WO2022050208A1 - 樹脂組成物および成形体 - Google Patents
樹脂組成物および成形体 Download PDFInfo
- Publication number
- WO2022050208A1 WO2022050208A1 PCT/JP2021/031652 JP2021031652W WO2022050208A1 WO 2022050208 A1 WO2022050208 A1 WO 2022050208A1 JP 2021031652 W JP2021031652 W JP 2021031652W WO 2022050208 A1 WO2022050208 A1 WO 2022050208A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copolymer
- film
- mol
- methyl
- mass
- Prior art date
Links
Classifications
-
- 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
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- 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
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/32—Wound capacitors
Definitions
- the present invention relates to a resin composition containing a 4-methyl-1-pentene copolymer and a molded product such as a film for a capacitor containing the resin composition.
- 4-Methyl-1-pentene polymer is widely used in various applications because it is superior in heat resistance, transparency, electrical characteristics, etc. to polyethylene and polypropylene. Specifically, a film for a capacitor made of a 4-methyl-1-pentene copolymer is known.
- Patent Document 1 describes 4-methyl-1-pentene (co) in which a 4-methyl-1-pentene (co) polymer and a 4-methyl-1-pentene / ⁇ -olefin copolymer are blended in a specific ratio.
- a polymer composition is described, and it is described that the hollow molded product made of the composition is excellent in transparency, heat resistance, electrical properties, mechanical properties, uniform stretchability, and dimensional stability.
- a film for a capacitor obtained from a 4-methyl-1-pentene copolymer having specific physical properties has a small capacitance decrease rate and stable dielectric loss characteristics at high temperature and long-term charging. It is described as having properties.
- Patent Document 3 describes a 4-methyl-1-pentene copolymer composition containing a specific 4-methyl-1-pentene (co) polymer and 4-methyl-1-pentene copolymer (B). It is described that the polymer has high impact resistance while having transparency and rigidity, and further has high heat resistance.
- Patent Document 4 the specific 4-methyl-1-pentene polymer particles reduce their rigidity, that is, improve their flexibility, without impairing their properties such as high stereoregularity and excellent heat resistance. It is stated that it can be done.
- Capacitor films need to prevent the films from blocking each other strongly in order to properly operate the safety function, and it is required to control the surface roughness appropriately. Further, if the surface roughness of the film for a capacitor is rough, there are problems that the dielectric property is deteriorated and the life is shortened.
- both the properties applicable to the capacitor for example, electrical properties, heat resistance, stretchability
- the surface roughness can be kept small. I could't get a satisfactory film.
- the present invention provides 4-methyl-1-pentene, which has properties such as heat resistance, has a small surface roughness, can obtain a smooth film, and can be suitably used for a molded product such as a film for a capacitor.
- An object of the present invention is to provide a resin composition containing a copolymer.
- the present inventors have made diligent studies to solve the above problems. As a result, they have found that a resin composition containing two specific 4-methyl-1-pentene copolymers in a specific ratio can solve the above-mentioned problems, and have completed the present invention.
- the present invention relates to, for example, the following [1] to [7].
- the amount (U1) of the structural unit derived from 4-methyl-1-pentene is 80.0 to 99.9 mol%, and is selected from linear ⁇ -olefins having 2 to 20 carbon atoms.
- the total amount (U2) of the constituent units derived from at least one species is 20.0 to 0.1 mol% (provided that the total of the U1 and the U2 is 100 mol%).
- the ultimate viscosity [ ⁇ ] A measured in decalin at 135 ° C. is 0.5 to 5.0 dL / g.
- the amount of eluted components peaks in the range of 100 to 140 ° C. There is at least one.
- (Ad) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the elution component in the range of 100 to 140 ° C. when the copolymer (A) is measured by the CFC.
- the molecular weight distribution (Mw / Mn) is 1.0 to 4.5.
- (BA) The amount (U3) of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and is selected from linear ⁇ -olefins having 2 to 20 carbon atoms.
- the total amount (U4) of the constituent units derived from at least one species is 80.0 to 2.0 mol% (provided that the total of the U3 and the U4 is 100 mol%).
- the ultimate viscosity [ ⁇ ] B measured in decalin at 135 ° C. is 2.0 to 8.0 dL / g.
- B When the copolymer (B) is measured by a cross-separation chromatograph device (CFC) using an infrared spectrophotometer as a detection unit, the amount of elution components is in the range of 0 ° C. or higher and lower than 100 ° C. There is at least one peak of.
- Bd The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the elution component in the range of 0 ° C. or higher and lower than 100 ° C.
- the molecular weight distribution (Mw / Mn) is 1.0 to 7.0.
- the total content of the copolymers (A) and (B) is 100 parts by mass, the content of the copolymer (A) is 5 to 95 parts by mass, and the copolymer weight.
- the content of the coalescence (B) is 95 to 5 parts by mass.
- the value (U4-U2) obtained by subtracting the U2 (mol%) described in the requirement (Aa) from the U4 (mol%) described in the requirement (BA) is 0 mol% or more. It is 6.5 mol% or less.
- [5] A film containing the resin composition according to any one of [1] to [3].
- [6] A film that meets the following requirements (I) to (III).
- (I) Contains at least two 4-methyl-1-pentene copolymers.
- (II) The surface roughness (Ra) of the film is less than 100 nm.
- (III) The surface roughness (Rz) of the film is less than 500 nm.
- the resin composition of the present invention contains a 4-methyl-1-pentene copolymer, has properties such as heat resistance, has a small surface roughness, can obtain a smooth film, and is a film for capacitors and the like. Can be suitably used for the molded body of. Since the surface roughness of the film for a capacitor of the present invention is small and smooth, problems such as deterioration of dielectric properties and shortening of life are solved.
- the resin composition of the present invention contains the 4-methyl-1-pentene copolymer (A) and the 4-methyl-1-pentene copolymer (B) described below, and the following requirements (1) and Satisfy (2).
- the 4-methyl-1-pentene copolymer (A) (hereinafter, also referred to as "copolymer (A)”) is a structural unit derived from 4-methyl-1-pentene and a linear chain having 2 to 20 carbon atoms. It has a structural unit derived from the state ⁇ -olefin and satisfies the following requirements (Aa) to (Ad). It is preferable that the copolymer (A) further satisfies the following requirements (A-e).
- the copolymer (A) may contain only one type of copolymer, or may contain two or more types of copolymers. When the copolymer (A) contains two or more kinds of copolymers, it is preferable that each copolymer satisfies the above requirements (Aa) to (Ae).
- the amount (U1) of the structural unit derived from 4-methyl-1-pentene is 80.0 to 99.9 mol%, and the linear ⁇ -olefin having 2 to 20 carbon atoms is used.
- the total amount (U2) of the constituent units derived from at least one selected from is 20.0 to 0.1 mol%.
- U1 is preferably 85.0 to 99.9 mol%, more preferably 90.0 to 99.9 mol%.
- U2 is preferably 15.0 to 0.1 mol%, more preferably 10.0 to 0.1 mol%.
- the total of the U1 and the U2 is 100 mol%.
- the 100 mol% means the total of the U1 and the U2, and does not mean 100 mol% of all the constituent units constituting the copolymer (A).
- linear ⁇ -olefin having 2 to 20 carbon atoms examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1 -Hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene can be mentioned.
- ethylene is included in ⁇ -olefin.
- linear ⁇ -olefins having 10 to 20 carbon atoms are preferable, and direct ⁇ -olefins having 10 to 18 carbon atoms are preferable from the viewpoint that a smooth film having a smaller surface roughness can be obtained from the resin composition of the present invention.
- Chained ⁇ -olefins are more preferred.
- 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferable.
- the linear ⁇ -olefin having 2 to 20 carbon atoms it is preferable to use 1-hexadecene and 1-octadecene in combination.
- the copolymer (A) may have only one type of structural unit derived from a linear ⁇ -olefin having 2 to 20 carbon atoms, or may have two or more types.
- the copolymer (A) is a structural unit derived from a polymerizable compound other than 4-methyl-1-pentene and a linear ⁇ -olefin having 2 to 20 carbon atoms, as long as the object of the present invention is not impaired. Can further have.
- Examples of other polymerizable compounds include branched ⁇ -olefins having 20 or less carbon atoms other than 4-methyl-1-pentene; vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornene; acetic acid.
- Vinyl esters such as vinyl; unsaturated organic acids such as maleic anhydride or derivatives thereof; conjugated diene such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadien, 2- Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadien, dicyclopentadiene, cyclohexadiene, dicyclooctadien, methylenenorbornene, 5-vinylnorbornene, 5- Echilidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2- Examples thereof include non-conju
- the content ratio of the constituent units derived from other polymerizable compounds is usually 10 mol% or less, preferably 5 in 100 mol% of all the constituent units constituting the copolymer (A). It is mol% or less, more preferably 3 mol% or less.
- the ultimate viscosity [ ⁇ ] A of the copolymer (A) measured in decalin at 135 ° C. is 0.5 to 5.0 dL / g.
- the [ ⁇ ] A is preferably 0.5 to 4.5 dL / g, more preferably 0.5 to 4.0 dL / g.
- the copolymer (A) in which [ ⁇ ] A is in the above range exhibits good fluidity during preparation and molding of the resin composition. Further, it is considered that when combined with the 4-methyl-1-pentene copolymer (B), it contributes to the improvement of stretchability.
- the copolymer (A) preferably has no peak in the amount of eluted components in the range of 0 ° C. or higher and lower than 100 ° C.
- the copolymer (A) satisfying the requirement (A-c) contains a component having high crystallinity, and the obtained molded product tends to exhibit high heat resistance.
- the content ratio of the eluted component at 135 ° C. or higher in the total amount of the eluted component at 0 to 145 ° C. of the copolymer (A) is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass. It is as follows.
- the copolymer (A) satisfying this requirement is preferable from the viewpoint of uniform stretchability.
- the resin composition containing the copolymer (A) having Mw / Mn in the above range tends to have a low content of relatively low molecular weight components. Therefore, the possibility that the transparency of the molded product is lowered due to the bleed-out of the low molecular weight component and the possibility that the low molecular weight component weakens the crystal structure is reduced. As a result, it is considered that there is a favorable effect on the mechanical properties of the molded product.
- the copolymer (A) having Mw / Mn in the above range can be obtained, for example, by using a metallocene catalyst described later.
- ⁇ Requirements (A-e) >> The copolymer (A) has a melting point (Tm) measured by a differential scanning calorimeter (DSC), preferably 210 to 260 ° C, more preferably 220 to 260 ° C, and even more preferably 225 to 260 ° C.
- Tm melting point measured by a differential scanning calorimeter
- the melting point tends to depend on the stereoregularity of the copolymer and the content ratio of the structural unit derived from the linear ⁇ -olefin having 2 to 20 carbon atoms.
- the melting point can be adjusted by using a metallocene catalyst described later and by controlling the content ratio of the structural unit.
- the copolymer (A) having a melting point in the above range is preferable from the viewpoint of heat resistance and moldability.
- ⁇ 4-Methyl-1-pentene copolymer (B)> The 4-methyl-1-pentene copolymer (B) (hereinafter, also referred to as "copolymer (B)”) is a structural unit derived from 4-methyl-1-pentene and a linear chain having 2 to 20 carbon atoms. It has a structural unit derived from the state ⁇ -olefin and satisfies the following requirements (Ba) to (Bd). It is preferable that the copolymer (B) further satisfies the following requirement (B). It is preferable that the copolymer (B) further satisfies the following requirement (BF).
- the copolymer (B) may contain only one type of copolymer, or may contain two or more types of copolymers. When the copolymer (B) contains two or more kinds of copolymers, it is preferable that each copolymer satisfies the above-mentioned requirements (Ba) to (Bf).
- the amount (U3) of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the linear ⁇ -olefin having 2 to 20 carbon atoms is used.
- the total amount (U4) of the constituent units derived from at least one selected from is 80.0 to 2.0 mol%.
- U3 is preferably 20.0 to 97.0 mol%, more preferably 25.0 to 97.0 mol%.
- U4 is preferably 80.0 to 3.0 mol%, more preferably 75.0 to 3.0 mol%.
- the total of the U3 and the U4 is 100 mol%.
- the 100 mol% means the total of the U3 and the U4, and does not mean 100 mol% of all the constituent units constituting the copolymer (B).
- linear ⁇ -olefin having 2 to 20 carbon atoms examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1 -Hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene can be mentioned.
- linear ⁇ -olefins having 10 to 20 carbon atoms are selected from the viewpoint that the molded product obtained from the resin composition of the present invention can be stretched more highly and can maintain high transparency even after stretching.
- a linear ⁇ -olefin having 10 to 18 carbon atoms is preferable, and a linear ⁇ -olefin having 10 to 18 carbon atoms is more preferable.
- 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferable.
- the linear ⁇ -olefin having 2 to 20 carbon atoms it is preferable to use 1-hexadecene and 1-octadecene in combination.
