Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • 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
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
• • 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
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
• • 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
  • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
  • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C09J131/04—Homopolymers or copolymers of vinyl acetate

Definitions

• the present invention relates to recycled plastics, pellets, and molded bodies.
• laminated films produced by a lamination method using an adhesive have been developed and evolved for laminating films of the same or different resins in order to meet the demand for a single packaging material that is not only useful for packaging purposes but also has various high functions such as barrier properties, moisture resistance, and retort resistance (see, for example, Patent Document 1).
• these laminated films reduce the quality of recycled plastics, and there is a demand for packaging materials that are not only highly functional but also recyclable.
• Laminated films of the same resin type are expected to be recyclable packaging materials.
• a laminated film of the same resin type suitable for material recycling has been disclosed, which has layers A, B, C, and D containing an ethylene polymer (A) that contains a specific amount of structural units derived from ethylene, which is an olefin resin, and a barrier layer or adhesive layer between layers C and D (see, for example, Patent Document 2), and it has been disclosed that a resin material containing a recycled ethylene polymer can be suitably used as a molding material for food, detergent, and cosmetics (see, for example, paragraph 0101 of Patent Document 2).
• the objective of the present invention is to provide recycled plastics that can be used for general-purpose packaging materials such as unstretched polyolefin films and molded products made by injection molding, etc.
• Non-oriented polyolefin films are indispensable as sealant materials (sealant layers) in laminated films used for packaging materials.
• cited document 2 discloses that a resin material containing recycled ethylene polymers can be suitably used as a molding material for food, detergent, and cosmetic applications, it does not specifically mention the applicability of the material as a sealant material or as a molded product produced by injection molding or the like.
• recycled plastics also contain recycled resins derived from oriented olefin resins, but for example, isotactic polypropylene, the main component of oriented polypropylene film, is known to produce relatively large spherulites when used in molded products made by injection molding, etc., and although it has excellent heat resistance and rigidity, it has poor low-temperature impact strength, so there is little mention of the uses of recycled plastics.
• the present invention provides a recycled plastic made from a laminated film in which at least one stretched polyolefin substrate is laminated with an adhesive, the recycled plastic having a loss product of molecular chain mobility due to stretching in the range of 1 x 10 3 to 1 x 10 4 .
• the present invention also provides pellets made primarily from the recycled plastic described above.
• the present invention also provides a molded body made primarily from the recycled plastic described above.
• the present invention also provides an unstretched polyolefin film made primarily from the recycled plastic described above.
• the present invention makes it possible to provide recycled plastics that can be used for general-purpose packaging materials such as unstretched polyolefin films and molded products made by injection molding, etc.
• the recycled plastic of the present invention is a recycled plastic made from a laminated film in which at least one stretched polyolefin substrate is laminated with an adhesive, and has a loss product of molecular chain mobility due to stretching in the range of 1 x 10 3 to 1 x 10 4 .
• the loss product of molecular chain mobility due to stretching is a value defined by the following method.
• (1) The laminated film was cut into strips with a width of 10 mm and a length of 300 mm.
• the strips were melt-kneaded for 3 minutes at 240° C. and 100 rpm using a twin-screw kneading extrusion device (manufactured by Technovel Co., Ltd., ULT nano 15TW), and then extruded from a nozzle and immediately cooled with tap water to obtain strand-shaped resin.
• the strand-shaped resin was then cut into pellet samples.
• the pulse NMR of the dumbbell test piece obtained above is measured before and after the tensile test, and the relaxation time T2 (s) of the amorphous phase is obtained.
• the difference between the amorphous phase relaxation time after the tensile test and the amorphous phase relaxation time before the tensile test is ⁇ T2 (s).
• a minispec mq20 manufactured by BRUKER was used for the pulse NMR, and a free induction decay curve was obtained at a measurement temperature of 40°C.
• the spin-spin relaxation time T2 of the three components was obtained by curve fitting using analysis software manufactured by BRUKER.
• the integral value of the difference between the elongation at break ⁇ L (mm) and the amorphous phase relaxation time ⁇ T2 (s) is defined as the loss product of molecular chain mobility due to stretching of the recycled polyolefin.
• the decrease in relaxation time due to tension suggests an increase in the number of tensile molecules, and the change can be assumed to be linear because it is determined by the number of molecular chains. It can also be assumed that the elastic deformation at the initial stage of tension is independent of the relaxation time T2 of the amorphous phase. Therefore, it is assumed that the molecular chain mobility changes linearly due to the stretching of the sample in the tensile test.
