Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
  • A61L31/04—Macromolecular materials
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
  • A61L31/04—Macromolecular materials
  • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
  • A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
  • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
• • 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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • 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
  • C08L23/04—Homopolymers or copolymers of ethene
• • 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
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

• the present invention relates to a hydrogenated composition, a resin composition, and various uses thereof. More specifically, there are a composition containing a hydrogenated block copolymer having a structural unit having an alicyclic skeleton in the main chain, a resin composition containing the composition, and various uses thereof.
• Block copolymers having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound and their hydrogenated products have vibration damping properties. It is already known that some of them have, and have been used as damping materials. Further, the block copolymer and its hydrogenated additive may have physical properties such as sound insulation, heat resistance, impact resistance, and adhesiveness in addition to vibration damping properties, and there are various types. Used for applications.
• styrene compounds and isoprene, butadiene, etc. whose peak temperature of tan ⁇ and vinyl bond amount are specified in order to improve mechanical properties such as vibration damping, flexibility, heat resistance, tensile strength and impact resistance.
• Hydrogenated block copolymers with conjugated diene compounds are disclosed (see, for example, Patent Documents 1 to 4). Further, by blending the hydrogen additive of the block copolymer and the polyolefin-based resin to prepare a resin composition utilizing the respective characteristics, a material for a wide range of applications such as food transportation, home appliance parts, and medical use can be used. It is known that it can be used for (see, for example, Patent Documents 5 and 6).
• Japanese Unexamined Patent Publication No. 2002-284830 International Publication No. 2000/015680
• Japanese Unexamined Patent Publication No. 2006-117879 Japanese Unexamined Patent Publication No. 2010-0533319 International Publication No. 2016/136760 International Publication No. 2017/159800
• the present invention provides a hydrogenated composition containing a hydrogenated composition, a resin composition containing the composition, and various uses capable of providing a molded product having excellent handleability and good vibration damping property, transparency, and flexibility. To do.
• the present invention is as follows.
• [1] Contains a block copolymer hydrogenated product (I) and an anti-blocking agent.
• the hydrogenated product (I) of the block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound.
• the polymer block (B) has a structural unit containing one or more alicyclic skeletons (X) represented by the following formula (X) in the main chain, and the hydrogenation rate of the polymer block (B) is 50 to 99.
• R 1 to R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R 1 to R 3 may be the same or different.
• a resin composition containing the hydrogenated composition and a resin (II) different from the hydrogenated compound (I) of the block copolymer [3] A molded product, a container, or a medical device made of the resin composition.
• a hydrogenated composition containing an additive-containing composition capable of providing a molded product having excellent handleability and good vibration damping property, transparency and flexibility, a resin composition containing the composition, and various uses. Can be provided.
• the hydrogenated composition of the present invention contains the hydrogenated block copolymer (I) and the anti-blocking agent.
• the hydrogenated product (I) of the block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound.
• the polymer block (B) has a structural unit containing one or more alicyclic skeletons (X) represented by the formula (X) in the main chain, and the hydrogenation rate of the polymer block (B) is 50 to 99. It is characterized by being a molar%.
• the hydrogenated additive (I) of the block copolymer, the blocking inhibitor, and the like will be described below.
• the hydrogenated product (I) of the block copolymer (hereinafter, may be referred to as "hydrogenated product”) is used. It is an essential ingredient for exhibiting excellent vibration damping, transparency and flexibility.
• the hydrogenated product is a hydrogenated product of a block copolymer containing a polymer block (A) and a polymer block (B), and details will be described below.
• the polymer block (A) constituting the block copolymer preferably has a structural unit derived from an aromatic vinyl compound used as a monomer from the viewpoint of vibration damping and mechanical properties.
• the polymer block (A) contains more than 70 mol% of a structural unit derived from an aromatic vinyl compound (hereinafter, may be abbreviated as “aromatic vinyl compound unit”) in the polymer block (A). From the viewpoint of mechanical properties, it is more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 100 mol% or more. ..
• aromatic vinyl compound examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, and ⁇ .
• aromatic vinyl compounds may be used alone or in combination of two or more.
• styrene, ⁇ -methylstyrene, p-methylstyrene, and a mixture thereof are preferable, and styrene is more preferable, from the viewpoint of production cost and physical property balance.
• the polymer block (A) is a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter, “other unsaturated monomer unit”” as long as it does not interfere with the object and effect of the present invention. It may be abbreviated as 30 mol% or less in the polymer block (A), but preferably less than 20 mol%, more preferably less than 15 mol%, still more preferably. It is less than 10 mol%, more preferably less than 5 mol%, and particularly preferably 0 mol%.
• Examples of the other unsaturated monomer include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, ⁇ -pinene, 8, At least one selected from the group consisting of 9-p-mentene, dipentene, methylenenorbornene, 2-methylene tetrahydrofuran and the like can be mentioned.
• the bonding form is not particularly limited and may be random or tapered.
• the block copolymer may have at least one of the polymer blocks (A).
• the polymer blocks (A) may be the same or different.
• “the polymer block is different” means the monomer unit constituting the polymer block, the weight average molecular weight, the stereoregularity, and the ratio of each monomer unit when having a plurality of monomer units. It means that at least one of the forms of polymerization (random, gradient, block) is different.
• the weight average molecular weight of the polymer block (A) is not particularly limited, but the total weight average molecular weight of the polymer blocks (A) contained in the block copolymer is preferably 3,000 to 60,000, more preferably. Is 4,000 to 50,000.
• the total weight average molecular weight of the polymer blocks (A) means, when the block copolymer contains two or more polymer blocks (A), the total weight average molecular weight of the block copolymers, and the block copolymer weight. When the coalescence contains only one polymer block (A), it means the weight average molecular weight of the polymer block (A).
• the weight average molecular weight of the polymer block (A) is within the above range, the mechanical strength is further improved and the molding processability is also excellent.
• the weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) measurement.
• the content of the polymer block (A) in the block copolymer is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 16% by mass or less, and 14% by mass. It is particularly preferable that it is% or less. If it is 50% by mass or less, a hydrogenated composition having appropriate flexibility and excellent vibration damping property can be obtained without lowering the tan ⁇ peak top strength.
• the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 6% by mass or more. If it is 1% by mass or more, it can be a hydrogenated composition having mechanical properties and molding processability suitable for various uses.
• the content of the polymer block (A) in the block copolymer is a value obtained by 1 1 H-NMR measurement, and more specifically, a value measured according to the method described in Examples.
• the polymer block (B) constituting the block copolymer is a structural unit derived from a conjugated diene compound, and has one or more alicyclic skeletons (X) represented by the following formula (X) as a main chain. It has a structural unit contained in (hereinafter, may be abbreviated as "alicyclic skeleton-containing unit”).
• the polymer block (B) may also contain a structural unit derived from a conjugated diene compound that does not contain an alicyclic skeleton (X) (hereinafter, may be abbreviated as "conjugated diene unit").
• the total amount of the alicyclic skeleton-containing unit and the conjugated diene unit in the polymer block (B) is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably, from the viewpoint of exhibiting excellent vibration damping properties. Is 90 mol% or more, and it is particularly preferable that it is substantially 100 mol%.
• the polymer blocks (B) may be the same or different.
• R 1 to R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R 1 to R 3 may be the same or different from each other.
• the hydrocarbon group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 (that is, a methyl group). Further, the hydrocarbon group may be a straight chain or a branched chain, or may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and formation of the alicyclic skeleton (X), it is particularly preferable that R 1 to R 3 are independently hydrogen atoms or methyl groups, respectively.
