JP2010167581A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet which is excellent in balance between transparency and flaw resistance and free from whitening by bending processing of a V cut etc. <P>SOLUTION: The decorative sheet includes a layer 1 containing a propylene homopolymer (A) which is polymerized by using a metallocene catalyst system and includes an MFR (ASTM D 1238 230°C, load 2.16 kg) of 0.1-30 g/10 min, a melting point measured by DSC of 155°C or above, and the sum of the amount of 2, 1-insertion bond and the amount of 1, 3-insertion bond of propylene of 0.1 mole% or below. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a decorative sheet having an excellent balance between transparency and scratch resistance.

  Conventionally, as a decorative sheet used for building materials, home appliances, automobile interior materials, etc., makeup mainly composed of vinyl chloride resin, which has a good balance of scratch resistance, whitening resistance when bent, transparency, etc. Sheets have been used. However, with the growing awareness of the environment, decorative sheets using polyolefin-based materials have been proposed as an alternative to vinyl chloride resin.

For example, Patent Document 1 discloses a decorative sheet having a polypropylene film as a main constituent layer.
Patent Document 2 proposes a decorative sheet having an olefin-based thermoplastic elastomer as a main constituent layer.

  In the case of a decorative sheet having a polypropylene film proposed in Patent Document 1 as a constituent layer, since the degree of crystallinity and melting point of polypropylene is high, flexibility is lowered, and when bending processing such as V-cutting is performed, There were problems such as cracks and whitening.

  In addition, in the case of a decorative sheet comprising an olefinic thermoplastic elastomer proposed in Patent Document 2 as a constituent layer, it is excellent in flexibility and hardly causes cracking and whitening of the bent surface, but transparency and mechanical strength are insufficient. There were problems such as.

  In order to solve such problems, Patent Document 3 proposes a decorative sheet using a layer made of a resin composition containing a specific amorphous polyolefin and a crystalline polypropylene in a specific ratio. .

However, although this decorative sheet has improved cracking and whitening of the bent surface, it cannot be said to have sufficient mechanical strength, scratch resistance and heat resistance.
Further, as a countermeasure against whitening at the time of bending, a decorative sheet using a layer made of polypropylene which has been made low in rigidity by adding an elastomer or the like (Patent Document 4 and Patent Document 5), and conversely made of a high crystal type polypropylene, high rigidity Although decorative sheets using a layer made into a layer (Patent Documents 6 and 7) have been proposed, decorative sheets using low-rigidity polypropylene have poor scratch resistance, and decorative sheets using high-rigidity polypropylene are There is a problem that transparency is lowered due to cracks and heat during secondary processing. That is, the conventional technology cannot provide a decorative sheet having a good balance between transparency and scratch resistance.

JP-A-6-198830 JP-A-6-16832 JP 2000-281807 A Japanese Patent Laid-Open No. 11-221888 JP 2000-326443 A JP 2001-270054 A Japanese Patent Laid-Open No. 2001-181985

  An object of the present invention is to provide a decorative sheet that is excellent in balance between transparency and scratch resistance and that is hardly whitened by bending such as V-cut.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a decorative sheet having a layer containing a specific propylene homopolymer has an excellent balance between transparency and scratch resistance, and further bends such as V-cut. It was found that there was almost no whitening depending on the processing, and the present invention was completed.

  That is, the present invention is polymerized using a metallocene catalyst system, MFR (ASTM D 1238 230 ° C., load 2.16 kg) is 0.1-30 g / 10 min, melting point measured by DSC is 155 ° C. or more, A decorative sheet comprising a layer containing a propylene homopolymer (A) in which the sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene is 0.1 mol% or less is there.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which is excellent in the balance of transparency and scratch resistance, and hardly has whitening by bending processes, such as V cut, is provided. In this specification, being excellent in transparency and scratch resistance means that the layer containing the propylene homopolymer (A) described later is excellent in transparency and scratch resistance.

FIG. 1 shows an example of an embodiment of a decorative sheet of the present invention. FIG. 1 is a view showing a configuration in which the decorative sheet of the present invention is bonded to an adherend through an adhesive layer. FIG. 2 shows an example of the configuration of the decorative sheet of the present invention when the base material layer (3) includes a pattern layer or a print layer. FIG. 2 is a diagram showing a configuration in which the decorative sheet of the present invention is bonded to an adherend through an adhesive layer.

