HK1118074B

HK1118074B - Resin material for cosmetic sheet and cosmetic sheet

Info

Publication number: HK1118074B
Application number: HK08108976.3A
Authority: HK
Inventors: 远藤雅彦; 椋井美佐夫; 松本淳一
Original assignee: 普瑞曼聚合物有限公司
Priority date: 2005-02-01
Filing date: 2006-02-01
Publication date: 2013-01-18

Description

Resin material for decorative plate and decorative plate

Technical Field

The present invention relates to a propylene-ethylene copolymer which is useful as a sheet or film for building materials such as wall and floor materials, and particularly promotes non-polyvinyl chloride, and a resin material for a decorative sheet and a decorative sheet comprising the copolymer and the like, which are suitable for use as a decorative sheet.

Background

Conventionally, a polyvinyl chloride resin has been used as a sheet for building materials, but development of a non-polyvinyl chloride resin material has been promoted due to environmental problems caused by sick house syndrome (シツクハウスシンドロ - ム) and dioxin, and in particular, a product mainly composed of a polyolefin material such as polypropylene, polypropylene/styrene elastomer, low-regularity polypropylene, and the like, which are widely used, has been developed.

Polypropylene materials that are widely used have insufficient whitening resistance, and if the curvature during bending is small (stretching is large), there is a problem of whitening or the like.

As an improvement of this drawback, polypropylene/styrene-based elastomer additive systems and the like have been developed in the direction of softening, but in terms of morphology, stress at the time of deformation concentrates on the interface of the rubber portion, and therefore, the balance between whitening resistance, rigidity, heat resistance and the like is poor, or the cost increases, and there are many problems in industry.

In order to improve the above problems, a material using TPO (polyolefin-based thermoplastic resin) in which polypropylene having different stereoregularity is combined has been developed (for example, patent document 1), and although the balance between whitening resistance and heat resistance is improved, the balance between whitening resistance and rigidity is still insufficient.

TPO has a problem that, because it has low crystallinity and undergoes a large change with time, the film surfaces adhere to each other, and appearance defects are caused by peeling and whitening, in particular.

Further, when the polypropylene material is thickened, transparency is greatly reduced, and there is a problem that originality in lamination is reduced.

Patent document 1: japanese unexamined patent publication No. 9-226071

Disclosure of Invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a propylene-ethylene copolymer having an improved balance between whitening resistance and rigidity (scratch resistance), and having good transparency even at a constant thickness without causing appearance defects such as peeling and whitening due to mutual adhesion, and a resin material for decorative plate materials and a decorative plate material comprising the copolymer.

As a result of intensive studies to achieve the above object, the present inventors have found that a propylene-ethylene copolymer or the like satisfying specific conditions is most suitable as a resin material for decorative plate materials.

The present invention has been completed based on such findings.

Namely, the present invention provides the following:

1. a resin material for a decorative plate material, comprising the following component (A) or (B):

(A) a resin composition comprising a propylene-ethylene copolymer (a) satisfying the following conditions:

(1)[EEE]three unit group chain ratio (f)_EEE) Less than 0.1 mol%,

(2) The product (Re. Rp) of the reactivity ratios of ethylene and propylene is 0.5 or more,

(3) A molecular weight distribution (Mw/Mn) of 3.5 or less,

(4) A melting enthalpy (. DELTA.H) of 50 to 105J/g,

(5) A melting point (Tm) of 125 ℃ or higher, and

(6) an ethylene content of 10 mol% or less;

(B) a resin composition comprising a combination of 80 to 30% by mass of a polypropylene-based resin (b-1) and 20 to 70% by mass of a propylene-ethylene copolymer (b-2), wherein the polypropylene-based resin (b-1) comprises a propylene homopolymer or propylene and ethylene and/or butene-1, and Δ H is 80J/g or more, and the propylene-ethylene copolymer (b-2) satisfies the following conditions:

(1)[EEE]three unit group chain ratio (f)_EEE) Is 0.1 mol%The following components,

(3) A molecular weight distribution (Mw/Mn) of 3.5 or less,

(4) A melting enthalpy (Δ H) of 50J/g or less, and

(5) the ethylene content is 10 mol% or less.

2. A decorative plate material, wherein a surface layer or a coloring sheet is formed by laminating a printed pattern layer on a surface layer or a coloring sheet, the surface layer or the coloring sheet containing the resin material for a decorative plate material as described in 1 above.

According to the present invention, there can be obtained a propylene-ethylene copolymer, a resin material for a decorative plate material comprising the copolymer and the like, and a decorative plate material, the propylene-ethylene copolymer having the following characteristics: excellent balance between tensile whitening resistance and rigidity, good impact resistance, improved peeling whitening due to mutual adhesion during storage, and reduced thickness dependence of transparency.

Detailed Description

The resin material for a decorative plate material of the present invention comprises the following component (a):

(1)[EEE]three unit group chain ratio (f)_EEE) Less than 0.1 mol%,

(3) A molecular weight distribution (Mw/Mn) of 3.5 or less,

(4) A melting enthalpy (. DELTA.H) of 50 to 105J/g,

(5) A melting point (Tm) of 125 ℃ or higher, and

(6) the ethylene content is 10 mol% or less.

The propylene-ethylene copolymer (a) is described.

The measurement method thereof will be described later.

f_EEEPreferably 0.08 mol% or less, more preferably 0.05 mol% or less.

If the amount exceeds 0.1 mol%, the transparency may deteriorate.

If a Mg/Ti-based catalyst is used, f_EEETherefore, in order to make the catalyst content larger than 0.1 mol%, the catalyst system of the present invention described later is preferably used.

Re. Rp is preferably 1.0 or more, more preferably 1.1 or more.

If the content is not more than 0.5, the heat resistance may be insufficient.

Re. Rp can be controlled by the ratio of the amount of homopolymerization to the amount of random copolymerization.

That is, the Re. Rp can be set to 0.5 or more, for example, 5 mass% or more.

The Mw/Mn is preferably 3.3 or less, more preferably 3.0 or less.

If the content is not more than 3.5, the transparency may change with time due to the influence of the low molecular weight component or whitening may occur due to the influence of the high molecular weight component.

The Δ H is preferably 60 to 90J/g, more preferably 65 to 85J/g.

If Δ H is less than 50J/g, the rigidity (scratch resistance) is poor, and if Δ H exceeds 105J/g, the whitening resistance is poor.

The Tm is preferably 135 ℃ or higher, more preferably 145 ℃ or higher.

If the temperature is not 125 ℃ or higher, for example, the temperature is increased when bonding with another material or the temperature is set to a high temperature when applying an adhesive, wrinkles may occur or the appearance may change.

The ethylene content is preferably 1 to 7 mol%, more preferably 2 to 6 mol%.

If the amount is less than 1 mol%, the low-temperature impact resistance may be deteriorated, and if the amount exceeds 7 mol%, the heat resistance may be deteriorated.

Further, the resin material for a decorative plate material of the present invention comprises the following component (B):

(1)[EEE]three unit group chain ratio (f)_EEE) Less than 0.1 mol%,

(3) A molecular weight distribution (Mw/Mn) of 3.5 or less,

(4) A melting enthalpy (Δ H) of 50J/g or less, and

(5) the ethylene content is 10 mol% or less.

The resin material for decorative sheet material (B) of the present invention preferably contains 75 to 30 mass% of a combination of polypropylene resin (B-1) and 25 to 70 mass% of propylene-ethylene copolymer (B-2), and more preferably contains 70 to 30 mass% of polypropylene and 30 to 70 mass% of propylene-ethylene copolymer (B-2).

Next, the propylene-ethylene copolymer (B-2) used for the resin material for decorative plate material (B) will be described.

DELTA.H is preferably 45J/g or less, more preferably 40J/g or less.

If the content is not more than 50J/g, sufficient performance may not be obtained with respect to whitening resistance.

In addition, f_EEERe. Rp and Mw/Mn are the same as those of the propylene-ethylene copolymer (a).

F above_EEERe. Rp and the ethylene content in the copolymer can be determined as follows.

In the propylene (P) -ethylene (E) copolymer of the present invention, the following three unit group chains may be represented by the following three unit group chains in the formulae "Macromolecules", to "A.Zambelli et al,8687 (1975)'¹³The peak assignment of C-NMR was calculated from the following formula.

EPE＝I₈

PPE＝I₉+(I₁₀/2)+I₁₁

EEE＝(EEE/2)+(PEE/4)＝(I₁₂/2)+(I₁₃/4)

PPP＝I₁₄+(I₁₀/2)

PEE＝I₁₅

PEP＝I₁₆+(I₁₇+I₁₈)/4

Wherein, I₈Strength, I ═ 33.3ppm₉Strength, I ═ 31.1ppm₁₀Strength, I ═ 31.2ppm₁₁Strength, I ═ 34.1ppm₁₂Strength, I ═ 30.0ppm₁₃Strength, I ═ 30.4ppm₁₄Strength, I ═ 29.2ppm₁₅Strength, I ═ 27.3ppm₁₆Strength, I ═ 24.7ppm₁₇Strength, I ═ 34.9ppm₁₈Strength 34.6 ppm.

If T ═ EPE + PPE + EEE + PPP + PEE + PEP, the respective triad chain ratio (mol%) can be calculated from the following formula.

f_EPE＝(EPE/T)×100

f_PPE＝(PPE/T)×100

f_EEE＝(EEE/T)×100

f_PPP＝(PPP/T)×100

f_PEE＝(PEE/T)×100

f_PEP＝(PEP/T)×100

The two-unit group chain ratio can be calculated from the above three-unit group chain ratio as follows.

f_PP＝f_PPP+[f_PPE/2]

f_PE＝f_EPE+f_PEP+[(f_PPE+f_PEE)/2]

f_EE＝f_EEE+[f_PEE/2]

Re. Rp (the product of the reactivity ratios of ethylene and propylene) can be calculated from the two-unit group chain ratio as follows.

