JP2000085002A - Decorative sheet for three-dimensional molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet for three-dimensional molding not generating a toxious substance such as chlorine gas or the like at a time of combustion and excellent in three-dimensional moldability such as vacuum molding or the like. SOLUTION: The decoration processing of pattern layers 3 is applied to a base material sheet 1 comprising a thermoplastic resin characterized by that dynamic elastic modulus to frequency of 10 Hz at 50-90 deg.C is(4.0×108)-(1.0×1010) Pa and dynamic loss (6.0.×107)-(6.0×108) Pa or less. Pref., a transparent resin layer 2 is provided on the surface thereof to constitute a decorative sheet for three-dimensional molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior and exterior materials for buildings such as houses, construction materials, building materials such as fittings, furniture and fixtures, and the like.
The present invention relates to a decorative sheet for use in surface decoration of household equipment, home appliances, and the like, and in particular, for the surface decoration of fittings such as interior doors, kitchen doors, and storage doors, for example, by a vacuum molding method or a vacuum pressure method. The present invention relates to a decorative sheet suitable for use by being formed into a three-dimensional shape by a forming method or the like.

[0002]

2. Description of the Related Art Conventionally, decorative sheets used for the purpose of forming into a three-dimensional shape as described above have a unique excellent thermoformability, and furthermore, such as surface hardness, abrasion resistance and chemical resistance. A decorative sheet made of polyvinyl chloride resin with a wide range of well-balanced properties in various surface physical properties, weather resistance, secondary workability, etc.
Most widely used. However, in recent years, it has been pointed out that polyvinyl chloride resin may generate toxic gases such as hydrogen chloride and highly toxic substances such as dioxin during combustion. However, there is a strong demand from society.

To meet such demands, decorative sheets using various non-halogen thermoplastic resins such as polyolefin resins, polyester resins and acrylic resins have already been proposed (JP-A-6-16832). JP, JP-A-6-166159, JP-A-8-480
No. 14, etc.). These decorative sheets have been developed to have excellent performance for the most common decorative sheet applications such as flat decorative panels, V-cut processing, and wrapping processing. Replacement of decorative sheets made of plastic is gradually progressing.

However, the decorative sheet made of the conventional polyvinyl chloride resin has a problem in that the surface of the base material having a three-dimensional unevenness is formed by utilizing the excellent thermoformability inherent in the polyvinyl chloride resin. The above-mentioned various non-halogen-based decorative sheets are not necessarily the same as polyvinyl chloride resin decorative sheets, while they have been widely used for applications such as thermoforming by vacuum forming method. It was not sexual. More specifically, there is an example in which a relatively hard resin is selected as a result of giving priority to surface physical properties such as surface hardness and abrasion resistance, abrasion resistance, and solvent resistance required for a final product. In many cases, thermoformability is necessarily inferior, and in many cases, it cannot follow the uneven shape of the substrate surface.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and it is an object of the present invention to solve the above problems by using toxic substances such as chlorine gas during combustion. An object of the present invention is to provide a decorative sheet for three-dimensional molding, which does not cause blemishes and is excellent in three-dimensional moldability such as vacuum molding.

[0006]

SUMMARY OF THE INVENTION The present invention provides a temperature range of 50.
The dynamic elastic modulus at a frequency of 10 Hz at a temperature of from 90 ° C. to 90 ° C. is from 4.0 × 10 ⁸ Pa to 1.0 × 10 ¹⁰ Pa, and the dynamic loss is from 6.0 × 10 ⁷ Pa to 6.0 × 10 ^8.
A decorative sheet for three-dimensional molding, wherein a decorative sheet is formed on a base sheet made of a thermoplastic resin having a pressure of Pa or less.

The present invention also provides a decorative sheet for three-dimensional molding, comprising a transparent resin layer on a surface of the base sheet.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic sectional view of an example of a three-dimensionally formed decorative sheet of the present invention. The decorative sheet for three-dimensional molding of the present invention is configured such that a decoration process such as a pattern layer 3 is applied to a base sheet 1 and a transparent resin layer 2 is preferably provided on the surface thereof. The base sheet 1
Dynamic elastic modulus at a frequency of 10 Hz in a temperature range of 50 ° C. to 90 ° C. is 4.0 × 10 ⁸ Pa or more and 1.0 × 10 ¹⁰
And a dynamic loss of 6.0 × 10 ⁷ Pa or more and 6.0 × 10 ⁸ Pa or less.