Hereinafter, the present invention will be described in detail.
The decorative sheet of the present invention is polymerized using a metallocene catalyst system, MFR (ASTM D 1238 230 ° C., load 2.16 kg) is 0.1 to 30 g / 10 min, and the melting point measured by DSC is 155 ° C. or more. And having a layer containing the propylene homopolymer (A) in which the sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene is 0.1 mol% or less.

[Propylene Homopolymer (A)]
The propylene homopolymer (A) used in the decorative sheet of the present invention is polymerized using a metallocene catalyst system, and MFR (ASTM D 1238 230 ° C., load 2.16 kg) is 0.1 to 30 g / 10 min. The melting point measured by DSC is 155 ° C. or higher, and the sum of the 2,1-insertion bond amount and the 1,3-insertion bond amount of propylene is 0.1 mol% or less. Hereinafter, each of these physical properties will be described.

<Melt flow rate>
The propylene homopolymer (A) used in the present invention has an MFR (ASTM D 1238 230 ° C., load 2.16 kg) of 0.1 to 30 g / 10 min, preferably 5 to 20 g / 10 min. The MFR can be adjusted by changing the polymerization temperature or using hydrogen as a chain transfer agent.
When the MFR of the propylene homopolymer (A) is within the above range, it is preferable because the balance of transparency, bending whitening resistance and scratch resistance is excellent.

<Melting point>
The propylene homopolymer (A) used in the present invention has a melting point measured by DSC of 155 ° C. or higher, preferably 156 to 167 ° C., more preferably 156 to 163 ° C. By using a metallocene catalyst system described later as the catalyst, a polymer having a melting point within the above range can be obtained. Moreover, the polymer from which melting | fusing point differs can be manufactured by changing the metallocene compound to be used.
When the melting point measured by DSC of the propylene homopolymer (A) is less than 155 ° C., the decorative sheet is poor in scratch resistance, which is not preferable.

<The sum of 2,1-insertion bond amount and 1,3-insertion bond amount of propylene>
The propylene homopolymer (A) used in the present invention has a propylene 2,1-insertion bond amount and a 1,3-insertion bond amount determined from a ¹³ C-NMR spectrum of 0.1 mol% or less, Preferably it is 0.05 mol% or less. By using a metallocene catalyst system, which will be described later, as a catalyst, it is possible to obtain a polymer in which the sum of the proportions of heterogeneous bonds is within the above range.

When the sum of the proportion of heterogeneous bonds based on 2,1-insertion and the proportion of heterogeneous bonds based on 1,3-insertion in the propylene homopolymer (A) is within the above range, transparency, bending whitening resistance and scratch resistance This is preferable because a decorative sheet having an excellent balance of adhesion can be obtained.
Hereinafter, other physical properties of the propylene homopolymer (A) will be described.

<Mw / Mn>
The propylene homopolymer (A) used in the present invention has a molecular weight distribution index (Mw / Mn) measured by GPC of usually 3.5 or less, preferably in the range of 2 to 3. By using a metallocene catalyst system described later as a catalyst, a polymer having Mw / Mn within the above range can be obtained. Moreover, the polymer from which Mw / Mn differs can be manufactured by changing the metallocene compound to be used.

  When the Mw / Mn of the propylene homopolymer (A) is in the above range, since there are few low molecular weight components, there is little bleeding out, and the resulting decorative sheet is excellent in transparency and blocking resistance.

<Integrated elution up to 90 ° C measured by CFC method>
The propylene homopolymer (A) used in the present invention has an elution integral amount of up to 90 ° C. measured by a cross chromatography fractionation (CFC) method is usually 1% or less, preferably 0.5% or less. By using a metallocene catalyst system, which will be described later, as a catalyst, a polymer having an integrated elution amount in the above range can be obtained. Moreover, the polymer from which an elution integral amount differs can be manufactured by changing the metallocene compound to be used.

  When the integral amount of elution from 0 ° C. to 90 ° C. measured by the CFC method of the propylene homopolymer (A) is in the above range, the propylene homopolymer (A) has few low molecular weight components, so there is little bleed out, The resulting decorative sheet is excellent in transparency and blocking resistance.

