JP7333188B2 - makeup sheet - Google Patents

Description

The present invention relates to a decorative sheet.

Along with the development of the housing industry, the development of building materials has progressed, and in recent years, the conversion of building materials from natural materials to artificial materials is progressing. The use of natural materials is also contributing to deforestation and environmental destruction, adding to the trend.

Among artificial materials, the demand for decorative sheets has increased in recent years.
Decorative sheets have been developed and advanced in the process of developing residential construction as an industry. In particular, use in collective housing such as apartments and condominiums, and individual housing such as prefabricated buildings has been the driving force behind the development of decorative sheets.

For example, a so-called sheet flooring material is widely used as a flooring material. The surface of such a floor material, that is, the surface of the decorative sheet, is required to have scratch resistance (see Patent Document 1).

Japanese Patent No. 5045180

Furthermore, with the diversification of housing specifications, decorative sheets are now required to have functions that have never existed before.

An object of the present invention is to provide a decorative sheet having novel functions in addition to scratch resistance.

In order to solve the above problems, the present invention comprises a thermoplastic resin substrate sheet, a transparent thermoplastic resin layer, and a transparent surface protective layer, and the transparent thermoplastic resin layer is the thermoplastic resin substrate. material sheet and the transparent surface protective layer, and at least the surface of the thermoplastic resin base sheet on the transparent surface protective layer side has a pattern, or the thermal Provided is a decorative sheet further comprising a pattern layer between a plastic resin substrate sheet and the transparent thermoplastic resin layer, and wherein the transparent surface protective layer contains microcapsules.
In the decorative sheet of the present invention, it is preferable that the microcapsules have a heat storage property or a fragrance sustained release property.

ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which has a new function other than scratch resistance is provided.

It is a sectional view showing typically an example of the decorative sheet of this embodiment. FIG. 4 is a cross-sectional view schematically showing another example of the decorative sheet of the present embodiment; FIG. 4 is a cross-sectional view schematically showing still another example of the decorative sheet of the present embodiment; FIG. 4 is a cross-sectional view schematically showing still another example of the decorative sheet of the present embodiment;

<<Cosmetic sheet>>
A decorative sheet according to one embodiment of the present invention comprises a thermoplastic resin base sheet, a transparent thermoplastic resin layer, and a transparent surface protective layer, and the transparent thermoplastic resin layer is made of the thermoplastic resin. It is arranged between the base sheet and the transparent surface protective layer, and at least the surface of the thermoplastic resin base sheet on the side of the transparent surface protective layer has a pattern, or the A pattern layer is further provided between the thermoplastic resin base sheet and the transparent thermoplastic resin layer, and the transparent surface protective layer contains microcapsules.
Since the transparent surface protective layer contains microcapsules, the decorative sheet of the present embodiment has novel functions according to the type of the microcapsules. In addition, the decorative sheet of the present embodiment has a scratch resistance that makes it difficult to be scratched by including the transparent surface protective layer.

In the decorative sheet in which the transparent surface protective layer, which is a microcapsule-containing layer, is the outermost layer, the effect of using microcapsules is higher than in the case of the decorative sheet in which the microcapsule-containing layer is not the outermost layer.

Hereinafter, the decorative sheet of this embodiment will be described in detail with reference to the drawings.
In addition, in the drawings used in the following description, in order to make the features of the present invention easier to understand, there are cases where the main parts are enlarged for convenience, and the dimensional ratios of each component are the same as the actual ones. not necessarily.

FIG. 1 is a cross-sectional view schematically showing an example of the decorative sheet of this embodiment.
The decorative sheet 1 shown here comprises a thermoplastic resin base sheet 11, a transparent thermoplastic resin layer 13, and a transparent surface protective layer 14, and the transparent thermoplastic resin layer 13 is a thermoplastic resin base material. It is arranged between the sheet 11 and the transparent surface protection layer 14 .
The transparent thermoplastic resin layer 13 further comprises a first transparent thermoplastic resin layer 131 and a second transparent thermoplastic resin layer 132 laminated in this order from the thermoplastic resin base sheet 11 side. there is
The transparent surface protective layer 14 contains microcapsules.

The decorative sheet 1 further includes a pattern layer 12 between the thermoplastic resin base sheet 11 and the transparent thermoplastic resin layer 13 (more specifically, the first transparent thermoplastic resin layer 131). I have.
The decorative sheet 1 further includes a transparent adhesive layer 15 between the pattern layer 12 and the transparent thermoplastic resin layer 13 (more specifically, the first transparent thermoplastic resin layer 131). .
In the decorative sheet 1, the surface 11b of the thermoplastic resin base sheet 11 opposite to the transparent surface protective layer 14 side (in this specification, may be referred to as the "second surface") 11b is coated with a primer. A layer 16 is provided.

That is, the decorative sheet 1 includes a primer layer 16, a thermoplastic resin base sheet 11, a pattern layer 12, a transparent adhesive layer 15, a transparent thermoplastic resin layer 13 (more specifically, a first transparent thermoplastic resin layer 131, the second transparent thermoplastic resin layer 132), and the transparent surface protective layer 14 are stacked in this order in the thickness direction.
Each layer will be described below.

<Transparent surface protective layer>
The transparent surface protective layer 14 is a layer for protecting the layers arranged below it in the decorative sheet 1, and the decorative sheet 1 (transparent surface protective layer 14) is hard to be damaged, Scratch resistant.
In addition, the transparent surface protective layer 14 is transparent, and when the decorative sheet 1 is observed from the outside on the transparent surface protective layer 14 side, the layers arranged below the transparent surface protective layer 14 are visible. It's becoming
The transparent surface protective layer 14 may be either colorless or colored, but is preferably colorless.

The transparent surface protective layer 14 has recesses 140 on the surface 14a opposite to the thermoplastic resin base sheet 11 (in this specification, sometimes referred to as the "first surface") 14a. there is
The first surface 14 a of the transparent surface protective layer 14 is one outermost surface of the decorative sheet 1 .
The concave portion 140 functions as a non-slip in the decorative sheet 1 .
The concave portion 140 has an arbitrary configuration, and the decorative sheet 1 does not have to have the concave portion 140 . However, since the decorative sheet 1 is provided with the concave portions 140, the decorative sheet 1 is less slippery.

The recesses 140 are groove-shaped in the cross section, and are provided in plurality within the first surface 14 a of the transparent surface protective layer 14 .
When the transparent surface protective layer 14 is viewed from above and viewed from above, the planar shape of the concave portion 140 is linear.

The width W ₁₄₀ of the opening of the recess 140 is preferably 0.5 to 2 mm. When W ₁₄₀ is within such a range, the effect obtained by having the concave portion 140 is further enhanced.

The depth D ₁₄₀ of the recess 140 is preferably 10-80 μm. When D ₁₄₀ is within such a range, the effect obtained by having the concave portion 140 is further enhanced.

The planar shape of the concave portion 140 may be a shape other than a linear shape.
Generally, the planar shape of the groove-shaped concave portion of the transparent surface protective layer 14 may be, for example, a linear shape, a curved shape, or a linear shape having both a straight portion and a curved portion.

The planar shape of the concave portion 140 of the transparent surface protective layer 14 may be of only one type, or may be of two or more types. You can choose.

When the recesses of the transparent surface protective layer 14 are not groove-shaped (non-groove-shaped), the patterns formed by the recesses on the first surface 14a of the transparent surface protective layer 14 include, for example, wood grain board conduit grooves, Stone slab surface unevenness (granite cleavage plane, etc.), cloth surface texture, satin finish, grain, hairline, parallel grooves, and the like can be mentioned.
The recesses of the transparent surface protective layer 14 may be a combination of these non-grooved ones and the above-described grooved ones.

The transparent surface protective layer 14 contains microcapsules (not shown).
The decorative sheet 1 has the transparent surface protection layer 14 containing the microcapsules, so that it has new functions according to the type of the microcapsules.

The microcapsules are configured by enclosing a core substance with a wall material.
Microcapsules may be known.

The microcapsules may be, for example, a sustained-release type in which the encapsulated core substance is gradually released to the outside of the capsule over time, or the encapsulated core substance is gradually released into the capsule over time. It may be non-sustained release without the property of being released to the outside. The non-sustained-release microcapsules may be pressure-sensitive, for example, having the characteristic that the encapsulated core substance is released to the outside of the capsule when pressure above a certain value is applied to the microcapsules. However, it may be non-pressure sensitive without such properties.

Said wall material is film-forming, preferably oligomeric or polymeric, forming microcapsules.
The core substance is a component that expresses the main activity of the microcapsules. In microcapsules, the solvent, emulsifier, etc. used during the production thereof may be encapsulated by the wall material, but in the present specification, these encapsulated components (solvent, emulsifier, etc.) are not classified as core substances.

In the microcapsules, the constituent component of the wall material (in this specification, it may be abbreviated as "wall material component") and the core substance are not particularly limited, and can be arbitrarily selected according to the purpose. .

Regardless of whether it is sustained-release or non-sustained-release, the core substance encapsulated in the microcapsules may be of only one type, may be of two or more types, or may be of two or more types. , the combination and ratio thereof can be arbitrarily selected.

Examples of the microcapsule wall material component include polyurea, polyurethane, polyamide, melamine resin (also known as melamine-formaldehyde resin), and the like.

Examples of the core substance of the microcapsules include aromatic agents and heat storage agents.
That is, the microcapsules include those that have heat storage properties or those that have sustained release properties for aromatic agents.

Examples of the aromatic agent include cypress oil, cedar oil, tea tree oil, sunplace oil, rosewood oil, cedarwood oil, fraxense oil, benzoin oil, myrrh oil, herbal oil, rose oil, lavender oil, and Roman chamomile. oil, jasmine oil, geranium oil, lily oil and the like.

Examples of the heat storage agent include aliphatic hydrocarbons such as n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, and n-henicosane; caprylic acid, pelargonic acid, undecylic acid, capric acid, and the like; vegetable oils such as coconut oil, palm kernel oil and palm oil; fatty alcohols such as lauryl alcohol and myristyl alcohol; fatty acid esters such as methyl myristate, butyl stearate, methyl palmitate and methyl stearate; paraffin wax etc.
The melting point of the heat storage agent is preferably 10 to 40°C.

