KR101311906B1 - Resin material for cosmetic sheet and cosmetic sheet - Google Patents

Abstract

The present invention is excellent in the balance between stretch whitening resistance and stiffness, good impact resistance characteristics, improved delamination whitening due to mutual adhesion in storage of soft materials, improved transparency, and small thickness dependency of propylene. The present invention provides a cosmetic material and a cosmetic sheet comprising an ethylene copolymer, the copolymer, and the like.

Toilet seat, resin material

Description

Resin materials and cosmetic sheets for cosmetic sheets {RESIN MATERIAL FOR COSMETIC SHEET AND COSMETIC SHEET}

This invention is useful for the sheet | seat film for building materials, such as a closet and a flooring material, Especially the propylene ethylene copolymer suitable for the cosmetic sheet to which non polyvinyl chloride advances, The resin for cosmetic sheets which consists of the said copolymer A material and a cosmetic sheet are related.

Conventionally, polyvinyl chloride resin has been used for the building material sheet, but due to environmental problems in which chic house syndrome and dioxins originate, development of non-polyvinyl chloride resin materials is progressed, and in particular, polyolefin materials, For example, products mainly made of general-purpose polypropylene, polypropylene / styrene-based elastomers, low order polypropylene, and the like have been developed.

In the case of the general-purpose polypropylene-based material, there is a problem that the whitening resistance is not sufficient, and if the curvature during bending processing is severe (when the stretching is large), the whitening occurs.

As a remedy of this drawback, polypropylene / styrene-based elastomer-added materials and the like have been developed in the direction of softening, but the stress at the time of deformation concentrates at the interface of the rubber part morphologically, so that whitening resistance and rigidity In the case of poor balance of heat resistance and the like, and high cost, industrially, there are many problems.

In order to improve the above-mentioned problem, the use of TPO (polyolefin-based thermoplastic resin) in combination with polypropylene having different stereoregularity has been developed (for example, Patent Document 1), but the balance of whitening resistance and heat resistance is improved. The balance of whitening resistance and stiffness was still insufficient.

Moreover, since TPO is low crystallinity, the change with time is large, especially the film surface mutually adhere | attached, and there also existed a problem of the appearance defect by peeling change, etc.

In addition, when the polypropylene-based material is thickened, transparency greatly decreases, and thus there is a problem such as deterioration in designability when laminated.

Patent Document 1: Japanese Patent Application Laid-Open No. 9-226071

(Initiation of invention)

This invention is made | formed in view of the said situation, The balance of whitening resistance and rigidity (damage resistance) improves, and it does not produce the appearance defects, such as peeling whitening by mutual adhesion, etc., and even if it has thickness, it is favorable propylene- It is an object to provide an ethylene copolymer, a resin material for a makeup sheet and a makeup sheet comprising the copolymer.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors discovered that the propylene ethylene copolymer etc. which satisfy | fill specific requirements were the optimal as a resin material for cosmetic sheets.

The present invention has been completed based on this recognition.

That is, the present invention,

1. Resin material for cosmetic sheets which consists of following (A) or (B).

(A) Resin composition containing the propylene-ethylene copolymer (a) which satisfy | fills the following requirements,

(1) The triad chain fraction (f _EEE ) of [EEE] is 0.1 mol% or less,

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

(3) the molecular weight distribution (Mw / Mn) is 3.5 or less,

(4) melting enthalpy (ΔH) of 50 to 105 J / g,

(5) melting point (Tm) is 125 ℃ or more,

(6) ethylene content is 10 mol% or less,

(B) 80-30 mass% of polypropylene resins (b-1) which (D) H consists of a propylene homopolymer or propylene and ethylene and / or butene-1 of 80 J / g or more, and the propylene ethylene copolymer which satisfy | fills the following requirements (b-2) Resin composition containing the combination with 20-70 mass%,

(1) The triad chain fraction (f _EEE ) of [EEE] is 0.1 mol% or less,

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

(3) the molecular weight distribution (Mw / Mn) is 3.5 or less,

(4) fusion enthalpy (ΔH) of 50 J / g or less,

(5) Ethylene content is 10 mol% or less

2. Cosmetic sheet which any one of surface layer or colored sheet consists of resin material for cosmetic sheets of said 1st item, and laminates printing pattern layer

To provide.

Advantageous Effects of Invention The present invention has excellent balance of stretch whitening resistance and rigidity, good impact resistance characteristics, improved peeling whitening due to mutual adhesion during storage of soft materials, and low thickness dependence of transparency. A propylene-ethylene copolymer, a resin material for a makeup sheet and a makeup sheet composed of this copolymer and the like are obtained.

Best Mode for Carrying Out the Invention [

The resin material for makeup sheets of this invention consists of following (A).

(A) Resin composition containing the propylene-ethylene copolymer (a) which satisfy | fills the following requirements,

(1) The triad chain fraction (f _EEE ) of [EEE] is 0.1 mol% or less,

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

(3) the molecular weight distribution (Mw / Mn) is 3.5 or less,

(4) melting enthalpy (ΔH) of 50 to 105 J / g,

(5) melting point (Tm) is 125 ℃ or more,

(6) ethylene content is 10 mol% or less,

The propylene-ethylene copolymer (a) will be described.

In addition, these measuring methods are mentioned later.

f _EEE becomes like this. Preferably it is 0.08 mol% or less, More preferably, it is 0.05 mol% or less.

When it exceeds 0.1 mol%, transparency may deteriorate.

Since f _EEE becomes large when using an Mg / Ti system catalyst, it is preferable to use the catalyst system of this invention mentioned later in order to make it 0.1 mol% or less.

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

If it does not satisfy 0.5 or more, heat resistance may become inadequate.

In addition, Re * Rp can be controlled by the ratio of homopolymerization amount and random copolymerization amount.

That is, in order to make Re * Rp into 0.5 or more, the homopolymerization amount may be 5 mass% or more, for example.

Mw / Mn becomes like this. Preferably it is 3.3 or less, More preferably, it is 3.0 or less.

If 3.5 or less is not satisfied, transparency may change with time under the influence of a low molecular weight component, or it may whiten under the influence of a high molecular weight component.

(DELTA) H becomes like this. Preferably it is 60-90 J / g, More preferably, it is 65-85 J / g.

If ΔH is less than 50 J / g, the stiffness (damage resistance) is poor, and if it exceeds 105 J / g, the whitening resistance is poor.

Tm becomes like this. Preferably it is 135 degreeC or more, More preferably, it is 145 degreeC or more.

If it does not satisfy 125 degreeC or more, when it raises temperature, for example, when adhering with another material, or makes it high temperature when apply | coating an adhesive, wrinkles may arise or an external appearance may change.

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

If it is less than 1 mol%, low-temperature impact resistance may deteriorate, and if it exceeds 7 mol%, heat resistance may become poor.

 In addition, the resin material for makeup sheets of this invention consists of following (B).

(B) 80-30 mass% of polypropylene resins (b-1) which (D) H consists of a propylene homopolymer or propylene and ethylene and / or butene-1 of 80 J / g or more, and the propylene ethylene copolymer which satisfy | fills the following requirements (b-2) Resin composition containing the combination with 20-70 mass%,

(1) The triad chain fraction (f _EEE ) of [EEE] is 0.1 mol% or less,

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

(3) the molecular weight distribution (Mw / Mn) is 3.5 or less,

(4) fusion enthalpy (ΔH) of 50 J / g or less,

(5) Ethylene content is 10 mol% or less

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

Next, the propylene-ethylene copolymer (b-2) used for the resin material for makeup sheets of (B) is demonstrated.

(DELTA) H becomes like this. Preferably it is 45 J / g or less, More preferably, it is 40 J / g or less.

If 50 J / g or less is not satisfied, sufficient performance may not be obtained with respect to whitening resistance.

In addition, _fEEE , Re * Rp, Mw / Mn are the same as that of the propylene ethylene copolymer (a).

The ethylene content in the said f _EEE , Re * Rp, and a copolymer can be calculated | required as follows.

In the propylene (P) -ethylene (E) copolymer of the present invention, the following three chains are bound to the peak of ¹³ C-NMR proposed by A.Zambelli et al. In "Macromolecules, 8 , 687 (1975)". Therefore, it can be calculated by the following equation.

EPE = I ₈

_{PPE = I 9 + (I 10} /2) + I 11

EEE = (EEE / 2) + (PEE / 4) = (I 12/2) + (I 13/4)

PPP = I ₁₄ + (I _10/2 )

PEE = I ₁₅

PEP = I ₁₆ + (I ₁₇ + I ₁₈ ) / 4

Where I ₈ = 33.3 ppm, I ₉ = 31.1 ppm, I ₁₀ = 31.2 ppm, I ₁₁ = 34.1 ppm, I ₁₂ = 30.0 ppm, I ₁₃ = 30.4 ppm, I ₁₄ = 29.2 ppm, I ₁₅ = 27.3 ppm, I ₁₆ = 24.7 ppm, I ₁₇ = 34.9 ppm, and I ₁₈ = 34.6 ppm.