By including the propylene homopolymer (A) in the layer constituting the decorative sheet, a decorative sheet excellent in transparency and scratch resistance can be obtained.
More specifically, the makeup with excellent scratch resistance does not deteriorate the transparency of the layer containing the propylene homopolymer (A) due to the heat at the time of thermoforming when producing a decorative sheet, which will be described later. A sheet is obtained.

<Producing method of propylene homopolymer (A)>
Hereinafter, the manufacturing method of a propylene homopolymer (A) is demonstrated.
The method for producing the propylene homopolymer (A) used in the present invention is such that the propylene homopolymer (A) is polymerized using a metallocene catalyst system, the melt flow rate, the melting point measured by DSC, and 2 of propylene. , 1-insertion bond amount and 1,3-insertion bond amount, preferably as long as the other physical properties are satisfied, a ligand having a cyclopentadienyl skeleton is usually used. Produced by homopolymerizing propylene in the presence of a polymerization catalyst containing a metallocene compound in the molecule.

  The metallocene compound having a ligand having a cyclopentadienyl skeleton in the molecule is represented by a non-bridged metallocene compound represented by the following general formula [I] and the following general formula [II] from its chemical structure. Two types of bridged metallocene compounds can be exemplified. Among these, a bridged metallocene compound represented by the general formula [II] is preferable.

前記一般式［Ｉ］および［II］において、Ｍはチタン原子、ジルコニウム原子またはハフニウム原子を示し、
Ｑはハロゲン原子、炭化水素基、アニオン配位子、および孤立電子対で配位可能な中性配位子から選ばれ、
ｊは１〜４の整数であり、ｊが２以上の時は、Ｑは互いに同一でも異なっていてもよく、
Ｃｐ¹およびＣｐ²は、互いに同一か又は異なっていてもよく、Ｍと共にサンドイッチ構造を形成することができるシクロペンタジエニル基または置換シクロペンタジエニル基である。ここで、置換シクロペンタジエニル基は、インデニル基、フルオレニル基、アズレニル基およびこれらが一つ以上の炭化水素基で置換された基も包含し、インデニル基、フルオレニル基、アズレニル基の場合はシクロペンタジエニル基に縮合する不飽和環の二重結合の一部ないし全部は水添されていてもよい。

In the general formulas [I] and [II], M represents a titanium atom, a zirconium atom or a hafnium atom,
Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair of electrons,
j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same as or different from each other;
Cp ¹ and Cp ² may be the same or different from each other, and are a cyclopentadienyl group or a substituted cyclopentadienyl group that can form a sandwich structure with M. Here, the substituted cyclopentadienyl group includes an indenyl group, a fluorenyl group, an azulenyl group, and a group in which these are substituted with one or more hydrocarbon groups, and in the case of an indenyl group, a fluorenyl group, an azulenyl group, Some or all of the double bonds of the unsaturated ring condensed to the pentadienyl group may be hydrogenated.

In the general formula [II], Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or divalent germanium. -Containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO _2- , -Ge-, -Sn-, -NR ^a- , -P (R ^a ) -, - P (O) ( R a) -, - BR a - or -AlR ^a - are shown (however, R ^a is a hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms And a nitrogen compound residue in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a hydrogenated hydrocarbon group, a hydrogen atom, a halogen atom or a nitrogen atom.

  The polymerization catalyst preferably used in the present invention includes a bridged metallocene compound represented by the following general formula [III] disclosed in International Publication (WO01 / 27124) relating to the application of the present applicant, and an organometallic compound. And a metallocene catalyst comprising at least one compound selected from compounds capable of reacting with an organoaluminum oxy compound and a metallocene compound to form an ion pair, and, if necessary, a particulate carrier.

前記一般式［III］において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は水素原子、炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよい。

In the general formula [III], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are It is selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and each may be the same or different.

  Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, linear hydrocarbon group such as n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl- Branched hydrocarbon groups such as 1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, Cyclic saturated hydrocarbon groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group, etc. Unsaturated hydrocarbon group; saturated hydrocarbon group substituted with cyclic unsaturated hydrocarbon group such as benzyl group, cumyl group, 1,1-diphenylethyl group, triphenylmethyl group; methoxy group, ethoxy group, phenoxy group And a heteroatom-containing hydrocarbon group such as a furyl group, an N-methylamino group, an N, N-dimethylamino group, an N-phenylamino group, a pyryl group, and a thienyl group.

  Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

Moreover, the adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [III], R ¹ , R ² , R ³ and R ⁴ substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² And R ⁴ are more preferably a hydrocarbon group having 1 to 20 carbon atoms, R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are linear or branched having 1 to 5 carbon atoms. Particularly preferred is an alkyl group.

In the general formula [III], R ⁵ to R ¹² substituted on the fluorenyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-described hydrocarbon groups. The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. A preferred embodiment is a fluorenyl ring in which R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not simultaneously hydrogen atoms.

  In the general formula [III], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a Group 14 element, more preferably carbon, silicon, or germanium, and even more preferably a carbon atom.

R ¹³ and R ¹⁴ substituted on Y may be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms which may be bonded to each other to form a ring, preferably a carbon atom It is selected from an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 20 carbon atoms. As such a substituent, a methyl group, an ethyl group, a phenyl group, a tolyl group and the like are preferable. R ¹³ and R ¹⁴ are R ⁵ to R ¹² optional substituents (usually R ⁵ or R ¹² ) or R ¹ to R ⁴ optional substituents (provided that R ¹ is usually R ^1). Or R ⁴ ) may be bonded to each other to form a ring.

In the general formula [III], M is preferably a Group 4 transition metal, more preferably a titanium atom, a zirconium atom, or a hafnium atom.
Q is selected from the same or different combinations from halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons.

j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.
Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and specific examples of the hydrocarbon group include the same as described above.

  Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

  Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxy. And ethers such as ethane.

It is preferable that at least one Q is a halogen or an alkyl group.
Preferred bridged metallocene compounds include dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, 1-phenylethylidene (4-tert -Butyl-2-methylcyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10 '-Octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride it can.

  In the metallocene catalyst used for the production of the propylene homopolymer (A), ions react with the organometallic compound, organoaluminum oxy compound and metallocene compound used together with the metallocene compound represented by the general formula [III]. Regarding at least one compound (cocatalyst) selected from the compounds forming a pair, and the particulate carrier used as necessary, the above-mentioned publications (WO01 / 27124) and JP-A-11-315109 by the applicant of the present application. The compounds disclosed in the publication can be used without limitation.

  The propylene homopolymer (A) uses a polymerization apparatus in which one reactor or one or more reactors are connected in series, and in the presence of the metallocene catalyst and cocatalyst, for example, at a polymerization temperature of 0 to 100 ° C. It can be produced by homopolymerizing propylene under polymerization conditions of normal pressure to 5 MPa gauge pressure.

[Decorative sheet]
The decorative sheet of the present invention is characterized by having a layer (transparent polypropylene layer (1)) containing the propylene homopolymer (A) satisfying specific requirements as described above, and an example of the embodiment is shown in FIG. It is shown in 1.

  In general, a decorative sheet includes a base material layer (3), a transparent polypropylene layer (1), and a transparent protective layer (2) through an adhesive layer (4) on an adherend (5) such as a plywood or an aluminum plate. It consists of a laminated structure. Note that an adhesive layer (4) may be provided between the layers (2)-(1)-(3) depending on the material used. Moreover, a base material layer (3) is good also as a layer containing a printing layer or a pattern layer.

  The adherend (5) is a wood material such as a wood veneer or plywood, a metal material such as iron or aluminum, a resin material such as polycarbonate or acrylic resin, a plate material such as a flat plate, a curved plate, a three-dimensional object, or the like. It has various shapes like a sheet.

  As the adhesive layer (4), various known layers such as acrylic, polyester and polyurethane adhesives or rubber adhesives (styrene-butadiene rubber, ethylene-propylene rubber, natural rubber, etc.) The thickness is usually 2 to 20 μm. Moreover, there is no restriction | limiting in particular also in the coating method to the base material layer (3) of an adhesive agent.

  As the base material layer (3), polyethylene, polypropylene, thermoplastic elastomer and the like are generally colored and used, and the thickness is usually 30 to 200 μm. A propylene homopolymer (A) can also be used for the base material layer (3). The colorant used for the coloring is an inorganic pigment such as ultramarine blue, titanium white or carbon black, or an organic pigment such as quinacridone or phthalocyanine blue.