In the present invention, the values of the dynamic elastic modulus and the dynamic loss of the thermoplastic resin constituting the base sheet 1 are defined in the above ranges because the dynamic elastic modulus exceeds 1.0 × 10 ¹⁰ Pa. Insufficient deformation responsiveness during three-dimensional molding due to heat,
It causes cracks, whitening, molding defects, etc., while 4.0
If it is less than × 10 ⁸ Pa, it will be too soft during three-dimensional molding,
It causes drawdown and pattern flow. Further, if the dynamic loss exceeds 6.0 × 10 ⁸ Pa, the resin is inherently easily plastically deformed with high stress relaxation, and this also causes drawdown and pattern flow. If the pressure is less than 10 ⁷ Pa, the stress relaxation is too slow, and it is difficult to follow the molding speed during three-dimensional molding, resulting in poor molding and residual internal stress.

In the present invention, the kind of the resin constituting the base sheet 1 is not particularly limited, but in view of the object of the present invention, the use of a resin containing a halogen atom such as a polyvinyl chloride resin is preferable. Preferably, a non-halogen resin is used. Specifically, for example, polyolefin resin, polyester resin, acrylic resin, polyvinyl resin, polyamide resin, styrene resin,
Among various non-halogen resins such as cellulose derivatives, and mixtures, copolymers, laminates, and composites of two or more kinds selected from them, the values of the dynamic elastic modulus and the dynamic loss are the above numerical values. A range can be selected and used.

For example, the above-mentioned polyolefins may be specifically homopolymers such as polyethylene, polypropylene, polybutene-1 and poly-4-methylpentene-1 and mixtures thereof, and their average molecular weight and molecular weight. The values of the dynamic elastic modulus and the dynamic loss are appropriately adjusted by adjusting the distribution, the branch density, the average branch length, the three-dimensional molecular structure, the degree of crystallinity or the orientation, and the mixing ratio. For example, in the case of polypropylene, a homopolymer, a random polypropylene, a block polypropylene, or the like is appropriately blended, and an atactic polypropylene is appropriately added thereto, to thereby prepare a polypropylene resin having desired properties.

A copolymer of a plurality of types of olefin monomers may be used. For example, in the case of a polypropylene-based copolymer, α-olefins having 2 to 20 carbon atoms other than propylene, preferably ethylene, butene A propylene-α-olefin copolymer obtained by copolymerizing at least 15 mol% of one or more comonomers of -1,4-methylpentene-1, hexene-1 or octene-1; -Polypropylene copolymer having desired and appropriate physical properties by appropriately adding a modifier such as -α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, etc. A resin is prepared.

On the other hand, as the polyester resin,
For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, other than polycarbonate, etc., in the condensation polymerization reaction of dicarboxylic acid or dicarboxylic acid ester and diol,
Aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid and / or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and aliphatic diols such as ethylene glycol and 1,4-butanediol and / or alicyclic rings such as cyclohexanediol Hard structural unit using an aromatic diol, polyethylene glycol as a diol,
Polyether diols having hydroxyl groups at both ends such as polytetramethylene glycol and / or aliphatic dicarboxylic acids such as sebacic acid, eicoic acid, dodecanedioic acid and dimer acid and / or alicyclic dicarboxylic acids. There is a copolymerized polyester resin or the like comprising a-(AB) -n-type block copolymer with a soft structural unit using an aromatic dicarboxylic acid and exhibiting the properties of a thermoplastic elastomer. By appropriately adjusting the composition ratio of the hard and soft structural units and the mixing ratio of these with the homopolymer, a polyester resin having desired and appropriate physical properties is prepared.

The acrylic resin may be, for example, a thermosetting resin obtained by homopolymerizing or copolymerizing an acrylic acid derivative such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylate or methacrylate as a main component. It is a plastic resin, particularly preferably a resin containing a methacrylic acid ester such as methyl methacrylate as a main component, for the purpose of improving flexibility and thermoformability, for example, a long-chain alkyl ester of methacrylic acid such as butyl methacrylate Or, an acrylate such as methyl acrylate, a monomer selected from methacrylic acid or acrylic acid or the like is added as a copolymerization component, and if necessary, other appropriate copolymerization components for the purpose of improving physical properties and the like. Additives and the like are appropriately added to prepare an acrylic resin having desired and appropriate physical properties.

Although the description of the other thermoplastic resins is omitted, the compounding ratio of various monomers, average molecular weight, molecular weight distribution, branch density and average branch length, stereomolecular structure, crystallinity or orientation state are basically omitted. It is basically common that the polymer is adjusted to the proper physical properties specified in the present invention by adjusting the compounding ratio and dispersion state of various polymers.

