WO2017150265A1 - 4-メチル-1-ペンテン系重合体、樹脂組成物および成形体 - Google Patents
4-メチル-1-ペンテン系重合体、樹脂組成物および成形体 Download PDFInfo
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- WO2017150265A1 WO2017150265A1 PCT/JP2017/006278 JP2017006278W WO2017150265A1 WO 2017150265 A1 WO2017150265 A1 WO 2017150265A1 JP 2017006278 W JP2017006278 W JP 2017006278W WO 2017150265 A1 WO2017150265 A1 WO 2017150265A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/18—Polymers of hydrocarbons having four or more carbon atoms, e.g. polymers of butylene, e.g. PB, i.e. polybutylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
Definitions
- the present invention relates to a 4-methyl-1-pentene polymer having specific physical properties, a resin composition containing the polymer, and a molded article.
- 4-Methyl-1-pentene / ⁇ -olefin copolymer with 4-methyl-1-pentene as the main constituent monomer is excellent in heat resistance, releasability and chemical resistance, so it is widely used in various applications.
- a film made of the copolymer is used for an FPC release film, a composite material molding or a release film, taking advantage of good release properties and the like, or chemical resistance, water resistance and transparency. Taking advantage of these features, it is used in laboratory instruments and rubber hoses manufacturing mandrels.
- a molded article made of a resin composition containing a conventional 4-methyl-1-pentene polymer needs to be improved from the viewpoint of shape retention when a load is applied at a high temperature, that is, from the viewpoint of heat resistance.
- a load is applied at a high temperature
- the viewpoint of heat resistance There are cases (see, for example, Patent Document 1).
- the molded product has a certain amount of low molecular weight components derived from the polymer, improvement is required from the viewpoint of contamination resistance, and it is used for applications requiring high purity. There are cases where this is not possible (see, for example, Patent Document 2).
- Patent Document 3 discloses a 4-methyl-1-pentene polymer having a high stereoregularity and a high heat of fusion
- Patent Document 4 discloses a shape at high temperature utilizing the characteristics of the polymer. A molded body with improved retention and contamination resistance is disclosed.
- the 4-methyl-1-pentene polymers and molded articles described in Patent Documents 3 and 4 have high stereoregularity and high heat of fusion, and have excellent heat resistance. According to the study by the present inventors, it has been found that white turbidity may occur when the molded body is sterilized using steam, that is, steam sterilized. In applications where steam sterilization is required and transparency and appearance are important, the occurrence of white turbidity is a problem.
- the film obtained from the 4-methyl-1-pentene polymer described in Patent Documents 3 and 4 has excellent characteristics in heat resistance and the like, according to the study by the present inventors, the elongation of the film is It has been found that the film may be insufficient, and the film may be easily cut when the film is wound.
- an object of the present invention is to suppress white turbidity at the time of steam sterilization of the obtained molded product without impairing the properties such as high heat resistance of the 4-methyl-1-pentene polymer. It is to improve the elongation of the resulting film without impairing the properties such as high heat resistance of the 4-methyl-1-pentene polymer.
- the present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by a 4-methyl-1-pentene polymer having a specific composition and specific characteristics, and has completed the present invention.
- the present invention relates to the following [1] to [9].
- the content of structural units derived from 4-methyl-1-pentene is 90 to 100 mol%, and is selected from ethylene and ⁇ -olefins other than 4-methyl-1-pentene having 3 to 20 carbon atoms.
- the ratio (Mz / Mw) of the Z average molecular weight Mz to the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is in the range of 2.5-20.
- C The ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn measured by gel permeation chromatography (GPC) is in the range of 3.6-30.
- D The melt flow rate (MFR) measured under conditions of 260 ° C. and 5 kg load in accordance with ASTM D1238 is in the range of 0.1 to 500 g / 10 min.
- E 23 degreeC decane soluble part amount is 5.0 mass% or less.
- [5] A molded article comprising the 4-methyl-1-pentene polymer according to any one of [1] to [3] or the resin composition according to [4].
- [6] The molded product according to [5], wherein the maximum thickness is 100 mm or less and the minimum thickness is 0.001 mm or more.
- a 4-methyl-1-pentene polymer can be obtained which has a high stereoregularity and a high heat of fusion, and can provide a molded product that can suppress the occurrence of cloudiness even when subjected to steam sterilization.
- a resin composition can be provided. Furthermore, by using the 4-methyl-1-pentene polymer and the resin composition of the present invention, it is possible to provide a molded article such as a film having heat resistance, rigidity and excellent elongation.
- FIG. 1 is a graph showing the relationship between the heat of fusion and the melting point in Examples and Comparative Examples.
- the 4-methyl-1-pentene polymer (X) of the present invention has a content of constituent units derived from 4-methyl-1-pentene of 90 to 100 mol% with respect to all constituent units contained in the polymer (X). And the content of structural units derived from at least one olefin (hereinafter also referred to as comonomer) selected from ethylene and ⁇ -olefins other than 4-methyl-1-pentene having 3 to 20 carbon atoms is 0 to 10 Mol%, which satisfies the following requirements (a) to (e), and preferably further satisfies one or more of the following requirements (f) and (g).
- comonomer olefin
- the 4-methyl-1-pentene polymer (X) is a blend of a plurality of 4-methyl-1-pentene polymers
- the blend must satisfy the requirements (a) to It means that (e) is satisfied, preferably one or more of the requirements (f) and (g) are satisfied.
- the 4-methyl-1-pentene polymer (X) is, for example, a homopolymer of 4-methyl-1-pentene (that is, the content of the constituent unit derived from 4-methyl-1-pentene is 100 mol%). Some polymers) and copolymers of 4-methyl-1-pentene with other olefins.
- the 4-methyl-1-pentene polymer (X) a configuration derived from 4-methyl-1-pentene for all the structural units contained in the polymer (X).
- the unit content is preferably 92 to 100 mol%, more preferably 95 to 100 mol%, and is selected from ethylene and ⁇ -olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).
- the total content of structural units derived from at least one olefin is preferably 0 to 8 mol%, more preferably 0 to 5 mol%.
- 4-methyl-1-pentene polymer (X) is a copolymer
- specific examples of ethylene and ⁇ -olefin having 3 to 20 carbon atoms copolymerized with 4-methyl-1-pentene include: Ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples include 1-hexadecene, 1-octadecene, and 1-eicocene.
- ⁇ -olefins ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.
- ⁇ -olefins may be used alone or in combination of two or more.
- a structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (X), and ethylene and an ⁇ -olefin having 3 to 20 carbon atoms (4-methyl-
- the amount of the structural unit derived from at least one olefin selected from (excluding 1-pentene) is 4-methyl-1-pentene added during the polymerization reaction, and ethylene and ⁇ -carbon having 3 to 20 carbon atoms. It can be adjusted by the amount of at least one olefin selected from olefins (excluding 4-methyl-1-pentene).
- the mesodyad fraction (m) measured by 13 C-NMR is in the range of 98 to 100%, preferably in the range of 98.5 to 100%.
- a molded product containing the 4-methyl-1-pentene polymer (X) is sufficient. It will be equipped with performance such as heat resistance and rigidity.
- the mesodyad fraction (m) of the 4-methyl-1-pentene polymer (X) can be adjusted according to the type of olefin polymerization catalyst described later.
- the ratio (Mz / Mw) of the Z-average molecular weight Mz to the weight-average molecular weight Mw measured by gel permeation chromatography (GPC) is in the range of 2.5 to 20, preferably 2.5 to 15, more preferably Is in the range of 2.7-15, more preferably 2.8-15.
- the ratio (Mz / Mw) When the ratio (Mz / Mw) is in the above range, a molded article such as a film containing 4-methyl-1-pentene polymer (X) has excellent toughness, and internal cracks that cause whitening are generated. Decrease, and the elongation of the film is excellent. Further, the ratio (Mz / Mw) being in the above range suggests that a considerable amount of a polymer having a large molecular weight is contained in the 4-methyl-1-pentene polymer (X). The method for adjusting the ratio (Mz / Mw) to the above range will be described later in detail.
- the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn measured by gel permeation chromatography (GPC) is in the range of 3.6 to 30, preferably 3.6 to 25, more preferably. Is in the range of 3.8 to 25, more preferably 4.0 to 25, and particularly preferably 4.0 to 15.
- a molded article such as a film containing 4-methyl-1-pentene polymer (X) has excellent toughness, and internal cracks that cause whitening occur. Decrease, and the elongation of the film is excellent.
- the ratio (Mw / Mn) being in the above range suggests that there is a considerable amount of a polymer having a large molecular weight in the 4-methyl-1-pentene polymer (X).
- the method for adjusting the ratio (Mw / Mn) of the 4-methyl-1-pentene polymer (X) to the above range will be described in detail later.
- the 4-methyl-1-pentene polymer (X) has a melt flow rate (MFR) of 0.1 to 500 g / 10 min measured under conditions of 260 ° C. and 5 kg load in accordance with ASTM D1238, preferably It is 1 to 300 g / 10 min, more preferably 2 to 100 g / 10 min, still more preferably 5 to 80 g / 10 min.
- MFR melt flow rate
- the MFR of the 4-methyl-1-pentene polymer (X) is in the above range, it is preferable from the viewpoint of resin fluidity during the production of a molded product.
- the method for adjusting the MFR of the 4-methyl-1-pentene polymer (X) includes adjusting the amount of hydrogen in the reactor during the polymerization reaction, or having a plurality of different MFRs during or after the polymerization. There are methods of blending different types of polymers.
- the 4-methyl-1-pentene polymer (X) has a decane soluble part amount at 23 ° C. of 5.0% by mass or less, preferably 3.0% by mass or less, more preferably 1.0% by mass or less. It is.
- the amount of the 23 ° C. decane-soluble part means that, as will be described in detail in Examples below, 4-methyl-1-pentene polymer (X) is added to n-decane and 1 at 145 ° C.
- the small amount of the 23 ° C. decane soluble part of the 4-methyl-1-pentene polymer (X) indicates that the amount of the low molecular weight polymer contained in the polymer (X) is small.
