WO2012060371A1 - 混合樹脂及び多層構造体 - Google Patents
混合樹脂及び多層構造体 Download PDFInfo
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- WO2012060371A1 WO2012060371A1 PCT/JP2011/075173 JP2011075173W WO2012060371A1 WO 2012060371 A1 WO2012060371 A1 WO 2012060371A1 JP 2011075173 W JP2011075173 W JP 2011075173W WO 2012060371 A1 WO2012060371 A1 WO 2012060371A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- 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
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- 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
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
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- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- 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
- B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L31/06—Homopolymers or copolymers of esters of polycarboxylic acids
Definitions
- the present invention relates to a mixed resin containing a saponified product of polyolefin and ethylene-vinyl acetate copolymer.
- the present invention also relates to a multilayer structure having a layer obtained by melt molding the mixed resin.
- a layer made of a thermoplastic resin typified by polyolefin such as polyethylene and polypropylene and a layer made of a saponified ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVOH) having excellent barrier properties are included.
- Multilayer structures are widely used in various applications, particularly food packaging containers and fuel containers, taking advantage of their barrier properties.
- Such a multilayer structure is used as various molded products such as films, sheets, cups, trays, and bottles.
- end portions or defective products generated when obtaining the above various molded products are collected, melt-molded and reused as at least one layer of a multilayer structure including a thermoplastic resin layer and an EVOH layer. .
- Such a recovery technique is useful in terms of waste reduction and economy, and is widely adopted.
- Patent Document 1 discloses, as a resin composition to be blended in a pulverized product containing EVOH, an olefin-carboxylic acid vinyl ester copolymer and / or a saponified product thereof, a fatty acid metal salt, and A resin composition containing a metal compound is described. According to this resin composition, there is no mixing of polyolefin and EVOH phase-separated foreign matter into the molded product even during repeated scrap returns and continuous operation for a long time, and the impact resistance of the regrind layer. It is said that there is no deterioration in mechanical properties.
- Patent Document 2 describes a resin composition containing an acid graft-modified polyolefin resin, a fatty acid metal salt and / or a metal compound as a resin composition to be blended with a pulverized product containing EVOH. According to this resin composition, there is no mixing of polyolefin and EVOH phase-separated foreign matter into the molded product even during repeated scrap returns and continuous operation for a long time, and the impact resistance of the regrind layer. It is said that there is no deterioration in mechanical properties.
- JP 2002-234971 A Japanese Patent Laid-Open No. 2002-121342
- the present invention has been made in order to solve the above problems, and contains polyolefin and EVOH, and has a small amount of screw adhesion of a deteriorated product even in continuous melt molding for a long time.
- An object of the present invention is to provide a mixed resin in which generation of streaks and streaks is reduced.
- the above-mentioned problems include polyolefin (A), saponified ethylene-vinyl acetate copolymer (B), acid-modified olefin-carboxylic acid vinyl ester copolymer (C), and the acid-modified olefin-carboxylic acid vinyl ester copolymer.
- the olefin content of the polymer (C) is 50 to 95 mol%
- the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) has an acid modification amount of 0.01 to 2 mmol / g.
- the ethylene-vinyl acetate copolymer saponified product (B) has an ethylene content of 20 to 60 mol% and a saponification degree of 80% or more. Further, the total of the carboxylic acid units (I) and lactone ring units (II) at the polymer ends of the ethylene-vinyl acetate copolymer saponified product (B) is the ethylene unit (III), vinyl alcohol unit (IV) and The ratio ((I + II) / (III + IV + V)) to the total of vinyl ester units (V) is more preferably 0.03 mol% or more.
- the content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) may be 0.1 to 30% by mass with respect to the mass of the ethylene-vinyl acetate copolymer saponified product (B). Is preferred. It is also preferable that the content of the saponified ethylene-vinyl acetate copolymer (B) is 0.1 to 30% by mass with respect to the total mass of the mixed resin.
- the difference between the solubility parameter of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) and the solubility parameter of the ethylene-vinyl acetate copolymer saponified product (B) is 0.5 to 4.0 (cal / cm 3 ) A range of 1/2 is also suitable.
- an alkali metal is contained, and the molar ratio between the alkali metal content and the acid modification amount of the mixed resin is in the range of 0.05 to 75. Further, it contains an unmodified olefin-carboxylic acid vinyl ester copolymer (D), and the unmodified olefin-carboxylic acid vinyl ester copolymer (D) has an olefin content of 50 to 98 mol%, It is also preferable that the content of the modified olefin-carboxylic acid vinyl ester copolymer (D) is 0.01 to 20% by mass with respect to the total mass of the mixed resin.