The kind of resin constituting the base sheet 1 used in the thermoformable decorative sheet of the present invention is basically not limited as described above, but among them, the above-mentioned acrylic resin can be used. Most desirable. The reason is that acrylic resin is essentially an amorphous resin and does not have a heterogeneous sea-island structure inside the resin, or even if it does, the difference in physical properties between them is small and peeling and stress concentration at the interface This is because they are unlikely to occur, so that local non-uniform deformation is less likely to occur during plastic deformation during thermoforming, and molding defects such as necking are less likely to occur.

When the intended decorative sheet for three-dimensional molding requires hiding, it is preferable to add a hiding pigment for imparting hiding to the thermoplastic resin constituting the base sheet 1. . As a method for imparting hiding properties to a decorative sheet, in addition to a method of adding a hiding pigment to the base sheet 1, for example, a printing ink or a coating agent containing the hiding pigment on the front or back surface of the base sheet 1 is used. There are also a method of providing a concealed solid layer, a method of applying a metal deposition layer on the front surface or the back surface of the base sheet 1, and the like. However, in the case of a decorative sheet for three-dimensional molding, in the case of a concealed solid layer or a metal vapor-deposited layer, the concealing property tends to be insufficient because these concealing layers are thinned or cracked by stretching during three-dimensional molding. On the other hand, if the concealing pigment is added to the base sheet 1 having a sufficient thickness compared to these, there is no such fear.
Even if a phenomenon (for example, a fine crack inside the resin or a change in the arrangement state of the resin molecules) that may cause whitening occurs in the base sheet 1 during molding, the base sheet 1 may As a result of being concealed by the concealing pigment contained therein, the design is not substantially affected as whitening.

As described above, the concealing pigment is a fine powdery pigment having a refraction index significantly higher than that of a resin serving as a dispersion medium, and reflects or refracts light at an interface due to a difference in the refractive index. The direct light transmission between the front and back surfaces of the sheet is prevented by the light scattering effect of the sheet, and the concealing property is developed. Since the refractive index of a general thermoplastic resin is about 1.5, a pigment having a refractive index of about 2.0 or more is generally selected as the opaque pigment, and light (visible light) In general, the particle size is 0.1 to 1 μm from the viewpoint of the scattering ability with respect to
A range of about m is used. In addition, the addition amount of the concealing pigment is preferably as large as possible from the viewpoint of concealing property. However, if the amount is too large, the resin may be embrittled and thermoformability may be impaired. Is preferably within the range.

Among such concealing pigments, pigments having high light absorbency are called color pigments because they exhibit a coloring effect by absorbing a part of the incident light. ,
It is referred to as a white pigment because it exhibits the effect of reflecting most of the incident light in the incident direction by the light scattering effect to make the color tone bright (white). Then, by selecting a pigment having a good balance between the light absorption coefficient and the refractive index, or by mixing and using the above-described color pigment and white pigment in an appropriate ratio, it is possible to obtain an arbitrary desired color tone. Can be done.

As the concealing pigment, various organic and inorganic pigments are known. In general, an inorganic pigment has a higher refractive index and an excellent concealing property than an organic pigment, and has a light fastness (fastness). It is preferable to use an inorganic pigment also from the viewpoint of durability and fastness because it is excellent in discoloration) and chemical resistance. Particularly in the case of a decorative sheet for three-dimensional molding as in the present invention, when the resin is stretched by three-dimensional molding, micro-peeling occurs between the resin and the inorganic pigment, and as a result of absorbing internal stress, excellent results are obtained. This has the effect of exhibiting improved moldability, which is not seen when organic pigments are used.

Among the inorganic pigments, coloring pigments include, for example, graphite, yellow iron oxide, cadmium yellow, titanium yellow, barium yellow, aureoline, molybdate orange, cadmium red, red stalk, leadtan, cinnabar, mars violet, Manganese violet, cobalt violet, cobalt blue, cerulean blue, ultramarine,
Navy blue, emerald green, chrome vermillion, chromium oxide, viridian, iron black, carbon black, etc. Examples of white pigments include titanium oxide (titanium white, titanium white), zinc oxide (zinc white), and basic lead carbonate (lead white). ), Basic lead sulfate, zinc sulfide, lithopone, titanox and the like.

Among them, pigments which are excellent in concealing properties and light resistance and which are suitable for decorative sheets in terms of color tone in terms of design, and iron oxide pigments such as red iron oxide, yellow iron oxide and iron black, and white pigments as coloring pigments It is preferable to use a titanium oxide pigment.