• the breaking elongation is a value that fluctuates depending on foreign matter, sample conditions, measurement conditions, etc.
• the relaxation time T2 is a quantitative value, and the change is heavily dependent on the tie molecules, but since it includes tie molecules, one free end, and both free ends, it is difficult to refer to only the tie molecules. Therefore, by using ⁇ T2 as the change in relaxation time, the contribution of tie molecules, which is deeply involved in tensile elongation, is made apparent, and it is an index quantified as an integral value.
• the recycled plastic of the present invention has physical properties almost equivalent to those of the virgin plastic raw material of the unstretched film, since the loss product of molecular chain mobility due to stretching is in the range of 1 x 10 3 to 1 x 10 4.
• the loss product is preferably in the range of 2 x 10 3 to 1 x 10 4 , and more preferably in the range of 2 x 10 3 to 7 x 10 3 .
• the recycled plastic of the present invention is a recycled plastic made from a laminated film in which at least one or more stretched polyolefin substrates are laminated with an adhesive.
• a recycled plastic made from a laminated film using an adhesive whose main component is an olefin resin (A) modified with an acid, an acid anhydride, and/or vinyl acetate is preferred.
• the recycled plastic of the present invention it is presumed that the loss product of molecular chain mobility due to stretching is affected by the type and amount of resins and additives that make up the laminated film before recycling.
• the inventors have discovered that after the laminated film has been recycled (mixed extrusion, molding), components equivalent to adhesive raw materials are present between the lamellae (amorphous phase) of the olefin thermoplastic resin, which is present in the greatest amount by weight in the recycled plastic. Therefore, it is presumed that the components equivalent to adhesive raw materials contribute to preventing a decrease in the physical properties of the recycled plastic, and in particular, to preventing a decrease in the extensibility of the olefin thermoplastic resin due to tension.
• the at least one or more stretched polyolefin substrates can be any film (sometimes called a sheet, but in the present invention called a film) obtained by stretching a thermoplastic resin whose main component is an olefin-based resin, without any particular limitation.
• the olefin resin include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear (linear) low-density polyethylene, polypropylene, ethylene-propylene copolymers, ⁇ -olefin polymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl acrylate copolymers, cyclic olefin resins, ionomer resins, and polymethylpentene; and modified olefin resins obtained by modifying olefin resins with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or other unsaturated carboxylic acids.
• polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear (line
• Biomass films are sold by various companies, and for example, sheets such as those listed in the list of biomass certified products listed by the Japan Organics Resources Association can be used.
• biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass.
• biomass-derived ethylene glycol can be obtained by a conventional method of producing ethylene glycol from biomass ethanol via ethylene oxide.
• Commercially available biomass ethylene glycol may also be used; for example, biomass ethylene glycol available from India Glycoal Limited can be suitably used.
• Radioactive carbon-14C exists in the atmosphere at a ratio of 1 in 1012 particles, and this ratio does not change with atmospheric carbon dioxide, so this ratio does not change even in plants that fix this carbon dioxide through photosynthesis. For this reason, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin with an accelerator mass spectrometer, the proportion of plant-derived resin in the resin, i.e., the biomass plastic degree, can be determined.
• plant-derived low-density polyethylene which is a biomass plastic with a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO16620 or ASTM D6866
• plant-derived low-density polyethylene examples include Braskem products with trade names such as "SBC818”, “SPB608”, “SBF0323HC”, “STN7006”, “SEB853”, and “SPB681”, and films using these as raw materials can be suitably used.
• biomass polyolefin films such as biomass polyethylene films containing polyethylene resins made from biomass-derived ethylene glycol and biomass polyethylene-polypropylene films are also known.
• the polyethylene-based resin is not particularly limited except that ethylene glycol derived from biomass is used as a part of the raw material.
• examples of the polyethylene-based resin include an ethylene homopolymer and a copolymer of ethylene and an ⁇ -olefin containing ethylene as a main component (ethylene- ⁇ -olefin copolymer containing 90% by mass or more of ethylene units), and these can be used alone or in combination of two or more.
• the ⁇ -olefin constituting the copolymer of ethylene and ⁇ -olefin is not particularly limited, and examples thereof include ⁇ -olefins having 4 to 8 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.
• Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used.
• linear low density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred, and linear low density polyethylene resin having a density of 0.910 to 0.925 g/cm3 is more preferred.
• the biomass film may be a laminate of multiple biomass films, or a laminate of a conventional petroleum-based film and a biomass film.