- the lubricant (E) is contained, and the content of the lubricant (E) is 0.005 to 1.0% by mass with respect to the total mass of the mixed resin. Further, it is also preferable that a pigment is contained and the content of the pigment is 0.0001 to 10% by mass with respect to the total mass of the mixed resin.
- the above problem can be solved by a multilayer structure having a layer obtained by melt-molding the mixed resin.
- the above-mentioned problems include the recovery of a multilayer structure having a layer made of a resin composition containing polyolefin (A) and a layer made of saponified ethylene-vinyl acetate copolymer (B), and an acid-modified olefin-carbon.
- This can also be solved by the method for producing the mixed resin including a step of mixing a recovery aid comprising a resin composition containing the acid vinyl ester copolymer (C).
- the mixed resin of the present invention it is possible to provide a molded article, particularly a multilayer structure, in which the amount of deteriorated screw attached is small even in continuous melt molding for a long time and the occurrence of fish eyes, streaks and streaks is reduced. .
- 1 is a chart of a typical EVOH 1 H-NHR measurement.
- 1 is a chart of a typical EVOH 1 H-NHR measurement.
- 1 is a chart of a typical EVOH 1 H-NHR measurement.
- the mixed resin of the present invention comprises a polyolefin (A), a saponified ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVOH) (B), an acid-modified olefin-carboxylic acid vinyl ester copolymer (C). Containing.
- A polyolefin
- EVOH saponified ethylene-vinyl acetate copolymer
- C acid-modified olefin-carboxylic acid vinyl ester copolymer
- polystyrene resin examples include polyethylene (low density, linear low density, medium density, high density, etc.); ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene, etc.
- Copolymers of ⁇ -olefins such as ethylene-based copolymers obtained by copolymerizing ⁇ -olefins or acrylic acid esters; polypropylene; and propylene and ⁇ -olefins such as ethylene, 1-butene, 1-hexene and 4-methyl-1-pentene.
- polyolefin (A) polypropylene resins such as polypropylene and propylene copolymers, or polyethylene resins such as polyethylene and ethylene copolymers are preferable.
- Polyolefin (A) may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- the melt index (MI; measured at 190 ° C. under a load of 2160 g) of the polyolefin (A) is preferably 0.03 g / 10 min or more, more preferably 0.05 g / 10 min or more. Moreover, 100 g / 10min or less is preferable, 80 g / 10 min or less is more preferable, and 70 g / 10 min or less is more preferable.
- the content of the polyolefin (A) is preferably 50 to 99.8% by mass relative to the total mass of the mixed resin. If it is less than 50% by mass, the adhesion to the polyolefin layer may be lowered in a multilayer structure having a layer obtained by melt molding a mixed resin.
- the content is more preferably 55% by mass or more, and further preferably 60% by mass or more. On the other hand, if it exceeds 99.8% by mass, the effect of cost reduction by recovery is poor, which is not preferable from an economical viewpoint.
- the content is more preferably 99.5% by mass or less.
- EVOH (B) used in the present invention is obtained by saponifying vinyl acetate units in an ethylene-vinyl acetate copolymer.
- EVOH (B) has a carboxylic acid unit (I) and a lactone ring unit (II) at the end of the polymer, and ethylene units (III), vinyl alcohol units (IV) and vinyl ester units as units forming the skeleton. (V).
- Each of the above units (I) to (V) is represented by the following formula.
- X represents a hydrogen atom, a hydroxyl group or an esterified hydroxyl group
- Y represents a hydrogen atom, an alkali metal or an alkaline earth metal.
- R 1 represents a linear or branched alkyl group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, or a trifluoromethyl group.
- the ethylene content is the ratio of the ethylene unit (III) to the total of the ethylene unit (III), vinyl alcohol unit (IV) and vinyl ester unit (V) (III / (III + IV + V)).
- the degree of saponification of vinyl ester units refers to the ratio (IV / (IV + V)) of vinyl alcohol units (IV) to the total of vinyl alcohol units (IV) and vinyl ester units (V).
- the ethylene content of EVOH (B) is preferably 20 to 60 mol%. When the ethylene content is less than 20 mol%, the compatibility with the polyolefin (A) tends to be poor. The ethylene content is more preferably 25 mol% or more. On the other hand, when the ethylene content exceeds 60 mol%, the gas barrier properties are lowered. The ethylene content is more preferably 55 mol% or less, and further preferably 50 mol% or less.
- the saponification degree of the vinyl ester unit of EVOH (B) is preferably 80% or more, more preferably 98% or more, and further preferably 99% or more from the viewpoint of gas barrier properties. In particular, EVOH having an ethylene content of 20 to 55 mol% and a caking degree of 99% or more is used as a container having excellent barrier properties, so that it may be laminated with polyolefin and contained in the recovered material. Many.