• the vinyl group in the above formula (X) can be hydrogenated according to the hydrogenation rate. Therefore, the meaning of the alicyclic skeleton (X) in the hydrogenated additive also includes the skeleton in which the vinyl group in the above formula (X) is hydrogenated.
• the polymer block (B) is a structural unit derived from the conjugated diene compound, and the alicyclic skeleton (X) is derived from the conjugated diene compound.
• the alicyclic skeleton (X) is produced by anionic polymerization of a conjugated diene compound by a method described later, and at least one alicyclic skeleton (X) is the main alicyclic skeleton-containing unit depending on the conjugated diene compound used. Included in the chain.
• conjugated diene compound examples include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1,3-pentadiene. , 1,3-Hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, farnesene, milsen and the like. Of these, butadiene, isoprene, farnesene, or a combination of butadiene and isoprene is preferable. That is, the polymer block (B) preferably contains a structural unit derived from at least one selected from isoprene, butadiene, and farnesene.
• the blending ratio [isoprene / butadiene] (mass ratio) thereof is not particularly limited, but is preferably 5/95 to 95/5, more preferably 10/90 to 90/10. It is more preferably 40/60 to 70/30, and particularly preferably 45/55 to 65/35.
• the mixing ratio [isoprene / butadiene] is expressed in molar ratio, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 40/60 to 70/30, particularly. It is preferably 45/55 to 55/45.
• an alicyclic skeleton (X) mainly produced when butadiene, isoprene, or both butadiene and isoprene is used as the conjugated diene compound will be described.
• an alicyclic skeleton (X) having the following combination of substituents (i) is produced. That is, in this case, the alicyclic skeleton (X) is only an alicyclic skeleton in which R 1 to R 3 are hydrogen atoms at the same time.
• the polymer block (B) in the block copolymer has one alicyclic skeleton in which R 1 to R 3 are hydrogen atoms at the same time.
• R 1 to R 3 are hydrogen atoms at the same time.
• examples thereof include those having a structural unit containing X) in the main chain.
• (X) is preferably an alicyclic skeleton (X') in which at least one of R 1 to R 3 is a hydrocarbon group having 1 to 11 carbon atoms.
• the alicyclic skeleton can be efficiently generated from the conjugated diene compound, and the hydrocarbon group in the alicyclic skeleton (X') is a methyl group from the viewpoint of the balance between vibration damping property and mechanical properties. Is more preferable.
• R 1 to R 3 each independently represent a hydrogen atom or a methyl group, and R 1 to R 3 are alicyclic skeletons that are not hydrogen atoms at the same time. That is, it is more preferable that the polymer block (B) has a structural unit containing at least one of the alicyclic skeletons having a combination of the substituents (ii) to (vi) in the main chain. ..
• the structural unit constituting the polymer block (B) is any of an isoprene unit, a butadiene unit, and a mixture unit of isoprene and butadiene, isoprene and butadiene other than the bonded form forming the alicyclic skeleton (X).
• X alicyclic skeleton
• the hydrogenated product preferably has a total content of 3,4-bonding units and 1,2-bonding units (hereinafter, may be simply referred to as "vinyl bond amount") in the polymer block (B). It is 50 to 95 mol%, more preferably 55 to 93 mol%, still more preferably 60 to 90 mol%. Within the above range, excellent vibration damping properties can be exhibited.
• the vinyl bond amount is a value calculated by 1 H-NMR measurement according to the method described in Examples.
• the above-mentioned "contents of 3,4-bonding unit and 1,2-bonding unit" is "content of 1,2-bonding unit". And apply.
• the polymer block (B) may contain a structural unit containing an alicyclic skeleton (X) in the main chain, but from the viewpoint of obtaining a more excellent anti-vibration effect, the polymer block (B) ) Contains 1 mol% or more of the alicyclic skeleton (X), more preferably 1.1 mol% or more, still more preferably 1.4 mol% or more, still more preferably 1.8. It is mol% or more, more preferably 4 mol% or more, even more preferably 10 mol% or more, and particularly preferably 13 mol% or more.
• the upper limit of the content of the alicyclic skeleton (X) in the polymer block (B) is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of productivity, 40 mol. % Or less, preferably 30 mol% or less, 20 mol% or less, or 18 mol% or less. From the viewpoint of further improving the vibration damping property, it is more preferable that the polymer block (B) contains 1 mol% or more of the alicyclic skeleton (X'), and more preferably 1.3 mol% or more. , More preferably 1.6 mol% or more.
• the upper limit of the content of the alicyclic skeleton (X') is the same as the upper limit of the content of the alicyclic skeleton (X).
• the alicyclic skeleton content in each case is as follows.
• isoprene when used as the conjugated diene compound, when one or more alicyclic skeletons (X') having a combination of the substituents (v) and (vi) are present in the polymer block (B).
• the total content of these compounds is preferably 1 mol% or more from the viewpoint of obtaining a better anti-vibration effect, more preferably 1.5 mol% or more, and excellent control over a wide temperature range.
• the upper limit of the total content when isoprene is used is the same as the upper limit of the content of the alicyclic skeleton (X).
• the content of the alicyclic skeleton (X) in the polymer block (B) when it is present is 3 mol% or more, which is more excellent vibration damping. From the viewpoint of obtaining a sexual effect, it is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, and 20 mol% or more. Is even more preferable, and 30 mol% or more is particularly preferable.
• the upper limit of the content when butadiene is used is the same as the upper limit of the content of the alicyclic skeleton (X).
• the upper limit of the total content when butadiene and isoprene are used in combination is the same as the upper limit of the content of the alicyclic skeleton (X). Further, when butadiene and isoprene are used in combination as a conjugated diene compound, one alicyclic skeleton (X) having a combination of the substituents (i) to (vi) described above is contained in the polymer block (B).
• the total content of them in the presence of the above is preferably 1 mol% or more from the viewpoint of obtaining a more excellent anti-vibration effect, and more preferably 5 mol% or more.
• the upper limit of the total content when butadiene and isoprene are used in combination is the same as the upper limit of the content of the alicyclic skeleton (X).
• the content of the alicyclic skeleton (X) (including (X')) contained in the hydrogenated additive was determined by 13 C-NMR measurement of the block copolymer before hydrogenation, and the polymer block (B) was measured. It is a value obtained from an integrated value derived from the alicyclic skeleton (X) inside, and more specifically, it is a value measured according to the method described in Examples.
• the hydrogenated material includes a vinyl group bonded to the alicyclic skeleton (X) and a vinyl group bonded to the main chain.
• the content molar ratio of can be specified.
• the chemical shift of the carbon atom ((a) of the following chemical formula) in 13 C-NMR appears in the vicinity of 107 to 110 ppm, and the 13 C of the carbon atom at the terminal of the vinyl group bonded to the main chain ((b) of the following chemical formula).
• -Chemical shift in NMR appears around 110-116 ppm.
• the peak area ratio [peak area of chemical shift value 107 to 110 ppm] / [peak area of chemical shift value 110 to 116 ppm] measured by 13 C-NMR is usually It is in the range of 0.01 to 3.00.
• the hydrogenated product, 13 but C-NMR peaks derived from the carbon atom on the alicyclic skeleton (X) in the measurement is hardly observed
• the substituent R 3 is a hydrocarbon group having 1 to 11 carbon atoms Yes
• a peak derived from a carbon atom on the alicyclic skeleton (X) that binds to a branched alkyl group derived from a vinyl group having R 3 can be observed.