- the amount of the 23 ° C. decane soluble part of the 4-methyl-1-pentene polymer (X) is within the above range, a low molecular weight that becomes a contamination component from a molded product obtained from a resin composition containing the polymer. Since it becomes possible to suppress the outflow of components, it can be suitably used for applications such as films that require high purity.
- the amount of the 23 ° C. decane soluble part of the 4-methyl-1-pentene polymer (X) can be adjusted according to the type of the olefin polymerization catalyst described later.
- the ratio of the polymer having a molecular weight of 1 ⁇ 10 6 or more measured by gel permeation chromatography (GPC) is 15% by mass or more, preferably 16% by mass or more, more preferably 17% by mass or more. is there.
- GPC gel permeation chromatography
- the ratio of the polymer having a molecular weight of 1 ⁇ 10 6 or more being in the above range suggests that there is a considerable amount of a component having a large molecular weight.
- the proportion of the polymer having a molecular weight of 1 ⁇ 10 6 or more in the 4-methyl-1-pentene polymer (X) can be obtained by allowing hydrogen to coexist in the reactor during the polymerization reaction and increasing or decreasing the amount thereof. It is possible to adjust to the above range.
- the heat of fusion ( ⁇ HmJ / g) measured by differential scanning calorimetry (DSC) (temperature increase rate: 10 ° C./min) is preferably 5 to 80 J / g, more preferably 10 ⁇ 60 J / g.
- the melting point (Tm ° C.) measured by differential scanning calorimetry (DSC) is preferably 200 to 250 ° C., more preferably 205 to It is 250 ° C, more preferably 210 to 245 ° C.
- the above requirement (i) indicates that the 4-methyl-1-pentene polymer (X) according to the present invention has a high heat of fusion.
- the 4-methyl-1-pentene polymer (X) according to the present invention has a feature that the heat of fusion with respect to the melting point is large, that is, the crystallinity is high.
- FIG. 1 shows the relationship between the heat of fusion and the melting point in Examples and Comparative Examples of the present invention described later.
- the heat of fusion of the 4-methyl-1-pentene polymer (X) can be adjusted within the specified range by using an olefin polymerization catalyst described later.
- the melting point can be adjusted by adjusting the proportion of the constituent unit of 4-methyl-1-pentene in the requirement (a) at the same time as using the olefin polymerization catalyst.
- microcracks are more likely to occur as the residual strain due to molding such as injection molding is larger, and it is normal that the residual strain becomes larger when the polymer contains more high molecular weight components. is there. Nevertheless, in the 4-methyl-1-pentene polymer of the present invention, it is estimated that the occurrence of microcracks is greatly suppressed, which is an unexpected effect. By including a considerable amount of the high molecular weight component, the number of entanglement points per unit volume is increased, so that toughness is improved and whitening is suppressed.
- the 4-methyl-1-pentene polymer of the present invention has a high degree of crystallinity, there is a concern that the physical properties are lowered when it is formed into a film, and there are many high molecular weight components in the polymer. When it is contained, the orientation becomes higher and the film elongation is usually lowered. Nevertheless, the 4-methyl-1-pentene polymer of the present invention shows a significant improvement in film elongation, contrary to expectations. This is also presumed to be an effect of improving the toughness by increasing the number of entanglement per unit volume by containing a considerable amount of the high molecular weight component.
- the 4-methyl-1-pentene polymer (X) is obtained by polymerizing 4-methyl-1-pentene in the presence of an olefin polymerization catalyst described later, or 4-methyl-1-pentene and ethylene and carbon. It can be obtained by copolymerizing with at least one olefin selected from ⁇ -olefins having 3 to 20 atoms (excluding 4-methyl-1-pentene).
- the catalyst comprising is preferred.
- the bridged metallocene compound (A) is preferably a compound represented by the general formula [A1], and more preferably a compound represented by the general formula [A2].
- M is a Group 4 transition metal such as a titanium atom, a zirconium atom or a hafnium atom, and Q is a halogen atom, a hydrocarbon group or a neutral conjugated or nonconjugated diene having 10 or less carbon atoms.
- An anionic ligand and a neutral ligand capable of coordinating with a lone pair are selected in the same or different combinations
- j is an integer of 1 to 4
- R A and R B are the same or different from each other
- Y is a carbon atom or a silicon atom
- R C and R D may be the same or different from each other
- R 1 is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group
- R 2 to R 10 are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group.
- M is a Group 4 transition metal in the periodic table
- Q is a neutral atom capable of coordinating with a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a lone electron pair.
- the ligands are selected from the same or different combinations, and j is an integer of 1 to 4.
- the bridged metallocene compound represented by the general formula [A3] is particularly preferable from the viewpoint of obtaining a polymer satisfying the above-described requirements, polymerization characteristics, availability.
- R 1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group
- R 2b to R 12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group.
- Each may be the same or different, and each substituent may be bonded to each other to form a ring.
- M is a group 4 transition metal in the periodic table
- n is an integer of 1 to 3
- Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and
- the neutral ligands that can be coordinated by a lone pair are selected from the same or different combinations
- j is an integer of 1 to 4.
- R 1 to R 10 , R 1b to R 12b examples include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a saturated hydrocarbon group. And a group formed by substituting one or two or more hydrogen atoms possessed by a cyclic unsaturated hydrocarbon group.
- the carbon number of the hydrocarbon group is usually 1-20, preferably 1-15, more preferably 1-10.
- linear hydrocarbon group examples include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl.
- straight-chain alkyl groups such as n-decanyl group; straight-chain alkenyl groups such as allyl group.
- Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1
- Examples thereof include branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.
- cyclic saturated hydrocarbon group examples include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and methylcyclohexyl group; and polycyclic groups such as norbornyl group, adamantyl group, and methyladamantyl group. It is done.
- cyclic unsaturated hydrocarbon group examples include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group; a cycloalkenyl group such as a cyclohexenyl group; and 5-bicyclo [2.2. 1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group.
- Examples of the group formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, a triphenylmethyl group, and the like. And a group formed by substituting one or two or more hydrogen atoms of the alkyl group with an aryl group.
- Examples of the silicon-containing group in R 1 to R 10 and R 1b to R 12b include a formula —SiR 3 (wherein trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, etc.) And a plurality of R's are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group.).
- Examples of the halogen-containing hydrocarbon group in R 1 to R 10 and R 1b to R 12b are formed by substituting one or more hydrogen atoms of the hydrocarbon group such as a trifluoromethyl group with a halogen atom. Groups.
- Examples of the halogen atom in R 2 to R 10 and R 2b to R 12b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- substituents R 2 to R 10 and R 2b to R 12b may be bonded to each other to form a ring, and there are two or more ring formations in the molecule. May be.
- examples of the ring (spiro ring or additional ring) formed by bonding two substituents to each other include an alicyclic ring and an aromatic ring.
- Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, and a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring are preferable.
- Such a ring structure may further have a substituent such as an alkyl group on the ring.
- R 1b is preferably a hydrocarbon group from the viewpoint of stereoregularity, more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, and a linear hydrocarbon.
- Group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferable, and a substituent having a free valence (carbon bonded to a cyclopentadienyl ring) being a tertiary carbon is particularly preferable.
- a substituent having a free valence (carbon bonded to a cyclopentadienyl ring) being a tertiary carbon is particularly preferable.
- a substituent having a free valence (carbon bonded to a cyclopentadienyl ring) being a tertiary carbon is particularly preferable.
- R 1b examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group.
- a substituent in which the carbon having a free valence is a tertiary carbon such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group, particularly preferably a tert-butyl group, 1- An adamantyl group;
- the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but R 4b and R 5b are preferably hydrogen atoms from the viewpoint of stereoregularity and molecular weight.
- R 2b , R 3b , R 6b and R 7b are preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, and still more preferably a hydrocarbon group having 1 to 20 carbon atoms.
- R 2b and R 3b may be bonded to each other to form a ring, and R 6b and R 7b may be bonded to each other to form a ring.
- Examples of such a substituted fluorenyl group include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2.
- R 8b is preferably a hydrogen atom.
- R 9b is more preferably a hydrocarbon group, and R 9b is more preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group, or a cycloalkenyl group, R 9b is particularly preferably an alkyl group having 2 or more carbon atoms. From the viewpoint of synthesis, R 10b and R 11b are also preferably hydrogen atoms.
- R 9b and R 10b are more preferably bonded to each other to form a ring, and the ring is particularly preferably a 6-membered ring such as a cyclohexane ring.
- R 11b is preferably a hydrogen atom.
- R 12b is preferably a hydrocarbon group, and particularly preferably an alkyl group.
- ⁇ About M, Q, n, and j> M is a Group 4 transition metal of the periodic table, for example, Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.
- Q represents a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair.
- halogen atom for Q include fluorine, chlorine, bromine and iodine.
- the hydrocarbon group in Q is preferably an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms.
- alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, , 1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1, Examples include a 1,3-trimethylbutyl group and a neopentyl group; examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexylmethyl group, a cyclohexyl group, and a 1-methyl-1-cyclohexyl group. More
- Neutral conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis- or s-trans- ⁇ 4 -1,3-butadiene, s-cis- or s-trans- ⁇ 4 -1,4- Diphenyl-1,3-butadiene, s-cis- or s-trans- ⁇ 4 -3-methyl-1,3-pentadiene, s-cis- or s-trans- ⁇ 4 -1,4-dibenzyl-1, 3-butadiene, s-cis- or s-trans- ⁇ 4 -2,4-hexadiene, s-cis- or s-trans- ⁇ 4 -1,3-pentadiene, s-cis- or s-trans- ⁇ 4 -1,4-ditolyl-1,3-butadiene, s- cis - or s-trans eta 4 -1,4-bis (trimethylsilyl) -1
- anion ligand examples include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.
- Neutral ligands that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Examples are ethers such as ethane.
- Q is preferably a halogen atom or an alkyl group having 1 to 5 carbon atoms.
- N is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
- n is the above value, it is preferable from the viewpoint of efficiently obtaining a polymer to be produced.
- J is an integer of 1 to 4, preferably 2.