Re·Rp＝(4f_EE·f_PP)/(f_EP·f_EP)

The ethylene content (mol%) can be calculated from the following formula.

Ethylene content (mol%) < f_EE+(f_PE/2)

[¹³Measurement of C-NMR]

220mg of a sample was collected from an NMR sample tube having a diameter of 10mm, and 3mL of a mixed solvent of 1, 2, 4-trichlorobenzene and deuterated benzene (90/10 vol%) was added thereto.

Using an aluminum block heater (ァルミブロックヒ - タ) -, after uniformly dissolving at 140 deg.C, measuring¹³C-NMR spectrum.

The NMR measurement conditions were as follows.

NMR apparatus EX400(400MHz NMR apparatus) manufactured by Japan electronics

Pulse width 7.5 mus (45 degree pulse)

Pulse repetition time 4 seconds

Number of integration 1000

The measurement temperature was 130 deg.C

The Mw/Mn is measured by Gel Permeation Chromatography (GPC).

(GPC measurement device)

Column: TOSO GMHHR-H (S) HT

A detector: detector WATERS 150C for liquid chromatography

Measurement conditions

Solvent: 1, 2, 4-trichlorobenzene

Measuring temperature: 145 deg.C

Flow rate: 1.0 ml/min

Sample concentration: 2.2 mg/ml

Injection amount: 160 microliter

And (3) correcting a curve: universal calibration

And (3) analysis program: HT-GPC (Ver.1.0)

The Tm and Δ H are values obtained as follows.

10mg of a sample was melted at 230 ℃ for 3 minutes in a nitrogen atmosphere using a differential scanning calorimeter (manufactured by パ - キン. エルマ, DSC-7), and then cooled to 0 ℃ at 1 ℃/min, held at 0 ℃ for 3 minutes, and then heated at 10 ℃/min, and the enthalpy of fusion obtained therefrom was defined as Δ H.

The melting point (Tm) was defined as the peak top of the maximum peak of the melting endothermic curve obtained at this time.

After keeping at 230 ℃ for 3 minutes, the temperature was lowered to 0 ℃ at 10 ℃/min.

The peak top of the maximum peak of the crystallization heat generation curve obtained at this time was defined as the crystallization temperature (Tc).

The method for producing the propylene-ethylene copolymers (a) and (b-2) of the present invention is not limited, but it is preferable to use a mixture of (1) a metallocene catalyst imparting high crystallinity polypropylene and (2) a metallocene catalyst imparting low crystallinity polypropylene.

The metallocene catalyst (1) for imparting high crystallinity to polypropylene may be a single-crosslinking metallocene catalyst.

As the single-crosslinked metallocene catalyst, a transition metal compound represented by the general formula (I) can be exemplified.

[ chemical formula 1]

(in the formula, E¹Represents a binding group for crosslinking two conjugated five-membered ring ligands; r¹And R²Each represents a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; r³～R⁶Each represents a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; m¹Represents a transition metal of groups 4 to 6 of the periodic Table; x¹、Y¹Each represents a covalent ligand; in addition, X¹And Y¹They may also be bonded to each other to form a ring structure. )

As R¹～R⁶The hydrocarbon group of (1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 12 carbon atoms.

The hydrocarbon group may be bonded as a monovalent group to a cyclopentadienyl group as a conjugated five-membered ring, and additionally, may be presentWhen a plurality of such hydrocarbon groups are present, R¹、R³、R⁴2 or R in (1)²、R⁵、R⁶2 of them may be combined.

As the conjugated five-membered ring, substituted or unsubstituted cyclopentadienyl, indenyl and fluorenyl are mentioned.

Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and examples of the alkoxy group include alkoxy groups having 1 to 12 carbon atoms.

As E¹The following groups may be mentioned: (1) alkylene and cycloalkylene having 1 to 4 carbon atoms such as methylene, ethylene, isopropylene, methylphenylmethylene, diphenylmethylene, cyclohexylene, or a substituent of a lower alkyl or phenyl group in the side chain thereof; (2) silylene, oligosilylene, or a side chain lower alkyl or phenyl substituent thereof, such as silylene, dimethylsilylene, methylphenylene, diphenylsilylene, disilylene, tetramethyldisilylene, etc.; (3) hydrocarbyl [ lower alkyl, phenyl, hydrocarbyloxy (preferably lower alkoxy), etc.) containing germanium, phosphorus, nitrogen, boron or aluminum]Specifically, (CH) can be enumerated₃)₂Ge radical, (C)₆H₅)₂Ge radical, (CH)₃) P radical, (C)₆H₅) P radical, (C)₄H₉) N radical, (C)₆H₅) N radical, (CH)₃) B group, (C)₄H₉) B group, (C)₆H₅) B group, (C)₆H₅) Al radical, (CH)₃O) Al group, etc.

Among them, alkylene and silylene are preferable.

M¹The transition metal of groups 4 to 6 of the periodic table includes, specifically, titanium, zirconium, hafnium, niobium, molybdenum, tungsten, etc., among which titanium, zirconium and hafnium are preferable, and zirconium is particularly preferable.

X¹And Y¹Each is a covalent ligand, specifically a hydrogen atom, a halogen atom, a C1-20, preferably C1-10 hydrocarbyl group, a C1-20, preferably C1-10 alkoxy groupA group, an amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (e.g., diphenylphosphine, etc.), a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (e.g., trimethylsilyl, etc.), a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen-containing boron compound (e.g., BF)₄、B(C₆H₅)₄)。

Of these, halogen atoms and hydrocarbon groups are preferable.

The X is¹And Y¹May be the same or different.

Specific examples of the transition metal compound represented by the general formula (I) include the following compounds.

(a) Methylene bis (indenyl) titanium dichloride, ethylene bis (indenyl) titanium dichloride, methylene bis (indenyl) titanium hydrochloride, ethylene bis (indenyl) titanium methylchloride, ethylene bis (indenyl) titanium methoxychloride, ethylene bis (indenyl) diethoxytitanium, ethylene bis (indenyl) dimethyltitanium, ethylene bis (4, 5, 6, 7-tetrahydroindenyl) titanium dichloride, ethylene bis (2-methylindenyl) titanium dichloride, ethylene bis (2, 4, 7-trimethylindenyl) titanium dichloride, ethylene bis (2-methyl-4, 5-benzindenyl) titanium dichloride, ethylene bis (2-methyl-4-phenylindenyl) titanium dichloride, ethylene bis (2-methyl-4, 5, 6, 7-tetramethylindenyl) titanium dichloride, Ethylene bis (2-methyl-5, 6-dimethylindenyl) titanium dichloride, ethylene bis (2-methyl-4- (1-naphthyl) indenyl) titanium dichloride, ethylene bis (2-methyl-4- (2-naphthyl) indenyl) titanium dichloride, ethylene bis (2-methyl-4-isopropylindenyl) titanium dichloride, ethylene bis (2-ethyl-4-phenylindenyl) titanium dichloride, ethylene bis (2-methyl-4-toluoylindenyl) titanium dichloride, ethylene bis (2, 4-dimethylindenyl) titanium dichloride, ethylene bis (2-methyl-4-trimethylsilylindenyl) titanium dichloride, ethylene bis (2, 4-dimethyl-5, 6, 7-trihydroindenyl) titanium dichloride, ethylene (2, 4-dimethylcyclopentadienyl) (3 ', 5 ' -dimethylcyclopentadienyl) titanium dichloride, ethylene (2-methyl-4-tert-butylcyclopentadienyl) (3 ' -tert-butyl-5 ' -methylcyclopentadienyl) titanium dichloride, ethylene (2, 3, 5-trimethylcyclopentadienyl) (2 ', 4 ', 5 ' -trimethylcyclopentadienyl) titanium dichloride, isopropylidene bis (2-methylindenyl) titanium dichloride, isopropylidene bis (indenyl) titanium dichloride, isopropylidene bis (2, 4-dimethylindenyl) titanium dichloride, isopropylidene (2, 4-dimethylcyclopentadienyl) (3 ', 5 ' -dimethylcyclopentadienyl) titanium dichloride, titanium (2, 4-dimethyl, Alkylene-crosslinked transition metal compounds having 2 conjugated five-membered ring ligands such as isopropylene (2-methyl-4-t-butylcyclopentadienyl) (3 '-t-butyl-5' -methylcyclopentadienyl) titanium dichloride, ethylene bis (2-methylbenzindenyl) titanium dichloride, ethylene bis (benzindenyl) titanium dichloride and the like;

(b) dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (indenyl) titanium methylchloride, dimethylsilylenebis (indenyl) titanium methoxychloride, dimethylsilylenebis (indenyl) diethoxytitanium, dimethylsilylenebis (indenyl) titanium dimethylchloride, dimethylsilylenebis (4, 5, 6, 7-tetrahydroindenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2, 4, 7-trimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4, 5-benzindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4, 5, 6, 7-tetramethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-5, 6-dimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4- (1-naphthyl) indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4- (2-naphthyl) indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylenebis (2-ethyl-4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-toluoylindenyl) titanium dichloride, dimethylsilylenebis (2, 4-dimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-trimethylsilylindenyl) titanium dichloride, dimethylsilylenebis (2, 4-dimethyl-5, 6, 7-trihydroindenyl) titanium dichloride, dimethylsilylene (2, 4-dimethylcyclopentadienyl) (3 ', 5 ' -dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (2-methyl-4-tert-butylcyclopentadienyl) (3 ' -tert-butyl-5 ' -methylcyclopentadienyl) titanium dichloride, dimethylsilylene (2, 3, 5-trimethylcyclopentadienyl) (2 ', 4 ', 5 ' -trimethylcyclopentadienyl) titanium dichloride, titanium dioxide, a transition metal compound having 2 conjugated five-membered cyclic ligands crosslinked by silylene group, such as isopropylidene bis (2-methylindenyl) titanium dichloride, isopropylidene bis (indenyl) titanium dichloride, isopropylidene bis (2, 4-dimethylindenyl) titanium dichloride, isopropylidene (2, 4-dimethylcyclopentadienyl) (3 ', 5' -dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-tert-butylcyclopentadienyl) (3 '-tert-butyl-5' -methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylbenzindenyl) titanium dichloride, and dimethylsilylene bis (benzindenyl) titanium dichloride;

further, there may be mentioned compounds obtained by substituting chlorine atoms in the compounds described in the above (a) to (b) with bromine atoms, iodine atoms, methyl groups, phenyl groups, etc.; or compounds obtained by substituting titanium as the central metal of the transition metal compounds with zirconium, hafnium, niobium, tungsten, etc.