If we put T = EPE + PPE + EEE + PPP + PEE + PEP

Each triad chain fraction (mol%) can be calculated by following Formula.

f _EPE = (EPE / T) × 100

f _PPE = (PPE / T) × 100

f _EEE = (EEE / T) x 100

f _PPP = (PPP / T) × 100

f _PEE = (PEE / T) × 100

f _PEP = (PEP / T) × 100

The dyad chain fraction can be calculated from the triad chain fraction in the following equation.

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 ratio of propylene and ethylene) can be calculated from the following equation.

Re · Rp = (4f _{EEf PP} ) / (f _EPf f _EP )

In addition, ethylene content (mol%) can be calculated by following Formula.

Ethylene content (mol%) = f _EE + (f _PE / 2)

[Measurement of ¹³ C-NMR]

220 mg of the sample is taken into a 10 mm diameter NMR sample tube, and 3 mL of 1,2,4-trichlorobenzene / heavy benzene (90/10% by volume) mixed solvent is added.

Using an aluminum block heater, ¹³ C-NMR spectra were measured after uniform dissolution at 140 ° C.

NMR measurement conditions are as follows.

NMR device: EX400 (400 MHz NMR device) manufactured by Nippon Denshi City

Pulse width: 7.5㎲ (45 degree pulse)

Pulse repetition time: 4 seconds

Number of multiplications: 1,000

Measuring temperature: 130 ℃

The Mw / Mn is measured by the gel permeation (GPC) method.

(GPC measuring device)

Column: TOSO GMHHR-H (S) HT

Detector: RI detector WATERS 150C for liquid chromatogram

Measuring conditions

Solvent: 1,2,4-trichlorobenzene

Measurement temperature: 145 degrees Celsius

Flow rate: 1.0 milliliters / minute

Sample concentration: 2.2 mg / milliliter

Injection volume: 160 microliters

Calibration curve ： Universal Calibration

Analysis program: HT-GPC (Ver.1.0)

The said Tm and (DELTA) H are the values calculated | required as follows.

After using a differential scanning calorimeter (DSC-7 manufactured by Parkin Elmar), 10 mg of the sample was melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to 0 ° C. at 1 ° C./min. Furthermore, after hold | maintaining again at 0 degreeC for 3 minutes, fusion enthalpy obtained by heating up at 10 degree-C / min was made into (DELTA) H.

In addition, the peak top of the largest peak of the melting endothermic curve obtained at this time was made into melting | fusing point (Tm).

Furthermore, after holding at 230 ° C. for 3 minutes, the temperature is lowered to 0 ° C. at 10 ° C./min.

The peak top of the largest peak of the crystallization heat generation curve obtained at this time was made into crystallization temperature (Tc).

Although there is no restriction | limiting in the manufacturing method of the propylene-ethylene copolymers (a) and (b-2) of this invention, (1) Metallocene catalyst which gives a high crystalline polypropylene, and (2) Low crystalline polypropylene is provided It is preferable to mix and use a metallocene catalyst.

(1) As a metallocene catalyst which gives high crystalline polypropylene, a monocrosslinked metallocene catalyst is mentioned.

As a monocrosslinked metallocene catalyst, the transition metal compound represented by general formula (I) is mentioned.

(Wherein E ¹ represents a bonding group which crosslinks two conjugated 5-membered ring ligands. R ¹ and R ² each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group and a nitrogen-containing hydrocarbon). represents a group or a boron-containing hydrocarbon group, R ³ ~R ⁶ represents each a hydrogen, 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. M ¹ is Transition metals of the Periodic Tables 4 to 6. In addition, X ¹ and Y ¹ each represent a covalent ligand, and X ¹ and Y ¹ may be bonded to each other to form a ring structure.)

As a hydrocarbon group of R <^1> -R <^6> , it is preferable that it is C1-C20, and it is especially preferable that it is C1-C12.

This hydrocarbon group may be a monovalent group and may be bonded to a cyclopentadienyl group which is a conjugated five-membered ring group, and when two or more thereof are present, two of R ¹ , R ³ , and R ⁴ or R ² , R ⁵ , and R ⁶ Two of them may be combined.

Examples of the conjugated five-membered ring include a substituted or unsubstituted cyclopentadienyl group, indenyl group, and fluorenyl group.

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

As E <^1> , (1) C1-C4 alkylene groups, cycloalkylene groups, or its side chain lower alkyl or phenyl, such as a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group, and a cyclohexylene group Substituent, (2) Silylene group, oligosilylene group, or its side chain lower alkyl or phenyl substituent, such as a silylene group, a dimethylsilylene group, a methylphenylene group, a diphenylsilylene group, a disilylene group, and a tetramethyl disilylene group, (3) Hydrocarbon groups containing germanium, phosphorus, nitrogen, boron or aluminum [lower alkyl groups, phenyl groups, hydrocarbyloxy groups (preferably lower alkoxy groups), etc.], specifically, (CH ₃ ) ₂ Ge groups, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆ H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ ) B group, (C ₄ And H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H ₅ ) Al group, and (CH ₃ O) Al group.

Of these, alkylene groups and silylene groups are preferable.

M ¹ represents a transition metal of Groups 4 to 6 of the periodic table, and specific examples include titanium, zirconium, hafnium, niobium, molybdenum, tungsten, and the like. Among them, titanium, zirconium and hafnium are preferable, and zirconium is particularly preferable. .

X ¹ and Y ¹ each represent a covalent ligand, and specifically, a hydrogen atom, a halogen atom, a C 1-20 hydrocarbon group, preferably 1-10 hydrocarbon group, C 1-20, preferably 1-10 Alkoxy group, amino group, phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (for example, diphenylphosphine group, etc.) or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms ( for example, trimethylsilyl group and the like), 1 to 20 carbon atoms, preferably (for example, BF _4, B (C ₆ H _5), a hydrocarbon group or a halogen-containing boron compound for 1 to 12 ₄₎ are shown.

Of these, halogen atoms and hydrocarbon groups are preferred.

These X <^1> and Y <^1> may mutually be same or different.

The following compounds are mentioned as a specific example of the transition metal compound represented by general formula (I).

(a) methylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, methylenebis (indenyl) titanium chlorohydride, ethylenebis (indenyl) methyltitanium chloride, ethylenebis (indenyl) Methoxychlorotitanium, ethylenebis (indenyl) titaniumdiethoxide, ethylenebis (indenyl) dimethyltitanium, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2- Methylinyl) titanium dichloride, ethylenebis (2,4,7-trimethylinyl) titanium dichloride, ethylenebis (2-methyl-4,5-benzoindenyl) titanium dichloride, ethylenebis (2-methyl 4-phenylindenyl) titanium dichloride, ethylenebis (2-methyl-4,5,6,7-tetramethylindenyl) titaniumdichloride, ethylenebis (2-methyl-5,6-dimethylindenyl) Titanium dichloride, ethylenebis (2-methyl-4- (1-naphthyl) indenyl) titanium dichloride, Ethylenebis (2-methyl-4- (2-naphthyl) indenyl) titanium dichloride, ethylenebis (2-methyl-4-i-propylinyl) titanium dichloride, ethylenebis (2-ethyl-4- Phenylindenyl) titanium dichloride, ethylenebis (2-methyl-4-toluylindenyl) titanium dichloride, ethylenebis (2,4-dimethylindenyl) titanium dichloride, ethylenebis (2-methyl-4- Trimethylsilylindenyl) titanium dichloride, ethylenebis (2,4-dimethyl-5,6,7-trihydroindenyl) titaniumdichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5 '-Dimethylcyclopentadienyl) titanium dichloride, ethylene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) titanium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-methylindenyl) titanium dichloride , Isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (2,4-dimethylindenyl) titaniumdichloride, isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5' -Dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) titanium dichloride, Transition metal compounds having two conjugated five-membered ring ligands crosslinked with alkylene groups such as ethylenebis (2-methylbenzoindenyl) titanium dichloride and ethylenebis (benzoindenyl) titanium dichloride,

(b) Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (indenyl) methyltitanium chloride, dimethylsilylenebis (indenyl) methoxychlorotitanium, dimethylsilylenebis (indenyl) titaniumdie Toxoxide, dimethylsilylenebis (indenyl) dimethyltitanium, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titaniumdichloride , Dimethylsilylenebis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) titanium dichloride, dimethylsilylenebis (2-methyl- 4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4,5,6,7-tetramethylindenyl) titaniumdichloride, dimethylsilylenebis (2-methyl-5,6-dimethyl Indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4- (1-naphthyl) indenyl) titanium dichloride, Methylsilylenebis (2-methyl-4- (2-naphthyl) indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-i-propylindenyl) titanium dichloride, dimethylsilylenebis (2-ethyl-4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-toluylindenyl) 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, dimethylsilyl Ethylene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) titanium dichloride, dimethylsilylene (2,3,5-trimethylcy Lofendienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-methylindenyl) titanium dichloride, isopropylidenebis (indenyl) titaniumdi Chloride, isopropylidenebis (2,4-dimethylindenyl) titanium dichloride, isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, Isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-methylbenzoindenyl A transition metal compound having two silylene group crosslinked conjugated 5-membered ring ligands such as titanium dichloride and dimethylsilylene bis (benzoindenyl) titanium dichloride;

Furthermore, in the compounds described in the above (a) to (b), a chlorine atom of these compounds is substituted with a bromine atom, an oxo atom, a methyl atom, a phenyl atom, or the like, and the titanium of the center metal of the transition metal compound And substituted with zirconium, hafnium, niobium, tungsten and the like.

