JP2006056128A - Decorative polyolefin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a decorative polyolefin sheet or a building material protecting sheet which is excellent in flexibility, scratch resistance, abrasion resistance, whitening resistance at folding, heat resistance, folding wrinkle resistance, and water resistance. <P>SOLUTION: A layer mainly containing a resin composition comprising (A) 0-90 wt.% of isotactic polypropylene, (B) 0-90 wt.% of syndiotactic polypropylene containing more than 90 mole% of a unit derived from propylene, and (C) 10-100 wt.% of a syndiotactic propylene-α-olefin copolymer containing 90-55 mole% of a unit derived from propylene and 10-45 mole% of a unit derived from a 2-20C α-olefin excluding propylene is included in constitutional layers. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyolefin decorative sheet or a building material protective sheet excellent in flexibility, scratch resistance, whitening resistance during bending, crease resistance, heat resistance, and water resistance.

  Conventionally, as a sheet used for surface decoration or surface protection of interior materials and exterior materials for building materials, home appliances, automobiles, etc., the balance of scratch resistance, whitening resistance during bending, crease resistance, transparency, etc. A film mainly composed of a vinyl chloride resin, which is excellent in resistance, has been used. However, these have problems such as the generation of toxic gases during incineration, and the plasticizer contained in them has an adverse effect on the environment and the human body, and development is proceeding mainly with polyolefin-based materials that have less impact on the human body and the environment. ing.

  For example, JP-A-6-198830 discloses a decorative sheet having a polypropylene film as a main constituent layer (Patent Document 1).

  Japanese Patent Application Laid-Open No. 6-16832 proposes a decorative sheet mainly composed of an olefinic thermoplastic elastomer (Patent Document 2).

  In the case of a decorative sheet comprising a polypropylene film as a constituent layer proposed in Japanese Patent Laid-Open No. 6-198830, the crystallinity and melting point of polypropylene is high. There were problems such as whitening.

  In addition, in the case of a decorative sheet comprising an olefinic thermoplastic elastomer proposed in Japanese Patent Laid-Open No. 6-16832 as a constituent layer, it is excellent in flexibility and hardly causes cracking and whitening of the bent surface, but it has poor transparency and mechanical strength. There were problems such as becoming sufficient.

  In order to solve such problems, Japanese Patent Application Laid-Open No. 2000-281807 discloses a decorative sheet using a layer made of a resin composition containing a specific amorphous polyolefin and a crystalline polypropylene in a specific ratio. It has been proposed (Patent Document 3).

  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.

  On the other hand, Japanese Patent Application Laid-Open No. 10-258488 proposes a decorative sheet using a polyester film as a surface protective layer (Patent Document 4).

By using a polyester film as a surface protective layer, mechanical strength and scratch resistance are greatly improved. However, a material having such a polar group in a molecular chain is inferior in water resistance (water vapor resistance).
JP-A-6-198830 JP-A-6-16832 JP 2000-281807 A JP-A-10-258488

  The present inventors are diligent in order to obtain a polyolefin-based decorative sheet or a building material protective sheet excellent in flexibility, scratch resistance, abrasion resistance, whitening resistance during bending, heat resistance, crease resistance, and water resistance. As a result of investigation, the above problems were solved by using a layer obtained from the specific resin composition, and the present invention was completed.

  The polyolefin-based decorative sheet or building material protective sheet of the present invention comprises (A) 0 to 90% by weight of isotactic polypropylene and (B) syndiotactic polypropylene 0 containing more than 90 mol% of structural units derived from propylene. -90 wt% and (C) 90-55 mol% of structural units derived from propylene, and 10-45 mol of structural units derived from an α-olefin having 2 to 20 carbon atoms excluding propylene %. A layer composed mainly of a resin composition comprising 10 to 100% by weight of a syndiotactic propylene / α-olefin copolymer contained in an amount of% is a constituent layer.

  The polyolefin-based decorative sheet or building material protective sheet of the present invention is excellent in flexibility, scratch resistance, abrasion resistance, whitening resistance during bending, heat resistance, crease resistance, water resistance, and at the time of incineration. It is possible to prevent problems such as generation of dioxins and use of plasticizers on the human body.

Hereinafter, the present invention will be described in detail.