The metallocene catalyst (2) for imparting low-crystalline polypropylene used in the process for producing the propylene-ethylene copolymers (a) and (b-2) of the present invention includes a dicross-linked metallocene catalyst.

Examples of the double-crosslinking metallocene catalyst include transition metal compounds represented by the general formula (II) or the general formula (III).

[ chemical formula 2]

[ chemical formula 3]

(in the formula, E²And E³Represents a binding group for crosslinking two conjugated five-membered ring ligands; r⁹～R¹⁸Each represents a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; r⁷、R⁸、R¹⁹And R²⁰Each represents a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; m²Represents a transition metal of groups 4 to 6 of the periodic Table; x²、Y²Each represents a covalent ligand; in addition, X¹And Y¹They may also be bonded to each other to form a ring structure. )

As R⁷～R²⁰The hydrocarbon group of (1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 12 carbon atoms.

The hydrocarbon group may be bonded to the cyclopentadienyl group as a conjugated five-membered ring as a monovalent group, and when a plurality of the hydrocarbon groups are present, in the general formula (II), R⁷And R⁹Or R⁸And R¹⁰May be combined, in the general formula (III), R¹¹～R¹⁴、R²⁰Or R¹⁵～R¹⁹2 of them may be combined.

As the E²And E³The following groups may be mentioned: (1) alkylene and cycloalkylene having 1 to 4 carbon atoms such as methylene, ethylene, isopropylene, methylphenylmethylene, diphenylmethylene, cyclohexylene, or a substituent of a lower alkyl or phenyl group in the side chain thereof; (2) silylene, dimethylmethyleneSilylene group, oligosilylene group, or side chain lower alkyl or phenyl substituent thereof, such as silylene group, methylphenylene group, diphenylsilylene group, disilylene group, tetramethyldisilylene group, etc.; (3) hydrocarbyl [ lower alkyl, phenyl, hydrocarbyloxy (preferably lower alkoxy), etc.) containing germanium, phosphorus, nitrogen, boron or aluminum]Specifically, (CH) can be enumerated₃)₂Ge radical, (C)₆H₅)₂Ge radical, (CH)₃) P radical, (C)₆H₅) P radical, (C)₄H₉) N radical, (C)₆H₅) N radical, (CH)₃) B group, (C)₄H₉) B group, (C)₆H₅) B group, (C)₆H₅) Al radical, (CH)₃O) Al group, etc.

Among them, alkylene and silylene are preferable.

E²And E³May be the same or different.

M²The transition metal of groups 4 to 6 of the periodic table includes, specifically, titanium, zirconium, hafnium, niobium, molybdenum, tungsten, etc., among which titanium, zirconium and hafnium are preferable, and zirconium is particularly preferable.

X²And Y²Each is a covalent ligand, specifically a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (e.g., diphenylphosphine, etc.), a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (e.g., trimethylsilyl, etc.), a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen-containing boron compound (e.g., BF)₄、B(C₆H₅)₄)。

Of these, halogen atoms and hydrocarbon groups are preferable.

The X is²And Y²May be the same or different.

Examples of the transition metal compound represented by the general formula (II) include (1, 2 '-ethylene) (2, 1' -ethylene) -bis (3-trimethylsilylcyclopentadienyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-trimethylsilylcyclopentadienyl) titanium dichloride, (1, 2 '-ethylene) (2, 1' -ethylene) -bis (3-trimethylsilyl-4-methylcyclopentadienyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-trimethylsilyl-4-methylcyclopentadienyl) titanium dichloride and the like.

Further, among the above-mentioned compounds, compounds obtained by substituting chlorine atom in these compounds with bromine atom, iodine atom, methyl group, phenyl group, etc.; or compounds obtained by substituting titanium as the central metal of the transition metal compounds with zirconium, hafnium, niobium, tungsten, etc.

Examples of the transition metal compound represented by the general formula (III) include (1, 2 '-ethylene) (2, 1' -ethylene) -bis (3-methylindenyl) titanium dichloride, (1, 2 '-ethylene) (2, 1' -ethylene) -bis (3-methyl-4-isopropylindenyl) titanium dichloride, (1, 2 '-ethylene) (2, 1' -ethylene) -bis (3-methyl-5, 6-benzindenyl) titanium dichloride, (1, 2 '-ethylene) (2, 1' -isopropylene) -bis (3-methylindenyl) titanium dichloride, (1, 2 '-methylene) (2, 1' -ethylene) -bis (3-methylindenyl) titanium dichloride, titanium dichloride, (1, 2 '-methylene) (2, 1' -isopropylidene) -bis (3-methylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-n-butylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-isopropylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-trimethylsilylmethindenyl) titanium dichloride, titanium (I, II, III) and titanium (II), (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-phenylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-methyl-4, 5-benzoindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-methyl-4-isopropylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3, 5, 6-trimethylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-methyl-4, 7-diisopropylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-methyl-4-phenylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) -bis (3-methyl-4-isopropylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -isopropylidene) -bis (3-methylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -isopropylidene) -bis (3-isopropylidene) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -isopropylidene) -bis (3-isopropylindenyl) titanium dichloride, (1, 2 '-dimethylsilylene) (2, 1' -isopropylidene) -bis (3-n-butylindenyl) titanium dichloride, titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -isopropylidene) -bis (3-trimethylsilylmethyl indenyl) titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -isopropylidene) -bis (3-methylsilylindenyl) titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -isopropylidene) -bis (3-phenylindenyl) titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -methylene) -bis (3-methylindenyl) titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -methylene) -bis (3-isopropylindenyl) titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -methylene) -bis (3-n-butylindenyl) titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -methylene) -bis (3-trimethylsilylmethyl indenyl) titanium dichloride, (1, 2 ' -dimethylsilylene) (2, 1 ' -methylene) -bis (3-methylsilylindenyl) titanium dichloride, (1, 2 ' -diphenylsilylene) (2, 1 ' -methylene) -bis (3-methylindenyl) titanium dichloride, (1, 2 ' -diphenylsilylene) (2, 1 ' -methylene) -bis (3-isopropylindenyl) titanium dichloride, (1, 2 ' -diphenylsilylene) (2, 1 ' -methylene) -bis (3-n-butylindenyl) titanium dichloride, titanium, (1, 2 '-diphenylsilylene) (2, 1' -methylene) -bis (3-trimethylsilylmethyl indenyl) titanium dichloride, (1, 2 '-diphenylsilylene) (2, 1' -methylene) -bis (3-methylsilylindenyl) titanium dichloride, and the like.

The mixing ratio (molar ratio) of the metallocene catalyst for imparting high-crystallinity polypropylene and the metallocene catalyst for imparting low-crystallinity polypropylene is usually 1/1000 to 1000/1, preferably 1/1000 to 100/1, and more preferably 1/1000 to 10/1.

If the amount is within this range, propylene-ethylene copolymers (a) and (b-2) having sufficient softness can be obtained.

Next, as the (3-1) catalyst component among the (3) catalyst components, any compound may be used as long as it can react with the transition metal compounds of the above-mentioned (1) catalyst component and (2) catalyst component to form an ionic compound, but it is preferable to use a compound represented by the following general formula (IV) or (V).

([L¹-R²¹]^k+)_a([Z]^-)_b...(IV)

([L²]^k+)_a([Z]^-)_b...(V)

(wherein, L²Is M³、R²²R²³M⁴、R²⁴ ₃C or R²⁵M⁵。)

[ (IV), (V) wherein L¹Is a Lewis base, [ Z ]]^-Is a non-coordinating anion [ Z¹]^-And [ Z²]^-，[Z¹]^-Anions bound to the element as a plurality of radicals, i.e. [ M ]³G¹G²...G^f]^-(wherein, M³Represents an element of groups 5 to 15 of the periodic table, preferably an element of groups 13 to 15 of the periodic table. G¹G^fEach represents a hydrogen atom or a halogen atomAn alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an organometalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. G¹～G^f2 or more of them may form a ring. f represents [ (central metal M)³Valence of (2) +1]An integer of (a),

[Z²]^-A conjugate base of a bronsted acid alone or a combination of a bronsted acid and a lewis acid, or an acid generally defined as a super acid, which represents that the logarithm of the reciprocal of the acid dissociation constant (pKa) is-10 or less. In addition, Lewis bases may also be coordinated.

R²¹Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, R²²And R²³Each represents cyclopentadienyl, substituted cyclopentadienyl, indenyl or fluorenyl, R²⁴Represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms.

R²⁵Represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine.

K is [ L ]¹-R²¹]、[L²]The ion valence of (a) is an integer of 1 to 3, a is an integer of 1 or more, and b is (k × a).

M⁴Is a group containing an element of groups 1 to 3, 11 to 13, 17 of the periodic Table, M⁵Represents an element of groups 7 to 12 of the periodic table.]

Wherein as L¹Specific examples of the organic solvent include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N-dimethylaniline, trimethylamine, triethylamine, tri-N-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylanilineAmines such as aniline; phosphines such as triethylphosphine, triphenylphosphine, and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; nitriles such as acetonitrile and benzonitrile.

As R²¹Specific examples of (3) include hydrogen, methyl, ethyl, benzyl and trityl, and R is²²、R²³Specific examples thereof include cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, and pentamethylcyclopentadienyl.

As R²⁴Specific examples of (3) include phenyl, p-tolyl and p-methoxyphenyl, and R is²⁵Specific examples of the compound include tetraphenylporphin, phthalocyanine, allyl group and methallyl group.