• the film may have been subjected to some kind of surface treatment, such as physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, flame treatment, etc., or chemical treatments such as oxidation treatment using chemicals, or other treatments.
• surface treatment such as physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, flame treatment, etc.
• chemical treatments such as oxidation treatment using chemicals, or other treatments.
• the film can be produced by a conventionally known film-forming method such as extrusion, cast molding, T-die, cutting, or inflation of the above-mentioned resin.
• the stretching method may be longitudinal stretching in the film flow direction by tension between stretching rolls, transverse stretching perpendicular to the film flow direction by a tenter method, a combination of longitudinal and transverse stretching, or tubular stretching in one or two axial directions.
• the film may contain additives as necessary.
• plastic compounding agents and additives such as elastomers, lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, and pigments can be added for the purpose of improving or modifying processability, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, slipperiness, release properties, flame retardancy, mold resistance, electrical properties, strength, etc.
• the amount of additives added is adjusted within a range that does not affect other performance properties or recyclability.
• the thickness of the film is not particularly limited, and may be appropriately selected in the range of 0.1 to 300 ⁇ m from the viewpoint of formability and transparency.
• the range is preferably 0.3 to 100 ⁇ m. If the thickness is less than 0.1 ⁇ m, the strength is insufficient, and if it exceeds 300 ⁇ m, the rigidity is too high, which may make processing difficult.
• the film may be provided with a barrier layer for the purpose of providing a barrier against water vapor, oxygen, alcohol, inert gases, volatile organic substances (fragrances), etc.
• a barrier layer for the purpose of providing a barrier against water vapor, oxygen, alcohol, inert gases, volatile organic substances (fragrances), etc.
• coating layers such as polyvinylidene chloride coat (K-coat), metal vapor deposition layers such as aluminum, and inorganic vapor deposition layers such as silica and alumina.
• the film may be provided with a coating layer for the purpose of improving ink acceptance when providing a printing layer, which will be described later.
• the adhesive layer used in the present invention is characterized by being made of an adhesive containing as a main component an olefin-based resin (A) modified with an acid, an acid anhydride, and/or vinyl acetate.
• the acid-modified olefin resin which is a copolymer of an olefin monomer and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, is referred to as "acid-modified olefin resin (A-1)"
• An acid-modified olefin resin which is a resin obtained by graft-modifying a polyolefin with an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, is referred to as "acid-modified olefin resin (A-2)".
• the olefin resin having an acid group and/or an acid anhydride group examples include an acid-modified olefin resin (A-1) which is a copolymer of an olefin monomer and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, and an acid-modified olefin resin (A-2) which is a resin in which a polyolefin is graft-modified with an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride.
• Olefin monomers used to prepare the acid-modified olefin resin (A-1) include olefins having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, and vinylcyclohexane. Of these, olefins having 2 to 8 carbon atoms are preferred because they provide particularly good adhesive strength, with ethylene, propylene, and 1-butene being more preferred, and it is particularly preferred to use them in combination.
• ethylenically unsaturated carboxylic acids or ethylenically unsaturated carboxylic anhydrides used in copolymerization with olefin monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene ...
• Suitable anhydrides include norbornene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norbornene-5-ene-2,3-dicarboxylic anhydride, and norborn-5-ene-2,3-dicarboxylic anhydride.
• maleic anhydride is particularly preferred because it has excellent reactivity with olefin monomers, excellent reactivity of the acid anhydride after copolymerization, and the molecular weight of the compound itself is small, resulting in a high functional group concentration when copolymerized.
• These can be used alone or in combination of two or more.
• the acid-modified olefin resin (A-1) in addition to the olefin monomer, ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride, other compounds having ethylenically unsaturated groups, such as styrene, butadiene, isoprene, etc., may be used in combination.
• ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride other compounds having ethylenically unsaturated groups, such as styrene, butadiene, isoprene, etc., may be used in combination.
• the polyolefins used to prepare the acid-modified olefin resin (A-2) include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and copolymers of olefins having 2 to 8 carbon atoms with other monomers.
• polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene resins, polypropylene, polyisobutylene, poly(1-butene), poly(4-methyl-1-pentene), polyvinylcyclohexane, ⁇ -olefin copolymers such as ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-hexene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, propylene-1-butene copolymers, and ethylene-propylene-1-butene copolymers.
• HDPE high density polyethylene
• LDPE low density polyethylene
• linear low density polyethylene resins polyprop
• homopolymers of olefins having 2 to 8 carbon atoms and copolymers of two or more types of olefins having 2 to 8 carbon atoms are preferred because they have particularly good adhesive strength, with polyethylene, polypropylene, and ethylene-propylene copolymers being particularly preferred.