• the hydrogenated product of the present embodiment since the hydrogenation rate of the polymer block (B) is 50 to 99 mol%, cycloaliphatic binds branched alkyl group derived from a vinyl group having the R 3 It is also possible to specify the molar ratio of the carbon atom on the skeleton (X) to the carbon atom on the main chain bonded to the branched alkyl group derived from the vinyl group.
• the hydrogenation rate is 40 to 99 mol%
• the peak area ratio measured by 13 C-NMR [peak area of chemical shift value 50.0 to 52.0 ppm] / [chemical shift value 43.0 to 45].
• the peak area of .0 ppm is usually in the range of 0.01 to 3.00, and the area ratio is preferably in the range of 0.01 to 1.50, more preferably from the viewpoint of exhibiting better vibration damping properties.
• the range is 0.01 to 1.00, more preferably 0.01 to 0.50, and even more preferably 0.01 to 0.25.
• the total weight average molecular weight of the polymer blocks (B) contained in the block copolymer is preferably 15 in the state before hydrogenation from the viewpoints of vibration damping property and molding processability when forming a film or a laminate. It is 000 to 800,000, more preferably 50,000 to 700,000, still more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000. It is ⁇ 450,000.
• the polymer block (B) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound as long as it does not interfere with the object and effect of the present invention.
• the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound in the polymer block (B) is preferably less than 50 mol%, more preferably less than 30 mol%, and further. It is preferably less than 20 mol%, more preferably less than 10 mol%, and particularly preferably 0 mol%.
• Examples of the other polymerizable monomer include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, and N.
• -Aromatic vinyl compounds such as vinylcarbazole, vinylnaphthalene and vinylanthracene, as well as methyl methacrylate, methylvinyl ether, ⁇ -pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylene tetrahydrofuran, 1,3- At least one compound selected from the group consisting of cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadien and the like is preferably mentioned.
• the block copolymer may have at least one of the above-mentioned polymer blocks (B). When the block copolymer has two or more polymer blocks (B), the polymer blocks (B) may be the same or different.
• Block copolymer As a method for producing a block copolymer, for example, a polymer block having a structural unit containing the alicyclic skeleton (X) in a main chain by polymerizing one or more kinds of conjugated diene compounds as monomers by an anionic polymerization method. (B) is formed, the monomer of the polymer block (A) is added, and if necessary, the monomer of the polymer block (A) and the conjugated diene compound are sequentially added to obtain a block copolymer. be able to.
• a known technique can be used (see, for example, US Pat. No.
• the alicyclic skeleton is formed at the end of the polymer due to the depletion of the monomer, and the polymerization can be restarted from the alicyclic skeleton by sequentially adding the monomer to the terminal. Therefore, the presence or absence of formation of the alicyclic skeleton and its content can be adjusted by the sequential addition time of the monomers, the polymerization temperature, the type and addition amount of the catalyst, the combination of the monomer and the catalyst, and the like. Further, in the anionic polymerization method, an anionic polymerization initiator, a solvent, and if necessary, a Lewis base can be used.
• organolithium compound that can be used as a polymerization initiator for anionic polymerization in the above method examples include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium.
• dilithium compound that can be used as the polymerization initiator examples include naphthalenedilithium and dilithiohexylbenzene.
• Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenylbenzoate, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycidoxypropyl. Examples thereof include methyldiethoxysilane and ⁇ -glycidoxypropylmethyldimethoxysilane. The amount of these polymerization initiators and coupling agents used is appropriately determined by the desired weight average molecular weight of the target hydrogenated product.
• the initiator such as an alkyllithium compound or a dilithium compound is 0.01 to 0.2 parts by mass per 100 parts by mass of the monomer of the polymer block (A) used for polymerization and the monomer such as a conjugated diene compound.
• a coupling agent it is preferably used in a ratio of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the monomers.
• the solvent is not particularly limited as long as it does not adversely affect the anion polymerization reaction.
• aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane and n-pentane; aromatic hydrocarbons such as benzene, toluene and xylene. And so on.
• the polymerization reaction is usually carried out at a temperature of 0 to 100 ° C., preferably 10 to 70 ° C. for 0.5 to 50 hours, preferably 1 to 30 hours.
• Lewis bases such as dimethyl ether, diethyl ether, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane (DTHP); ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.
• Glycol ethers such as tetraethylene glycol dimethyl ether; amines such as triethylamine, N, N, N', N'-tetramethylenediamine, N, N, N', N'-tetramethylethylenediamine (TMEDA), N-methylmorpholin.
• These Lewis bases can be used alone or in combination of two or more.
• the amount of the Lewis base added includes how much the content of the alicyclic skeleton (X) is controlled, and the structural unit in which the polymer block (B) is particularly derived from isoprene and / or butadiene. In the case, it is determined by how much the vinyl bond amount of the isoprene unit and / or the butadiene unit constituting the polymer block (B) is controlled. Therefore, the amount of Lewis base added is not strictly limited, but is usually 0.1 to 1,000 mol per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as the polymerization initiator. It is preferably used in the range of 1 to 100 mol.
• the average feed rate of the conjugated diene compound (hereinafter, may be referred to as “average diene feed rate”) is 150 kg / h or less per mol of the active terminal from the viewpoint of increasing the content of the alicyclic skeleton (X).
• the lower limit is preferably 1 kg / h or more, more preferably 3 kg / h or more, further preferably 5 kg / h or more, and may be 7 kg / h or more per mole of the active terminal. It may be 10 kg / h or more, or 15 kg / h or more.
• a block copolymer can be obtained by adding an active hydrogen compound such as alcohols, carboxylic acids and water to stop the polymerization reaction.
• a hydrogenation reaction (hydrogenation reaction) is carried out in the presence of a hydrogenation catalyst in an inert organic solvent.
• a hydrogenation reaction By hydrogenation reaction, the carbon-carbon double bond derived from the conjugated diene compound in the polymer block (B) in the block copolymer is hydrogenated to obtain a hydrogenated product.
• the hydrogen pressure is about 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa
• the reaction temperature is about 20 to 250 ° C., preferably 50 to 180 ° C., more preferably. Can be carried out at 70 to 180 ° C.
• the reaction time is usually about 0.1 to 100 hours, preferably 1 to 50 hours.
• the hydrogenation catalyst include Raney nickel; a heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a single substance such as carbon, alumina, or diatomaceous earth; a transition metal compound, an alkylaluminum compound, or an alkyllithium.
• a transition metal catalyst composed of a combination with a compound or the like; a metallocene catalyst or the like can be mentioned.
• the hydrogenated product thus obtained is coagulated by pouring the polymerization reaction solution into methanol or the like and then heated or dried under reduced pressure, or the polymerization reaction solution is poured into hot water together with steam and the solvent is azeotropically heated. It can be obtained by subjecting so-called steam stripping to remove the mixture, and then heating or drying under reduced pressure.
• the hydrogenation rate of the polymer block (B) is 50 to 99 mol%.
• the hydrogenation rate of the carbon-carbon double bond in the polymer block (B) in the hydrogenated additive can be specified according to the performance desired in various applications. For example, the lower the hydrogenation rate of the hydrogenated product, the easier it is for cross-linking to occur. Therefore, it is possible to form a foam molded product having high strength by cross-linking foam molding. Further, the higher the hydrogenation rate of the hydrogenated product, the more the hydrogenated product can be obtained with improved heat resistance and weather resistance.