Of the above-mentioned acid iron-based pigments, the petiole is ferric oxide F
a red pigment consisting of e ₂ O ₃ (also called hematite),
Those having an average particle size of about 0.2 to 0.6 μm are used. For example, Anchor FR-110G manufactured by Toho Pigment Co., Ltd.
D, Ferro Color NF-150-P, manufactured by Nippon Fellow, Tetsuhara
NAT, Tone Sangyo SR-580, Toda Kogyo Toda Color 12
0ED, commercially available as Morishita Red Cloisonne, manufactured by Morishita Benara.

The yellow iron oxide is iron oxide hydroxide γ-FeO (O
H) A yellow pigment composed of (also known as leucite) or a hydrate thereof, and having an average particle size of about 0.3 to 0.8 μm, for example, Anchor FY-766 manufactured by Toho Pigment Co., Morishita dialect Morishita Yellow MTY-10 manufactured by Pattern Company, NYB-40 manufactured by Nippon Benza Pattern Company,
Toda Industry's Toda Color Y-1, Tone Sangyo's YP-100SB,
Toyo Shigyo Co., Ltd., Toshiki Synthetic Iron Yellow, BASF Sicotrans Ye
Commercially available as llow L 1916 and the like.

Iron black is a black pigment composed of ferrous tetroxide Fe ₃ O ₄ (also called magnetite), and has an average particle size of about 0.5 μm. For example, Morishita Bl.
ackMTB-10, Tone Sangyo's TB-50SB, Toda Kogyo's Toda
Color KN-320, commercially available as Toyo Synthetic Iron Black manufactured by Toyo Pigment Co., Ltd. By appropriately combining and using these iron oxide pigments, a wide range of color tones from yellow to ocher, brown, and black can be obtained.

The titanium oxide pigment is titanium dioxide TiO.
_{It is} a white pigment consisting of _{2, two} types of anatase type (also known as anatase) and rutile type (also called kinkoishi),
The refractive indices are 2.45 to 2.55 and 2.61 to 2.61, respectively.
It is 2.90, and the rutile type is preferable because it has excellent concealing properties due to the higher refractive index and also has excellent chemical stability and light resistance. Those having an average particle size of about 0.1 to 0.5 μm are used. For example, KR-310 manufactured by Titanium Industry Co., Ltd.
Commercially available as JR, Furukawa Mining Co., Ltd. FR-41, Ishihara Sangyo Co., Ltd. CR-50.

In addition, in addition to the iron oxide pigment and the titanium oxide pigment described in detail above, it is possible to use a small amount of another concealable or non-concealable inorganic or organic pigment for the purpose of adjusting the color tone. Absent. However, it is imperative that iron oxide pigments and titanium oxide pigments be mainly used,
The amount of other pigments used is preferably about 20% by weight or less as a percentage of the total pigment. It is preferable to select a pigment having high light resistance as the pigment used in combination, and it is preferable to use a phthalocyanine pigment such as cobalt blue or carbon black among inorganic pigments and a phthalocyanine pigment such as phthalocyanine blue among organic pigments. In addition, extenders such as silica, calcium carbonate, barium sulfate and the like can be used in combination as needed.

In addition, the thermoplastic resin constituting the base sheet 1 may include, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, One or more kinds of conventionally known various additives such as a lubricant, an antistatic agent, a flame retardant, and a filler may be added.

As the antioxidant, for example, phenol type,
For example, benzophenone, benzotriazole, salicylate, etc.
Cyanoacrylates, formamidines, oxanilides, etc., as light stabilizers, for example, hindered amines,
For example, a hindered phenol type, a sulfur type, a hydrazine type, etc. as a heat stabilizer, a phthalate ester type, a phosphate ester type, a fatty acid ester type, a fat, etc. Group A dibasic acid ester type, oxybenzoic acid ester type, epoxy type, polyester type, etc. Examples of the lubricant include fatty acid ester type, fatty acid type, metal soap type, fatty acid amide type, higher alcohol type, paraffin type, etc. As, for example, cationic, anionic, nonionic, zwitterionic, etc.
Examples of the flame retardant include bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium,
As a filler such as a boron-based or zirconium-based filler, for example, one or a mixture of two or more selected from calcium carbonate, barium sulfate, talc, rubble, kaolin, and the like is used.

The thickness of the base sheet 1 is not particularly limited.
For example, a sheet having the same thickness as a base sheet of a conventional decorative sheet for three-dimensional molding made of polyvinyl chloride resin can be used. Specifically, it is generally selected from the range of about 20 to 200 μm, and particularly preferably about 50 to 100 μm, although it depends on the use of the molded product, the type of the resin, the molding conditions, and the like. There is no particular limitation on the method of forming the base sheet 1,
For example, the base sheet 1 formed by any conventionally known molding method such as an extrusion molding method, an inflation molding method, a calendar molding method, and a cast molding method can be used.