• the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride used for graft modification with polyolefin may be the same as that used for copolymerization with olefin monomer in preparing the acid-modified olefin resin (A-1) described above.
• Maleic anhydride is preferred because it has high reactivity of functional groups after graft modification and also increases the functional group concentration of the graft-modified polyolefin. These may be used alone or in combination of two or more.
• Specific methods for reacting ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic anhydride with polyolefin by graft modification include melting the polyolefin and adding the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic anhydride (graft monomer) to carry out the graft reaction, dissolving the polyolefin in a solvent to form a solution and adding the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic anhydride to carry out the graft reaction, and mixing the polyolefin dissolved in an organic solvent with the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic anhydride and heating to a temperature above the softening temperature or melting point of the polyolefin to simultaneously carry out radical polymerization and hydrogen abstraction reaction in the molten state.
• the graft reaction in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the graft reaction in the presence of a radical initiator.
• the graft reaction is usually carried out under conditions of 60 to 350°C.
• the proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight per 100 parts by weight of the polyolefin before modification.
• organic peroxides are preferred, such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxidebenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate,
• the radical initiator can be selected optimally depending on the grafting reaction process, but dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,4-bis(tert-butylperoxyisopropyl)benzene are usually preferably used.
• dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,4-bis(tert-butylperoxyisopropyl)benzene are usually preferably used.
• acid-modified olefin resin (A-1) or acid-modified olefin resin (A-2) it is preferable to use one having an acid value of 1 to 200 mg KOH/g.
• the vinyl acetate-containing olefin resin (A-3) may be a copolymer of polyolefin and vinyl acetate.
• the polyolefin may be the same as that used to prepare the olefin resin (A-2).
• the modification method may be the same as that used to prepare the acid-modified olefin resin (A-1).
• the polyolefin is preferably polyethylene, polypropylene, or an ethylene-propylene copolymer.
• an olefin resin (A-3) having a hydroxyl group As the olefin resin (A), it is preferable to use one containing 5 to 20 mol % vinyl acetate.
• the polyolefin used to prepare the above-mentioned acid-modified olefin resin (A-2) or the olefin resin containing vinyl acetate (A-3) may be used as is without modification.
• the weight average molecular weight of the olefin resin (A) is preferably 40,000 or more. In order to ensure adequate fluidity, the weight average molecular weight of the olefin resin (A) is preferably 300,000 or less.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions:
• Measuring device Tosoh Corporation HLC-8320GPC Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation Detector: RI (differential refractometer)
• Data processing Multistation GPC-8020 model II manufactured by Tosoh Corporation Measurement conditions: Column temperature: 40°C Solvent: tetrahydrofuran Flow rate: 0.35 ml/min Standard: monodisperse polystyrene Sample: 100 ⁇ l of a tetrahydrofuran solution containing 0.2% by mass of resin solids filtered through a microfilter
• the melting point of the olefin resin (A) is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher.
• the melting point of the olefin resin (A) is preferably 120°C or lower, more preferably 90°C or lower, and even more preferably 85°C or lower.
• the melting point of olefin resin is measured by DSC (differential scanning calorimetry). Specifically, the temperature is raised at 10°C/min from the cooling temperature to the heating temperature, then cooled at 10°C/min to the cooling temperature to remove the thermal history, and then heated again at 10°C/min to the heating temperature. The peak temperature at the second heating is taken as the melting point.
• the cooling temperature is set to a temperature 50°C or more lower than the crystallization temperature
• the heating temperature is set to a temperature 30°C or more higher than the melting point temperature. The cooling temperature and heating temperature are determined by trial measurements.
• the olefin resin (A) contains polypropylene and is modified with maleic anhydride, the content of the polypropylene is 85 to 99 mol %, and the modification rate of maleic anhydride is 0.1 mol % or more. It is also preferred that (2) the olefin resin (A) contains polyethylene and is modified with maleic anhydride, the polyethylene content being 70 to 99 mol % and the maleic anhydride modification rate being 0.1 mol % or more. In addition, (3) it is preferable that the olefin resin (A) is modified with vinyl acetate, and the modification rate of the vinyl acetate is 5 to 20 mol % or more.
• the adhesive used in the present invention may contain a curing agent (B).
• a curing agent include metal compounds.
• the metal compound can be used without any particular limitation as long as it forms an ionic crosslink with the olefin resin (A).