- the total of the carboxylic acid units (I) and the lactone ring units (II) at the terminal of the EVOH (B) copolymer is based on the total units of the ethylene units (III), vinyl alcohol units (IV), and vinyl ester units (V).
- the ratio ((I + II) / (III + IV + V)) is preferably 0.03 mol% or more. Normally, when the above ratio is high, EVOH (B) reacts with each other at the time of melt molding and the long-run property tends to decrease. In the present invention, however, an acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is included.
- EVOH (B) may be copolymerized with other polymerizable monomers in a range that does not impair the effects of the present invention, generally in a range of 5 mol% or less.
- polymerizable monomers include ⁇ -olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene; (meth) acrylic acid esters; maleic acid, fumaric acid, itaconic acid An unsaturated carboxylic acid such as: alkyl vinyl ether; N- (2-dimethylaminoethyl) methacrylamide or a quaternized product thereof, N-vinylimidazole or a quaternized product thereof, N-vinylpyrrolidone, N, N-butoxymethylacrylamide, Examples include vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane.
- the melt index (MI; measured at 190 ° C. under a load of 2160 g) of EVOH (B) is preferably 0.1 g / 10 min or more, and more preferably 0.5 g / 10 min or more. Further, it is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and most preferably 30 g / 10 min or less.
- MI of EVOH (B) is MI (B) and MI of polyolefin (A) (measured at 190 ° C.
- MI (A) under a load of 2160 g) is MI (A)
- the ratio [MI (B) / MI (A)] is preferably 0.1 to 100, more preferably 0.3 to 50.
- MI of melting point near 190 ° C or over 190 ° C is measured under a load of 2160g and at a plurality of temperatures above the melting point.
- the reciprocal absolute temperature is plotted on the horizontal axis and the logarithm of MI is plotted on the vertical axis. The value extrapolated to 190 ° C. is used.
- the content of EVOH (B) is preferably 0.1 to 30% by mass with respect to the total mass of the mixed resin.
- the content of EVOH (B) is less than 0.1% by mass, the effect of cost reduction by recovery is poor, which is not preferable from an economical viewpoint.
- As for content 1.0 mass% or more is more preferable.
- the content of EVOH (B) exceeds 30% by mass, dispersion of EVOH (B) in the polyolefin (A) becomes insufficient, and any of streak, streak, fish eye generation, and screw adhesion However, there is a possibility that a sufficient suppression effect cannot be obtained.
- the content is more preferably 20% by mass or less.
- the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) used in the present invention is obtained by grafting an acid to an olefin-carboxylic acid vinyl ester copolymer.
- Examples of the olefin monomer constituting the olefin-carboxylic acid vinyl ester copolymer include ethylene, propylene, n-butylene, isobutylene and the like. Among these, ethylene is preferably used.
- vinyl carboxylate monomer examples include vinyl formate, vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl palmitate, Examples thereof include vinyl stearate, vinyl oleate, and vinyl pivalate.
- vinyl acetate is most preferably used from the viewpoint of cost and handling properties.
- an unsaturated carboxylic acid or a derivative thereof can be used, for example, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid; Examples include methyl ester or ethyl ester of acid; maleic anhydride, itaconic anhydride and the like. These may be used alone or in combination of two or more. Of these, maleic anhydride is most preferably used.
- a compound having a boron-containing group that can be converted to a boronic acid group in the presence of a boronic acid group or water can also be used as an acid to be grafted to the olefin-carboxylic acid vinyl ester copolymer.
- the boronic acid group is represented by the following formula (VI).
- a boron-containing group that can be converted to a boronic acid group in the presence of water is a boron-containing group that can be converted to a boronic acid group by hydrolysis in the presence of water.
- a boron-containing functional group is a boron-containing group that can be converted to a boronic acid group by hydrolysis in the presence of water.
- water alone, a mixture of water and an organic solvent (toluene, xylene, acetone, etc.), a mixture of a 5% boric acid aqueous solution and the organic solvent, etc. are used as a solvent at room temperature to 150 ° C.
- Representative examples of such functional groups include boronic acid ester groups represented by the following formula (VII), boronic acid anhydride groups represented by the following formula (VIII), boronic acid groups represented by the following formula (IX),
- R 2 and R 3 are a hydrogen atom, an aliphatic hydrocarbon group (a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, etc.), an alicyclic hydrocarbon group (cycloalkyl Group, a cycloalkenyl group, etc.) and an aromatic hydrocarbon group (phenyl group, biphenyl group, etc.), and R 2 and R 3 may be the same group or different. However, the case where both R 2 and R 3 are hydrogen atoms is excluded.
- the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a substituent, and R 2 and R 3 may be bonded.
- R 4 are the same hydrogen atom and R 2 and R 3, an aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group, R 4, R 5 and R 6 may be the same group or different from each other.
- M represents an alkali metal.