- the copolymer (B) may have only one type of structural unit derived from a linear ⁇ -olefin having 2 to 20 carbon atoms, or may have two or more types.
- the copolymer (B) can further have a structural unit derived from the above-mentioned other polymerizable compounds in the copolymer (A) as long as the object of the present invention is not impaired.
- the content ratio of the constituent units derived from other polymerizable compounds is usually 10 mol% or less, preferably 5 in 100 mol% of all the constituent units constituting the copolymer (B). It is mol% or less, more preferably 3 mol% or less.
- the ultimate viscosity [ ⁇ ] B of the copolymer (B) measured in decalin at 135 ° C. is 2.0 to 8.0 dL / g.
- the [ ⁇ ] B is preferably 2.5 to 7.5 dL / g, more preferably 2.7 to 7.0 dL / g, still more preferably 3.0 to 7.0 dL / g, and particularly preferably 3.0 to 7.0 dL / g. It is 3.5 to 7.0 dL / g.
- the copolymer (B) in which [ ⁇ ] B is in the above range exhibits good fluidity during preparation and molding of the resin composition. Further, it is considered that when combined with the 4-methyl-1-pentene copolymer (A), it contributes to the improvement of stretchability. In particular, when [ ⁇ ] B is at least the above lower limit value, the stretchability when formed into a film tends to be superior, and the rigidity tends to be excellent.
- the copolymer (B) preferably has no peak in the amount of eluted components in the range of 100 to 140 ° C.
- the copolymer (B) satisfying the requirement (B-c) contains a component having lower crystallinity than the copolymer (A), and the obtained molded product tends to exhibit high flexibility.
- the resin composition containing the copolymer (B) having Mw / Mn in the above range tends to have a low content of relatively low molecular weight components. Therefore, the possibility that the transparency of the molded product is lowered due to the bleed-out of the low molecular weight component and the possibility that the low molecular weight component weakens the crystal structure is reduced. As a result, it is considered that there is a favorable effect on the mechanical properties of the molded product.
- the copolymer (B) having Mw / Mn in the above range can be obtained, for example, by using a metallocene catalyst described later.
- ⁇ Requirements (BE) >>
- the copolymer (B) is measured by a cross-separation chromatograph device (CFC) using an infrared spectrophotometer as a detection unit, in one embodiment, the number average molecular weight (Mn) of the eluted components at 0 ° C. is It is 5000 or more, or there is no elution component at 0 ° C.
- the copolymer (B) containing an elution component at 0 ° C. in the CFC contains a component having very low crystallinity (or completely amorphous).
- the copolymer (B) in which the Mn of the elution component at 0 ° C. is 5000 or more is usually a high comonomer-containing material having very low crystallinity.
- Such a polymer has low crystallinity but has a high molecular weight, and is preferable from the viewpoint that it is considered that the transparency of the molded product is lowered due to the bleed-out of the low molecular weight component and the roll stain during film molding is unlikely to occur.
- Copolymers polymerized using a metallocene catalyst tend to have a large Mn of the elution component at 0 ° C. or no elution component at 0 ° C.
- the Mn of the elution component at 0 ° C. is preferably 15,000 or more, more preferably 20,000 or more.
- the upper limit of Mn is not particularly limited, but may be, for example, 1 million.
- the content ratio of the eluted component at 0 ° C. in the total amount of the eluted component at 0 to 145 ° C. of the copolymer (B) is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less. be.
- the melting point (Tm) of the copolymer (B) measured by a differential scanning calorimeter (DSC) is preferably 220 ° C. or lower, or a peak indicating the melting point does not appear in the DSC measurement, and the melting point is more preferable.
- Tm is 210 ° C. or lower, or no peak indicating the melting point appears in the DSC measurement, and more preferably, the melting point (Tm) is 100 to 200 ° C., or a peak indicating the melting point appears in the DSC measurement. do not do.
- the copolymer (B) satisfying the requirement (B-f) is preferable from the viewpoint of stretchability.
- ⁇ Requirement (1)> In the resin composition of the present invention, when the total content of the copolymers (A) and (B) is 100 parts by mass, the content of the copolymer (A) is 5 to 95 parts by mass. The content of the copolymer (B) is 95 to 5 parts by mass.
- the obtained molded product tends to have a good balance between rigidity and extensibility.
- the content of the copolymer (B) is larger than the content of the copolymer (A)
- the stretchability is further improved, which is preferable.
- the content of the copolymer (A) is preferably 5 parts by mass or more and less than 50 parts by mass.
- the content of the copolymer (B) preferably exceeds 50 parts by mass. It is 95 parts by mass or less, more preferably 60 to 90 parts by mass, further preferably 62 to 85 parts by mass, and particularly preferably 65 to 85 parts by mass.
- the value (U4-U2) obtained by subtracting the U2 (mol%) described in the requirement (Aa) from the U4 (mol%) described in the requirement (BA) is the value (U4-U2). , 0 mol% or more and 6.5 mol% or less.
- the difference (U4-U2) is preferably 0 mol% or more and 5.5 mol% or less, more preferably 0 mol% or more, 5.0 mol% or less, still more preferably 0 mol% or more, 4.5. It is mol% or less, particularly preferably 0 mol or more and 4.0 mol% or less.
- “Compatibility” in the present invention means the property that the components are evenly mixed in one phase.
- “compatibility” means the property that the sea phase and the island phase of the sea-island structure are dispersed, and is different from the compatibility.
- the resin composition of the present invention has an intrinsic viscosity [ ⁇ ] measured in decalin at 135 ° C., usually 2.0 to 8.0 dL / g, preferably 2.5 to 7.0 dL / g. It is more preferably 2.8 to 6.0 dL / g, further preferably 3.0 to 5.0 dL / g, and particularly preferably 3.3 to 4.5 dL / g.
- the ultimate viscosity [ ⁇ ] is higher than 8.0 dL / g, the moldability tends to be poor, and when the ultimate viscosity [ ⁇ ] is lower than 2.0 dL / g, the stretchability tends to be deteriorated.
- the content of the comonomer copolymerized with 4-methyl-1-pentene contained in the resin composition is usually 1.0 to 6.0 mol%, preferably 1.0 to 6.0 mol%. It is 1.5 to 5.5 mol%, more preferably 2.0 to 5.0 mol%, still more preferably 2.5 to 5.0 mol%, and particularly preferably 2.5 to 4 It is 0.7 mol%, most preferably 2.5 to 4.5 mol%.
- the content of comonomer is higher than 6.0 mol%, the dielectric breakdown strength tends to decrease, and when the content of comonomer is lower than 1.0 mol%, the stretchability tends to deteriorate.
- the total content of the comonomer is an average value of the content of the comonomer copolymerized with 4-methyl-1-pentene in the copolymer (A) and the copolymer (B) in consideration of the mass ratio. Can also be calculated as.
- the resin composition of the present invention has at least one elution component amount peak in the range of 100 to 140 ° C. when measured by a cross fractionation chromatograph device (CFC) using an infrared spectrophotometer in the detection unit. Moreover, it is preferable that at least one peak of the amount of eluted components is present in the range of 0 ° C. or higher and lower than 100 ° C.
- CFC cross fractionation chromatograph device
- the resin composition of the present invention has a melting point (Tm) of usually 200 to 260 ° C, preferably 205 to 250 ° C, more preferably 210 to 240 ° C, and even more preferably 215 to 230 ° C.
- Tm melting point
- the melting point (Tm) can be measured with respect to the composition before the molded product, or can be measured with respect to the molded product such as a film obtained only from the resin composition.
- the total content of the copolymer (A) and the copolymer (B) in the resin composition of the present invention is usually 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more. Is.
- the upper limit of the content ratio of the copolymer (A) and the copolymer (B) may be 100% by mass of the resin composition. When the resin composition contains other components (for example, other polymer components and additives described later), the upper limit is defined by the content ratio of the other components.
- the resin composition of the present invention can contain one kind or two or more kinds of copolymers (A). Further, the resin composition of the present invention can contain one kind or two or more kinds of copolymers (B).
- the copolymer (A) has a relatively low ultimate viscosity [ ⁇ ] with respect to the copolymer (B) and is a hard component, and the copolymer (B) is a relatively soft component. ..
- the hardness of each polymer is considered to be due to the content of comonomer contained in each polymer. Since the resin composition of the present invention contains the copolymer (A) and the copolymer (B), the molded product obtained from the resin composition is a 4-methyl-1-pentene copolymer. It has excellent stretchability while maintaining the transparency and heat resistance derived from. Therefore, the resin composition of the present invention is suitable for producing a film for a capacitor, which requires heat resistance and stretchability.
- the copolymer (A) and the copolymer (B) are, for example, 4-methyl-1-pentene, a linear ⁇ -olefin having 2 to 20 carbon atoms, and the other polymerization as required. It can be obtained by polymerizing with a sex compound. By carrying out the polymerization in the presence of a metallocene catalyst, the copolymers (A) and (B) satisfying the above-mentioned requirements can be preferably obtained.
- metallocene catalyst examples include International Publication No. 01/53369, International Publication No. 01/27124, JP-A-3-193996, JP-A-02-41303, International Publication No. 06/025540 or International Publication No.
- the metallocene catalyst described in 2013/099876 can be mentioned.
- Metallocene catalyst for example, Metallocene compound (a) and Examples thereof include a catalyst composed of at least the carrier (b).
- Metallocene compound (a) is represented by, for example, the general formula (1) or (2).
- R 1 to R 14 are independently hydrogen atoms, hydrocarbon groups, substituted hydrocarbon groups or silicon-containing groups, respectively. Adjacent substituents from R 1 to R 4 may combine with each other to form a ring. Adjacent substituents from R 5 to R 12 may combine with each other to form a ring.
- Y is a carbon atom or a silicon atom.
- A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain unsaturated bonds and / or aromatic rings.
- A may include two or more ring structures, including a ring formed with Y.
- M is a metal (transition metal) selected from Group 4 of the periodic table, and examples thereof include titanium, zirconium, and hafnium.
- Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand that can be coordinated with a lone electron pair. When j is 2 or more, each Q may be the same or different.
- j is an integer of 1 to 4, preferably 2.
- the hydrocarbon group in R 1 to R 14 include a hydrocarbon group having 1 to 20 carbon atoms, and specifically, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms. , An arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms.
- substituted hydrocarbon groups excluding silicon-containing groups
- some or all of the hydrogen atoms contained in the hydrocarbon groups are halogen atoms (fluorine, chlorine, bromine, iodine) and hydroxyl groups.
- a group substituted with a functional group such as an amino group.
- Examples of the silicon-containing group in R 1 to R 14 include an alkylsilyl group or an arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl and tert-butyl. Examples thereof include dimethylsilyl and triphenylsilyl.
- Adjacent substituents from R 5 to R 12 on the fluorene ring may combine with each other to form a ring.
- substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl.
- the fluorene ring moiety is preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-2-disubstituted fluorene or 2,3,6,7-4-substituted fluorene.
- the 3rd, 6th, 2nd, and 7th positions on the fluorene ring correspond to R 7 , R 10 , R 6 , and R 11 , respectively.
- R 13 and R 14 are independently hydrogen atoms, hydrocarbon groups or substituted hydrocarbon groups, respectively.
- R 13 and R 14 are bonded to Y to form a substituted methylene group or a substituted silylene group as a crosslinked portion.
- the substituted methylene group and the substituted silylene group include, for example, dialkylmethylene, dicycloalkylmethylene, alkylcycloalkylmethylene, alkylarylmethylene, diarylmethylene, dialkylsilylene, dicycloalkylcilylene, alkylcycloalkylcilylene, and alkylaryl. Examples thereof include silylene, diallylsilylene, and groups obtained by halogenating these.
- Y is bonded to the divalent hydrocarbon group A to form a cycloalkylidene group, a cyclomethylenecilylene group, or the like.
- the cycloalkylidene group and the cyclomethylenecilylene group include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, and adaman.
- Examples thereof include chiliden, tetrahydronaphthylidene, dihydroindanylidene, cyclodimethylene syrylene, cyclotrimethylene srylene, cyclotetramethylene sillirene, cyclopentamethylene sillirene, cyclohexamethylene sillirene and cycloheptamethylene sillirene.
- examples of the halogen atom include fluorine, chlorine, bromine, and iodine
- examples of the hydrocarbon group having 1 to 20 carbon atoms include groups similar to those of the hydrocarbon groups R1 to R14 ; anionic arrangement.
- examples of the position include an alkoxy group, an aryloxy group, a carboxylate group, a sulfonate group and the like
- examples of a neutral ligand capable of coordinating with an isolated electron pair include trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethyl.
- Examples thereof include organic phosphorus compounds such as phosphine, ethers such as tetrahydrofuran, diethyl ether, dioxane and 1,2-dimethoxyethane.
- At least one of Q is preferably a halogen atom or an alkyl group having 1 to 20 carbon atoms.