One example of preferred microcapsules includes sustained-release or non-sustained-release aromatic microcapsules containing an aromatic agent as a core substance.
When the decorative sheet 1 containing sustained-release fragrant microcapsules is used, the aromatic agent is released little by little in the application area of the decorative sheet 1 over a long period of time.
When the decorative sheet 1 containing the non-sustained-release, pressure-sensitive aromatic microcapsules is used, when a person walks on the decorative sheet 1, a certain pressure or more is applied to the transparent surface protective layer 14. When added, the fragrance is released little by little in the application area of the decorative sheet 1 .

Other examples of preferred microcapsules include non-sustained-release, non-pressure-sensitive heat storage microcapsules containing a heat storage agent as a core substance.
When the decorative sheet 1 containing non-sustained-release, non-pressure-sensitive heat-storage microcapsules is used, the transparent surface protective layer 14 is exposed to heat when placed in a heat-retaining environment, exposed to sunlight, or exposed to a heat source. When warmed by contact or the like, even after a certain period of time has passed, the heat-accumulating microcapsules maintain the state in which heat is accumulated. be.

Among these, the microcapsules having heat storage properties or the sustained release properties of fragrances are more preferable.
The microcapsules are slow-release and fragrant microcapsules in which the wall material component is polyurea and contain a fragrance, or the wall material component is melamine resin and contain a heat storage agent. Particularly preferred are non-slow-release, non-pressure-sensitive and heat-storage microcapsules.

The average particle size of microcapsules is not particularly limited. For example, the average particle size may be any one of 0.5-20 μm, 1-16 μm, 1.5-13 μm, and 2-10 μm. Such microcapsules have moderate strength, and are prevented from being broken at unintended timing without impairing the properties of the microcapsules. Here, "unintended timing" means, for example, that the decorative sheet 1 is stored in a state where it is laid flat or wound into a roll, while pressure is applied under conditions different from those during actual use. means when

As used herein, the term "average particle size" means the median diameter of volume particle size distribution of particles measured using a particle size distribution meter, unless otherwise specified.

The thickness of the wall material film or layer is not particularly limited, and may be, for example, 50 to 1000 nm. A microcapsule having such a wall material has an appropriate strength, and destruction at an unintended timing is suppressed without impairing the properties of the microcapsule. Here, "unintended timing" is the same as above.

Examples of microcapsules include those produced by known methods such as an interfacial polycondensation method and an in situ polycondensation method, but the method for producing microcapsules is not limited thereto.

Regardless of whether the microcapsules are sustained release or non-sustained release, the transparent surface protective layer 14 may contain only one type of microcapsule, or two or more types. When there are more than one species, their combination and ratio can be arbitrarily selected.

The transparent surface protective layer 14 is preferably a layer containing the microcapsules and resin.
Hereinafter, such a transparent surface protective layer 14 will be described.

The resin contained in the transparent surface protective layer 14 may be a curable resin, a cured product of a curable resin, or a non-curable resin, but is preferably a curable resin or a cured product thereof. Since the transparent surface protective layer 14 is formed using a curable resin, the decorative sheet has higher scratch resistance, abrasion resistance, impact resistance, stain resistance, weather resistance, and the like.
The curable resin in the transparent surface protective layer 14 may be either a thermosetting resin or an ionizing radiation curable resin.
Examples of the non-curable resin in the transparent surface protective layer 14 include thermoplastic resins.

As used herein, the term "ionizing radiation" means an electromagnetic wave or charged particle beam having energy capable of causing a curing reaction of an ionizing radiation-curable resin, and specific examples thereof include ultraviolet rays, electron beams, visible rays, and X-rays. , ion beams, and the like.

Examples of ultraviolet light sources include light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, and metal halide lamps.
The wavelength of the ultraviolet rays is preferably 190-380 nm.

Examples of electron beam sources include various electron beam accelerators such as Cockcroft-Walton type, Vandegraft type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type.
The electron beam source is preferably one capable of emitting electrons having an energy of, for example, preferably 100 to 1000 keV, more preferably 100 to 300 keV.

As the ionizing radiation-curable resin in the transparent surface protective layer 14, for example, a transparent resin containing, as a main component, a prepolymer, an oligomer or a monomer having a radically polymerizable double bond capable of polymerizing and cross-linking by irradiation with ionizing radiation. and flexible resins.
The prepolymers, oligomers and monomers in the curable resin may be of only one type, or may be of two or more types. can be selected to

Examples of the prepolymers, oligomers and monomers include compounds having radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups in the molecule, or cationically polymerizable functional groups such as epoxy groups. be done.
The prepolymer or oligomer also includes a polyene/thiol prepolymer or oligomer obtained by combining a polyene and a polythiol.

In addition, in this specification, "(meth)acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group". The same applies to terms similar to (meth)acryloyl group, for example, "(meth)acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid", and "(meth)acrylate ” is a concept that includes both “acrylate” and “methacrylate”.

Examples of prepolymers or oligomers having radically polymerizable unsaturated groups include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, silicone (meth)acrylate, ) acrylates and the like.
The molecular weight of these prepolymers or oligomers is preferably, for example, 250-100,000.

Among monomers having a radically polymerizable unsaturated group, monofunctional monomers include, for example, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate and the like.
Among monomers having a radically polymerizable unsaturated group, polyfunctional monomers include, for example, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri (Meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

Examples of prepolymers or oligomers having a cationic polymerizable functional group include epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins; and vinyl ether type resins such as fatty acid vinyl ethers and aromatic vinyl ethers.

Examples of the thiol in the polyene/thiol-based prepolymer or oligomer include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.
Examples of the polyene in the polyene/thiol-based prepolymer or oligomer include those obtained by adding allyl alcohol to both ends of a polyurethane molecular structure obtained from a diol and a diisocyanate.

Examples of the thermosetting resin contained in the transparent surface protective layer 14 include polyfunctional acrylic urethane resins and polyester resins.

Examples of the non-hardening resin contained in the transparent surface protective layer 14 include fluororesins (resins having fluorine atoms).
For example, a transparent surface protective layer 14 containing a curable resin and a fluororesin is a preferred example.

The resin contained in the transparent surface protective layer 14 may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

The transparent surface protective layer 14 may contain other components that are neither the microcapsules nor the resin.
The other components contained in the transparent surface protective layer 14 are not particularly limited and can be arbitrarily selected according to the purpose.
The other components contained in the transparent surface protective layer 14 may be one type or two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrarily selected. can.

Other components contained in the transparent surface protective layer 14 include, for example, weather resistant agents (ultraviolet absorbers, light stabilizers, etc.), plasticizers, stabilizers, fillers, dispersants, colorants (dyes, pigments, etc.). , solvents and the like.

When the transparent surface protective layer 14 contains the microcapsules and the resin, the ratio of the content of the resin in the transparent surface protective layer 14 to the total mass of the transparent surface protective layer 14 ([in the transparent surface protective layer 14 Amount of resin (parts by mass)]/[Total mass of transparent surface protective layer 14 (parts by mass)]×100) is preferably 80 to 99% by mass, regardless of the type of microcapsules and resin. More preferably, it is up to 98% by mass.

When the transparent surface protective layer 14 contains the microcapsules and resin, the content of the microcapsules in the transparent surface protective layer 14 can be appropriately adjusted according to the type of microcapsules.

For example, when the microcapsules are aromatic microcapsules, the ratio of the content of the microcapsules to the content of the resin in the transparent surface protective layer 14 ([the amount of microcapsules in the transparent surface protective layer 14 (parts by mass)]/[amount of resin in transparent surface protective layer 14 (parts by mass)]×100) is preferably 2 to 13 mass %, for example, 2 to 10 mass %, 2 to 8.0 mass %. It may be either 5% by mass or 2 to 7% by mass. When the ratio is equal to or higher than the lower limit, the effect of using microcapsules can be obtained more remarkably. Excessive use of microcapsules is suppressed when the ratio is equal to or less than the upper limit.

For example, when the microcapsules are heat storage microcapsules, the ratio of the content of the microcapsules to the content of the resin in the transparent surface protective layer 14 ([amount of microcapsules in the transparent surface protective layer 14 (parts by mass)]/[amount of resin in transparent surface protective layer 14 (parts by mass)]×100) is preferably 4 to 13 mass %, for example, 4 to 10 mass %, 4.5 to 8.5% by mass, and 5 to 7% by mass. When the ratio is equal to or higher than the lower limit, the effect of using microcapsules can be obtained more remarkably. Excessive use of microcapsules is suppressed when the ratio is equal to or less than the upper limit.

When the transparent surface protective layer 14 contains the microcapsules and the resin, the ratio of the total content of the microcapsules and the resin to the total mass of the transparent surface protective layer 14 in the transparent surface protective layer 14 (([transparent surface Amount of microcapsules in protective layer 14 (parts by mass)]+[Amount of resin in transparent surface protective layer 14 (parts by mass)])/[Total mass of transparent surface protective layer 14 (parts by mass)]×100) is preferably 80% by mass or more, regardless of the type of microcapsules and resin, and may be, for example, 90% by mass or more, 95% by mass or more, or 99% by mass or more.
In the transparent surface protective layer 14, the ratio of the total content is 100% by mass or less.

Although the transparent surface protective layer 14 is shown here as a single layer, it may be a multiple layer of two or more layers. When the transparent surface protective layer 14 has multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.
In the present specification, not only in the case of the transparent surface protective layer, "multiple layers may be the same or different" means "all the layers may be the same or all the layers may be may be different, and only some of the layers may be the same.” Further, “multiple layers are different from each other” means “at least one of the material and thickness of each layer is different from each other.” means that

When the transparent surface protective layer 14 is one layer, this layer is used. The layer farthest from the thermoplastic resin base sheet 11 in the thickness direction of the sheet 1) contains, as the resin, either one or both of a thermosetting resin and a cured product thereof, and an ionizing radiation curable resin. and either one or both of its cured products. Of the transparent surface protective layer 14, such a layer not only has scratch resistance, but also has a high effect of suppressing the occurrence of whitening and cracking at the bent portion when bent.
Among them, the effect of suppressing the occurrence of such whitening and cracking is remarkably high, and in the layer containing the combination of the above-described curable resins, etc. of the transparent surface protective layer 14, [thermosetting resin and the total content of its cured product (parts by mass)]:[the total content of the ionizing radiation-curable resin and its cured product (parts by mass)] is preferably 4:6 to 2:8.