  A transparent polypropylene layer (1) is a layer containing the propylene homopolymer (A) of this invention, and thickness is 10-150 micrometers normally. In addition, for the purpose of improving the low temperature impact strength, various known propylene elastomers (propylene-ethylene copolymer, propylene-butene copolymer, etc.) and polyethylene (LLDPE, LDPE) are added to the layer (1) in an amount of 20 wt% or less. You may make it contain separately or in combination by quantity.

  The transparent protective layer (2) is formed on the layer (1) in order to further improve the performance of the transparent polypropylene layer (1). As the transparent protective layer (2), various known hard coat agents such as polyurethane, epoxy, acrylic and polyester are used, and the thickness is usually 1 to 5 μm. There is no restriction | limiting in particular in the coating method to the layer (1) of a hard-coat agent.

  In the layers (1) to (4), a weathering stabilizer, a heat stabilizer, a light stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an anti-blocking agent may be added to the layers as long as the purpose of the present invention is not impaired. Additives such as a clouding agent, a lubricant, a pigment, a dye, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, an antioxidant, a crystal nucleating agent, and an inorganic filler can be contained.

  The method for producing the decorative sheet of the present invention is not particularly limited. For example, a film or a sheet can be molded from a propylene homopolymer (A) or a propylene homopolymer (A) and a propylene-based resin composition containing the additive and the like. The layer (1) is formed using a possible molding method, the base layer (3) is laminated on the layer (1), and the surface opposite to the surface in contact with the layer (1) of the base layer (3) A pattern layer or a printing layer is laminated on the surface. As described above, the base material layer (3) may be a layer including a pattern layer or a printing layer. In this case, the base material layer (3) is laminated on the layer (1). Furthermore, the decorative sheet of the present invention can be produced by laminating the transparent protective layer (2) on the surface of the layer (1) opposite to the surface in contact with the base material layer (3). The example of a structure of a decorative sheet in case a base material layer (3) contains a pattern layer or a printing layer is shown in FIG. The layer (1) may have a multilayer structure including a layer containing the propylene homopolymer (A) and a layer made of other polypropylene resin or other resin. However, in that case, the part which is in contact with the transparent protective layer (2) of the layer (1) must be a layer containing the propylene homopolymer (A).

  The printing layer or the pattern layer can be laminated on the base material layer (3) by, for example, direct gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, dry lamination, and the like.

Lamination of the transparent polypropylene layer (1) to the base material layer (3) can be performed by dry lamination, extrusion lamination, or the like.
Lamination of the transparent protective layer (2) to the transparent polypropylene layer (1) can be performed by general coating.

  The decorative sheet of the present invention has a transparent polypropylene layer (1) and a base material layer (3) as essential layers. Although the thickness of a decorative sheet is not specifically limited, Usually, it is 50-300 micrometers.

  Moreover, the ratio of the thickness of each layer is not particularly limited, but the base material layer (3) / layer (1) / transparent protective layer (2) is 3 to 40/1 to 30 / from the viewpoint of performance balance. A ratio of 1-2 is preferred.

  In such a decorative sheet of the present invention, the layer (1) having the propylene homopolymer (A) is excellent in balance between transparency and scratch resistance, and is hardly whitened by bending such as V-cut.

  Furthermore, when a decorative sheet is attached to a resin sheet such as a curved plate or a three-dimensional object, the resin sheet with the decorative sheet attached may be thermoformed to form a three-dimensional shape. It has the characteristic that there is little fall of the transparency of the transparent polypropylene layer (1) by the heat | fever at the time of thermoforming.

  The decorative sheet of the present invention can be used for various purposes. For example, home appliances and furniture products such as TV cabinets, stereo speaker boxes, video cabinets, various storage furniture, unit furniture, doors, door frames, window frames, Suitable for applications such as housing components such as rims, baseboards, and open frames, furniture components such as kitchens and storage furniture doors, flooring materials, ceiling materials, wallpaper materials, automobile interior materials, home appliances, stationery, office supplies, etc. Can be used for

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example. The analysis method employed in the present invention is as follows.