• it is a compound containing a metal ion, and examples thereof include metal oxides, hydroxides, carbonates, bicarbonates, acetates, formates, methoxides, ethoxides, etc.
• the metal ion include monovalent ions such as Li + , Na + , K + , Ag + , and Cu + , and divalent ions such as Cu 2+ , Ba 2+ , Zn 2+ , and Fe 2+ . Two or more of these metal ions can be mixed and included as necessary.
• aziridine group-containing compounds examples include N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tri- ⁇ (2-methylaziridine)propionate, bisisophthaloyl-1-2-methylaziridine, tri-1-aziridinylphosphine oxide, and tris-1-2-methylaziridinephosphine oxide.
• Oxazolines include monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, and 2,4-diphenyl-2-oxazoline, as well as 2,2'-(1,3-phenylene)-bis(2-oxazoline), 2,2'-(1,2-ethylene)-bis(2-oxazoline), 2,2'-(1,4butylene)-bis(2-oxazoline), and 2,2'-(1,4-phenylene)-bis(2-oxazoline).
• monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, and 2,4-diphenyl-2-oxazoline, as well as 2,2'-(1,3-phenylene)-bis(2-oxazoline), 2,2'-(1,2-ethylene)-bis(2-oxazo
• Amino resins include melamine resins, benzoguanamine resins, urea resins, etc.
• the amount of the curing agent (B) is preferably 0.01 parts by mass or more per 100 parts by mass of the olefin resin (A), more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more.
• the amount of the curing agent (B) is preferably 50 parts by mass or less per 100 parts by mass of the olefin resin (A), more preferably 35 parts by mass or less, and even more preferably 25 parts by mass or less. This allows excellent adhesion to be achieved.
• the adhesive used in the present invention can be blended with an organic solvent to ensure fluidity and develop appropriate coatability.
• organic solvents are not particularly limited as long as they can be removed by volatilization through heating in the drying process when the adhesive is applied, and examples of such organic solvents include aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as n-hexane and n-heptane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; halogenated organic solvents such as trichloroethylene, dichloroethylene, chlorobenzene and chloroform; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; ethanol, methanol, n-propanol, 2-prop
• suitable solvents include alcohol-based solvents such as ethyl alcohol, butanol, and hexanol; ether-based solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, and butyl carbitol; glycol ether-based solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether; and glycol ester-based solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more.
• alcohol-based solvents such as ethyl alcohol, butanol, and hexanol
• ether-based solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane,
• an olefin resin having an acid group or an acid anhydride group or an olefin resin having vinyl acetate is used as the olefin resin (A)
• a mixed solvent of an alicyclic organic solvent and an ester solvent since this solvent has excellent solubility.
• an olefin resin having an acid group, an acid anhydride group, and/or vinyl acetate is used, it is preferable to use a mixed solvent of methylcyclohexane, ethyl acetate, and 2-propanol, since this solvent has excellent solubility.
• the amount of organic solvent used is preferably such that the ratio of olefin resin (A) to the total mass of olefin resin (A) and organic solvent is 5 to 20 mass %. This makes it possible to produce an adhesive with excellent coatability and wettability to substrates.
• the adhesive used in the present invention may contain various additives, such as silane coupling agents, tackifiers, plasticizers, thermoplastic elastomers, reactive elastomers, phosphoric acid compounds, silane coupling agents, adhesion promoters, metal catalysts, amine catalysts, aliphatic cyclic amide compounds, titanium chelate complexes, esterification catalysts, etc.
• additives such as silane coupling agents, tackifiers, plasticizers, thermoplastic elastomers, reactive elastomers, phosphoric acid compounds, silane coupling agents, adhesion promoters, metal catalysts, amine catalysts, aliphatic cyclic amide compounds, titanium chelate complexes, esterification catalysts, etc.
• the content of these additives may be appropriately adjusted within a range that does not impair the function of the adhesive of the present invention.
• silane coupling agent examples include aminosilanes such as ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, and N-phenyl- ⁇ -aminopropyltrimethoxysilane; epoxysilanes such as ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane
• tackifiers include rosin-based or rosin ester-based tackifiers, terpene-based or terpene phenol-based tackifiers, saturated hydrocarbon resins, coumarone-based tackifiers, coumarone-indene-based tackifiers, styrene resin-based tackifiers, xylene resin-based tackifiers, phenol resin-based tackifiers, and petroleum resin-based tackifiers. These may be used alone or in combination of two or more.
