WO2012141264A1 - Corps stratifié et dispositif médical - Google Patents

Corps stratifié et dispositif médical Download PDF

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Publication number
WO2012141264A1
WO2012141264A1 PCT/JP2012/060066 JP2012060066W WO2012141264A1 WO 2012141264 A1 WO2012141264 A1 WO 2012141264A1 JP 2012060066 W JP2012060066 W JP 2012060066W WO 2012141264 A1 WO2012141264 A1 WO 2012141264A1
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Prior art keywords
resin layer
adhesive resin
layer
polyolefin
alicyclic
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PCT/JP2012/060066
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English (en)
Japanese (ja)
Inventor
中川　淳
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三菱化学株式会社
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Publication of WO2012141264A1 publication Critical patent/WO2012141264A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/10—Bag-type containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/804—Disposable containers or packages with contents which are mixed, infused or dissolved in situ, i.e. without having been previously removed from the package
    • B65D85/808—Disposable containers or packages with contents which are mixed, infused or dissolved in situ, i.e. without having been previously removed from the package for immersion in the liquid to release part or all of their contents, e.g. tea bags
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • a polyolefin bag such as polyethylene or polypropylene is used.
  • the infusion bag made of polyolefin has good hygiene because it does not contain a plasticizer, but it is low in flexibility and has insufficient impact resistance, particularly low temperature impact resistance. Absent.
  • Patent Document 1 discloses a material useful for sealing and construction as a hard vinyl chloride resin and a copolyester elastomer or a styrene block. A fusion-bonded copolymer or the like is disclosed.
  • Patent Document 2 discloses a multilayer film having a polypropylene resin layer as a surface layer through a sulfone group-containing polyester resin layer and a modified polyolefin layer (adhesive layer) as an antifouling film for vinyl chloride resin wallpaper. Has been.
  • Patent Document 3 discloses various bonds between a poly (vinylidene chloride) layer and a polypropylene homopolymer layer as a second layer as a multi-layer structure for producing a medical solution container. Layers are illustrated.
  • Patent Document 4 as a medical device, a multilayer film having a connecting layer containing polyester between a vinyl chloride resin layer as a first layer and a layer containing polyolefin as a second layer. Tubing is disclosed.
  • the multi-layer structure disclosed in Patent Document 3 can be used even when any bonding layer is used, even when stress is applied to the structure or when a delamination test is performed between layers. It does not have enough adhesiveness to withstand. Therefore, when this was used for an infusion bag, there was anxiety in practical use. Further, the laminate manufactured in Patent Document 4 has insufficient transparency and adhesiveness.
  • the present inventor can solve the above problems by using an adhesive resin layer made of a specific resin composition for the soft vinyl chloride resin layer and the polyolefin layer.
  • the headline and the present invention were completed. That is, the gist of the present invention resides in the following [1] to [14].
  • the styrenic elastomer is composed of at least two polymer blocks P mainly composed of a vinyl aromatic compound and at least one heavy body mainly composed of butadiene and / or isoprene. [1] to [1] to [1] to [1] to [1] to [1] to [5] a block copolymer comprising the combined block Q and the polymer block P occupying 5 to 55% by weight. 3] The laminate according to any one of [1].
  • a laminate comprising an alicyclic polyester and an adhesive resin layer (B3) containing a styrene elastomer and a modified polyolefin resin.
  • the alicyclic polyester includes a segment mainly composed of units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol;
  • a medical container comprising the laminate according to any one of [1] to [8].
  • a resin composition comprising an alicyclic polyester and a styrene elastomer, wherein the alicyclic polyester has a melting point of 130 to 200 ° C., and the styrene elastomer has a number average molecular weight of 190,000 or less. object.
  • the alicyclic polyester has a segment mainly composed of a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol, and a polyalkylene ether polyol segment [ [11] or [12].
  • the styrenic elastomer comprises at least two polymer blocks P mainly composed of a vinyl aromatic compound and at least one polymer block Q mainly composed of butadiene and / or isoprene.
  • a laminate and a medical container that have good flexibility, hygiene, transparency and impact resistance, and good adhesion between layers. Moreover, according to this invention, the softness
  • the laminate according to the first aspect of the present invention includes an adhesive resin layer containing a soft vinyl chloride resin layer (A), an alicyclic polyester having a melting point of 130 to 200 ° C., and a styrene elastomer having a number average molecular weight of 190,000 or less. It has (B1) and a polyolefin layer (C).
  • A soft vinyl chloride resin layer
  • B1 alicyclic polyester having a melting point of 130 to 200 ° C.
  • C polyolefin layer
  • the laminate according to the second aspect of the present invention includes a soft vinyl chloride resin layer (A), an adhesive resin layer (B2) containing an alicyclic polyester, an adhesive resin containing a styrene elastomer and a modified polyolefin resin. It has a layer (B3) and a polyolefin layer (C) in this order.
  • the resin composition according to the third aspect of the present invention includes an alicyclic polyester and a styrene elastomer, the alicyclic polyester has a melting point of 130 to 200 ° C., and the number average of the styrene elastomer.
  • the molecular weight is 190,000 or less.
  • the soft vinyl chloride resin layer (A) in the present invention contains at least a vinyl chloride resin.
  • the vinyl chloride resin which comprises a soft vinyl chloride resin layer (A) is not limited, The homopolymer or copolymer of vinyl chloride is mentioned.
  • Monomers that can be copolymerized with vinyl chloride are not limited, and examples include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or an ester thereof, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, and vinylidene chloride.
  • a partially crosslinked resin may be used.
  • a polymer blend of a polyvinyl chloride resin for example, a polymer blend composed of a vinyl chloride resin and polyvinylidene chloride may be used.
  • a vinyl chloride resin used for the soft vinyl chloride resin layer (A) a vinyl chloride homopolymer is preferable.
  • the average degree of polymerization of the vinyl chloride resin used for the soft vinyl chloride resin layer (A) is not limited, but is preferably 500 to 6000, more preferably 800 to 3000.
  • the reduced viscosity (K value) of the vinyl chloride resin used in the present invention is not limited, but is preferably 50 to 110, more preferably 60 to 90 as a value based on JIS K7367-2 (1999). .
  • the production method of the vinyl chloride resin is not limited, and examples thereof include a production method such as a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method. Further, it may be a plastisol or an aqueous latex in which vinyl chloride resin fine particles are dispersed in an organic medium.
  • the soft vinyl chloride resin layer (A) in the present invention preferably contains a plasticizer together with the vinyl chloride resin.