As a metallocene catalyst which gives (2) low crystalline polypropylene used for the manufacturing method of the propylene-ethylene copolymer (a) and (b-2) of this invention, a bicrosslinked metallocene catalyst is mentioned.

As a bicrosslinked metallocene catalyst, the transition metal compound represented by general formula (II) or general formula (III) is mentioned.

In the formulae, E ² and E ³ represent a bonding group that crosslinks two conjugated 5-membered ring ligands. R ⁹ to R ¹⁸ each represent hydrogen, a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, and phosphorus-containing. A hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and R ⁷ , R ⁸ , R ¹⁹ and R ²⁰ each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group and a nitrogen-containing hydrocarbon group Or a boron-containing hydrocarbon group, M ² represents a transition metal of Groups 4 to 6 of the periodic table, and X ² and Y ² each represent a covalent ligand, and X ² and Y ² are bonded to each other; You may form a ring structure.)

As the hydrocarbon group of R ⁷ ~R ²⁰ preferably from 1 to 20 carbon atoms, and particularly preferably having 1 to 12 carbon atoms.

This hydrocarbon group may be a monovalent group and may be bonded to a cyclopentadienyl group which is a conjugated five-membered ring group, and in the case where a plurality of these hydrocarbon groups are present, in general formula (II), R ⁷ and R ⁹ , or R ⁸ And R ¹⁰ may be bonded, and in General Formula (III), R ¹¹ to R ¹⁴ , R ²⁰ , or two of R ¹⁵ to R ¹⁹ may be bonded.

As said conjugated 5-membered ring, it is a substituted or unsubstituted cyclopentadienyl group, an indenyl group, and a fluorenyl group.

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

As the E ² and E ^3, (1) methylene group, an ethylene group, an isopropylene group, a phenyl methyl group, a diphenylmethylene group, a cyclohexylene group having a carbon number of an alkylene group, a cycloalkylene group or from 1 to 4, such as Side chain lower alkyl or phenyl substituent, (2) Silylene group, oligosilylene group, or a side chain lower alkyl or phenyl substituent, such as a silyl group, a dimethylsilylene group, a methylphenylene group, a diphenylsilylene group, a disilylene group, and a tetramethyl disilylene group , (3) hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [lower alkyl group, phenyl group, hydrocarbyloxy group (preferably lower alkoxy group)], specifically, (CH ₃ ) ₂ Ge group , (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆ H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ ) B there may be mentioned groups, (C ₄ H ₉₎ B group, (C ₆ H ₅₎ B group, (C ₆ H ₅₎ Al group, (CH ₃ O) Al group, and the like.

Of these, alkylene groups and silylene groups are preferable.

E ² and E ³ may be the same as or different from each other.

M ² represents a transition metal of Groups 4 to 6 of the periodic table, and specifically titanium, zirconium, hafnium, niobium, molybdenum, tungsten, and the like, among these, titanium, zirconium and hafnium are preferable, and zirconium is particularly suitable. .

X ² and Y ² are each a covalent ligand, and specifically, a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and an alkoxy of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Groups, amino groups, phosphorus-containing hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (e.g., diphenylphosphine groups, etc.) or silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (e.g., for example, a trimethylsilyl group, etc.) having 1 to 20 carbon atoms, preferably (e.g., BF _4, B (C ₆ H _5), a hydrocarbon group or a halogen-containing boron compound for 1 to 12 ₄₎ are shown.

Of these, halogen atoms and hydrocarbon groups are preferred.

These X <^2> and Y <^2> may mutually be same or different.

Specific 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-methyl Cyclopentadienyl) titanium dichloride, etc. are mentioned.

In the compounds described above, chlorine atoms of these compounds are substituted with bromine atoms, oxo atoms, methyl atoms, phenyl atoms, etc., and titanium of the center metal of the transition metal compound is substituted with zirconium, hafnium, niobium, tungsten, or the like. The substituted thing is mentioned.

Specific examples of the transition metal compound represented by General Formula (III) include (1,2'-ethylene) (2,1'-ethylene) -bis (3-methylindenyl) titanium dichloride and (1,2'- Ethylene) (2,1'-ethylene) -bis (3-methyl-4-isopropylindenyl) titanium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (3-methyl -5,6-benzoindenyl) titanium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) -bis (3-methyl-indenyl) titanium dichloride, (1,2 ' Methylene) (2,1'-ethylene) -bis (3-methyl-indenyl) titanium dichloride, (1,2'-methylene) (2,1'-isopropylidene) -bis (3-methyl- Indenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methyl-indenyl) titanium dichloride, (1,2'-dimethylsilylene ) (2,1'-dimethylsilylene) -bis (3-n-butylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3 -i-propylindenyl) titanium Dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride, (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-isopropylinyl) 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-di-i-propylindenyl) 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-i-propylindenyl) Titanium dichloride, (1,2,- Dimethylsilylene) (2,1'-isopropylidene) -bis (3-methylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis ( 3-i-propylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) titanium dichloride, (1, 2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropyl) Idene) -bis (3-trimethylsilylindenyl) 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-i-propylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) titanium dichloro Id, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride, (1,2'-dimethylsilylene) (2,1 ' -Methylene) -bis (3-trimethylsilylindenyl) titanium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-methylindenyl) titanium dichloride, ( 1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) titanium dichloride, (1,2'-diphenylsilylene) (2,1'- Methylene) -bis (3-n-butylindenyl) titanium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) titanium dichloride And (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) titanium dichloride and the like.

In the compounds described above, chlorine atoms of these compounds are substituted with bromine atoms, oxo atoms, methyl atoms, phenyl atoms and the like, and titanium of the center metal of the transition metal compound is zirconium, hafnium, niobium, tungsten or the like. The thing substituted by is mentioned.

The mixing ratio (molar ratio) of the metallocene catalyst giving high crystalline polypropylene and the metallocene catalyst giving low crystalline polypropylene is usually 1/1000 to 1000/1, preferably 1/1000 to 100 / 1, More preferably, it is 1 / 1000-10 / 10.

If it is this range, the propylene ethylene copolymer (a) and (b-2) which have sufficient softness can be obtained.

Next, as the (3-1) catalyst component in the (3) catalyst component, any compound can react with the transition metal compound of the (1) catalyst component and the (2) catalyst component to form an ionic complex. Although it can also use, what is represented by the following general formula (IV) or (V) can be used suitably.

([L ¹ -R ²¹ ] ^{k +} ) _a ([Z] ^- ) _b ... (IV)

([L ² ] ^{k +} ) _a ([Z] ^- ) _b ... (V)

(Wherein L ² is M ³ , R ²² R ²³ M ⁴ , R ²⁴ ₃ C or R ²⁵ M ⁵ )

[(IV), the formula (V), L ¹ is a Lewis base, [Z] ^- is a non-coordination anion [Z ^{1] -,} and [Z ^{2] -,} wherein [Z ^{1] -} is a plurality of groups are bonded to an element Anion, that is, [M ³ G ¹ G ² ..G ^f ] ^- (wherein M ³ represents an element of Groups 5-15 of the periodic table, preferably an element of Groups 13-15 of the periodic table. G ¹ -G ^f is A hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, a dialkylamino group of 2 to 40 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, and 7 carbon atoms, respectively An alkylaryl group of 40 to 40 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, a halogen substituted hydrocarbon group of 1 to 20 carbon atoms, an acyloxy group of 1 to 20 carbon atoms, an organometalloid group, or a hetero atom-containing hydrocarbon of 2 to 20 carbon atoms G ¹ -G ^f Two or more of them may form a ring. f represents the integer of [(valence of the center metal M ³ ) +1].),

[Z ^{2] -} is a conjugated base of the acid number (pKa) of a reciprocal of an acid dissociation constant is -10 or less Brent's conjugate base of the acid alone or Brent's ted ted acid, and combinations of a Lewis acid, or generally defined as a superacid Indicates. In addition, the Lewis base may be coordinated.

R ²¹ represents 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, R ²² and R ²³ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, Indenyl group or fluorenyl group, R <^24> represents a C1-C20 alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group.

R ²⁵ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine.

k is an ion valence of [L ¹ -R ²¹ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a).

M ⁴ includes periodic table elements 1 to 3, 11 to 13, and group 17 elements, and M ⁵ represents a periodic table group 7 to 12 elements.]

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butyl Amines such as amine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, etc. Thioethers such as phosphine and tetrahydrothiophene, esters such as ethyl benzoate, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ²¹ include hydrogen, a methyl group, an ethyl group, a benzyl group, and a trityl group. Specific examples of R ²² and R ²³ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and penta. A methyl cyclopentadienyl group etc. are mentioned.

Specific examples of R ²⁴ include a phenyl group, p-tril group, p-methoxyphenyl group, and the like, and specific examples of R ²⁵ include tetraphenylporpin, phthalocyanine, allyl, metallyl and the like.