Mw / Mn Measurement Mw / Mn (wherein Mw is a weight average molecular weight and Mn is a number average molecular weight) of a propylene homopolymer was measured as follows using GPC-150C Plus manufactured by Waters. The separation columns are TSKgel GMH6-HT and TSK gel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) Industry) and 0.025 wt% BHT (Wako Pure Chemical Industries) as antioxidant, moved at 1.0 ml / min, sample concentration 0.1 wt%, sample injection volume 500 microliters, differential refraction as detector A total was used. Standard polystyrene is converted to polypropylene using a general-purpose calibration method using molecular weight Mw <1000 and Mw> 4 × 10 ⁶ made by Tosoh Corporation, and 1000 ≦ Mw ≦ 4 × 10 ⁶ made by Pressure Chemical Co. did. The Mark-Houwink coefficients of polystyrene and polypropylene are the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)). Was used.

Melting point (Tm)
The melting point (Tm) of the propylene homopolymer was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak in the third step was defined as the melting point (Tm).

<Sample creation conditions>
Molding method: Press mold: Thickness 0.2mm (sample is sandwiched between aluminum foils, press mold using mold)
Molding temperature: 240 ° C
Press pressure: 300 kg / cm ² , press time: 1 minute After press molding, the sheet is cooled with ice water, and about 0.4 g of sheet is sealed in the following measurement container.
Measuring container: DSC PANS 10 μl BO-14-3015
DSC COVER BO14-3003.

(Measurement condition)
First step: Increase the temperature to 240 ° C at 10 ° C / min and hold for 10 min.
Second step: Decrease the temperature to 60 ° C at 10 ° C / min.
Third step: Increase the temperature to 240 ° C at 10 ° C / min.

[MFR (melt flow rate)]
The MFR of the propylene homopolymer was measured according to ASTM D1238 (230 ° C., load 2.16 kg).

Cross chromatographic fractionation measurement (CFC)
Measurement of the amount of the propylene homopolymer soluble in o-dichlorobenzene up to 90 ° C. was performed by cross-chromatographic fractionation measurement (CFC).
Analysis of components soluble in orthodichlorobenzene at each temperature was performed by cross-chromatographic fractionation measurement (CFC). CFC is a composition of components that are soluble in orthodichlorobenzene at each temperature using the following equipment equipped with a temperature rising elution fractionation (TREF) part for compositional fractionation and a GPC part for molecular weight fractionation. The amount was calculated.
Measuring device: CFC T-150A, manufactured by Mitsubishi Yuka Co., Ltd. Column: Shodex AT-806MS (× 3)
Dissolved solution: o-dichlorobenzene Flow rate: 1.0 ml / min
Sample concentration: 0.3 wt% / vol% (with 0.1% BHT)
Injection volume: 0.5 ml
Solubility: Complete dissolution Detector: Infrared absorption detection method, 3.42μ (2924 cm ^-1 ), NaCl plate Elution temperature: 0 to 135 ° C, 28 fractions (0, 10, 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 94, 97, 100, 103, 106, 109, 112, 115, 118, 121, 124, 127, 135 (° C.).

Details of the measurement will be described below. The sample was dissolved by heating at 145 ° C. for 2 hours, held at 135 ° C., then cooled to 0 ° C. at 10 ° C./hr, and further held at 0 ° C. for 60 minutes to coat the sample on the column. The temperature rising elution column volume is 0.83 ml, and the pipe volume is 0.07 ml. The detector used an infrared spectrometer MIRAN 1A CVF type (CaF ₂ cell) manufactured by FOXBORO, and infrared light with a wavelength of 3.42 μm (2924 cm ⁻¹ ) was detected by setting the absorbance mode with a response time of 10 seconds. The elution temperature was divided into 28 fractions from 0 ° C to 135 ° C.

  All temperature indications are integers. For example, the elution fraction at 94 ° C. indicates a component eluted at 91 to 94 ° C. The molecular weight of components not coated even at 0 ° C. and the fraction eluted at each temperature were measured, and the molecular weight in terms of polypropylene was determined using a general calibration curve. Data processing was performed using the analysis program “CFC data processing (version 1.50)” included with the device (data sampling time was 0.50 seconds).

Measurement of 2,1-insertion bond and 1,3-insertion bond
^{Using 13} C-NMR, the amount of 2,1-insertion bond and the amount of 1,3-insertion bond of propylene were measured according to the method described in JP-A-7-152212.