  • the plasticizer used for the soft vinyl chloride resin layer (A) is not limited, but specific examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate.
  • Phthalates having 1 to 12 carbon atoms such as diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, diundecyl phthalate, ditridecyl phthalate, didodecyl phthalate, diisocumyl phthalate and dinonyl phthalate Acid esters; diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl a Rate, dihexyl azelate, diisooctyl azelate, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate,
  • the amount of the plasticizer used in the present invention is not limited, but it is preferably 1 to 150 parts by weight, more preferably 15 to 120 parts by weight, still more preferably 20 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. 100 parts by weight.
  • the blending amount of the plasticizer By setting the blending amount of the plasticizer to be equal to or more than the lower limit, the flexibility of the laminate of the present invention is improved. On the other hand, by making the compounding quantity of a plasticizer below the said upper limit, while preventing a plasticizer from bleeding out from the laminated body of this invention, the deterioration of a moldability can be prevented.
  • the soft vinyl chloride resin layer (A) in the present invention may contain a stabilizer together with the vinyl chloride resin.
  • the stabilizer used for the soft vinyl chloride resin layer (A) is not limited, but can be appropriately selected from known stabilizers for vinyl chloride resin, such as tribasic lead sulfate and dibasic phthalates.
  • Lead silicate, lead silicate, lead orthosilicate-silica gel coprecipitate, dibasic lead stearate, cadmium-barium stabilizer, barium-zinc stabilizer, calcium-zinc stabilizer, tin stabilizer, and Examples thereof include stabilizers mainly composed of inorganic salts such as magnesium, aluminum or silicon such as hydrotalcite. These stabilizers may use only 1 type of compound, or may use 2 or more types of compounds together.
  • the amount of the stabilizer used in the present invention is not limited, but it is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, still more preferably 3 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. 15 parts by weight.
  • the stabilizer is blended in the above range, the thermal stability or moldability tends to be good.
  • the adhesive resin layer (B1) in the present invention contains at least an alicyclic polyester and a styrene-based elastomer.
  • the adhesive resin layer (B1) contains at least an alicyclic polyester and a styrene-based elastomer.
  • both the vinyl chloride resin layer (A) and the polyolefin layer (C) can exhibit good adhesiveness. It becomes possible.
  • alicyclic polyester expresses an affinity and adhesive effect with soft vinyl chloride resin
  • styrene elastomer expresses an affinity and adhesive effect with polyolefin
  • the alicyclic polyester and the styrene elastomer have a good affinity.
  • the resin composition containing the alicyclic polyester and styrene elastomer used for the adhesive resin layer (B1) is the resin composition according to the third aspect of the present invention.
  • the content of the alicyclic compound constituting the alicyclic polyester is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more.
  • the adhesive performance as an adhesive resin layer (B1) can be improved by making the content rate of the alicyclic compound which comprises alicyclic polyester more than the said lower limit.
  • the upper limit of the content rate of the alicyclic compound which comprises this alicyclic polyester is 100 weight% normally.
  • the alicyclic polyester in the present invention contains a polyalkylene ether polyol as a soft segment
  • the content of the alicyclic compound constituting the alicyclic polyester the weight of the alkylene ether polyol is excluded and handled.
  • the compound is not limited.
  • cyclopentane diol such as 1,2-cyclopentanediol and 1,3-cyclopentanediol
  • 5-membered ring diols such as 2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol and cyclopentanedimethanol bis (hydroxymethyl) tricyclodecane
  • 1,2-cyclohexanediol, 1,3-cyclohexanediol and 1 Cyclohexanediol such as 1,4-cyclohexanediol
  • cyclohexanedimethanol such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol
  • cyclohexanedimethanol is preferred, and 1,4-cyclohexanedimethanol is particularly preferred. Two or more of these alicyclic diols can be used in combination.
  • the ratio of the trans form is not less than the lower limit, the heat resistance and moldability of the alicyclic polyester tend to be improved. Further, the trans isomer content is usually 100 mol% or less, and more preferably 85 mol% or less. When the ratio of the transformer body is not more than the above upper limit value, the moldability during coextrusion tends to be improved.
  • a compound other than the alicyclic compound can be used in combination as a raw material monomer.
  • the compound that can be used as the raw material monomer for the alicyclic polyester is not limited, and various dicarboxylic acids, diols, oxycarboxylic acids, caprolactones, polyfunctional compounds, and the like can be used.
  • dicarboxylic acids other than alicyclic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 4,4 ′.
  • Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethane dicarboxylic acid and 4,4′-diphenylsulfone dicarboxylic acid; succinic acid, glutaric acid, adipic acid And aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid and dodecadicarboxylic acid. Among these, terephthalic acid or 2,6-naphthalenedicarboxylic acid is preferable, and terephthalic acid is particularly preferable. Two or more dicarboxylic acids other than these alicyclic dicarboxylic acids can be used in combination.
  • diols other than alicyclic diols in addition to polyalkylene ether polyols described later, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, Aliphatic diols such as decamethylene glycol, neopentyl glycol and diethylene glycol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′- and aromatic diols such as ⁇ -hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone and bis (4- ⁇ -hydroxyethoxyphenyl) sulfonic acid.
  • 1,4-butanediol or ethylene glycol is preferable in addition to the polyalkylene ether polyol described later, and 1,4-butanediol is particularly preferable.
  • Two or more diols other than these alicyclic diols can be used in combination.
  • polyfunctional compound examples include polyols such as trimellitic acid, pyromellitic acid, and pentaerythritol, tricarboxylic acid, and tetracarboxylic acid.
  • polyols such as trimellitic acid, pyromellitic acid, and pentaerythritol, tricarboxylic acid, and tetracarboxylic acid.
  • units derived from 1,4-cyclohexanedicarboxylic acid are preferably 50 mol% or more, more preferably 60 mol%, in all dicarboxylic acid units. As mentioned above, it is more preferable that it is 70 mol% or more.
  • the upper limit of the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in all dicarboxylic acid units is 100 mol%. If the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in the total dicarboxylic acid units is within the above range, the proportion of unreacted substances or low molecular weight components is small, so that hygiene tends to be good.
  • the upper limit of the proportion of 1,4-cyclohexanedimethanol-derived units in all diol units is usually 100 mol%.
  • the proportion of units derived from 1,4-cyclohexanedimethanol in all diol units excluding polyalkylene ether polyol is within the above range, the proportion of unreacted substances and low molecular weight components is small, and thus hygiene tends to be good. It becomes.