- bridged metallocene compound represented by the general formula [A2] or [A3], that is, R 1 to R 10 , R 1b to R 12b , M, n, Q, and j have been described above.
- any combination of the preferred embodiments is also a preferred embodiment.
- Such a bridged metallocene compound can be suitably used to obtain the polymer of the present invention having the above physical properties.
- Examples of the bridged metallocene compound represented by the general formula [A3] include (8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5, 6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride or (8- (2,3,6,7-tetramethylfluorene) -12'-yl- (2- (adamantane-1 -Yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride is particularly preferred.
- octamethylfluorene is 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b , h] Fluorene.
- the catalyst for olefin polymerization is (B-1) Organometallic compound (B-2) Organoaluminum oxy compound (B-3) At least one compound selected from compounds that react with (A) to form an ion pair (hereinafter referred to as “compound (B)” Also called.) It is preferable to contain.
- the compound (B), the carrier (C), and the organic compound component (D) described later are as disclosed in Patent Documents 3 and 4 or International Publication No. 2014-123212.
- the carrier (C) examples disclosed in International Publication No. 2010-055652, International Publication No. 2011-142400, International Publication No. 2013-146337, and Japanese Patent Application Laid-Open No. 2015-74645 can be applied.
- the olefin polymerization catalyst further contains a carrier (C).
- Examples of the carrier (C) include inorganic or organic compounds, and granular or fine particle solids.
- the transition metal compound (A) is preferably used in a form supported on the carrier (C).
- the olefin polymerization catalyst of the present invention may further contain (D) an organic compound component, if necessary.
- the organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary.
- Examples of the organic compound (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.
- the ratio (Mz / Mw) and ratio (Mw / Mn) of 4-methyl-1-pentene polymer (X) are determined by a multistage polymerization method such as single-stage or two-stage polymerization. Adjustment is possible by blending during or after polymerization.
- the ratio (Mz / Mw) and (Mz / Mw) were determined by dividing hydrogen into “initial stage of polymerization” and “in the middle of polymer production” while being single-stage polymerization.
- Mw / Mn) is adjusted to an arbitrary value, and adjustment is also possible by such a method. More specifically, a high molecular weight polymer is polymerized by reducing the amount of hydrogen introduced at the initial stage of polymerization, and a relatively low molecular weight polymer is polymerized by feeding a larger amount of hydrogen at a stage where the polymerization has progressed to some extent.
- the ratio (Mz / Mw) and (Mw / Mn) of the finally obtained polymer can be adjusted.
- the resin composition containing the 4-methyl-1-pentene polymer (X) in the present invention comprises the 4-methyl-1-pentene polymer (X) as an essential component, and other moldings according to the present invention. Various components are included depending on the purpose of the body.
- the resin composition containing the 4-methyl-1-pentene polymer (X) can optionally contain other resins, polymers, additives for resins, and the like within a range that does not impair the effects of the present invention. Can be contained.
- thermoplastic resins (E) can be widely used as other resins or polymers to be added.
- the amount of the resin or polymer added is preferably 0.1 to 30% by mass with respect to the total mass of the resin composition.
- thermoplastic resin (E) is not particularly limited as long as it is different from the 4-methyl-1-pentene polymer (X) according to the present invention, and examples thereof include the following resins.
- Thermoplastic polyolefin resins such as low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3 -Methyl-1-pentene, poly-3-methyl-1-butene, ethylene / ⁇ -olefin copolymer, propylene / ⁇ -olefin copolymer, 1-butene / ⁇ -olefin copolymer, 4-methyl-1 A pentene / ⁇ -olefin copolymer, a cyclic olefin copolymer, a chlorinated polyolefin, and a modified polyolefin resin obtained by modifying these olefin resins;
- Thermoplastic polyamide resin for example, aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612),
- Polypropylene includes isotactic polypropylene and syndiotactic polypropylene.
- the isotactic polypropylene may be a homopolypropylene, a propylene / ⁇ -olefin having 2 to 20 carbon atoms (however, excluding propylene) or a propylene block copolymer.
- the poly-4-methyl-1-pentene and the 4-methyl-1-pentene / ⁇ -olefin copolymer are polymers different from the 4-methyl-1-pentene polymer (X). It is a homopolymer of 1-pentene or a 4-methyl-1-pentene / ⁇ -olefin random copolymer. In the case of a 4-methyl-1-pentene / ⁇ -olefin random copolymer, ethylene, propylene, 1-butene, 1-hexene, 1-octene can be used as the ⁇ -olefin copolymerized with 4-methyl-1-pentene.
- melt flow rate (MFR; ASTM D1238, 260 ° C, 5.0 kg load) is preferably 0.1 to 200 g / 10 min, and more preferably 1 to 150 g / 10 min.
- a commercially available product can be used as poly-4-methyl-1-pentene, and examples thereof include TPX (trade name) manufactured by Mitsui Chemicals. Poly 4-methyl-1-pentene from other manufacturers can be preferably used as long as the above requirements are satisfied.
- low-density polyethylene low-density polyethylene, medium-density polyethylene, high-density polyethylene, and high-pressure method low-density polyethylene, which are produced by a conventionally known method, can be used.
- polybutene examples include a homopolymer of 1-butene, or a copolymer of 1-butene and an olefin excluding 1-butene.
- olefin copolymerized with polybutene examples include the ⁇ -olefins mentioned as the ⁇ -olefin copolymerized with 4-methyl-1-pentene. These olefins may be used alone or in admixture of two or more. It is done.
- the copolymer examples include 1-butene / ethylene random copolymer, 1-butene / propylene random copolymer, 1-butene / methylpentene copolymer, 1-butene / methylbutene copolymer, 1-butene / Examples include propylene / ethylene copolymers.
- the content of the structural unit derived from 1-butene is preferably 50 mol% or more, more preferably 70 mol% or more, and 85% or more. It is particularly preferred.
- the modified polyolefin resin can be obtained by graft-modifying the above-described polyolefin resin with an ethylenically unsaturated bond-containing monomer using an organic peroxide.
- functional groups possessed by the modified polyolefin include halogen atoms, carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, amino groups, amide groups, imide groups, ester groups, alkoxysilane groups, acid halide groups, and nitrile groups. Is mentioned.
- rosin-based resins include natural rosin, polymerized rosin, modified rosin and rosin derivatives modified with maleic acid, fumaric acid, (meth) acrylic acid, and the like.
- examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof.
- hydrogenated substances can also be mentioned.
- terpene resins include resins comprising ⁇ -pinene, ⁇ -pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, etc., and ⁇ -pinene, ⁇ -pinene, limonene, dipentene and the like such as styrene.
- An aromatic modified terpene resin obtained by polymerizing an aromatic monomer may also be used.
- these hydrogenated substances can also be mentioned.
- Examples of the petroleum resin include an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and a copolymer petroleum resin thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) A co-polymer of styrene and indene, coumarone and other dicyclopentadiene, p-tertiarybutylphenol, and the like. Examples thereof include alkylphenol resins represented by condensates of acetylene, xylene resins obtained by reacting o-xylene, p-xylene or m-xylene with formalin.
- one or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins are preferably hydrogenated derivatives because they are excellent in weather resistance and discoloration resistance.
- the softening point of the resin by the ring and ball method is preferably in the range of 40 to 180 ° C.
- the number average molecular weight (Mn) molecular weight measured by GPC of the resin is preferably in the range of about 100 to 10,000. Commercially available products can be used for the rosin resin, terpene resin and petroleum resin.
- thermoplastic resins (E) preferred are low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4- Methyl-1-pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene / ⁇ -olefin copolymer, propylene / ⁇ -olefin copolymer, 1-butene / ⁇ -olefin copolymer Polymers, styrene elastomers, vinyl acetate copolymers, ethylene / methacrylic acid acrylate copolymers, ionomers, fluorine resins, rosin resins, terpene resins and petroleum resins, more preferred are improved heat resistance, In terms of improved low-temperature resistance and flexibility, polyethylene, isotactic polypropylene, thin Otectic polypropylene, poly 1-buten
- thermoplastic resin (E) preferably includes poly-3-methyl-1-pentene, poly-3-methyl-1-butene, and the like. These are the 4-methyl-1-pentene polymers (X ) Contributes to improving the rigidity of the resulting film and the like.
- thermoplastic resin (E) one of the above thermoplastic resins can be used alone, or two or more of them can be used in combination.
- additives for resins include nucleating agents, anti-blocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, Antistatic agent, weathering stabilizer, heat resistance stabilizer, anti-slip agent, foaming agent, crystallization aid, antifogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent, Examples include a co-crosslinking agent, a crosslinking aid, a pressure-sensitive adhesive, a softening agent, and a processing aid. These additives can be used singly or in appropriate combination of two or more.
- a known nucleating agent may be used to further improve the moldability of the 4-methyl-1-pentene polymer (X), that is, to increase the crystallization temperature and increase the crystallization speed.
- X 4-methyl-1-pentene polymer
- the amount of the nucleating agent is not particularly limited, but is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the 4-methyl-1-pentene polymer (X).
- the nucleating agent can be appropriately added during polymerization, after polymerization, or at the time of molding processing.
- antiblocking agent known antiblocking agents can be used. Specifically, fine powder silica, fine powder aluminum oxide, fine powder clay, powdered or liquid silicon resin, tetrafluoroethylene resin, fine powder cross-linked resin, for example, cross-linked acrylic, methacrylic resin powder, etc. it can. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.
- pigment examples include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake, thioindigo, phthalocyanine, anthraquinone).
- organic pigments examples include azo series, anthraquinone series, and triphenylmethane series.
- the addition amount of these pigments and dyes is not particularly limited, but is generally 5% by mass or less, preferably 0.1 to 3% in total with respect to the total mass of the 4-methyl-1-pentene polymer resin composition. % By mass.
- Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide ( Iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate, etc.) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes and the like. These fillers may be used alone or in combination of two or more.
- lubricant examples include wax (carnauba wax etc.), higher fatty acid (eg stearic acid), higher alcohol (stearyl alcohol etc.), higher fatty acid amide (eg stearic acid amide) and the like.
- Plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methyl acetyl ricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatic tricarboxylic acids.
- aromatic carboxylic acid esters such as dibutyl phthalate
- aliphatic carboxylic acid esters such as methyl acetyl ricinoleate
- aliphatic dialcolic acid esters such as adipic acid-propylene glycol polyester
- aliphatic tricarboxylic acids include esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.
- Release agents include higher fatty acid lower (C1-4) alcohol esters (butyl stearate, etc.), fatty acid (C4-30) polyhydric alcohol esters (hardened castor oil, etc.), fatty acid glycol esters, liquid paraffin, etc. Is mentioned.
- antioxidants known antioxidants can be used. Specifically, phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol, etc.), phosphorus System (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate etc.), sulfur system (dilauryl thiodipropionate etc.), amine system (N, N-diisopropyl-p-) Phenylenediamine, etc.), lactone-based antioxidants, and the like.
- phenolic 2,6-di-t-butyl-4-methylphenol, etc.
- phosphorus System tetrakis (2,4-di-t-butylphenyl) -4,4-b
- flame retardants examples include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). Can be mentioned.
- UV absorber examples include benzotriazole, benzophenone, salicylic acid, and acrylate.
- Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.
- Nonionic surfactants include nonionic, anionic, cationic or amphoteric surfactants.
- Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyethylene oxide and glycerin.
- Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc.
- sulfate salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, Include a phosphoric acid ester salts such as grade alcohol phosphate ester salt, the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts.
- amphoteric surfactants include amino acid-type double-sided surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.
- antistatic agent examples include the above-mentioned surfactants, fatty acid esters, and polymer type antistatic agents.
- fatty acid esters examples include esters of stearic acid and oleic acid
- polymer antistatic agents include polyether ester amides.
- additives such as the above fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and the like impairs the purpose of the present invention.
- it is 0.1 to 30% by mass with respect to the total mass of the resin composition containing the 4-methyl-1-pentene polymer (X), respectively. It is preferable.
- the method for producing a resin composition containing 4-methyl-1-pentene polymer (X) according to the present invention is not particularly limited.
- 4-methyl-1-pentene polymer (X) and other components are mixed at the above-described addition ratio and then melt-kneaded.
- the method of melt kneading is not particularly limited, and can be performed using a melt kneading apparatus such as a commercially available extruder.
- the cylinder temperature of the kneading part in the kneader is usually 220 to 320 ° C., preferably 250 to 300 ° C.
- the cylinder temperature is lower than 220 ° C.
- kneading becomes insufficient due to insufficient melting, and it is difficult to improve the physical properties of the resin composition.
- the temperature is higher than 320 ° C.
- the 4-methyl-1-pentene polymer (X) may be thermally decomposed.
- the kneading time is usually 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes.
- the 4-methyl-1-pentene polymer (X) may be thermally decomposed. .
- a molded body is obtained by molding the resin composition.
- Molding method As the molding method of the resin composition, various known molding methods can be applied. For example, injection molding, extrusion molding, injection stretch blow molding method, blow molding method, cast iron molding method, calendar one molding. Various molding methods such as a method, press molding, stamping molding, inflation molding and roll molding can be mentioned. By these molding methods, it can be processed into a desired molded body, for example, a film, a sheet, a hollow molded body, an injection molded body, a fiber and the like. The molding conditions are the same as those for a conventionally known 4-methyl-1-pentene polymer.
- Shape There are no particular restrictions on the shape of the molded body. Examples of the shape include a tube shape, a film shape, a sheet shape, a membrane (membrane) shape, a tape shape, a plate shape, a rod shape, a fiber shape, and a nonwoven fabric shape.
- the thickness of the minimum thickness portion of the molded body is preferably 0.001 mm or more, more preferably 0.01 mm or more, still more preferably 0.05 mm or more, and the maximum thickness of the molded body.
- the thickness of the thick part is preferably 100 mm or less, more preferably 50 mm or less, still more preferably 6 mm or less, and still more preferably 3 mm or less.
- the thickness means the distance between the plates when sandwiched between parallel plates if the compact is a lump, and the thickness if it is a tube, film, sheet, film, tape, or plate. If it is rod-like or fiber-like, it means its thickness.
- the maximum value is the thickness of the maximum thickness portion
- the minimum value is the thickness of the minimum thickness portion.
- the term “film” is a general term for a planar molded body, and is a concept including a sheet, a tape, and the like.
- the molded product of the present invention can be used without any restrictions in applications where conventional 4-methyl-1-pentene polymers can be used, but for applications requiring heat resistance and low contamination. Is suitable.
- it can be used as a molded object obtained through the use including the sterilization process by water vapor
- the elongation of the film is required as a characteristic during film formation, but there is no restriction on the use of the film.
- film applications include foods, meat, processed fish, vegetables, fruits, fermented foods, retort foods, confectionery, pharmaceuticals, bulbs, seeds, mushrooms and other packaging materials, wrap films, cell culture bags, and cell inspection films. , Heat-resistant vacuum forming containers, sugar beet containers, beet lids, baking cartons, various release films, and the like.
- containers examples include food containers such as tableware, tempering containers, kitchenware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, frozen dessert cups, cups, baby bottles, beverage bottles, Bottle containers, etc., transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, chemical containers, detergent containers, softener containers, bleaching agent containers, Shampoo container, rinse container, cosmetic container, perfume container, bottle container, powder container, adhesive container, gasoline tank container, kerosene container, food container, heat-resistant container, medical container, animal cage, physics and chemistry experiment Such as appliances.
- food containers such as tableware, tempering containers, kitchenware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, frozen dessert cups, cups, baby bottles, beverage bottles, Bottle containers, etc., transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags
- packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorbent packaging materials, retort food packaging materials, and freshness.
- Retaining film pharmaceutical packaging material, cell culture bag, cell inspection film, bulb, packaging material, seed packaging material, film for vegetable / mushroom cultivation, heat-resistant vacuum forming container, side dish container, side dish cover, commercial wrap film, household Wrap film, baking cartons and the like.
- films other than those described above include, for example, release films for flexible printed boards, release films for ACM boards, release films for rigid boards, release films for rigid flexible boards, release films for advanced composite materials, carbon fiber composites Release film for curing material, Release film for curing glass fiber composite, Release film for curing aramid fiber composite, Release film for curing nanocomposite, Release film for curing filler filler, Release for semiconductor sealing Mold film, release film for polarizing plate, release film for diffusion sheet, release film for prism sheet, release film for reflection sheet, cushion film for release film, release film for fuel cell, release for various rubber sheets Mold film, release film for urethane curing, release film for epoxy curing, solar Cell sealing sheet, solar cell back sheet, plastic film for solar cell, battery separator, separator for lithium ion battery, electrolyte membrane for fuel cell, adhesive / adhesive separator, light guide plate, optical disc, dicing tape / back grind tape ⁇ Process substrate for semiconductors such as die-bonding film, double-layer FCCL, film for film capacitor ,
- Other applications include, for example, mandrels for rubber hose manufacture, sheaths, sheaths for rubber hose manufacture, hoses, tubes, release paper for synthetic leather, medical tubes, industrial tubes, cooling water piping, hot water piping, wire coating materials, millimeters Wave signal cable covering material, high-frequency signal cable covering material, eco wire covering material, automotive cable covering material, signal cable covering material, insulator for high voltage wire, wiring duct, cosmetic / perfume spray tube, medical tube, infusion tube, Pipes, wire harnesses, interior / exterior materials for automobiles / motorcycles / railway vehicles / aircrafts / ships, etc., wear resistant automotive interior / exterior materials, instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seats Back garnish, console box, armrest, airbag case Switch, shift knob, assist grip, side step mat, meter cover, battery cap, fuse, automatic flush sensor parts, ignition, coil bobbin, bushing, bumper, car heater fan, radiator grill, wheel cap
- coating materials films obtained by coating, sheets, release materials, water imaging materials, insulating films, adhesives, adhesive materials, coated paper, transparent sealants, sealants, hot melt adhesives, solvent adhesives It is also suitably used for adhesives, film-like adhesives, cloth tapes, craft tapes, elastic adhesives and the like.
- the 4-methyl-1-pentene polymer (X) can also be processed into a fine powder by pulverization.
- the fine powder obtained is used as an additive for ink compositions and coating compositions, as an additive for powder compositions for metallurgy, as an additive for powder compositions for sintering ceramics, as an additive for adhesives, and as a rubber As an additive, it can be used as a mold release agent or the like as a toner release agent.
- the obtained fine powder is used as a resin additive for shafts, gears, cams, electrical parts, camera parts, automobile parts, parts for household goods, wax, grease, engine oil, fine ceramics, plating, etc. It can also be used as a resin additive.
- the organic layer was separated, and the aqueous layer was extracted with 200 ml of hexane, and the organic liquid obtained by combining the extracted hexane with the previous organic layer was washed with water.
- the organic liquid was dried over magnesium sulfate, and then the solvent was distilled off.
- the obtained solid was purified using a silica gel column chromatograph to obtain 4.2 g of a crude product.
- the target product was identified from the measurement result of 1 H-NMR.
- the measurement results are as follows.
- the target product was identified from the measurement results of 1 H-NMR and GC-MS.
- the measurement results are as follows.
- the obtained solid was washed with acetone, so that the target product, 8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,5, 6,7,7a, 8-octahydrocyclopenta [a] indene).
- the yield was 1.51 g and the yield was 54%.
- the target product was identified from the FD-MS measurement results.
- the measurement results are as follows.
- the precipitated powder was collected by filtration, washed with hexane, and the target product (8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4, 5,6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride was obtained.
- the yield was 0.220 g and the yield was 17%.
- the target product was identified from the measurement result of 1 H-NMR.
- the measurement results are as follows.
- Example 1 Purified decane 425 mL, diisobutylaluminum hydride decane solution (2.0 mmol / mL in terms of aluminum atoms) 0.5 mL (1 mol) in a SUS polymerizer equipped with a stirrer with an internal volume of 1 L at room temperature under a nitrogen stream I was charged. Next, 0.0005 mmol of the previously prepared decane slurry solution (C) of the prepolymerized catalyst component was added in terms of zirconium atom, and hydrogen was charged at 50 NmL (first hydrogen charging).