(A) Isotactic polypropylene The isotactic polypropylene (A) used in the present invention is a polypropylene having an isotactic pentad fraction measured by NMR method of 0.9 or more, preferably 0.95 or more.
The isotactic pentad fraction (mmmm) is measured and calculated by the method described in Japanese Patent Application Laid-Open No. 2003-147135.

Examples of the isotactic polypropylene (A) include a propylene homopolymer or a copolymer of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene. Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like, and ethylene or α-olefin having 4 to 10 carbon atoms is preferable.
These α-olefins may form a random copolymer with propylene or a block copolymer.

  The structural unit derived from these α-olefins may be contained in the polypropylene in a proportion of 35 mol% or less, preferably 30 mol% or less. Isotactic polypropylene (A) has a melt flow rate (MFR) of 0.01 to 1000 g / 10 minutes, preferably 0.05 to 100 g measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D 1238. It is desirable to be in the range of / 10 minutes.

  Further, a plurality of (A) isotactic polypropylenes can be used together as necessary, and for example, two or more kinds of components having different melting points and rigidity can be used.

  Such an isotactic polypropylene (A) catalyzes, for example, a Ziegler catalyst system comprising a solid catalyst component, an organoaluminum compound and an electron donor containing magnesium, titanium, halogen and an electron donor as essential components, or a metallocene compound. It can be produced by polymerizing propylene with a metallocene catalyst system used as one component or copolymerizing propylene with another α-olefin.

(B) Syndiotactic polypropylene The syndiotactic polypropylene (B) used in the present invention is a homopolymer of propylene or a copolymer of propylene and olefins other than propylene, and has a substantially syndiotactic structure. Polypropylene having

  Examples of olefins other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Olefins other than propylene may be copolymerized in a small amount, for example, less than 10 mol%, preferably 5 mol% or less, particularly preferably 3 mol% or less. When these olefins are copolymerized in the above amounts, a composition having excellent physical properties tends to be obtained.

  Here, the substantially syndiotactic structure means that the propylene homopolymer has a syndiotactic pentad fraction (rrrr, pentad syndiotacticity) of 0.5 or more, preferably Is 0.6 or more, more preferably 0.7 or more, particularly preferably 0.80 or more, and those having a syndiotactic tick pentad fraction of 0.5 or more are excellent in heat resistance and moldability. The properties as crystalline polypropylene are favorable and preferable.

  In addition, said syndiotactic pentad fraction (rrrr) is measured and calculated by the method described in prior publication Unexamined-Japanese-Patent No. 2003-147135.

  Further, in the case of a copolymer of propylene and other olefins, the substantially syndiotactic structure is about 20.2 ppm by C13-NMR measured by a 1,2,4-trichlorobenzene solution. The peak intensity observed in 1 is 0.3 or more of the peak intensity attributed to all methyl groups of the propylene unit, preferably 0.5 or more. This is preferable because of good adhesion and impact resistance.

  Syndiotactic polypropylene (B) has an intrinsic viscosity [η] measured with a tetralin solution at 135 ° C. of usually 0.1 to 20 dl / g, preferably about 0.5 to 10 dl / g.

  The syndiotactic polypropylene (B) has an MFR in the range of 0.001 to 1000 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes. Yes. When the MFR is in such a range, it exhibits good fluidity, it is easy to mix this syndiotactic polypropylene (B) with other components, and a molded product having excellent mechanical strength can be obtained from the obtained composition. There is a tendency to be obtained.

  Syndiotactic polypropylene (B) has a density of 0.86-0. 91 g / cm 3, preferably 0. It is desirable to be in the range of 865 to 0.905 g / cm3. When a material having such a density is used, the molding processability is improved, and a molded product having sufficient flexibility tends to be obtained.

  A method for synthesizing such a syndiotactic polypropylene (B) is described in JP-A-2003-147135.

(C) Syndiotactic propylene / α-olefin copolymer The syndiotactic propylene / α-olefin copolymer (C) used in the present invention has a substantially syndiotactic structure and is derived from propylene. 10 to 45 structural units derived from an α-olefin having 2 to 20 carbon atoms other than propylene in an amount of 90 to 55 mol%, preferably 85 to 60 mol%, particularly preferably 80 to 65 mol%. It is contained in an amount of mol%, preferably 15 to 40 mol%, particularly preferably 20 to 35 mol%.