  • the alicyclic polyester used for the adhesive resin layer (B1) in the present invention may be a so-called block copolymer having a hard segment and a soft segment and containing a polyalkylene ether polyol as the soft segment.
  • the structure of the alicyclic polyester described above corresponds to the hard segment.
  • the alicyclic polyester contains a polyalkylene ether polyol as a soft segment because the crystallization speed is improved and the transparency after heat sterilization tends to be good.
  • the polyalkylene ether polyol is an embodiment of “diol other than alicyclic diol” as described above.
  • the laminate of the present invention can further improve flexibility, impact resistance, soft touch, and the like.
  • the polyalkylene ether polyol constituting the soft segment is not limited, but among them, polyalkylene ether glycol is preferable.
  • polyalkylene ether glycol examples include polyethylene ether glycol, polypropylene ether glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol. Particularly preferred is polytetramethylene ether glycol. These polyalkylene ether glycols may be used in combination.
  • a block copolymer having a hard segment and a soft segment is used as the alicyclic polyester in the present invention
  • a structure derived from 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol Is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, and polytetramethylene ether glycol is preferably used as the soft segment.
  • the number average molecular weight of the soft segment that is, the number average molecular weight of the polyalkylene ether polyol is preferably 200 to 4000, more preferably 300 to 3000, and still more preferably 500 to 2500.
  • Good flexibility can be obtained by setting the number average molecular weight of the polyalkylene ether polyol to the lower limit value or more. Moreover, by making a number average molecular weight below the said upper limit, the phase-separation within alicyclic polyester can be suppressed and it can prevent that the transparency or heat resistance of a laminated body falls.
  • the “number average molecular weight” referred to here is measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a POLYTETRAHYDROFURAN calibration kit manufactured by POLYMERLABORATORIES, UK may be used.
  • the content of the polyalkylene ether polyol in the alicyclic polyester is not limited, but is preferably 3 to 40% by weight, more preferably 6 to 30% by weight.
  • the content of the polyalkylene ether polyol that is a soft segment is set to the above lower limit value or more, the flexibility, adhesiveness, and tackiness tend to be improved. Moreover, it can suppress that transparency and heat resistance of a laminated body fall by making content of a soft segment below the said upper limit.
  • the content of the structural unit derived from the polyalkylene ether polyol can be calculated from the charged ratio at the time of production or quantified by an instrumental analysis method such as 1 H-NMR spectrum analysis.
  • the alicyclic polyester used for the adhesive resin layer (B1) in the present invention has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg (kgf) according to test condition 4 of JIS K7210 (1999).
  • MFR melt flow rate
  • it is in the range of 0.1 to 100 (g / 10 minutes), more preferably 0.5 to 80 (g / 10 minutes), and still more preferably 1.0 to 60 (g / 10 minutes). Is preferred.
  • the melting point of the alicyclic polyester used for the adhesive resin layer (B1) in the present invention is 130 ° C. or higher, preferably 160 ° C. or higher, and 200 ° C. or lower, in terms of the balance between processability and transparency. Preferably it is 190 degrees C or less.
  • the melting point of the alicyclic polyester was determined by using a differential scanning calorimeter (DSC) or the like at a rate of temperature increase of 100 ° C./min from room temperature to 250 ° C. and held for 3 minutes, and then cooled to ⁇ 100 ° C. It is the temperature of the melting peak when the temperature is raised to 250 ° C. at a rate of temperature increase of 10 ° C./min after cooling at 10 ° C./min.
  • DSC differential scanning calorimeter
  • the styrenic elastomer in the present invention is not limited as long as it has a polymer block mainly composed of a vinyl aromatic compound and a polymer block imparting flexibility, and specifically, for example, vinyl aromatic A block copolymer having at least two polymer blocks P mainly composed of a compound and at least one polymer block Q mainly composed of butadiene and / or isoprene and / or hydrogenating the block copolymer. (Hereinafter, the polymer block P may be abbreviated as “block P” and the polymer block Q may be abbreviated as “block Q”).
  • a polymer mainly composed of a vinyl aromatic compound means a polymer obtained by polymerizing a monomer mainly composed of a vinyl aromatic compound, and “a polymer mainly composed of butadiene and / or isoprene”.
  • the term “polymerized” means a monomer mainly composed of butadiene and / or isoprene.
  • “mainly” here means 50 mol% or more.
  • the monomeric vinyl aromatic compound constituting the block P is not limited, but a styrene derivative such as styrene or ⁇ -methylstyrene is preferable. Of these, styrene is the main component.
  • the block P may contain a monomer other than the vinyl aromatic compound as a raw material.
  • Block Q may be a hydrogenated derivative obtained by hydrogenating a double bond having after polymerization.
  • the hydrogenation rate of the block Q is not limited, but is preferably 50 to 100%, more preferably 80 to 100%.
  • the weight ratio of the block P in the styrenic elastomer is not limited, but is preferably 5% by weight or more, more preferably 10% by weight or more, on the other hand, 55% by weight or less, preferably 50% by weight. More preferably, it is more preferably 45% by weight or less.
  • the weight ratio of the block P is in the above range, the adhesiveness of the laminate of the present invention tends to be good.
  • the 1,2-addition structure of isoprene in the microstructure of the block Q is preferably 20% by weight or more, more preferably 30% by weight or more.
  • the upper limit is 100% by weight.
  • the block copolymer represented by the following formula (1) or (2) is more preferably a hydrogenated derivative (hereinafter sometimes abbreviated as a hydrogenated block copolymer).
  • a hydrogenated block copolymer a hydrogenated block copolymer
  • the adhesiveness of the laminate of the present invention tends to be good.
  • m and n are preferably larger in terms of lowering the order-disorder transition temperature as a rubbery polymer, but smaller in terms of ease of production and cost. .
  • m and n are preferably given as integers of 1 to 5, more preferably 2 to 4.
  • the block copolymer or hydrogenated block copolymer (hereinafter collectively referred to as “(hydrogenated) block copolymer”) is represented by the formula (2) because it has excellent rubber elasticity. )
  • a (hydrogenated) block copolymer represented by formula (1) is preferred to a block copolymer, and (hydrogenated) block copolymer represented by formula (1) wherein m is 3 or less.
  • (Hydrogenated) block copolymer represented by the formula (1) in which m is 2 or less is more preferable.
  • the number average molecular weight of the styrene elastomer in the first embodiment of the present invention is 190,000 or less. If the number average molecular weight of the styrene-based elastomer exceeds the upper limit, the fluidity is lowered. As a result, the styrene-based elastomer forms a domain in the adhesive resin layer (B1), so that the adhesiveness to other resin layers is reduced. In particular, the adhesion with the polyolefin layer is deteriorated.
