JPH1017679A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet having excellent impact resistance and good elongation and therefore being ready for notching by using a specified flexible polypropylene resin composition as the material. SOLUTION: This sheet S is prepared by forming a patterned layer 4 on a sheet 1 made from a flexible polypropylene resin composition comprising 10-90wt.% boiling-heptane-soluble polypropylene obtained by polymerizing propylene in the presence of a catalyst comprising a solid catalyst component essentially consisting of Mg, Ti, a halogen and an electron donor, an organoaluminum compound and an alkoxylated aromatic compound represented by the formula (wherein R<1> is a 1-20C alkyl; R<2> is a 1-10C hydrocarbon group or the like; m is 1-6; and n is 0 or an integer of 1 to (6-m)) and having a number-average molecular weight, Mn, of 25,000 or above and a Mw to Mn ratio of 7 or below (wherein Mn is the number-average molecular weight) and 90-10wt.% boiling-heptane-insoluble polypropylene having a melt index of 0.1-4g/10min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet suitably used for interior decoration of buildings, surface decoration of fittings, interior decoration of vehicles, and the like.

[0002]

Conventionally, as a decorative sheet used for the above-mentioned applications, a polyvinyl chloride resin sheet has been used, and a decorative sheet has been subjected to a decorative treatment by printing, embossing or the like. JP-B-28-5036 and JP-B-58-14312) have been used for a long time. However, in recent years, a decorative sheet using a polyolefin resin sheet such as polyethylene or polypropylene has been used instead. (Japanese Patent Laid-Open No. 54-62
No. 255 gazette) has appeared.

[0003] Among them, the former decorative sheet using a polyvinyl chloride resin sheet has a drawback that heat resistance is insufficient or bleeding (exudation) of a plasticizer results in poor surface contamination resistance. . Further, in the latter decorative sheet using a polyolefin-based resin sheet, usually isotactic resin is used as the polyolefin-based resin, and since it becomes a sheet having high crystallinity, the above-mentioned polyvinyl chloride-specific Although the drawback can be improved, there is a drawback that cracking occurs during V-cut processing due to lack of flexibility or low impact resistance. In particular, the heat history at the time of embossing from heating softening to embossing plate pressing to cooling causes crystallization to progress and the sheet becomes brittle, and this tendency is strengthened.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a decorative sheet which is excellent in impact resistance and has a good elongation, and therefore has a good V-cut processing. Is to do.

[0005]

Means for Solving the Problems To solve the above problems, in the present invention, (A)
(A) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an organoaluminum compound, and (c) a general formula

Embedded image (Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, n is 0 or 1 to (6 The number average molecular weight (Mn) obtained by polymerizing propylene in the presence of a catalyst comprising a combination of an alkoxy group-containing aromatic compound represented by the following formula:
10 to 90% by weight of a boiling heptane-soluble polypropylene having a ratio Mw / Mn of 0 or more and a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 7 or less; and (B) a melt index of 0.1 to 4 g / A sheet made of a soft polypropylene resin composition composed of 90 to 10% by weight of a heptane-insoluble polypropylene boiling for 10 minutes was used, and a decorative sheet was formed on the sheet to obtain a decorative sheet.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The soft polypropylene resin composition used as a base sheet of a decorative sheet in the present invention has an elongation at break (T _B ) of 400% or more, preferably 500-70.
Residual elongation (PS ₁₀₀ ) after elongation of 0% and 100% is 80%
Or less, preferably 50% to 75%, and the ratio M _B / M _Y at break Stress and (M _B) and at yield stress (M _Y) is 1.
It is important that it is at least 0, preferably in the range of 1.5 to 3.5. If these mechanical properties deviate from the above ranges, the object of the present invention cannot be sufficiently achieved.