- metallocene compound (a) examples include the compounds exemplified in International Publication No. 01/27124, International Publication No. 2006/025540 or International Publication No. 2007/308607.
- the metallocene compound (a) the compound represented by the general formula [A2] described in International Publication No. 2014/050817 or the like is particularly preferable.
- 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. They may be the same or different from each other, and the respective substituents may be bonded to each other to form a ring.
- M is a Group 4 transition metal of the periodic table
- n is an integer of 1 to 3
- Q is synonymous with Q in the general formula (1) or (2)
- j is an integer of 1 to 4. be.
- Examples of the hydrocarbon group in R 1b to R 12b include a linear hydrocarbon group such as a linear alkyl group and a linear alkenyl group; a branched hydrocarbon group such as a branched alkyl group; a cycloalkyl group, Cyclic saturated hydrocarbon groups such as norbornyl group and adamantyl group; Cyclic unsaturated hydrocarbon groups such as aryl group and cycloalkenyl group; Cyclic unsaturated with one or more hydrogen atoms of saturated hydrocarbon groups such as aralkyl group. Examples thereof include a group substituted with a hydrocarbon group.
- the hydrocarbon group usually has 1 to 20, preferably 1 to 15, and more preferably 1 to 10.
- each of the plurality of Rs is independently an alkyl group or a phenyl group having 1 to 15 carbon atoms. Can be mentioned.
- Examples of the halogen-containing hydrocarbon group in R 1b to R 12b include a group formed by substituting one or more hydrogen atoms of the above-mentioned hydrocarbon group with a halogen atom, such as a trifluoromethyl group.
- Examples of the halogen atom in R 2b to R 12b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other in the formula [A2] include an alicyclic ring and an aromatic ring. Specific examples thereof include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, preferably a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.
- R 1b is a substituent in which the carbon having a free valence (carbon bonded to the cyclopentadienyl ring) is a tertiary carbon.
- R 1b is a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group.
- the fluorene ring moiety is not particularly limited as long as it has a structure obtained from a known fluorene derivative, but R 4b and R 5b are preferably hydrogen atoms from the viewpoint of molecular weight.
- R 2b , R 3b , R 6b and R 7b are preferably hydrocarbon groups having 1 to 20 carbon atoms. Further, 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.
- substituted fluorenyl groups 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 preferably an alkyl group having 2 or more carbon atoms. From a synthetic point of view, it is also preferable that R 10b and R 11b are hydrogen atoms.
- R 9b and R 10b are bonded to each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring.
- R 11b is preferably a hydrogen atom.
- R 12b is preferably an alkyl group.
- 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.
- n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
- j is an integer of 1 to 4, preferably 2.
- Examples of the compound represented by the general formula [A2] include (8-octamethylfluorene-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- (adamantan-1-yl)) )-8-Methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta [a] indene)) Zyroxide 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.
- Carrier (b) is preferably in the form of particles, and the metallocene catalyst is formed by immobilizing the metallocene compound (a) on the surface and inside thereof.
- a form of catalyst is generally referred to as a metallocene-supported catalyst.
- the carrier (b) contains an organoaluminum compound (b-1), an organoboron compound (b-2), an inorganic compound (b-3), or a complex of two or more selected from these as a main component.
- organoaluminum compound (b-1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and trinormal octylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, tricycloalkylaluminum, and aluminoxane.
- Typical examples include organoaluminum oxy compounds.
- organoaluminum compounds (b-1 ) For example, an organoaluminum oxy compound containing a boron atom, an aluminoxane containing a halogen as exemplified in International Publication No. 2005/066191, International Publication No. 2007/131010, International Publication No. 2003/082879. Ionic aluminoxane as exemplified in the above can also be mentioned.
- organoboron compound (b-2) examples include trialkylammonium tetraarylborate, trialkylammonium tetra (aryl halide) borate, dioctadecylmethylammonium tetraarylborate, and dioctadecylmethylammonium tetra (aryl halide) borate.
- Examples of the inorganic compound (b-3) include porous oxides, inorganic halides, clays, clay minerals, and ion-exchange layered compounds.
- Examples of the porous oxide include oxides such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , or a composite containing these. Examples include mixtures.
- natural or synthetic zeolite SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 , SiO 2 -TiO 2 -MgO, etc.
- the inorganic halide examples include MgCl 2 , MgBr 2 , MnCl 2 , and MnBr 2 .
- the inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitating agent.
- a carrier containing an aluminum atom is preferable from the viewpoint of high activity and further suppressing the amount of the solvent-soluble portion.
- the content of aluminum atoms in the carrier (b) is preferably 20% by mass or more, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and particularly preferably 35 to 47% by mass.
- solid aluminoxane is preferably used, and is disclosed in, for example, International Publication No. 2010/055652, International Publication No. 2013/146337, or International Publication No. 2014/123212. Solid aluminoxane is particularly preferably used.
- Solid state means that the aluminoxane maintains a substantially solid state in a reaction environment in which the solid aluminoxane is used. More specifically, for example, when preparing an olefin polymerization solid catalyst component by contacting each component constituting the olefin polymerization catalyst, a specific temperature and pressure are used in an inert hydrocarbon medium such as hexane or toluene used in the reaction. It indicates that the aluminoxane is in a solid state in an environment.
- the solid aluminoxane preferably contains an aluminoxane having at least one structural unit selected from the structural unit represented by the following formula (1) and the structural unit represented by the following formula (2), and more preferably the following. It contains an aluminoxane having a structural unit represented by the formula (1), and more preferably a polymethylaluminoxan having only a structural unit represented by the following formula (1).
- Me is a methyl group.
- R 1 is a hydrocarbon group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 15 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
- the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aryl group.
- the structure of the solid aluminoxane has not always been clarified, and it is usually presumed to have a structure in which the structural units represented by the formula (1) and / or the formula (2) are repeated by about 2 to 50.
- the configuration is not limited to this.
- the binding mode of the constituent units varies, for example, linear, cyclic or clustered, and aluminoxane is usually presumed to consist of one of these or a mixture thereof. ..
- the aluminoxane may be composed of only the structural unit represented by the formula (1) or the formula (2).
- solid aluminoxane a solid polymethylaluminoxane is preferable, and a solid polymethylaluminoxane composed of only the structural unit represented by the formula (1) is more preferable.
- the solid aluminoxane functions as a catalyst carrier. Therefore, in addition to the solid aluminoxane, it is not necessary to use, for example, a solid inorganic carrier such as silica, alumina, silica-alumina, magnesium chloride, or a solid organic carrier such as polystyrene beads as the catalyst carrier.
- the solid aluminoxane can be prepared, for example, by the methods described in WO2010 / 055652 and WO 2014/123212.
- Organic compound component (c) The metallocene catalyst may further contain the organic compound component (c), if necessary.
- the organic compound component (c) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary.
- the organic compound component (c) the above-mentioned organoaluminum compound (b-1) can be used as the organic compound component (c).
- Other examples include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.
- an inert hydrocarbon solvent can be used, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; cyclopentane, Alicyclic hydrocarbons such as cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane; Two or more mixed solvents selected may be mentioned. Further, the olefin itself containing 4-methyl-1-pentene can be used as the polymerization solvent.
- aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octan
- the usage and addition order of each component are arbitrarily selected, and the following methods are exemplified.
- the metallocene compound (a), the carrier (b), and the organic compound component (c) are also referred to as “components (a) to (c)”, respectively.
- component (a) and the component (b) are also referred to as “components (a) to (c)”, respectively.
- (I) A method of adding the component (a) and the component (b) to the polymerizer in an arbitrary order.
- IIi) A method of adding a catalyst component having the component (a) supported on the component (b) to a polymerizer.
- the component (c) may be further added at any stage. Further, at least two of each catalyst component may be contacted in advance. Further, in the solid catalyst component in which the component (a) is supported on the component (b), olefins such as 4-methyl-1-pentene and 3-methyl-1-pentene may be prepolymerized, and the prepolymerization may be performed. A catalyst component may be further supported on the solid catalyst component.
- the amount of each component that can constitute the metallocene catalyst is as follows. Further, in the metallocene catalyst, the content of each component can be adjusted as follows.
- the component (a) is usually used in an amount of 10 -10 to 10-2 mol, preferably 10 -8 to 10 -3 mol, per liter of the reaction volume.
- the molar ratio [Al / M] of the aluminum atom in the component (b-1) to the total transition metal atom (M) in the component (a) is usually 10 to 10000, preferably 10 to 10000. It can be used in an amount of 30 to 2000, particularly preferably 150 to 500.
- the molar ratio [(b-2) / M] of the component (b-2) to the total transition metal atom (M) in the component (b-2) is usually 10 to 10000, preferably 10 to 10000. It can be used in an amount of 30 to 2000, more preferably 150 to 500.
- the molar ratio [(b-3) / M] of the component (b-3) to the total transition metal atom (M) in the component (b-3) is usually 10 to 10000, preferably 10 to 10000. It can be used in an amount of 30 to 2000, more preferably 150 to 500.
- the molar ratio of the aluminum atom in the component (b-1) to the component (c) [Al / (c)]. Is usually 0.002 to 500, preferably 0.01 to 60, and when the component (b) is the component (b-2), the component (b-2) and the component (c) When the molar ratio [(b-2) / (c)] is usually 0.002 to 500, preferably 0.01 to 60, and the component (b) is the component (b-3). Is used in an amount such that the molar ratio [(b-3) / (c)] of the component (b-3) to the component (c) is usually 0.002 to 500, preferably 0.01 to 60. be able to.
- the polymerization temperature is usually ⁇ 50 to 200 ° C., preferably 0 to 100 ° C., and more preferably 20 to 100 ° C.
- the polymerization pressure is usually under the conditions of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure.
- the polymerization reaction can be carried out by any method of batch type, semi-continuous type and continuous type.
- Hydrogen can be added to the polymerization system for the purpose of controlling the molecular weight or polymerization activity of the produced polymer, and the amount of hydrogen added is appropriately about 0.001 to 100 NL per 1 kg of olefin.
- the polymerization condition it is also possible to adopt multi-stage polymerization in which two or more stages of polymerization have different reaction conditions.
- the desired molecular weight is obtained by carrying out the polymerization stepwise under two conditions having different hydrogen usage or the ratio of 4-methyl-1-pentene to the linear ⁇ -olefin having 2 to 20 carbon atoms. It is possible to obtain polymers with a distribution or composition distribution.
- the mixture of the copolymers (A) and (B) is a combination obtained in the step (1) for producing the 4-methyl-1-pentene copolymer (A) by slurry polymerization and the step (1).
- the 4-methyl-1-pentene copolymer (B) is a copolymer (when the total amount of the polymers (A) and (B) is 100 parts by mass. It can be produced by a multi-stage polymerization method including the step (2) of producing by slurry polymerization in a range where the amount of B) is 5 to 90 parts by mass.
- the multi-stage polymerization method has a step (1) and a step (2) having different polymerization conditions, but the two-step polymerization of the steps (1) and (2) may be used, and in addition to the steps (1) and (2).
- the polymerization may be a three-stage or higher type including further steps.
- Step (1) the 4-methyl-1-pentene copolymer (A) is produced by slurry polymerization.
- the supply amount ratios of 4-methyl-1-pentene and the linear ⁇ -olefin having 2 to 20 carbon atoms are set so that the amount of the structural unit derived from each is within the above-mentioned range.
- step (1) a slurry containing the copolymer (A) is obtained.
- the slurry concentration, that is, the copolymer (A) particle concentration is usually 0.015 to 45% by mass, preferably 0.03 to 35% by mass.
- Step (2) the 4-methyl-1-pentene copolymer (B) is produced by slurry polymerization in the presence of the copolymer (A) obtained in the step (1).
- step (2) the supply amount ratios of 4-methyl-1-pentene and the linear ⁇ -olefin having 2 to 20 carbon atoms are set so that the amount of the structural unit derived from each is within the above-mentioned range.
- the copolymer (2) when the total amount of the copolymer (A) obtained in the step (1) and the copolymer (B) obtained in the step (2) is 100 parts by mass, the copolymer (2) The copolymer (B) is produced in a range where the amount of B) is 5 to 90 parts by mass.
- step (2) in one embodiment, 4-methyl-1-pentene and a linear ⁇ -olefin having 2 to 20 carbon atoms are added to the slurry containing the copolymer (A), and the slurry of these monomers is added. Polymerization can be performed.
- a slurry containing the copolymer (A) and the particles containing the copolymer (B) is obtained.
- the slurry concentration that is, the particle concentration is usually 3 to 50% by mass, preferably 5 to 40% by mass.
- slurry polymerization In the multi-stage polymerization method, slurry polymerization is adopted, but in “slurry polymerization", the polymer produced by the polymerization is dispersed in the medium as fine particles, for example, without being substantially dissolved in the medium used at the time of polymerization. It refers to a polymerization characterized by being present in.