The thickness of the transparent surface protective layer 14 is not particularly limited and can be appropriately selected depending on the purpose. ˜10 μm, and 1-5 μm. When the thickness of the transparent surface protective layer 14 is equal to or more than the lower limit, the effect (for example, scratch resistance) due to the provision of the transparent surface protective layer 14 becomes higher. When the thickness of the transparent surface protective layer 14 is equal to or less than the upper limit, the handleability of the decorative sheet 1 is improved, such as easier bending of the decorative sheet 1 .
As used herein, the term "thickness of the transparent surface protective layer" means the thickness of the entire transparent surface protective layer. means the total thickness of all layers

<Thermoplastic resin base sheet>
The thermoplastic resin base sheet 11 contains a thermoplastic resin.
The thermoplastic resin contained in the thermoplastic resin base sheet 11 may be a known one.

Examples of the thermoplastic resin include polyolefins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer; polyvinyl chloride; ethylene-vinyl acetate copolymer; Acrylic resins such as ethylene-acrylic acid copolymers; polyolefin thermoplastic elastomers;
The acrylic resin is a resin having a structural unit derived from (meth)acrylic acid or (meth)acrylic acid ester, other than structural units derived from (meth)acrylic acid or (meth)acrylic acid ester , may or may not have other structural units.

The thermoplastic resin contained in the thermoplastic resin base sheet 11 is selected in consideration of, for example, the required environmental compatibility, workability, price, ease of sheeting, printability, or bending workability. and composition can be selected as appropriate.

The thermoplastic resin contained in the thermoplastic resin base sheet 11 may be of only one type, or may be of two or more types. Can be selected arbitrarily.

The thermoplastic resin contained in the thermoplastic resin base sheet 11 is preferably polyolefin, for example, in terms of environmental compatibility, workability, price, and the like.

The thermoplastic resin base sheet 11 may contain other components that do not correspond to the thermoplastic resin.
The other components contained in the thermoplastic resin base sheet 11 are not particularly limited and can be arbitrarily selected according to the purpose.
The other components contained in the thermoplastic resin base sheet 11 may be of only one kind, or may be of two or more kinds. Can be selected arbitrarily.

Examples of other components contained in the thermoplastic resin base sheet 11 include coloring agents, fillers, flame retardants, antioxidants, lubricants, and foaming agents.

The colorant contained in the thermoplastic resin base sheet 11 may be a known one, and may be either a pigment or a dye, for example.
Examples of the coloring agent include inorganic pigments such as titanium white, zinc white, red iron oxide, vermillion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, and carbon black; isoindolinone, Hansa Yellow A, quinacridone, and permanent red 4R. , phthalocyanine blue, indanthrene blue RS, aniline black, and other organic pigments or organic dyes; metal pigments, such as aluminum and brass; mentioned.

The filler contained in the thermoplastic resin base sheet 11 may be a known one, and is not particularly limited.
Examples of the filler include calcium carbonate and clay.

The flame retardant contained in the thermoplastic resin base sheet 11 may be a known one and is not particularly limited.
Examples of the flame retardant include magnesium hydroxide.

In the thermoplastic resin base sheet 11, the ratio of the content of the thermoplastic resin to the total mass of the thermoplastic resin base sheet 11 ([The amount of thermoplastic resin in the thermoplastic resin base sheet 11 ( parts by mass)]/[total mass (parts by mass) of the thermoplastic resin base sheet 11]×100) is preferably 90% by mass or more, for example, 95% by mass or more, 99% by mass or more, may be either
In the thermoplastic resin base sheet 11, the ratio is 100% by mass or less.

When the thermoplastic resin base sheet 11 contains the coloring agent, the ratio of the content of the coloring agent to the content of the thermoplastic resin in the thermoplastic resin base sheet 11 ([thermoplastic resin Colorant amount (parts by mass) in base sheet 11 made of thermoplastic resin]/[Amount of thermoplastic resin in base sheet 11 made of thermoplastic resin (parts by mass)]×100) is 30 to 70% by mass. is preferred. When the ratio is equal to or higher than the lower limit, the effect of using the colorant can be obtained more remarkably. Excessive use of the coloring agent is suppressed when the ratio is equal to or less than the upper limit.

Although the thermoplastic resin base sheet 11 is shown here as having only one layer, it may have multiple layers of two or more layers. When the thermoplastic resin base sheet 11 has multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

Although the thickness of the thermoplastic resin base sheet 11 is not particularly limited, it is preferably 40 to 150 μm, more preferably 50 to 100 μm. When the thickness of the thermoplastic resin base sheet 11 is equal to or greater than the lower limit, the mechanical strength of the decorative sheet 1 is further increased. By setting the thickness of the thermoplastic resin base sheet 11 to be equal to or less than the upper limit, the decorative sheet 1 can be prevented from becoming excessively thick. The handleability of the decorative sheet 1 may be improved.
As used herein, the term "thickness of the thermoplastic resin base sheet" means the thickness of the entire thermoplastic resin base sheet. Thickness means the total thickness of all layers constituting the thermoplastic resin base sheet.

<Transparent thermoplastic resin layer>
The transparent thermoplastic resin layer 13 (that is, the first transparent thermoplastic resin layer 131 and the second transparent thermoplastic resin layer 132) is transparent, and the decorative sheet 1 is observed from the outside on the transparent surface protective layer 14 side. In some cases, the appearance of the decorative sheet 1 is adjusted by adjusting the texture of the layers arranged below the transparent thermoplastic resin layer 13 when viewed. The pattern layer 12 is an example of the layer whose texture is adjusted.

The transparent thermoplastic resin layer 13 (that is, the first transparent thermoplastic resin layer 131 and the second transparent thermoplastic resin layer 132) may be either colorless or colored, but is preferably colorless.

[First transparent thermoplastic resin layer]
The first transparent thermoplastic resin layer 131 contains a thermoplastic resin layer.
Examples of the thermoplastic resin contained in the first transparent thermoplastic resin layer 131 include the same thermoplastic resins contained in the thermoplastic resin base sheet 11 described above.

The thermoplastic resin contained in the first transparent thermoplastic resin layer 131, for example, in consideration of the required environmental compatibility, processability, price, ease of sheeting, printability, or bending workability, etc. and composition can be selected as appropriate.

The thermoplastic resin contained in the first transparent thermoplastic resin layer 131 may be of only one type, or may be of two or more types. Can be selected arbitrarily.

The thermoplastic resin contained in the first transparent thermoplastic resin layer 131 is preferably polyolefin in terms of, for example, environmental compatibility, workability, and price.

The first transparent thermoplastic resin layer 131 may contain other components that do not correspond to the thermoplastic resin.
The other components contained in the first transparent thermoplastic resin layer 131 are not particularly limited and can be arbitrarily selected according to the purpose.
The other components contained in the first transparent thermoplastic resin layer 131 may be only one type, or may be two or more types, and when there are two or more types, the combination and ratio thereof are Can be selected arbitrarily.

Examples of the other components contained in the first transparent thermoplastic resin layer 131 include weather resistance agents such as ultraviolet absorbers and light stabilizers.

The ultraviolet absorber contained in the first transparent thermoplastic resin layer 131 may be a known one and is not particularly limited.
Examples of the ultraviolet absorbent include benzophenone-based ultraviolet absorbents, benzotriazole-based ultraviolet absorbents, and triazine-based ultraviolet absorbents.

The light stabilizer contained in the first transparent thermoplastic resin layer 131 may be a known one and is not particularly limited.
Examples of the light stabilizer include hindered amine light stabilizers.

In the first transparent thermoplastic resin layer 131, the ratio of the content of the thermoplastic resin to the total mass of the first transparent thermoplastic resin layer 131 ([the amount of thermoplastic resin in the first transparent thermoplastic resin layer 131 ( parts by mass)]/[total mass of the first transparent thermoplastic resin layer 131 (parts by mass)]×100) is, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 99% by mass or more, may be either
In the first transparent thermoplastic resin layer 131, the ratio is 100% by mass or less.

When the first transparent thermoplastic resin layer 131 contains the weather resistant agent (ultraviolet absorber, light stabilizer, etc.), in the first transparent thermoplastic resin layer 131, the total mass of the first transparent thermoplastic resin layer 131 , the ratio of the content of the weathering agent ([amount of the weathering agent in the first transparent thermoplastic resin layer 131 (parts by mass)]/[total mass of the first transparent thermoplastic resin layer 131 (parts by mass)] × 100 ) is not particularly limited, but is preferably 0.001 to 0.01% by mass. When the ratio is equal to or higher than the lower limit, the effect of using the weathering agent can be obtained more remarkably. Excessive use of the weathering agent is suppressed when the ratio is equal to or less than the upper limit. The above-mentioned "content of weathering agent" means "total content of components corresponding to weathering agents such as ultraviolet absorbers and light stabilizers".

When the decorative sheet 1 is observed from the outside on the side of the transparent surface protective layer 14, the surface of the first transparent thermoplastic resin layer 131 on the side of the transparent surface protective layer 14 (in this specification, the "first surface") ) 131a has a glossy surface (which may be referred to herein as a “glossy surface”) and a non-glossy surface (which may be referred to herein as a “matte surface”). It may be either) or

Whether the first surface 131a of the first transparent thermoplastic resin layer 131 is a glossy surface or a matte surface is determined, for example, by the type or content of the components contained in the first transparent thermoplastic resin layer 131, or the first It can be adjusted by adjusting the surface condition (for example, roughness) of the surface 131a.
For example, the first transparent thermoplastic resin layer 131 is made to contain a matting agent in a content of a specific value or more, or the first surface 131a is subjected to a roughening treatment so that the first surface 131a is Surface 131a can be a matte surface.
On the other hand, the first transparent thermoplastic resin layer 131 contains a matting agent in a content less than a specific value, or does not contain a matting agent, and has a rough surface with respect to the first surface 131a. By not performing the hardening treatment, the first surface 131a can be a glossy surface.