In addition, specific examples of M ⁴ include Li, Na, K, Ag, Cu, Br, I, I ₃ And the like, and specific examples of M ⁵ include Mn, Fe, Co, Ni, Zn, and the like.

Further, in [Z ¹ ] ^- , namely, [M ³ G ¹ G ² ..G ^f ], specific examples of M ³ include B, Al, Si, P, As, Sb, and the like, and preferably B and Al. Can be mentioned.

In addition, G ^1, G ² ~G Specific examples of ^f, dimethylamino group, diethylamino group etc., alkoxy group or aryloxy group as a methoxy group as a dialkylamino group, an ethoxy group, n- butoxy group, a phenoxy group, etc., a hydrocarbon group As methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-ecosyl group, phenyl group, p-tril group, benzyl group, 4-t-butylphenyl group, P-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5- as a halogen atom, such as a fluorine, chlorine, bromine, oxo, and hetero atom containing hydrocarbon group, such as a 3, 5- dimethylphenyl group As an organometalloid group, such as a trifluorophenyl group, pentafluorophenyl group, a 3, 5-bis (trifluoromethyl) phenyl group, and a bis (trimethylsilyl) methyl group, a pentamethyl antimony group, a trimethylsilyl group, a trimethylgeryl group, and di A phenyl arsine group, a dicyclohexyl antimony group, diphenyl boron, etc. are mentioned.

Further, bibae anion, i.e. pKa of -10 or less Brandel Stedman acid alone or Brent's Ted conjugated base of an acid, and a combination of a Lewis acid [Z ^2] of the ^{satellite-specific} example, the methanesulfonic acid anion trifluoromethyl (CF ₃ SO ₃ ) ^- , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ^- , trifluor Roacetic acid anion (CF ₃ CO ₂ ) ^- , hexafluoroantimony anion (SbF ₆ ) ^- , fluorosulfonic anion (FSO ₃ ) ^- , chlorosulfonic anion (ClSO ₃ ) ^- , fluorosulfonic anion / 5 -Antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonic acid anion / 5-arsenic fluoride (FSO ₃ / AsF ₅ ) ^- , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅₎ ^), and the like.

Specific examples of the ionic compound that reacts with the transition metal compound of the catalyst component (1) and the catalyst component (2) to form an ionic complex, that is, the catalyst component compound (3-1), include triphenylammonium tetraphenylborate, Tetraphenylborate tri-n-butylammonium, tetraphenylborate trimethylammonium, tetraphenylborate tetraethylammonium, tetraphenylborate methyl (tri-n-butyl) ammonium, tetraphenylborate benzyl (tri-n-butyl) ammonium, tetra Diphenyl ammonium phenyl diphenyl ammonium, tetraphenyl borate triphenyl (methyl) ammonium, tetraphenyl borate trimethylanilinium, tetraphenyl borate methylpyridinium, tetraphenyl borate benzylpyridinium, tetraphenyl borate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium , Tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) tetraethylammonium, tetrakis (pentafluorophenyl) benzyl borate (tri-n-butyl) ammonium, tetra Kis (pentafluorophenyl) borate methyldiphenylammonium, tetrakis (pentafluorophenyl) borate triphenyl (methyl) ammonium, tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (pentafluorophenyl) Dimethylanilin borate, tetrakis (pentafluorophenyl) trimethylaniline borate, tetrakis (pentafluorophenyl) methylpyridinium borate, tetrakis (pentafluorophenyl) benzylpyridinium, tetrakis (pentafluoro Rophenyl) methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) benzyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium ), Tetrakis (Pentaflu) Rophenyl) triphenyl phosphonium, tetrakis [bis (3, 5- ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenyl borate, tetraphenylboric acid, triphenyl borate, tetraphenyl Tetraphenyl porphyrin manganese borate, tetrakis (pentafluorophenyl) ferrocene borate, tetrakis (pentafluorophenyl) boric acid (1,1'-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferro Cerium, tetrakis (pentafluorophenyl) boric acid, tetrakis (pentafluorophenyl) triborate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis ( Pentafluorophenyl) borate tetraphenylporphyrin manganese, tetrafluoroboric acid, silver hexafluorophosphoric acid, silver hexafluorobisoric acid, silver perchloric acid, silver trifluoroacetic acid, silver trifluoromethanesulfonic acid, etc. There.

(3-1) One type of catalyst component may be used, or may be used in combination of 2 or more type.

On the other hand, as an aluminoxane of (3-2) catalyst component, the chain | strand-shaped aluminoxane represented by general formula (VI), and the cyclic aluminoxane represented by general formula (VII) are mentioned.

In the formula, R ²⁶ represents a hydrocarbon group or a halogen atom such as an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, an alkenyl group, an aryl group, or an arylalkyl group, w represents an average degree of polymerization, and is usually 2 to 50. Preferably, it is an integer of 2-40.

In addition, each R <^26> may be same or different.)

(Wherein, R ²⁶ and w are the same as those in General Formula (VI))

As a manufacturing method of the said aluminoxane, the method of contacting condensing agents, such as alkyl aluminum and water, is mentioned, Although there is no limitation in particular about the means, What is necessary is just to react according to a well-known method.

For example, (1) a method of dissolving an organoaluminum compound in an organic solvent and contacting it with water, (2) a method of initially adding an organoaluminum compound at the time of polymerization, and then adding water, (3) a metal salt And a method of reacting the crystallized water or the adsorbed water to an inorganic or organic substance with an organoaluminum compound, (4) a trialkylaluminum to tetraalkyldialumino acid and reacting water again.

In addition, as an aluminoxane, toluene insoluble may be sufficient.

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

The total amount of the (1) catalyst component, the (2) catalyst component, and the use ratio of the (3) catalyst component, when the (3-1) catalyst component compound is used as the (3) catalyst component, are preferably 10: 10: 1-1: 100, More preferably, the range of 2: 1-1: 10 is preferable, and if it is in the said range, the catalyst cost per unit mass polymer is inexpensive and practical.

In the case of using the (3-2) catalyst component compound, the molar ratio is preferably in the range of 1: 1 to 1: 1 million, more preferably in the range of 1:10 to 1: 10000.

Within this range, the catalyst cost per unit mass polymer is inexpensive and practical.

In addition, as (3) catalyst component, you may use (3-1) catalyst component and (3-2) catalyst component individually or in combination of 2 or more types.

In addition, the catalyst for polymerization at the time of producing a propylene ethylene copolymer (a) and (b-2) is a (4) catalyst in addition to the said (1) catalyst component, (2) catalyst component, and (3) catalyst component. An organoaluminum compound can be used as a component.

Here, as an organoaluminum compound of (4) catalyst component, the compound represented by general formula (VIII) is used.

R ²⁷ _v AlJ _{3 -v} ... (VIII)

[Wherein, R ²⁷ represents 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 general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride and dimethyl Aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride, etc. are mentioned.

1 type may be used for these organoaluminum compounds, and may be used for them in combination of 2 or more type.

In the process for producing the propylene-ethylene copolymers (a) and (b-2), the preliminary contact is made by using the above-mentioned (1) catalyst component + (2) catalyst component, (3) catalyst component and (4) catalyst component. You can also do

Preliminary contact can be performed by contacting (1) catalyst component + (2) catalyst component, for example, (3) catalyst component, Although there is no restriction | limiting in particular in the method, A well-known method can be used.

These preliminary contacts are effective for reducing the catalyst cost, such as improving the catalytic activity and reducing the use ratio of the catalyst component (3), which is a cocatalyst.

The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, and more preferably 0 ° C to 80 ° C.

In preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon, etc. can be used as an inert hydrocarbon of a solvent.

Especially preferred among these are aliphatic hydrocarbons.

The total amount of the above-mentioned (1) catalyst component, (2) catalyst component, and the use ratio of (4) catalyst component are in a molar ratio, Preferably it is 1: 1-1: 10000, More preferably, it is 1: 5-1: 2000, More preferably, the range of 1:10 to 1: 1000 is preferable.

Although the polymerization activity of a transition metal sugar can be improved by using the said (4) catalyst component, when too much, an organoaluminum compound will become useless and it will remain in a large quantity in a polymer, and it is unpreferable.

Specific examples of the porous carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and mixtures thereof, such as silica. Alumina, zeolite, ferrite, glass fiber, etc. are mentioned.

Among these, SiO ₂ and Al ₂ O ₃ are particularly preferable.

In addition, the porous carrier may contain a small amount of carbonate, nitrate, sulfate, or the like.

On the other hand, as a carrier other than the above and the like _{MgCl 2, Mg (OC 2 H} 5) 2 , represented by the general formula MgR ²⁸ _{x X} ³ _y such as magnesium compounds and their complex salts represented by the following.

R ²⁸ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ³ represents 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 = 2.

Each R <^28> and each X <^3> may be the same respectively, and may differ.

Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymers, polyethylene, poly1-butenes, substituted polystyrenes, and polyarylates, starch, carbon, and the like.