- Example 2 Polymer [A-2]
- Polymerization [A-2] was carried out in the same manner as in Example 1 except that the amount of 1-decene charged was 1.3 ml. The yield was 125g.
- Table 1 shows the results of measurement of 13 C-NMR, GPC, MFR and decane soluble part of the polymer [A-2].
- ⁇ Pellet preparation> Polymerization was carried out a plurality of times as necessary to prepare a sufficient amount of polymer for pellet production. For 100 parts by mass of each polymer, 0.1 part by mass of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- (4 0.1 parts by mass of '-hydroxy-3', 5'-di-t-butylphenyl) propinate was blended.
- a press sheet was prepared by hot pressing the evaluation pellets with a hot press.
- a spacer and an evaluation pellet were sandwiched between two brass plates and pressed to prepare a press sheet.
- a press sheet having a desired thickness was obtained by appropriately changing the thickness of the spacer.
- the hot pressing was performed by holding at 270 ° C. until the resin was completely melted, pressing for 3 minutes under the condition of 100 KG / cm 2 , and immediately thereafter pressing for 3 minutes under the conditions of 20 ° C. and 100 KG / cm 2 .
- the obtained press sheet was subjected to Vicat softening temperature (using a 3 mm thick press sheet) and steam resistance evaluation (using 3 mm and 10 mm thick press sheets) by the methods described below. The results are shown in Table 1.
- a coat hanger type T die (lip shape 270 ⁇ 0.8 mm) is mounted on a single screw extruder (screw diameter 20 mm ⁇ , L / D 28) manufactured by Thermo Plastic Co., Ltd., and the die temperature is set. Molding was performed at a roll temperature of 70 ° C. and a winding speed of 2.0 m / min under the condition of 270 ° C. to obtain a film having a thickness of 50 ⁇ m.
- the resulting film was evaluated for steam resistance, high temperature elastic modulus and tensile elongation by the methods described below. The results are shown in Table 1.
- FIG. 1 shows the relationship between the heat of fusion and the melting point in Examples and Comparative Examples. 1 is a range satisfying “ ⁇ Hm ⁇ 0.5 ⁇ Tm ⁇ 76” above the solid line and above the solid line, and a range not satisfying “ ⁇ Hm ⁇ 0.5 ⁇ Tm ⁇ 76” below the solid line. .
- the solvent is an o-dichlorobenzene / benzene-d 6 (4/1 v / v) mixed solvent
- the sample concentration is 55 mg / 0.6 mL
- the observation nucleus is 13 C (125 MHz)
- the sequence is single pulse proton broadband decoupling
- the pulse width is 5.0 ⁇ sec (45 ° pulse)
- the repetition time is 5.5 seconds
- the number of integrations is 64 times. 128 ppm of benzene-d 6 was measured as a reference value for chemical shift.
- the integral value of the main chain methine signal the content of the comonomer-derived structural unit was calculated according to the following formula.
- the meso-dyad isotacticity (meso-dyad fraction) of 4-methyl-1-pentene polymer represents any two head-to-tail linked 4-methyl-1-pentene unit chains in the polymer chain in a planar zigzag structure
- the isobutyl branching direction was defined as the same ratio and determined from the 13 C-NMR spectrum by the following formula.
- Isodiad tacticity (%) [m / (m + r)] ⁇ 100 (In the formula, m and r represent the absorption intensity derived from the main chain methylene of 4-methyl-1-pentene units bonded head-to-tail represented by the following formula.)
- the 13 C-NMR spectrum was measured using an AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by VALQUA Biospin, the solvent was an o-dichlorobenzene / benzene-d6 (4/1 v / v) mixed solvent, and the sample concentration was 60 mg / 0.6 mL, measurement temperature is 120 ° C., observation nucleus is 13 C (125 MHz), sequence is single pulse proton broadband decoupling, pulse width is 5.0 ⁇ sec (45 ° pulse), repetition time is 5.5 seconds, 128 ppm of benzene-d6 was measured as a reference value for chemical shift.
- the peak region was divided into 41.5 to 43.3 ppm regions by the minimum points of the peak profile, and the high magnetic field side was classified as the first region and the low magnetic field side was classified as the second region.
- the main chain methylene in the 2-chain 4-methyl-1-pentene unit represented by (m) resonates, but the integrated value regarded as a 4-methyl-1-pentene homopolymer is “m”. It was.
- the main chain methylene in the two 4-methyl-1-pentene units represented by (r) resonated, and the integrated value was designated as “r”. In addition, less than 0.01% was made into the detection limit or less.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and Z average molecular weight (Mz) were measured by GPC.
- the weight average molecular weight (Mw), the number average molecular weight (Mn), and the Z average molecular weight (Mz) were determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
- the ratio of the integrated area value of 1,000,000 or more components to the total area of the chart is defined as the component ratio of 1 ⁇ 10 6 or more.
- MFR Melt flow rate
- [Amount of decane soluble part] 200 g of n-decane was added to 5 g of each polymer and dissolved by heating at 145 ° C. for 1 hour. It was cooled to 23 ° C. and left for 30 minutes. Thereafter, the precipitate (n-decane insoluble part) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate was filtered off from acetone and dried. The mass of the precipitate was measured. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following formula.
- n-decane soluble part amount (% by mass) [amount of precipitated substance / polymer mass] ⁇ 100 [Melting point, heat of fusion]
- DSC220C DSC measuring device manufactured by Seiko Instruments Inc.
- the temperature was raised to 280 ° C. at 10 ° C./min. After maintaining at 280 ° C. for 5 minutes, the temperature was lowered to 20 ° C. at 10 ° C./min. After maintaining at 20 ° C. for 5 minutes, the temperature was raised to 280 ° C. at 10 ° C./min.
- the temperature at which the peak of the crystal melting peak observed at the second temperature increase appears was defined as the melting point. Further, the heat of fusion was calculated from the integrated value of the crystal melting peak.
- the tensile elongation which is a tensile property, was measured at a tensile speed of 200 mm / min using an all-purpose tensile tester 3380 manufactured by Instron, using the above-mentioned film as a test piece in accordance with JIS K678.