  Examples of olefins other than propylene include ethylene; α-olefins having 4 or more carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene, vinylcyclohexane, 1- Hexadecene, norbornene, etc .; dienes such as hexadiene, octadiene, decadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, etc. are mentioned, with ethylene being particularly preferred, and such syndiotactic propylene / ethylene copolymers. Since the polymer is excellent in cold resistance and low temperature characteristics, it can be suitably used in the present invention.

  The syndiotactic propylene / α-olefin copolymer (C) containing the propylene unit and the α-olefin unit in such an amount has good compatibility with the syndiotactic polypropylene (B), and the resulting polypropylene resin. The composition tends to exhibit sufficient transparency, flexibility, heat resistance, and scratch resistance.

  A substantially syndiotactic structure means that a peak intensity observed at about 20.2 ppm by C13-NMR measured in a 1,2,4-trichlorobenzene solution is attributed to all methyl groups of propylene units. The strength is 0.3 or more, preferably 0.5 or more, particularly preferably 0.6 or more, and particularly when this value is 0.3 or more, transparency, scratch resistance and impact resistance are good. It is preferable because it becomes good.

  The syndiotactic propylene / α-olefin copolymer (C) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g. It is desirable to be in When the intrinsic viscosity [η] of the syndiotactic propylene / α-olefin copolymer (C) is within the above range, the weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, dynamic fatigue resistance, etc. Excellent characteristics.

  Moreover, it is preferable that molecular weight distribution Mw / Mn (polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC is 4.0 or less.

  This syndiotactic propylene / α-olefin copolymer (C) has a single glass transition temperature and a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) is usually −10 ° C. Hereinafter, it is desirable that the temperature is in the range of −15 ° C. or lower. When the glass transition temperature (Tg) of the syndiotactic propylene / α-olefin copolymer (C) is within the above range, the cold resistance and the low temperature characteristics are excellent. The syndiotactic propylene / α-olefin copolymer (C) used in the present invention preferably has no DSC melting peak observed.

  Such a syndiotactic propylene / α-olefin copolymer (C) synthesis method is described using the catalyst described in Japanese Patent Application No. 2002-332243 in addition to the method described in the Japanese Patent Application Laid-Open No. 2003-147135. However, the present invention is not limited to these.

(D) Ethylene / α-Olefin Random Copolymer The ethylene / α-olefin random copolymer (D) used as necessary in the present invention has ethylene and 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. It means what is α-olefin copolymerized up to, but those having the following characteristics can be preferably used.
(A) Density (ASTM 1505 23 ° C.) is 0.850 to 0.910 g / cm 3, preferably 0.860 to 0.905 g / cm 3, more preferably 0.865 to 0.895 g / cm 3
(B) MFR measured at 190 ° C. and a load of 2.16 kg is 0.1 to 150 g / 10 minutes, preferably 0.3 to 100 g / 10 minutes.

  The production method of the ethylene / α-olefin random copolymer (D) is not particularly limited, but the ethylene and α-olefin are co-polymerized using a radical polymerization catalyst, a Phillips catalyst, a Ziegler-Natta catalyst, or a metallocene catalyst. It can be produced by polymerization. In particular, a copolymer produced using a metallocene catalyst usually has a molecular weight distribution (Mw / Mn) of 3 or less and can be preferably used in the present invention.

  The ethylene / α-olefin random copolymer (D) used in the present invention has a crystallinity measured by an X-ray diffraction method of usually 40% or less, preferably 0 to 39%, more preferably 0 to 35%. It is.

  Specific examples of the α-olefin having 3 to 20 carbon atoms used as a comonomer include propylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1, 1-octene, 1-decene, 1 -Dodecene is mentioned, These can be used alone or in combination of two or more, and among them, propylene, 1-butene, 1-hexene and 1-octene are preferable. Further, if necessary, other conomomers, for example, dienes such as 1,6-hexadiene and 1,8-octadiene, cyclic olefins such as cyclopentene, and the like may be contained in a small amount. The olefin content is 3 to 50 mol%, usually 5 to 30 mol%, preferably 5 to 25 mol%.

  The molecular structure may be linear or branched having long or short side chains. It is also possible to use a mixture of a plurality of different ethylene / α-olefin random copolymers (D).