The decorative processing to be performed on the base sheet 1 is performed for the purpose of imparting any desired design, such as a desired pattern or unevenness, to the intended decorative sheet for three-dimensional molding. For example, typical examples include formation of a pattern layer 3 and provision of an emboss 6 on the surface. Also,
For example, when the surface coloring and the color adjustment can be sufficiently achieved by coloring the base sheet 1 as in a plain decorative sheet for the purpose of merely surface coloring and color adjustment, the decoration is performed by coloring the base sheet 1. It is also possible to process, and instead of providing the picture layer 3 as a layer independent of the base sheet 1, the base sheet 1 itself is kneaded with a pigment or by sublimation or migration of a dye capable of melting and transferring. You may give a picture. Further, these decorative processes need not necessarily be performed directly on the base sheet 1, but may be performed indirectly via, for example, a transparent resin layer 2 described later.
However, in general, an appropriate pattern layer 3 is often provided on the front surface of the base sheet 1 or the back surface of the transparent resin layer 2 by a method such as a printing method.

The constituent material and the forming method of the picture layer 3 are not limited at all, and any image forming material or image forming method which has been conventionally applied to the picture layer of the decorative sheet for three-dimensional molding is appropriately applied. Can be. Specifically, for example, a printing ink or a coating agent obtained by dissolving or dispersing a colorant such as a dye or a pigment in a suitable solvent together with a suitable binder resin can be used.

Examples of the coloring agent include inorganic pigments such as carbon black, titanium white, zinc white, red iron oxide, navy blue and cadmium red, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazines. Organic pigments such as pigments, metal powder pigments such as gold powder, silver powder, copper powder, aluminum powder, bronze powder, fish scale powder, pearlescent pigments such as basic lead carbonate, bismuth oxide chloride, titanium oxide coated mica, fluorescent pigments, luminous Pigments and the like, or a mixture of two or more kinds selected therefrom can be used.

Further, as the binder resin, for example,
Acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, cellulose derivative , Various synthetic resins such as rubber-based resins, or their 2
Mixtures of more than one species, copolymers and the like can be used.
However, especially in the case of being provided in a solid form over a relatively large area, in order to follow the elongation of the base sheet 1 that is stretched along the uneven shape of the base material surface during three-dimensional molding, a flexible resin that is easily stretched is used. It is preferable to select.

Examples of the solvent include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane, and ethyl acetate, butyl acetate and acetic acid-2.
Ester organic solvents such as -methoxyethyl, acetic acid-2-ethoxyethyl, etc., alcoholic organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, methyl Ketone organic solvents such as isobutyl ketone and cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; various organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene and other organic solvents; and inorganic materials such as water. A solvent or a mixed solvent of two or more thereof can be used.

In addition, various types of additives such as extenders, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, stabilizers, curing agents, curing accelerators or retarders, if necessary. Can be appropriately added.

The method of forming the picture layer 3 is not particularly limited.
For example, conventionally known various printing methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method can be used. In addition, for example, when the entire surface is solid, in addition to the various printing methods described above, for example, a roll coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, and a flow coating method And various coating methods such as a dip coating method. In addition, for example, the hand-drawing method, the sumi-shi method,
Of course, it is also possible to perform a photographic method, a laser beam or electron beam drawing method, a partial vapor deposition method of metal or the like, an etching method, or the like, or a combination of a plurality of these methods.

When the transparent resin layer 2 is provided, the picture layer 3 may be provided on the base sheet 1 side before the base sheet 1 and the transparent resin layer 2 are laminated. It may be provided on the layer 2 side. Prior to the formation of the picture layer 3, if necessary, the printing surface of the base sheet 1 or the transparent resin layer 2 may be subjected to, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer. By performing a surface treatment such as a treatment, the base sheet 1
Alternatively, the adhesion between the transparent resin layer 2 and the picture layer 3 can be improved.

There is no particular limitation on the type of pattern constituted by the pattern layer 3 described above. For example, a wood pattern, a stone pattern, an abstract pattern, etc., which are widely used in the field of decorative sheets according to the prior art, or a simple coloring. For the purpose of adjusting color or color, a single-color solid color may be used. In short, any desired pattern can be adopted according to the intended use of the decorative sheet.

In the decorative sheet for three-dimensional molding of the present invention,
For the purpose of protecting the base sheet 1 and the picture layer 3 on the surface thereof from the outside, a transparent resin layer 2 may be provided on the surface thereof. Here, “transparent” of the transparent resin layer 2 preferably has high transparency, but it is sufficient that the transparent resin layer 2 has at least transparency enough to allow the picture layer 3 to be seen through. May be translucent or colored and transparent.