- Solid-liquid separation process The slurry containing the 4-methyl-1-pentene polymer particles containing the copolymers (A) and (B) obtained in the step (2) is solid-liquid separated, for example, filtered. Particles can be separated and recovered.
- Post-treatment process For the 4-methyl-1-pentene polymer particles obtained by the above-mentioned multi-stage polymerization method, for example, the particles obtained by the above-mentioned solid-liquid separation step, after being produced by the above-mentioned method, a known catalyst is required. Post-treatment steps such as a deactivation treatment step, a catalyst residue removal step, and a drying step may be performed.
- the resin composition of the present embodiment can further contain other polymer components other than the above-mentioned copolymers (A) and (B).
- examples of other polymer components include ⁇ -olefin polymers (E) (excluding the above-mentioned copolymers (A) and (B)) and elastomers other than these.
- the ⁇ -olefin polymer (E) is, for example, a polymer of ⁇ -olefin having 2 to 20 carbon atoms (however, excluding the above-mentioned copolymers (A) and (B)), and has 2 to 20 carbon atoms. Examples thereof include homopolymers or copolymers of ⁇ -olefins.
- Examples of the ⁇ -olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene and 1-tetradecene.
- Linear ⁇ -olefins such as 1-hexadecene, 1-octadecene, 1-eicosene; isobutene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- Branches of 1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like
- the state ⁇ -olefin can be mentioned. Among these, ⁇ -olefins having 15 or less carbon atoms are preferable, and ⁇ -olefins having 10 or less carbon atoms are more preferable.
- the ⁇ -olefin polymer (E) can further have a structural unit derived from the above-mentioned other polymerizable compounds in the copolymer (A) as long as the object of the present invention is not impaired.
- the content ratio of the structural unit derived from the other polymerizable compound is usually 10 mol% or less, preferably 5 in 100 mol% of all the structural units constituting the (E). It is mol% or less, more preferably 3 mol% or less.
- ⁇ -olefin polymer (E) examples include low-density polyethylene, high-density polyethylene, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, and ethylene / propylene / 1-butene random.
- Polymers ethylene / 1-hexene random copolymers, ethylene / 1-octene random copolymers, ethylene / propylene / ethylidenenorbornene random copolymers, ethylene / propylene / 1-butene / ethylidenenorbornene random copolymers, Ethylene copolymers such as ethylene / 1-butene / 1-octene random copolymers, propylene homopolymers, propylene / 1-butene random copolymers, propylene / 1-hexene random copolymers, propylene / 1-octene
- a propylene copolymer such as a random copolymer, a 1-butene homopolymer, a 1-butene / 1-hexene random copolymer, a butene copolymer such as 1-butene / 1-octene random copolymer, 4- Examples thereof include 4-methyl
- the ultimate viscosity [ ⁇ ] E of the ⁇ -olefin polymer (E) measured in decalin at 135 ° C. is usually 0.1 to 10 dL / g, preferably 0.5 to 5 dL / g.
- the melting point (Tm) measured by the differential scanning calorimetry (DSC) of the ⁇ -olefin polymer (E) is not particularly limited, but is preferably 60 ° C. or higher, more preferably 70 to 300 ° C., for the reasons of heat resistance and strength. preferable.
- the ⁇ -olefin polymer (E) can be produced, for example, by a conventionally known method using a vanadium-based catalyst, a titanium-based catalyst, a metallocene-based catalyst, or the like.
- the resin composition of the present embodiment can contain one kind or two or more kinds of ⁇ -olefin polymers (E).
- the content of the ⁇ -olefin polymer (E) in the resin composition of the present embodiment is usually 50 parts by mass or less with respect to the total content of the copolymers (A) and (B) of 100 parts by mass. It is preferably 40 parts by mass or less.
- the content of the 4-methyl-1-pentene homopolymer in the resin composition of the present embodiment is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less. be.
- the resin composition of the present invention can contain conventionally known additives.
- Additives include, for example, secondary antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. Examples include fillers and hydrochloric acid absorbers.
- the content of the additive is not particularly limited, but is usually 0 to 50 parts by mass, preferably 0 to 10 parts by mass, respectively, with respect to 100 parts by mass of the polymer component including the copolymers (A) and (B). It is a department.
- the resin composition of the present invention may contain one or more additives.
- Manufacturing method of resin composition The method for producing the resin composition of the present invention will be described.
- the resin composition of the present invention can be obtained, for example, by mixing the above-mentioned copolymers (A) and (B) with other polymer components and additives, if necessary. ..
- the mixture of the copolymers (A) and (B) can also be obtained by the above-mentioned multi-stage polymerization method.
- each component various known methods, for example, a method of mixing each component using a device such as a plast mill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler, a blender, a kneader ruder, etc .; A method can be adopted in which the obtained mixture is further melt-kneaded with an apparatus such as a uniaxial extruder, a twin-screw extruder, a kneader, and a Banbury mixer, and then the obtained melt-kneaded product is granulated or pulverized.
- a device such as a plast mill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler, a blender, a kneader ruder, etc .
- a method can be adopted in which the obtained mixture is further melt-kneaded with an apparatus such as a uniaxial extruder, a twin-screw extru
- the resin composition of the present invention has a temperature of 135 ° C. or higher from the viewpoint of improving the stretchability of the obtained molded product when measured by a cross-separation chromatograph (CFC) using an infrared spectrophotometer in the detection unit.
- the amount of the eluted component in the range of is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, based on the total amount of the eluted component in the resin composition at 0 to 145 ° C. ..
- a 4-methyl-1-pentene homopolymer usually corresponds to the elution component in the range of 135 ° C. or higher.
- the molded product of the present invention comprises the resin composition of the present invention, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, stamping molding, vacuum molding, calendar. It is obtained by a known heat molding method such as molding, filament molding, foam molding, powder slush molding and the like.
- the molded product of the present invention may be a molded product obtained by further processing a primary molded product obtained by a method such as extrusion molding, injection molding, or solution casting by a method such as blow molding or stretching. ..
- a film is preferable as the molded product of the present invention.
- the film of the present invention has small surface roughness and smoothness in addition to the conventional characteristics of 4-methyl-1-pentene copolymer such as heat resistance, mechanical characteristics, electrical characteristics (dielectric breakdown strength, etc.), and releasability. It is also excellent in stretchability and flexibility.
- the film of the present invention contains the resin composition of the present invention, and can be obtained, for example, by melt molding in the range of usually 180 to 300 ° C.
- the thickness of the film of the present invention is usually 1000 ⁇ m or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, still more preferably 30 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
- the lower limit of the thickness of the film of the present invention is not particularly limited, but is usually 1 ⁇ m.
- the film of the present invention has a film surface roughness (Ra) of preferably less than 100 nm, more preferably 60 nm or less, and further preferably 40 nm or less.
- the surface roughness (Ra) of the film is preferably close to 0 without any limitation on the lower limit because the film of the present invention is preferably smoother.
- the film of the present invention has a film surface roughness (Rz) of preferably less than 500 nm, more preferably 400 nm or less, and further preferably 300 nm or less.
- the surface roughness (Rz) of the film is preferably close to 0 without any limitation on the lower limit because the film of the present invention is preferably smoother.
- the film of the present invention has at least two 4-methyl-1-pentene copolymers such as the 4-methyl-1-pentene copolymer (A) and the 4-methyl-1-pentene copolymer (B). Contains coalescing.
- examples of the film of the present invention include films satisfying the following requirements (I) to (III).
- (I) Contains at least two 4-methyl-1-pentene copolymers.
- (II) The surface roughness (Ra) of the film is less than 100 nm.
- (III) The surface roughness (Rz) of the film is less than 500 nm.
- the film of the present invention may be, for example, a single-layer film obtained from the resin composition of the present invention, or a laminated film having a layer obtained from the resin composition of the present invention.
- a method for obtaining a laminated film for example, a method of laminating another layer on a surface layer film previously obtained by T-die molding or inflation molding by a known laminating method such as extrusion lamination or extrusion coating; A method in which films are independently molded and then each film is laminated by dry lamination; a coextrusion molding method in which a plurality of components are subjected to a multi-layer extruder to be molded can be mentioned.
- the surface layer film is, for example, a layer obtained from the resin composition of the present invention.
- Stretched film For example, a film for capacitors;
- Semiconductor process film For example, dicing tape, back grind tape, die bonding film, polarizing plate film;
- Packaging film For example, food packaging film, stretch film, wrap film, breathable film, shrink film, easy peel film;
- Separator For example, battery separator, separator for lithium ion battery, electrolyte membrane for fuel cell, adhesive / adhesive separator;
- Films for electronic members For example, diffusion films, reflective films, radiation resistant films, gamma ray resistant films, porous films; Release film: For example, for flexible printed substrates, for ACM substrates, for rigid flexible substrates, for advanced composite materials, for curing carbon fiber composites, for curing glass fiber composites, for curing aramid fiber composites, for curing nanocomposites.
- polarizing plate For, filler filler curing, urethane curing, epoxy curing, semiconductor encapsulation, polarizing plate, diffusion sheet, prism sheet, reflective sheet, fuel cell or various rubber sheet release films;
- Surface protective film For example, protective film for polarizing plate, liquid crystal panel, optical component, lens, electrical component / electric appliance, mobile phone, personal computer or touch panel, masking film;
- Building material film For example, window film for building material, film for laminated glass, bulletproof material, film for bulletproof glass, heat shield sheet, heat shield film; Can be mentioned.
- the film of the present invention is preferably a stretched film.
- a primary molded product obtained by molding the resin composition of the present invention into a film or sheet by a T-die extrusion molding method or the like is further uniaxially stretched.
- it is preferably a stretched film obtained by biaxial stretching.
- the draw ratio can be 1.05 to 20 times independently in the MD direction and the TD direction.
- the stretched film include a film for a capacitor.
- Capacitor films may need to be thinned by stretching and increased in strength by orientation.
- a film for a capacitor having excellent thin film processability and high strength can be obtained.
- the film for a capacitor using the resin composition of the present invention tends to have a small surface roughness, excellent smoothness, and can maintain transparency even after stretching.
- the thickness of the film for a capacitor of the present invention is preferably 1 to 20 ⁇ m, more preferably 2 to 15 ⁇ m, and even more preferably 2.5 to 10 ⁇ m.
- the capacitor film of the present invention preferably has a ratio V (120 ° C.) / V (23 ° C.) of the dielectric breakdown strength V (23 ° C.) at 23 ° C. and the dielectric breakdown strength V (120 ° C.) at 150 ° C. Is 0.50 or more, more preferably 0.55 or more, still more preferably 0.60 or more.
- the electrical characteristics during long-term power application are stable, and it is useful as a capacitor.
- the higher the upper limit of the ratio the better the electrical characteristics, but in one embodiment, it may be 0.95.
- the capacitor film of the present invention has a dielectric breakdown strength V (120 ° C.) at 120 ° C., preferably 200 kV / mm or more, and more preferably 250 kV / mm or more.
- the upper limit of the dielectric breakdown strength V (120 ° C.) is not particularly limited, but may be 700 kV / mm in one embodiment.
- the film for a capacitor of the present invention is obtained by biaxially stretching a film made of the resin composition. More specifically, the capacitor film is produced by forming a film using the resin composition by, for example, a T-die extrusion molding method in the range of 180 to 300 ° C., and biaxially stretching the film. To.
- the stretch ratio is preferably 1.1 to 100 times, more preferably 2 to 90 times, still more preferably 4 to 80 times, and particularly preferably 10 to 60 times in terms of area.
- the draw ratio is within the above range, the electrical characteristics required for the film capacitor are likely to be exhibited.
- the stretching method either a sequential biaxial stretching method or a simultaneous biaxial stretching method may be used, but the sequential biaxial stretching method is preferable from the viewpoint of film formation stability and thickness uniformity.
- the sequential biaxial stretching method for example, an unstretched film is obtained by extruding the resin composition onto a cooling roll by a T-die extrusion molding method or the like. Next, this unstretched film is stretched in the film longitudinal direction (MD direction) through a preheating roll set to a predetermined stretching temperature (longitudinal stretching). Then, the film is stretched in the film width direction (TD direction) while passing through a heating oven set to a predetermined stretching temperature (transverse stretching).
- the stretching temperature for both longitudinal stretching and transverse stretching is preferably between the glass transition temperature (Tg) and the melting point (Tm) of a polymer such as 4-methyl-1-pentene copolymer (A) used for stretching. ..
- Tg glass transition temperature
- Tm melting point
- the stretching temperature is preferably 85 ° C. to 210 ° C., more preferably 90 ° C. to 210 ° C., and particularly preferably 90 ° C. to 180 ° C.
- the draw ratio is usually 1.2 to 11.0 times, preferably 1.4 to 9.5 times, and more preferably 2 to 9 times independently in the film longitudinal direction and the film width direction, respectively.