  • the production method of the styrene elastomer in the present invention is not particularly limited as long as the above structure and physical properties can be obtained. Specifically, for example, it can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or the like. In addition, a known method such as hydrogenation (hydrogenation) of the block copolymer can be employed, for example, in an inert solvent in the presence of a hydrogenation catalyst.
  • Examples of commercially available hydrogenated block copolymers include “KRATON (registered trademark) -G” manufactured by Kraton Japan Co., Ltd., “Septon (registered trademark)” and “Hibler (registered trademark)” manufactured by Kuraray Co., Ltd. And “Tuftec (registered trademark)” manufactured by Asahi Kasei Corporation.
  • a rubber softener may be contained in the adhesive resin layer (B1) within the range where the effects of the present invention are exhibited.
  • Usable rubber softeners are not limited as long as the flexibility of the adhesive resin layer (B1) can be adjusted, and among them, hydrocarbon rubber softeners are preferable.
  • Adhesiveness to the polyolefin layer (C) can be improved by setting the blending ratio of the styrene elastomer to the lower limit value or more. Moreover, affinity with a soft vinyl chloride resin can be improved by making the mixture ratio of a styrene-type elastomer below the said upper limit.
  • the blending of the alicyclic polyester and the styrene elastomer constituting the adhesive resin layer (B1) in the present invention may be made in advance as a uniform resin composition, or when molding a laminate described later, May be used by appropriately blending (dry blending).
  • the method is not limited.
  • a method of mixing with a Henschel mixer, a V-blender, a ribbon blender or a tumbler blender The mixture obtained by such a method can be obtained by further kneading with a single screw extruder, twin screw extruder, kneader or Banbury mixer, and then granulating. Moreover, it can also mix using a kneader or a roll.
  • the production conditions for producing the resin composition by these methods are not limited, and can be appropriately set under known conditions.
  • the temperature at the time of melt mixing may be any temperature at which at least one of the raw material components is in a molten state, but usually the temperature at which all the components used are melted is selected, and the temperature is generally 150 to 250 ° C.
  • the adhesive resin layer (B2) in the second aspect of the present invention contains at least alicyclic polyester.
  • the vinyl chloride resin layer (A) and the adhesive resin layer (B3) can exhibit good adhesiveness and / or affinity. It becomes possible. Although the cause is not clear, it is considered that the alicyclic polyester has high affinity with both the soft vinyl chloride resin (A) and the resin constituting the adhesive resin layer (B3).
  • the content of the alicyclic polyester in the adhesive resin layer (B2) is not limited, but is preferably 50% by weight or more, and more preferably 70% by weight or more.
  • the upper limit is preferably 100% by weight.
  • the alicyclic polyester in this invention will not be limited if it has an alicyclic compound as a raw material monomer, It is preferable that it is polyester which has an alicyclic compound as a main component.
  • “having an alicyclic compound as a main component” means a polyester containing 50% by weight or more of an alicyclic compound as a structural unit of the polyester (in other words, as a raw material monomer).
  • the content of the alicyclic compound constituting the alicyclic polyester is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more.
  • Adhesive performance as the adhesive resin layer (B2) can be improved by setting the content of the alicyclic compound constituting the alicyclic polyester to the lower limit value or more.
  • the upper limit of the content rate of the alicyclic compound which comprises the said alicyclic polyester is 100 weight% normally.
  • the alicyclic polyester in the present invention contains a polyalkylene ether polyol as a soft segment
  • the content of the alicyclic compound constituting the alicyclic polyester the weight of the alkylene ether polyol is excluded and handled.
  • the alicyclic compound constituting the alicyclic polyester in the present invention is the same as that described in the adhesive resin layer (B1) in the laminate according to the first aspect of the present invention as a raw material monomer. Can do.
  • the 6-membered ring compound may be a trans isomer or a cis isomer, or a mixture thereof.
  • the trans isomer content is preferably 50 mol% or more, more preferably 60 mol% or more, based on the total amount of the trans isomer and the cis isomer. 70 mol% or more is more preferable.
  • the ratio of the trans form is not less than the lower limit, the heat resistance and moldability of the alicyclic polyester tend to be improved.
  • the upper limit of the trans isomer content is usually 100 mol%, and more preferably 85 mol% or less.
  • the ratio of the transformer body is not more than the above upper limit value, the moldability during coextrusion tends to be improved.
  • a compound other than the alicyclic compound can be used in combination as a raw material monomer.
  • the compounds other than the alicyclic compounds that can be used here are the same as those mentioned in the description of the adhesive resin layer (B1).
  • the unit derived from 1,4-cyclohexanedicarboxylic acid is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably, among all dicarboxylic acid units. It is 70 mol% or more.
  • the upper limit of the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in all dicarboxylic acid units is usually 100 mol%.
  • 1,4-cyclohexanedimethanol is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol in all diols excluding the polyalkylene ether polyol described later. % Or more is preferable.
  • the upper limit of the proportion of 1,4-cyclohexanedimethanol-derived units in all diol units is usually 100 mol%.
  • the alicyclic polyester used for the adhesive resin layer (B2) in the present invention may be a so-called block copolymer having a hard segment and a soft segment and containing a polyalkylene ether polyol as the soft segment.
  • the structure of the alicyclic polyester described above corresponds to the hard segment.
  • the alicyclic polyester contains a polyalkylene ether polyol as a soft segment, the crystallization speed is improved and the transparency after heat sterilization tends to be good, which is preferable.
  • the polyalkylene ether polyol is an embodiment of “diol other than alicyclic diol” as described above.
  • the laminate of the present invention can further improve flexibility, impact resistance, soft touch, and the like.
  • a block copolymer having a hard segment and a soft segment is used as the alicyclic polyester in the present invention
  • a structure derived from 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol Is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, and polytetramethylene ether glycol is preferably used as the soft segment.
  • the number average molecular weight of the soft segment that is, the number average molecular weight of the polyalkylene ether polyol is preferably 200 to 4000, more preferably 300 to 3000, and still more preferably 500 to 2500.
  • the “number average molecular weight” referred to here is measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a POLYTETRAHYDROFURAN calibration kit manufactured by POLYMERLABORATORIES, UK may be used.
  • the content of the polyalkylene ether polyol in the alicyclic polyester is not limited, but is preferably 3 to 40% by weight, more preferably 6 to 30% by weight.
  • the content of the polyalkylene ether polyol which is a soft segment
  • flexibility, adhesiveness, and tackiness tend to be improved.