In the soft polypropylene resin composition, the atactic polypropylene as the component (A) is soluble in boiling heptane and has a number average molecular weight (M
n) is 25,000 or more, preferably 30,000 to 6
Weight average molecular weight (Mw) in the range of 000
And a number average molecular weight (Mn) having a ratio Mw / Mn of 7 or less, preferably 2 to 6. This M
If the n is less than 25,000 or the Mw / Mn ratio exceeds 7, the effect of the resulting resin on the mechanical properties of the atactic polypropylene is not sufficiently exhibited, and the stress at break of the obtained resin ( The object of the present invention is achieved when the ratio of (M _B ) to the stress at yield (M _Y ) is less than 1.0, or the residual elongation (PS ₁₀₀ ) after 100% elongation exceeds 80%. Absent.

The atactic polypropylene of component (A) may be a homopolymer of propylene, or may contain other propylene units having a carbon number of not more than 40% by weight, preferably not more than 30% by weight. It may be a propylene copolymer containing an olefin unit. Further, this atactic polypropylene may be used alone or in combination of two or more.

The atactic polypropylene of the component (A) can be produced by a known method (JP-A-63-243106). In particular,
(A) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an organoaluminum compound, and (c) a general formula

Embedded image (Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, n is 0 or 1 to (6 The desired atactic polypropylene can be obtained by polymerizing propylene in the presence of a catalyst comprising a combination of an alkoxy group-containing aromatic compound represented by -m).

In the above soft polypropylene resin composition, a melt index (MI) is used as a component (B).
However, boiling heptane-insoluble crystalline isotactic polypropylene of 0.1 to 4 g / 10 min is used. If the melt index is less than 0.1 g / 10 minutes, the melting properties are low, and sheet forming becomes difficult. If the melt index exceeds 4 g / 10 minutes, the mechanical strength becomes insufficient and V-cut processing cannot be performed well.

The isotactic polypropylene as the component (B) may be a homopolymer of polypropylene having isotactic stereoregularity, or a copolymer of propylene having the stereoregularity with another α-olefin. It may be a copolymer. Other α- used in this copolymer
As the olefin, those having 2 to 8 carbon atoms, for example, ethylene, butene-1, pentene-1, heptene-1, octene-1 and the like are preferable, and among them, ethylene and butene-
1 is preferred. As the copolymer, a block copolymer or a random copolymer containing the other α-olefin unit in an amount of usually 40% by weight or less, preferably 30% by weight or less is used.

The preferred isotactic polypropylene of the component (B) is propylene homopolymer and 1 to 30% by weight of ethylene unit, preferably 3 to 30% by weight.
A random copolymer or block copolymer of propylene and ethylene containing 25% by weight is exemplified. The method for producing such isotactic polypropylene is not particularly limited, and any method can be selected from the methods conventionally used for producing crystalline polypropylene.

In the flexible polypropylene resin composition used in the present invention, the isotactic polypropylene of the component (B) may be used alone or in combination of two or more. Further, the atactic polypropylene of the component (A) and the isotactic polypropylene of the component (B) have a content of the component (A) of 10 to 90% by weight,
It is preferably used in an amount of 25 to 80% by weight, and the content of the component (B) is 90 to 10% by weight, preferably 75 to 20% by weight. When the content of the component (A) is 10
Is less than weight percent, at yield stress of the resin (M _Y) becomes too large, the ratio M _B / M _Y with at break stress (M _B) and at yield stress (M _Y) is less than 1.0, And the residual elongation (PS ₁₀₀ ) after 100% elongation is also larger than 80%,
If the object of the present invention is not achieved, on the other hand, if it exceeds 90% by weight, the stress at break (M _B ) becomes too small, and the M _B /
_MY ratio is less than 1.0, and mechanical strength decreases,
The object of the present invention cannot be achieved.

Although it is possible to directly print a pattern or apply an adhesive on the flexible polypropylene resin sheet itself, it is necessary to make the adhesive strength between the ink or the adhesive and the flexible polypropylene resin sheet stronger. In some cases, the surface of the soft polypropylene resin sheet is subjected to easy adhesion treatment such as application of an easy adhesion layer, corona discharge treatment, and plasma treatment. Acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, and chlorinated polyethylene are used as the easy-adhesion layer (also called a primer layer or an anchor layer), and chlorinated polypropylene is particularly desirable. .