• the hydrogenation rate of the hydrogenated product is preferably 80 mol% or more, preferably 85 mol% or more. More preferably, 90 mol% or more is further preferable.
• the upper limit of the hydrogenation rate is not particularly limited, and may be 99 mol% or less, or 98 mol% or less.
• the hydrogenation rate is the content of carbon-carbon double bonds in the conjugated diene compound in the polymer block (B) and the structural unit derived from the alicyclic skeleton (X), which is 1 H after hydrogenation.
• -It is a value obtained by NMR measurement, and more specifically, it is a value measured according to the method described in Examples.
• the block copolymer is not limited in its bonding form, and is linear, branched, radial, or two of these. Any of the above-mentioned combined modes may be used. Above all, the bonding form of the polymer block (A) and the polymer block (B) is preferably linear, and as an example, the polymer block (A) is A and the polymer block (B) is.
• B the diblock copolymer represented by AB
• the triblock copolymer represented by ABA or BAB the tetra represented by ABAB.
• Block copolymer pentablock copolymer represented by ABABA or BABAB, (AB) nZ type copolymer (Z is the coupling agent residue) A group is represented, and n represents an integer of 3 or more) and the like.
• ABABA or BABAB ABABA or BABAB
• nZ type copolymer Z is the coupling agent residue
• a group is represented, and n represents an integer of 3 or more
• linear triblock copolymers or diblock copolymers are preferable, and ABA type triblock copolymers are preferable from the viewpoints of flexibility, ease of production, and the like.
• the entire bonded polymer blocks are treated as one polymer block. Is done.
• the polymer block which should be strictly described as YZZ (Z represents a coupling residue), including the above examples, needs to be particularly distinguished from the single polymer block Y. Except in some cases, it is displayed as Y as a whole.
• this type of polymer block containing the coupling agent residue is treated as described above, for example, it contains the coupling agent residue and is strictly ABZBA (The block copolymer that should be described as (Z represents a coupling agent residue) is described as ABA and is treated as an example of a triblock copolymer.
• the block copolymer may contain a polymer block composed of a monomer other than the polymer blocks (A) and (B) as long as it does not interfere with the object and effect of the present invention.
• the total content of the polymer block (A) and the polymer block (B) is preferably 90% by mass or more, more preferably 95% by mass or more, and substantially 100% by mass. Is particularly preferable.
• the hydrogenated composition is more likely to be excellent in vibration damping property and molding processability, and can be suitably used for various purposes.
• the weight average molecular weight (Mw) of the block copolymer and its hydrogenated product obtained in terms of standard polystyrene by gel permeation chromatography is preferably 15,000 to 800,000, more preferably 50,000 to 700,000. , More preferably 60,000 to 600,000, even more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450,000.
• Mw weight average molecular weight
• the weight average molecular weight of the block copolymer and its hydrogenated product obtained in terms of standard polystyrene by gel permeation chromatography is preferably 15,000 to 800,000, more preferably 50,000 to 700,000. , More preferably 60,000 to 600,000, even more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450,000.
• the weight average molecular weight of the block copolymer and its hydrogenated product is 15,000 or more, the heat resistance is high, and when it is 800,000
• [Tan ⁇ ] Peak top temperature and intensity of tan ⁇ ) tan ⁇ (loss tangent) is the ratio of loss elastic modulus / storage elastic modulus at a frequency of 1 Hz in dynamic viscoelasticity measurement, and the peak top temperature and intensity of tan ⁇ greatly contribute to vibration damping and other physical properties.
• the peak top intensity of tan ⁇ is the value of tan ⁇ when the peak of tan ⁇ is maximized.
• the peak top temperature of tan ⁇ is the temperature at which the peak of tan ⁇ is maximized.
• a single-layer sheet having a thickness of 1.0 mm is prepared by pressurizing the hydrogenated product at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes, and the single-layer sheet is cut into a disk shape to form a test piece, and the test piece is used. Then, the peak top intensity and temperature of tan ⁇ are measured.
• the measurement conditions are a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of ⁇ 70 to 100 ° C., and a heating rate of 3 ° C./min in accordance with JIS K 7244-10 (2005).
• the hydrogenated additive can have a peak top intensity of tan ⁇ of 1.0 or more. Some of the higher ones are 1.5 or more, and even 1.9 or more. The higher the peak top strength of tan ⁇ , the better the physical properties such as vibration damping at that temperature, and if it is 1.0 or more, sufficient vibration damping can be obtained in an actual use environment. Further, the hydrogenated additive has a peak top temperature of tan ⁇ of preferably ⁇ 50 ° C. or higher, more preferably ⁇ 40 ° C. or higher, further preferably ⁇ 30 ° C. or higher, still more preferably ⁇ 25 ° C. or higher, and 0 ° C. It may be the above.
• the upper limit of the peak top temperature of tan ⁇ may be 50 ° C. or lower, 40 ° C. or lower, or 35 ° C. or lower as long as the effect of the present invention is not impaired. Good.
• the range of the peak top temperature of tan ⁇ is, for example, preferably -50 to 50 ° C, more preferably -40 to 40 ° C, still more preferably -30 to 30 ° C, and even more preferably -25 to 25 ° C. .. If the peak top temperature of tan ⁇ is -50 ° C or higher, sufficient vibration damping properties can be obtained in an actual use environment, and if it is 50 ° C or lower, hardness requirements according to the application, adhesive or adhesion can be obtained. It can satisfy the desired adhesiveness when used as an agent.
• the hydrogenated additive has a series of temperature regions in which tan ⁇ is 1.0 or more at ⁇ 70 to 100 ° C. measured under the above measurement conditions, and the maximum width of the temperature region is preferably 12 ° C. or more. , More preferably 13 ° C. or higher, even more preferably 15 ° C. or higher, and even more preferably 17 ° C. or higher.
• the alicyclic skeleton (X) is incorporated in the main chain, and since it can have a higher vinyl bond amount, the molecular motion becomes smaller, so that the glass The transition temperature rises, and the glass transition becomes gentle with respect to temperature changes.
• the temperature range in which the tan ⁇ of the hydrogenated product is 1 or more becomes wide, and it becomes possible to exhibit the damping property in a wide temperature range.
• the maximum width of the temperature region in which tan ⁇ is 1.0 or more is 12 ° C. or higher, and further, 13 ° C. or higher, better vibration damping properties can be obtained in an actual use environment.
• the maximum width of the temperature region has no particular upper limit, but for example, from the viewpoint of productivity, the upper limit may be 35 ° C, 30 ° C, or 25 ° C. May be good.
• the hydrogenated composition can be obtained by adding a blocking inhibitor, which will be described later, to the above hydrogenated product.
• a blocking inhibitor which will be described later
• it can be obtained by adding an antiblocking agent when pelletizing a hydrogenated additive by a known method.
• a method of pelletizing for example, a hydrogenated product is extruded in a strand shape from a uniaxial or biaxial extruder and cut in water by a rotary blade installed in front of the die portion; from a uniaxial or biaxial extruder. Examples thereof include a method in which the hydrogenated material is extruded into a strand shape, water-cooled or air-cooled, and then cut with a strand cutter.
• the hydrogenated composition contains an antiblocking agent from the viewpoint of improving handleability.
• the handleability of the hydrogenated composition and the resin composition containing the resin which will be described later, will be improved, and the compatibility between the resin such as polypropylene and the hydrogenated material will be easily improved.