In addition, as M⁴Specific examples of (3) include Li, Na, K, Ag, Cu, Br, I and I₃Etc. as M⁵Specific examples of the metal include Mn, Fe, Co, Ni and Zn.

In [ Z ]¹]^-I.e., [ M³G¹G²...G^f]^-In (b) as M³Specific examples of (3) include B, Al, Si, P, As and Sb, and B and Al are preferable.

As G¹、G²～G^fSpecific examples of the dialkylamino group include a dimethylamino group, a diethylamino group and the like, and an alkoxy group or aryloxy group, examples of the hydrocarbon group include a methoxy group, an ethoxy group, an n-butoxy group and a phenoxy group, examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-octyl group, an n-eicosyl group, a phenyl group, a p-tolyl group, a benzyl group, a 4-tert-butylphenyl group and a 3, 5-dimethylphenyl group, and examples of the halogen atom, examples of the heteroatom-containing hydrocarbon group include a p-fluorophenyl group, a 3, 5-difluorophenyl group, a pentachlorophenyl group, a 3, 4, 5-trifluorophenyl group, a pentafluorophenyl group, a 3, 5-bis (trifluoromethyl) phenyl group, a bis (trimethylsilyl) methyl group and the like, and examples of the organometalloid group include a pentamethylantimo group and a trimethylsilane group.Alkyl, trimethylgermyl, diphenylarsine, dicyclohexylantimony, diphenylboron, and the like.

As a non-coordinating anion, i.e. a conjugate base [ Z ] of a Bronsted acid alone or in combination with a Lewis acid having a pKa of-10 or less²]^-Specific examples of (3) include trifluoromethanesulfonic acid anion (CF)₃SO₃)^-Bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide group, and perchlorate anion (ClO)₄)^-Trifluoroacetic acid anion (CF)₃CO₂)^-Antimony hexafluoride anion (SbF)₆)^-Fluorosulfonic acid anion (FSO)₃)^-Chlorosulfonic acid anion (ClSO)₃)^-Fluorosulfonic acid anion/antimony pentafluoride (FSO)₃/SbF₅)^-Fluorosulfonic acid anion/arsenic pentafluoride (FSO)₃/AsF₅)^-Trifluoromethanesulfonic acid/antimony pentafluoride (CF)₃SO₃/SbF₅)^-And the like.

Specific examples of the ionic compound which reacts with the transition metal compound of the catalyst component (1) and the catalyst component (2) to form an ionic complex compound, i.e., (3-1) the catalyst component compound, include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenylmethylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, picolinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl (2-cyanopyridinium) tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetraphenylborate, tetramethylammonium tetraphenylborate, and the like, Triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenylmethylammonium tetrakis (pentafluorophenyl) borate, methylphenylammonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium tetrakis (pentafluorophenyl) borate, methyl (4-cyanopyridinium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [ bis (3), 5-bis (trifluoromethyl)) phenyl ] ammonium dimethylbenzyl borate, ferrocene tetraphenyl borate, silver tetraphenyl borate, trityl tetraphenyl borate, manganese tetraphenyl porphyrin tetraphenyl borate, ferrocene tetrakis (pentafluorophenyl) borate, 1' -dimethylferrocene tetrakis (pentafluorophenyl) borate, decamethylferrocene tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, manganese tetraphenyl porphyrin tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate, and the like.

The catalyst component (3-1) may be used singly or in combination of two or more.

On the other hand, as the aluminoxane of the catalyst component (3-2), there can be mentioned a chain aluminoxane represented by the general formula (VI):

[ chemical formula 4]

(in the formula, R²⁶Represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, aralkyl group or the like having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen atom, and w represents an integer having an average degree of polymerization of usually 2 to 50, preferably 2 to 40. Each R²⁶May be the same or different); and

a cyclic aluminoxane represented by the general formula (VII):

[ chemical formula 5]

(in the formula, R²⁶And w is the same as R in the above general formula (VI)²⁶And w are the same).

The method for producing the aluminoxane is exemplified by a method of contacting an alkylaluminum with a condensing agent such as water, but the method is not particularly limited and the reaction can be carried out by a known method.

For example, the following methods are available: (1) a method in which an organoaluminum compound is dissolved in an organic solvent and then contacted with water; (2) a method of adding an organoaluminum compound at the beginning of polymerization, followed by addition of water; (3) a method of reacting crystal water contained in a metal salt or the like, or water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound; (4) a method of reacting trialkylaluminum with tetraalkyldialuminoxane and then reacting water, and the like.

As the aluminoxane, it may be insoluble in toluene.

These aluminoxanes may be used singly or in combination of two or more.

(1) The ratio of the total amount of the catalyst component (3) and the catalyst component (2) to the catalyst component (3) is preferably in the range of 10:1 to 1:100, more preferably 2:1 to 1:10 in terms of molar ratio when the catalyst component (3-1) compound is used as the catalyst component (3), and if the ratio is in the above range, the catalyst cost per unit mass of the polymer is low, and it is practical.

When the catalyst component compound (3-2) is used, the molar ratio is preferably in the range of 1:1 to 1:1000000, more preferably 1:10 to 1: 10000.

If the amount is within this range, the cost of the catalyst per unit mass of the polymer is low, and it is practical.

Further, as the catalyst component (3), the catalyst component (3-1) and the catalyst component (3-2) may be used singly or in combination of two or more.

The polymerization catalyst for producing the propylene-ethylene copolymers (a) and (b-2) may contain an organoaluminum compound as (4) the catalyst component in addition to the above-mentioned catalyst components (1), (2) and (3).

As the organoaluminum compound as the catalyst component (4), a compound represented by the general formula (VIII) can be used.

R²⁷ _vAlJ_3-v...(VIII)

[ in the formula, R²⁷Represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a halogen atom, and v is an integer of 1 to 3.]

Specific examples of the compound represented by the above general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisopropylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride.

One kind of these organoaluminum compounds may be used, or two or more kinds thereof may be used in combination.

In the process for producing the propylene-ethylene copolymers (a) and (b-2), the above-mentioned (1) catalyst component + (2) catalyst component, (3) catalyst component and (4) catalyst component may be used for preliminary contact.

The pre-contact can be carried out by, for example, (3) contacting the catalyst component with (1) the catalyst component + (2) the catalyst component, and the method is not particularly limited, and a known method can be used.

The use of such precontacting is effective for improving the catalyst activity, reducing the use ratio of the catalyst component (3) as a co-catalyst, and the like, and reducing the catalyst cost.

The precontacting temperature is usually-20 ℃ to 200 ℃, preferably-10 ℃ to 150 ℃, more preferably 0 ℃ to 80 ℃.

In the precontacting, as the inert hydrocarbon of the solvent, an aliphatic hydrocarbon, an aromatic hydrocarbon or the like can be used.

Among them, aliphatic hydrocarbons are particularly preferable.

The molar ratio of the total amount of the catalyst component (1) and the catalyst component (2) to the catalyst component (4) is preferably 1:1 to 1:10000, more preferably 1:5 to 1:2000, and still more preferably 1:10 to 1: 1000.

The use of the catalyst component (4) can improve the polymerization activity per the transition metal, but if the amount is too large, the organoaluminum compound is wasted and remains in the polymer in a large amount, which is not preferable.

As the porous carrier, specifically, SiO can be cited₂、Al₂O₃、MgO、ZrO₂、TiO₂、Fe₂O₃、B₂O₃、CaO、ZnO、BaO、ThO₂Or mixtures thereof, such as silica alumina, zeolites, ferrites, glass fibers, and the like.

Among them, SiO is particularly preferable₂、Al₂O₃。

The porous carrier may also contain small amounts of carbonates, nitrates, sulfates, etc.

On the other hand, as a carrier other than those mentioned above, MgCl may be mentioned₂、Mg(OC₂H₅)₂Is represented by the general formula MgR²⁸ _xX¹ _yThe magnesium compound represented by the formula (I) or a complex salt thereof.

Wherein R is²⁸Represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atomsOr an aryl group having 6 to 20 carbon atoms, X¹Represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y is 2.

Each R²⁸And each X¹Each may be the same or different.

Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly-1-butene, substituted polystyrene, and polyarylate, starch, and carbon.

MgCl is preferred as a carrier for the catalyst used in the production of the propylene-ethylene copolymers (a) and (b-2)₂、MgCl(OC₂H₅)、Mg(OC₂H₅)₂And the like.

The carrier has an average particle diameter of usually 1 to 300. mu.m, preferably 10 to 200. mu.m, and more preferably 20 to 100. mu.m, depending on the type and production method thereof.

When the particle diameter is small, the fine powder in the polymer increases, and when the particle diameter is large, the coarse particles in the polymer increase, which causes a decrease in bulk density or hopper clogging.

The specific surface area of the carrier is usually 1 to 1000m²Preferably 50 to 500 m/g²The pore volume is usually 0.1-5 cm³A preferred concentration is 0.3 to 3cm³/g。

When the specific surface area or pore volume is within the above range, the catalyst activity is increased.

The specific surface area and the pore volume can be determined from the volume of nitrogen adsorbed by the BET method, for example.

When the carrier is an inorganic oxide carrier, it is generally desirable to use the carrier after sintering at 150 to 1000 ℃, preferably 200 to 800 ℃.

When at least one of the catalyst components is supported on the carrier, it is desirable to support at least one of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component, and it is preferable to support both of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component.

A method of supporting at least one of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component on the carrier is not particularly limited, and there can be used, for example, (a) a method of mixing at least one of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component with the carrier; (b) a method of treating a carrier with an organoaluminum compound or a halogenosilicon compound and then mixing the treated carrier with at least one of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component in an inert solvent; (c) a method of reacting a carrier with (1) a catalyst component + (2) a catalyst component, and/or (3) a catalyst component and an organoaluminum compound or a halogenosilicon compound; (d) a method in which (1) the catalyst component + (2) the catalyst component or (3) the catalyst component is supported on a carrier and then mixed with (3) the catalyst component or (1) the catalyst component + (2) the catalyst component; (e) a method of mixing a contact reactant of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component with a carrier; (f) a method of allowing the carrier to coexist during the contact reaction of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component.