When the matting agent is used, for example, in the first transparent thermoplastic resin layer 131, the ratio of the content of the matting agent to the content of the thermoplastic resin ([in the first transparent thermoplastic resin layer 131 Amount of matting agent (parts by mass)]/[Amount of thermoplastic resin in first transparent thermoplastic resin layer 131 (parts by mass)]×100) is preferably 10% by mass or more.

Examples of the matting agent include inorganic fine particles such as silica, calcium carbonate, synthetic mica, titanium oxide, and glass particles; organic fine particles such as polyethylene fine particles, acrylic resin fine particles, urethane resin fine particles, urea resin fine particles, nylon resin fine particles, and balloons. is mentioned.

Although the first transparent thermoplastic resin layer 131 is shown here as a single layer, it may be a multiple layer of two or more layers. When the first transparent thermoplastic resin layer 131 has multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.
The first transparent thermoplastic resin layer 131 is preferably a single layer, as shown here.

Although the thickness of the first transparent thermoplastic resin layer 131 is not particularly limited, it is preferably 1 to 10 μm, more preferably 2 to 6 μm. When the thickness of the first transparent thermoplastic resin layer 131 is equal to or greater than the lower limit value, the effect of providing the first transparent thermoplastic resin layer 131 is enhanced. Since the thickness of the first transparent thermoplastic resin layer 131 is equal to or less than the upper limit, excessive thickness of the decorative sheet 1 can be avoided. The handleability of the decorative sheet 1 may be improved.
As used herein, the term "thickness of the first transparent thermoplastic resin layer" means the thickness of the entire first transparent thermoplastic resin layer. Thickness means the total thickness of all layers constituting the first transparent thermoplastic resin layer.

[Second transparent thermoplastic resin layer]
The second transparent thermoplastic resin layer 132 has a concave portion 1320 on the surface 132a on the side of the transparent surface protective layer 14 (in this specification, this may be referred to as the "first surface").
The recess 1320 has a groove shape in the cross section, and a plurality of recesses 1320 are provided in the first surface 132a of the recess 1320 .
Looking down on the decorative sheet 1 from above the transparent surface protective layer 14 side in a plan view, and comparing the concave portions 1320 in the second transparent thermoplastic resin layer 132 with the concave portions 140 in the transparent surface protective layer 14, it is found that these concave portions The shape and arrangement position are almost or completely the same. Here, "the shape and arrangement position of these recesses are substantially the same" means that the difference in the shape and arrangement position of these recesses is minute, and the effect of the difference on the decorative sheet 1 is negligible. It means that it is as minor as it gets.
The recess 1320 is formed to form the recess 140 or is formed at the same time as the recess 140 is formed.
As long as the recess 140 can be properly formed, the recess 1320 may not be formed.

Although the thickness of the second transparent thermoplastic resin layer 132 is not particularly limited, it is preferably 1 to 12 μm, more preferably 3 to 8 μm. When the thickness of the second transparent thermoplastic resin layer 132 is equal to or greater than the lower limit, the effect of providing the second transparent thermoplastic resin layer 132 becomes more remarkable. Since the thickness of the second transparent thermoplastic resin layer 132 is equal to or less than the upper limit value, excessive thickness of the decorative sheet 1 can be avoided. The handleability of the decorative sheet 1 may be improved.
As used herein, the term "thickness of the second transparent thermoplastic resin layer" means the thickness of the entire second transparent thermoplastic resin layer. Thickness means the total thickness of all layers constituting the second transparent thermoplastic resin layer.

The second transparent thermoplastic resin layer 132 is similar to the first transparent thermoplastic resin layer 131 except for the points mentioned above.
For example, whether the first surface 132a of the second transparent thermoplastic resin layer 132 is a glossy surface or a matte surface can be adjusted in the same manner as the first surface 132a of the first transparent thermoplastic resin layer 131.

When the decorative sheet 1 is observed from the outside on the side of the transparent surface protective layer 14 and the first surface 131a of the first transparent thermoplastic resin layer 131 is a matte surface, the second transparent thermoplastic resin layer 132 The first surface 132a of is preferably a glossy surface. Conversely, when the first surface 131a of the first transparent thermoplastic resin layer 131 is a glossy surface, the second transparent thermoplastic resin layer 132 The first surface 132a of is preferably a matte surface. By making the optical characteristics of the first surface 131a and the first surface 132a different from each other in this way, the effect of adjusting the appearance of the decorative sheet 1 is remarkably increased.

In the decorative sheet 1, of the first transparent thermoplastic resin layer 131 and the second transparent thermoplastic resin layer 132, those having matte first surfaces are provided over the entire area of the surfaces of the adjacent layers. may be provided, or may be provided only in a part of the region.

<Pattern layer>
Since the decorative sheet 1 is provided with the pattern layer 12, the decorative sheet 1 has a design property when the decorative sheet 1 is observed from the outside on the transparent surface protective layer 14 side.

The pattern of the pattern layer 12 can be arbitrarily selected according to the purpose, and is not particularly limited.
Preferred patterns include, for example, wood grain, cork, stone (for example, marble) grain, grain, tile, brick, texture, leather, geometric figures, letters, symbols, and abstract patterns. , single-color plain, and composite patterns formed by combining two or more selected from these patterns (wood grain pattern to single-color plain).

Examples of the pattern layer 12 include those containing a resin and a colorant.

The resin contained in the pattern layer 12 may be a known resin, and may be a binder resin.
Examples of the resin contained in the pattern layer 12 include curable resins and cured products thereof. The pattern layer 12 containing a curable resin or a cured product thereof has high durability even in an environment exposed to light.
The curable resin contained in the pattern layer 12 may be either a thermosetting resin or an ionizing radiation curable resin.
The thermosetting resin contained in the pattern layer 12, the cured product of the thermosetting resin, the ionizing radiation-curable resin, and the cured product of the ionizing radiation-curable resin include the thermosetting resin contained in the transparent surface protective layer 14, The same as the cured product of the thermosetting resin, the ionizing radiation-curable resin, and the cured product of the ionizing radiation-curable resin can be used.

The resin contained in the pattern layer 12 may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

The colorant contained in the pattern layer 12 may be a known one, and may be either a pigment or a dye, for example.
Examples of the coloring agent include inorganic pigments such as carbon black, titanium white (titanium oxide), zinc oxide, iron composite oxides, iron oxide, red iron oxide, Prussian blue, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, Organic pigments such as quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; A pigment etc. are mentioned. The iron composite oxide can be used as a heat shielding pigment.

The colorant contained in the pattern layer 12 may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

The pattern layer 12 may contain other components that are neither the resin nor the colorant.
The other components contained in the pattern layer 12 are not particularly limited and can be arbitrarily selected according to the purpose.
The other components contained in the pattern layer 12 may be of one kind or may be of two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

Examples of other components contained in the picture layer 12 include fillers such as silica; organic beads; neutralizers; and surfactants.

In the picture layer 12, the ratio of the content of the resin to the total mass of the picture layer 12 ([amount of resin in picture layer 12 (parts by mass)]/[total mass of picture layer 12 (parts by mass)] x 100 ) is preferably 27 to 91% by mass.

In the pattern layer 12, the ratio of the content of the coloring agent to the content of the resin ([amount of coloring agent in pattern layer 12 (parts by mass)]/[amount of resin in pattern layer 12 (parts by mass) ]×100) is preferably 10 to 50% by mass. When the ratio is equal to or higher than the lower limit, the effect of using the colorant can be obtained more remarkably. Excessive use of the coloring agent is suppressed when the ratio is equal to or less than the upper limit.

In the pattern layer 12, the ratio of the total content of the resin and the colorant to the total mass of the pattern layer 12 (([amount of resin in pattern layer 12 (parts by mass)] + [colorant content in pattern layer 12 Amount (parts by mass)])/[total mass of pattern layer 12 (parts by mass)]×100) is preferably 40% by mass or more, for example, 45% by mass or more, 50% by mass or more, and 55% by mass. % or more.
In the pattern layer 12, the ratio of the total content is 100% by mass or less.

Although the pattern layer 12 is shown here as a single layer, it may be a multiple layer of two or more layers. When the pattern layer 12 has multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

Although the thickness of the pattern layer 12 is not particularly limited, it is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. When the thickness of the pattern layer 12 is equal to or more than the lower limit value, the effect of providing the pattern layer 12 (for example, the design of the decorative sheet 1) is enhanced. Since the thickness of the pattern layer 12 is equal to or less than the upper limit value, the excessive thickness of the decorative sheet 1 can be avoided, and the handling of the decorative sheet 1 can be facilitated, for example, by making the folding of the decorative sheet 1 easier. properties may be better.
As used herein, the term “thickness of the pattern layer” means the thickness of the entire pattern layer. means

<Transparent adhesive layer>
The transparent adhesive layer 15 adheres two adjacent layers, that is, the pattern layer 12 and the transparent thermoplastic resin layer 13 (more specifically, the first transparent thermoplastic resin layer 131).
The configuration of the transparent adhesive layer 15 is arbitrary, and the decorative sheet 1 may not have the transparent adhesive layer 15 . However, since the decorative sheet 1 is provided with the transparent adhesive layer 15, the adhesive strength between the two layers is remarkably improved, the structure of the decorative sheet 1 is more stable, and the decorative sheet 1 can be formed on a curved surface or at a right angle. The bending workability that follows the surface is improved.

The transparent adhesive layer 15 is transparent, and when the decorative sheet 1 is observed from the outside on the transparent surface protective layer 14 side, the layers arranged below the transparent adhesive layer 15 are visible. there is
The transparent adhesive layer 15 may be either colorless or colored, but is preferably colorless.

The transparent adhesive layer 15 may be of any known type.
Examples of the transparent adhesive layer 15 include those containing transparent adhesive resins, for example, thermoplastic resins such as polyamide, acrylic resins, and vinyl acetate resins; curable resins such as thermosetting urethane resins; Examples include those formed using a two-component curing type polyurethane or polyester as an agent.