- boronic acid ester group represented by formula (VII) examples include boronic acid dimethyl ester group, boronic acid diethyl ester group, boronic acid dipropyl ester group, boronic acid diisopropyl ester group, boronic acid dibutyl ester group, boron Acid dihexyl ester group, boronic acid dicyclohexyl ester group, boronic acid ethylene glycol ester group, boronic acid propylene glycol ester group, boronic acid 1,3-propanediol ester group, boronic acid 1,3-butanediol ester group, boronic acid neo Examples include pentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group, boronic acid trimethylolethane ester group, boronic acid trimethylolpropane ester group, boronic acid diethanolamine ester group, etc. It is
- examples of the boronic acid base represented by the general formula (IX) include an alkali metal base of boronic acid. Specific examples include sodium boronate base and potassium boronate base.
- a boronic acid cyclic ester group is preferable from the viewpoint of thermal stability.
- the boronic acid cyclic ester group include a boronic acid cyclic ester group containing a 5-membered ring or a 6-membered ring. Specific examples include a boronic acid ethylene glycol ester group, a boronic acid propylene glycol ester group, a boronic acid 1,3-propanediol ester group, a boronic acid 1,3-butanediol ester group, and a boronic acid glycerin ester group. .
- the grafting of the acid onto the olefin-carboxylic acid vinyl ester copolymer can be performed by a known method.
- the olefin-carboxylic acid vinyl ester copolymer is dissolved in an appropriate solvent or melted with an extruder.
- An acid-modified olefin-carboxylic acid vinyl ester copolymer (C) can be obtained by adding a radical initiator in the state and activating it, and then adding an acid and grafting.
- the olefin content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) used in the present invention is 50 to 95 mol%. If it is less than 50 mol%, the compatibility with the polyolefin (A) becomes poor, and fish eyes are likely to be generated in the molded product.
- the olefin content is preferably 70 mol% or more, and more preferably 80 mol% or more. On the other hand, if it exceeds 95 mol%, the reactivity with EVOH (B) becomes poor, and EVOH becomes difficult to uniformly disperse, so that streaks and streaks are likely to occur in the molded product.
- the olefin content is preferably 93 mol% or less, and more preferably 91 mol% or less.
- the acid-modified amount of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is preferably 0.01 to 2 mmol / g. If it is less than 0.01 mmol / g, the reactivity with EVOH (B) becomes poor, and streaks and streaks are likely to occur in the molded product.
- the acid modification amount is more preferably 0.02 mmol / g or more, and further preferably 0.05 mmol / g or more. On the other hand, if it exceeds 2 mmol / g, the reactivity with EVOH (B) becomes excessive, and fish eyes are likely to occur.
- the amount of acid modification is more preferably 1.9 mmol / g or less, and further preferably 1.5 mmol / g or less.
- the acid modification amount of the present invention refers to the amount of the acidic component calculated by dividing the acid value measured based on JIS standard K2501 by the molecular weight of potassium hydroxide.
- the melt index (MI; measured at 190 ° C. under a load of 2160 g) of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is preferably 0.03 g / 10 min or more, more preferably 0.05 g / 10 min or more. . Moreover, 100 g / 10min or less is preferable, 80 g / 10 min or less is more preferable, and 70 g / 10 min or less is more preferable.
- the difference between the ethylene content of EVOH (B) and the olefin content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is in the range of 20 to 70 mol%.
- the compatibility between the EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) and the polyolefin (A) becomes poor, and the acid-modified olefin-carboxylic acid vinyl ester copolymer Since it becomes difficult to obtain the compatibility improving effect of the polyolefin (A) and EVOH (B) by the polymer (C), fish eyes, streaks, and streaks are likely to occur in the molded product.
- the difference is preferably 30 mol% or more, more preferably 35 mol% or more, and further preferably 40 mol%.
- the compatibility between EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is deteriorated.
- the acid-modified olefin-carboxylic acid vinyl ester copolymer is also deteriorated. Since it becomes difficult to obtain the compatibility improving effect of polyolefin (A) and EVOH (B) by (C), fish eyes, streaks and streaks are likely to occur in the molded product.
- the difference is preferably within 68 mol%, more preferably within 65 mol%.
- the difference between the solubility parameter of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) and the solubility parameter of EVOH (B) is 0.5 to 4.0 (cal / cm 3 ) 1/2 .
- the solubility parameter means a solubility parameter calculated from the Fedors equation.
- the difference is more preferably 0.7 (cal / cm 3 ) 1/2 or more, further preferably 1.0 (cal / cm 3 ) 1/2 or more, and 1.2 (cal / cm 3 ) 1/2 or more. Is particularly preferred. On the other hand, if it exceeds 4.0 (cal / cm 3 ) 1/2 , the compatibility between EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) becomes poor. And streaks and streaks are likely to occur.