- the film may be re-stretched in the film longitudinal direction or the film width direction, or in the film longitudinal direction and the film width direction. Further, after biaxial stretching, annealing treatment may be performed.
- the annealing temperature is usually 100 to 230 ° C, preferably 130 to 220 ° C.
- Elution category The boundary of the elution category is 0, 5, 10, 15, 20, 25, 30, 35, 50, 70, 90, 95, 100, 102, 104, 106 ° C in the range of 0 to 108 ° C. In the range of 108 to 135 ° C., the temperature was set in 1 ° C increments, and in the range of 135 to 145 ° C., the temperature was set to 135,140,145 ° C., and the elution amount in each category was evaluated.
- GPC column Shodex HT-806M x 3 (Showa Denko)
- GPC column temperature 145 ° C
- GPC column calibration monodisperse polystyrene (Tosoh)
- Molecular weight calibration method Standard calibration method (polystyrene conversion)
- Mobile phase o-dichlorobenzene (ODCB), BHT added Flow rate: 1.0 mL / min [Manufacturing Examples 1 to 24] Obtained by changing the ⁇ -olefin to the ⁇ -olefin shown in Table 1-1 and Table 1-2 according to the polymerization method described in Comparative Example 1 ([0158]) of International Publication No. 2017/150265.
- Tori (2,4-di-t-) as a secondary antioxidant with respect to 35 parts by mass of the copolymer (A-1) and 65 parts by mass of the copolymer (B-1) obtained in the above production example.
- 0.1 part by mass of butylphenyl) phosphate and 0.1 part by mass of n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butylphenyl) propionate as a heat-resistant stabilizer were blended. ..
- the obtained pellets were supplied to a single-screw extruder (manufactured by Tanaka Iron Works Co., Ltd.), melt-kneaded at a cylinder of 270 ° C., and melt-extruded into a film from a T-shaped slit die at a die temperature of 270 ° C.
- the obtained film was taken up under the condition of a taking-up speed of 0.9 m / min while being brought into close contact with a metal cooling roll controlled at 80 ° C. by air pressure.
- An unstretched film having a thickness of 200 ⁇ m was obtained by cooling and solidifying.
- Examples 2 to 10 Comparative Examples 1 to 2
- the unstretched film was blended in the same manner as in Example 1 except that the copolymers shown in Table 2 were blended as the 4-methyl-1-pentene copolymer and the blending amount was the blending amount shown in Table 2. And a biaxially stretched film was obtained. Then, a sample for evaluation was obtained in the same manner as in Example 1.
- Examples 11 to 14 A 4-methyl-1-pentene copolymer, an unstretched film and a biaxially stretched film were obtained in the same manner as in Example 3 except that the stretching conditions shown in Table 2 were changed. Then, a sample for evaluation was obtained in the same manner as in Example 1.
- ⁇ Melting point (Tm)> the biaxially stretched film obtained above was used as a sample.
- the melting point was measured by the following procedure using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc. First, about 5 mg of the sample was placed in an aluminum pan for measurement and sealed. The temperature was raised to 290 ° C. at 100 ° C./min, held at 290 ° C. for 5 minutes, then lowered to -100 ° C. at 10 ° C./min, and then raised from -100 ° C. to 290 ° C. at 10 ° C./min. ..
- the melting point (Tm) was calculated from the peak apex of the crystal melting peak in the calorific value curve at the time of the second temperature rise. When multiple peaks were detected, the one with the highest temperature was defined as the melting point (Tm).
- ⁇ Dielectric breakdown strength The dielectric breakdown strength (V / ⁇ m) was measured according to ASTM-D149 using a dielectric breakdown tester manufactured by Yamayo Tester Co., Ltd. For the sample for evaluation, a voltage was applied at a boosting speed of 500 V / sec at 23 ° C. and 120 ° C., and the dielectric breakdown withstand voltage was measured to determine the dielectric breakdown strength (V / ⁇ m). Next, these ratios V (120 ° C.) / V (23 ° C.) were calculated from the dielectric breakdown strength V (23 ° C.) at 23 ° C. and the dielectric breakdown strength V (120 ° C.) at 120 ° C.
- ⁇ Average thickness> The thickness of the evaluation sample was measured at 10 points in the width direction and 10 points in the length direction using a micrometer, and the average value was taken as the thickness of the biaxially stretched film or the unstretched film.
- ⁇ Surface roughness Ra> Using a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd., the state of unevenness on the surface of the sample for evaluation was evaluated as a roughness curve.
- the value obtained by the following formula expressed in nanometers (nm) was defined as Ra.
- the measurement length was 10 mm.
- Ra was less than 100, it was evaluated as AA, and when it was 100 or more, it was evaluated as BB.
- ⁇ Surface roughness Rz> Using a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd., the state of unevenness on the surface of the sample for evaluation was evaluated as a roughness curve. Only the measured length was extracted from the roughness curve in the direction of the average line, and the measurement was performed in the direction of the vertical magnification from the average line of the extracted portion. The sum of the average value of the absolute values of the elevation (Yp) of the highest peak to the fifth peak and the average value of the absolute value (Yv) of the elevation (Yv) of the lowest valley bottom to the fifth is as shown in the following formula. The value expressed in nanometers (nm) was taken as Rz. The measurement length was 10 mm.
- Rz was less than 500, it was evaluated as AA, and when it was 500 or more, it was evaluated as BB.
- Table 2 shows the evaluation results of the above physical properties of each film.
Abstract
Description
[1] 下記要件(A-a)~(A-d)を満たす4-メチル-1-ペンテン共重合体(A)と、下記要件(B-a)~(B-d)を満たす4-メチル-1-ペンテン共重合体(B)とを含有し、
下記要件(1)および(2)を満たす樹脂組成物。
(A-a)4-メチル-1-ペンテンから導かれる構成単位の量(U1)が80.0~99.9モル%であり、炭素数2~20の直鎖状α-オレフィンから選ばれる少なくとも1種から導かれる構成単位の総量(U2)が20.0~0.1モル%(ただし、前記U1および前記U2の合計を100モル%とする)である。
(A-b)135℃のデカリン中で測定した極限粘度[η]Aが、0.5~5.0dL/gである。
(A-c)検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で前記共重合体(A)を測定した場合に、100~140℃の範囲に溶出成分量のピークが少なくとも1つ存在する。
(A-d)前記CFCで前記共重合体(A)を測定した場合に、100~140℃の範囲の溶出成分における、重量平均分子量(Mw)と数平均分子量(Mn)との比である分子量分布(Mw/Mn)が、1.0~4.5である。
(B-a)4-メチル-1-ペンテンから導かれる構成単位の量(U3)が20.0~98.0モル%であり、炭素数2~20の直鎖状α-オレフィンから選ばれる少なくとも1種から導かれる構成単位の総量(U4)が80.0~2.0モル%(ただし、前記U3および前記U4の合計を100モル%とする)である。
(B-b)135℃のデカリン中で測定した極限粘度[η]Bが、2.0~8.0dL/gである。
(B-c)検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で前記共重合体(B)を測定した場合に、0℃以上100℃未満の範囲に溶出成分量のピークが少なくとも1つ存在する。
(B-d)前記CFCで前記共重合体(B)を測定した場合に、0℃以上100℃未満の範囲の溶出成分における、重量平均分子量(Mw)と数平均分子量(Mn)との比である分子量分布(Mw/Mn)が、1.0~7.0である。
(1)前記共重合体(A)および(B)の含有量の合計を100質量部とした場合に、前記共重合体(A)の含有量が5~95質量部であり、前記共重合体(B)の含有量が95~5質量部である。
(2)前記要件(A-a)に記載のU2(モル%)を前記要件(B-a)に記載のU4(モル%)から差し引いた値(U4-U2)が、0モル%以上、6.5モル%以下である。
[2] 前記共重合体(A)および共重合体(B)の含有量の合計を100質量部とした場合に、前記共重合体(A)の含有量が5質量部以上50質量部未満であり、前記共重合体(B)の含有量が50質量部を超え95質量部以下である、[1]に記載の樹脂組成物。
[3] 前記共重合体(A)および(B)における直鎖状α-オレフィンが、それぞれ独立に炭素数10~20の直鎖状α-オレフィンである、[1]または[2]に記載の樹脂組成物。
[4] [1]~[3]のいずれかに記載の樹脂組成物を含んでなる成形体。
[5] [1]~[3]のいずれかに記載の樹脂組成物を含んでなるフィルム。