• the blocking inhibitor in this embodiment include inorganic particles and organic particles.
• the inorganic particles include oxides, hydroxides, sulfides, and nitridants of Group IA, Group IIA, Group IVA, Group VIA, Group VIA, Group 8IA, Group IB, Group IIB, Group IIIB, and Group IVB elements.
• organic particles examples include higher fatty acid metal salts, higher fatty acid amides, polystyrenes, acrylic resins, methacrylic resins, silicon resins, fluororesins, melamine resins, styrene-divinylbenzene copolymers, acrylic resin silicones and crosslinked products thereof.
• the preferable blocking inhibitor differs depending on the application.
• safety is particularly required, and it is suitable as it is difficult to bleed.
• the blocking inhibitor is preferably at least one selected from polypropylene-based resins and polyethylene-based resins, and more preferably polypropylene-based wax, from the viewpoint of maintaining safety, handleability, and transparency. And at least one selected from polyethylene waxes.
• the shape of the blocking inhibitor is not limited as long as the effect of the present invention is not impaired, and any of spherical, plate-shaped, columnar, amorphous and the like can be used.
• the blocking inhibitor is preferably spherical.
• the average particle size of the blocking inhibitor is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 15 ⁇ m, and even more preferably 0.8 to 10 ⁇ m. Within the above range, sufficient anti-blocking property can be obtained, handleability can be improved more easily, good transparency can be maintained, and vibration damping property and vibration damping property and vibration damping property and without large voids being generated in the molded product. Better flexibility.
• the average particle size of the blocking inhibitor can be measured using, for example, a laser diffraction type particle size distribution measuring device.
• a commercially available product can be used as the blocking inhibitor.
• the average particle size can be referred to the catalog value.
• the content of the blocking inhibitor is not limited as long as the effect of the present invention is not impaired.
• the content of the blocking inhibitor in 100% by mass of the hydrogenated composition is preferably 0.01 to 3% by mass. Further, from the viewpoint of easily suppressing the occurrence of blocking, it is more preferably 0.03% by mass or more, still more preferably 0.06% by mass or more. Further, from the viewpoint of achieving both the maintenance of transparency and the blocking prevention effect, the content is more preferably 2% by mass or less, still more preferably 1.5% by mass or less. If the content of the blocking inhibitor is within the above range, it is considered that the above-mentioned behavior of tan ⁇ is hardly affected.
• component (I) Since the above-mentioned hydrogenated product (hereinafter, may be abbreviated as “component (I)”) has good compatibility with other resin materials, this embodiment is a hydrogenated product-containing composition. And a resin (II) (hereinafter, may be abbreviated as “component (II)”).
• the component (II) is not particularly limited as long as it is a resin different from the component (I), and examples thereof include resins such as thermosetting resins and thermoplastic resins. From the viewpoint of compatibility and moldability, thermoplastic resins (heat) It is preferably (including a plastic elastomer).
• thermoplastic resin examples include olefin resins, styrene resins, polyphenylene ether resins, polycarbonate resins, polyamide resins, isobutylene-isoprene copolymer rubbers, and polyurethane thermoplastic elastomers. These thermoplastic resins can be used alone or in combination of two or more.
• the olefin resin examples include polyethylene resin, polypropylene resin, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, ethylene-vinyl acetate copolymer, and the like.
• examples thereof include ethylene-acrylic acid copolymers and olefin-based dynamic crosslinked thermoplastic elastomers (TPVs).
• TPVs olefin-based dynamic crosslinked thermoplastic elastomers
• the polyethylene-based resin include ethylene homopolymers such as high-density polyethylene, medium-density polyethylene, and low-density polyethylene; ethylene / butene-1 copolymer, ethylene / hexene copolymer, and ethylene / heptene.
• Polymers ethylene / octene copolymers, ethylene / 4-methylpentene-1 copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, ethylene / acrylic acid ester copolymers, ethylene / methacryl
• polyethylene-based copolymers such as acid copolymers, ethylene / methacrylic acid ester copolymers, ethylene-propylene-diene copolymer rubber (EPDM), and ethylene-vinyl acetate copolymers (EVA).
• polypropylene-based resin examples include homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, and propylene-pentene random copolymer.
• examples thereof include coalescence, propylene-hexene random copolymer, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer, propylene-ethylene-hexene random copolymer and the like.
• unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid
• unsaturated dicarboxylic acids such as maleic anhydride, citraconic acid, and itaconic acid
• these unsaturated monocarboxylic acids or unsaturated dicarboxylic acids are added to these polypropylene-based resins.
• a modified polypropylene resin obtained by graft-copolymerizing a modifier such as an unsaturated dicarboxylic acid anhydride such as an acid ester, amide or imide; maleic anhydride, citraconic anhydride or itaconic anhydride can also be used.
• styrene-based resin examples include polyalkylstyrenes such as polystyrene, polymethylstyrene, polydimethylstyrene, and polyt-butylstyrene; polyhalogenated styrenes such as polychlorostyrene, polybromostyrene, and polyfluorostyrene; and polychloromethylstyrene and the like.
• polyphenylene ether-based resin examples include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2-methyl-6-ethyl-1).
• 4-phenylene) ether poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl) -1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6-dibromomethyl) -1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-ditril-1,4-phenylene) ether, poly (2,6-dichloro-1) , 4-Phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether and the like.
• the polycarbonate resin may be either an aliphatic polycarbonate or an aromatic polycarbonate.
• divalent phenols such as bisphenol A, hydroquinone, 2,2-bis (4-hydroxyphenyl) pentane, 2,4-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, and bis (4-hydroxyphenyl) methane.
• polycarbonate-based resins produced from phosgens, halogen formates, and carbonate precursors such as carbonate esters.
• polyamide resin examples include polycaproamide (nylon 6), polyundecaneamide (nylon 11), polylauryl lactam (nylon 12), polyhexamethylene adipamide (nylon 6,6), and polyhexamethylene sebacamide (nylon 6,6).
• Homopolymers such as nylon 6,12), caprolactam / lauryllactam copolymer (nylon 6/12), caprolactam / aminoundecanoic acid copolymer (nylon 6/11), caprolactam / ⁇ -aminononanoic acid copolymer (nylon 6/11) Nylon 6,9), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/6, 6), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sevacate copolymer (nylon 6/6, 6/6 / Examples thereof include copolymers of 6, 12) and the like.
• polyurethane-based thermoplastic elastomer examples include a linear multi-block copolymer of a polyurethane obtained by a reaction of a low molecular weight polyol and an isocyanate as a hard segment and a polyurethane obtained by a reaction of a high molecular weight polyol and an isocyanate as a soft segment.
• the low molecular weight polyol may be any of an aliphatic diol, an alicyclic diol, and an aromatic diol
• the high molecular weight polyol includes a polyester polyol, a polyether polyol, a polycarbonate polyol, and the like
• the isocyanate is an isocyanate. It may be any of an aliphatic diisocyanate, an alicyclic diisocyanate, and an aromatic diisocyanate.
• the content ratio [(I) / (II)] of the component (I) to the component (II) is preferably 1/99 to 99/1, more preferably 3/97 to 80/20, and further in terms of mass ratio. It is preferably 5/95 to 50/50, and particularly preferably 10/90 to 40/60.