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Abstract
Description
[1]4-メチル-1-ペンテン由来の構成単位の含有量が90~100モル%であり、エチレンおよび炭素原子数3~20の4-メチル-1-ペンテン以外のα-オレフィンから選ばれる少なくとも1種のオレフィン由来の構成単位の含有量が0~10モル%であり、下記要件(a)~(e)をすべて満たす、4-メチル-1-ペンテン系重合体。
(a)13C-NMRで測定されるメソダイアッド分率(m)が98~100%の範囲にある。
(b)ゲルパーミエーションクロマトグラフィー(GPC)で測定した、Z平均分子量Mzと重量平均分子量Mwとの比(Mz/Mw)が2.5~20の範囲にある。
(c)ゲルパーミエーションクロマトグラフィー(GPC)で測定した、重量平均分子量Mwと数平均分子量Mnとの比(Mw/Mn)が3.6~30の範囲にある。
(d)ASTM D1238に準拠して260℃、5kg荷重の条件で測定したメルトフローレート(MFR)が0.1~500g/10分の範囲にある。
(e)23℃デカン可溶部量が5.0質量%以下である。
(f)ゲルパーミエーションクロマトグラフィー(GPC)で測定した、分子量が1×106以上である重合体の割合が15質量%以上である。
[3]さらに下記要件(g)を満たす[1]または[2]に記載の4-メチル-1-ペンテン系重合体。
(g)示差走査型熱量測定(DSC)で測定される前記4-メチル-1-ペンテン系重合体の融解熱量および融点が以下の要件(i)および(ii)を満たす。
(式(1)において、融解熱量をΔHmJ/gとし、融点をTm℃とする。)
(ii)融点が200~260℃の範囲にある。
[4][1]~[3]のいずれかに記載の4-メチル-1-ペンテン系重合体を含む樹脂組成物。
[6]最大肉厚が100mm以下であり、最小肉厚が0.001mm以上である[5]に記載の成形体。
[8]フィルムである、[5]に記載の成形体。
[9][5]~[8]いずれかに記載の成形体である医療、介護、乳幼児、理化学実験用、食品、生活または薬品向けの器具または容器。
本発明の4-メチル-1-ペンテン系重合体(X)は、重合体(X)に含まれる全構成単位に対する4-メチル-1-ペンテン由来の構成単位の含有量が90~100モル%であり、エチレンおよび炭素原子数3~20の4-メチル-1-ペンテン以外のα-オレフィンから選ばれる少なくとも1種のオレフィン(以下、コモノマーともいう)由来の構成単位の含有量が0~10モル%であり、下記要件(a)~(e)を満たし、好ましくはさらに下記要件(f)および(g)のうち一つ以上を満たす。なお、前記規定は、4-メチル-1-ペンテン系重合体(X)が、複数の4-メチル-1-ペンテン系重合体のブレンド物である場合は、そのブレンド物が要件(a)~(e)を満たし、好ましくはさらに要件(f)および(g)のうち一つ以上を満たすことを意味する。
(要件(a))
13C-NMRで測定されるメソダイアッド分率(m)が98~100%の範囲にあり、好ましくは98.5~100%の範囲にある。
(要件(b))
ゲルパーミエーションクロマトグラフィー(GPC)で測定した、Z平均分子量Mzと重量平均分子量Mwとの比(Mz/Mw)が2.5~20の範囲にあり、好ましくは2.5~15、より好ましくは2.7~15、更に好ましくは2.8~15の範囲にある。比(Mz/Mw)が上記範囲にあることで、4-メチル-1-ペンテン系重合体(X)を含むフィルムなどの成形体は靭性に優れるようになり、白化の原因である内部クラックが減少し、フィルムの伸びが優れる。また、比(Mz/Mw)が上記範囲にあることは、4-メチル-1-ペンテン系重合体(X)中に分子量の大きい重合体が相当量含まれることを示唆している。比(Mz/Mw)を上記範囲に調節する方法は詳しくは後述する。
ゲルパーミエーションクロマトグラフィー(GPC)で測定した、重量平均分子量Mwと数平均分子量Mnとの比(Mw/Mn)が3.6~30の範囲にあり、好ましくは3.6~25、より好ましくは3.8~25、更に好ましくは4.0~25、とりわけ好ましくは4.0~15の範囲にある。比(Mw/Mn)が上記範囲にあることで、4-メチル-1-ペンテン系重合体(X)を含むフィルムなどの成形体は靭性に優れるようになり、白化の原因である内部クラックが減少し、フィルムの伸びが優れる。また、比(Mw/Mn)が上記範囲にあることは、4-メチル-1-ペンテン系重合体(X)中に分子量の大きい重合体が相当量あることを示唆している。4-メチル-1-ペンテン系重合体(X)の比(Mw/Mn)を上記範囲に調節する方法は詳しくは後述する。
4-メチル-1-ペンテン系重合体(X)は、ASTM D1238に準拠して260℃、5kg荷重の条件で測定したメルトフローレート(MFR)が0.1~500g/10minであり、好ましくは1~300g/10min、より好ましくは2~100g/10min、さらに好ましくは5~80g/10minである。
(要件(e))
4-メチル-1-ペンテン系重合体(X)は、23℃デカン可溶部量が5.0質量%以下であり、好ましくは3.0質量%以下、より好ましくは1.0質量%以下である。
(要件(f))
ゲルパーミエーションクロマトグラフィー(GPC)で測定した、分子量が1×106以上である重合体の割合が15質量%以上であり、好ましくは16質量%以上であり、より好ましくは17質量%以上である。上記範囲にあることで、4-メチル-1-ペンテン系重合体(X)を含むフィルムなどの成形体は靭性に優れるようになり、白化の原因である内部クラックが減少し、フィルム伸びが優れる。また、分子量が1×106以上である重合体の割合が上記範囲にあることは分子量の大きい成分が相当量あることを示唆している。4-メチル-1-ペンテン系重合体(X)における分子量が1×106以上である重合体の割合は、重合反応中に反応器内に水素を併存させ、その量を増減させることにより、上記範囲に調節することが可能である。
示差走査型熱量測定(DSC)で測定される4-メチル-1-ペンテン系重合体(X)の融解熱量および融点が以下の要件(i)および(ii)を満たす。
(式(1)において、融解熱量をΔHmJ/gとし、融点をTm℃とする。)
(ii)融点が200~260℃の範囲にある。
<4-メチル-1-ペンテン系重合体(X)の特徴>
本発明の4-メチル-1-ペンテン系重合体は、後述の実施例および比較例の対比から明らかなように、スチーム滅菌を経ても白濁が発生しにくい特性を有する。比較例において、スチーム滅菌によって白濁が生じた理由は明らかではないが、滅菌時に成形体の内部に水分が入り込み、膨張し、滅菌後の冷却にともなう成形体の収縮時に歪みが生じてマイクロクラックが生じているものと推測している。
4-メチル-1-ペンテン系重合体(X)は、後述するオレフィン重合用触媒の存在下、4-メチル-1-ペンテンを重合することで、または4-メチル-1-ペンテンとエチレンおよび炭素原子数3~20のα-オレフィン(4-メチル-1-ペンテンを除く)から選ばれる少なくとも1種のオレフィンとを共重合することで得ることができる。
オレフィン重合用触媒としては、
架橋メタロセン化合物(A)と、
(B-1)有機金属化合物
(B-2)有機アルミニウムオキシ化合物
(B-3)(A)と反応してイオン対を形成する化合物
から選ばれる少なくとも1種以上の化合物(B)と、を含む触媒が好ましい。
架橋メタロセン化合物(A)は、一般式[A1]で表される化合物が好ましく、一般式[A2]で表される化合物がより好ましい。
R1からR10およびR1bからR12bにおける炭化水素基としては、例えば、直鎖状炭化水素基、分岐状炭化水素基、環状飽和炭化水素基、環状不飽和炭化水素基、飽和炭化水素基が有する1または2以上の水素原子を環状不飽和炭化水素基に置換してなる基が挙げられる。炭化水素基の炭素数は、通常1~20、好ましくは1~15、より好ましくは1~10である。
以上存在してもよい。
Mは周期表第4族遷移金属であり、例えばTi、ZrまたはHfであり、好ましくはZrまたはHfであり、特に好ましくはZrである。
Qでのハロゲン原子としては、例えば、フッ素、塩素、臭素、ヨウ素が挙げられる。
オレフィン重合用触媒は、
(B-1)有機金属化合物
(B-2)有機アルミニウムオキシ化合物
(B-3)(A)と反応してイオン対を形成する化合物
から選ばれる少なくとも1種の化合物(以下「化合物(B)」ともいう。)
を含有することが好ましい。
オレフィン重合用触媒は、さらに担体(C)を含有することがより好ましい。
本発明のオレフィン重合用触媒は、さらに必要に応じて、(D)有機化合物成分を含有することもできる。有機化合物成分(D)は、必要に応じて、重合性能および生成ポリマーの物性を向上させる目的で使用される。有機化合物(D)としては、例えば、アルコール類、フェノール性化合物、カルボン酸、リン化合物、アミド、ポリエーテルおよびスルホン酸塩等が挙げられる。
4-メチル-1-ペンテン系重合体(X)の比(Mz/Mw)および比(Mw/Mn)は、単段もしくは二段重合等の多段重合法で、分子量の異なる複数の重合体を重合中もしくは重合後にブレンドすることによって調節が可能である。
本発明における4-メチル-1-ペンテン系重合体(X)を含む樹脂組成物は、前記4-メチル-1-ペンテン系重合体(X)を必須の構成成分とし、その他本発明にかかる成形体の用途に応じて各種成分を含む。
4-メチル-1-ペンテン系重合体(X)を含む樹脂組成物は、その用途に応じて、本発明の効果を阻害しない範囲で他の樹脂や重合体、樹脂用添加剤等を任意に含有することができる。
熱可塑性ポリアミド系樹脂、たとえば、脂肪族ポリアミド(ナイロン6、ナイロン11、ナイロン12、ナイロン66、ナイロン610、ナイロン612)、
熱可塑性ポリエステル系樹脂;たとえば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエステル系エラストマー;
熱可塑性ビニル芳香族系樹脂、たとえば、ポリスチレン、ABS樹脂、AS樹脂、スチレン系エラストマー(スチレン・ブタジエン・スチレンブロックポリマー、スチレン・イソプレン・スチレンブロックポリマー、スチレン・イソブチレン・スチレンブロックポリマー、前述の水素添加物);
熱可塑性ポリウレタン;塩化ビニル樹脂;塩化ビニリデン樹脂;アクリル樹脂;エチレン・酢酸ビニル共重合体;エチレン・メタクリル酸アクリレート共重合体;アイオノマー;エチレン・ビニルアルコール共重合体;ポリビニルアルコール;フッ素系樹脂ポリカーボネート;ポリアセタール;ポリフェニレンオキシド;ポリフェニレンサルファイドポリイミド;ポリアリレート;ポリスルホン;ポリエーテルスルホン;ロジン系樹脂;テルペン系樹脂および石油樹脂;
共重合体ゴム、たとえば、エチレン・α-オレフィン・ジエン共重合体、プロピレン・α-オレフィン・ジエン共重合体、1-ブテン・α-オレフィン・ジエン共重合体、ポリブタジエンゴム、ポリイソプレンゴム、ネオプレンゴム、ニトリルゴム、ブチルゴム、ポリイソブチレンゴム、天然ゴム、シリコーンゴム等が例示される。
本発明にかかる4-メチル-1-ペンテン系重合体(X)を含む樹脂組成物の製造方法は特に限定されないが、例えば、4-メチル-1-ペンテン系重合体(X)と他の成分とを上述の添加割合で混合したのち、溶融混練して得られる。
前記樹脂組成物を成形することにより成形体が得られる。
(1)成形方法
前記樹脂組成物の成形方法としては、公知の各種の成形方法が適用でき、例えば射出成形や押出成形、射出延伸ブロー成形法、ブロー成形法、キャス卜成形法、カレンダ一成形法、プレス成形、スタンピング成形、インフレーション成形、ロール成形等の各種成形法を挙げることができる。これらの成形方法により、目的とする成形体、例えばフィルム、シート、中空成形体、射出成形体、繊維等に加工することができる。成形条件は従来公知の4-メチル-1-ペンテン系重合体の成形条件と同様である。
成形体の形状には特に制約はない。例えば、チューブ状、フィルム状、シート状、膜(メンブレン)状、テープ状、板状、棒状、繊維状、不織布状、などである。
(3)用途
本発明の成形体は、従来の4-メチル-1-ペンテン系重合体が用いられうる用途に制約なく用いられうるが、耐熱性や低汚染性を要求される用途にはさらに適している。また本発明の特性である、スチーム滅菌による白濁抑制効果から、水蒸気による滅菌工程を含む用途や、水蒸気による滅菌工程を経て得られる成形体として用いられうる。より具体的な用途には、医療用器具、医療用包装材、実験用器材、化粧品容器、乳幼児用品、食品容器、電子レンジスチーム滅菌用容器および器材がある。
[遷移金属錯体の合成]
(8-オクタメチルフルオレン-12’-イル-(2-(アダマンタン-1-イル)-8-メチル-3,3b,4,5,6,7,7a,8-オクタヒドロシクロペンタ[a]インデン))ジルコニウムジクロライド(触媒A)の合成
(1)1-アダマンチルシクロペンタジエニルリチウムの合成
窒素雰囲気下、200ml三口フラスコに1.0M濃度のエチルマグネシウムブロマイドのtert-ブチルメチルエーテル溶液40mlを装入した。この溶液を氷浴で冷却しつつシクロペンタジエン2.64gを20分間かけて滴下し、室温に戻し17時間攪拌し、溶液Aを調製した。
窒素雰囲気下、100ml三口フラスコにTHF40ml、塩化マグネシウム1.57gを装入した。この溶液に、1-アダマンチルシクロペンタジエニルリチウム3.09gをTHF10mlに溶解させて得られた溶液を5分間かけて滴下し、室温で2時間、さらに50℃で3時間攪拌した。氷/アセトン浴下、1-アセチルシクロヘキセン1.96g(15.75mmol)をTHF10mlに溶解させて得られた溶液を10分間かけて滴下し、室温で19時間攪拌した。氷/アセトン浴下、酢酸1.0ml、ピロリジン3.1mlを装入し、室温で17時間攪拌した。氷/アセトン浴下、この溶液に飽和塩化アンモニウム水溶液30mlを加えた。この溶液にヘキサン100mlを加えた後、有機層を分離し、水層に対しヘキサン200mlで抽出を行い、抽出後のヘキサンを先の有機層と合わせて得られた有機液を水で二回洗浄した。この有機液を硫酸マグネシウムで乾燥した後、溶媒を留去した。得られた固形物をメタノールから再結晶することにより、目的物である2-(アダマンタン-1-イル)-8-メチル-3,3b,4,5,6,7,7a,8-オクタヒドロシクロペンタ[a]インデンを得た。収量2.134g、収率47%であった。
GC-MS:m/Z=306(M+).