• Plasticizers include polyisoprene, polybutene, and procell oil
• thermoplastic elastomers include styrene-butadiene copolymer (SBS), hydrogenated styrene-butadiene copolymer (SEBS), SBBS, hydrogenated styrene-isoprene copolymer (SEPS), styrene block copolymer (TPS), and olefin elastomer (TPO), and reactive elastomers include these elastomers that have been acid-modified.
• SBS styrene-butadiene copolymer
• SEBS hydrogenated styrene-butadiene copolymer
• SBBS hydrogenated styrene-isoprene copolymer
• SEPS styrene block copolymer
• TPO olefin elastomer
• reactive elastomers include these elastomers that
• Examples of phosphoric acid compounds include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid; condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid; monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, Examples include mono- and diesters of di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, dimethyl phosphite, diethyl phosphite, diprop
• Adhesion promoters include imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undecene (DBU), 1,5-diazabicyclo[4.3.0]nonene, and 6-dibutylamino-1,8-diaza
• Examples of such compounds include tertiary amines such as bicyclo[5.4.0]undecene, compounds obtained by converting these tertiary amines into amine salts with phenol, octylic acid, quaternized tetrapheny
• Metal catalysts include metal complex, inorganic metal, and organic metal catalysts.
• Metal complex catalysts include acetylacetonate salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.
• iron acetylacetonate Fe(acac)3
• manganese acetylacetonate Mn(acac)2
• Inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, etc. These may be used alone or in combination of two or more.
• Organometallic catalysts include organic zinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; organic tin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organic nickel compounds such as nickel octylate and nickel naphthenate; organic cobalt compounds such as cobalt octylate and cobalt naphthenate; organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, and bismuth naphthenate; and titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetra
• Amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxy
• aliphatic cyclic amide compounds examples include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enantholactam, ⁇ -capryllactam, and ⁇ -propiolactam.
• ⁇ -caprolactam is more effective in promoting hardening. These may be used alone or in combination of two or more types.
• Titanium chelate complexes are compounds whose catalytic activity is enhanced by exposure to ultraviolet light, and titanium chelate complexes having an aliphatic or aromatic diketone as a ligand are preferred because of their excellent cure-accelerating effect.
• titanium chelate complexes having an aliphatic or aromatic diketone as a ligand are preferred because of their excellent cure-accelerating effect.
• those having an alcohol with 2 to 10 carbon atoms as a ligand in addition to an aromatic or aliphatic diketone are preferred because the effects of the present invention are more pronounced. These may be used alone or in combination of two or more types.
• the esterification catalyst is preferably a polymerization catalyst made of at least one metal selected from the group consisting of Groups 2, 4, 12, 13, 14, and 15 of the periodic table, or a compound of that metal.
• Polymerization catalysts made of such metals or metal compounds include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, and Ge, and compounds of these metals, more specifically titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, tin octanoate, 2-ethylhexane tin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium. These may be used alone or in
• the adhesive used in the present invention may contain leveling agents, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate-based organic fine particles, defoamers, anti-sagging agents, wetting and dispersing agents, viscosity adjusters, UV absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brightening agents, inorganic heat ray absorbers, flame retardants, antistatic agents, dehydrating agents, etc.
• the content of these additives may be appropriately adjusted within a range that does not impair the function of the adhesive of the present invention.
• the adhesive used in the present invention can be prepared by mixing the above-mentioned components.
• the components may be mixed at the same time to prepare the adhesive, but it is preferable to mix the components other than the hardener (B) in advance to prepare a premixture, and then mix the hardener (B) when using the adhesive to prepare a two-liquid adhesive, as this provides excellent stability and workability of the adhesive.
• the laminated film used in the present invention is a laminated film in which at least one or more stretched polyolefin substrates are laminated with an adhesive.
• the laminated film includes a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, and the first substrate and the second substrate are bonded together with the adhesive.
• the layer structure is as simple as possible, but from the viewpoint of the distribution of packaging materials, printing is often necessary to indicate the contents of the packaging material and the product's description and name.
• Liquid inks such as gravure printing inks and flexographic printing inks are often used for this purpose.
• the printed layer is a layer on which characters, figures, symbols, and other desired patterns are printed using liquid ink or the like.
• the laminate may be provided at any position.
• liquid ink is a general term for solvent-based ink used in gravure printing or flexographic printing. It may be an ink containing a resin, a colorant, and a solvent as essential components, or it may be a so-called clear ink containing a resin and a solvent but substantially no colorant.