[6] 下記要件(I)~(III)を満たすフィルム。
(I)少なくとも2種の4-メチル-1-ペンテン共重合体を含有する。
(II)フィルムの表面粗さ(Ra)が100nm未満である。
(III)フィルムの表面粗さ(Rz)が500nm未満である。
[7] キャパシタ用フィルムである、[5]または[6]に記載のフィルム。
[樹脂組成物]
本発明の樹脂組成物は、以下に説明する4-メチル-1-ペンテン共重合体(A)と4-メチル-1-ペンテン共重合体(B)とを含有し、下記要件(1)および(2)を満たす。
4-メチル-1-ペンテン共重合体(A)(以下「共重合体(A)」ともいう)は、4-メチル-1-ペンテンから導かれる構成単位と、炭素数2~20の直鎖状α-オレフィンから導かれる構成単位とを有し、下記要件(A-a)~(A-d)を満たす。共重合体(A)は、下記要件(A-e)をさらに満たすことが好ましい。
共重合体(A)において、4-メチル-1-ペンテンから導かれる構成単位の量(U1)は80.0~99.9モル%であり、炭素数2~20の直鎖状α-オレフィンから選ばれる少なくとも1種から導かれる構成単位の総量(U2)は20.0~0.1モル%である。U1は、好ましくは85.0~99.9モル%、より好ましくは90.0~99.9モル%である。U2は、好ましくは15.0~0.1モル%、より好ましくは10.0~0.1モル%である。ただし、前記U1および前記U2の合計を100モル%とする。なお、この100モル%とは、前記U1および前記U2の合計を意味するのであって、共重合体(A)を構成する全構成単位100モル%を意味するものではない。
共重合体(A)は、本発明の目的を損なわない範囲で、4-メチル-1-ペンテンおよび炭素数2~20の直鎖状α-オレフィン以外の他の重合性化合物から導かれる構成単位をさらに有することができる。他の重合性化合物としては、例えば、4-メチル-1-ペンテン以外の炭素数20以下の分岐状α-オレフィン;スチレン、ビニルシクロペンテン、ビニルシクロヘキサン、ビニルノルボルナン等の環状構造を有するビニル化合物;酢酸ビニル等のビニルエステル;無水マレイン酸等の不飽和有機酸またはその誘導体;ブタジエン、イソプレン、ペンタジエン、2,3-ジメチルブタジエン等の共役ジエン;1,4-ヘキサジエン、1,6-オクタジエン、2-メチル-1,5-ヘキサジエン、6-メチル-1,5-ヘプタジエン、7-メチル-1,6-オクタジエン、ジシクロペンタジエン、シクロヘキサジエン、ジシクロオクタジエン、メチレンノルボルネン、5-ビニルノルボルネン、5-エチリデン-2-ノルボルネン、5-メチレン-2-ノルボルネン、5-イソプロピリデン-2-ノルボルネン、6-クロロメチル-5-イソプロペンル-2-ノルボルネン、2,3-ジイソプロピリデン-5-ノルボルネン、2-エチリデン-3-イソプロピリデン-5-ノルボルネン、2-プロペニル-2,2-ノルボルナジエン等の非共役ポリエンが挙げられる。
共重合体(A)の、135℃のデカリン中で測定した極限粘度[η]Aは、0.5~5.0dL/gである。前記[η]Aは、好ましくは0.5~4.5dL/g、より好ましくは0.5~4.0dL/gである。
検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で共重合体(A)を測定した場合に、100~140℃の範囲に溶出成分量のピークが少なくとも1つ存在する。前記溶出成分量のピークは、好ましくは100~135℃の範囲に存在する。なお、前記溶出成分量のピークの位置は、ピークトップの位置にて判断する。
要件(A-c)を満たす共重合体(A)は、結晶性が高い成分を含み、得られる成形体は高い耐熱性を示す傾向にある。
検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で共重合体(A)を測定した場合に、100~140℃の範囲の溶出成分における、重量平均分子量(Mw)と数平均分子量(Mn)との比である分子量分布(Mw/Mn)は、1.0~4.5である。前記Mw/Mnは、好ましくは1.5~4.5、より好ましくは2.0~4.5である。前記各平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定され、ポリスチレン換算の値である。
《要件(A-e)》
共重合体(A)は、示差走査熱量計(DSC)により測定した融点(Tm)が、好ましくは210~260℃、より好ましくは220~260℃、さらに好ましくは225~260℃である。
<4-メチル-1-ペンテン共重合体(B)>
4-メチル-1-ペンテン共重合体(B)(以下「共重合体(B)」ともいう)は、4-メチル-1-ペンテンから導かれる構成単位と、炭素数2~20の直鎖状α-オレフィンから導かれる構成単位とを有し、下記要件(B-a)~(B-d)を満たす。共重合体(B)は、下記要件(B-e)をさらに満たすことが好ましい。共重合体(B)は、下記要件(B-f)をさらに満たすことが好ましい。
共重合体(B)において、4-メチル-1-ペンテンから導かれる構成単位の量(U3)は20.0~98.0モル%であり、炭素数2~20の直鎖状α-オレフィンから選ばれる少なくとも1種から導かれる構成単位の総量(U4)は80.0~2.0モル%である。U3は、好ましくは20.0~97.0モル%、より好ましくは25.0~97.0モル%である。U4は、好ましくは80.0~3.0モル%、より好ましくは75.0~3.0モル%である。ただし、前記U3および前記U4の合計を100モル%とする。なお、この100モル%とは、前記U3および前記U4の合計を意味するのであって、共重合体(B)を構成する全構成単位100モル%を意味するものではない。
共重合体(B)は、本発明の目的を損なわない範囲で、共重合体(A)において前述した他の重合性化合物から導かれる構成単位をさらに有することができる。
共重合体(B)の、135℃のデカリン中で測定した極限粘度[η]Bは、2.0~8.0dL/gである。前記[η]Bは、好ましくは2.5~7.5dL/g、より好ましくは2.7~7.0dL/g、さらに好ましくは3.0~7.0dL/gであり、特に好ましくは3.5~7.0dL/gである。
と、フィルムとした際の延伸性により優れ、また剛性により優れる傾向にある。
検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で共重合体(B)を測定した場合に、0℃以上100℃未満の範囲に溶出成分量のピークが少なくとも1つ存在する。前記溶出成分量のピークは、好ましくは0~80℃の範囲に存在する。なお、前記溶出成分量のピークの位置は、ピークトップの位置にて判断する。
要件(B-c)を満たす共重合体(B)は、共重合体(A)と比較して結晶性が低い成分を含み、得られる成形体は高い柔軟性を示す傾向にある。
検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で共重合体(B)を測定した場合に、0℃以上100℃未満の範囲の溶出成分における、重量平均分子量(Mw)と数平均分子量(Mn)との比である分子量分布(Mw/Mn)は、1.0~7.0である。前記Mw/Mnは、好ましくは1.0~6.5、より好ましくは1.2~6.0である。前記各平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定され、ポリスチレン換算の値である。
《要件(B-e)》
検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で共重合体(B)を測定した場合に、一実施態様において、0℃の溶出成分の数平均分子量(Mn)は5000以上であるか、または0℃の溶出成分が存在しない。
共重合体(B)は、示差走査熱量計(DSC)により測定した融点(Tm)が、好ましくは220℃以下であるか、またはDSC測定において融点を示すピークが出現せず、より好ましくは融点(Tm)が210℃以下であるか、またはDSC測定において融点を示すピークが出現せず、さらに好ましくは融点(Tm)が100~200℃であるか、またはDSC測定において融点を示すピークが出現しない。
<要件(1)>
本発明の樹脂組成物においては、前記共重合体(A)および(B)の含有量の合計を100質量部とした場合に、前記共重合体(A)の含有量が5~95質量部であり、前記共重合体(B)の含有量が95~5質量部である。
さらに、本発明の樹脂組成物においては、共重合体(B)の含有量が共重合体(A)の含有量よりも多いと、延伸性がより向上する点で好ましい。具体的には、共重合体(A)および(B)の含有量の合計を100質量部とした場合に、共重合体(A)の含有量は、好ましくは5質量部以上50質量部未満、より好ましくは10~40質量部、さらに好ましくは15~38質量部であり、特に好ましくは15~35質量部であり;共重合体(B)の含有量は、好ましくは50質量部を超え95質量部以下、より好ましくは60~90質量部、さらに好ましくは62~85質量部であり、特に好ましくは65~85質量部である。
<要件(2)>
本発明の樹脂組成物においては、前記要件(A-a)に記載のU2(モル%)を前記要件(B-a)に記載のU4(モル%)から差し引いた値(U4-U2)が、0モル%以上、6.5モル%以下である。
コモノマー含有量=(1.4モル%×35質量%+4.6モル%×75質量%)/(35質量%+75質量%)=3.4モル%。
本発明の樹脂組成物中の、共重合体(A)および共重合体(B)の合計の含有割合は、通常は50質量%以上、好ましくは60質量%以上、より好ましくは70質量%以上である。共重合体(A)および共重合体(B)の含有割合の上限は樹脂組成物100質量%であってもよい。前記樹脂組成物がその他の成分(例えば、後述するその他の重合体成分、添加剤)を含有する場合は、前記上限はその他の成分の含有割合により画定される。
<共重合体(A)および(B)の製造方法>
共重合体(A)および共重合体(B)は、それぞれ、例えば、4-メチル-1-ペンテンと、炭素数2~20の直鎖状α-オレフィンと、必要に応じて前記他の重合性化合物とを重合することにより得ることができる。前記重合をメタロセン触媒の存在下で行うことにより、以上に記載した各要件を満たす共重合体(A)および(B)を好適に得ることができる。
メタロセン化合物(a)と、
担体(b)と
から少なくとも構成される触媒が挙げられる。
メタロセン化合物(a)は、例えば、一般式(1)または(2)で表される。
Aは、不飽和結合および/または芳香族環を含んでいてもよい炭素数2~20の2価の炭化水素基である。Aは、Yと共に形成する環を含めて2つ以上の環構造を含んでいてもよい。
Qは、ハロゲン原子、炭素数1~20の炭化水素基、アニオン配位子、または孤立電子対で配位可能な中性配位子である。jが2以上であるときは、各々のQは同一でも異なってもよい。
R1~R14における炭化水素基としては、例えば、炭素数1~20の炭化水素基が挙げられ、具体的には、炭素数1~20のアルキル基、炭素数3~20のシクロアルキル基、炭素数7~20のアリールアルキル基、炭素数6~20のアリール基、炭素数7~20のアルキルアリール基が挙げられる。
一般式(1)の場合、R13およびR14はYと結合し、架橋部として置換メチレン基または置換シリレン基を構成する。置換メチレン基および置換シリレン基の具体例としては、例えば、ジアルキルメチレン、ジシクロアルキルメチレン、アルキルシクロアルキルメチレン、アルキルアリールメチレン、ジアリールメチレン、ジアルキルシリレン、ジシクロアルキルシリレン、アルキルシクロアルキルシリレン、アルキルアリールシリレン、ジアリールシリレン、これらがハロゲン化された基が挙げられる。
式[A2]において2つの置換基が互いに結合して形成された環(スピロ環、付加的な環)としては、例えば、脂環、芳香環が挙げられる。具体的には、シクロヘキサン環、ベンゼン環、水素化ベンゼン環、シクロペンテン環が挙げられ、好ましくはシクロヘキサン環、ベンゼン環および水素化ベンゼン環である。また、このような環構造は、環上にアルキル基等の置換基をさらに有していてもよい。
R2b、R3b、R6bおよびR7bは、好ましくは炭素数1~20の炭化水素基である。また、R2bとR3bが互いに結合して環を形成し、かつR6bとR7bが互いに結合して環を形成していてもよい。このような置換フルオレニル基としては、例えば、ベンゾフルオレニル基、ジベンゾフルオレニル基、オクタヒドロジベンゾフルオレニル基、1,1,4,4,7,7,10,10-オクタメチル-2,3,4,7,8,9,10,12-オクタヒドロ-1H-ジベンゾ[b,h]フルオレニル基、1,1,3,3,6,6,8,8-オクタメチル-2,3,6,7,8,10-ヘキサヒドロ-1H-ジシクロペンタ[b,h]フルオレニル基、1',1',3',6',8',8'-ヘキサメチル-1'H,8'H-ジシクロペンタ[b,h]フルオレニル基が挙げられる。
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。
jは1~4の整数であり、好ましくは2である。
担体(b)は、好ましくは粒子状であり、その表面および内部にメタロセン化合物(a)を固定化させることで、前記メタロセン触媒が形成される。このような形態の触媒は一般にメタロセン担持触媒と呼ばれる。
有機アルミニウム化合物(b-1)としては、例えば、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、トリノルマルオクチルアルミニウム等のトリアルキルアルミニウム、ジイソブチルアルミニウムハイドライド等のジアルキルアルミニウムハイドライド、トリシクロアルキルアルミニウムや、アルミノキサンに代表される有機アルミニウムオキシ化合物が挙げられる。また、有機アルミニウム化合物(b-1
)としては、例えば、ホウ素原子を含む有機アルミニウムオキシ化合物や、国際公開第2005/066191号、国際公開第2007/131010号に例示されているようなハロゲンを含むアルミノキサン、国際公開第2003/082879号に例示されているようなイオン性アルミノキサンを挙げることもできる。
固体状アルミノキサンは、触媒担体として機能する。このため、固体状アルミノキサンの他に、触媒担体として、例えば、シリカ、アルミナ、シリカ・アルミナ、塩化マグネシウム等の固体状無機担体、またはポリスチレンビーズ等の固体状有機担体を用いなくともよい。
《有機化合物成分(c)》
メタロセン触媒は、さらに必要に応じて、有機化合物成分(c)を含有することもできる。有機化合物成分(c)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。有機化合物成分(c)としては、前述の有機アルミニウム化合物(b-1)を用いうる。その他に例えば、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が挙げられる。
共重合体(A)および(B)を得るための4-メチル-1-ペンテンと炭素数2~20の直鎖状α-オレフィンとの重合は、溶解重合、懸濁重合等の液相重合法または気相重合法のいずれにおいても実施できる。液相重合法においては、不活性炭化水素溶媒を用いることができ、具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロペンタン、メチルシクロヘキサン等の脂環族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;エチレンクロリド、クロロベンゼン、ジクロロメタン、トリクロロメタン、テトラクロロメタン等のハロゲン化炭化水素;これらから選ばれる2種以上の混合溶媒が挙げられる。また、4-メチル-1-ペンテンを含むオレフィン自身を重合溶媒として用いることができる。
(i)成分(a)と成分(b)を任意の順序で重合器に添加する方法。
(ii)成分(a)を成分(b)に担持した触媒成分を重合器に添加する方法。
また、成分(b)に成分(a)が担持された固体触媒成分においては、4-メチル-1-ペンテン、3-メチル-1-ペンテン等のオレフィンが予備重合されていてもよく、予備重合された固体触媒成分上に、さらに触媒成分が担持されていてもよい。
、成分(b-3)と成分(a)中の全遷移金属原子(M)とのモル比〔(b-3)/M〕が通常は10~10000、好ましくは30~2000、さらに好ましくは150~500となるような量で用いることができる。
工程(1)では、4-メチル-1-ペンテン共重合体(A)をスラリー重合により製造する。工程(1)において、4-メチル-1-ペンテンおよび炭素数2~20の直鎖状α-オレフィンの供給量比は、それぞれから導かれる構成単位の量が上述した範囲にあるように設定される。