Propylene as the carrier of the catalyst for use in the production of the ethylene copolymer (a) and (b-2), etc. are preferred _{MgCl 2, MgCl (OC 2 H} 5), Mg (OC 2 H 5) 2.

In addition, although the property of a support | carrier changes with the kind and manufacturing method, an average particle diameter is 1-300 micrometers normally, Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers.

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

The specific surface area of the carrier is usually 1 to 1000 m 2 / g, preferably 50 to 500 m 2 / g, and the pore volume is usually 0.1 to 5 cm 3 / g, preferably 0.3 to 3 cm 3 / g. .

If the specific surface area or pore volume is in the above range, the catalytic activity is increased.

In addition, the specific surface area and pore volume can be calculated | required from the volume of nitrogen gas adsorbed according to the BET method, for example.

In addition, when the said support | support is an inorganic oxide support, it is preferable to bake at 150-1000 degreeC normally, Preferably it is 200-800 degreeC.

In the case where at least one kind of catalyst component is supported on the carrier, at least one of (1) catalyst component + (2) catalyst component and (3) catalyst component is preferably (1) catalyst component + (2) catalyst. It is preferable to support both of the component and (3) the catalyst component.

The method of supporting at least one of (1) catalyst component + (2) catalyst component and (3) catalyst component on the carrier is not particularly limited, but for example, (a) (1) catalyst component + (2) A method for mixing at least one of the catalyst component and (3) the catalyst component with the carrier, (b) treating the carrier with an organoaluminum compound or a halogen-containing silicon compound, and then (1) catalyst component + (2) catalyst in an inert solvent A method of mixing with at least one of the component and (3) the catalyst component, (c) the carrier and (1) the catalyst component + (2) the catalyst component, and / or (3) the catalyst component and the organoaluminum compound or halogen-containing silicon compound (D) (1) catalyst component + (2) catalyst component or (3) catalyst component on a carrier, and then (3) catalyst component or (1) catalyst component + (2) catalyst component The method of mixing, (e) (1) catalyst component + (2) catalyst component and the contact reaction product of (3) catalyst component carrier The time of contact reaction in the method of mixing, (f) (1) + the catalyst component (2) the catalyst component and (3) a catalyst component, or the like can be used a method of co-existence of the carrier.

Moreover, in the said (d), (e) and (f) method, the organoaluminum compound of (4) catalyst component can also be added.

In preparation of the catalyst used for manufacture of a propylene ethylene copolymer (a) and (b-2), the said (1) catalyst component + (2) catalyst component, (3) catalyst component, and (4) catalyst component When making a contact, you may irradiate an acoustic wave and prepare a catalyst.

The acoustic wave is usually acoustic waves, and particularly preferably ultrasonic waves.

Specifically, the ultrasonic wave whose frequency is 1-1000 kHz, Preferably the ultrasonic wave which is 10-500 kHz is mentioned.

The catalyst obtained in this way may be used for superposition | polymerization after performing solvent distillation once and taking out as a solid, and may be used for superposition | polymerization as it is.

In the production of the propylene-ethylene copolymer, a catalyst is produced by carrying out (1) catalyst component + (2) catalyst component and (3) at least one support component of the catalyst component in a polymerization system. Can be.

For example, at least one of (1) catalyst component + (2) catalyst component and (3) catalyst component and a support | carrier, and also the organoaluminum compound of said (4) catalyst component are added as needed, and olefin, such as ethylene, is added In addition to atmospheric pressure to 2 MPa, a method of producing catalyst particles by prepolymerizing at -20 to 200 ° C. for about 1 minute to 2 hours can be used.

The use ratio of the catalyst component (3-1) and the carrier in the catalyst used for the production of the propylene-ethylene copolymers (a) and (b-2) is preferably 1: 5 to 1: 10000 in mass ratio. More preferably, it is 1: 10-1: 500, and the use ratio of (3-2) component and a support agent is mass ratio, Preferably it is 1: 0.5-1: 1000, More preferably, it is 1: 1. It is preferable to set it as -1: 50.

(3) When using 2 or more types as a catalyst component mixed, it is preferable that the use ratio of each (3) catalyst component and a support | carrier exists in the said range by mass ratio.

In addition, the use ratio of (1) catalyst component + (2) catalyst component and a support | carrier is mass ratio, Preferably it is 1: 5-1: 10000, More preferably, it is preferable to set it as 1: 10-1: 500. .

(3) the use ratio of the catalyst component [(3-1) catalyst component or (3-2) catalyst component] and the support, or (1) the use ratio of the catalyst component + (2) the catalyst component and the carrier is within the above range. The activity is elevated or powder morphology is also improved.

The average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200 µm, preferably 10 to 150 µm, particularly preferably 20 to 100 µm, and the specific surface area is usually 20 to 1000 m 2 / g, preferably Preferably it is 50-500 m <2> / g.

If the average particle diameter is 2 µm or more, the fine powder in the polymer decreases, and if it is 200 µm or less, the coarse particles in the polymer decrease.

When the specific surface area is 20 m 2 / g or more, the activity is increased, and when the specific surface area is 1000 m 2 / g or less, the bulk density of the polymer is increased.

Moreover, in the catalyst used for manufacture of a propylene ethylene copolymer (a) and (b-2), it is preferable that the amount of transition metals in 100 g of carriers is 0.05-10 g normally, especially 0.1-2 g.

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

The polymerization of propylene in the first step can be selected from slurry polymerization or mass polymerization.

Copolymerization of propylene and ethylene in the second step can be selected from a slurry, agglomerate, and gas phase polymerization.

The first step and the second step can also be multistage polymerization.

As polymerization conditions in propylene homopolymerization, the polymerization pressure does not have a restriction | limiting in particular, Usually, atmospheric pressure-8 MPa, Preferably it is 0.2-5 MPa, and polymerization temperature is 0-200 degreeC normally, Preferably it is 30-100 It is suitably selected in the range of ° C.

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

There is no restriction | limiting in particular as polymerization conditions of a copolymerization part, Usually, atmospheric pressure-8 MPa, Preferably it is 0.2-5 MPa, and polymerization temperature is 0-200 degreeC normally, Preferably it is in the range of 20-100 degreeC. Appropriately selected.

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

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

The molecular weight of the polymer in the propylene homopolymerization part and the copolymerization part can be adjusted by adding a chain transfer agent, preferably by adding hydrogen.

Moreover, you may exist inert gas, such as nitrogen.

When using a polymerization solvent, For example, aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, alicyclic hydrocarbons, such as cyclopentane, cyclohexane, and methylcyclohexane, aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, Halogenated hydrocarbons, such as chloroform and dichloromethane, etc. can be used.

These solvent may be used individually by 1 type, and may combine 2 or more types.

Moreover, depending on the polymerization method, it can be performed without a solvent.

At the time of superposition | polymerization, prepolymerization can be performed using the said catalyst for superposition | polymerization.

Although prepolymerization can be performed by making a solid catalyst component contact a small amount of olefins, for example, there is no restriction | limiting in particular in the method, A well-known method can be used.

There is no restriction | limiting in particular about the olefin used for prepolymerization, The same thing as what was illustrated above, for example, ethylene, C3-C20 alpha olefin, a mixture thereof, etc. are mentioned, It is used in the said superposition | polymerization. It is advantageous to use ethylene or propylene.

In addition, the prepolymerization temperature is usually -20 to 200 ° C, preferably -10 to 130 ° C, more preferably 0 to 80 ° C.

In prepolymerization, an aliphatic hydrocarbon, an aromatic hydrocarbon, etc. can be used as a solvent.

Among them, particularly preferred are aliphatic hydrocarbons.

In addition, you may perform prepolymerization without a solvent.

In prepolymerization, the intrinsic viscosity [η] of the prepolymerization product (measured in 135 ° C. decalin) is 0.2 dl / g or more, in particular 0.5 dl / g or more, and the prepolymerized product per milliliter of the transition metal component in the catalyst. It is preferable to adjust the conditions so that the amount may be 1 to 10,000 g, particularly 10 to 1000 g.

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

In addition, by using a metallocene catalyst, the internal haze can be controlled to less than 55%.

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

The polypropylene resin (b-1) in the present invention can be produced by a conventional method irrespective of catalyst systems such as Mg / Ti catalysts and metallocene catalysts, and preferably Tm is 135 ° C. As described above, the tensile modulus is 800 MPa or more.

There is no restriction | limiting in particular in the manufacturing method of the resin material for cosmetics sheets of this invention, The resin composition containing the said propylene ethylene copolymer (a), or propylene resin (b-1) 80- of ΔH is 80 J / g or more. Each component (resin component and various additives used as desired) constituting the resin composition comprising a combination of 30 mass% and 20 to 70 mass% of the propylene-ethylene copolymer (b-2) was subjected to a Henschel mixer. Dry blending), and melt kneading by a single screw or twin screw extruder, a Banbury mixer, or the like.

It is also possible to use a masterbatch.

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

As the various stabilizers, the use of stabilizers against oxidative deterioration, thermal deterioration, etc. is most commonly used, for example, phenolic stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, and the like. It is available.