In the above-mentioned methods (d), (e) and (f), an organoaluminum compound of the catalyst component (4) may be further added.

In the production of the catalyst used for the production of the propylene-ethylene copolymers (a) and (b-2), the catalyst can be prepared by irradiating an elastic wave while bringing the catalyst component (1), (2), (3) and (4) into contact with each other.

As the elastic wave, acoustic waves are generally used, and ultrasonic waves are particularly preferred.

Specifically, the ultrasonic wave having a frequency of 1 to 1000kHz, preferably 10 to 500kHz, can be mentioned.

The catalyst thus obtained may be used for polymerization after distilling off the solvent to prepare a solid and then taking out the solid, or may be used for polymerization as it is.

In addition, in the production of the propylene-ethylene copolymer, the catalyst can be produced by carrying at least one of (1) the catalyst component + (2) the catalyst component and (3) the catalyst component on a carrier in the polymerization system.

For example, the following method may be used: the catalyst particles are produced by adding (1) the catalyst component + (2) at least one of the catalyst component and (3) the catalyst component and, if necessary, the organoaluminum compound of the catalyst component (4), adding an olefin such as ethylene under normal pressure to 2MPa, and prepolymerizing at-20 to 200 ℃ for about 1 minute to 2 hours.

In the catalyst used for producing the propylene-ethylene copolymers (a) and (b-2), the ratio of the catalyst component (3-1) to the carrier is preferably 1:5 to 1:10000, more preferably 1:10 to 1:500, and the ratio of the component (3-2) to the carrier is preferably 1:0.5 to 1:1000, more preferably 1:1 to 1:50, in terms of mass ratio.

When two or more catalyst components (3) are mixed and used, the ratio of each catalyst component (3) to the carrier is preferably within the above range.

The ratio of (1) the catalyst component to (2) the catalyst component to the carrier is preferably 1:5 to 1:10000, more preferably 1:10 to 1:500, in terms of mass ratio.

(3) When the ratio of the catalyst component [ (3-1) catalyst component or (3-2) catalyst component ] to the carrier or the ratio of (1) catalyst component + (2) catalyst component to the carrier falls within the above range, the activity increases or the powder form also increases.

The average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200. mu.m, preferably 10 to 150. mu.m, particularly preferably 20 to 100. mu.m, and the specific surface area is usually 20 to 1000m²Preferably 50 to 500 m/g²/g。

When the average particle diameter is 2 μm or more, the fine particles in the polymer decrease, and when the average particle diameter is 200 μm or less, the coarse particles in the polymer decrease.

If the specific surface area is 20m²When the specific molecular weight is 1000m or more, the activity increases²When the ratio is less than g, the bulk density of the polymer increases.

In the catalyst used for producing the propylene-ethylene copolymers (a) and (b-2), the amount of the transition metal in 100g of the carrier is usually 0.05 to 10g, and particularly preferably 0.1 to 2 g.

When the amount of the transition metal is within the above range, the activity is increased.

The polymerization of propylene in the first step may be selected from slurry polymerization or bulk polymerization.

The copolymerization of propylene and ethylene in the second step may be selected from slurry, bulk and gas phase polymerizations.

The first and second processes may also be a multi-stage polymerization.

The polymerization conditions for homopolymerization of propylene are not particularly limited, but the polymerization pressure is usually from atmospheric pressure to 8MPa, preferably from 0.2 to 5MPa, and the polymerization temperature is usually from 0 to 200 ℃, preferably from 30 to 100 ℃.

The polymerization time is usually 5 minutes to 20 hours, preferably about 10 minutes to 10 hours.

The polymerization conditions in the copolymerization part are not particularly limited, but the polymerization pressure is usually from atmospheric pressure to 8MPa, preferably from 0.2 to 5MPa, and the polymerization temperature is usually from 0 to 200 ℃, preferably from 20 to 100 ℃.

The polymerization time is usually 1 minute to 20 hours, preferably about 1 minute to 10 hours.

The ratio of propylene to ethylene supplied is 0.01 to 9, preferably 0.05 to 2.3 in terms of a molar ratio.

The molecular weight of the polymer in the propylene homo-and copolymerization portions can be adjusted by adding a chain transfer agent, preferably by performing hydrogen addition.

In addition, an inert gas such as nitrogen may be present.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aliphatic hydrocarbons such as pentane, hexane, heptane and octane; halogenated hydrocarbons such as chloroform and methylene chloride.

These solvents may be used alone or in combination of two or more.

In addition, depending on the polymerization method, it may be carried out in the absence of a solvent.

In the polymerization, the catalyst for polymerization may be used for preliminary polymerization.

The prepolymerization can be carried out by, for example, bringing a small amount of an olefin into contact with the solid catalyst component, and the method is not particularly limited, and a known method can be used.

The olefin used in the preliminary polymerization is not particularly limited, and the same olefins as those listed above, for example, ethylene, an α -olefin having 3 to 20 carbon atoms, or a mixture thereof can be used.

The temperature of the prepolymerization is usually-20 to 200 ℃, preferably-10 to 130 ℃, and more preferably 0 to 80 ℃.

In the preliminary polymerization, as a solvent, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used.

Among them, aliphatic hydrocarbons are particularly preferable.

The prepolymerization can also be carried out in the absence of a solvent.

In the preliminary polymerization, it is desirable to adjust the conditions so that the intrinsic viscosity [ eta ] (measured in decalin at 135 ℃) of the preliminary polymerization product is 0.2dl/g or more, particularly 0.5dl/g or more, and the amount of the preliminary polymerization product is 1 to 10000g, particularly 10 to 1000g, per 1 mmol of the transition metal component in the catalyst.

The higher the ratio of the metallocene catalyst imparting low-crystallinity polypropylene/the metallocene catalyst imparting high-crystallinity polypropylene used, the more the amount of ethylene used, and the more flexible propylene-ethylene copolymers (a) and (b-2) can be obtained.

If a metallocene catalyst is used, the internal haze value can be controlled to less than 55%.

As the polypropylene resin (b-1) having a Δ H of 80J/g or more in the present invention, a polypropylene homopolymer having a Δ H of 80J/g or more, or a random copolymer or a block copolymer of propylene and ethylene and/or butene-1 is used.

The polypropylene resin (b-1) of the present invention can be produced by a usual method regardless of the catalyst system such as Mg/Ti-based catalyst or metallocene-based catalyst, and preferably has a Tm of 135 ℃ or higher and a tensile elastic modulus of 800MPa or higher.

The resin material for decorative plate materials of the present invention is not particularly limited, and can be produced by dry-blending each component (resin component and various additives used as needed) constituting a resin composition containing the above-mentioned propylene-ethylene copolymer (a) or a resin composition containing a combination of 80 to 30 mass% of a polypropylene resin (b-1) having a Δ H of 80J/g or more and 20 to 70 mass% of the above-mentioned propylene-ethylene copolymer (b-2) using a henschel mixer or the like, and melt-kneading the dry-blended resin composition by a uniaxial or biaxial extruder, a banbury mixer or the like.

Alternatively, a masterbatch may be used.

Examples of the various additives to be used as needed include various stabilizers, softeners, inorganic fillers, organic fillers, pigments, foaming agents, flame retardants, and other nucleating agents.

As the various stabilizers, stabilizers against oxidative deterioration, thermal deterioration and the like are most commonly used, and for example, phenol stabilizers, organophosphate stabilizers, thioether stabilizers, hindered amine stabilizers and the like can be used.

Examples of the phenol-based stabilizer include conventionally known ones, such as 2, 6-di-t-butyl-4-methylphenol, 2, 6-di-t-butyl-4-ethylphenol, 2, 6-dicyclohexyl-4-methylphenol, 2, 6-diisopropyl-4-ethylphenol, 2, 6-di-t-amyl-4-methylphenol, 2, 6-di-t-octyl-4-n-propylphenol, 2, 6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, and the like, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, dl-alpha-tocopherol, t-butylhydroquinone, 2 ' -methylenebis (4-methyl-6-t-butylphenol), 4 ' -butylidenebis (3-methyl-6-t-butylphenol), 4 ' -thiobis (3-methyl-6-t-butylphenol), 2 ' -thiobis (4-methyl-6-t-butylphenol), 4 ' -butylidenebis (2, 6-di-t-butylphenol), 2 ' -methylenebis [6- (1-methylcyclohexyl) p-cresol ], 2 ' -ethylenebis (4, 6-di-t-butylphenol), 2, 2 ' -butylidenebis (2-tert-butyl-4-methylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 ' -thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N ' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamide), diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphate, N ' -butylidene hydrochloride, N ' -, 1, 3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1, 3, 5-tris [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, tris (4-tert-butyl-2, 6-dimethyl-3-hydroxybenzyl) isocyanurate, 2, 4-bis (n-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylanilino) -1, 3, 5-triazine, tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, bis (3, 5-di-tert-butyl-4-hydroxybenzyl ethyl phosphate) calcium, sodium, potassium, sodium, Bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonate) nickel, bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid ] ethylene glycol ester, N '-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 2' -ethanediamide bis [ ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis [ 2-tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl ] terephthalate, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, alkyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionates such as 3, 9-bis {1, 1-dimethyl-2- [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2, 4, 8, 10-tetraoxaspiro [5, 5] deca-decane, 2-bis {4- [2- (3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ] ethoxyphenyl } propane and stearyl β - (4-hydroxy-3, 5-di-tert-butylphenol) propionate. Of these, 2, 6-di-t-butyl-4-methylphenol, stearyl β - (4-hydroxy-3, 5-di-t-butylphenol) propionate, 2' -ethylenebis (4, 6-di-t-butylphenol), and tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane are preferred.