• the content ratios of the component (I) and the component (II) may be adjusted from the viewpoints of vibration damping property, mechanical properties, molding processability and the like. By increasing the content ratio of the component (I), the vibration damping property tends to be further improved. Further, by suppressing the content ratio of the component (II) to be small, it becomes easy to suppress the deterioration of the mechanical properties and the moldability, and to suppress the component (II) from bleeding out from the resin composition.
• the hydrogen additive is not particularly limited to the intended use, and as the component (II), the above-mentioned olefin resin, styrene resin, polyphenylene ether resin, polycarbonate resin, polyamide resin can be used as long as the effect of the present invention is not impaired.
• Isobutylene-isoprene copolymer rubber, and a polymer other than the thermoplastic resin selected from the polyurethane-based thermoplastic elastomer hereinafter, may be simply referred to as “polymer”
• the thermoplastic resin and the polymer may be used in combination as the component (II).
• polystyrene resin examples include polyphenylene sulfide resin; polyacetal resin; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; acrylic resin such as methyl polyacrylate and polymethylmethacrylate; polyoxymethylene homo.
• Polyoxymethylene resins such as polymers and polyoxymethylene copolymers; ethylene-propylene copolymer rubber (EPM); styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber or hydrogenated products thereof or modified products thereof; Natural rubber; synthetic isoprene rubber, liquid polyisoprene rubber and its hydrogenated or modified products; chloroprene rubber; acrylic rubber; butyl rubber; acrylonitrile-butadiene rubber; epichlorohydrin rubber; silicone rubber; fluororubber; chlorosulfonated polyethylene; urethane Examples include rubber; polyurethane-based elastomer; polyamide-based elastomer; styrene-based elastomer; polyester-based elastomer; and soft vinyl chloride resin.
• EPM ethylene-propylene copolymer rubber
• Natural rubber synthetic isoprene rubber, liquid polyisoprene
• the styrene-butadiene copolymer rubber, the styrene-isoprene copolymer rubber or the hydrogenated product thereof or a modified product thereof may be, for example, a styrene-butadiene block copolymer or the hydrogenated product thereof, styrene-. Examples thereof include isoprene block copolymers and hydrogenated products thereof.
• the component (II) in the resin composition molding is performed. From the viewpoint of processability, it is preferable to use it in combination with the above-mentioned thermoplastic resin.
• the thermoplastic resin is used in combination with at least one selected from the styrene-butadiene block copolymer and its hydrogenated product, and the styrene-isoprene block copolymer and its hydrogenated product, the above (I) It can be used in the content ratio of the component and the component (II).
• the content of at least one selected from the styrene-butadiene block copolymer and its hydrogenated product, and the styrene-isoprene block copolymer and its hydrogenated product is, for example, the component (I).
• it can be 1% by mass or more and 60% by mass or less, and 1% by mass or more and 50% by mass or less.
• the resin composition further contains various additives in addition to the above-mentioned hydrogen additive-containing composition containing the component (I) and the blocking inhibitor and the component (II) as long as the effects of the present invention are not impaired. It may be a thing.
• additives include processing aids, reinforcing agents, fillers, plasticizers, communicating air bubbles, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, lubricants, antistatic agents, and antibacterial agents.
• the resin composition is not particularly limited to the intended use, and the hydrogenated kumaron-inden resin, the hydrogenated rosin resin, the hydrogenated terpene resin, and the alicyclic hydrogenated petroleum are used as long as the effects of the present invention are not impaired.
• Hydrophilic resins such as resins; tackifier resins such as aliphatic resins composed of olefins and diolefin polymers; other weights such as hydrogenated polyisobutylene, hydrogenated polybutadiene, butyl rubber, polyisobutylene, polybutene, polyolefin-based elastomers, etc.
• the coalescence may be mixed and used as an additive.
• the content of the above-mentioned additive in the resin composition is not particularly limited, and can be appropriately adjusted according to the type of the additive, the use of the resin composition, and the like.
• the content of the above-mentioned additive is, for example, 50% by mass or less, 45% by mass or less, 30% by mass or less, 20% by mass with respect to 100% by mass of the total amount of the resin composition.
• it may be 10% by mass or less, 5% by mass or less, or 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, and 3% by mass or more.
• the method for preparing the resin composition of the present invention is not particularly limited, and can be prepared by using known means.
• the above component (I), anti-blocking agent, and component (II), and if necessary, various additives may be mixed using a mixer such as a Henschel mixer, V blender, ribbon blender, tumbler blender, or conical blender.
• the resin composition of the present invention can be prepared by melt-kneading at 80 to 250 ° C. using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or a roll. ..
• a resin composition can be prepared by dissolving each component in a solvent in which each component [at least the component (I) and the component (II)] is soluble, mixing the components, and removing the solvent to foam the resin composition.
• a resin composition obtained by dry-blending a foaming agent with a resin composition is injection-foamed into a mold having a cavity having a desired shape.
• the above-mentioned hydrogenated composition and resin composition are excellent in vibration damping property, transparency and flexibility due to the inclusion of the hydrogenated substance (I), and the handleability is improved by the blocking inhibitor. Further, it can be expected to be excellent in sound insulation, heat resistance, adhesiveness, impact resistance and the like. Therefore, the above-mentioned hydrogenated additive-containing composition and resin composition can be suitably used for applications requiring the above characteristics. Specific examples of the application include vibration damping materials, sound insulating materials, interlayer films for laminated glass, dam rubbers, sole materials, flooring materials, adhesives, weather seals and the like.
• the hydrogenated composition and the resin composition containing the resin (II) are suitable for molded articles such as containers, films and sheets that are useful for various purposes.
• the molded product can be used for medical use, food use and other applications requiring safety by appropriately selecting an antiblocking agent.
• One of the preferred embodiments of the food molded body includes food utensils such as food trays and food packaging containers for packaging retort pouch foods, mayonnaise, ketchup, soft drinks, ice cream and the like.
• one of the preferred embodiments of the medical molded article will be described below.
• the resin composition of the present embodiment can be used as a medical film suitable for a liquid packaging container such as a protective film, a blood bag, and an infusion bag by taking advantage of the above characteristics.
• a liquid packaging container is produced using the resin composition of the present embodiment, it is excellent in vibration damping property, transparency and flexibility.
• the medical film used for the liquid packaging container may be a single-layer film in which one type of the resin composition of the present embodiment is used alone, or two or more types are combined and laminated, and the composition differs for each layer. It may be a multilayer film. In the case of multiple layers, at least one layer may contain the resin composition of the present embodiment.
• the thickness of the film for a liquid packaging container is not particularly limited, but is preferably 100 to 500 ⁇ m, and more preferably 110 to 400 ⁇ m.
• the liquid packaging container formed from the medical film is excellent in flexibility before and after the high-pressure steam sterilization treatment, and therefore, is excellent in bag breaking strength even after the high-pressure steam sterilization treatment.
• the liquid packaging container may be a multi-chamber packaging container that is partially partitioned. Further, this partition may be opened by a constant pressure so that the divided chambers become one.
• the resin composition of the present embodiment contains a hydrogenated composition and a resin (II), and the resin (II) is used in the use of medical devices from the viewpoint of handleability, flexibility and transparency.
• An olefin-based resin is preferable, and a polypropylene-based resin is more preferable.
• a preferred embodiment of the liquid packaging container includes the following liquid packaging containers [1] to [4].
• a liquid packaging container composed of a laminated body having two or more layers having an inner layer and an outer layer. The inner layer comprises the resin composition of the present embodiment.