Although the transparent adhesive layer 15 is shown here as a single layer, it may be a multiple layer of two or more layers. When the transparent adhesive layer 15 has multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.
Normally, one transparent adhesive layer 15 is sufficient.

Although the thickness of the transparent adhesive layer 15 is not particularly limited, it is preferably 0.1 to 30 μm, more preferably 1 to 20 μm. When the thickness of the transparent adhesive layer 15 is equal to or greater than the lower limit, the adhesive strength between the two adjacent layers becomes higher. Since the thickness of the transparent adhesive layer 15 is equal to or less than the upper limit value, it is possible to prevent the decorative sheet 1 from becoming excessively thick. may be easier to handle.
As used herein, the term "thickness of the transparent adhesive layer" means the thickness of the entire transparent adhesive layer. means the total thickness of all layers

<Primer layer>
The primer layer 16 is a layer for fixing the decorative sheet 1 to an intended application site.
A surface 16b of the primer layer 16 opposite to the thermoplastic resin base sheet 11 (in this specification, may be referred to as a “second surface”) 16b is the other outermost surface of the decorative sheet 1. .

The primer layer 16 has an arbitrary configuration, and the decorative sheet 1 does not have to be provided with the primer layer 16 . However, since the decorative sheet 1 is provided with the primer layer 16, when the decorative sheet 1 is used, for example, the step of applying a primer to the second surface 11b of the thermoplastic resin base sheet 11 can be omitted.

The primer layer 16 may be of any known type.
Examples of the primer layer 16 include those containing a primer resin. For example, a urethane resin-based primer made of an acrylic-modified urethane resin or the like, a resin-based primer made of a block copolymer of acrylic and urethane, or a two-liquid urethane. Examples include those formed using a resin-based primer agent.
The primer layer 16 may further contain a filler such as silica powder.

Although the primer layer 16 is shown here as a single layer, it may be a multiple layer of two or more layers. When the primer layer 16 is a multiple layer, these multiple layers may mutually be the same or different, and the combination of these multiple layers is not specifically limited.
Normally, one primer layer 16 is sufficient.

Although the thickness of the primer layer 16 is not particularly limited, it is preferably 0.01 to 10 μm, more preferably 0.1 to 3 μm. When the thickness of the primer layer 16 is equal to or greater than the lower limit, the fixing strength of the decorative sheet 1 to the fixing target is increased. Since the thickness of the primer layer 16 is equal to or less than the upper limit value, excessive thickness of the decorative sheet 1 can be avoided, and the decorative sheet 1 can be handled more easily, for example, by making the folding of the decorative sheet 1 easier. properties may be better.
As used herein, the term "thickness of the primer layer" means the thickness of the entire primer layer. means

In the decorative sheet 1, when observed from the outside on the side of the transparent surface protective layer 14, the transparent surface protective layer 14 and the transparent thermoplastic resin layer 13 (first transparent thermoplastic resin layer 131 and second transparent thermoplastic resin layer 131) are observed. The pattern layer 12 is visible through the layer 132) and the transparent adhesive layer 15, and the presence of the pattern layer 12 gives the decorative sheet 1 its design.
The decorative sheet 1 also has a transparent surface protective layer 14 containing microcapsules, and has new functions depending on the type of microcapsules.

When the decorative sheet 1 is used, the primer layer 16 is brought into contact with a target portion to fix the decorative sheet 1 to the target portion.

The decorative sheet of the present embodiment is not limited to the one shown in FIG. 1, but may be the one shown in FIG. 1 with some modifications, deletions, or additions within the scope of not impairing the effects of the present invention. There may be.

For example, the decorative sheet 1 shown in FIG. The thermoplastic resin layer 131, the second transparent thermoplastic resin layer 132), and the transparent surface protective layer 14) are provided, but the decorative sheet of the present embodiment includes other layers that do not correspond to any of these layers. may be
The other layer is not particularly limited, and its type and thickness can be arbitrarily selected according to the purpose.

Further, the decorative sheet 1 shown in FIG. 1 includes a transparent adhesive layer 15 between the pattern layer 12 and the transparent thermoplastic resin layer 13 (more specifically, the first transparent thermoplastic resin layer 131). However, a transparent adhesive layer similar to the transparent adhesive layer 15 may be provided at other locations.

Moreover, in the decorative sheet 1 shown in FIG. When the surface 11a has a pattern, the decorative sheet 1 may not have the pattern layer 12. - 特許庁

FIG. 2 is a cross-sectional view schematically showing another example of such a decorative sheet of this embodiment.
In the drawings after FIG. 2, the same constituent elements as those shown in already explained figures are given the same reference numerals as in the already explained figures, and detailed explanations thereof will be omitted.

Except that the decorative sheet 2 shown in FIG. It is the same as the decorative sheet 1 shown in FIG.
That is, the decorative sheet 2 includes a primer layer 16, a thermoplastic resin base sheet 21, a transparent adhesive layer 15, a transparent thermoplastic resin layer 13 (more specifically, a first transparent thermoplastic resin layer 131, and a 2 transparent thermoplastic resin layer 132) and transparent surface protective layer 14 are laminated in this order in the thickness direction, and at least the first surface 21a of the thermoplastic resin base sheet 21 has a pattern. have.
In FIG. 2, reference numeral 21b indicates the second surface of the base sheet 21 made of thermoplastic resin.

The design of the thermoplastic resin base sheet 21 is the same as the design of the design layer 12 of the decorative sheet 1 .

When the decorative sheet 2 is observed from the outside on the side of the transparent surface protective layer 14, the transparent surface protective layer 14 and the transparent thermoplastic resin layer 13 (the first transparent thermoplastic resin layer 131 and the second transparent thermoplastic resin layer 131) are observed. The thermoplastic resin base sheet 21 is visible through the layer 132) and the transparent adhesive layer 15, and the presence of the thermoplastic resin base sheet 21 gives the decorative sheet 2 its design.
The decorative sheet 2 also has a transparent surface protection layer 14 containing microcapsules, and has new functions according to the type of microcapsules.

The method of using the decorative sheet 2 is the same as the method of using the decorative sheet 1 described above.

Further, the decorative sheet 1 shown in FIG. 1 may not have the primer layer 16 as described above.
3 and 4 are cross-sectional views schematically showing still another example of the decorative sheet of this embodiment.

The decorative sheet 3 shown in FIG. 3 is the same as the decorative sheet 1 shown in FIG. 1 except that the primer layer 16 is not provided.
That is, the decorative sheet 3 includes a thermoplastic resin base sheet 11, a pattern layer 12, a transparent adhesive layer 15, a transparent thermoplastic resin layer 13 (more specifically, a first transparent thermoplastic resin layer 131, and a Two transparent thermoplastic resin layers 132) and a transparent surface protection layer 14 are laminated in this order in the thickness direction.
The second surface 11 b of the thermoplastic resin base sheet 11 is the other outermost surface of the decorative sheet 3 .

The decorative sheet 3 has the pattern layer 12 and the transparent surface protective layer 14, so that the same effect as the decorative sheet 1 can be obtained.
When the decorative sheet 3 is used, the second surface 11b of the thermoplastic resin base sheet 11 is treated with a primer to form a primer layer similar to the primer layer 16, and the primer layer is applied to the intended location. The decorative sheet 3 is fixed at this location by bringing it into contact.

The decorative sheet 4 shown in FIG. 4 is the same as the decorative sheet 2 shown in FIG. 2 except that the primer layer 16 is not provided.
That is, the decorative sheet 4 includes a thermoplastic resin base sheet 21, a transparent adhesive layer 15, a transparent thermoplastic resin layer 13 (more specifically, a first transparent thermoplastic resin layer 131 and a second transparent thermoplastic resin layer 131). The resin layer 132) and the transparent surface protection layer 14 are stacked in this order in the thickness direction.
The second surface 21 b of the thermoplastic resin base sheet 21 is the other outermost surface of the decorative sheet 4 .

Since the decorative sheet 4 includes the thermoplastic resin base sheet 21 and the transparent surface protective layer 14, the same effect as the decorative sheet 2 can be obtained.
When the decorative sheet 4 is used, the second surface 21b of the thermoplastic resin base sheet 21 is treated with a primer to form a primer layer similar to the primer layer 16, and the primer layer is applied to the intended location. The decorative sheet 4 is fixed at this location by bringing it into contact.

<<Method for manufacturing decorative sheet>>
Among the decorative sheets of the present embodiment, a decorative sheet in which at least the transparent surface protective layer side of the thermoplastic resin base sheet has a pattern and does not have the pattern layer is, for example, the above The transparent thermoplastic resin layer is composed of the thermoplastic resin base sheet and the transparent surface protective layer, with the pattern-bearing surface of the thermoplastic resin base sheet facing the transparent surface protective layer. It can be manufactured by laminating these layers so that they are arranged between the layers.
On the other hand, among the decorative sheets of the present embodiment, in the decorative sheet provided with the pattern layer, for example, the transparent thermoplastic resin layer is positioned between the thermoplastic resin base sheet and the transparent surface protective layer. and furthermore, these layers are laminated such that the pattern layer is arranged between the thermoplastic resin base sheet and the transparent thermoplastic resin layer.

Furthermore, the decorative sheet provided with the primer layer can be produced, for example, by laminating the thermoplastic resin base sheet and the transparent surface protective layer, followed by the above steps, followed by the thermoplastic resin base sheet. A primer layer is laminated on the surface (second surface) opposite to the transparent surface protective layer side, or the thermoplastic resin base sheet and the transparent surface protective layer are laminated. Before, in addition to the above steps, by laminating a primer layer on the side of the thermoplastic resin base sheet opposite to the transparent surface protective layer side (second side), can be manufactured.