Examples of the acrylic include poly (methyl meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate / (meth) acryl. Such as butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate, ethylene / methyl (meth) acrylate, and styrene / methyl (meth) acrylate A) Acrylic resin composed of a homopolymer or a copolymer containing an acrylate ester (however, (meth) acryl here means acryl or methacryl is the same hereinafter) is used.

Polyurethane is mainly composed of polyol (polyhydric alcohol) and isocyanate as a crosslinking agent (curing agent).
Polyurethane. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, and polyether polyol. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4
Aromatic isocyanates such as diphenylmethane diisocyanate, or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used.

The decoration treatment applied to the soft polypropylene resin sheet includes coloring (transparent or opaque) by adding a pigment, printing of a pattern, embossing (heating press),
There are irregular pattern shaping by hairline processing and the like. FIG. 1 shows a decorative sheet produced by performing these decorative treatments.

The decorative sheet S shown in FIG. 1A is obtained by adding a pigment 2 to a soft polypropylene resin sheet 1 and coloring the sheet. Pigments include titanium white, zinc white, red petals,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, etc .; Dyes), metal pigments such as aluminum and brass, and pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. These are added and dispersed as powder or flaky foil pieces. Coloring by adding a pigment may be either transparent coloring or opaque (concealing) coloring.

The decorative sheet S shown in FIG. 1B is obtained by forming an easy-adhesion layer 3 on a soft polypropylene resin sheet 1 and forming a pattern layer 4 thereon by printing. The pattern is printed by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like, and the pattern is formed with ink (or paint). Examples of the pattern include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather crest pattern, a geometric figure, a character, a symbol, and a solid surface. The pattern is provided on the front, back, front and back surfaces, or between layers of the sheet. As the ink (or paint), chlorinated polyethylene, chlorinated polyolefin such as chlorinated polypropylene, polyester, polyurethane, acrylic, vinyl acetate, vinyl chloride / vinyl acetate copolymer, cellulose resin, or the like may be used. A mixture of two or more kinds, to which known pigments listed above are added, is used. When printing directly on a soft polypropylene resin sheet, chlorinated polyolefin, polyurethane or the like is preferred as a binder in terms of adhesiveness, but if an easy-adhesion primer is appropriately selected and a layer is formed, other binders may be used. High adhesiveness is obtained.

The decorative sheet S shown in FIG. 1 (c) is obtained by forming an embossed pattern (concave portion 5) on the soft polypropylene resin sheet 1 by embossing (heating press), hairline processing or the like. The embossing process heats and softens the soft polypropylene resin sheet 1, presses it with an embossing plate,
It is shaped, cooled and fixed to form a concavo-convex pattern, and can be performed using a known single-wafer or rotary embossing machine. Examples of the uneven shape include a wood grain board conduit groove, a stone board surface unevenness (granite cleavage face, etc.), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like.

Further, if necessary, as shown in FIG.
The colored ink 6 may be filled into the concave portion 5 having the concave and convex pattern by a known wiping method (for example, see Japanese Patent Publication No. 58-14312). The same coloring ink as described above can be used. However, in terms of wear resistance,
It is preferable to use a two-component curable urethane resin as the binder.

As a decoration process, a soft polypropylene resin sheet may be provided with a metal thin film. The metal thin film is formed using a metal such as aluminum, chromium, gold, silver, and copper by a method such as vacuum evaporation and sputtering. Alternatively, a combination of these may be used. The metal thin film may be provided on the entire surface or partially in a pattern.

The decorative sheet S shown in FIGS. 1 and 2 is a single-layer soft polypropylene resin sheet 1 which has been subjected to a decoration process, while the decorative sheet S shown in FIG. 3 is a soft polypropylene resin sheet 1a, 1b are laminated in two layers.