The kind of the resin constituting the transparent resin layer 2 is not particularly limited. For example, a melamine resin, an epoxy resin, an unsaturated polyester resin, a diallyl phthalate resin, a urethane resin, an aminoalkyd resin, etc. Thermosetting resin, or a curable resin such as an ionizing radiation curable resin such as an acrylate resin may be used. However, when these curable resins are used, the thickness is reduced in terms of flexibility and three-dimensional moldability. Is limited to an extremely thin layer, and sufficient surface protection performance cannot always be obtained. Therefore, the transparent resin layer 2 is preferably formed from a thermoplastic resin.

The kind of the thermoplastic resin constituting the transparent resin layer 2 is not particularly limited, but it is preferable to use a non-halogen resin in view of the object of the present invention. Specifically, for example, various non-halogen-based thermoplastic resins listed as candidates for the constituent resin of the base sheet 1 can be given, and even if the constituent resin of the base sheet 1 is the same kind of resin. It may be different. The thermoplastic resin forming the transparent resin layer 2 also has a dynamic elastic modulus of 4.0 at a frequency of 10 Hz in a temperature range of 50 ° C. to 90 ° C., similarly to the case of the thermoplastic resin forming the base sheet 1. × 10
It is generally considered preferable that the pressure is ⁸ Pa or more and 1.0 × 10 ¹⁰ Pa or less, and the dynamic loss is 6.0 × 10 ⁷ Pa or more and 6.0 × 10 ⁸ Pa or less. However, when the transparent resin layer 2 is thinner than the base sheet 1 or when the transparent resin layer 2 is made of a resin softer than the base sheet 1, the base sheet 1 has sufficient three-dimensional moldability. Is achieved, the dynamic elastic modulus and dynamic loss of the constituent resin of the transparent resin layer 2 do not necessarily need to be within the above numerical ranges.

Among the various thermoplastic resins described above, it is most preferable to use a thermoplastic olefin resin as the constituent resin of the transparent resin layer 2. The reason is that the thermoplastic olefin-based resin has a surface property such as whitening resistance at the time of stretching or bending, and solvent resistance, as compared with, for example, a thermoplastic acrylic resin recommended as a constituent resin of the base sheet 1. This is because a decorative sheet for three-dimensional molding can be easily realized with a good balance between three-dimensional moldability, design properties and surface physical properties.

The thermoplastic olefin resin includes:
For example, various homopolymers and copolymers including polyethylene resin, polypropylene resin, polybutene-1 resin, poly-4-methylpentene-1 resin and the like are known, and among them, polypropylene is most preferable for the purpose of the present invention. A series resin, that is, a homopolymer or a copolymer mainly composed of polypropylene, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and carbon other than propylene. Α-olefins of numbers 2 to 20, preferably ethylene, butene-1,4-methylpentene-
1, a co-monomer of hexene-1 or octene-1
A propylene-α-olefin copolymer containing 5 mol% or more can be exemplified. It is also possible to add modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber which are usually used for softening a polypropylene resin. .

The above-mentioned thermoplastic olefin-based resin may be added, if necessary, depending on the intended use of the decorative sheet for three-dimensional molding, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant. One or more conventionally known various additives such as an antistatic agent, a flame retardant, and a filler may be added. Specifically, for example, those exemplified as the additives to be added to the thermoplastic resin constituting the base sheet 1 can be used.

The thickness of the transparent resin layer 2 made of a thermoplastic olefin resin is not particularly limited, and may be, for example, equal to the thickness of the transparent resin layer in a conventional general multi-layer decorative sheet. In general, thicker sheets are more advantageous in terms of surface properties such as abrasion resistance and solvent resistance, weather resistance, design feeling such as painting feeling, depth feeling, emboss depth, etc. This is disadvantageous in terms of flexibility, conformability to the surface shape of the substrate during thermoforming, and the like, so that a thickness range that balances both is selected. Specifically, it is generally selected from the range of about 20 to 200 μm, and particularly preferably about 50 to 100 μm, although it depends on the use of the decorative sheet and the required quality corresponding thereto, the kind of the thermoplastic resin to be used, and the like. .

The method for forming the transparent resin layer 2 is not particularly limited, and any conventionally known method can be appropriately applied. Specifically, for example, the transparent resin layer 2 previously formed into a film or sheet shape is applied via a suitable adhesive such as a dry laminating adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, or an ionizing radiation-curable adhesive. A method of bonding, a method of directly bonding by means of thermocompression bonding or ultrasonic welding without using an adhesive, or a method of heating and melting a thermoplastic resin to form the transparent resin layer 2 and extruding it into a film or sheet. At the same time, a method suitable for the characteristics of the resin can be appropriately selected from various conventionally known methods, such as a method of laminating and bonding on the surface of the base sheet 1, and used.