Further, among the decorative sheets provided with the transparent adhesive layer, a decorative sheet having a pattern on at least one surface of the thermoplastic resin base sheet and not provided with the pattern layer is, for example, the above In addition to the step of , the transparent adhesive layer is arranged between the thermoplastic resin base sheet and the transparent thermoplastic resin layer (more specifically, the first transparent thermoplastic resin layer). It can be manufactured by stacking these layers.
On the other hand, among the decorative sheets provided with the transparent adhesive layer, the decorative sheet provided with the pattern layer is produced by, for example, adding the pattern layer and the transparent thermoplastic resin layer (more specifically, can be manufactured by laminating these layers such that the transparent adhesive layer is arranged between the first transparent thermoplastic resin layer).

Further, the decorative sheet having recesses on the surface (first surface) of the transparent surface protective layer opposite to the thermoplastic resin base sheet is, for example, the thermoplastic resin base sheet and the After laminating the transparent surface protective layer, in addition to the above steps, a concave portion is formed on the surface (first surface) of the transparent surface protective layer opposite to the thermoplastic resin base sheet side. Alternatively, before laminating the thermoplastic resin base sheet and the transparent surface protective layer, in addition to the above steps, the transparent surface protective layer is formed on the side opposite to the thermoplastic resin base sheet side It can be manufactured by forming a concave portion on the side surface (the surface serving as the first surface).

Furthermore, the decorative sheet having recesses on the surface (first surface) of the second transparent thermoplastic resin layer on the side of the transparent surface protective layer can be obtained, for example, by performing the transparent surface protective layer as described above in addition to the above steps. It can be manufactured by forming recesses in the second transparent thermoplastic resin layer in the same manner as forming recesses in the layer. The concave portions in the second transparent thermoplastic resin layer may be formed before forming the concave portions in the transparent surface protective layer, or may be formed simultaneously when forming the concave portions in the transparent surface protective layer. good.
Next, a more specific formation method and lamination method for each layer will be described.

The thermoplastic resin base sheet, the first transparent thermoplastic resin layer, and the second transparent thermoplastic resin layer are all, for example, a single resin for composing them, or contain a resin for composing them. It can be formed by molding a resin composition that does.
Commercially available products may be used as the thermoplastic resin base sheet, the first transparent thermoplastic resin layer, and the second transparent thermoplastic resin layer.

The transparent surface protective layer may be formed by, for example, using a composition containing components for forming the transparent surface protective layer (in this specification, may be referred to as a "transparent surface protective layer composition"). It can be formed by coating on the symmetrical surface, drying and, if necessary, curing (curing the components contained in the transparent surface protective layer).

Examples of the transparent surface protective layer composition include those containing the microcapsules, resin and solvent.
In this specification, unless otherwise specified, the component corresponding to the dispersion medium in the dispersion is also referred to as "solvent".
The contents of the microcapsules and the resin in the composition for the transparent surface protective layer may be adjusted so that the contents of the microcapsules and the resin in the transparent surface protective layer satisfy the conditions described above.

Examples of methods for applying the transparent surface protective layer composition include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, and kiss coating. method, blade coating method, smooth coating method, comma coating method and the like.
Drying of the transparent surface protective layer composition may be carried out by a known method, for example, under normal pressure, under reduced pressure, or under air blowing conditions, under air or under an inert gas atmosphere. Either drying by heating or drying at normal temperature may be used. The drying temperature is not particularly limited, and may be, for example, 30 to 100°C.

The composition for a transparent surface protective layer can be thermally cured, for example, by heating at 40 to 60° C. for 0.5 to 2 minutes, but this curing condition is an example.
The composition for a transparent surface protective layer can be cured, for example, by ionizing radiation under known conditions.

When forming recesses on the first surface of the transparent surface protective layer (for example, forming recesses 140 on the first surface 14a of the transparent surface protective layer 14 in the decorative sheets 1 to 4 shown in FIGS. 1 to 4) can apply, for example, a normal embossing technique. For example, in any stage of the manufacturing process of the decorative sheet, the first surface of the transparent surface protective layer having no recesses is heated to soften, and the first surface in this state is used to form the recesses. The depressions can be formed by applying pressure from the convex side surface of the plate having the projections, which will be the mold, and then cooling. At this time, when the transparent surface protective layer and the transparent thermoplastic resin layer (more specifically, the second transparent thermoplastic resin layer) are already laminated, on the first surface of the transparent thermoplastic resin layer (For example, in the decorative sheets 1 to 4 shown in FIGS. 1 to 4, the first surface 132a of the second transparent thermoplastic resin layer 132 may also be formed with a recess 1320 at the same time. good).

When manufacturing the decorative sheet, a transparent thermoplastic resin layer having no recesses (more specifically, a second transparent thermoplastic resin layer) is formed instead of the above-described method of forming recesses on the first surface of the transparent surface protective layer. Form recesses on the first surface of the transparent surface protective layer in the same manner as in the case of the above-described transparent surface protective layer, and then apply the above-described transparent surface protective layer composition to the first surface after forming the recesses. A transparent surface protective layer having concave portions may be formed by drying and, if necessary, curing (hardening the components contained in the transparent surface protective layer).

The composition for the transparent surface protective layer can be produced by blending the constituent components.
For example, during the production of the microcapsules, the microcapsules can be obtained as a dispersion such as an aqueous dispersion thereof. ), etc., or the dispersion of microcapsules may be dried by a drying treatment such as a spray drying method, and the obtained powder may be blended.
The contents of the microcapsules, the resin and the solvent in the composition for the transparent surface protective layer may be adjusted so that the contents of the microcapsules and the resin in the transparent surface protective layer satisfy the conditions described above.

The picture layer is formed by, for example, attaching a composition containing components for constituting the picture layer (in this specification, sometimes referred to as a "picture layer composition") to the formation symmetrical surface of the picture layer, It can be formed by drying and, if necessary, curing (hardening components contained in the pattern layer).
The pattern layer composition can be produced by blending components for constituting the composition.

Examples of the pattern layer composition include those containing the above resin, colorant and solvent.
The contents of the resin, colorant and solvent in the pattern layer composition may be adjusted so that the content of the resin and colorant in the pattern layer satisfies the conditions described above.

As the pattern layer composition, for example, water-based ink or solvent-based ink can be used. In that case, the type of ink can be appropriately selected in consideration of the compatibility with the device, the performance required of the decorative sheet, and the like.

Examples of methods for attaching the pattern layer composition include a printing method, a coating method, a hand-painting method, and a suminagashi method.
Examples of the printing method include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing.
Examples of the coating method include gravure coating, roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating. .
Further, these methods may be combined with one or more other methods such as a photo method, a transfer method, a laser beam drawing method, an electron beam drawing method, a partial vapor deposition method of metals and the like, an etching method, and the like. good.

Drying and curing of the picture layer composition can be carried out, for example, in the same manner as in the case of the transparent surface protective layer composition.

The transparent adhesive layer is formed by, for example, applying a composition containing components for constituting this (in this specification, sometimes referred to as a "transparent adhesive") to the surface to be formed of the transparent adhesive layer. It can be formed by processing, drying and, if necessary, curing (curing the components contained in the transparent adhesive layer).
A transparent adhesive can be produced by blending components for constituting it.
A commercially available product may be used as the transparent adhesive layer or the transparent adhesive.

Examples of methods for applying the transparent adhesive include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, and blade coating. method, smooth coat method, comma coat method, and the like.
Drying and curing of the transparent adhesive can be carried out, for example, in the same manner as in the case of the composition for the transparent surface protective layer.

The primer layer is formed by, for example, applying a composition containing components for constituting this (in this specification, sometimes referred to as a "primer agent") to the surface on which the primer layer is to be formed, followed by drying. can be formed by curing (curing the components contained in the primer layer) as necessary.
A primer agent can be produced by blending components for constituting the primer agent.
A commercially available product may be used as the primer agent.

Coating, drying and curing of the primer can be carried out, for example, in the same manner as for the transparent adhesive.

At the time of manufacturing the decorative sheet, each of the above-mentioned layers may be laminated singly at the target location, or two or more layers may be laminated in advance to form a laminate, and then this laminate may be laminated at the target location. .

<<Floor decorative materials>>
The above-described decorative sheet of the present embodiment can constitute a floor decorative material by bonding it to various adherends via the primer layer therein.
Examples of the decorative floor material include a decorative floor board in which the adherend is plate-shaped.

Examples of the constituent material of the adherend include inorganic nonmetals, metals, wood, resins, and the like.

Examples of the inorganic nonmetal include paper cement, extruded cement, slag cement, lightweight cellular concrete (ALC), glass fiber reinforced concrete (GRC), pulp cement, wood chip cement, asbestos cement, calcium silicate, gypsum, and gypsum slag. ceramics such as earthenware, earthenware, porcelain, setware, glass, and enamel.

Examples of the metal include iron, aluminum, and copper. These metals can be used, for example, as metal steel sheets.

Examples of the wood include cedar, cypress, oak, lauan, and teak. These woods can be used, for example, as veneers, plywoods, particle boards, fiberboards, and laminated lumber.

Examples of the resin include polypropylene, ABS resin, and phenol resin.

The present invention will be described in more detail below with reference to specific examples. However, the present invention is by no means limited to the examples shown below.

[Example 1]
<<Manufacturing of decorative sheets>>
<Production of aromatic microcapsules>
Bis(2-ethylhexyl) sebacate (manufactured by Toyokuni Oil Co., Ltd., 37.5 g) and a trimethylolpropane adduct of tolylene-2,4-diisocyanate having a concentration of 75% by mass (hereinafter, "TDI-TMP adduct") Hinoki oil (22.5 g) was added to a mixture of an ethyl acetate solution ("Takenate D-103H" manufactured by Mitsui Chemicals, Inc., 26.7 g, solid content 20.0 g) and dissolved. .
Next, the obtained mixture was added to a polyvinyl alcohol aqueous solution (150 g, 7.5 g as polyvinyl alcohol) having a concentration of 5% by mass, and an emulsifier (manufactured by Primix) was used at a rotation speed of 10000 rpm for 5 minutes. was emulsified under the conditions of to obtain an emulsion.
Separately, diethylenetriamine (manufactured by Tokyo Kasei Co., Ltd., 2.0 g) was dissolved in distilled water (10.0 g) to prepare an aqueous diethylenetriamine solution.
The total amount of the diethylenetriamine aqueous solution obtained above was added to the total amount of the emulsified liquid obtained above, and the mixture was stirred at 80°C for 2 hours to perform interfacial polycondensation.
As described above, a polycondensate of diethylenetriamine and a TDI-TMP adduct is used as a film-forming component, cypress oil as a fragrance, and bis(2-ethylhexyl) sebacate and ethyl acetate as solvents, respectively. Sustained-release fragrant microcapsules were obtained as an aqueous dispersion.