- the difference is more preferably 3.5 (cal / cm 3) 1/2 or less, 3.0 (cal / cm 3) 1/2 or less is particularly preferred.
- the content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is preferably 0.1 to 30% by mass with respect to the mass of EVOH (B).
- the ratio is more preferably 1.0% by mass or more, and further preferably 2.0% by mass or more.
- the proportion is preferably 28% by mass or less, and more preferably 25% by mass or less.
- the content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is preferably 0.01 to 10% by mass with respect to the total mass of the mixed resin. If it is less than 0.01% by mass, the reactivity with EVOH (B) becomes poor, fish eyes, streaks, and streaks tend to occur in the molded product, and the screw adhesion amount also tends to increase.
- the content is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, based on the total mass of the mixed resin.
- the content is more preferably 5% by mass or less, and further preferably 3% by mass or less, based on the total mass of the mixed resin.
- the mixed resin of the present invention contains an alkali metal.
- an alkali metal By containing an alkali metal, the reactivity between EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) at the time of melt molding can be increased. Therefore, EVOH (B ) Can be finely dispersed.
- the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium, and sodium and potassium are preferably used from the viewpoint of reactivity and economy.
- the molar ratio between the alkali metal content and the acid modification amount in the mixed resin is preferably in the range of 0.05 to 75. If it is less than 0.05, the effect of increasing the reactivity between EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) may not be obtained.
- the molar ratio is more preferably 0.1 or more, and further preferably 0.16 or more. On the other hand, if it exceeds 75, EVOH (B) and acid-modified olefin-carboxylic acid vinyl ester copolymer (C) may be cross-linked by excessive reaction, and fish eyes may be remarkably increased.
- the ratio is more preferably 50 or less, and still more preferably 10 or less.
- the method for containing the alkali metal in the mixed resin is not particularly limited, and the polyolefin (A), EVOH (B), acid-modified olefin-carboxylic acid vinyl ester copolymer (C) or other components contained in the resin composition May be included in advance. Moreover, when mixing each component and obtaining mixed resin, you may mix
- the components constituting the mixed resin of the present invention include an unmodified olefin-carboxylic acid vinyl ester copolymer. It is preferable to blend the polymer (D). By containing the unmodified olefin-carboxylic acid vinyl ester copolymer (D), the dispersion of EVOH (B) can be further stabilized.
- the unmodified olefin-carboxylic acid vinyl ester copolymer (D) used in the present invention is the olefin-carboxylic acid vinyl ester copolymer used in the acid-modified olefin-carboxylic acid vinyl ester copolymer (C). Can be used.
- the olefin content of the unmodified olefin-carboxylic acid vinyl ester copolymer (D) is preferably 50 to 98 mol%.
- the olefin content is less than 50 mol%, the compatibility with the polyolefin (A) becomes poor, and the streaks and streaks of the molded product tend to increase. More preferably, it is 55 mol% or more, More preferably, it is 60 mol% or more.
- the difference between the olefin content of the unmodified olefin-carboxylic acid vinyl ester copolymer (D) and the olefin content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is in the range of 0 to 15 mol%. Preferably there is. If the difference is larger than 15 mol%, the compatibility between the acid-modified olefin-carboxylic acid vinyl ester (C) and the unmodified olefin-carboxylic acid vinyl ester copolymer (D) is deteriorated, and the unmodified olefin-vinyl carboxylate is deteriorated. It becomes difficult to obtain the effect of adding the ester copolymer (D).
- the difference is more preferably 10 mol% or less, and further preferably 7 mol% or less.
- the melt index (MI; measured at 190 ° C. under a load of 2160 g) of the unmodified olefin-carboxylic acid vinyl ester copolymer (D) is preferably 0.1 to 50 g / 10 min, preferably 0.5 to More preferably, it is 30 g / 10 minutes, and even more preferably 1 to 20 g / 10 minutes.
- the content of the unmodified olefin-carboxylic acid vinyl ester copolymer (D) is preferably 0.01 to 20% by mass relative to the total mass of the mixed resin.
- the content is more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more.
- the content exceeds 20% by mass, incompatible components with respect to the polyolefin (A) are excessively added, and thus streaks and streaks are likely to occur.
- the content is more preferably 10% by mass or less, and further preferably 8% by mass or less.
- a lubricant (E) may be blended as a component constituting the mixed resin of the present invention. preferable. By making the mixed resin contain the lubricant (E), the screw adhesion amount can be suppressed.