  Such an ethylene / α-olefin copolymer can be produced by a conventionally known method using a vanadium-based catalyst, a titanium-based catalyst, a metallocene-based catalyst, or the like. For example, the method described in Japanese Patent Publication No. 10-212382 Is mentioned.

Polypropylene resin composition, resin composition The polypropylene resin composition according to the present invention comprises the isotactic polypropylene (A), the syndiotactic polypropylene (B), and the syndiotactic propylene / α-olefin copolymer. (C), and the resin composition according to the present invention comprises the polypropylene resin composition and an ethylene / α-olefin random copolymer (D), and the following inorganic fillers as necessary. And additives.

  Examples of the inorganic filler that can be used in the present invention include talc, clay, calcium carbonate, mica, silicates, carbonates, and glass fibers. Among these, talc and calcium carbonate are preferable, and talc is particularly preferable. Talc has an average particle diameter of 1 to 5 μm, preferably 1 to 3 μm. An inorganic filler (E) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Furthermore, within a range not impairing the object of the present invention, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, a lubricant, a pigment, a dye, a plasticizer, an anti-aging agent, hydrochloric acid Additives such as an absorbent, an antioxidant, and a crystal nucleating agent can be blended.

  The isotactic polypropylene (A) is 0 to 90 with respect to the entire composition ((A) + (B) + (C), where the total amount of (A), (B) and (C) is 100% by weight). % By weight, preferably 0 to 70% by weight, particularly preferably 0 to 60% by weight. It is preferable to add isotactic polypropylene because the heat resistance and formability of the sheet are improved.

  Syndiotactic polypropylene (B) is 0 to 0 with respect to the entire composition ((A) + (B) + (C), where the total amount of (A), (B) and (C) is 100% by weight). 90% by weight, preferably 5 to 85% by weight, more preferably 10 to 80% by weight. It is preferable to add syndiotactic polypropylene because the heat resistance, flexibility and transparency of the sheet are improved.

The syndiotactic propylene / α-olefin copolymer (C) is the entire composition ((A) + (B) + (C), where the total amount of (A) (B) (C) is 100% by weight. 10) to 100% by weight, preferably 20 to 100% by weight, and more preferably 30 to 90% by weight.
The weight ratio (B / C) of the syndiotactic polypropylene (B) and the syndiotactic propylene / α-olefin copolymer (C) is 10/90 to 90/10, preferably 50/50 to 90 /. Those in the range of 10 tend to have improved flexibility, scratch resistance, transparency and heat resistance, as well as excellent whitening resistance and crease resistance when folded.

  The ethylene / α-olefin random copolymer (D) used in the resin composition of the present invention is the entire composition ((A) + (B) + (C) + (D), where (A) (B ) (C) The total amount of (D) is usually 1 to 40% by weight, preferably 5 to 30% by weight, based on 100% by weight. When the ethylene / α-olefin random copolymer (D) is contained in the above amounts, a composition capable of preparing a molded article excellent in flexibility, surface hardness, impact resistance, particularly low temperature impact strength can be obtained. .

Polyolefin-based decorative sheet or building material protective sheet The polyolefin-based decorative sheet of the present invention is, for example, plywood, steel plate, aluminum plate, particle board, MDF (medium fiber board), inorganic board (such as gypsum board), concrete wall, resin board , For use in a well-known decorative board bonded to the surface of a base material made of foam, heat insulator, etc. by an adhesive or other methods, while a building material protective sheet is, for example, a floor, a wall, a ceiling or other part Both are for the purpose of imparting design properties such as patterns and printing, and surface protection.

  As a typical example of the polyolefin-based decorative sheet of the present invention, for example, as shown in FIG. 1, the polypropylene resin composition and the layer composed of the resin composition are used as at least one of the constituent layers of the polyolefin-based decorative sheet. Can be mentioned.

  As the polyolefin-based decorative sheet of the present invention, in addition to the polypropylene resin composition and the layer composed of the resin composition, a printed layer, a design layer, a protective coat layer, a gloss adjusting layer, a concealing layer, It is possible to use a constituent layer of a known decorative sheet such as an adhesive layer for adhering these layers.

  The layer comprising the polypropylene resin composition and the resin composition of the present invention is excellent in scratch resistance, abrasion resistance, whitening resistance during folding, crease resistance, heat resistance, and transparency. It can be suitably used as the outermost layer for protecting the picture layer.