As a result of measuring the volume particle size distribution of the microcapsules obtained above using an electrical detection band type particle size distribution meter (Beckman Coulter "Multusizer 3"), the median diameter, that is, the average particle diameter is 9 0 μm.

Using a spray-drying device (“ADL-311SA” manufactured by Yamato Scientific Co., Ltd.), water is removed from the aqueous dispersion obtained above by a spray-drying method, and the aromatic microcapsule powder is obtained by drying. Obtained.

<Production of Composition for Transparent Surface Protective Layer>
At room temperature, a resin composition containing a thermosetting polyfunctional acrylic urethane resin (manufactured by DIC Graphics) (100 parts by mass as the amount of thermosetting polyfunctional acrylic urethane resin), Powder of aromatic microcapsules (3 parts by mass) was added and stirred to obtain a composition for a transparent surface protective layer.

<Production of decorative sheet>
A colored polyethylene film (“FZ” manufactured by Riken Technos, thickness 55 μm) was prepared as a thermoplastic resin base sheet.
A picture layer (thickness: 1.5 μm) was formed by printing on one side (first side) of the colored polyethylene film using the picture layer composition.
Also, a primer layer (thickness 1 μm) was formed by gravure printing a two-liquid urethane primer resin containing silica powder on the other side (second side) of the colored polyethylene film. .
As described above, a first laminated sheet was obtained, which was configured by laminating the primer layer, the thermoplastic resin base sheet, and the pattern layer in this order in the thickness direction thereof.

On the exposed surface of the pattern layer in the first laminated sheet obtained above (that is, the surface opposite to the thermoplastic resin base sheet side), as a transparent adhesive, polyester polyol is used as the main agent, and isophorone diisocyanate is cured. A transparent adhesive layer (thickness: 10 μm) was formed by applying a two-pack curable polyurethane as an agent.
Next, a resin composition (“W480” manufactured by DIC Corporation) for forming the first transparent thermoplastic resin layer is prepared, and a resin composition (“UV230” manufactured by DIC Corporation) for forming the second transparent thermoplastic resin layer is prepared. did.
Then, on the exposed surface of the transparent adhesive layer formed above (that is, the surface opposite to the pattern layer side), these resins are co-extruded in the order described above, and further on the pattern layer. , a first transparent thermoplastic resin layer (5 μm thick) and a second transparent thermoplastic resin layer (6.5 μm thick) were laminated in this order. The surface (first surface) of the first transparent thermoplastic resin layer on the side of the second transparent thermoplastic resin layer (first surface) is a matte surface, and the surface of the second transparent thermoplastic resin layer opposite to the first transparent thermoplastic resin layer side is The face (first face) was the gloss face.
As described above, the primer layer, the thermoplastic resin base sheet, the pattern layer, the transparent adhesive layer, the first transparent thermoplastic resin layer, and the second transparent thermoplastic resin layer are laminated in this order in the thickness direction. A structured, second laminated sheet was obtained.

The transparent surface protective layer obtained above is applied to the exposed surface of the second transparent thermoplastic resin layer in the second laminated sheet obtained above (that is, the surface opposite to the first transparent thermoplastic resin layer side). was applied, dried and heat-cured at 60° C. to form a transparent surface protective layer (thickness: 2 μm) on the second transparent thermoplastic resin layer to obtain a third laminated sheet.

The design layer in the third laminated sheet obtained above was cured.
As described above, the primer layer (thickness 1 μm), the thermoplastic resin base sheet (thickness 55 μm), the pattern layer (thickness 1.5 μm), the transparent adhesive layer (thickness 10 μm), the first transparent thermoplastic resin A decorative sheet comprising a layer (thickness 5 μm), a second transparent thermoplastic resin layer (thickness 6.5 μm) and a transparent surface protective layer (thickness 2 μm) laminated in this order in the thickness direction. Obtained.

<<Evaluation of decorative sheet>>
<Production of veneer for floor>
The exposed surface (second surface) of the primer layer in the decorative sheet obtained above was attached to one surface of MDF (medium density fiberboard, thickness 3 mm). This MDF is made of hardwood.
As described above, a decorative floor panel comprising MDF and the decorative sheet provided on one surface of the MDF was obtained.
Using this decorative floor board, the following items were evaluated for the decorative sheet therein.

<Evaluation of chemical resistance>
An aqueous sodium carbonate solution with a concentration of 1% by mass, an acetic acid aqueous solution with a concentration of 5% by mass, lacquer thinner, petroleum benzine and ethanol are applied to the exposed surface (first surface) of the transparent surface protective layer in the decorative floor board. , 0.1 mL of each was added dropwise.
Next, on the exposed surface of the transparent surface protective layer, the locations where these five chemicals were dropped were covered with a plate to isolate these dropping locations. placed.
Next, the covering plate was removed, and the portions of the transparent surface protective layer where the five kinds of chemicals had been dropped were washed with water and a neutral detergent, and then the liquid was wiped off from the washed portions. Then, the appearance of the portion where the chemical was dropped was visually observed, and the chemical resistance of the decorative sheet was evaluated according to the following criteria. Table 1 shows the results.
-Evaluation Criteria A: There is no change at all, or only a slight change is observed at all of the dropping points of the five kinds of chemicals.
B: The gloss clearly changes at the locations where one or more chemicals are dropped.

<Evaluation of pencil hardness>
The exposed surface (first surface) of the transparent surface protective layer in the decorative floor board was subjected to a pencil hardness test in accordance with JIS K 5600, and the pencil hardness of the decorative sheet was evaluated according to the following criteria. Table 1 shows the results.
A: The maximum hardness at which the exposed surface of the transparent protective surface layer is not recessed is B or higher.
B: The maximum hardness at which the exposed surface of the transparent surface protective layer is not recessed is 2B or less.

<Evaluation of scratch resistance (1) (coin scratch test)>
The exposed surface (first surface) of the transparent surface protective layer in the decorative floor board is brought into contact with the edge of a 10-yen coin tilted at an angle of 45° from the upright state, and the 10-yen coin is touched. The load to be applied was set in four stages of 1 kg, 2 kg, 3 kg and 4 kg, and in each case a 10-yen coin was scratched in the inclined direction. Then, the scratched portions of the transparent surface protective layer were visually observed, and the scratch resistance (1) of the decorative sheet was evaluated according to the following criteria. Table 1 shows the results.
Evaluation Criteria A: The initial load when the transparent surface protective layer was peeled off was 3 kg or more.
B: The initial load when the transparent surface protective layer was peeled off was 2 kg or less.

<Evaluation of scratch resistance (2) (Hoffman scratch test)>
Using a Hoffman scratch hardness tester (manufactured by BYK-Gardner), the load applied to the exposed surface (first surface) of the transparent surface protective layer in the decorative floor panel was increased from 200 g to 2000 g in increments of 200 g. set and scratched in each case. Then, the scratched portions of the transparent surface protective layer were visually observed, and the scratch resistance (2) of the decorative sheet was evaluated according to the following criteria. Table 1 shows the results.
Evaluation Criteria A: The initial load when the transparent surface protective layer was peeled off was 1400 g or more.
B: The initial load when the transparent surface protective layer was peeled off was 1200 g or less.

<Evaluation of fragrance>
Five evaluators smelled the decorative floor board, and evaluated the fragrance (comfortability) of the decorative sheet according to the following criteria based on the strength of the perceived smell. Table 1 shows the results.
A: The number of evaluators who judged that the strength of the odor was appropriate and comfortable was 3 or more out of 5.
B: The number of evaluators who judged that the odor was too strong and unpleasant or that the odor was not felt was 3 or more out of 5 persons.

<<Production and Evaluation of Decorative Sheet>>
[Example 2]
Cosmetics were prepared in the same manner as in Example 1, except that the amount of the aromatic microcapsule powder added was changed to 3 parts by mass and 6 parts by mass during the production of the composition for a transparent surface protective layer. Sheets were manufactured and evaluated. Table 1 shows the results.

[Reference example 1]
Cosmetics were prepared in the same manner as in Example 1, except that the amount of the aromatic microcapsule powder added was 1 part by mass instead of 3 parts by mass during the production of the composition for a transparent surface protective layer. Sheets were manufactured and evaluated. Table 1 shows the results.

[Reference example 2]
Cosmetics were prepared in the same manner as in Example 1, except that the amount of the aromatic microcapsule powder added was changed to 3 parts by mass and 15 parts by mass during the production of the composition for a transparent surface protective layer. Sheets were manufactured and evaluated. Table 1 shows the results.

[Comparative Example 1]
In the production of the transparent surface protective layer composition, the amount of the aromatic microcapsule powder added was changed to 0 parts by mass instead of 3 parts by mass, that is, the resin composition was used as the transparent surface protective layer composition. A decorative sheet was manufactured and evaluated in the same manner as in Example 1, except that the was used as it was. Table 1 shows the results.

As is clear from the above results, the decorative sheets of Examples 1 and 2 had good fragrance and possessed characteristics not found in conventional decorative sheets. Furthermore, the decorative sheets of Examples 1 and 2 had good scratch resistance and pencil hardness, and had particularly excellent properties as decorative sheets. Above all, the decorative sheet of Example 1 was excellent in all items including chemical resistance, and had remarkably excellent properties as a decorative sheet.

The decorative sheet of Reference Example 1 was inferior in fragrance to the decorative sheets of Examples 1 and 2 because the amount of the aromatic microcapsules used was too small.
The decorative sheet of Reference Example 2 was inferior in fragrance to the decorative sheets of Examples 1 and 2 because the amount of the fragrant microcapsules used was too large.

On the other hand, the decorative sheet of Comparative Example 1 did not use aromatic microcapsules and thus had no fragrance at all.