- Examples of the lubricant (E) used in the present invention include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, methylol stearic acid amide, N-oleyl palmitoamide, N- Fatty acid amides such as stearyl erucamide; aliphatic hydrocarbon lubricants such as liquid paraffin, natural paraffin, synthetic paraffin, polyolefin wax and their partial oxides, fluorides and chlorides; aliphatic such as stearyl alcohol and lauryl alcohol Examples include alcohols; fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, and montanic acid; and metal salts thereof; aliphatic esters such as stearyl stearate and stearyl laurate. Among these, fatty acid metal salts, fatty acid esters, and fatty acid amides are preferably used
- a fatty acid metal salt as the lubricant (E) because the generation of fish eyes derived from the aggregation of deteriorated products can be suppressed.
- the fatty acid metal salts include higher aliphatic metal salts having 10 to 26 carbon atoms such as lauric acid, stearic acid, myristic acid, behenic acid, and montanic acid, particularly those of Group 1, Group 2 or Group 3 of the periodic table.
- Metal salts such as sodium salt, potassium salt, calcium salt and magnesium salt can be mentioned.
- zinc salts and lead salts of the above fatty acids can also be used.
- metal salts belonging to Group 2 of the Periodic Table such as calcium salts and magnesium salts exhibit the effects of the present invention when added in a small amount.
- a metal salt of a metal having an electronegativity of 1.5 or more such as zinc salt, lead salt, or allred (EG Allred) or rogue (EG Rochow)
- EG Allred zinc salt, lead salt, or allred
- EG Rochow a screw of a deteriorated product is used. Adhesion to the surface can be suppressed, and deterioration products such as burns and burns when melt extruded for a long time can be reduced.
- a metal salt of Group 2 of the Periodic Table and a metal salt of a metal having an electronegativity of 1.5 or more according to All Red and AL Rochow are used in combination. It is effective.
- the content of the lubricant (E) is preferably 0.005 to 1.0% by mass with respect to the total mass of the mixed resin. If the amount is less than 0.005% by mass, the effect of suppressing screw adhesion may not appear.
- the content is more preferably 0.01% by mass or more, and further preferably 0.02% by mass or more. On the other hand, when the amount exceeds 1% by mass, the screw adhesion amount may increase. This is considered to be because the resin composition is plasticized at the time of melt molding, or the lubricant is compatible with the resin composition and offsets the lubricity with the screw.
- the content is more preferably 0.9% by mass or less, and further preferably 0.8% by mass or less.
- hydrotalcite is preferably blended in addition to the above-described polyolefin (A), EVOH (B) and acid-modified olefin-carboxylic acid vinyl ester copolymer.
- M represents one or more of Mg, Ca, Sr, Ba, Zn, Cd, Pb, Sn
- A represents CO 3 or HPO 4
- x, y, z are positive numbers, and a is 0 or Positive number, 2x + 3y-2z> 0
- Hydrotalcite (G) which is a double salt represented by
- M is preferably Mg, Ca or Zn, and a combination of two or more thereof is more preferable.
- the content of hydrotalcite is preferably 0.01 to 2.0% by mass with respect to the total mass of the mixed resin. If it is less than 0.01% by mass, it is difficult to obtain the effect of suppressing thermal deterioration during melt molding.
- the content is more preferably 0.02% by mass or more, and further preferably 0.03% by mass or more. On the other hand, if it exceeds 2% by mass, the dispersibility of hydrotalcite in the polyolefin (A) may deteriorate, and fish eyes may increase.
- the content is more preferably 1.8% by mass or less, and further preferably 1.6% by mass or less.
- a pigment can be blended in addition to the above-described polyolefin (A), EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer.
- the pigment used in the present invention is not particularly limited, and various organic pigments and inorganic pigments are employed depending on the color of the target multilayer structure. Examples of organic pigments include azo pigments, quinacridone pigments, and phthalocyanine pigments, and one or more of these are used.
- inorganic pigments examples include oxide pigments such as titanium oxide, zinc oxide, and chromium oxide; sulfide pigments such as zinc sulfide, lithopone, cadmium yellow, vermilion, and cadmium red; alumina white, iron oxide yellow, and viridian.
- Hydroxide pigments such as precipitated barium sulfate and barite powder
- carbonate pigments such as calcium carbonate and lead white
- phosphate pigments such as manganese violet
- carbon black such as lead white
- lead pigments such as lead pigments
- cadmium Pigments Cobalt pigments
- Iron pigments such as iron black
- Chromium pigments such as chrome lead, molybdate orange, zinc chromate and strontium chromate
- Ultramarine and bitumen Silicate pigments such as white carbon, clay and talc 1 type or 2 types or more of these are used.
- inorganic pigments are preferable, and oxide pigments are more preferable because they can be uniformly colored without spotting and the thermal stability of the composition is hardly impaired.
- oxide pigments titanium oxide (titanium dioxide) and zinc oxide are preferable from the viewpoint of food hygiene, and titanium oxide (titanium dioxide) is particularly preferable.