In the decorative sheet S shown in FIG. 3A, a pattern layer 4 is formed by printing on one soft polypropylene resin sheet 1a, and another soft polypropylene resin sheet 1 is formed thereon.
b is laminated. The decorative sheet S shown in FIG. 3B is obtained by forming a pattern layer 4 on a soft polypropylene resin sheet 1a colored by adding a pigment 2 by printing, and laminating another soft polypropylene resin sheet 1b thereon. is there. The decorative sheet S shown in FIG. 3C is obtained by forming a pattern layer 4 by printing on a soft polypropylene resin sheet 1a colored by adding a pigment 2 and laminating another soft polypropylene resin sheet 1b thereon. The uneven pattern 5 is formed by embossing.

The decorative sheet shown in FIG. 4 is obtained by laminating a transparent resin sheet other than polyolefin on a soft polypropylene resin sheet. In this example, a pattern layer 4 is formed by printing on a colored soft polypropylene resin sheet 1 to which a pigment 2 has been added, a transparent resin sheet 7 is laminated thereon, and an embossed pattern 5 is formed by embossing. is there. As the resin other than the polyolefin, a resin selected from any of an acrylic resin, an ethylene / vinyl alcohol copolymer resin, and a thermoplastic polyester resin is used.

As the acrylic resin, poly (methyl meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate / (meth) acrylate Such as butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate, ethylene / methyl (meth) acrylate, and styrene / methyl (meth) acrylate Acrylic resin consisting of a homo- or copolymer containing (meth) acrylic acid ester. The thickness of this acrylic resin sheet is 20-100μ
m.

The ethylene / vinyl alcohol copolymer resin layer is formed by lamination by hot melting or by using an adhesive such as a two-component curable urethane resin or melt-extrusion (extrusion) coated polyethylene. It is formed by laminating a film on a resin layer serving as a substrate, and has a thickness of 10 to 100 μm.
And more preferably 12 to 25 μm. As the film, a film obtained by molding a random copolymer of ethylene and vinyl alcohol into a film is generally used. The ethylene / vinyl alcohol copolymer resin film may be any of a stretched film and an unstretched film. However, it is preferable to use an unstretched film in terms of film flexibility, bending workability, embossability, and the like. preferable. Ethylene-vinyl alcohol copolymer films have different thermoplastic copolymers and water resistance, as well as the rigidity, oil resistance, solvent resistance, and chargeability of vinyl alcohol, by changing the proportion of copolymerized components. Can be arbitrarily adjusted, but the ethylene component is preferably 30 to 45 mol% in order to obtain a film having both characteristics as much as possible and having excellent workability. If it is less than 30 mol%, the thermoplasticity, heat processing suitability and water resistance are inferior, and if it exceeds 45%, the rigidity, oil resistance, solvent resistance, and antistatic properties are inferior.

The thermoplastic polyester resin is represented by polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate / isophthalate copolymer and the like, and aromatic components such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as acid components. It is a copolymer obtained as an ester of an aliphatic dicarboxylic acid and an aliphatic diol such as ethylene glycol, diethylene glycol, butanediol, or hexanediol as an alcohol component. Although any of stretched and unstretched sheets can be used, unstretched sheets are preferable from the viewpoint of suitability for embossing and forming such as V-cutting.

In order to impart better weather resistance (light resistance) to the transparent resin sheet, an ultraviolet absorber and / or a light stabilizer can be added. The addition amount of the ultraviolet absorber and the light stabilizer is usually about 0.5 to 10% by weight, but it is generally preferable to use the ultraviolet absorber and the light stabilizer together. Organic substances such as benzotriazole, benzophenone, salicylate, etc.
Alternatively, inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used. As the light stabilizer, a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a radical scavenger such as a piperidine radical scavenger can be used. The above ultraviolet absorbers and light stabilizers are common to acrylic, ethylene / vinyl alcohol copolymer, polyester and polyolefin.

As the filler, calcium carbonate,
Powders such as barium sulfate, clay, and talc are used, and these are added in appropriate amounts as needed.

As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy. The addition amount is about 10 to 150 parts by weight based on 100 parts by weight of the polyolefin resin.