[Example 3]
<<Manufacturing of decorative sheets>>
<Production of heat storage microcapsules>
A heat storage agent, heptadecane ("PCM-17", 95.0 g, manufactured by Energy Absolute Co., Ltd.) and a supercooling inhibitor, stearic acid (manufactured by Kanto Chemical Co., Ltd., 5.0 g), were mixed and heated at 80°C. Dissolved to obtain a solution.
In addition, as an emulsifier, an aqueous solution of styrene-maleic anhydride copolymer having a concentration of 5.0% by mass and adjusted to pH 4.5 with sodium hydroxide (manufactured by Solenis Co., Ltd., "Script Set 520", 150 g) was prepared. , and the solution obtained above were placed in a beaker. Then, using an emulsifier (manufactured by Primix), emulsification was performed under the conditions of 10000 rpm for 5 minutes to obtain an emulsified liquid.

Separately, melamine (manufactured by Kanto Chemical Co., Ltd., 7.0 g) and formaldehyde aqueous solution having a concentration of 37% by mass (manufactured by Kanto Chemical Co., Ltd., 9.1 g) were mixed, and water having a concentration of 40% by mass was added thereto. An aqueous sodium oxide solution was added to adjust the pH of the resulting mixture to 8.5 to 9.5, and the mixture was heated and stirred at 80° C. to obtain a methylolated melamine precondensate.
Then, the whole amount of this methylolated melamine precondensate was added to the whole amount of the emulsified liquid obtained above, and the mixture was stirred at 80° C. for 120 minutes to carry out polycondensation.

Next, the obtained reaction solution was cooled to room temperature, and the pH of the reaction solution was adjusted to about 7 by adding an aqueous sodium hydroxide solution having a concentration of 40% by mass to the cooled reaction solution. .
As described above, non-sustained-release and non-pressure-sensitive heat-storage microcapsules containing melamine resin as a wall material component, encapsulating heptadecane as a heat-storage agent, and stearic acid as a supercooling-preventive agent, respectively, are prepared as water dispersions. Obtained.

The volume particle size distribution of the heat-storage microcapsules obtained above was measured using an electrical detection band type particle size distribution meter ("Multusizer 3" manufactured by Beckman Coulter, Inc.). was 2.5 μm.

Using a spray-drying device (“ADL-311SA” manufactured by Yamato Scientific Co., Ltd.), water is removed from the aqueous dispersion obtained above by a spray-drying method, and the heat-storage microcapsule powder is obtained by drying. Obtained.

<Production of composition for transparent surface protective layer and decorative sheet>
In the same manner as in Example 1, except that the heat storage microcapsule powder (6 parts by mass) obtained above was used instead of the aromatic microcapsule powder (3 parts by mass). A composition for a transparent surface protective layer was produced to produce a decorative sheet.

<<Evaluation of decorative sheet>>
<Evaluation of pencil hardness, scratch resistance (1) and scratch resistance (2)>
A decorative floor board was manufactured in the same manner as in Example 1, except that the decorative sheet obtained above was used.
Using this decorative floor board, the decorative sheet therein was evaluated in the same manner as in Example 1 for pencil hardness, scratch resistance (1) and scratch resistance (2). Table 2 shows the results.

<Evaluation of heat storage>
The above-mentioned decorative floor board was stored in an air atmosphere at 25°C for 5 hours, and then stored in an air atmosphere at 5°C for 2 hours. Next, the temperature of the exposed surface (first surface) of the transparent surface protective layer in the decorative floor board was immediately measured, and the heat storage property of the decorative sheet was evaluated according to the following criteria. Table 2 shows the results.
- Evaluation Criteria A: The temperature is 10°C or higher.
B: The temperature is less than 10°C.

<<Production and Evaluation of Decorative Sheet>>
[Reference example 3]
Cosmetic preparation was carried out in the same manner as in Example 3, except that the amount of the heat storage microcapsule powder added was changed to 1 part by mass instead of 6 parts by mass during the production of the composition for the transparent surface protective layer. Sheets were manufactured and evaluated. Table 2 shows the results.

[Reference Example 4]
Cosmetics were applied in the same manner as in Example 3, except that the amount of heat-storage microcapsule powder added was changed to 3 parts by mass in place of 6 parts by mass during the production of the composition for a transparent surface protective layer. Sheets were manufactured and evaluated. Table 2 shows the results.

[Reference Example 5]
Cosmetic preparation was carried out in the same manner as in Example 3, except that the amount of the heat-storage microcapsule powder added was changed to 15 parts by mass in place of 6 parts by mass during the production of the composition for the transparent surface protective layer. Sheets were manufactured and evaluated. Table 2 shows the results.

[Comparative Example 2]
In the production of the transparent surface protective layer composition, the amount of heat storage microcapsule powder added was changed to 0 parts by mass instead of 6 parts by mass. A decorative sheet was manufactured and evaluated in the same manner as in Example 3, except that the was used as it was. Table 2 shows the results.

As is clear from the above results, the decorative sheet of Example 3 had good heat storage properties, and had properties that were not observed in conventional decorative sheets. Furthermore, the decorative sheet of Example 3 had good scratch resistance and pencil hardness, and had particularly excellent characteristics as a decorative sheet.

The decorative sheets of Reference Examples 3 and 4 were inferior to the decorative sheet of Example 3 in heat storage performance because the amount of heat storage microcapsules used was too small.
The decorative sheet of Reference Example 5 contained an excessive amount of heat-storing microcapsules, so that the heat-storing properties were good, but the scratch resistance and pencil hardness were inferior to those of the decorative sheet of Example 3.

On the other hand, the decorative sheet of Comparative Example 2 did not have heat accumulating properties because it did not use heat accumulating microcapsules.

INDUSTRIAL APPLICABILITY The present invention can be used as a building material.

1, 2, 3, 4... Decorative sheet 11, 21... Thermoplastic resin base sheet 11a, 21a... First surface of thermoplastic resin base sheet 12... Design Layer 13... Transparent thermoplastic resin layer 131... First transparent thermoplastic resin layer 132... Second transparent thermoplastic resin layer 14... Transparent surface protective layer

Claims (3)

Composed of a thermoplastic resin base sheet, a transparent thermoplastic resin layer, and a transparent surface protective layer,
The transparent thermoplastic resin layer is arranged between the thermoplastic resin base sheet and the transparent surface protective layer,
At least the surface of the thermoplastic resin base sheet on the side of the transparent surface protective layer has a pattern, or between the thermoplastic resin base sheet and the transparent thermoplastic resin layer , and has a pattern layer,
The transparent surface protective layer contains microcapsules and a resin ,
The resin is a thermosetting resin or a cured product thereof ,
The microcapsules contain polyurea as a wall material component and contain an aromatic agent, or contain a melamine resin as a wall material component and contain a heat storage agent,
When the microcapsules contain the polyurea as the wall material component and the aromatic agent, the ratio of the content of the microcapsules to the content of the resin in the transparent surface protective layer is 2 to 13% by mass,
When the microcapsules contain the melamine resin as the wall material component and the heat storage agent, the content of the microcapsules in the transparent surface protective layer is , 4 to 13% by mass,
The transparent thermoplastic resin layer further comprises a first transparent thermoplastic resin layer and a second transparent thermoplastic resin layer laminated in this order from the thermoplastic resin base sheet side,
The surface of the first transparent thermoplastic resin layer on the transparent surface protective layer side is a glossy surface , and the surface of the second transparent thermoplastic resin layer on the transparent surface protective layer side is a matte surface,
The first transparent thermoplastic resin layer contains a thermoplastic resin and does not contain a matting agent,
The second transparent thermoplastic resin layer contains a thermoplastic resin and a matting agent, and the matting agent includes silica, calcium carbonate, synthetic mica, titanium oxide, glass particles, polyethylene fine particles, acrylic resin fine particles, urethane resin fine particles, urea resin fine particles, nylon resin fine particles or balloons,
The decorative sheet, wherein the ratio of the content of the matting agent to the content of the thermoplastic resin in the second transparent thermoplastic resin layer is 10% by mass or more. Composed of a thermoplastic resin base sheet, a transparent thermoplastic resin layer, and a transparent surface protective layer,
The transparent thermoplastic resin layer is arranged between the thermoplastic resin base sheet and the transparent surface protective layer,
At least the surface of the thermoplastic resin base sheet on the side of the transparent surface protective layer has a pattern, or between the thermoplastic resin base sheet and the transparent thermoplastic resin layer , and has a pattern layer,
The transparent surface protective layer contains microcapsules and a resin ,
The resin is a thermosetting resin or a cured product thereof ,
The microcapsules contain polyurea as a wall material component and contain an aromatic agent, or contain a melamine resin as a wall material component and contain a heat storage agent,
When the microcapsules contain the polyurea as the wall material component and the aromatic agent, the ratio of the content of the microcapsules to the content of the resin in the transparent surface protective layer is 2 to 13% by mass,
When the microcapsules contain the melamine resin as the wall material component and the heat storage agent, the content of the microcapsules in the transparent surface protective layer is , 4 to 13% by mass,
The transparent thermoplastic resin layer further comprises a first transparent thermoplastic resin layer and a second transparent thermoplastic resin layer laminated in this order from the thermoplastic resin base sheet side,
The surface of the first transparent thermoplastic resin layer on the transparent surface protective layer side is a matte surface , and the surface of the second transparent thermoplastic resin layer on the transparent surface protective layer side is a glossy surface,
The first transparent thermoplastic resin layer contains a thermoplastic resin and a matting agent, and the matting agent includes silica, calcium carbonate, synthetic mica, titanium oxide, glass particles, polyethylene fine particles, acrylic resin fine particles, urethane resin fine particles, urea resin fine particles, nylon resin fine particles or balloons,
In the first transparent thermoplastic resin layer, the ratio of the content of the matting agent to the content of the thermoplastic resin is 10% by mass or more,
The decorative sheet, wherein the second transparent thermoplastic resin layer contains a thermoplastic resin and does not contain a matting agent . The decorative sheet according to claim 1 or 2, wherein the microcapsules have a sustained release property of a fragrance .

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