  In addition, since the polypropylene resin composition and the layer comprising the resin composition of the present invention are excellent in scratch resistance and transparency, the surface protective layer for protecting the printing / pattern layer (protecting the printing / pattern layer) It is possible to perform a known treatment such as a protective coat layer and a gloss adjustment layer on the layer made of the polypropylene resin composition of the present invention within a range not impairing the object of the present invention. The polyolefin-based decorative sheet and the building material protective sheet having such a structure are particularly suitable.

  In addition, the polypropylene resin composition and the layer made of the resin composition of the present invention are excellent in flexibility and water resistance, and therefore can be suitably used as one layer when combined with a layer made of other components. At this time, the polypropylene resin composition and the layer composed of the resin composition of the present invention can be bonded without using a known adhesive or an adhesive having the same effect as the known adhesive. Specifically, sufficient adhesive strength can be exhibited by heat fusion such as a known thermal lamination method, extrusion lamination / sandwich lamination method, co-extrusion method, or the like. Therefore, the polypropylene resin composition and the layer made of the resin composition of the present invention can be suitably used as a polyolefin-based decorative sheet combined with a layer made of another polyolefin-based resin (including a known adhesive polyolefin resin layer).

  Although there is no restriction | limiting in particular as thickness of the layer which consists of a polypropylene resin composition and a resin composition of this invention, Usually, it is 5-2000 micrometers. The polyolefin decorative sheet or building material protective sheet may be subjected to known embossing, embossing, wiping, and the like.

  The polyolefin decorative sheet or building material protective sheet of the present invention is a state in which the back surface of a layer mainly composed of a polypropylene resin composition or a resin composition is laminated with other polyolefin resin layers without using an adhesive Preferably used. At this time, the other polyolefin-based resin is not particularly limited as long as it is other than the polypropylene resin composition or the composition itself constituting the layer mainly composed of the resin composition. Specific examples include polyethylene, polypropylene, poly α-olefin, ethylene / α-olefin copolymer, ethylene / polar vinyl monomer copolymer, and mixed resin compositions thereof. The state of being laminated without using an adhesive refers to the state of being directly heat-sealed and laminated.

  There is no restriction | limiting in particular as a manufacturing method of the polyolefin-type decorative sheet or building material protective sheet of this invention, A well-known method can be used.

  The use of the above-mentioned polyolefin-based decorative sheet is not particularly limited, and home appliances and furniture products such as TV cabinets, stereo speaker boxes, video cabinets, various storage furniture, unit furniture, doors, door frames, window frames, peripheral edges, Suitable for applications such as housing materials such as baseboards, opening frames, furniture members such as kitchens, storage furniture doors, flooring materials, ceiling materials, building materials such as wallpaper, automobile interior materials, home appliances, stationery, office supplies, etc. Can be used.

[Example]
EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The test methods evaluated in the examples and comparative examples are shown below.

i) Physical property test items Transparency The internal haze (%) was measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.

2. Scratch resistance A Martens hardness scratch hardness tester manufactured by Tokyo Shiki Co., Ltd. was used to measure the width of a groove generated when a sample was scratched by applying a 20 g scratch indenter to a 3 mm thick test piece, and the reciprocal number was calculated. .

3. In accordance with JIS K7196, a needle intrusion temperature (° C.) was determined from a TMA curve by applying a pressure of 2 kg / cm 2 to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min.

4). The whitening resistance test specimen was bent at 180 ° C. so as to be bilaterally symmetric, and the degree of whitening after placing a cylindrical weight having a radius of 5 cm 2 and a weight of 10 kg for 1 hour was visually evaluated.
○: No whitening, Δ: slight whitening, x marked whitening.

5. Abrasion resistance Using a Toyo Seiki, Gakushin Abrasion Tester, using a test piece with a thickness of 2 mm, the tip of a 45R, SUS wear indenter 470 g was covered with cotton canvas # 10, which was placed at 23 ° C. The sample was worn at a reciprocation frequency of 100 times, a reciprocation speed of 33 times / min, and a stroke of 100 mm, and the gloss change rate ΔGloss before and after that was determined as follows.
ΔGloss = (Gloss before wear−Gloss after wear) / Gloss × 100 before wear.