The surface of the decorative sheet according to claim 1, further comprising an acrylic resin, an ethylene / vinyl alcohol copolymer resin,
Or a method of laminating a transparent resin sheet selected from thermoplastic polyester resin, such as melt extrusion coating (extrusion coating), fusion by hot pressing, or two-component curable polyurethane resin, polyester resin, etc. Dry lamination using an adhesive of the type described above.

The decorative sheet of the present invention may be a single-layer soft polypropylene resin sheet subjected to a decoration treatment (FIGS. 1 and 2), a laminate of two soft polypropylene resin sheets (FIG. 3), or a soft polypropylene sheet. A transparent resin sheet other than polyolefin selected from acrylic resin, ethylene-vinyl alcohol copolymer resin, and thermoplastic polyester resin laminated on the surface of the resin sheet (Fig. 4), a laminate of three or more layers (Not shown).

The decorative sheet of the present invention can be laminated on another adherend (backing material). The adherend is the final product, and a decorative sheet may be laminated to make up the surface, or if necessary, may be applied to the back of the decorative sheet to reinforce the mechanical strength of the decorative sheet or to provide concealment. In some cases, bodies are stacked. When laminating on the adherend, the adhesive layer may be omitted if the decorative sheet itself can be adhered to the adherend (at a thermal melting point or the like). If the decorative sheet itself does not adhere to the adherend, an appropriate adhesive is used.

FIGS. 5 and 6 are sectional views showing a decorative sheet laminated on an adherend together with the adherend. FIG. 5 shows the decorative sheet S shown in FIG. 6 shows a decorative sheet S obtained by printing a pattern layer 4 on a soft polypropylene resin sheet 1 by printing on a flat plate, which is an adherend 9, via an uneven body as an adherend 10. It is obtained by laminating on the surface of a product by a simultaneous molding lamination method (described later).

The object to be adhered may be a plate material of various materials (FIG. 5), a plate material such as a curved surface plate, a three-dimensionally shaped article (FIG. 6), or an article of various shapes such as a sheet (or film).
Examples of materials used for board materials, three-dimensionally shaped articles, and sheets (films) include wood veneer, wood plywood, particle board, wood board such as medium density fiber board (MDF), wood board such as wood fiber board, Metals such as iron and aluminum, acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS, phenolic resin, polyvinyl chloride, cellulose resin, and rubber are resins. Materials used exclusively as plate materials or three-dimensional articles include ceramics such as glass and ceramics, and ALC
There are non-cement ceramic materials such as cement, such as (foamed lightweight concrete), calcium silicate, and gypsum. Materials used exclusively as a sheet (or film) include paper such as high-quality paper and Japanese paper, and nonwoven fabric or woven fabric made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resin.

As a method of laminating a decorative sheet on these various adherends, for example, a method of laminating a plate-like base material by pressing with a pressure roller via an adhesive layer, Japanese Patent Publication No. Sho 50
As described in JP-A-19132, JP-B-43-27488, etc., a decorative sheet is inserted between the male and female molds for injection molding, the molds are closed, and the molten resin is injected from the male gate. After filling and cooling, the decorative sheet is adhered and laminated on the surface simultaneously with the molding of the resin molded product, so-called simultaneous injection molding laminating method, JP-B-56-45768,
As described in Japanese Patent Publication No. 60-58014, etc.,
A so-called vacuum press lamination method in which a decorative sheet is opposed to or placed on the surface of a molded article with an adhesive layer therebetween, and the decorative sheet is laminated on the surface of the molded article by a pressure difference due to vacuum suction from the molded article side, JP-B-61-5895, JP-B-3
As described in JP-A-2666, etc., while supplying a decorative sheet through an adhesive layer in the long axis direction of a columnar substrate such as a cylinder and a polygonal column, a plurality of rollers having different directions are used to form a columnar substrate. A so-called lapping method in which a decorative sheet is sequentially adhered to a plurality of side surfaces constituting a body by pressure bonding, which is a so-called lapping method, disclosed in Japanese Utility Model Publication No. 15-31122, and Japanese Patent Laid-Open No. 48-47972.
As described in Japanese Patent Laid-Open Publication No. H10-15095, first, a decorative sheet is laminated on a plate-like base material via an adhesive layer, and then the decorative sheet and the plate-like base material are provided on the surface of the plate-like base material opposite to the decorative sheet. Cut into a V-shaped or U-shaped groove reaching the interface with the material, then apply an adhesive in the groove, and then bend the groove to form a box or columnar body. There is a V-cut or U-cut processing method or the like. FIG. 7 is an explanatory view of the V-cut processing method.
FIG. 7A is a cross-sectional view showing a state in which a V-shaped groove 12 is cut in an adherend 11 on which a decorative sheet S is bonded via an adhesive layer 8, and FIG. It is sectional drawing which shows the state which bent.