In the latter method (extrusion laminating method), when the adhesiveness between the substrate sheet 1 and the transparent resin layer 2 is inferior, it is also known that the heat-sensitive adhesive Or an adhesive resin between the base sheet 1 and the transparent resin layer 2 is formed by co-extruding and laminating the constituent resin of the transparent resin layer 2 and a separately prepared thermal adhesive resin. By sandwiching the layer 5, the adhesiveness can be improved. Of course, both may be used in combination as needed.

On the surface of the transparent resin layer 2, an emboss 6 having a desired and appropriate pattern can be provided as necessary, as is conventionally known. There is no particular limitation on the type of the pattern of the emboss 6, and for example, various patterns such as a woodgrain (particularly a conduit pattern), a stonegrain, a Japanese paper, a cloth, a geometric pattern, or the like may be used. For example, it may be a simple matte, grain, hairline, suede, or the like. Further, the design of the embossment 6 can be synchronized with the pattern of the pattern layer 3 to further improve the design, but if it is not necessary, the pattern may be out of synchronization. It is also possible to provide a pattern emboss 6 including both a pattern synchronized with the picture and a pattern not synchronized with the picture.

The method of forming the emboss 6 is not particularly limited, but a mechanical embossing method using a metal embossing plate is most common. There is no particular limitation on the timing of forming the embossment 6, and any timing can be selected before, simultaneously with or after lamination of the transparent resin layer 2 with the base sheet 1. The embossing 6 having the same or different pattern can be applied a plurality of times at a plurality of times selected from the following. The concave portion of the embossment 6 may be filled with a coloring agent 7 by a technique such as a wiping method as necessary, so that a decorative sheet having a color pattern synchronized with the surface irregularity pattern and having excellent design properties. Can be obtained.

Further, a top coat layer 8 can be provided on the surface of the transparent resin layer 2 for the purpose of imparting more excellent surface physical properties to the surface of the decorative sheet. As the constituent material of the top coat layer 8, any material selected from various known top coat agents conventionally used as constituent materials of the top coat layer of the decorative sheet according to the related art can be used. In general, it is necessary to have at least transparency so that the base can be seen through, and to have surface properties such as abrasion resistance, abrasion resistance, solvent resistance, and stain resistance required by the use of the decorative sheet. For this purpose, it is preferable to use a material containing a curable resin as a main component.

Specific examples of the constituent material of the top coat layer 8 include melamine resins, phenol resins,
Urea resin, epoxy resin, aminoalkyd resin,
A thermosetting resin such as a urethane resin, a polyester resin, or a silicone resin, or an ionizing radiation-curable resin such as an acrylic resin can be suitably used. If necessary, various additives such as a gloss adjusting agent, a lubricant, an antistatic agent, an anti-condensation agent, an antibacterial agent and an antifungal agent can be appropriately added.

The method of forming the top coat layer 8 is not particularly limited. For example, gravure coating, roll coating, dip coating, air knife coating, knife coating, comma coating, die coating, lip coating,
A conventionally known arbitrary coating method such as a kiss coating method, a rod coating method, a spray coating method, a flow coating method and the like can be appropriately applied.

If the adhesion between the transparent resin layer 2 and the top coat layer 8 is insufficient, the surface of the transparent resin layer 2 may be subjected to, for example, corona treatment, ozone By performing a surface treatment such as treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment, the adhesion between the transparent resin layer 2 and the top coat layer 8 can be improved.

As described above, the decorative sheet for three-dimensional molding according to the present invention, like the conventional decorative sheet for three-dimensional molding, can be applied to the surface of various base materials such as a wooden base material and an inorganic base material, for example, by vacuum coating. It is used by being adhered and laminated (laminated) by a three-dimensional molding method such as a molding method or a vacuum pressure molding method. Generally, in the case of the adhesion, for example, a urethane-based or vinyl acetate-based suitable Is used, but the adhesiveness with the thermoplastic resin constituting the base sheet 1 may be insufficient depending on the kind of the adhesive. In preparation for such a case, it is preferable to provide a primer layer 9 made of a resin having excellent adhesion to the laminating adhesive on the back surface of the base sheet 1.