工程(2)では、工程(1)で得られた共重合体(A)の存在下で、4-メチル-1-ペンテン共重合体(B)をスラリー重合により製造する。工程(2)において、4-メチル-1-ペンテンおよび炭素数2~20の直鎖状α-オレフィンの供給量比は、それぞれから導かれる構成単位の量が上述した範囲にあるように設定される。
工程(2)で得られた、共重合体(A)および(B)を含有する4-メチル-1-ペンテン系重合体粒子を含むスラリーを、固液分離する、例えば濾過することにより、前記粒子を分離回収することができる。
上記多段重合法で得られた4-メチル-1-ペンテン系重合体粒子、例えば上記固液分離工程で得られた粒子に対しては、上記方法で製造した後に、必要に応じて公知の触媒失活処理工程、触媒残渣除去工程、乾燥工程等の後処理工程を行ってよい。
<その他の重合体成分>
本実施形態の樹脂組成物は、上述した共重合体(A)および(B)以外のその他の重合体成分をさらに含有することができる。その他の重合体成分としては、例えば、α-オレフィン重合体(E)(ただし、上述した共重合体(A)および(B)を除く)や、これら以外のエラストマーが挙げられる。
α-オレフィン重合体(E)において、他の重合性化合物から導かれる構成単位の含有割合は、前記(E)を構成する全構成単位100モル%中、通常は10モル%以下、好ましくは5モル%以下、より好ましくは3モル%以下である。
α-オレフィン重合体(E)の示差走査熱量計(DSC)により測定した融点(Tm)は、特に限定されないが、耐熱性、強度の理由から、60℃以上が好ましく、70~300℃がより好ましい。
本実施形態の樹脂組成物は、1種または2種以上のα-オレフィン重合体(E)を含有することができる。
本発明の樹脂組成物は、従来公知の添加剤を含有することができる。
添加剤としては、例えば、二次抗酸化剤、耐熱安定剤、耐候安定剤、帯電防止剤、スリップ剤、アンチブロッキング剤、防曇剤、滑剤、染料、顔料、天然油、合成油、ワックス、充填剤、塩酸吸収剤が挙げられる。添加剤の含有量は特に制限されないが、共重合体(A)および(B)等を含む重合体成分100質量部に対して、それぞれ、通常は0~50質量部、好ましくは0~10質量部である。
[樹脂組成物の製造方法]
本発明の樹脂組成物の製造方法について説明する。
本発明の成形体は、本発明の樹脂組成物を含んでなり、例えば、押出成形、射出成形、インフレーション成形、ブロー成形、押出ブロー成形、射出ブロー成形、プレス成形、スタンピング成形、真空成形、カレンダー成形、フィラメント成形、発泡成形、パウダースラッシュ成形等の公知の熱成形方法により得られる。
本発明の成形体としてはフィルムが好ましい。本発明のフィルムは、耐熱性、機械物性、電気特性(絶縁破壊強さ等)、離型性といった従来からある4-メチル-1-ペンテン共重合体の特性に加え、表面粗さが小さく平滑であり、また延伸性および柔軟性に優れる。本発明のフィルムは、本発明の樹脂組成物を含んでなり、例えば、通常は180~300℃の範囲で溶融成形して得ることができる。本発明のフィルムの厚さは、通常は1000μm以下、好ましくは100μm以下、より好ましくは50μm以下、さらに好ましくは30μm以下、特に好ましくは15μm以下である。本発明のフィルムの厚さの下限は特に限定されないが、通常1μmである。
(I)少なくとも2種の4-メチル-1-ペンテン共重合体を含有する。
(II)フィルムの表面粗さ(Ra)が100nm未満である。
(III)フィルムの表面粗さ(Rz)が500nm未満である。
延伸フィルム:例えば、キャパシタ用フィルム;
半導体工程フィルム:例えば、ダイシングテープ、バックグラインドテープ、ダイボンディングフィルム、偏光板用フィルム;
包装用フィルム:例えば、食品包装用フィルム、ストレッチフィルム、ラップフィルム、通気性フィルム、シュリンクフィルム、イージーピールフィルム;
セパレーター:例えば、バッテリーセパレーター、リチウムイオン電池用セパレーター、燃料電池用電解質膜、粘着・接着材セパレーター;
電子部材用フィルム:例えば、拡散フィルム、反射フィルム、耐放射線フィルム、耐γ線フィルム、多孔フィルム;
離型フィルム:例えば、フレキシブルプリント基板用、ACM基板用、リジットフレキシブル基板用、先端複合材料用、炭素繊維複合材硬化用、ガラス繊維複合材硬化用、アラミド繊維複合材硬化用、ナノ複合材硬化用、フィラー充填材硬化用、ウレタン硬化用、エポキシ硬化用、半導体封止用、偏光板用、拡散シート用、プリズムシート用、反射シート用、燃料電池用または各種ゴムシート用の離型フィルム;
表面保護フィルム:例えば、偏光板用、液晶パネル用、光学部品用、レンズ用、電気部品・電化製品用、携帯電話用、パソコン用またはタッチパネル用の保護フィルム、マスキングフィルム;
建材フィルム:例えば、建材用ウインドウフィルム、合わせガラス用フィルム、防弾材、防弾ガラス用フィルム、遮熱シート、遮熱フィルム;
が挙げられる。
[キャパシタ用フィルム]
本発明のキャパシタ用フィルムの厚さは、好ましくは1~20μm、より好ましくは2~15μm、さらに好ましくは2.5~10μmである。
[キャパシタ用フィルムの製造方法]
本発明のキャパシタ用フィルムは、前記樹脂組成物からなるフィルムを二軸延伸して得られる。より具体的には、前記キャパシタ用フィルムは、前記樹脂組成物を用いて、例えば180~300℃の範囲でTダイ押出成形法などによりフィルムを形成し、このフィルムを二軸延伸して製造される。
逐次二軸延伸法の場合、例えば、前記樹脂組成物をTダイ押出成形法などによって冷却ロール上に押し出すことによって未延伸フィルムを得る。次いでこの未延伸フィルムを、所定の延伸温度に設定された予熱ロールを経てフィルム長手方向(MD方向)に延伸する(縦延伸)。その後、所定の延伸温度に設定された加熱オーブン内を通過させながらフィルム幅方向(TD方向)に延伸する(横延伸)。
[各種物性の測定法]
<4-メチル-1-ペンテン共重合体中の構成単位含量>
4-メチル-1-ペンテンから導かれる構成単位の量(4-メチル-1-ペンテン含量)および4-メチル-1-ペンテン以外のα-オレフィンから導かれる構成単位の量(α-オレフィン含量)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。
極限粘度[η]は、デカリン溶媒を用いて、135℃で測定した。すなわち重合パウダー、ペレットまたは樹脂塊約20mgをデカリン15mLに溶解し、135℃のオイルバス中で比粘度ηspを測定した。このデカリン溶液にデカリン溶媒を5mL追加して希釈後、同様にして比粘度ηspを測定した。この希釈操作をさらに2回繰り返し、濃度(C)を0に外挿したときのηsp/Cの値を極限粘度として求めた(下式参照)。
<CFCおよび分子量測定>
CFCおよび分子量測定は以下の条件で行った。
検出器(内蔵):IR4型赤外分光光度計(Polymer Char)
検出波長:3.42μm(2,920cm-1);固定
試料濃度:30mg/30mL(o-ジクロロベンゼン(ODCB)で希釈)
注入量 :0.5mL
温度条件:40℃/minで145℃まで昇温して30分間保持し、1℃/minで0℃まで冷却して60分間保持した後に、下記溶出区分ごとの溶出量を評価した。区分間の温度変化は40℃/minとした。
GPCカラム温度:145℃
GPCカラム較正:単分散ポリスチレン(東ソー)
分子量較正法 :標品較正法(ポリスチレン換算)
移動相 :o-ジクロロベンゼン(ODCB)、BHT添加
流量 :1.0mL/min
[製造例1~24]
国際公開第2017/150265号の比較例1([0158])に記載の重合方法に準じて、α-オレフィンを表1-1および表1-2に記載のα-オレフィンに変更し、得られる共重合体中の物性が表1-1および表1-2の値になるように、4-メチル-1-ペンテン、α-オレフィン、水素の使用割合を変更することによって、4-メチル-1-ペンテン共重合体(A-1)~(A-12)および(B-1)~(B-12)を得た。
[樹脂組成物の製造]
前記製造例で得られた共重合体(A-1)35質量部および共重合体(B-1)65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)プロピオネートを0.1質量部配合した。
[フィルムの作成]
得られた前記ペレットを単軸押出機((株)田中鉄工所製)に供給し、シリンダ270℃で溶融混練して、270℃のダイス温度でT型スリットダイよりフィルム状に溶融押出した。次いで、得られたフィルムを80℃に制御した金属冷却ロール上にエアー圧で密着させながら、引取速度0.9m/minの条件で引き取った。冷却固化された厚さ200μmの未延伸フィルムを得た。
[フィルムの延伸]
得られた未延伸フィルムを加熱金属ロールにより予熱してフィルム温度を160℃まで昇温し、周速差をつけた1対のロール間で3倍に縦延伸して、一軸延伸フィルムとした。次いで前記一軸延伸フィルムの幅方向の両端をクリップで把持して加熱オーブンへと導き、160℃に予熱したあと、幅方向に5倍に横延伸して、二軸延伸フィルムとした。この後、前記二軸延伸フィルムを200℃に加熱してアニール処理した。このようにして得られた二軸延伸フィルムの両端部を、レザー刃を用いたレザーカットで切断したのち、ロール状に巻き取って評価用のサンプルを得た。
[実施例2~10、比較例1~2]
4-メチル-1-ペンテン共重合体として表2に記載の共重合体を配合し、その配合量を表2に記載の配合量としたこと以外は実施例1と同様にして、未延伸フィルムおよび二軸延伸フィルムを得た。その後、実施例1と同様にして、評価用のサンプルを得た。
[実施例11~14]
表2に記載の延伸条件に変更したこと以外は実施例3と同様にして、4-メチル-1-ペンテン共重合体、未延伸フィルムおよび二軸延伸フィルムを得た。その後、実施例1と同様にして、評価用のサンプルを得た。
<極限粘度[η]>
上記の測定方法により極限粘度[η]を測定した。
測定には、上記で得られた二軸延伸フィルムを試料として用いた。セイコーインスツル社製DSC測定装置(DSC220C)を用い、以下の手順で融点を測定した。まず、測定用アルミパンに試料を約5mg設置し、封止した。100℃/minで290℃まで昇温し、290℃で5分間保持した後、10℃/minで-100℃まで降温させ、ついで-100℃から10℃/minで290℃まで昇温させた。2回目の昇温時の熱量曲線において結晶溶融ピークのピーク頂点から融点(Tm)を算出した。ピークが複数検出された場合は、温度が最大のものを融点(Tm)とした。
絶縁破壊強さ(V/μm)は、ASTM-D149に準じ、ヤマヨ試験器有限会社製絶縁破壊試験機を用いて測定した。上記評価用のサンプルついて、23℃および120℃において昇圧速度500V/secにて電圧を印加して絶縁破壊耐電圧を測定し、絶縁破壊強さ(V/μm)を求めた。次いで、23℃における絶縁破壊強さV(23℃)および120℃における絶縁破壊強さV(120℃)から、これらの比V(120℃)/V(23℃)を算出した。
評価用サンプルの厚さは、マイクロメーターを用いて幅方向に10点および長さ方向に10点測定し、その平均値を二軸延伸フィルムまたは未延伸フィルムの厚さとした。
株式会社東京精密社製の表面粗さ計を用いて、評価用のサンプル表面の凹凸の状態を粗さ曲線として評価した。その平均線の方向に測定長さ(l)分を抜き取り、この抜き取り部分の平均線の方向にX軸を、縦倍率の方向にY軸を取り、粗さ曲線をy=f(x)で表したときに、次の式によって求められる値をナノメートル(nm)で表したものをRaとした。測定長さは10mmとした。
株式会社東京精密社製の表面粗さ計を用いて、評価用のサンプル表面の凹凸の状態を粗さ曲線として評価した。粗粗さ曲線からその平均線の方向に測定長さだけを抜き取り、この抜取り部分の平均線から縦倍率の方向に測定した。最も高い山頂から5番目までの山頂の標高(Yp)の絶対値の平均値と、最も低い谷底から5番目までの谷底の標高(Yv)の絶対値の平均値との和を下式のように求め、この値をナノメートル (nm)で表したものをRzとした。測定長さは10mmとした。
Claims (7)
- 下記要件(A-a)~(A-d)を満たす4-メチル-1-ペンテン共重合体(A)と、下記要件(B-a)~(B-d)を満たす4-メチル-1-ペンテン共重合体(B)とを含有し、
下記要件(1)および(2)を満たす樹脂組成物。
(A-a)4-メチル-1-ペンテンから導かれる構成単位の量(U1)が80.0~99.9モル%であり、炭素数2~20の直鎖状α-オレフィンから選ばれる少なくとも1種から導かれる構成単位の総量(U2)が20.0~0.1モル%(ただし、前記U1および前記U2の合計を100モル%とする)である。
(A-b)135℃のデカリン中で測定した極限粘度[η]Aが、0.5~5.0dL/gである。
(A-c)検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で前記共重合体(A)を測定した場合に、100~140℃の範囲に溶出成分量のピークが少なくとも1つ存在する。
(A-d)前記CFCで前記共重合体(A)を測定した場合に、100~140℃の範囲の溶出成分における、重量平均分子量(Mw)と数平均分子量(Mn)との比である分子量分布(Mw/Mn)が、1.0~4.5である。
(B-a)4-メチル-1-ペンテンから導かれる構成単位の量(U3)が20.0~98.0モル%であり、炭素数2~20の直鎖状α-オレフィンから選ばれる少なくとも1種から導かれる構成単位の総量(U4)が80.0~2.0モル%(ただし、前記U3および前記U4の合計を100モル%とする)である。
(B-b)135℃のデカリン中で測定した極限粘度[η]Bが、2.0~8.0dL/gである。
(B-c)検出部に赤外分光光度計を用いたクロス分別クロマトグラフ装置(CFC)で前記共重合体(B)を測定した場合に、0℃以上100℃未満の範囲に溶出成分量のピークが少なくとも1つ存在する。
(B-d)前記CFCで前記共重合体(B)を測定した場合に、0℃以上100℃未満の範囲の溶出成分における、重量平均分子量(Mw)と数平均分子量(Mn)との比である分子量分布(Mw/Mn)が、1.0~7.0である。
(1)前記共重合体(A)および(B)の含有量の合計を100質量部とした場合に、前記共重合体(A)の含有量が5~95質量部であり、前記共重合体(B)の含有量が95~5質量部である。
(2)前記要件(A-a)に記載のU2(モル%)を前記要件(B-a)に記載のU4(モル%)から差し引いた値(U4-U2)が、0モル%以上、6.5モル%以下である。 - 前記共重合体(A)および共重合体(B)の含有量の合計を100質量部とした場合に、前記共重合体(A)の含有量が5質量部以上50質量部未満であり、前記共重合体(B)の含有量が50質量部を超え95質量部以下である、請求項1に記載の樹脂組成物。
- 前記共重合体(A)および(B)における直鎖状α-オレフィンが、それぞれ独立に炭素数10~20の直鎖状α-オレフィンである、請求項1または2に記載の樹脂組成物。
- 請求項1~3のいずれか1項に記載の樹脂組成物を含んでなる成形体。
- 請求項1~3のいずれか1項に記載の樹脂組成物を含んでなるフィルム。
- 下記要件(I)~(III)を満たすフィルム。
(I)少なくとも2種の4-メチル-1-ペンテン共重合体を含有する。
(II)フィルムの表面粗さ(Ra)が100nm未満である。
(III)フィルムの表面粗さ(Rz)が500nm未満である。 - キャパシタ用フィルムである、請求項5または6に記載のフィルム。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202180053515.6A CN115989249A (zh) | 2020-09-01 | 2021-08-30 | 树脂组合物和成型体 |
JP2022546299A JPWO2022050208A1 (ja) | 2020-09-01 | 2021-08-30 | |
US18/023,339 US20230331969A1 (en) | 2020-09-01 | 2021-08-30 | Resin composition and molded article |
KR1020237006643A KR20230043957A (ko) | 2020-09-01 | 2021-08-30 | 수지 조성물 및 성형체 |