Examples of the organic phosphate stabilizers include trioctyl phosphate, trilauryl phosphate, tridecyl phosphate, triisodecyl phosphate, phenyldiisooctyl phosphate, phenyldiisodecyl phosphate, phenylditridecyl phosphate, diphenylisooctyl phosphate, diphenylisodecyl phosphate, diphenyltridecyl phosphate, triphenyl phosphate, tris (nonylphenyl) phosphate, tris (2, 4-di-t-butylphenyl) phosphate, tris (butoxyethyl phosphate), tetrakis (tridecyl) -4, 4 ' -butylidenebis (3-methyl-6-t-butylphenol) diphosphate, 4 ' -isopropylidenebis-phenol alkyl phosphate (in which the alkyl group has about 12 to 15 carbon atoms), 4 ' -isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphate, tri (tridecyl) phosphate, tri (nonylphenyl) phosphate, triisodecyl phosphate, phenyl phosphate, and the, Tris (biphenyl) phosphate, tetrakis (tridecyl) -1, 1, 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphate, tris (3, 5-di-tert-butyl-4-hydroxyphenyl) phosphate, hydrogenated-4, 4 '-isopropylidenediphenol polyphosphate, bis (octylphenyl) -bis [4, 4' -butylidenebis (3-methyl-6-tert-butylphenol) ]. 1, 6-hexanediol diphosphate, hexa (tridecyl-1, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphate, tris [4, 4 '-isopropylidenebis (2-tert-butylphenol) ] phosphate, hexa (tert-butyl-phenyl) phosphate, tris (4, 4' -isopropylidenebis-4-hydroxy-5-tert-butyl-phenyl) diphosphate, tris (2-tert-butylphenol) ] phosphate, tris (, Tris (1, 3-distearoyloxyisopropyl) phosphate, 9, 10-dihydro-9- ホスファフエナンスレン -10-oxide, tetrakis (2, 4-di-t-butylphenyl) -4, 4 '-biphenylene diphosphate, distearylpentaerythritol diphosphate, bis (nonylphenyl) pentaerythritol diphosphate, phenyl 4, 4' -isopropylidenediphenol pentaerythritol diphosphate, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphate, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, and phenylphenol-A-pentaerythritol diphosphate.

Of these, tris (2, 4-di-t-butylphenyl) phosphate, tris (nonylphenyl) phosphate and tetrakis (2, 4-di-t-butylphenyl) -4, 4' -biphenylene diphosphate are preferred, and tris (2, 4-di-t-butylphenyl) phosphate is particularly preferred.

Further, as the organic thioether-based stabilizer, a dialkyl thiodipropionate and a polyol ester of an alkyl thiopropionic acid are preferably used.

The dialkyl thiodipropionate used herein is preferably a dialkyl thiodipropionate having an alkyl group having 6 to 20 carbon atoms, and the polyol ester of an alkyl thiopropionic acid is preferably a polyol ester of an alkyl thiopropionic acid having an alkyl group having 4 to 20 carbon atoms.

In this case, examples of the polyol constituting the polyol ester include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate.

Examples of the dialkyl thiodipropionate include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate.

On the other hand, examples of the polyol ester of alkylthiopropionic acid include glycerol tributylthiopropionate, glycerol trioctylthiopropionate, glycerol trilaurylthiopropionate, glycerol tristearylthiopropionate, trimethylolethane tributylthiopropionate, trimethylolethane trioctylthiopropionate, trimethylolethane trilaurylthiopropionate, trimethylolethane tristearylthiopropionate, pentaerythritol tetrabutylthiopropionate, pentaerythritol tetraoctylthiopropionate, pentaerythritol tetralaurylthiopropionate, pentaerythritol tetrastearylthiopropionate, and the like.

Of these, dilaurylthiodipropionate, distearylthiodipropionate and pentaerythritol tetralaurylthiopropionate are preferred.

Examples of the hindered amine-based stabilizer include bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2, 2, 6, 6-tetramethylpiperidine polycondensate, poly [6- (1, 1, 3, 3-tetramethylbutyl) imino-1, 3, 5-triazine-2, 4-diyl ] [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imino ] hexamethylene [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imine ], tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butanetetracarboxylate, and the like, 2, 2, 6, 6-tetramethyl-4-piperidyl benzoate, bis (1, 2, 6, 6-pentamethyl-4-piperidyl) -2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-N-butylmalonate, bis (N-methyl-2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 1' - (1, 2-ethanediyl) bis (3, 3, 5, 5-tetramethylpiperazinone), (mixed 2, 2, 6, 6-tetramethyl-4-piperidyl/tridecyl) -1, 2, 3, 4-butanetetracarboxylate, (mixed 1, 2, 2, 6, 6-pentamethyl-4-piperidyl/tridecyl) -1, 2, 3, 4-butanetetracarboxylate, mixed {2, 2, 6, 6-tetramethyl-4-piperidyl/beta, beta ' -tetramethyl-3, 9- [2, 4, 8, 10-tetraoxaspiro (5, 5) deca-alkane ] diethyl } -1, 2, 3, 4-butanetetracarboxylate, mixed {1, 2, 2, 6, 6-pentamethyl-4-piperidyl/beta, beta ' -tetramethyl-3, 9- [2, 4, 8, 10-tetraoxaspiro (5, 5) deca-alkane ] diethyl } -1, 2, 3, 4-butanetetracarboxylate, N ' -bis (3-aminopropyl) ethylenediamine-2, 4-bis [ N-butyl-N- (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) amino ] -6-chloro-1, 3, 5-triazine condensate, poly [ 6-N-morpholinyl-1, 3, 5-triazine-2, 4-diyl ] [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imino ] hexamethylene [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imine ], a condensate of N, N' -bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 1, 2-dibromoethane, [ N- (2, 2, 6, 6-tetramethyl-4-piperidyl) -2-methyl-2- (2, 2, 6, 6-tetramethyl-4-piperidyl) imino ] propionamide, and the like.

Among these hindered amine-based stabilizers, particularly preferred are dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2, 2, 6, 6-tetramethylpiperidine polycondensate, poly [6- (1, 1, 3, 3-tetramethylbutyl) imino-1, 3, 5-triazine-2, 4-diyl ] [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imino ] hexamethylene [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imine ], tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butanetetracarboxylate, bis (1, 2, 6, 6-pentamethyl-4-piperidyl) -2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1 ' - (1, 2-ethanediyl) bis (3, 3, 5, 5-tetramethylpiperazinone), (mixed 2, 2, 6, 6-tetramethyl-4-piperidinyl/tridecyl) -1, 2, 3, 4-butanetetracarboxylate, (mixed 1, 2, 2, 6, 6-pentamethyl-4-piperidinyl/tridecyl) -1, 2, 3, 4-butanetetracarboxylate, mixed {2, 2, 6, 6-tetramethyl-4-piperidinyl/β, β, β ' β ' -tetramethyl-3, 9- [2, 4, 8, 10-tetraoxaspiro (5, 5) undecane ] diethyl } -1, 2, 3, 4-butanetetracarboxylate, mixed {1, 2, 2, 6, 6-pentamethyl-4-piperidinyl/β, β, β ' β ' -tetramethyl-3, 9- [2, 4, 8, 10-tetraoxaspiro (5, 5) undecane ] diethyl } -1, 2, 3, 4-butanetetracarboxylate, N ' -bis (3-aminopropyl) ethylenediamine-2, 4-bis [ N-butyl-N- (1, 2, 6, 6-pentamethyl-4-piperidinyl) amino ] -6-chloro-1, 3, 5-triazine condensate, poly [ 6-N-morpholinyl-1, 3, 5-triazine-2, 4-diyl ] [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imino ] hexamethylene [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imine ], a condensate of N, N' -bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 1, 2-dibromoethane, [ N- (2, 2, 6, 6-tetramethyl-4-piperidyl) -2-methyl-2- (2, 2, 6, 6-tetramethyl-4-piperidyl) imino ] propionamide.

As the softener, process oil is preferable, and as such process oil, process oil used as a softener used in processing synthetic rubber can be generally used as it is.

The process oil may be any of mineral oils and synthetic oils, and specific examples of the mineral oil include distillate oils obtained by atmospheric distillation of paraffin-based crude oil, mixed-base crude oil or naphthenic crude oil, refined oils of distillate components obtained by vacuum distillation of the atmospheric distillation residue oil, deep dewaxed oils, and the like.

Examples of the synthetic oil include alkylbenzenes, polybutenes, and poly (. alpha. -olefins).

The properties required for the process oil usable in the present invention are not particularly limited, but the process oil preferably has a dynamic viscosity of 100 to 10000mm at 40 ℃²An operating oil having a dynamic viscosity at 40 ℃ of 200 to 7000mm is particularly preferably used²A process oil in sec.

Examples of the inorganic filler include spherical fillers, plate-like fillers, and fibrous fillers. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, beaded iron, natural vitreous hollow microspheres, sericite, diatomaceous earth, calcium sulfite, calcined alumina, crystalline zeolite, and amorphous zeolite, examples of the plate-like filler include talc and mica, examples of the fibrous filler include needle-like materials such as wollastonite, fibrous materials such as magnesium oxysulfate (マグネシゥムオキシサルフエイト), potassium titanate fibers and fibrous calcium carbonate, and completely fibrous materials such as glass fibers.

On the other hand, examples of the organic filler include wood particles such as wood flour and cotton flour, rice hull powder, crosslinked rubber powder, plastic powder, and collagen powder.

Examples of the flame retardant include hydrated aluminum, hydrated gypsum, zinc borate, barium borate, borax, kaolin, clay, calcium carbonate, alunite, basic magnesium carbonate, calcium hydroxide, and magnesium hydroxide.

Among these additives, those having an adverse effect on transparency are not filled in the surface layer but are exclusively filled in the base material.

Specific examples of the nucleating agent in the present invention include high-melting polymers, organic carboxylic acids or metal salts thereof, aromatic sulfonic acid salts or metal salts thereof, organic phosphoric acid compounds or metal salts thereof, dibenzylidene sorbitol or derivatives thereof, partial metal salts of abietic acid (ロジン acid), inorganic fine particles, imides, amides, quinacridones, quinones, or mixtures thereof.