In particular, as a method of bonding the decorative sheet of the present invention to a three-dimensional object having irregularities, of the above-mentioned methods, a simultaneous injection molding laminating method, a vacuum press laminating method, a lapping method, a V-cut method and the like are preferable.

The decorative sheet of the present invention is used for various applications by laminating on various adherends and subjecting it to a predetermined molding process. For example, interior decoration of buildings such as walls, ceilings and floors, doors, surface makeup of fittings such as handrails, furniture, surface makeup of cabinets for light electric and OA equipment, vehicle interiors such as cars and trains, aircraft interiors, window glass Such as makeup.

[0040]

【Example】

(Example 1) 100 parts by weight of a soft polypropylene resin (“E-2900” manufactured by Idemitsu Petrochemical) was used as a base and styrene-
The surface of a transparent unstretched sheet (top sheet) having a thickness of 80 μm to which 10 parts by weight of butadiene rubber, 3 parts by weight of a hindered amine radical scavenger, and 2 parts by weight of a benzotriazole ultraviolet absorber are added, is subjected to corona treatment, Hexamethylene diisocyanate as a curing agent, a urethane-based two-component curable resin having acrylic polyol as a main component as a binder, and using an ink obtained by adding a pigment to the binder,
A plate pattern was formed by gravure, and a 3 μm-thick easily-adhesive primer layer was formed by a gravure coating method using a chlorinated polypropylene-based primer.

The decorative sheet obtained above was placed on a polyethylene 100 with the primer surface facing the base sheet.
A styrene-butadiene rubber (10 parts by weight), calcium carbonate as a filler, and a 80 μm-thick base sheet to which a red pigment and carbon black are added as coloring pigments are superposed on a weight basis, and a rotary hot press embossing machine. The two sheets were laminated and adhered to each other. At that time, laminate (nip)
Using a metal roll as the roll coming to the top sheet side among the rolls, as a embossing roll formed by forming irregularities of zelkova wood channel grooves on the surface, the decorative sheet and the adherend base material are laminated and adhered, and at the same time the decorative sheet is bonded. An uneven pattern was embossed on the surface. The sheet heating temperature during embossing is 155 ° C
(Heating drum temperature), the pressing pressure of the embossing plate is 3 kg /
cm ² , the sheet feeding speed was 15 m / min, and the embossing plate surface temperature was 40 ° C.

(Comparative Example 1) Instead of the topsheet and the base sheet of Example 1, a sheet having a thickness of 80 μm and made of biaxially stretched isotactic polypropylene having a draw ratio of 3 to which 10 parts by weight of an olefin elastomer was added was used. Using.
Others were the same as Example 1.

[Performance Evaluation Test] Table 1 shows the results of comparing the decorative sheets of Examples 1 to 4 and the decorative sheets of Comparative Examples 1 to 3 in various physical properties.