  • it can suppress that transparency and heat resistance of a laminated body fall by making content of a soft segment below the said upper limit.
  • the content of the structural unit derived from the polyalkylene ether polyol can be calculated from the charged ratio at the time of production or quantified by an instrumental analysis method such as 1 H-NMR spectrum analysis.
  • the melting point of the alicyclic polyester used for the adhesive resin layer (B2) in the present invention is not limited, it is preferably 130 ° C. or higher, more preferably 160 ° C. or higher from the viewpoint of the balance between processability and transparency. 210 ° C. or less, more preferably 200 ° C. or less.
  • the laminate is manufactured by co-extrusion of the adhesive resin layer (B1) together with the soft vinyl chloride resin layer (A) because the melting point is not more than the above upper limit value, molding at a low temperature is possible.
  • generation of hydrogen chloride gas derived from a soft vinyl chloride resin can be prevented, and deterioration of the molding machine can be prevented.
  • the melting point of the alicyclic polyester was determined by using a differential scanning calorimeter (DSC) or the like at a rate of temperature increase of 100 ° C./min from room temperature to 250 ° C. and held for 3 minutes, and then cooled to ⁇ 100 ° C. It is the temperature of the melting peak when the temperature is raised to 250 ° C. at a rate of temperature increase of 10 ° C./min after cooling at 10 ° C./min.
  • DSC differential scanning calorimeter
  • the adhesive resin layer (B2) in the present invention has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg (kgf) in accordance with JIS K7210 (1999), preferably 0.1 to It is preferably 100 (g / 10 minutes), more preferably 0.5 to 80 (g / 10 minutes), and still more preferably 1.0 to 60 (g / 10 minutes).
  • MFR melt flow rate
  • the adhesive resin layer (B3) in the present invention contains at least a styrene elastomer and a modified polyolefin resin. Since the styrenic elastomer and the modified polyolefin resin have good affinity, the adhesive resin layer (B3) containing these as essential components can exist in a state where the phase structure is stable.
  • the adhesive resin layer (B3) contains both a styrene elastomer and a modified polyolefin resin, thereby exhibiting good adhesiveness and / or affinity with the adhesive resin layer (B2) and the polyolefin layer (C). It becomes possible to do.
  • the styrene elastomer in the adhesive resin layer (B3) exhibits tackiness, while the modified polyolefin resin chemically reacts with the alicyclic polyester constituting the adhesive resin layer (B2). It is considered that good adhesiveness with the adhesive resin layer (B2) is expressed. Moreover, since the modified polyolefin in the adhesive resin layer (B3) has high affinity with the polyolefin layer (C), it is considered that good adhesiveness is expressed.
  • the total content of the styrene-based elastomer and the modified polyolefin resin in the adhesive resin layer (B3) is not limited, but is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 40% by weight or more.
  • the upper limit is 100% by weight.
  • the styrenic elastomer in the present invention is not limited as long as it has a polymer block mainly composed of a vinyl aromatic compound and a polymer block imparting flexibility, except for the number average molecular weight described below, The thing similar to what was mentioned in description of the said adhesive resin layer (B1) can be used.
  • the number average molecular weight of the styrene-based elastomer in the present invention is not limited, it is preferably 20000 or more, more preferably as a value in terms of polystyrene measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC).
  • GPC gel permeation chromatography
  • the adhesiveness and / or affinity with the adhesive resin layer (B2) and the polyolefin layer (C) tend to be good.
  • the production method of the styrene elastomer in the present invention is not particularly limited as long as the above structure and physical properties can be obtained. Specifically, for example, it can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or the like. In addition, a known method such as hydrogenation (hydrogenation) of the block copolymer can be employed, for example, in an inert solvent in the presence of a hydrogenation catalyst.
  • Examples of commercially available hydrogenated block copolymers include “KRATON (registered trademark) -G” manufactured by Kraton Japan Co., Ltd., “Septon (registered trademark)” and “Hibler (registered trademark)” manufactured by Kuraray Co., Ltd. And “Tuftec (registered trademark)” manufactured by Asahi Kasei Corporation.
  • non-hydrogenated block copolymers examples include “KRATON (registered trademark) -A” manufactured by Kraton Japan Co., Ltd. Asahi Kasei Co., Ltd. “Tufprene (registered trademark)” and the like.
  • a rubber softener may be contained in the adhesive resin layer (B3) within the range where the effects of the present invention are exhibited.
  • Usable rubber softeners are not limited as long as the flexibility of the adhesive resin layer (B3) can be adjusted, and among them, hydrocarbon rubber softeners are preferable.
  • Modified polyolefin resin The modified polyolefin resin in the present invention is obtained by reacting a polyolefin resin and an unsaturated compound.
  • the polyolefin resin used for the production of the modified polyolefin resin is selected from known polyolefin resins, and specifically, the resins exemplified as the raw material of the polyolefin layer (C) described later can be used similarly.
  • the polyolefin resin is preferably a propylene resin.
  • the propylene-based resin means a polymer obtained from a monomer mainly composed of propylene, specifically, a propylene homopolymer, a propylene / ethylene copolymer, a propylene / 1-butene copolymer or a propylene / ethylene. -1-butene copolymer is preferred. Among them, a propylene homopolymer is particularly preferable.
  • the polyolefin resin may be any one of the above-mentioned various polyolefin resins, or may be a mixture of plural kinds.
  • the melt flow rate (MFR) of the polyolefin resin is not limited, but is preferably 0.01 to 80 g / 10 minutes, more preferably 0.1 to 40 g / 10 minutes from the viewpoint of moldability.
  • MFR means a value at 190 ° C. and a load of 2.16 kg when the polyolefin resin is ethylene or an ⁇ -olefin having 3 or more carbon atoms (molar conversion), and the polyolefin resin is propylene. Is the value at 230 ° C. and a load of 2.16 kg.
  • the unsaturated compound used in the present invention is not limited as long as it is an unsaturated compound that can react with the polyolefin resin.
  • “can react” includes not only the case of reacting with the polyolefin resin by the unsaturated group constituting the unsaturated compound, but also the case of reacting with the polyolefin resin without passing through the unsaturated group. .
  • reactive compounds include, but are not limited to, unsaturated carboxylic acids or derivatives thereof, and ethylenically unsaturated silane compounds. Of these, unsaturated carboxylic acids or derivatives thereof are preferred.
  • Examples of the unsaturated carboxylic acid or derivative thereof include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid TM (endocis-bicyclo [2,2,1 And unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid) and derivatives thereof such as acid halides, amides, imides, anhydrides and esters thereof.