Folding whitening of sheets The decorative sheets produced in Examples and Comparative Examples were cut into 10 cm squares, bent at 180 ° at 5 cm lengths, and visually checked for whitening of the bent portions.

Sheet scratch resistance test In accordance with JIS K5600, the pencil hardness of the decorative sheet surfaces produced in Examples and Comparative Examples was measured.

Transparency of sheet (HAZE)
The haze before and after thermoforming was measured according to ASTM D-1003.
Thermoforming conditions: A sample (30cm x 30cm decorative sheet) is attached to a vacuum / pneumatic molding machine manufactured by Asano Seisakusho, the decorative sheet is heated at a heater temperature of 300 ° C, and a 10cm vertical x 10cm horizontal x 0.5cm deep tray is vacuum compressed. After molding, the haze at the bottom of the tray is measured.

[Production Example 1]
(1) Production of Solid Catalyst Support 300 g of SiO ₂ (Sunsphere H121 manufactured by AGC S-Itech) was sampled in a 1 L branch flask, and 800 mL of toluene was put into a slurry. Next, the solution was transferred to a 5 L four-necked flask, and 260 mL of toluene was added. 2830 mL of methylaluminoxane (hereinafter MAO) -toluene solution (10 wt% solution) was introduced. The mixture was stirred for 30 minutes while remaining at room temperature. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 1.0 g of isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride was weighed in a 5 L four-necked flask. . The flask was taken out, 0.5 L of toluene and 2.0 L of MAO / SiO ₂ / toluene slurry prepared in (1) (100 g as a solid component) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The resulting isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99 in n-heptane. % Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 101 g of the solid catalyst component prepared in (2) above, 111 mL of triethylaluminum, and 80 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C. Inserted and allowed to react with stirring for 180 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration would be 1 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization An internal volume 58L jacketed circulation tubular polymerizer is 30kg / hour of propylene, 5NL / hour of hydrogen, 2.4g / hour of the catalyst slurry produced in (3) as a solid catalyst component, triethylaluminum. 1.0 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization vessel, propylene was supplied at 50 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization reactor, propylene was supplied at 13 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene homopolymer (P-1). The resulting propylene homopolymer (P-1) was vacuum dried at 80 ° C. The properties of the resulting propylene homopolymer (P-1) are shown in Table 1.

[Production Example 2]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
<Main polymerization>
Propylene 30 kg / hour, hydrogen 5 NL / hour, 1.7 g / hour of catalyst slurry prepared in (3) as solid catalyst component, 1.0 ml / hour of triethylaluminum Was continuously fed and polymerized in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization vessel, propylene was supplied at 50 kg / hour and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.40 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.40 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.40 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 13 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.40 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene homopolymer (P-2). The resulting propylene homopolymer (P-2) was vacuum dried at 80 ° C. The properties of the resulting propylene homopolymer (P-2) are shown in Table 1. Table 1 also shows the characteristics of a commercially available polypropylene resin (Y-2000GP manufactured by Prime Polymer Co., Ltd.) manufactured using a Ziegler catalyst.

［実施例１］
製造例１で製造されたプロピレン単独重合体（Ｐ−１）１００質量部に対して、熱安定剤IRGANOX1010（チバ・ジャパン（株）商標）０．１質量部、熱安定剤IRGAFOS168（チバ・ジャパン（株）商標）０．１質量部、ステアリン酸カルシウム０．１質量部，光安定剤 CHIMASSORB １１９（チバ・ジャパン（株）商標）０．５質量部、光安定剤 TINUVIN 234（チバ・ジャパン（株）商標）０．５質量部をタンブラーにて混合後、ナカタニ機械（株）製二軸押出機（同方向2軸混練機）を用いて２30℃にて溶融混練してペレット状のポリプロピレン樹脂組成物（Ａ−１）を調製し、東芝機械（株）製６５ｍｍφＴダイフィルム成形機（ダイ幅６００ｍｍ，リップギャップ１ｍｍ）にて、押出温度２3０℃，チルロール温度４０℃の条件で厚み８０μｍの単層フィルム（透明ポリプロピレン層（１））と厚み１５０μｍの単層フィルム（基材層（３））を製造した。