As the phenolic stabilizer, conventionally known ones, for example, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclo Hexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propyl Phenol, 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, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, dl-α-tocopherol, t-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis ( 3-methyl-6-t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol ), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2 ' -Butylidenebis (2-t-butyl-4-methylphenol), 1,1,3-tris ( 2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethyleneglycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylenebis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamid), 3,5-di- t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1, 3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydrate Oxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, bis (3,5-di-t-butyl-4-hi Hydroxybenzylphosphonate ethyl) calcium, bis (3,5-di-t-butyl-4-ethylhydroxybenzylphosphonic acid) nickel, bis [3,3-bis (3-t-butyl-4-hydroxyphenyl ) Butyric acid] glycol ester, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], bis [2-t-butyl-4-methyl-6- (3-t-butyl-5-methyl-2-hydrate Hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1, 1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane , 2,2-bis [4- [2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)] ethoxyphenyl] propane and stearyl-β- (4-hydroxy- Β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl esters such as 3,5-di-t-butylphenol) propionate, etc. may be mentioned. All. Among them, 2,6-di-t-butyl-4-methylphenol, stearyl-β- (4-hydroxy-3,5-di-t-butylphenol) propionate, 2,2'- Ethylidenebis (4,6-di-t-butylphenol) and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane are suitable.

As the organic phosphite stabilizer, for example, trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, trisisodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, Phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di -t-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4,4 '-Isopropylidene-diphenolalkyl phosphite (Alkyl has about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphite, tris (Biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane Diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenolpolyphosphite, bis (octylphenyl) bis [4, 4'-butylidenebis (3-methyl-6-t-butylphenol)] · 1,6-hexanedioldiphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy -5-t-butylphenol) diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 9,10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4, '-biphenylenediphosphite, distearylpentaerythritol Diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl 4,4'-isopropylidenediphenol pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphospha Agent and the like can be mentioned bisphenol -A- phenyl pentaerythritol diphosphite.

Among these, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4, -di-t-butylphenyl) -4,4'-ratio Phenylenediphosphite is preferred, and tris (2,4-di-t-butylphenyl) phosphite is particularly suitable.

Moreover, it is preferable to use the polyalcohol ester of dialkylthio dipropionate and alkylthio propionic acid as an organic thioether stabilizer.

As the dialkylthiodipropionate used here, a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms is preferable, and as a polyalcohol ester of alkylthiopropionic acid, an alkyl having a alkyl group having 4 to 20 carbon atoms is preferable. Polyhydric alcohol esters of thiopropionic acid are preferred.

In this case, examples of the polyhydric alcohol constituting the polyhydric alcohol ester include glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, trishydroxyethyl isocyanurate, and the like.

Examples of such dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, and the like.

On the other hand, as polyhydric alcohol ester of alkylthio propionic acid, for example, glycerin tributylthio propionate, glycerin trioctylthio propionate, glycerin trilaurylthio propionate, glycerin tristearylthio propionate, trimethyl Roll ethane tributyl thio propionate, trimethyl roll ethane trioctyl thio propionate, trimethyl roll ethane trilauryl thio propionate, trimethyl roll ethane tristearyl thio propionate, pentaerythritol tetrabutyl thio propionate Nate, pentaerythritol tetraoctyl thio propionate, pentaerythritol tetralauryl thio propionate, pentaerythritol tetrastearyl thio propionate, etc. are mentioned.

Among these, dilauryl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetralauryl thio propionate are suitable.

Examples of the hindered amine stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate. -2,2,6,6-tetramethylpiperidine polycondensate, poly [6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triadine-2,4- Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino], tetra Keith (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl Benzoate, bis- (1,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmaro Nate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 '-(1,2-ethanediyl) bis (3,3,5, 5-tetramethylpiperadinone), (mix 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mix 1, 2,2,6,6-pentamethyl-4-piperidyl / Lidesyl) -1,2,3,4-butanetetracarboxylate, mix [2,2,6,6-tetramethyl-4-piperidyl / 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-piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] Diethyl] -1,2,3,4-butanetetracarboxylate, N, 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-triadine condensate, poly [6-N-morpholinyl-1,3,5-triadine -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6, -tetramethyl-4-piperidyl ) Imide], a condensate of N, N'-bis (2,2,6,6, -tetramethyl-4-piperidyl) hexamethylenediamine with 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] prop Lopionamide, etc. may be mentioned.

Among these hindered amine stabilizers, in particular, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidyl polycondensate, poly [6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triadine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], 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-t-butyl-4-hydrate Oxybenzyl) -2-n-butylmaronate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperadinone), (mix 2,2,6, 6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (Mix1,2,2,6,6-pentamethyl-4-piperidyl / Tridecyl) -1,2,3,4-butanetetracarboxylate, mix [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ', β'-tetramethyl- 3,9- [2,4,8,10-tetraoxaspiro (5,5) CAN] diethyl] -1,2,3,4-butanetetracarboxylate, mix [1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β' -Tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, N, N ' -Bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6-pentamethyl-4-piperidyl) amino] -6-chloro-1, 3,5-triadine condensate, poly [6-N-morpholinyl-1,3,5-triadine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperi Dill) imino] hexamethylene [(2,2,6,6, -tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,6,6, -tetramethyl- Condensate of 4-piperidyl) hexamethylenediamine with 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2 -(2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide is suitable.

Process oil is preferable as a softener, and as this process oil, what is normally used as a softener at the time of processing synthetic rubber can be applied as it is.

The process oil can be applied regardless of mineral oil and synthetic oil. Specific examples of the mineral oil include effluent oil obtained by atmospheric distillation of paraffinic crude oil, intermediate mechanical crude oil or naphthenic crude oil, and the atmospheric pressure. The refined oil of the distillate obtained by distillation under reduced pressure of a distillation residue oil, deep-dewaxed oil, etc. are mentioned.

Examples of the synthetic oils include alkylbenzenes, polybutenes, poly (α-olefins), and the like.

As the characteristics required for the process oil which can be applied to the present invention, not particularly limited, but the kinematic viscosity of a 40 ℃ to the 100~10000mm ² / sec, especially 200~7000mm is preferably used in ² / sec .

As an inorganic filler, there exist a spherical filler, a plate-shaped filler, a fibrous filler, etc., for example. As the spherical filler, for example, calcium carbonate, kaolin (aluminum silicate), silica, pelite, syras balun, sericite, silicon earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, amorphous zeolite, etc. As the shape filler, for example, tar or mica, and the fibrous filler include, for example, a needle-like one such as wollastonite, a fibrous one such as magnesium oxalate, potassium titanate fiber, fibrous calcium carbonate, Furthermore, the thing of completely fibrous form, such as glass fiber, etc. are mentioned.

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

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

Moreover, among these additives, what adversely affects transparency is only filled in the base material, not the surface layer.

Specific examples of the nucleating agent in the present invention include a high melting point polymer, an organic carboxylic acid or a metal salt thereof, an aromatic sulfonate or a metal salt thereof, an organic phosphate compound or a metal salt thereof, dibenzylidene sorbitol or a derivative thereof, a rodinic acid partial metal salt, 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, poly3-methylpentene-1, poly3-methylbutene-1, Polyalkenylsilane, etc. are mentioned.

Examples of the metal salt include aluminum benzoate salt, p-t-butyl aluminum benzoate salt, sodium adipic acid, sodium thiophenecarboxylic acid, sodium pyrrole carboxylate, and the like.

Dibenzylidene sorbitol or its derivatives 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 etc. are mentioned.

Specific examples thereof include Gerol MD and Gerol MD-R (trade name) of Shin-Nihon Rica (manufactured).

As a rodinic acid partial metal salt, the fine crystal KM1600, the fine crystal KM1500, the fine crystal KM1300 (brand name) etc. of Arakawa Chemical Industries (manufactured) are mentioned. As the inorganic fine particles, tar, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice powder, Pumice balloon, aluminum hydride, magnesium hydride, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, molybdenum sulfide, etc. are mentioned.

As an amide compound, adipic acid dianilide, sperinic acid dianilide, etc. are mentioned.

One type of these nucleating agents may be used, and may be used for them combining two or more types.

As the resin material for a cosmetic sheet of the present invention, it is preferable to use inorganic fine particles such as organophosphate metal salts and / or tar represented by the following general formula as the nucleating agent due to the low occurrence of odors.

This resin material for makeup sheets is suitable for the use for a food object.

In the formula, R ²⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁸ and R ²⁹ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Any one of a metal, an alkaline earth metal, aluminum and zinc, m is 0 when M is an alkali metal, n is 1, n is 1 or 2 when M is an alkaline earth metal or zinc, n M is 1 when m is 1, m is 0 when n is 2, m is 1 when M is aluminum, and n is 2.)

As a specific example of an organophosphate metal salt, adecastatab NA-11 and adecastab NA-21 (Asahi Denka Co., Ltd.) (manufactured) are mentioned.

And in the resin material for cosmetics sheets of this invention, when inorganic fine particles, such as said tar, are used as a nucleating agent, when shape | molding to a film is excellent also in slipperiness | lubricacy, characteristics, such as printing characteristics, are preferable. Do.

Moreover, when said dibenzylidene sorbitol or its derivative is used as a nucleating agent, since it is excellent in transparency, it is preferable.