  • an acid anhydride is preferable.
  • unsaturated carboxylic acid or derivative thereof include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Of these, maleic acid or its anhydride is particularly preferred.
  • the kneader is not particularly limited, and for example, a single or twin screw extruder, a roll, a Banbury mixer, a kneader, and a Brabender mixer can be used.
  • the blending ratio of the polyolefin resin and the unsaturated compound is not limited, but the unsaturated compound is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 100 parts by weight of the polyolefin resin. Is preferably blended at a ratio of 0.1 to 1 part by weight.
  • the reaction aid for generating radicals is not limited, and specific examples include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate). ) Hexin-3, lauroyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert- Organic peroxides or organic peresters such as butyl perbenzoate, tert-butyl perisobutylate, tert-butyl perpivalate, and cumyl perpivalate, and azobisisobutyronitrile and dimethylazoisobutylene And azo compounds such as
  • reaction aids can be appropriately selected according to the type of polyolefin resin, the type of unsaturated compound, and the reaction conditions, and two or more types may be used in combination.
  • the compounding amount of the reaction aid is preferably 0.001 to 3 parts by weight, more preferably 0.005 to 0.5 parts by weight, and still more preferably 0.01 to 0 parts by weight based on 100 parts by weight of the polyolefin resin. .2 parts by weight, particularly preferably 0.01 to 0.1 parts by weight.
  • the adhesive resin layer (B3) in the present invention preferably contains an unmodified polyolefin resin in addition to the styrene elastomer and the modified polyolefin resin.
  • the unmodified polyolefin resin contained in the adhesive resin layer (B3) the resins exemplified as raw materials for the polyolefin layer (C) described later can be similarly used.
  • the unmodified polyolefin resin used for the adhesive resin layer (B3) may be the same as or different from the polyolefin resin used for the polyolefin layer (C) described later. Adhesiveness with a layer (C) may improve.
  • the blending ratio (weight ratio) of the styrene elastomer and modified polyolefin resin in the present invention is not limited, but is preferably in the range of 5/95 to 80/20, more preferably 5/95 to 60/40. preferable.
  • Formability can be improved by setting the blending ratio of the modified polyolefin resin to the lower limit value or more.
  • the adhesiveness with respect to an adhesive resin layer (B2) can be improved by making the mixture ratio of modified polyolefin resin into the said upper limit or less.
  • the content when the unmodified polyolefin resin is contained in the adhesive resin layer (B3) is not limited, but is preferably 10% by weight or more, more preferably 20% by weight or more in the adhesive resin layer (B3). More preferably, it is 30% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 70% by weight or less.
  • the styrene elastomer, the modified polyolefin resin, and the unmodified polyolefin resin used as necessary may be preliminarily made into a uniform resin composition to constitute the adhesive resin layer (B3) in the present invention. These may be appropriately blended (dry blended) when used to form a laminate described later.
  • the method is not limited, and examples thereof include a method of mixing with a Henschel mixer, a V-blender, a ribbon blender or a tumbler blender.
  • a mixture obtained by such a method may be further granulated after melt-kneading with a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, or the like.
  • the method of mixing using a kneader or a roll is mentioned, for example.
  • the production conditions for producing the resin composition by these methods are not limited, and can be appropriately set under known conditions.
  • the temperature at the time of melt mixing may be a temperature at which at least one of the raw material components is in a molten state, but usually a temperature at which all the components used are melted is selected, and it is generally preferable to carry out at 150 to 250 ° C.
  • the moldability of the laminate can be improved and the mechanical strength of the laminate can be improved.
  • liquidity becomes favorable and the moldability of a laminated body can be improved.
  • the polyolefin layer (C) in the present invention contains at least a polyolefin resin.
  • the polyolefin resin that can be used for the polyolefin layer (C) is not limited, but for example, homopolymers of ⁇ -olefins such as ethylene, propylene, or 1-butene, the ⁇ -olefins or the ⁇ -olefins thereof.
  • ⁇ -olefins having about 4 to 20 carbon atoms such as 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene or 1-decene, vinyl acetate, vinyl Examples thereof include a copolymer with alcohol, (meth) acrylic acid or (meth) acrylic acid ester.
  • polyolefin resins include, for example, ethylene homopolymers such as low, medium and high density polyethylene (branched or linear), ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene- 4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer (ethylene-vinyl acetate copolymer) Polymer saponified products), ethylene-based resins such as ethylene- (meth) acrylic acid copolymers and ethylene- (meth) acrylic acid ester copolymers; propylene homopolymers, propylene-ethylene copolymers and propylene- Propylene resins such as ethylene-1-butene copolymer; and 1-butene homopolymer, 1-butene-ethylene copolymer Coalescence and butene -
  • polyolefin resins may be used alone or in combination of two or more.
  • the polyolefin resin suitable for the polyolefin layer (C) varies depending on the use and required characteristics of the laminate of the present invention, but when used for an infusion bag, an ethylene resin or a propylene resin is preferable.
  • the chain form in the case of using a copolymer as the polyolefin resin is not limited and may be any of a block copolymer, a random copolymer, a graft copolymer, etc., but the block copolymer or the random copolymer may be used. Polymers are preferred.
  • the polyolefin resin used for the polyolefin layer (C) has a melt flow rate (MFR) of preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, and further preferably 0.5 g / 10 min. Above, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and still more preferably 10 g / 10 min or less.
  • MFR melt flow rate
  • the MFR of the polyolefin resin By setting the MFR of the polyolefin resin to be equal to or higher than the lower limit, the fluidity is increased and the molding becomes easy. Further, by setting the MFR to be equal to or less than the upper limit value, fluidity is suppressed and molding becomes easy.
  • MFR means a value at 190 ° C. and a load of 2.16 kg when the polyolefin resin is ethylene or an ⁇ -olefin having 3 or more carbon atoms (molar conversion), and the polyolefin resin is propylene. Is the value at 230 ° C. and a load of 2.16 kg.
  • the configuration of the layer in the laminate according to the first aspect of the present invention is not limited, but the soft vinyl chloride resin layer (A) and the adhesive resin layer (B1) are preferably adjacent to each other, and the adhesive resin layer It is preferable that (B1) and the polyolefin layer (C) are adjacent to each other.
  • the soft vinyl chloride resin layer (A), the adhesive resin layer (B1), and the polyolefin layer (C) are preferably adjacent to each other in this order.