- the pigment content depends on the type of pigment, it is preferably 0.0001 to 10% by mass relative to the total mass of the mixed resin. If it is less than 0.0001% by mass, particularly when the melt kneading time of the resin is short, the hue of the molded product may be uneven due to poor dispersion.
- the content is more preferably 0.0005% by mass, and further preferably 0.001% by mass or more.
- fish eyes may increase due to aggregation of the pigment in the polyolefin (A).
- the content is more preferably 9% by mass or less, and further preferably 7% by mass or less.
- S-EVOH is a saponified ethylene-vinyl acetate copolymer having an ethylene content of 68 to 98 mol% and a saponification degree of vinyl acetate units of 20% or more.
- the ethylene content of S-EVOH is preferably 70 mol% or more, and more preferably 72 mol% or more.
- the ethylene content is preferably 96 mol% or less, and more preferably 94 mol% or less.
- the degree of saponification of the vinyl acetate unit is more preferably 30% or more, and further preferably 40% or more.
- the upper limit of the saponification degree is not particularly limited and may be 99 mol% or more, and those having a saponification degree of substantially 100% can be used.
- the ethylene content is less than 68 mol%, when it exceeds 98 mol%, or when the degree of saponification of vinyl acetate units is less than 20%, the effect of improving the compatibility of polyolefin (A) and EVOH (B) Is insufficient.
- the melt index (measured at 190 ° C. under a load of 2160 g) of S-EVOH is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, and 1 g / 10 min or more. More preferably it is.
- the melt index of S-EVOH is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and further preferably 30 g / 10 min or less.
- the content of S-EVOH is preferably 0.01 to 2% by mass with respect to the total mass of the mixed resin. If it is less than 0.01% by mass, the effect of improving the compatibility of the polyolefin (A) and EVOH (B) may not be obtained.
- the content is more preferably 0.02% by mass, and further preferably 0.004% by mass or more.
- it exceeds 2% by mass it may excessively react with the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) or the acid-modified polyolefin contained in the adhesive resin during melt molding, and fish eyes may increase. is there.
- the content is more preferably 1.8% by mass or less, and further preferably 1.6% by mass or less.
- antioxidants It is also preferable to mix an agent. By adding an antioxidant, yellowing of a molded product after melt molding can be suppressed.
- antioxidants examples include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis (6-t-butylphenol), 2,2 '-Methylenebis (4-methyl-6-t-butylphenol), octadecyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis (6-t -Butylphenol) and the like.
- the content of the antioxidant is preferably 0.0001 to 2% by mass with respect to the total mass of the mixed resin. If it is less than 0.0001% by mass, the effect of improving thermal deterioration during melt molding is insufficient.
- the content is more preferably 0.0002% by mass or more, and further preferably 0.0004% by mass or more.
- the content exceeds 2% by mass, the adhesion to the adjacent layer may be lowered when a multilayer structure having a layer obtained by melt-molding the mixed resin is produced.
- the content is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less.
- additives can be blended with the mixed resin of the present invention within a range not impairing the effects of the present invention.
- additives include ultraviolet absorbers, plasticizers, antistatic agents, fillers, or other polymer compounds.
- Specific examples of the additive include the following. 30 mass% or less is preferable with respect to the total mass of mixed resin, and, as for content of an additive, 10 mass% or less is more preferable.
- UV absorber ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-) 5′-methylphenyl) 5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and the like.
- Plasticizer dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc.
- Antistatic agents pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, carbowax, etc.
- Filler Glass fiber, asbestos, ballastite, calcium silicate, etc.
- the mixing method for obtaining the mixed resin of the present invention is not particularly limited, and a method of mixing the polyolefin (A), EVOH (B), and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) at once; A), EVOH (B), a part of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) are mixed in advance, and then the other components are blended and mixed; polyolefin (A), EVOH ( B), a method of blending and mixing a multilayer structure containing a part of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) with other components.
- the method of mixing with the resin composition containing C) is suitable.
- the additive blended when the recovered scrap is melt-kneaded is called a recovery aid.
- the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is used as a recovery aid.
- a recovery aid is preferably blended into the scrap in the form of pellets.
- the scrap is preferably pulverized to an appropriate size, and the pelletized recovery aid is mixed with the pulverized scrap in a preferred method for producing the mixed resin of the present invention.
- the scrap obtained from one molded article may be used, and the related scraps obtained from two or more molded articles may be mixed and used.