• the resins used in the liquid ink are not particularly limited, and examples include acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc., and one or more of these can be used in combination.
• at least one or two or more selected from polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, and cellulose-based resin are used.
• Colorants used in liquid inks include inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite; organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments; and extender pigments such as calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
• inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite
• organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments
• the organic solvent used in the liquid ink preferably does not contain aromatic hydrocarbon organic solvents. More specifically, examples of the organic solvents include alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, and n-octane; and alicyclic hydrocarbon organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane. These can be used alone or in combination of two or more.
• the laminate film of the present invention is a laminate film including a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, but may further include a substrate other than the first substrate and the second substrate.
• the film may be a laminate film having a structure in which a plurality of substrates are laminated, such as those mentioned above.
• the raw material of the other substrates is a thermoplastic resin mainly composed of an olefin resin, because this has excellent recyclability.
• the type of the raw olefin resin, the film manufacturing method, the type of additives, the film thickness, etc. can be the same as those of the first substrate and the second substrate.
• the above-mentioned adhesive when laminating the laminated film of the present invention to another substrate, it is preferable to use the above-mentioned adhesive, since this has excellent recyclability and adhesiveness.
• the laminated film used in the present invention is a laminated film in which the first substrate and the second substrate are bonded together with the adhesive. Even when the laminated film contains other substrates, it is preferable to use the adhesive because it has excellent recyclability and adhesiveness.
• the adhesive is a solvent-based adhesive
• the adhesive is applied to either the first substrate or the second substrate using a roll such as a gravure roll, and the organic solvent is evaporated by heating in an oven or the like, and then the other substrate is laminated to obtain the laminated film of the present invention. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 80°C, and the aging time is preferably 12 to 240 hours.
• the adhesive is a solventless type
• the adhesive which has been preheated to about 40°C to 100°C, is applied to either the first substrate or the second substrate using a roll such as a gravure roll, and the other is immediately bonded to obtain the laminated film of the present invention. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 70°C, and the aging time is preferably 6 to 240 hours.
• the amount of the adhesive applied is adjusted appropriately.
• the amount of solids is adjusted to 0.1 g/ m2 or more and 10 g/ m2 or less, preferably 0.3 g/ m2 or more and 5 g/ m2 or less.
• the amount of the adhesive applied is adjusted to 0.1 g/ m2 or more and 10 g/ m2 or less, preferably 0.3 g/ m2 or more and 5 g/ m2 or less.
• the recycled plastic of the present invention can be obtained by a known processing method for recycling waste plastics.
• An example of the processing method is shown below.
• the present invention is not limited to this, and various known recycling plastic processing methods can be applied.
• the laminated film is crushed by a crusher, etc.
• the crusher is not particularly limited and any known crusher may be used.
• the crushed film pieces are physically blended by melt kneading, solvent cast blending, latex blending, polymer complex, etc.
• the melt kneading method is common.
• kneading devices include a tumbler, a Henschel mixer, a rotary mixer, a super mixer, a ribbon tumbler, a V blender, etc.
• the film pieces are melt kneaded by such a kneading device and then pelletized.
• a single-screw or multi-screw extruder is generally used for melt kneading pelletization, and the film pieces may be charged as they are or may be charged after being compressed and reduced in volume with or without heating.
• a Banbury mixer, a roller, a co-kneader, a blast mill, a Prabender blastograph, etc. can also be used, which are operated batchwise or continuously.
• the film pieces may be used as molding resins and melt kneaded in the heating cylinder of a molding machine without melt kneading.
• the pellets of the present invention which are mainly made from recycled plastic, can exert their maximum effect by being recycled into non-oriented polyolefin films or molded products by injection molding or the like.
• the method of regenerating the non-oriented polyolefin film is not particularly limited, and can be obtained by a known film production method.
• a melt-kneading method using a general mixer such as a single-screw extruder, a twin-screw extruder, or a multi-screw extruder, or a method of dissolving or dispersing and mixing each component and then removing the solvent by heating, can be used.
• twin-screw extruder In consideration of workability, it is particularly preferable to use a single-screw extruder or a twin-screw extruder.
• a single-screw extruder When a single-screw extruder is used, a full-flight screw, a screw with a mixing element, a barrier flight screw, a fluted screw, or the like can be used without any particular limitation.
• the twin-screw kneading device is not particularly limited to a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, and the screw shape is also not particularly limited to a full-flight screw or a kneading disk type.
• a method of melting the film using a single-screw extruder or a twin-screw extruder, etc., and then forming a film using a T-die via a feed block or a multi-manifold may be used.