• a liquid packaging container composed of a laminated body having three or more layers having an intermediate layer between an inner layer and an outer layer. At least one selected from the inner layer and the intermediate layer comprises the resin composition of the present embodiment.
• these liquid packaging containers have a layer made of the resin composition of the present embodiment, they are excellent in vibration damping property, transparency and flexibility, and can be expected to be excellent in flexibility before and after the high-pressure steam sterilization treatment. ..
• the materials used for each layer of the liquid packaging container of [1] to [4] will be described.
• the inner layer is a layer in contact with the liquid.
• the intermediate layer is a layer located between the inner layer and the outer layer.
• the liquid packaging container does not have to have an intermediate layer, but it can be expected to exhibit high bag breaking strength by having an intermediate layer.
• the inner layer is made of the resin composition of the present embodiment.
• at least one selected from the inner layer and the intermediate layer is made of the resin composition of the present embodiment.
• the inner layer may be made of the resin composition of the present embodiment, or may be made of other resin.
• the resin constituting the inner layer and the intermediate layer is not particularly limited, but may be made of the resin composition of the present embodiment, or may be made of other resins. May be good.
• a composition is also a preferred embodiment.
• the melting point MP in of the resin component constituting the inner layer and the melting point MP mid of the resin component constituting the intermediate layer are calculated by the following formula MP in ⁇ MP mid. It is also a preferable aspect that the liquid packaging container satisfies the above conditions.
• the outer layer is a resin composition containing 55% by mass or more of a polypropylene-based resin having a content of a structural unit derived from propylene of 60 mol% or more (hereinafter, resin composition). It is preferably composed of a thing (M).
• the polypropylene-based resin is described as a preferred embodiment of the resin contained in the resin composition of the present embodiment in the same manner as the polypropylene-based resin described in the above description of the polyolefin-based resin.
• the content of the structural unit derived from propylene of the polypropylene resin is preferably 80 mol% or more, more preferably 80 to 100 mol%, still more preferably 85 to 100 mol%, and particularly preferably 90 to 100 mol%.
• the melting point of the polypropylene resin is preferably 130 to 180 ° C. When the melting point of the polypropylene-based resin is 130 ° C. or higher, the thinning of the film during heat sealing is suppressed. Further, when the melting point of the polypropylene resin is 180 ° C. or lower, the film moldability is improved. From the same viewpoint, the melting point of the polypropylene resin is more preferably 140 to 175 ° C, further preferably 150 to 175 ° C.
• the polypropylene-based resin includes homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, and propylene-penten random copolymer. At least one selected from polymers, propylene-hexene random copolymers, propylene-octene random copolymers, propylene-ethylene-pentene random copolymers, propylene-ethylene-hexene random copolymers, and modifications thereof. It is preferably a seed, more preferably a homopolypropylene.
• the resin composition (M) is a hydrogenated block copolymer having a polymer block mainly composed of a structural unit derived from an aromatic vinyl compound and a polymer block mainly composed of a structural unit derived from a conjugated diene compound. May be contained.
• the hydrogenated block copolymer for example, the hydrogenated additive contained in the hydrogenated additive-containing composition of the present embodiment can be used, the preferred one is the same, and the production method is also described.
• the resin composition (M) contains a polypropylene-based resin in an amount of 55% by mass or more, preferably 60% by mass or more, more preferably 60 to 99% by mass, and further preferably 70 to 99% by mass. %, Especially preferably 85 to 99% by mass.
• the content of the polypropylene-based resin is 55% by mass or more, the mechanical strength and moldability tend to be good.
• the resin composition (M) contains the hydrogenated product, the content of the hydrogenated product is preferably less than 45% by mass, more preferably less than 40% by mass, and further preferably 1% by mass.
• the resin composition (M) when the content of each component is within the above range, the transparency, flexibility, heat sealability and heat resistance tend to be good.
• the resin composition (M) may be made of only a polypropylene resin, and in the present embodiment, it is considered that the outer layer is made of the resin composition (M) for convenience even in such a case.
• the resin composition (M) may contain other components as long as the effects of the present invention are not impaired.
• Other components include, for example, additives such as antioxidants, ultraviolet absorbers, light stabilizers, colorants, and crystal nucleating agents; hydrogenated chroman-inden resin, hydrogenated rosin resin, hydrogenated terpene resin, and fat.
• Hydrophilic resin such as ring-based hydrogenated petroleum resin; Adhesive-imparting resin such as aliphatic resin composed of olefin and diolefin polymer; Hydrophilic polyisobutylene, hydrogenated polybutadiene, hydrogenated styrene-butadiene random copolymer , Hydrogenated Styrene-Isoprene Random Copolymer, Butyl Rubber, Polyisobutylene, Polybutene and Other Polymers. From the viewpoint of the effect of the present invention, the total content of the other components in the resin composition (M) is preferably 45% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. It is more preferably 10% by mass or less, still more preferably 5% by mass or less.
• either one or both of the inner layer and the outer layer are made of the resin composition of the present embodiment.
• the outer layer is made of the resin composition of the present embodiment.
• the liquid packaging containers of the above [1] to [4] are not particularly limited in terms of the components constituting the other layers as long as the above constitution is satisfied.
• the resin composition of the present embodiment and the resin composition (M) A layer made of a resin other than the above can be used. Further, for example, in the liquid packaging containers [2] to [4], the resin composition (M) can be used for the inner layer and the intermediate layer.
• the plurality of layers constituting the liquid packaging container of the above [1] to [4] are made of the resin composition (M)
• the distinction between each layer is the type of polypropylene-based resin contained in the resin composition (M). It can be distinguished by the amount of compounding.
• the thicknesses of the inner layer, the intermediate layer and the outer layer are not particularly limited and can be appropriately adjusted according to the intended use.
• the thickness of the inner layer is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
• the thickness of the intermediate layer is preferably 100 to 300 ⁇ m, more preferably 100 to 200 ⁇ m, and even more preferably 100 to 180 ⁇ m.
• the thickness of the outer layer is preferably 10 to 120 ⁇ m, more preferably 15 to 80 ⁇ m, and even more preferably 15 to 70 ⁇ m.
• Further layers may be provided between the inner layer, the intermediate layer, the outer layer, and the surface of the outer layer as long as the effects of the present invention are not impaired.
• the other layer include an adhesive layer, a protective layer, a coating layer, a light reflecting layer, a light absorbing layer, and the like.
• the inner layer and the intermediate layer are in contact with each other, and it is preferable that the intermediate layer and the outer layer are in contact with each other.
• the method for manufacturing the liquid packaging container is not particularly limited.
• a laminated body is formed by using a known method for manufacturing a laminated body, and then heat-sealed and then separated (cut out) to obtain a liquid packaging container. For medical use, it is further sterilized.
• the film formability is improved, so that there is an advantage that it is easy to form a film (laminated body) free of fish eyes and foreign substances.
• the following method is preferably mentioned.
• each layer is kneaded using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, and a roll to prepare a resin composition for each layer.
• a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, and a roll to prepare a resin composition for each layer.
• a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, and a roll to prepare a resin composition for each layer.
• Each of the obtained resin compositions is molded into a film or tube by co-extrusion molding using a multilayer T-die, air-cooled or water-cooled inflation molding using a multilayer circular T-die, or the like.