  • the layer structure of the laminate according to the second aspect of the present invention is preferably such that the soft vinyl chloride resin layer (A) and the adhesive resin layer (B2) are adjacent to each other, and the adhesive resin layer (B2). And the adhesive resin layer (B3) are preferably adjacent to each other, and the adhesive resin layer (B3) and the polyolefin layer (C) are preferably adjacent to each other.
  • the soft vinyl chloride resin layer (A) and the polyolefin layer (C) can have the respective characteristics, and the flexibility, impact resistance, transparency and hygiene are good. It can be set as a laminated body.
  • Each of the laminates according to the first aspect and the second aspect of the present invention is not limited in shape, and may be a planar shape such as a film, a sheet, or a plate shape, a pipe shape, a bag shape, or an indefinite shape. Either may be sufficient.
  • the material constituting the other layer is not limited, but specifically, a thermoplastic resin such as a polyamide resin, a polyester resin, a styrene resin, an acrylic resin, or a polycarbonate resin is used. These resins may be a resin composition layer containing a plurality of resins.
  • the polyamide resin used for the other layers is not limited. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, MXD nylon, amorphous nylon or terephthalic acid / adipic acid / hexamethylenediamine copolymer is preferably used. These polyamide resins may be used alone or in combination. Among these, nylon 6, nylon 66, or nylon 6/66, which has an excellent melting point and rigidity, is preferable.
  • each layer of the laminate of the present invention is not limited, and can be arbitrarily set depending on the layer configuration, application, final product shape, required physical properties, and the like.
  • the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 55% or more, and preferably 94% or less with respect to the total thickness. More preferably, it is 90% or less.
  • the thickness of the soft vinyl chloride resin layer (A) is not less than the above lower limit value, the flexibility tends to be improved, and when it is not more than the above upper limit value, the hygiene tends to be improved.
  • the thickness of the adhesive resin layer (B1) is preferably 1% or more, more preferably 5% or more, preferably 20% or less, more preferably relative to the total thickness. 10% or less.
  • the thickness of the adhesive resin layer (B1) is equal to or greater than the lower limit value, the adhesiveness tends to be improved.
  • the thickness is equal to or smaller than the upper limit value, the film strength tends to be improved, and the cost is also advantageous. There is a tendency.
  • the thickness of the polyolefin layer (C) is preferably 5% or more, more preferably 10% or more, preferably 49% or less, more preferably 20%, based on the total thickness. % Or less.
  • the thickness of the polyolefin layer (C) is not less than the lower limit value, heat seal failure tends to be difficult to occur, and when it is not more than the upper limit value, flexibility tends to be improved.
  • the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 100% or more, preferably with respect to the thickness of the polyolefin layer (C). It is 2800% or less, more preferably 2000% or less.
  • the thickness of the soft vinyl chloride resin layer (A) is not less than the above lower limit value, the flexibility tends to be improved, and when it is not more than the above upper limit value, the heat sealability tends to be improved.
  • the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 55% or more, preferably 93% or less, more than the total thickness. Preferably it is 90% or less.
  • the thickness of the soft vinyl chloride resin layer (A) is not less than the lower limit, flexibility tends to be improved, and when it is not more than the upper limit, hygiene tends to be improved.
  • the thickness of the adhesive resin layer (B2) is preferably 1% or more, more preferably 5% or more, preferably 20% or less, more preferably relative to the total thickness. It is 15% or less, more preferably 10% or less.
  • the thickness of the adhesive resin layer (B2) is equal to or greater than the lower limit value, the adhesiveness tends to be improved, and when it is equal to or smaller than the upper limit value, the film strength tends to be improved, and further advantageous in terms of cost. It becomes.
  • the thickness of the adhesive resin layer (B3) is preferably 1% or more, more preferably 5% or more, preferably 20% or less, more preferably relative to the total thickness. It is 15% or less, more preferably 10% or less.
  • the thickness of the adhesive resin layer (B3) is not less than the lower limit value, the adhesion tends to be improved, and when it is not more than the upper limit value, the film strength tends to be improved, and further, it is advantageous in terms of cost. It becomes.
  • the thickness of the polyolefin layer (C) is preferably at least 5%, more preferably at least 10%, preferably at most 48%, more preferably at 30% of the total thickness. % Or less.
  • the thickness of the polyolefin layer (C) is not less than the lower limit value, heat sealing failure tends to be difficult to occur, and when the thickness is not more than the upper limit value, flexibility tends to be improved.
  • the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 100% or more, preferably with respect to the thickness of the polyolefin layer (C). It is 2800% or less, more preferably 2000% or less.
  • the thickness of the soft vinyl chloride resin layer (A) is not less than the lower limit, flexibility tends to be improved, and when it is not more than the upper limit, heat sealability tends to be improved.
  • a method for producing the laminate of the present invention various conventionally known methods can be employed. For example, a method of forming an inflation film, a T-die film, a sheet or a pipe by a coextrusion method in which individual molten resins melted by an extruder are supplied to a multilayer die and laminated in the die are formed. Examples thereof include co-injection molding in which individual molten resins are injected into the same mold with a time lag.
  • the laminated body of this invention can also be made into an extending
  • the stretched laminate may be heat-set, or may be a product without being heat-set. In the case where heat setting is not performed, the stretched laminate is heated to release stress and shrink, so that it can be used as a shrink film.
  • these can be made into a draw-formed container or the like through secondary processing such as vacuum forming or pressure forming.
  • the shape and use of the molded product obtained from the laminate of the present invention are not limited, but are suitable as a medical container, food packaging material or pharmaceutical packaging material because of its good flexibility, hygiene, transparency and impact resistance. And is particularly suitable for an infusion bag.
  • An infusion bag is usually composed of a main body of an infusion bag, a port for injecting a chemical solution, a cap including a rubber stopper for taking out the chemical solution, etc., but the laminate of the present invention is suitable as a main body of an infusion bag. Can be used.
  • the method for forming an infusion bag with the laminate of the present invention is not limited, but a method of forming a tubular (cylindrical) inflation film by the above-described coextrusion method and fusing the ends can be preferably employed. .
  • the polyolefin layer (C) having good hygiene is on the inside, that is, the side in contact with the infusion, and the soft vinyl chloride resin layer (A) having good flexibility is on the outside. It is preferable to use it as a configuration.
  • a packaging material such as food or electronic parts can be mentioned.
  • the present invention will be described in more detail with reference to examples.
  • the present invention is not limited to the following examples unless it exceeds the gist.
  • the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value.
  • a range defined by a combination of values of the following examples or values of the examples may be used.