• the recycled film can be subjected to a surface modification treatment to improve suitability for subsequent processes as necessary.
• the surface of the film that comes into contact with other substrates can be modified to improve printability when used as a single film, and lamination suitability when used in a laminated form.
• a method of expressing functional groups by oxidizing the film surface such as corona discharge treatment, plasma treatment, and frame treatment, or a method of modifying the film by a wet process, such as coating an easy-adhesion layer, can be suitably used.
• pellets made primarily from virgin plastic may be molded into a molded body using conventional molding methods other than the above-mentioned film-making, such as injection molding, extrusion molding, vacuum molding, compressed air molding, blow molding, etc., and used for various purposes.
• film-making such as injection molding, extrusion molding, vacuum molding, compressed air molding, blow molding, etc.
• it can be used for everyday items, stationery, toys, sporting goods, home appliances, and automotive parts used in ordinary households, as well as films, sheets, and fibers. If there are no problems with hygiene, it can also be used in medical equipment, food containers, and food packaging materials.
• Olefin Resin 1 Auroren S-5601S (olefin resin having an acid group and an acid anhydride group, manufactured by Nippon Paper Industries Co., Ltd.) was adjusted to a non-volatile content of 10% by mass with a mixed solution of methylcyclohexane, ethyl acetate, and isopropanol. This was designated as adhesive coating solution 1.
• Olefin Resin 2 Auroren S-5631S (olefin resin having an acid group and an acid anhydride group, manufactured by Nippon Paper Industries Co., Ltd.) was adjusted to a non-volatile content of 10% by mass with a mixed solution of methylcyclohexane, ethyl acetate, and isopropanol. This was designated as adhesive coating liquid 2.
• Ultrathene 13B53D (olefin resin modified with vinyl acetate groups, manufactured by Tosoh Corporation) was adjusted to a non-volatile content of 10% by mass using a mixed solution of methylcyclohexane, ethyl acetate, and isopropanol. This was designated as adhesive coating liquid 3.
• Olefin Resin 4 Auroren S-500S (olefin resin having an acid group and an acid anhydride group, manufactured by Nippon Paper Industries Co., Ltd.) was adjusted to a non-volatile content of 10% by mass with a mixed solution of methylcyclohexane, ethyl acetate, and isopropanol. This was used as adhesive coating solution 4.
• Example 1 The adhesive coating solution 1 was applied to a biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd., Pylen Film-OT P2161, 20 ⁇ m) as the substrate 1 using a bar coater so that the solid weight of the adhesive was approximately 1.5 g/ m2 , and after the solvent was evaporated, the substrate 2 was laminated to a biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd., Pylen Film-OT P2161, 20 ⁇ m) using a tabletop calendar roll, and aged at 50° C. for 72 hours to produce a laminated film 1.
• a biaxially oriented polypropylene film manufactured by Toyobo Co., Ltd., Pylen Film-OT P2161, 20 ⁇ m
• Example 2 A laminated film 2 was produced in the same manner as in Example 1, except that adhesive coating liquid 2 was used as the adhesive coating liquid.
• Example 3 A laminated film 3 was produced in the same manner as in Example 1, except that adhesive coating liquid 3 was used as the adhesive coating liquid.
• the adhesive coating solution 4 was applied to a biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd., Pylen Film-OT P2161, 20 ⁇ m) as the substrate 1 using a bar coater so that the solid weight of the adhesive was approximately 1.5 g/ m2 , and after the solvent was evaporated, the film was laminated to a biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd., Pylen Film-OT P2161, 20 ⁇ m) as the substrate 2 using a table calendar roll, and aged at 50° C. for 72 hours to produce a laminated film 1.
• a biaxially oriented polypropylene film manufactured by Toyobo Co., Ltd., Pylen Film-OT P2161, 20 ⁇ m
• the pulse NMR of the dumbbell test piece obtained above was measured before and after the tensile test, and the relaxation time T2 (s) of the amorphous phase was obtained.
• the difference between the amorphous phase relaxation time after the tensile test and the amorphous phase relaxation time before the tensile test was defined as ⁇ T2 (s).
• a minispec mq20 manufactured by BRUKER was used for the pulse NMR, and a free induction decay curve was obtained at a measurement temperature of 40°C.
• the spin-spin relaxation time T2 of the three components was obtained by curve fitting using analysis software manufactured by BRUKER.

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• 2023
  • 2023-12-07 JP JP2024521305A patent/JPWO2024135376A1/ja active Pending
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