6). Tensile modulus;
In accordance with JIS K6301, a JIS No. 3 dumbbell was used, and measurement was performed at 23 ° C. with a span interval of 30 mm and a pulling speed of 30 mm / min.

ii) Raw material physical property test items Melting point (Tm), crystallization temperature (Tc) and glass transition temperature (Tg);
The DSC exotherm / endotherm curve is obtained, and the temperature at the maximum exothermic peak position when the temperature is lowered is Tc, the temperature at the maximum melting peak position when the temperature is raised is Tm, and the endothermic curve is observed between −100 ° C. and 0 ° C. The secondary transition point was Tg. The sample is packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min and held at 200 ° C. for 5 minutes, then cooled to −150 ° C. at 10 ° C./min, and then heated at 10 ° C./min. It was determined from the exothermic / endothermic curve during the process.

2. Intrinsic viscosity [η];
Measurements were made at 135 ° C. in decalin.

3. Mw / Mn;
GPC (gel permeation chromatography) was used and measured at 140 ° C. with an orthodichlorobenzene solvent.

Hereinafter, the synthesis methods and physical properties of the raw materials used in the examples and comparative examples are shown.
Synthesis Example 1 (Synthesis of syndiotactic propylene / ethylene copolymer (sPER-1))
750 ml of heptane was added at room temperature to a 1.5 liter autoclave that had been dried under reduced pressure and purged with nitrogen, and then a 1.0 mmol / ml toluene solution of triisobutylaluminum converted to aluminum atoms, the amount was 0.3 0.3 ml was added so as to have a millimolar amount, and 50.7 liters (25 ° C., 1 atm) of propylene was charged with stirring, and the temperature was raised to reach 30 ° C. Thereafter, the inside of the system was pressurized to 5.5 kg / cm 2 G with ethylene, and a heptane solution (0.0002 mM / ml) of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride synthesized by a known method was added. .75 ml, 2.0 ml of a toluene solution (0.002 mM / ml) of (triphenylcarbenium tetra (pentafluorophenyl) borate) was added to initiate copolymerization of propylene and ethylene. The catalyst concentrations at this time were 0.001 mmol / liter of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and 0.004 mmol / liter of triphenylcarbenium tetra (pentafluorophenyl) borate relative to the total system. Liters.

  During the polymerization, ethylene was continuously supplied to maintain the internal pressure at 5.5 kg / cm 2 G. 30 minutes after starting the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution is taken out, and the polymer solution is washed with a 1: 1 ratio of “an aqueous solution in which 5 ml of concentrated hydrochloric acid is added to 1 liter of water” to remove the catalyst residue. The water phase was transferred. After this catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Subsequently, the polymer liquid phase separated from oil and water was brought into contact with 3 times the amount of acetone under strong stirring to precipitate a polymer, and then sufficiently washed with acetone, and the solid part (copolymer) was collected by filtration. The obtained (co) polymer was dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

The yield of the syndiotactic propylene / ethylene copolymer (sPER-1) obtained as described above is 50 g, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 2.4 dl / g. The glass transition temperature Tg was −28 ° C., the ethylene content determined by C13-NMR was 24.0 mol%, and the molecular weight distribution (Mw / Mn) measured by GPC was 2.9. Note that substantially no melting peak was observed under the aforementioned DSC measurement conditions.
Synthesis Example 2 (Synthesis of syndiotactic propylene / ethylene copolymer (sPER-2))
After charging 833 ml of dry hexane and triisobutylaluminum (1.0 mmol) into a 2000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the polymerization apparatus internal temperature was raised to 90 ° C. and the pressure in the system was reduced to 0 with propylene. After pressurizing to 0.66 MPa, the system internal pressure was adjusted to 0.69 MPa with ethylene. Then, a toluene solution in which 0.001 mmol of diphenylmethylene (cyclopentadienyl) (octamethyldihydrobenzoylfluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (made by Tosoh Finechem) in contact with aluminum was contacted with the polymerizer The polymer was polymerized for 20 minutes while maintaining the internal temperature at 0.69 MPa with ethylene, and 20 ml of methanol was added to stop the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer is 46.4 g, intrinsic viscosity [η] is 2.3 dl / g, glass transition temperature Tg is −24 ° C., ethylene content is 19.0 mol%, The measured molecular weight distribution (Mw / Mn) was 2.3. Moreover, substantially no melting peak was observed under the above-mentioned DSC measurement conditions.
Synthesis Example 3 (Synthesis of syndiotactic propylene polymer (sPP))
According to the method described in JP-A-2-274663, it was obtained by bulk polymerization of propylene in the presence of hydrogen using a catalyst comprising diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and methylaluminoxane. Syndiotactic polypropylene has an MFR (230 ° C.) of 7.2 g / 10 min, a molecular weight distribution by GPC of 2.3, a syndiotactic pentad fraction (rrrr) measured by C13-NMR of 0.823, and differential scanning. Tm measured by calorimetric analysis was 127 ° C, and Tc was 57 ° C.
・ Isotactic polypropylene (iPP)
table. A propylene random copolymer having the physical properties described in 2 was used.
・ Ethylene / α-olefin copolymer (POE)
An ethylene / 1-butene random copolymer having an MFR (190 ° C.) of 3.6 g / 10 min, a density of 0.885 g / cm 3, a 1-butene content of 10.7 mol% and Mw / Mn = 2.0 Using.