EP21864266.8A EP4209520A1 (en) | 2020-09-01 | 2021-08-30 | Resin composition and molded article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-146887 | 2020-09-01 | ||
JP2020146887 | 2020-09-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022050208A1 true WO2022050208A1 (ja) | 2022-03-10 |
Family
ID=80492419
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/031652 WO2022050208A1 (ja) | 2020-09-01 | 2021-08-30 | 樹脂組成物および成形体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230331969A1 (ja) |
EP (1) | EP4209520A1 (ja) |
JP (1) | JPWO2022050208A1 (ja) |
KR (1) | KR20230043957A (ja) |
CN (1) | CN115989249A (ja) |
TW (1) | TW202210532A (ja) |
WO (1) | WO2022050208A1 (ja) |
Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0241303B2 (ja) | 1982-12-03 | 1990-09-17 | ||
WO2001027124A1 (fr) | 1999-10-08 | 2001-04-19 | Mitsui Chemicals, Inc. | Compose metallocene, son procede de fabrication, catalyseur de polymerisation d'olefine, procede de production de polyolefine et polyolefine |
WO2001053369A1 (fr) | 2000-01-21 | 2001-07-26 | Mitsui Chemicals, Inc. | Copolymeres blocs d'olefine, procedes de fabrication et utilisation |
WO2003082879A1 (en) | 2002-03-28 | 2003-10-09 | Albemarle Corporation | Ionic aluminoxanate compositions and their use in catalysis |
WO2005066191A1 (en) | 2003-12-31 | 2005-07-21 | Albemarle Corporation | Haloaluminoxane compositions, their preparation, and their use in catalysis |
WO2006025540A1 (ja) | 2004-08-30 | 2006-03-09 | Mitsui Chemicals, Inc. | プロピレン系重合体の製造方法 |
WO2007131010A2 (en) | 2006-05-04 | 2007-11-15 | Albemarle Corporation | Aluminoxane compositions, their preparation, and their use in catalysis |
WO2010055652A1 (ja) | 2008-11-11 | 2010-05-20 | 東ソー・ファインケム株式会社 | 固体状ポリメチルアルミノキサン組成物およびその製造方法 |
WO2013099876A1 (ja) | 2011-12-27 | 2013-07-04 | 三井化学株式会社 | 4-メチル-1-ペンテン(共)重合体組成物、該組成物からなるフィルムおよび中空成形体 |
WO2013146337A1 (ja) | 2012-03-28 | 2013-10-03 | 東ソー・ファインケム株式会社 | 小粒径固体状ポリメチルアルミノキサン組成物の製造方法 |
JP2014011181A (ja) * | 2012-06-27 | 2014-01-20 | Mitsui Chemicals Inc | コンデンサ用フィルム、金属化フィルムおよびフィルムコンデンサ |
JP2014011183A (ja) * | 2012-06-27 | 2014-01-20 | Mitsui Chemicals Inc | コンデンサ用フィルム、金属化フィルムおよびフィルムコンデンサ |
JP2014011182A (ja) | 2012-06-27 | 2014-01-20 | Mitsui Chemicals Inc | コンデンサ用フィルム、金属化フィルムおよびフィルムコンデンサ |
WO2014050817A1 (ja) | 2012-09-25 | 2014-04-03 | 三井化学株式会社 | オレフィン重合体の製造方法およびオレフィン重合体 |
WO2014123212A1 (ja) | 2013-02-08 | 2014-08-14 | 三井化学株式会社 | 固体状ポリアルミノキサン組成物、オレフィン重合用触媒、オレフィン重合体の製造方法、および固体状ポリアルミノキサン組成物の製造方法 |
WO2017150265A1 (ja) | 2016-03-03 | 2017-09-08 | 三井化学株式会社 | 4-メチル-1-ペンテン系重合体、樹脂組成物および成形体 |
JP2018162408A (ja) | 2017-03-27 | 2018-10-18 | 三井化学株式会社 | 4−メチル−1−ペンテン共重合体組成物 |
WO2019198694A1 (ja) | 2018-04-11 | 2019-10-17 | 三井化学株式会社 | 4-メチル-1-ペンテン系重合体粒子および4-メチル-1-ペンテン系樹脂の製造方法 |
WO2020116368A1 (ja) * | 2018-12-04 | 2020-06-11 | 三井化学株式会社 | 4-メチル-1-ペンテン共重合体を含有する樹脂組成物、およびキャパシタ用フィルム |
-
2021
- 2021-08-30 KR KR1020237006643A patent/KR20230043957A/ko unknown
- 2021-08-30 WO PCT/JP2021/031652 patent/WO2022050208A1/ja unknown
- 2021-08-30 CN CN202180053515.6A patent/CN115989249A/zh active Pending
- 2021-08-30 JP JP2022546299A patent/JPWO2022050208A1/ja active Pending
- 2021-08-30 EP EP21864266.8A patent/EP4209520A1/en active Pending
- 2021-08-30 US US18/023,339 patent/US20230331969A1/en active Pending
- 2021-08-31 TW TW110132339A patent/TW202210532A/zh unknown
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0241303B2 (ja) | 1982-12-03 | 1990-09-17 | ||
WO2001027124A1 (fr) | 1999-10-08 | 2001-04-19 | Mitsui Chemicals, Inc. | Compose metallocene, son procede de fabrication, catalyseur de polymerisation d'olefine, procede de production de polyolefine et polyolefine |
WO2001053369A1 (fr) | 2000-01-21 | 2001-07-26 | Mitsui Chemicals, Inc. | Copolymeres blocs d'olefine, procedes de fabrication et utilisation |
WO2003082879A1 (en) | 2002-03-28 | 2003-10-09 | Albemarle Corporation | Ionic aluminoxanate compositions and their use in catalysis |
WO2005066191A1 (en) | 2003-12-31 | 2005-07-21 | Albemarle Corporation | Haloaluminoxane compositions, their preparation, and their use in catalysis |
WO2006025540A1 (ja) | 2004-08-30 | 2006-03-09 | Mitsui Chemicals, Inc. | プロピレン系重合体の製造方法 |
WO2007131010A2 (en) | 2006-05-04 | 2007-11-15 | Albemarle Corporation | Aluminoxane compositions, their preparation, and their use in catalysis |
WO2010055652A1 (ja) | 2008-11-11 | 2010-05-20 | 東ソー・ファインケム株式会社 | 固体状ポリメチルアルミノキサン組成物およびその製造方法 |
WO2013099876A1 (ja) | 2011-12-27 | 2013-07-04 | 三井化学株式会社 | 4-メチル-1-ペンテン(共)重合体組成物、該組成物からなるフィルムおよび中空成形体 |
WO2013146337A1 (ja) | 2012-03-28 | 2013-10-03 | 東ソー・ファインケム株式会社 | 小粒径固体状ポリメチルアルミノキサン組成物の製造方法 |
JP2014011181A (ja) * | 2012-06-27 | 2014-01-20 | Mitsui Chemicals Inc | コンデンサ用フィルム、金属化フィルムおよびフィルムコンデンサ |
JP2014011183A (ja) * | 2012-06-27 | 2014-01-20 | Mitsui Chemicals Inc | コンデンサ用フィルム、金属化フィルムおよびフィルムコンデンサ |
JP2014011182A (ja) | 2012-06-27 | 2014-01-20 | Mitsui Chemicals Inc | コンデンサ用フィルム、金属化フィルムおよびフィルムコンデンサ |
WO2014050817A1 (ja) | 2012-09-25 | 2014-04-03 | 三井化学株式会社 | オレフィン重合体の製造方法およびオレフィン重合体 |
WO2014123212A1 (ja) | 2013-02-08 | 2014-08-14 | 三井化学株式会社 | 固体状ポリアルミノキサン組成物、オレフィン重合用触媒、オレフィン重合体の製造方法、および固体状ポリアルミノキサン組成物の製造方法 |
WO2017150265A1 (ja) | 2016-03-03 | 2017-09-08 | 三井化学株式会社 | 4-メチル-1-ペンテン系重合体、樹脂組成物および成形体 |
JP2018162408A (ja) | 2017-03-27 | 2018-10-18 | 三井化学株式会社 | 4−メチル−1−ペンテン共重合体組成物 |
WO2019198694A1 (ja) | 2018-04-11 | 2019-10-17 | 三井化学株式会社 | 4-メチル-1-ペンテン系重合体粒子および4-メチル-1-ペンテン系樹脂の製造方法 |
WO2020116368A1 (ja) * | 2018-12-04 | 2020-06-11 | 三井化学株式会社 | 4-メチル-1-ペンテン共重合体を含有する樹脂組成物、およびキャパシタ用フィルム |
Also Published As
Publication number | Publication date |
---|---|
TW202210532A (zh) | 2022-03-16 |
EP4209520A1 (en) | 2023-07-12 |
JPWO2022050208A1 (ja) | 2022-03-10 |
US20230331969A1 (en) | 2023-10-19 |
CN115989249A (zh) | 2023-04-18 |
KR20230043957A (ko) | 2023-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5769821B2 (ja) | 4−メチル−1−ペンテン(共)重合体組成物、該組成物からなるフィルムおよび中空成形体 | |
US10017591B2 (en) | 1-butane-α-olefin copolymer composition | |
JP7389882B2 (ja) | キャパシタ用フィルム、金属化フィルム、およびフィルムキャパシタ | |
JPWO2007094378A1 (ja) | エチレン系重合体及びこれから得られる成形体 | |
JPWO2010074001A1 (ja) | プロピレン系樹脂組成物、成形体および容器 | |
KR20200044293A (ko) | 올레핀계 중합체 | |
US7662888B2 (en) | Polypropylene based heat shrinkable film | |
JP6000439B2 (ja) | 二軸延伸フィルムおよびエチレン系重合体組成物 | |
JP2001064426A (ja) | 多孔質フィルムおよびその製法 | |
JP4889241B2 (ja) | ポリプロピレン系熱収縮性フィルム | |
JP2014011181A (ja) | コンデンサ用フィルム、金属化フィルムおよびフィルムコンデンサ | |
CN114207012A (zh) | 丙烯系聚合物组合物、无拉伸膜和叠层体 | |
WO2022050208A1 (ja) | 樹脂組成物および成形体 | |
JP2022041965A (ja) | 樹脂組成物および成形体 | |
JP2008280359A (ja) | ポリプロピレン系発泡延伸フィルム | |
JP2007177020A (ja) | エチレン系重合体組成物およびこれから得られる成形体 | |
JP6068277B2 (ja) | オレフィン系重合体組成物、該組成物を含んで得られるシートおよび成形体 | |
JP7433108B2 (ja) | フィルム | |
JP2010189473A (ja) | エチレン系重合体からなる延伸フィルム | |
JP2021155595A (ja) | 二軸延伸フィルム | |
JP2020178066A (ja) | 金属化フィルムコンデンサ | |
JP7392088B2 (ja) | エチレン系樹脂組成物及び成形体 | |
JP2001172465A (ja) | プロピレン系樹脂組成物およびその製造方法 | |
JP2023102071A (ja) | 積層体およびその製造方法 | |
JP2023136762A (ja) | 樹脂組成物、フィルム、および二軸延伸フィルムの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21864266 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20237006643 Country of ref document: KR Kind code of ref document: A Ref document number: 2022546299 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021864266 Country of ref document: EP Effective date: 20230403 |