[Test Method] Transparency The haze value is measured with a direct-reading haze meter manufactured by Toyo Seiki Co., Ltd. It is intended for a single layer of a soft polypropylene resin sheet without decorative treatment. 2. Weather resistance Irradiation is performed for up to 3000 hours with a carbon arc lamp type sunshine weatherometer, and it stops when the appearance change such as cracks, whitening, discoloration, etc. becomes significant (visual judgment). Black panel temperature 63 ° C. The sample after irradiation is visually evaluated. 3. Heat resistance Heat in an 80 ° C. atmosphere for 3 minutes, and visually check the discolored state before and after the heating. 4. Sheet breakage / crack during V-cut Using a glue of ethylene-vinyl acetate copolymer emulsion, glue the base sheet side of the decorative sheet to lauan plywood with a thickness of 10 mm, and then laminate the sheet. On the opposite side to the section V reaching the interface between the plywood and the adhesive layer
The groove is cut in the shape of a letter, an adhesive of an ethylene / vinyl acetate copolymer emulsion is applied to the groove, and then the plywood is bent so that the groove is closed to form an L-shaped plywood (cross section). ). The ambient temperature during processing was 10 ° C. 5. Reproduction of uneven pattern Evaluation was made visually. 6. Adhesive force A sample obtained by cutting a laminate of a decorative sheet / base sheet or a face sheet / decorative sheet into a width of 1 cm was pulled in a direction perpendicular to the width direction at a pulling speed of 50 mm / min and an ambient temperature of 2.
At 0 ° C., a tensile test was performed such that the tensile directions of both samples were 180 ° with each other, and the tension at the time of peeling of the interlayer interface was measured. 7. Heating dimensional shrinkage ratio The decorative sheet is heated in an atmosphere of 100 ° C. for 30 minutes, and is obtained by [(dimension after heating) − (dimension before heating)] × 100 /
(Dimensions before heating) = Heat dimensional shrinkage (%) was determined for each of the longitudinal direction (MD) and the width direction (TD).

[0045]

[Table 1]

[0046]

As described above, the decorative sheet of the present invention uses a soft polypropylene resin having good mechanical properties as an elastomer for its base sheet, so that the decorative sheet has cracks and cracks during V-cut processing. Will not occur.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a decorative sheet according to the present invention.

FIG. 2 is a sectional view showing another example of the decorative sheet according to the present invention.

FIG. 3 is a sectional view showing another example of the decorative sheet according to the present invention.

FIG. 4 is a sectional view showing another example of the decorative sheet according to the present invention.

FIG. 5 is a cross-sectional view showing a decorative sheet laminated on an adherend together with the adherend.

FIG. 6 is a sectional view showing a decorative sheet laminated on an adherend together with the adherend.

FIG. 7 is an explanatory diagram of a V-cut processing method.

[Explanation of symbols]

 S Cosmetic sheet 1 Soft polypropylene resin sheet 2 Pigment 3 Easy adhesion layer 4 Pattern layer 5 Depression 6 Colored ink 7 Transparent resin sheet 8 Adhesive layer 9 Adherend 10 Adherend 11 Adherend 12 V-shaped groove

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B32B 27/36 B32B 27/36 33/00 33/00 C08F 4/642 MFG C08F 4/642 MFG C08L 23/12 LCD C08L 23/12 LCD

Claims (3)

[Claims] 1. (A) (a) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an organoaluminum compound, and (c) a general formula: (Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, n is 0 or 1 to (6 The number average molecular weight (Mn) obtained by polymerizing propylene in the presence of a catalyst comprising a combination of an alkoxy group-containing aromatic compound represented by the following formula:
10 to 90% by weight of a boiling heptane-soluble polypropylene having a ratio Mw / Mn of 0 or more and a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 7 or less; and (B) a melt index of 0.1 to 4 g / A decorative sheet, characterized in that a sheet made of a soft polypropylene resin composition consisting of 90 to 10% by weight of boiling heptane-insoluble polypropylene for 10 minutes is subjected to a decoration treatment. 2. An elongation at break (T _B ) of at least 400%
Residual elongation after 0% elongation (PS ₁₀₀₎ 80% or less, and at break stress (M _B) and at yield stress (M _Y) ratio of M _B /
Decorative sheet according to claim 1 using a soft polypropylene resin composition M _Y is 1.0 or more. 3. A decorative resin sheet according to claim 1, further comprising a transparent resin sheet selected from an acrylic resin, an ethylene / vinyl alcohol copolymer resin, and a thermoplastic polyester resin. A decorative sheet characterized by being made.