Furthermore, when the said amide compound is used as a nucleating agent, since it is excellent in rigidity, it is preferable.

The resin material for makeup sheets of this invention is excellent in moldability, little stickiness, and excellent in softness and transparency.

In the present invention, in order to mold the cosmetic sheet (film or sheet) used for the surface layer and / or the base material, the resin material for the cosmetic sheet is formed by a molding method such as cast molding, inflation molding, calendar molding, or the like, with a thickness of 30 to 500. It is advantageous to process into a film or sheet shape of 탆, preferably 50 to 300 탆, more preferably 60 to 120 탆.

 In order to improve adhesiveness, printability, etc., the film or sheet | seat obtained in this way is preferable to perform surface treatment, such as a corona treatment, an ozone treatment, and a plasma treatment.

In addition, when using this film or sheet | seat as a base material, you may provide a concealment effect by adding a pigment at the time of shaping | molding.

The makeup sheet (film or sheet) of the present invention may have a laminated structure composed of a surface layer, an adhesive layer, a pattern layer, an adhesive layer and a base material, a so-called doubling film, or a laminated structure composed of a surface layer, an adhesive layer and a pattern layer. Or a so-called back print film (which is printed directly on the surface layer and does not have a base material).

As the adhesive layer in the makeup sheet (film or sheet), for example, polyurethane resin, epoxy resin, acrylic resin, vinyl resin, vinyl acetate resin, polyester resin, ethylene-vinyl acetate copolymer resin, Preferable examples thereof include those having a thickness of about 1 to 20 µm and consisting of a known adhesive mainly composed of acryl-vinyl acetate copolymer resin, polyamide resin, ionomer resin, or the like, or modified polyolefin.

Here, as modified polyolefin, for example, polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-nonconjugated diene compound copolymer (for example, EPDM, etc.), ethylene-aromatic monovinyl compound -Esters of unsaturated carboxylic acids such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid, unsaturated carboxylic acids such as maleic anhydride, and unsaturated carboxylic acids such as methyl acrylate and monomethyl maleic acid And chemically modified using imides of unsaturated carboxylic acids such as amides of unsaturated carboxylic acids such as acrylic amide and maleic acid monoamide, maleimide, and N-butyl maleimide.

In addition, there is no restriction | limiting in particular about the form of the adhesive agent at the time of processing, Any of a liquid form, a semi-melt phase, and a film sheet form may be sufficient.

In addition, when there exists two layers of an adhesive bond layer, the adhesive layer of 1st layer and the adhesive layer of 2nd layer may consist of the same material, or may consist of another material.

On the other hand, the pattern layer is, for example, printed with a tree shape, stone shape, surface pattern of natural leather, cloth, abstract pattern, etc., and as a binder of the ink to form these pattern shapes, There is no restriction | limiting in particular, For example, a polyurethane resin, a vinyl chloride resin, a vinyl chloride-vinyl acetate type copolymer resin, a vinyl chloride-vinyl acetate type copolymer resin / acrylic resin, a chlorinated polypropylene resin, an acrylic resin, Any of polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, acetyl cellulose resin and the like are used.

In addition, the said ink is suitably mixed with coloring agents such as pigments and dyes, extender pigments, solvents and the like. The thickness of this patterned layer is about 1-5 micrometers normally.

In this invention, it is especially suitable that the said pattern layer consists of a two-layered structure of a patterned layer and a concealment layer.

As an ink used for formation of this concealment layer, what mixed suitably the coloring agent, a extender pigment, a solvent, a stabilizer, a plasticizer, a solvent, a hardening | curing agent, etc. with a pigment and a dye is used for a binder.

As said binder, the thing similar to what was illustrated as a binder of the ink used for forming the said patterned layer is mentioned.

As this concealment layer, the beta printed layer of about 1-20 micrometers in thickness is suitable.

This concealment layer is formed as a lower layer of the patterned layer.

In the cosmetic sheet (film or sheet) of the present invention, acrylic resins or polyurethane resins are optionally used on the surface layer for the purpose of improving abrasion resistance, weather resistance, emboss processability, damage resistance, stain resistance, and the like. A top coat layer having a thickness of about 1 to 20 µm and the like may be formed.

In addition, the surface layer may be embossed as desired or the recessed portion may be filled with wiping ink or the like.

As a manufacturing method of the makeup sheet (film or sheet) of this invention, what has the said laminated structure should just be a method obtained, and there is no restriction | limiting in particular, For example, the laminated layer which consists of a surface layer, an adhesive bond layer, a pattern layer, an adhesive bond layer, and a base material It is advantageous to have a structure by using the following two kinds of methods.

First, as a 1st method, an adhesive bond layer, a pattern layer, and an adhesive bond layer are laminated one by one by general printing methods, such as gravure printing, screen printing, offset printing, flexographic printing, on a base material, ) A method of adhering a film or sheet to be a surface layer by thermal lamination or the like, (2) A method of adhering a film or sheet to be a surface layer by dry lamination or a wet lamination or the like, (3) On a film or sheet to be a surface layer, gravure A general printing method such as printing, screen printing, offset printing, flexographic printing, or a method of forming an adhesive layer of the same composition by a coating method such as a roll coat, and bonding the adhesive layers to each other by laminating or the like, (4 ) The method of forming a surface layer by extrusion lamination of resin used as a surface layer, etc. are used.

As a 2nd method, after laminating | stacking an adhesive bond layer and a patterned layer on a base material sequentially by general printing methods, such as gravure printing, screen printing, offset printing, flexographic printing, (1) On the film or sheet used as a surface layer, The adhesive layer is formed by a general printing method such as gravure printing, screen printing, offset printing, flexographic printing, or a coating method such as a roll coat, which is then laminated so that the adhesive layer is in contact with the patterned layer, and the like. By a method similar to (2) (1), by forming an adhesive bond layer on a film or sheet to be a surface layer and adhering by dry lamination or wet lamination, or the like (3) by a pattern layer or a surface layer A method of extruding and adhering a resin, which becomes an adhesive layer, between films and sheets in a molten state (extrusion lamination), (4) Adhesive layer and surface By a resin which is a co-extrusion direct lamination, and a method of forming the adhesive layer and the surface layer is used.

The present invention can further provide a cosmetic material obtained by adhering the makeup sheet (film or sheet) obtained in this manner to various substrates.

As a base material used for this cosmetic material, it is a wood base material, such as a wood, a plywood, a laminated material, or a particle board, a hard board, for example, a steel plate, a stainless steel plate, an aluminum plate, etc. The metal base material and inorganic base material, such as gypsum board, are mentioned, for example.

In order to manufacture a cosmetic material, it is good to laminate the said cosmetic sheet (film or sheet) so that the said base material or a patterned layer may face the said base material using an adhesive agent.

At this time, there is no restriction | limiting in particular as an adhesive agent to be used, It can select from a conventionally well-known adhesive agent suitably, and can use.

Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Preparation Example 1 (Polymer 1)

(Adjustment of catalyst)

Dimethylsilylene bis (2-methyl-benzo [e] indenyl) zirconium (IV) dichloride (Compound A) and (1,2'- to silica-supported methylaluminoxane (supported MAO, supported amount of Al: 14 mass%) Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium (IV) dichloride (Complex B) is supported in a molar ratio of Zr in Complex A with respect to Al in MAO. Prepolymerization was performed at 30 degreeC and the propylene pressure of 0.13 Mpa for 1 hour using the catalyst supported so that Zr in 0.001 and the complex B might be set to 0.001.

(Polymer 1: Production of Propylene Block Copolymer)

100 L of liquid propylene was injected into a 350 L autoclave, 100 mmol of triisobutylaluminum was charged, and 200 micromol of the catalyst was added to zirconium at 55 ° C. to initiate polymerization.

After 30 minutes from the start of the polymerization, 0.1 MPa of ethylene was added at a partial pressure, ethylene was continuously added so that the ethylene partial pressure was constant, and polymerization was performed for 60 minutes.

After completion of the polymerization, propylene was flashed and then dried under an air stream of 80 ° C. for 2 hours.

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

To this polymer, as an antioxidant, Irganox 1010 (manufactured by Chiba Specialty Chemicals Co., Ltd.) 500 ppm, Irga hose 168 (manufactured by Chiba Specialty Chemicals Co., Ltd.) 1000 ppm, and a neutralizing agent, 300 ppm calcium stearate , A polymer in which 300 ppm of Px14 (manufactured by Kayaku Akujo Co., Ltd.) was added as a peroxide, and the melt flow rate (MFR: 230 ° C., load 21.18 N) was adjusted to 4 to 5 g / 10 minutes during melt kneading in an extruder. 1 was obtained.

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

[Measurement of Intrinsic Viscosity [η]]

It measured at the temperature of 135 degreeC in the decalin solvent using VMR-053 type | mold automatic viscometer by Rigoh Co., Ltd. product.

[Measurement of Tensile Modulus]

Tensile modulus was press-molded a sample, the test piece was created, and it measured based on JISK-7113.