As the primer layer 9, various primers such as urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer and the like are known. The material selected according to the base sheet 1 made of is used. When powder such as silica, alumina, calcium carbonate, barium sulfate, or the like is added to the primer layer 9, the surface of the primer layer 9 is roughened, so that blocking during winding and storage of the decorative sheet can be prevented. In addition, it is possible to improve the adhesiveness with the laminating adhesive by the anchoring effect.

[0057]

EXAMPLE The thickness of a pigment mainly composed of an inorganic pigment (iron oxide tea, iron oxide loess, titanium oxide white) and containing a small amount of carbon black black and cobalt blue (or phthalocyanine blue) in an amount of 5% by weight. 200 μm colored acrylic resin film manufactured by Kyowa Leather Industry Co., Ltd. (dynamic elastic modulus 1.0
× 10 ⁹ Pa, dynamic loss 8.0 × 10 ⁷ Pa), corona treatment on both sides to adjust the surface wetting index to 38 dyn / cm or more, and apply wood grain pattern on the surface with urethane gravure printing ink for building materials Is printed, and a thickness of 20 μm is printed on the printing surface.
m of an ethylene-ethyl acrylate adhesive resin layer,
A 90 μm thick transparent resin layer of a random polymerization polypropylene resin to which 0.2% by weight of a light stabilizer and 0.3% by weight of an ultraviolet absorber are added is sequentially laminated by a co-extrusion lamination method. A two-component curable urethane resin-based surface protective layer was formed on the surface of the film by a gravure coating method so as to have an applied amount of 4 g / m ² after drying, thereby producing a decorative sheet of the present invention.

The obtained decorative sheet was previously coated on the surface with aqueous 2
Coating amount of liquid urethane resin adhesive after drying 10 g / m ²
The surface of a wooden substrate having a surface irregularity with a radius of curvature of 0.5, which is obtained by coating and drying, is coated with a sheet temperature of 7 using a vacuum forming machine.
When three-dimensionally molded and laminated at 0 ° C., it sufficiently follows the molding speed and the residual of internal stress is small, molding defects such as necking and pattern flow, and design problems due to whitening of the transparent resin layer on the surface, etc. None, and a good laminated product could be obtained. Further, the surface physical properties such as surface hardness, scratch resistance, and solvent resistance were all practically acceptable.

[0059]

According to the decorative sheet for three-dimensional molding of the present invention, the dynamic elastic modulus at a temperature of 50 ° C. to 90 ° C. at a frequency of 10 Hz is 4.0 × 10 ⁸ Pa or more and 1.0 × 10 ¹⁰ Pa.
Or less, and the dynamic loss is 6.0 × 10 ⁷ Pa or more and 6.0 or more.
By using the substrate sheet comprising a thermoplastic resin or less × 10 ⁸ Pa, even those using a thermoplastic resin non-halogenated alternative to conventional polyvinyl chloride resin, for three-dimensional molding by thermal Excellent deformation response, such as cracks and whitening, poor molding, drawdown, pattern flow,
The present invention has an excellent advantage that a high-quality three-dimensional molded laminate product free from problems such as internal residual stress can be manufactured with high productivity.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a laminated structure of an example of a three-dimensionally formed decorative sheet of the present invention.

[Explanation of symbols]

 1 Base material sheet 2 Transparent resin layer 3 Picture layer 4 Anchor layer 5 Adhesive resin layer 6 Emboss 7 Colorant 8 Top coat layer 9 Primer layer

Continued on the front page (72) Inventor Takashi Tominaga 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. F-term (reference) 2E110 AA28 AB22 AB23 BA05 BA12 GA03Z GA32Z GB43Z GB44Z GB47Z GB52Z 4F100 AA01 AK01A AK01B AK07 AK21 AK25 AK71 AR00A BA03 BA10A BA10B CA05 CA07 CA13 CC03 EH20 GB08 GB48 GB81 HB00C HB01 HB21 HB31 JB16A JK07A JL01 JL02 JN01B 4F208 AA03 AA13 AA14 AA21 AA24 AA29 MB03 AD05 AD01 AD03 MB20 MG11 MG22

Claims (2)

[Claims] 1. Frequency 1 in a temperature range of 50 ° C. to 90 ° C.
The dynamic elastic modulus at 0 Hz is 4.0 × 10 ⁸ Pa or more and 1.0 × 10 ¹⁰ Pa or less, and the dynamic loss is 6.0 × 1 Pa.
0 ⁷ base sheet consisting Pa to 6.0 × 10 ⁸ Pa or less thermoplastic resin, the decorative sheet for three-dimensional molding, characterized by comprising the decorative processing is given. 2. The decorative sheet for three-dimensional molding according to claim 1, wherein a transparent resin layer is provided on the surface of the base sheet.