  • a polyether ester block copolymer comprising a polymer of 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol as a hard segment and polytetramethylene ether glycol (number average molecular weight: 2000) as a soft segment. Polymer. The content of polytetramethylene ether glycol is 15% by weight. Melt flow rate measured at 230 ° C. and 2.16 kg load (kgf) 30 g / 10 min. Melting point 197 ° C.
  • Aromatic polyester for comparative example (A-2) A block copolymer of polybutylene terephthalate and polytetramethylene ether glycol. Content of polytetramethylene ether glycol (number average molecular weight: 2000) is 77% by weight.
  • [Styrene elastomer] (B-1) “KRATON (registered trademark) -G1645MO” manufactured by Kraton Japan Co., Ltd .: a styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1).
  • Styrene (block P) content 13% by weight (measured by 13 C-NMR), number average molecular weight: 64000.
  • Styrene-isoprene-butadiene-styrene hydrogenated block copolymer It has the structure of the formula (1).
  • B-3 “KRATON (registered trademark) -G1641H” (for comparative example) manufactured by Kraton Japan Co., Ltd .: styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1).
  • (B-4) “H7135” (for comparative example) manufactured by Kuraray Co., Ltd .: Styrene-isoprene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1).
  • B-5 “KRATON (registered trademark) -G1651” (for comparative example) manufactured by Kraton Japan Co., Ltd .: styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1).
  • B-6 “KRATON (registered trademark) -A1535HU” (for comparative example) manufactured by Clayton Japan Co., Ltd .: styrene- (butadiene-styrene) -styrene hydrogenated block copolymer. It has the structure of the formula (1).
  • ⁇ Polyolefin layer (C)> ( ⁇ -1) “Zeras (registered trademark) 7025” manufactured by Mitsubishi Chemical Corporation: propylene-ethylene block copolymer, MFR (230 ° C., 2.16 kg) 1.6 g / 10 min)
  • Example 1-1 In advance, the alicyclic polyester polymer (a-1) and the styrene elastomer (b-1) were mixed with a twin-screw extruder (Nippon Steel Works, Ltd.) based on the blending ratio (parts by weight) shown in Table 1.
  • the resin composition pellets used for the adhesive resin layer (B1) were obtained by melting and kneading at a set temperature of 200 ° C. using “TEX-30 ⁇ II” (manufactured by cylinder 30 mm).
  • TEX-30 ⁇ II manufactured by cylinder 30 mm
  • a sample of the obtained laminated film was cut into a width of 15 mm, and a 180 ° peel test was performed at a speed of 100 mm / min in a 23 ° C. atmosphere.
  • the evaluation result of the laminated film of the adhesive resin layer (B1) and the soft vinyl chloride resin layer (A) is “adhesive to PVC”, and the laminated film of the adhesive resin layer (B1) and the polyolefin resin layer (C) is evaluated.
  • the result was defined as “adhesiveness to PP”.
  • the results are shown in Table 1.
  • Example 1-2 Comparative Examples 1-1 to 1-6
  • Resin composition pellets used for the resin composition (B1) were produced in the same manner as in Example 1-1 except that the raw materials used were as shown in Table 1.
  • a-1 or a-2 was used as it was as the adhesive resin layer (B1).
  • Example 1-1 a laminate was produced in the same manner as in Example 1-1, and evaluation of “adhesiveness to PVC”, “adhesiveness to PP” and “Japanese Pharmacopoeia Container Test” was performed. The results are shown in Table 1.
  • Comparative Example 1-6 was evaluated as “x” in the “Japanese Pharmacopoeia Container Test” because it did not satisfy the standards in the potassium permanganate consumption test and the ultraviolet absorption spectrum test.
  • ⁇ Adhesive resin layer (B3)> (C-1) “Zeras (registered trademark) MC748AP” manufactured by Mitsubishi Chemical Corporation: a resin composition containing a styrene elastomer and anhydrous maleic modified polypropylene. MFR (230 ° C, 2.16 kg) 2.0 g / 10 min) (C-2) “Modic (registered trademark) F512” manufactured by Mitsubishi Chemical Corporation: polyolefin adhesive resin (modified polyolefin resin). MFR (190 ° C., 2.16 kg) 1.5 g / 10 min) (for comparative example)
  • Example 2-1 [Adhesion evaluation] Using the materials for the soft vinyl chloride resin layer (A), the adhesive resin layer (B2), the adhesive resin layer (B3), and the polyolefin layer (C), the thickness is 100 ⁇ m by GSI Creos and T-die molding machine. A single layer film was obtained. The molding temperature was set to 190 ° C., and the molding speed was set to 5 m / min.
  • the adhesive strength between the respective layers was measured by the following method, thereby schematically evaluating the adhesive strength between the respective layers when the laminate was formed. That is, a single layer film of a soft vinyl chloride resin layer (A) and a single layer film of an adhesive resin layer (B2), a single layer film of an adhesive resin layer (B2) and a single layer film of an adhesive resin layer (B3), an adhesive resin One pair of single layer films of the single layer film of the layer (B3) and the single layer film of the polyolefin layer (C) were stacked, and heat-sealed under the conditions of 210 ° C. and 2 kg / cm 2 .

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Hematology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Engineering & Computer Science (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Bag Frames (AREA)

Abstract

La présente invention a trait à un corps stratifié qui est doté d'une flexibilité, de propriétés hygiéniques et d'une résistance au choc excellentes, en plus d'une remarquable adhérence entre les couches. La présente invention a également trait à un dispositif médical. La présente invention a en outre trait à un corps stratifié qui est doté d'une flexibilité, de propriétés hygiéniques, d'une transparence et d'une résistance au choc à basse température remarquables, en plus d'une excellente adhérence entre les couches, et qui est approprié pour être utilisé dans des poches de perfusion.
PCT/JP2012/060066 2011-04-15 2012-04-12 Corps stratifié et dispositif médical WO2012141264A1 (fr)

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JP2015019750A (ja) * 2013-07-17 2015-02-02 アロン化成株式会社 医療容器栓体用熱可塑性エラストマー組成物
CN112867592A (zh) * 2018-10-31 2021-05-28 日本瑞翁株式会社 粉体成型用氯乙烯树脂组合物、氯乙烯树脂成型体以及层叠体
JP2021147411A (ja) * 2020-03-16 2021-09-27 デンカ株式会社 熱収縮性フィルム

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US11904578B2 (en) 2019-06-06 2024-02-20 C.I. Takiron Corporation Stretchable film

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JP2021147411A (ja) * 2020-03-16 2021-09-27 デンカ株式会社 熱収縮性フィルム

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