(3)8-オクタメチルフルオレン-12’-イル-(2-(アダマンタン-1-イル)-8-メチル-3,3b,4,5,6,7,7a,8-オクタヒドロシクロペンタ[a]インデン)の合成
窒素雰囲気下、30mlシュレンク管にオクタメチルフルオレン1.546g、tert-ブチルメチルエーテル40mlを装入した。氷/アセトン浴下、この溶液に1.6Mのn-ブチルリチウムのヘキサン溶液2.62mlを15分間かけて滴下した。徐々に室温に戻しながら22時間攪拌した。この溶液に2-(アダマンタン-1-イル)-8-メチル-3,3b,4,5,6,7,7a,8-オクタヒドロシクロペンタ[a]インデン1.349gを加えた。室温で19時間、さらに50℃で8時間攪拌した後、反応溶液を飽和塩化アンモニウム水溶液100mlに加えた。有機層を分離し、水層に対しヘキサン100mlで抽出を行い、抽出後のヘキサンを先の有機層と合わせて得られた有機液を水で2回洗浄した。この有機液を硫酸マグネシウムで乾燥した後、溶媒を留去した。得られた固体をアセトンで洗浄することにより、目的物である8-オクタメチルフルオレン-12’-イル-(2-(アダマンタン-1-イル)-8-メチル-3,3b,4,5,6,7,7a,8-オクタヒドロシクロペンタ[a]インデン)を得た。収量1.51g、収率54%であった。
1H-NMRの測定結果より、得られた8-オクタメチルフルオレン-12’-イル-(2-(アダマンタン-1-イル)-8-メチル-3,3b,4,5,6,7,7a,8-オクタヒドロシクロペンタ[a]インデン)は複数の異性体の混合物であることが確認された。
窒素雰囲気下、100mlシュレンク管に8-オクタメチルフルオレン-12’-イル-(2-(アダマンタン-1-イル)-8-メチル-3,3b,4,5,6,7,7a,8-オクタヒドロシクロペンタ[a]インデン)1.039g、α-メチルスチレン0.47ml、ヘキサン30ml、シクロペンチルメチルエーテル2.62mlを装入した。25℃のオイルバス下、この溶液に1.6Mのn-ブチルリチウムのヘキサン溶液2.18mlを10分間かけて滴下した。50℃で4時間攪拌した後、析出物をろ過し、ヘキサンで洗浄することにより、桃色粉末を得た。100mlシュレンク管に、この桃色粉末、ジエチルエーテル30mlを装入した。この溶液をドライアイス/アセトンバスで冷却した後、この溶液に、四塩化ジルコニウム0.385g(1.65mmol)をジエチルエーテル30mlにて懸濁させて加えた。その後徐々に室温まで昇温しながら16時間攪拌した。
30℃下、充分に窒素置換した100mLの攪拌機を付けた三つ口フラスコ中に、窒素気流下で精製デカン32mL及び固体状ポリメチルアルミノキサン(東ソーファインケム社製)をアルミニウム原子換算で14.65mmol装入し、懸濁液とした。その懸濁液に、先に合成した触媒(A)50mg(ジルコニウム原子換算で0.059mmol)を4.6mmol/Lのトルエン溶液とし、この溶液12.75mLを撹拌しながら加えた。1.5時間後攪拌を止め、得られた触媒成分をデカンテーション法によりデカン50mLで3回洗浄し、デカンに懸濁させてスラリー液(B)50mLを得た。この触媒成分においてZr担持率は100%であった。
上記で調製したスラリー液(B)に、窒素気流下、ジイソブチルアルミニウムハイドライドのデカン溶液(アルミニウム原子換算で2.0mmol/mL)を2.0mL、さらに3-メチル-1-ペンテンを7.5mL(5.0g)装入した。1.5時間後攪拌を止め、得られた予備重合触媒成分をデカンテーション法によりデカン50mLで3回洗浄した。この予備重合触媒成分をデカンに懸濁させて、デカンスラリー(C)50mLを得た。デカンスラリー(C)における予備重合触媒成分の濃度は20g/L、1.05mmol-Zr/Lであり、Zr回収率は90%であった。
室温、窒素気流下で、内容積1Lの攪拌機を付けたSUS製重合器に、精製デカンを425mL、ジイソブチルアルミニウムハイドライドのデカン溶液(アルミニウム原子換算で2.0mmol/mL)を0.5mL(1mol)装入した。次いで、先に調製した予備重合触媒成分のデカンスラリー溶液(C)をジルコニウム原子換算で0.0005mmol加え、水素を50NmL装入した(1回目の水素装入)。次いで、4-メチル-1-ペンテン250mLと1-デセン3.3mLとの混合溶液を2時間かけて重合器内へ連続的に一定の速度で装入した。この装入開始時点を重合開始とし、重合開始から30分かけて45℃へ昇温した後、45℃で4時間保持した。重合開始から3時間後に水素を90NmL装入した(2回目の水素装入)。重合開始から4.5時間経過後、室温まで降温し、脱圧した後、ただちに白色固体を含む重合液を濾過して固体状物質を得た。この固体状物質を減圧下、80℃で8時間乾燥し、重合体[A-1]を得た。収量は131gであった。重合体[A-1]の13C-NMR、GPC、MFRおよびデカン可溶部測定の結果を表1に示す。
1-デセンの装入量を1.3mlとした以外は、実施例1と同様の重合反応を行い、重合体[A-2]を得た。収量は125gであった。重合体[A-2]の13C-NMR、GPC、MFRおよびデカン可溶部測定結果を表1に示す。
(1)重合体[A-3-1]の合成
水素装入回数を計3回とし、実施例1と同様の重合開始前の1回目の水素装入に加え、重合開始1時間後に2回目の水素装入、重合開始2時間後に3回目の水素装入を行い、1回目、2回目、3回目の水素装入量をそれぞれ60NmLとした以外は実施例1と同様の重合反応を行い、重合体[A-3-1]を得た。収量は126gであった。重合体[A-3-1]の13C-NMR、GPC、MFRおよびデカン可溶部測定結果を表1に示す。
1回目、2回目、3回目の水素装入量をそれぞれ35NmLとした以外は重合体[A-3-1]と同様の重合反応を行い、重合体[A-3-2]を得た。収量は126gであった。重合体[A-3-2]の13C-NMR、GPC、MFRおよびデカン可溶部測定の結果を表1に示す。
重合体[A-3-1]と重合体[A-3-2]とを、重合体[A-3-1]65、重合体[A-3-2]35の質量比率で十分混ぜ合わせて重合体[A-3]を得た。重合体[A-3]の13C-NMR、GPC、MFRおよびデカン可溶部測定の結果を表1に示す。
1回目、2回目、3回目の水素装入量をそれぞれ50NmLとした以外は重合体[A-3-1]と同様の重合反応を行い、重合体[B-1]を得た。収量は131gであった。重合体[B-1]の13C-NMR、GPC、MFRおよびデカン可溶部測定の結果を表1に示す。
重合体[C-1]および[C-2]は、国際公開2006/054613号パンフレットのそれぞれ、比較例7及び比較例9の方法に準じ、4-メチル―1―ペンテン、1-デセン、1-ヘキサデセン、1-オクタデセン、水素の割合を変更することによって得た。13C-NMR、GPC、MFRおよびデカン可溶部測定の結果を表1に示す。
必要に応じて重合を複数回実施してペレット作製に十分な量の重合体を用意した。各重合体100質量部に対して、二次抗酸化剤としてトリ(2,4-ジ-t-ブチルフェニル)フォスフェートを0.1質量部、耐熱安定剤としてn-オクタデシル-3-(4’-ヒドロキシ-3’,5’-ジ-t-ブチルフェニル)プロピネートを0.1質量部配合した。然る後に、(株)プラスチック工学研究所社製2軸押出機BT-30(スクリュー系30mmφ、L/D 46)を用い、設定温度260℃、樹脂押出量60g/minおよび回転数200rpmの条件で造粒して評価用ペレットを得た。
前記評価用ペレットを熱プレス機にて熱プレスすることによりプレスシートを作製した。2枚の真鍮板の間にスペーサーと評価用ペレットを挟み、これをプレスすることでプレスシートを作製した。スペーサーの厚みを適宜変えることで希望の厚みのプレスシートを得た。熱プレスは、270℃で樹脂が完全に溶融するまで保持後、100KG/cm2の条件で3分間プレス、その後すぐに20℃、100KG/cm2の条件で3分間プレスすることにより行った。
前記評価用ペレットを用いて、サーモ・プラスチック株式会社製単軸押出機(スクリュー径20mmφ、L/D 28)にコートハンガー式T型ダイス(リップ形状 270×0.8mm)を装着してダイス温度270℃の条件下、ロール温度70℃、巻き取り速度2.0m/minで成形を行い、厚み50μmのフィルムを得た。
4-メチル-1-ペンテン系重合体中のエチレンおよび炭素原子数3~20のα-オレフィン(4-メチル-1-ペンテンを除く)から選ばれる少なくとも1種のオレフィンに由来の構成単位(コモノマー)の含量は、以下の装置および条件により、13C-NMRスペクトルより算出した。
ここで、Pはコモノマー主鎖メチンシグナルの全ピーク面積を示し、Mは4-メチル-1-ペンテン主鎖メチンシグナルの全ピーク面積を示す。
4-メチル-1-ペンテン重合体のメソダイアドアイソタクティシティー(メソダイアッド分率)は、ポリマー鎖中の任意の2個の頭尾結合した4-メチル-1-ペンテン単位連鎖を平面ジグザグ構造で表現した時、そのイソブチル分岐の方向が同一である割合と定義し、13C-NMRスペクトルから下記式により求めた。
(式中、m、rは下記式で表される頭-尾で結合している4-メチル-1-ペンテン単位の主鎖メチレンに由来する吸収強度を示す。)
13C-NMRスペクトルは、バルカー・バイオスピン製AVANCEIIIcryo-500型核磁気共鳴装置を用いて、溶媒はo-ジクロロベンゼン/ベンゼン-d6(4/1 v/v)混合溶媒、試料濃度は60mg/0.6mL、測定温度は120℃、観測核は13C(125MHz)、シーケンスはシングルパルスプロトンブロードバンドデカップリング、パルス幅は5.0μ秒(45°パルス)、繰返し時間は5.5秒とし、ベンゼン-d6の128ppmをケミカルシフトの基準値として測定した。