Test piece (2 dumbbell) thickness: 1mm

Cross head speed: 50mm / min

Load cell: 100 kg

Preparation Example 2 (Polymer 2)

Polymer 2 was obtained in the same manner as polymer 1 except that the ethylene partial pressure was 0.2 MPa.

With respect to the obtained polymer 2, physical properties were measured in the same manner as in Production Example 1.

The results are shown in Table 1.

Preparation Example 3 (Polymer 3)

Polymer 3 was obtained in the same manner as Polymer 1 except that Complex A / Complex B was heated at 4/3 (molar ratio), initial polymerization temperature was 40 ° C., ethylene partial pressure was 0.15 MPa, and the temperature at the time of copolymerization was increased to 50 ° C. .

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.

Preparation Example 4 (Polymer 4)

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

About the obtained polymer 4, it carried out similarly to manufacture example 1, and measured physical properties.

The results are shown in Table 1.

Preparation Example 5 (Polymer 5)

Polymer 5 was obtained in the same manner as polymer 3 except that Complex A / Complex B was 2/3 (molar ratio), the initial polymerization temperature was 35 ° C., the ethylene partial pressure was 0.3 MPa, and the copolymerization temperature was 45 ° C.

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.

Production Example 1
Production Example 2
Preparation Example 3
Production Example 4
Preparation Example 5
Homo PP
(F-704NP)
Random PP
(F-724NP)

Idemitsu TPO
(F-3700)
Polymer 1
Polymer 2
Polymer 3
Polymer 4
Polymer 5
f _EEE (mol%)
0
0
0
0
0
Re · Rp
1.3
1.2
1.4
1.3
1.2
Mw / Mn
2.6
2.6
2.8
2.6
3.1
4.3
4.1
3.0
ΔH (J / g)
89
78
52
18
11
102
88
58
Tm (占 폚)
155
150
140
135
110
162
146
159
Ethylene
Content (mol%)
3.2
3.9
2.7
4.4
6.9
0
2.1
0
MFR (g / 10 min)
4.8
4.9
4.9
4.7
4.5
7.0
7.0
5.0 Seal
Elastic modulus
(MPa)
845
568
202
44
23
1100
1000
250

Example  One

The polymer 1 was extrusion-molded at the die | dye exit resin temperature of 240 degreeC using the 40 mm (phi) cast molding machine, and the film of 100 micrometers and 300 micrometers was obtained.

The following measurement was performed about the obtained film.

The results are shown in Table 2.

[Measurement of Stretch Whitening Resistance]

The obtained film was made into 2 cm x 8 cm single shape, the bending line was put in the center part perpendicularly to the longitudinal direction, and the whitening degree of the extending | stretching part at the time of 100% elongation at 2 cm between chucks and 200 m / min of tensile velocity was observed.

◎: No change in appearance.

(Circle): There is some whitening (light white).

(Triangle | delta): There is some whitening.

X: Whitening.

××: Whitening or breaking remarkably.

[Measurement of internal haze]

 Measurement was made using a head meter.

[Low temperature characteristics]

Solid viscoelasticity was measured and the peak of tan-delta was measured.

[Measurement of Change Over Time (Peeling Whitening Resistance)]

The obtained film was cut | disconnected to A4 plate size, 30 sheets were laminated | stacked, and it preserve | saved in 30 degreeC oven for 30 days, was taken out, it peeled off one by one, and the external appearance was observed.

◎: No change in appearance.

(Circle): There is almost no whitening, and the appearance changes a little.

(Triangle | delta): A department part is dotted with spots.

X: It whitens remarkably and a film increases at the time of peeling.

[Measurement of Melt Flow Rate (MFR)]

In accordance with JIS K 7210, it measured at 230 degreeC and the load of 21.18N.

Example  2

Except having used the polymer 2, pellets were obtained in the same manner as in Example 1, and then films of 100 µm and 300 µm were obtained, and the physical properties thereof were measured.

The results are shown in Table 2.

Example  3

Except having used the polymer 3, pellets were obtained in the same manner as in Example 1, and then films of 100 µm and 300 µm were obtained, and physical properties thereof were measured.

The results are shown in Table 2.

Example  4

Mass ratio of 25/75 as polymer 5 and propylene homopolymer (homo PP) [polypropylene F-704NP by Idemitsu Kosan, ΔH 102J / g, melt flow rate (MFR) 7 g / 10 min, tensile modulus of 1100 MPa] The pellets were obtained in the same manner as in Example 1, except that the blend was used as a blend, and then 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

Mass ratio of 50/50 as polymer 5 and propylene homopolymer (homo PP) [polypropylene F-704NP by Idemitsu Kosan, ΔH 102J / g, melt flow rate (MFR) 7g / 10min, tensile modulus of 1100MPa] The pellets were obtained in the same manner as in Example 1, except that the blend was used as a blend, and then 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

Polymer 5 and propylene random copolymer (Random PP) [polypropylene F-724 NP manufactured by Idemitsu Kosan Co., ΔH 88J / g, melt flow rate (MFR) 7 g / 10 min, tensile modulus of 1000 MPa] to 50/50 Except having used the thing blended by mass ratio, it carried out similarly to Example 1, and obtained pellets, and the film of 100 micrometers and 300 micrometers was obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Example  7

60/40 mass ratio of the polymer 4 and the propylene homopolymer (homo PP) [polypropylene F-704NP by Idemitsu Kosan, ΔH 102J / g, melt flow rate (MFR) 7g / 10min, tensile modulus of 1100MPa] The pellets were obtained in the same manner as in Example 1, except that the blend was used as a blend, and then 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  One

Except for using the propylene homopolymer (homo PP) [polypropylene F-704 NP, ΔH 102J / g, melt flow rate (MFR) 7 g / 10 minutes, tensile modulus 1100 MPa manufactured by Idemitsu Kosan Co., Ltd.) After pellets were obtained in the same manner, 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

Propylene homopolymer (homo PP) [polypropylene F-704NP manufactured by Idemitsu Kosan Corporation, ΔH 102J / g, melt flow rate (MFR) 7 g / 10 min, tensile modulus of elasticity 1100 MPa] and styrene elastomer (manufactured by JSR Corporation) Except having used the blend of dynaron 1320P) in the mass ratio of 80/20, pellets were obtained like Example 1 and the film of 100 micrometers and 300 micrometers was obtained.

The physical properties of the obtained film were measured.

The results are shown in Table 2.

Comparative Example  3

In the same manner as in Example 1, except that a low-stereoregular polypropylene (Idemitsu TPO) [F-3700, stereoregularity index 72 mol%, melt flow rate (MFR) 5 g / 10 min, tensile modulus 250 MPa] was used. After obtaining the pellets, 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

A pellet was obtained in the same manner as in Example 1 except that the chopped body 5 was used, films of 100 µm and 300 µm were obtained, and physical properties thereof were measured.

The results are shown in Table 2.

Example
Comparative Example
One
2
3
4
5
6
7
One
2
3
4
polymer

One
2
3
5
5
5
4
5
Addition amount (mass%)

100
100
100
25/75
50/50
50/50
60/40
100
80/20
100
100
ΔH (J / g)

89
78
52
87
78
80
83
102
88
58
30
Tm (占 폚)

155
150
140
161
161
149
160
162
162
159
110
Stretch Whitening Resistance

○
◎
◎
○
◎
◎
◎
×
○
◎
◎
Tensile Modulus (MPa)

845
568
202
810
600
630
750
1100
400
250
44
Low temperature characteristics (tanδ)

-3
-5
-6
-2
-3
-3
-2
5
One
3
-7

inside
Haze (%)
100 탆

1.0
0.6
0.4
1.1
0.8
0.9
1.0
2.5
1.0
0.6
0.2
300㎛

1.8
1.0
0.6
2.0
1.2
1.2
1.3
8.0
5.5
5.5
0.4
Change over time

◎
◎
○
◎
◎
◎
◎
◎
×
×
○

The makeup sheet (film or sheet) of the present invention has excellent balance of stretch whitening resistance and rigidity, and good impact resistance characteristics, improved peeling whitening due to mutual adhesion during storage unique to soft materials, and transparency thickness dependence. It has characteristics such as smallness, and furthermore, since no chlorine gas or the like is generated during incineration, there is no problem of disposal, and thus the commodity value is very high.

Therefore, since the makeup sheet (film or sheet) of the present invention has the above excellent characteristics, it can be suitably used for, for example, a member for furniture, a cabinet such as a refrigerator or a television, a building interior material, and the like.

Claims (2)

The resin material for makeup sheets which consists of following (A). (A) Resin composition containing the propylene-ethylene copolymer (a) which satisfy | fills the following requirements, (1) The triad chain fraction (f _EEE ) of [EEE] is 0.1 mol% or less, (2) The product of the reactivity ratio of ethylene and propylene (Re · Rp) is 0.5 or more, (3) the molecular weight distribution (Mw / Mn) is 3.5 or less, (4) fusion enthalpy (ΔH) of 60 to 90 J / g, (5) melting point (Tm) is 145 ℃ or more, (6) Ethylene content is 10 mol% or less. The cosmetic sheet in which any one of a surface layer or a coloring sheet consists of the resin material for cosmetic sheets of Claim 1, and is laminated | stacked a printed pattern layer.