10 and the substrate 11 in a high-temperature and high-humidity environment. The result of the force test was a failure "x".

In addition, in the decorative sheet of Comparative Example 5, the amount of cellulose resin added was less than the lower limit (0.5 parts by mass) of the appropriate range (range of 1 part by mass or more and 15 parts by mass or less). Therefore, the decorative sheet 10 of Comparative Example 5 was not provided with sufficient anti-blocking property, and the result of the blocking test was "X". In addition, in the decorative sheet of Comparative Example 5, polyester polyol was used as a component of the urethane resin that is the main component of the primer layer 6 in the same manner as in Comparative Example 4. Therefore, the adhesive strength test was performed in the 85° C. 85% environment after 4 weeks. The result of was a failure "x".
In addition, in the decorative sheet of Comparative Example 6, as in Comparative Example 4, polyester polyol was used as a component of the urethane resin that is the main component of the primer layer 6, and the addition amount of the cellulose resin was adjusted to an appropriate range (1 part by mass or more and 15 parts by mass). The value (18 parts by mass) exceeding the upper limit of the range of parts or less). Therefore, the decorative member 100 of Comparative Example 6 could not maintain stable adhesive strength between the decorative sheet 10 and the substrate 11 in a hot and humid environment. The result of the force test was a failure "x".

In contrast, the decorative sheet 10 of Example 1 contained a mixture of a urethane resin containing specific components (polycaprolactone polyol, polyalkylene glycol and polyisocyanate) and a vinyl chloride-vinyl acetate copolymer resin. Cellulose acetate butyrate (CAB) as a cellulose resin is added to the main component in an appropriate amount (10 parts by mass in this example), and an average particle size (2 μm in this example) and an amount of addition within an appropriate range are added. It has a primer layer 6 formed by adding silica particles (6 parts by mass in this example). Therefore, the decorative sheet 10 of Example 1 was imparted with sufficient anti-blocking properties, and the result of the blocking test was "Good". Furthermore, the decorative member 100 of Example 1 was able to maintain stable adhesive strength between the decorative sheet 10 and the substrate 11 in a hot and humid environment. Therefore, even after 4 weeks in an environment of 85.degree.

As described above, the decorative sheet 10 of Example 1 is superior in blocking resistance and moist heat resistance to the decorative sheets 10 of Comparative Examples 1 to 4, and is formed by bonding the decorative sheet 10 of Example 1 to the substrate 11. It was also confirmed that the decorative member 100 having the above-described structure was similarly excellent in blocking resistance and moist heat resistance.

The scope of the invention is not limited to the illustrated and described exemplary embodiments, but also includes all embodiments that provide equivalent results for which the invention is intended. Furthermore, the scope of the invention is not limited to the combination of inventive features defined by the claims, but may be defined by any desired combination of the particular features of all individual disclosed features.

1 base layer 1a, 2a, 3a, 4a, 5a, 11a front side 1b back side 2 pattern layer 3 adhesive resin layer 4 transparent resin layer 5 surface protective layer 6 primer layer 10 decorative sheet 11 substrate 15 uneven pattern 100 decorative member

Claims (5)

a substrate layer;
and a primer layer laminated on one surface of the base material layer,
The primer layer contains a main component containing a mixture of a urethane resin and a vinyl chloride-vinyl acetate copolymer resin, and a cellulose resin and silica added to the main component,
The urethane-based resin is composed of polycaprolactone polyol, polyalkylene glycol and polyisocyanate,
The average particle size of the silica is in the range of 1 μm or more and 20 μm or less,
The amount of silica added is in the range of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the main component.
A cosmetic sheet characterized by: The decorative sheet according to claim 1, wherein the cellulose resin is cellulose acetate butyrate. The decorative sheet according to claim 1 or 2, wherein the amount of the cellulose resin added is in the range of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the main component. The urethane-based resin further includes neopentyl glycol as the component,
The polyisocyanate is at least one of a diisocyanate and a hydrogenated product of the diisocyanate,
The following relational expression ( 1) to satisfy (3)
The decorative sheet according to any one of claims 1 to 3, characterized by:
3<(X+Y+Z)/N<50 (Formula 1)
0.1<X/Y<10 (Formula 2)
Z/(X+Y+Z+N)<0.5 (Formula 3) a substrate formed of a wood-based material or a metal-based material;
The decorative sheet according to any one of claims 1 to 4, which is attached to the surface side of the substrate;
A decorative member comprising:

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