Examples of the high-melting polymer include polyolefins such as polyethylene and polypropylene; polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane; syndiotactic polystyrene, poly-3-methylpentene-1, poly-3-methylbutene-1, polyalkenylsilane, etc.

Examples of the metal salt include aluminum benzoate, aluminum p-tert-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate.

Examples of dibenzylidene sorbitol or its derivative include dibenzylidene sorbitol, 1, 3:2, 4-bis (o-3, 4-dimethylbenzylidene) sorbitol, 1, 3:2, 4-bis (o-2, 4-dimethylbenzylidene) sorbitol, 1, 3:2, 4-bis (o-4-ethylbenzylidene) sorbitol, 1, 3:2, 4-bis (o-4-chlorobenzylidene) sorbitol, 1, 3:2, 4-dibenzylidene sorbitol, and the like.

Specifically, the compounds may be ゲルオ - ル MD or ゲルオ - ル MD-R (trade name) which are newly made by Nippon Japan chemical industry (manufactured by Nippon Japan Co., Ltd.).

Examples of the pinoresinoic acid partial metal salt include パインクリスタル KM1600, パインクリスタル KM1500 and パインクリスタル KM1300 (trade name) manufactured by Ishikawa chemical industry (product name). Examples of the inorganic fine particles include talc, clay, mica, asbestos, glass fiber, glass flake, glass bead, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, magnesium oxide, silica powder, silica spheres, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, and molybdenum sulfide.

Examples of the amide compound include adipamide and suberoylanide.

One of these nucleating agents may be used, or two or more of them may be used in combination.

The resin material for decorative plate materials of the present invention is preferably one which generates little odor when inorganic fine particles such as metal salts of organic phosphoric acids represented by the following general formula and/or talc are used as a nucleating agent.

The resin material for decorative plate is preferably used for food.

[ chemical formula 6]

(in the formula, R²⁷R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms²⁸And R²⁹Each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. M represents any one of alkali metal, alkaline earth metal, aluminum and zinc, when M is alkali metal, M represents 0, n represents 1; when M is alkaline earth metal or zinc, n represents 1 or 2, when n is 1, M represents 1, when n is 2, M represents 0; when M is aluminum, M represents 1 and n represents 2. )

Specific examples of the metal salt of organic phosphate include ァデカスタブ NA-11 and ァデカスタブ NA-21 (manufactured by Asahi Denka Co., Ltd.).

In the resin material for decorative plate members of the present invention, the use of the inorganic fine particles such as talc as a nucleating agent is preferable because the resin material is excellent in sliding property and can improve characteristics such as printing characteristics when formed into a film.

The use of the dibenzylidene sorbitol or a derivative thereof as a nucleating agent is preferable because it is excellent in transparency.

The use of the above amide compound as a nucleating agent is preferable because it is excellent in rigidity.

The resin material for decorative plate materials of the present invention has excellent moldability, little stickiness, and excellent softness and transparency.

In the present invention, in order to form a surface layer and/or a decorative plate (film or sheet) for a substrate, it is advantageous to process the resin material for a decorative plate into a film or sheet having a thickness of 30 to 500. mu.m, preferably 50 to 300. mu.m, more preferably 60 to 120. mu.m, by a molding method such as casting, blow molding or calender molding.

In order to improve adhesiveness, printability, and the like, it is desirable to perform surface treatment such as corona treatment, ozone treatment, plasma treatment, and the like on the film or sheet obtained in this manner.

When the film or sheet is used as a substrate, a masking effect can be imparted by adding a pigment at the time of molding.

The decorative plate material (film or sheet) of the present invention may be a so-called laminated film (ダブリングフイルム) having a laminated structure including a surface layer, an adhesive layer, a pattern layer, an adhesive layer and a base material, or a so-called single-sided printed film (バツクプリントフイルム) (printed directly on the surface layer without a base material) having a laminated structure including a surface layer, an adhesive layer and a pattern layer.

Examples of the adhesive layer in the decorative plate material (film or sheet) include a layer having a thickness of about 1 to 20 μm, which is made of a known adhesive or a modified polyolefin, containing, as a main component, a resin: polyurethane resins, epoxy resins, acrylic resins, vinyl acetate resins, polyester resins, ethylene-vinyl acetate copolymer resins, acrylic-vinyl acetate copolymer resins, polyamide resins, ionomer resins, and the like.

Examples of the modified polyolefin include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid; anhydrides of unsaturated acids such as maleic anhydride; esters of unsaturated carboxylic acids such as methyl acrylate and monomethyl maleate; amides of unsaturated carboxylic acids such as acrylamide and maleic acid monoamide; modified polyolefins obtained by chemically modifying polyolefins such as polyethylene, polypropylene, ethylene- α -olefin copolymers, ethylene-olefin-nonconjugated diene compound copolymers (e.g., EPDM), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer rubbers, and the like with imides of unsaturated carboxylic acids such as maleimide and N-butylmaleimide.

The form of the adhesive during processing is not particularly limited, and may be any of a liquid state, a semi-molten state, and a film/sheet state.

When the adhesive layer has two layers, the adhesive layer of the first layer and the adhesive layer of the second layer may be layers containing the same material or may be layers containing different materials.

On the other hand, printing is performed on the pattern layer to express, for example, a surface pattern of wood grain, stone grain, natural leather, cloth grain, abstract pattern, and the like, and the binder of the ink for providing these pattern patterns is not particularly limited, and any of polyurethane-based resins, vinyl chloride-vinyl acetate-based copolymer resins/acrylic resins, chlorinated polypropylene-based resins, acrylic resins, polyester-based resins, polyamide-based resins, butyral-based resins, polystyrene-based resins, nitrocellulose-based resins, acetyl cellulose-based resins, and the like can be used, for example.

The ink may be appropriately mixed with a colorant such as a pigment or a dye, a filler pigment, a solvent, and the like. The pattern layer is usually about 1 to 5 μm thick.

In the present invention, the pattern layer is particularly preferably a two-layer structure layer including a pattern layer and a shielding layer.

As the ink for forming the shielding layer, an ink obtained by appropriately mixing a colorant such as a pigment or a dye, a filler pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like with a binder can be used.

The adhesive may be the same adhesive as that used for the ink for forming the pattern layer.

The shielding layer is preferably a solid printing layer having a thickness of about 1 to 20 μm.

The shielding layer is disposed under the pattern layer.

In the decorative plate material (film or sheet) of the present invention, a top coat layer having a thickness of about 1 to 20 μm containing an acrylic resin, a polyurethane resin or the like may be formed on the surface layer as necessary in order to improve abrasion resistance, weather resistance, embossability, scratch resistance, stain resistance and the like.

If necessary, the surface layer may be embossed, or the recesses may be filled with ink for application.

The method for producing the decorative plate material (film or sheet) of the present invention is not particularly limited as long as it is a method for obtaining a decorative plate material having the above-described laminated structure, and for example, it is advantageous to produce a decorative plate material having a laminated structure including a surface layer, an adhesive layer, a pattern layer, an adhesive layer, and a base material by two methods shown below.

First, as a first method, the following method can be used: the adhesive layer, the pattern layer, and the adhesive layer are laminated in this order on the base material by a general printing method such as gravure printing, screen printing, offset printing, or flexography, and then (1) a method of laminating a film or sheet as a surface layer by thermal lamination or the like, (2) a method of laminating a film or sheet as a surface layer by dry lamination, wet lamination, or the like, (3) a method of providing an adhesive layer having the same composition on a film or sheet as a surface layer by a general printing method such as gravure printing, screen printing, offset printing, or flexography, or a coating method such as roll coating, and laminating by a thermal lamination method or the like, (4) a method of forming a surface layer from a resin as a surface layer by an extrusion lamination method, and the like.

As a second method, the following method may be used: after laminating an adhesive layer and a pattern layer in this order on a base material by a usual printing method such as gravure printing, screen printing, offset printing, flexographic printing or the like, (1) a method of providing an adhesive layer on a film or sheet as a surface layer by a usual printing method such as gravure printing, screen printing, offset printing, flexographic printing or the like or a coating method such as roll coating, and then laminating the film or sheet as a surface layer by heat lamination or the like while the adhesive layer is adjacent to the pattern layer, (2) a method of providing an adhesive layer on a film or sheet as a surface layer by the same method as (1) and laminating the film or sheet as a surface layer by dry lamination or wet lamination or the like, (3) a method of extruding and laminating a resin as an adhesive layer in a molten state between a pattern layer and a film or sheet as a surface layer (extrusion lamination), (4) a method of forming an adhesive layer and a surface layer from a resin as an adhesive layer and a surface layer by coextrusion Methods, and the like.

The present invention can also provide a cosmetic material obtained by bonding the decorative sheet (film or sheet) thus obtained to various substrates.

Examples of the material used for the base material of such a cosmetic material include wood base materials such as wood, plywood, laminated materials, particle board, and artificial boards; or a metal substrate such as a steel plate, a stainless steel plate, an aluminum plate; or an inorganic base material such as a gypsum board.

For manufacturing a cosmetic material, the decorative plate (film or sheet) may be laminated opposite to its base material or pattern layer using an adhesive.

In this case, the adhesive used is not particularly limited, and may be appropriately selected from conventionally known adhesives.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Production example 1 (Polymer 1)

(preparation of catalyst)

The following catalyst was used for prepolymerization at 30 ℃ and a propylene pressure of 0.13MPa for 1 hour: dimethylsilylenebis (2-methyl-benzo [ e ] indenyl) zirconium (IV) dichloride (complex a) and (1, 2 '-dimethylsilylene) (2, 1' -dimethylsilylene) bis (trimethylsilylmethylindenyl) zirconium (IV) dichloride (complex B) were supported on silica-supported methylaluminoxane (supported MAO, Al supporting amount: 14 mass%), and Zr in the complex a was 0.001 and Zr in the complex B was 0.001 in terms of molar ratio with respect to Al in the supported MAO.