[Example 1]
With respect to 100 parts by mass of the propylene homopolymer (P-1) produced in Production Example 1, 0.1 part by mass of thermal stabilizer IRGANOX 1010 (trademark of Ciba Japan), thermal stabilizer IRGAFOS168 (Ciba Japan) (Trademark) 0.1 part by mass, calcium stearate 0.1 part by mass, light stabilizer CHIMASSORB 119 (Ciba Japan Co., Ltd.) 0.5 part by mass, light stabilizer TINUVIN 234 (Ciba Japan Co., Ltd.) ) Trademark) After mixing 0.5 parts by mass with a tumbler, it is melt-kneaded at 230 ° C. using a twin screw extruder (same direction twin screw kneader) manufactured by Nakatani Machinery Co., Ltd. to form a pellet-shaped polypropylene resin composition A product (A-1) was prepared, and a single layer having a thickness of 80 μm was used on a 65 mmφ T die film molding machine (die width 600 mm, lip gap 1 mm) manufactured by Toshiba Machine Co., Ltd. under conditions of extrusion temperature 230 ° C. and chill roll temperature 40 ° C. the film( Akira polypropylene layer (1)) and the single-layer film (substrate layer (3) having a thickness of 150 [mu] m) were produced.

  Next, the obtained film was cut out (10 × 20 cm), the corona treatment (film wetting index 40Dyn) was applied to the adhesive surface, and the transparent polypropylene layer (1) and the substrate were coated with an adhesive for dry lamination (Takelac A310 made by Mitsui Chemicals Polyurethane). The corona-treated surface of layer (3) is pasted by hand (adhesive layer thickness is about 4μm), and after making a decorative sheet, it is dried in an oven at 80 ° C for 1 hour, HAZE (before and after thermoforming), scratch resistance (pencil hardness) The bending whitening was evaluated. The results are shown in Table 2. In addition, in order to confirm the scratch resistance of the transparent polypropylene layer (1) and the transparency after thermoforming, the transparent protective layer (2) was not laminated, and the base material layer (3) was also uncolored.

[Example 2]
A single-layer film (base material layer (3)) having a thickness of 150 μm was produced in the same manner as in Example 1 using the polypropylene resin composition (A-1). A transparent polypropylene layer (1) using the polypropylene resin composition (A-1) was laminated on this film by a laminator (65 mmφ) manufactured by Sumitomo Heavy Industries at a resin temperature of 250 ° C. and a chill roll temperature of 30 ° C. (thickness: 80 μm). A decorative sheet was prepared. The physical properties of the decorative sheet (HAZE (before and after thermoforming), scratch resistance (pencil hardness), bending whitening) were evaluated. The results are shown in Table 2. In addition, in order to confirm the scratch resistance of the transparent polypropylene layer (1) and the transparency after thermoforming, the transparent protective layer (2) was not laminated, and the base material layer (3) was also uncolored.

[Example 3]
The same procedure as in Example 1 was carried out except that the propylene homopolymer (P-2) produced in Production Example 2 was used instead of P-1. The results are shown in Table 2.

[Comparative Example 1]
The same procedure as in Example 1 was conducted except that the propylene resin composition (A-1) was changed to a commercially available PP resin (Y-2000GP manufactured by Prime Polymer Co., Ltd .: MFR = 18 g / 10 min, Tm = 161 ° C.). It was. The results are shown in Table 2.

[Comparative Example 2]
The same procedure as in Comparative Example 1 was conducted except that 1000 ppm of the nucleating agent (Adeka Adeka Stub NA-21) was added to Y-2000GP used in Comparative Example 1. The results are shown in Table 2.

  The decorative sheet of the present invention is excellent in the balance of transparency, folding whitening resistance, and scratch resistance, and therefore can be suitably used for various decorative sheet applications.

Claims (1)

  Polymerized using a metallocene catalyst system, MFR (ASTM D 1238 230 ° C., load 2.16 kg) is 0.1-30 g / 10 min, melting point measured by DSC is 155 ° C. or higher, -A decorative sheet comprising a layer containing a propylene homopolymer (A) in which the sum of the amount of insertion bonds and the amount of 1,3-insertion bonds is 0.1 mol% or less.

Images