• the cooling temperature during air-cooled or water-cooled inflation molding is preferably 7 to 70 ° C, more preferably 10 to 40 ° C. Further, from the viewpoint of ease of manufacturing the liquid packaging container, it is preferable to mold it into a tube shape. If it is a tubular molded product, a liquid packaging container can be manufactured by heat-sealing and then cutting (cutting out). On the other hand, in the case of a film-shaped molded product, it is necessary to superimpose the two sheets and then heat-seal. In the case of medical use, steam sterilization, high-pressure steam sterilization, autoclave sterilization and the like are further performed as sterilization treatments. By having a liquid discharge member including a port and a cap such as a rubber stopper, it becomes a liquid packaging container having a discharge port, and is effectively used as a medical container such as an infusion bag.
• the resin composition of the present embodiment makes use of the above-mentioned characteristics, and makes use of the above-mentioned characteristics, such as an extension tube of an infusion set and a blood transfusion set, a tube / catheter for digestive organs, a tube / catheter for respiratory organs, a tube / catheter for urinary organs, and a tube / catheter for blood vessels.
• IVR Minimally Invasive Endovascular Treatment
• the medical tube may be a single-layer tube in which one type of the resin composition of the present embodiment is used alone, or a multi-layered tube in which two or more types may be combined and the composition may be different for each layer.
• the layer made of the resin composition of the present embodiment may be one of the innermost layer, the intermediate layer, and the outermost layer, and may be a plurality of layers, depending on the desired performance to be imparted. You may. Further, a layer using another polymer may be laminated. Specific examples of other layers and applicable other polymers include those similar to those exemplified in the multilayer film of the medical film described above.
• the resin composition of the present embodiment makes use of the above-mentioned characteristics, for example, medical devices such as rubber stoppers for pharmaceuticals, packing for containers, syringes, artificial dialysers, blood component separators, artificial lungs, and wound dressings. It is also used for sanitary products, sanitary materials such as paper dialysis; medical equipment such as surgical clothing and disposable sheets for hospitals. It should be noted that these medical devices do not need to be entirely formed from the resin composition of the present embodiment.
• medical devices such as rubber stoppers for pharmaceuticals, packing for containers, syringes, artificial dialysers, blood component separators, artificial lungs, and wound dressings. It is also used for sanitary products, sanitary materials such as paper dialysis; medical equipment such as surgical clothing and disposable sheets for hospitals. It should be noted that these medical devices do not need to be entirely formed from the resin composition of the present embodiment.
• the total weight average molecular weight of the polymer block (A) was determined by gel permeation chromatography (GPC) as a standard polystyrene-equivalent molecular weight.
• GPC measuring device and measuring conditions -Device: GPC device "HLC-8020" (manufactured by Toso Co., Ltd.) Separation column: "TSKgel GMHXL", “G4000HXL” and "G5000HXL” manufactured by Toso Co., Ltd. were connected in series.
• X, X1 and X2 show the following alicyclic skeletons.
• X Alicyclic skeleton having a combination of the following (i) to (vi) substituents
• a distortion control type dynamic viscoelastic device "ARES-G2" with a disk diameter of 8 mm (TA Instruments) Ment Japan Co., Ltd.) was used as a parallel plate vibration rheometer.
• the test sheet completely fills the gap between the two flat plates, and with a strain amount of 0.1%, the test sheet is vibrated at a frequency of 1 Hz, and a constant temperature of 3 ° C./min is applied from ⁇ 70 ° C. to 100 ° C. The temperature rose quickly.
• the temperature of the test sheet and the disk was maintained until there was no change in the measured values of shear loss elastic modulus and shear storage elastic modulus, and the maximum value (peak top intensity) of the peak intensity of tan ⁇ and the maximum value were obtained.
• the temperature (peak top temperature) was determined. Further, the maximum width of the temperature region where tan ⁇ is 1.0 or more, and the tan ⁇ intensity at 20 ° C. and 30 ° C. were determined. The larger the value, the better the vibration damping property.
• a mixture of 20 kg and 6.44 kg of butadiene (1) is added at the average diene feed rate shown in Table 2 over 5 hours and then polymerized for 2 hours, and 1.50 kg of styrene (2) is further added and polymerized for 1 hour.
• a reaction solution containing a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer was obtained.
• a Ziegler-based hydrogenation catalyst formed of nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the reaction was carried out under the conditions of a hydrogen pressure of 1 MPa and 80 ° C. for 5 hours.
• TPE1 polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer
• TEDA tetramethylethylenediene
• TMEDA tetramethylethylenediene
• styrene (2) was further added and polymerized for 1 hour
• butadiene (2) was further polymerized.
• 0.81 kg was added at the average diene feed rate shown in Table 2 over 1 hour and then polymerized for 1 hour to obtain a reaction solution containing a polystyrene-polybutadiene-polystyrene-polybutadiene tetrablock copolymer.
• Palladium carbon (palladium carrying amount: 5% by mass) was added to this reaction solution as a hydrogenation catalyst in an amount of 5% by mass based on the block copolymer, and the reaction was carried out under the conditions of hydrogen pressure of 2 MPa and 150 ° C. for 10 hours. .. After allowing to cool and pressurize, palladium carbon was removed by filtration, the filtrate was concentrated, and vacuum dried to obtain a hydrogenated block copolymer (TPE5). The results of the physical property evaluation are shown in Table 3. The diene feed time "5/1" in Table 2 indicates that butadiene (1) was added over 5 hours and butadiene (2) was added over 1 hour.
• the average diene feed rate (kg / h) “13.8 / 4.05” per 1 mol of active terminal in Table 2 is the average diene feed rate of butadiene (1) of 13.8 (kg / h).
• the average diene feed rate of butadiene (2) is 4.05 (kg / h).
• Examples 1 to 9 have lower blocking strength and are superior in handleability as compared with Comparative Examples 1 to 4 to which the blocking inhibitor is not added. Further, from the comparison with Comparative Examples 1 to 4 in Examples 1 to 9, it can be seen that the pH shift is small even if the blocking inhibitor is contained.
• Polyolefin resin (PO1) "Prime Polypro (registered trademark) F327” (manufactured by Prime Polymer Co., Ltd.), propylene-ethylene-butene random copolymer (polypropylene resin), MFR 7.0 g / 10 minutes (230 ° C, 21.6 N), melting point 139 ° C
• the physical properties of PO1 are shown in Table 6.
• the resin composition containing the hydrogenated agent (I) containing the alicyclic skeleton (X), the blocking inhibitor, and the resin (II) has a low haze and Young's modulus. It can be seen that it is excellent in transparency and flexibility. Further, from Example 15, a resin containing two types of hydrogenators, TPE6 containing an alicyclic skeleton (X) and TPE7 not containing an alicyclic skeleton (X), an antiblocking agent, and a polyolefin resin PO1. It can be seen that the excellent physical properties of the composition are not lost. On the other hand, from Comparative Examples 5 to 7, it can be seen that the resin composition containing the alicyclic skeleton (X) and not containing the hydrogenated additive (I) has lower transparency and flexibility than the examples.
• the hydrogenated composition of the present invention and the resin composition containing the hydrogenated composition can be used for various purposes. Applications include, for example, damping materials, sound insulating materials, interlayer films for laminated glass, dam rubbers, sole materials, flooring materials, adhesives, and weather seals.
• the resin composition of the present invention can be effectively used as a food packaging container for packaging retort pouch foods, mayonnaise, ketchup, soft drinks, ice cream, etc., in addition to the above-mentioned medical containers.

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• 2020
  • 2020-05-22 WO PCT/JP2020/020209 patent/WO2020235664A1/ja active Application Filing
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