(Polymer 1: production of propylene Block copolymer)

A350-L autoclave was charged with 100L of liquid propylene, 100 mmol of triisobutylaluminum was charged, and then the above catalyst was charged at 55 ℃ in an amount of 200. mu. mol as zirconium to start polymerization.

30 minutes after the start of the polymerization, ethylene was fed at a partial pressure of 0.1MPa, and polymerization was carried out for 60 minutes while ethylene was continuously fed so that the partial pressure of ethylene was constant.

After completion of the polymerization, the propylene was flashed off and dried under a stream of nitrogen at 80 ℃ for 2 hours.

The ethylene content of the obtained polymer was 3.2 mol%, and the intrinsic viscosity [ viscosity ] was 1.8 dl/g.

To this polymer were added イルガノックス 1010[ チバ, スペシヤルテイ, ケミカルズ (products of the Co., Ltd.) ]500ppm, イルガホス 168[ チバ, スペシヤルテイ, ケミカルズ (products of the Co., Ltd.) ]1000ppm, calcium stearate 300ppm as a neutralizer and Px14[ chemicals アクゾ (products of the Co., Ltd.) ]300ppm as a peroxide as antioxidants, and the melt flow rate (MFR: 230 ℃ C., load: 21.18N) was adjusted at 4 to 5g/10 min during melt kneading with an extruder to obtain polymer 1.

The physical properties of the obtained polymer 1 are shown in table 1.

[ measurement of intrinsic viscosity [. eta. ])

The measurement was carried out in decalin solvent at 135 ℃ using a VMR-053 model automatic viscometer manufactured by Shigaku corporation.

[ measurement of tensile elastic modulus ]

The tensile modulus was measured in accordance with JIS K-7113 by press-molding a sample to prepare a test piece.

Thickness of test piece (dumbbell No. 2): 1mm

Right angle head speed: 50mm/min

A force sensor: 100kg of

Production example 2 (Polymer 2)

Polymer 2 was obtained in the same manner as for Polymer 1, except that the ethylene partial pressure was changed to 0.2 MPa.

The physical properties of the obtained polymer 2 were measured in the same manner as in production example 1.

The results are shown in Table 1.

Production example 3 (Polymer 3)

Polymer 3 was obtained in the same manner as Polymer 1 except that the complex A/complex B was 4/3 (molar ratio), the initial polymerization temperature was 40 ℃ and the ethylene partial pressure was 0.15MPa, and the temperature during polymerization was increased to 50 ℃.

The physical properties of the obtained polymer 3 were measured in the same manner as in production example 1.

The results are shown in Table 1.

Production example 4 (Polymer 4)

Polymer 4 was obtained in the same manner as in Polymer 3 except that the ratio of complex A/complex B was 2/3 (molar ratio) and the ethylene partial pressure was 0.2 MPa.

The physical properties of the obtained polymer 4 were measured in the same manner as in production example 1.

The results are shown in Table 1.

Production example 5 (Polymer 5)

Polymer 5 was obtained in the same manner as in Polymer 3 except that the complex A/complex B2 was changed to 2/3 (molar ratio), the initial polymerization temperature was changed to 35 ℃, the ethylene partial pressure was changed to 0.3MPa, and the copolymerization temperature was changed to 45 ℃.

The physical properties of the obtained polymer 5 were measured in the same manner as in production example 1.

The results are shown in Table 1.

Example 1

Use ofThe polymer 1 was extrusion-molded at a die outlet resin temperature of 240 ℃ to obtain films of 100 μm and 300. mu.m.

The obtained film was subjected to the following measurement.

The results are shown in Table 2.

[ measurement of tensile whitening resistance ]

The obtained film was formed into a 2cm × 8cm rectangular shape, folded at the center portion perpendicular to the longitudinal direction, stretched 100% at a stretching speed of 200m/min between clamps at a length of 2cm, and the degree of whitening at the stretched portion was observed.

Very good: appearance was not changed, o: partially whitened (pale white), Δ: partial whitening, x: whitening, xxx: significant whitening or cracking.

[ measurement of internal haze value ]

Measured using a haze meter.

[ Low temperature characteristics ]

The solid viscoelasticity was measured, and the peak of tan. delta. was measured.

[ measurement of Change with time (resistance to whitening by peeling) ]

The obtained film was cut into a size of a4 plate, stacked with 30 sheets, stored in an oven at 30 ℃ for 30 days, then taken out, peeled one by one, and observed for appearance.

Very good: appearance was not changed, o: almost without whitening, slightly changed appearance, Δ: non-uniform existence of whitening portion, x: whitening was significant and the film elongated upon peeling.

[ measurement of Melt Flow Rate (MFR) ]

Measured at 230 ℃ under a load of 21.18N in accordance with JIS K7210.

Example 2

Pellets were obtained in the same manner as in example 1 except that the polymer 2 was used, and films of 100 μm and 300 μm were obtained to measure the physical properties.

The results are shown in Table 2.

Example 3

Pellets were obtained in the same manner as in example 1 except that the polymer 3 was used, and films of 100 μm and 300 μm were obtained to measure the physical properties.

The results are shown in Table 2.

Example 4

Pellets were obtained in the same manner as in example 1 except that a mixture obtained by mixing polymer 5 and a propylene homopolymer (homopolyPP) [ polypropylene F-704NP manufactured by Shikino Co., Ltd.,. DELTA.H was 102J/g, Melt Flow Rate (MFR) was 7g/10 min, and tensile modulus of elasticity was 1100MPa ] in a mass ratio of 25/75, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Example 5

Pellets were obtained in the same manner as in example 1 except that a mixture obtained by mixing polymer 5 and a propylene homopolymer (homopolyPP) [ polypropylene F-704NP manufactured by Shikino Co., Ltd.,. DELTA.H was 102J/g, Melt Flow Rate (MFR) was 7g/10 min, and tensile modulus of elasticity was 1100MPa ] in a mass ratio of 50/50, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Example 6

Pellets were obtained in the same manner as in example 1 except that a mixture obtained by mixing polymer 5 and a propylene random copolymer (random PP) [ polypropylene F-724NP manufactured by Shikino Co., Ltd.,. DELTA.H was 88J/g, Melt Flow Rate (MFR) was 7g/10 min, and tensile modulus of elasticity was 1000MPa ] in a mass ratio of 50/50, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Example 7

Pellets were obtained in the same manner as in example 1 except that a mixture obtained by mixing polymer 4 and a propylene homopolymer (homopolyPP) [ polypropylene F-704NP manufactured by Shikino Co., Ltd.,. DELTA.H was 102J/g, Melt Flow Rate (MFR) was 7g/10 min, and tensile modulus of elasticity was 1100MPa ] in a mass ratio of 60/40, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Comparative example 1

Pellets were obtained in the same manner as in example 1 except that a propylene homopolymer (homopolyPP) [ polypropylene F-704NP manufactured by Shikino Co., Ltd.,. DELTA.H of 102J/g, Melt Flow Rate (MFR) of 7g/10 min, and tensile elastic modulus of 1100MPa ] was used, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Comparative example 2

Pellets were obtained in the same manner as in example 1 except that a mixture of a propylene homopolymer (homopolyPP) [ polypropylene F-704NP manufactured by Shikino Co., Ltd.,. DELTA.H was 102J/g, a Melt Flow Rate (MFR) was 7g/10 min, and a tensile elastic modulus was 1100MPa ] and a styrene-based elastomer (ダイナロン 1320P manufactured by JSR Co., Ltd.) was used in a mass ratio of 80/20, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Comparative example 3

Pellets were obtained in the same manner as in example 1 except that low stereoregularity polypropylene (gloss TPO) [ F-3700, stereoregularity index 72 mol%, Melt Flow Rate (MFR) 5g/10 min, and tensile modulus of elasticity 250MPa ] was used, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Comparative example 4

Pellets were obtained in the same manner as in example 1 except that the polymer 5 was used, and films of 100 μm and 300 μm were obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Industrial applicability

The decorative plate (film or sheet) of the present invention has the following features: the composition has excellent balance between tensile whitening resistance and rigidity, and also has good impact resistance, and also has excellent commercial value because peeling whitening due to mutual adhesion during storage, which is peculiar to soft materials, is improved, thickness dependence of transparency is small, and chlorine gas and the like are not generated during incineration, and therefore, the composition has no problem of waste and the like.

Therefore, the decorative sheet material (film or sheet) of the present invention has the above-described excellent characteristics, and thus can be suitably used for, for example, furniture parts, housings of refrigerators, televisions, and the like, interior materials for buildings, and the like.

Claims

(1) by f_EEEExpressed [ EEE]Has a chain ratio of three units of 0.1 mol% or less,

(2) The product of the reactivity ratios of ethylene and propylene expressed by Re & Rp is 0.5 or more,

(3) A molecular weight distribution represented by Mw/Mn of 3.5 or less,

(4) A melting enthalpy represented by Δ H of 50 to 105J/g,

(5) A melting point represented by Tm of 125 ℃ or higher, and

(6) the ethylene content is 1 to 7 mol%;

(B) a resin composition comprising a combination of 80 to 30% by mass of a polypropylene-based resin (b-1) and 20 to 70% by mass of a propylene-ethylene copolymer (b-2), wherein the polypropylene-based resin (b-1) comprises a propylene homopolymer or a random copolymer or a block copolymer of propylene and ethylene and/or butene-1, and Δ H is 80J/g or more, and the propylene-ethylene copolymer (b-2) satisfies the following conditions:

(3) A molecular weight distribution represented by Mw/Mn of 3.5 or less,

(4) Has a melting enthalpy represented by Δ H of 50J/g or less, and

(5) the ethylene content is 10 mol% or less.

2. A decorative plate material, wherein a surface layer or a coloring sheet is formed by laminating a printed pattern layer and the resin material for a decorative plate material according to claim 1.