重量平均分子量(Mw)、数平均分子量(Mn)およびZ平均分子量(Mz)は、GPCにより測定した。GPC測定は、以下の条件で行った。また、重量平均分子量(Mw)、数平均分子量(Mn)およびZ平均分子量(Mz)は、市販の単分散標準ポリスチレンを用いて検量線を作成し、下記の換算法に基づいて求めた。
装置:ゲル浸透クロマトグラフ HLC-8321 GPC/HT型 (東ソー社製)
有機溶媒:o-ジクロロベンゼン
カラム:TSKgel GMH6-HT 2本、TSKgel GMH6-HTLカラム 2本(何れも東ソー社製)
流速:1.0 ml/分
試料:0.15mg/mL o-ジクロロベンゼン溶液
温度:140℃
分子量換算 :PS換算/汎用較正法
なお、汎用較正の計算には、Mark-Houwink粘度式の係数を用いた。PSのMark-Houwink係数はそれぞれ、文献(J.Polym.Sci.,Part A-2,8,1803(1970))に記載の値を用いた。
[メルトフローレート(MFR)]
メルトフローレート(MFR)はASTM D1238に準拠して260℃、5kg荷重の条件で測定した。
各重合体5gにn-デカン200mLを加え、145℃で1時間加熱溶解した。23℃まで冷却し、30分間放置した。その後、析出物(n-デカン不溶部)をろ別した。ろ液を約3倍量のアセトン中に入れ、n-デカン中に溶解していた成分を析出させた。析出物をアセトンからろ別し、乾燥した。その析出物の質量を測定した。なお、ろ液側を濃縮乾固しても残渣は認められなかった。n-デカン可溶部量は、以下の式によって求めた。
[融点、融解熱量]
セイコーインスツルメンツ社製DSC測定装置(DSC220C)を用い、測定用アルミパンに約5mgの試料をつめて、10℃/minで280℃まで昇温した。280℃で5分間保持した後、10℃/minで20℃まで降温させた。20℃で5分間保持した後、10℃/minで280℃まで昇温した。2回目の昇温時に観測された結晶溶融ピークの頂点が現れる温度を融点とした。また、この結晶溶融ピークの積算値から融解熱量を算出した。
溶融張力の測定には、東洋精機製作所の装置であるキャピログラフ1Dを用いた。260℃に設定した溶融炉(径9.55 mm)にサンプルを仕込み十分溶融させた後に、押出速度15mm/minにて、L/D 8/ 2.095mm、流入角 180°であるキャピラリーを通過させ、キャピラリー下部から58cmの位置に固定した滑車を通過させ、溶融樹脂を15m/minの速度で巻取った際に滑車部にかかる応力を測定し、その応力を溶融張力とした。
厚み3mmのプレスシートについて、ASTM D1525に準拠して、安田精機株式会社製の試験機を用い、シリコーン油中、昇温速度50℃毎時間、試験荷重10Nにてビカット軟化温度試験を実施した。
耐スチーム性評価には、楠本化成株式会社製 HAST試験機 PLAMOUNT(PM252)を用いた。0.05mm(50μm)厚のフィルム、3mm厚および10mm厚のプレスシートを、135℃、RH95%の条件下で30分間保持後に23℃まで冷却する操作を2サイクル行った後の試験片の外観を確認した。試験片にボイドまたはクラックによる白化が明らかに生じた場合を×、ボイドまたはクラックによる白化が微量にある場合を△、ボイドまたはクラックによる白化が生じない場合を○と評価した。
上記のフィルムに対して、TA instruments社製 RSA-IIIを用いて、測定モードを引張とし、昇温速度4℃毎分、周波数1Hz、歪み0.1%の条件で、-20℃から250℃まで測定して、170℃における貯蔵弾性率E’の値を読み取った。
引張特性である引張伸びは、JIS K678に準拠して、上述のフィルムを試験片として、インストロン社製の万能引張試験機3380を用いて、引張速度200mm/minで測定した。
Claims (9)
- 4-メチル-1-ペンテン由来の構成単位の含有量が90~100モル%であり、エチレンおよび炭素原子数3~20の4-メチル-1-ペンテン以外のα-オレフィンから選ばれる少なくとも1種のオレフィン由来の構成単位の含有量が0~10モル%であり、下記要件(a)~(e)をすべて満たす、4-メチル-1-ペンテン系重合体。
(a)13C-NMRで測定されるメソダイアッド分率(m)が98~100%の範囲にある。
(b)ゲルパーミエーションクロマトグラフィー(GPC)で測定した、Z平均分子量Mzと重量平均分子量Mwとの比(Mz/Mw)が2.5~20の範囲にある。
(c)ゲルパーミエーションクロマトグラフィー(GPC)で測定した、重量平均分子量Mwと数平均分子量Mnとの比(Mw/Mn)が3.6~30の範囲にある。
(d)ASTM D1238に準拠して260℃、5kg荷重の条件で測定したメルトフローレート(MFR)が0.1~500g/10分の範囲にある。
(e)23℃デカン可溶部量が5.0質量%以下である。 - さらに下記要件(f)を満たす請求項1に記載の4-メチル-1-ペンテン系重合体。
(f)ゲルパーミエーションクロマトグラフィー(GPC)で測定した、分子量が1×106以上である重合体の割合が15質量%以上である。 - さらに下記要件(g)を満たす請求項1または2に記載の4-メチル-1-ペンテン系重合体。
(g)示差走査型熱量測定(DSC)で測定される前記4-メチル-1-ペンテン系重合体の融解熱量および融点が以下の要件(i)および(ii)を満たす。
(i)下記式(1)が成立する。
ΔHm≧0.5×Tm-76 ・・・式(1)
(式(1)において、融解熱量をΔHmJ/gとし、融点をTm℃とする。)
(ii)融点が200~260℃の範囲にある。 - 請求項1~3のいずれか1項に記載の4-メチル-1-ペンテン系重合体を含む樹脂組成物。
- 請求項1~3のいずれか1項に記載の4-メチル-1-ペンテン系重合体または請求項4に記載の樹脂組成物を含む成形体。
- 最大肉厚が100mm以下であり、最小肉厚が0.001mm以上である、請求項5に記載の成形体。
- 射出成形体または押出成形体である、請求項5または6に記載の成形体。
- フィルムである、請求項5に記載の成形体。
- 請求項5~8いずれかに記載の成形体である医療、介護、乳幼児、理化学実験用、食品、生活または薬品向けの器具または容器。
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SG11201807510VA SG11201807510VA (en) | 2016-03-03 | 2017-02-21 | 4-methyl-1-pentene polymer, resin composition and molded article |
EP17759731.7A EP3424963B1 (en) | 2016-03-03 | 2017-02-21 | 4-methyl-1-pentene polymer composition |
CN201780013717.1A CN108699180B (zh) | 2016-03-03 | 2017-02-21 | 4-甲基-1-戊烯系聚合物、树脂组合物及成型体 |
JP2018503053A JP6909778B2 (ja) | 2016-03-03 | 2017-02-21 | 4−メチル−1−ペンテン系重合体、樹脂組成物および成形体 |
US16/078,594 US11248069B2 (en) | 2016-03-03 | 2017-02-21 | 4-methyl-1-pentene polymer, resin composition and molded article |
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WO2020189676A1 (ja) | 2019-03-19 | 2020-09-24 | 三井化学株式会社 | プロピレン系樹脂組成物、成形体およびプロピレン重合体 |
WO2021025141A1 (ja) | 2019-08-08 | 2021-02-11 | 株式会社プライムポリマー | プロピレン系重合体組成物および成形体 |
WO2022050208A1 (ja) | 2020-09-01 | 2022-03-10 | 三井化学株式会社 | 樹脂組成物および成形体 |
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TW201800428A (zh) | 2018-01-01 |
CN108699180A (zh) | 2018-10-23 |
TWI775742B (zh) | 2022-09-01 |
CN108699180B (zh) | 2021-05-11 |
EP3424963A4 (en) | 2019-10-02 |
EP3424963A1 (en) | 2019-01-09 |
US11248069B2 (en) | 2022-02-15 |
JP6909778B2 (ja) | 2021-07-28 |
EP3424963B1 (en) | 2020-11-18 |
KR20200033991A (ko) | 2020-03-30 |
KR20180104034A (ko) | 2018-09-19 |
JPWO2017150265A1 (ja) | 2018-10-25 |
SG11201807510VA (en) | 2018-09-27 |
US20190048109A1 (en) | 2019-02-14 |
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