[Examples 1 to 5]
table. A film having a single layer of 100 μm composed of the composition described in 3 was molded with a T-die cast molding machine (molding temperature 230 ° C.). The result of evaluating the characteristics of the obtained film is shown in Table. 3 shows.
[Example 6]
table. A 100 μm film having a two-layer structure composed of a layer (20 μm) composed of the composition described in 3 and a layer composed of a single POE (80 μm) was prepared by coextrusion using the T-die cast molding machine of Examples 1 to 4. The result of evaluating the characteristics of the obtained film is shown in Table. 4 shows.
[Comparative Example 1]
table. A film having a single layer of 100 μm composed of the composition described in 3 was molded with a T-die cast molding machine (molding temperature 230 ° C.). The result of evaluating the characteristics of the obtained film is shown in Table. 3 shows.

The polyolefin decorative sheet or building material protective sheet of the present invention is excellent in flexibility, scratch resistance, abrasion resistance, whitening resistance during bending, heat resistance, crease resistance, and water resistance. Is not particularly limited, home appliances and furniture products such as TV cabinets, stereo speaker boxes, video cabinets, various storage furniture, unit furniture, doors, door frames, window frames, surrounding edges, baseboards, opening frames, etc. It can be suitably used for applications such as members, kitchens, furniture members such as storage furniture doors, flooring materials, ceiling materials, construction materials such as wallpaper, automobile interior materials, home appliances, stationery, office supplies.

1 is an example in which the resin composition according to claim 1 is included in the “layer of the present invention (single layer)”, and claim 1 is not limited to these drawings. FIG. 2 shows an example in which the “layer (multilayer) of the present invention” includes the resin composition according to claim 1, and claim 1 is not limited to these drawings.

Claims (4)

(A) 0 to 90% by weight of isotactic polypropylene, (B) 0 to 90% by weight of syndiotactic polypropylene containing more than 90 mol% of structural units derived from propylene, and (C) derived from propylene Syndiotactic propylene / α-olefin containing structural units in an amount of 90 to 55 mol% and containing structural units derived from an α-olefin having 2 to 20 carbon atoms excluding propylene in an amount of 10 to 45 mol% A layer mainly composed of a polypropylene resin composition comprising 10 to 100% by weight of a copolymer (here, the total amount of (A), (B) and (C) is 100% by weight) A polyolefin-based decorative sheet or a building material protective sheet.
The ethylene / α-olefin random copolymer (D) having a crystallinity of 40% or less with respect to 100 parts by weight of the resin composition according to claim 1 in an amount of 1 to 40 parts by weight with respect to the entire composition. A polyolefin-based decorative sheet or a building material protective sheet, characterized in that a layer containing a resin composition as a main component is contained as a constituent layer.
A polyolefin-based decorative sheet or building material protective sheet having a multilayer structure, wherein the polypropylene resin composition according to claim 1 or a layer mainly composed of the resin composition according to claim 2 is used as a surface protective layer.
The back surface of the layer mainly composed of the polypropylene resin composition according to claim 1 or the resin composition according to claim 2 is laminated with a layer made of another polyolefin resin without an adhesive. The polyolefin-based decorative sheet or building material protective sheet according to claim 1 or 2.

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