- a multilayer structure containing a layer composed of a resin composition containing polyolefin (A) and a layer composed of EVOH (B), an acid-modified olefin-carboxylic acid vinyl ester copolymer ( C)
- a method of mixing a recovery aid comprising a resin composition to be contained is a particularly preferred embodiment, a multilayer structure containing a layer composed of a resin composition containing polyolefin (A) and a layer composed of EVOH (B), an acid-modified olefin-carboxylic acid vinyl ester copolymer ( C)
- the scrap used as the raw material of the resin composition of the present invention may be composed of a multilayer structure containing a recovered material layer. That is, a molded product comprising a multilayer structure containing a recovered material layer obtained by melt-molding the mixed resin obtained from the recovered material is manufactured, and the scrap recovered material of the molded product is again converted into the same multilayer structure. It may be used as a raw material for the recovered material layer.
- the method of blending these components is not particularly limited.
- the above-mentioned components (A), (B), and (C) can be blended by the same operation.
- the mixed resin of the present invention contains an unmodified olefin-carboxylic acid vinyl ester copolymer (D), it should be used as a recovery aid in addition to the acid-modified olefin-carboxylic acid vinyl ester copolymer (C). Is preferred.
- the mixed resin of the present invention contains a lubricant, hydrotalcite, and antioxidant, it is preferable to use it as a recovery aid in addition to the acid-modified olefin-carboxylic acid vinyl ester copolymer (C). .
- the method similar to the above is employ
- the mixed resin of the present invention contains a lubricant, a hydrotalcite, an antioxidant and a pigment
- a lubricant such as burns and burns that occur when the mixed resin of the present invention is melt-extruded for a long time
- EVOH (B) is preliminarily used. It is preferable to contain a lubricant.
- a known mixing device such as a rocking mixer, a ribbon blender, a super mixer, a line mixer, or the like can be used.
- the obtained mixed resin can be supplied as it is to a molding machine to obtain a molded product, or it is melted and kneaded usually at 150 to 300 ° C. using an extruder in advance, and then re-pelletized. It can also be supplied to a molding machine to obtain a molded product. It is preferable to supply the mixed resin to the molding machine as it is without re-pelletizing because it is excellent in moldability and hue of the molded product, and is advantageous in terms of productivity and economy. It is also possible to mix an appropriate amount of an olefin polymer with the mixed resin and then supply it to the molding machine.
- the mixed resin of the present invention is a film, sheet using a known melt extrusion molding machine, compression molding machine, transfer molding machine, injection molding machine, blow molding machine, thermoforming machine, rotary molding machine, dip molding machine, etc. It can be formed into any molded article such as a tube, a bottle, or a cup.
- the extrusion temperature during molding is the type of polyolefin (A) constituting the mixed resin of the present invention, the melt index of polyolefin (A) and EVOH (B), the composition ratio of polyolefin (A) and EVOH (B), or the molding machine
- the temperature is appropriately selected depending on the kind of the material, but in many cases it is in the range of 170 to 350 ° C.
- a preferred embodiment of the present invention is a multilayer structure having a layer obtained by melt-molding the mixed resin, and more preferably, a layer obtained by melt-molding the mixed resin, and EVOH ( A multilayer structure comprising at least two of the layers comprising B).
- the layer structure when the mixed resin of the present invention is represented as c, polyolefin as a, EVOH as b, and adhesive resin as ad, for example, the following layer structure is represented.
- ad a modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof can be suitably used.
- the mixed resin of the present invention can be obtained from scrap of such a multilayer structure. Therefore, when the ad layer is present in the multilayer structure, the adhesive resin (ad) is contained as a constituent component in the mixed resin of the present invention.
- a number of extruders corresponding to the type of the resin layer are used, and so-called coextrusion molding is performed in which the flows of the resin melted in the extruder are co-extruded in a layered state.
- the method carried out by is preferred.
- a molding method such as extrusion coating or dry lamination may be employed.
- stretching such as uniaxial stretching, biaxial stretching or blow stretching of a multilayer structure including a layer obtained by melt-molding the mixed resin of the present invention or a mixed resin of the present invention, A molded product having excellent mechanical properties, gas barrier properties and the like can be obtained.
- the multilayer structure having the above-described layer structure contains EVOH having excellent gas barrier properties, it is useful as a packaging material for foods, pharmaceuticals, medical devices and the like that require gas barrier properties.
- the mixed resin of the present invention has a high EVOH dispersibility during melt molding, a molded product with a small amount of screw adhesion of deteriorated products and less occurrence of fish eyes, streaks, and streaks even during long-term continuous melt molding. Obtainable. Since a molded article having excellent mechanical properties and gas barrier properties and a beautiful appearance can be obtained, its industrial significance is great.
- B-1 EVOH [ethylene content 32 mol%, saponification degree 99.7%, density 1.19 g / cm 3 , melt index 1.6 g / 10 min (ASTM-D1238, 190 ° C., 2160 g load), solubility parameter 12.3 (cal / cm 3 ) 1/2 , terminal carboxylic acid and lactone ring amount 0.07 mol%]
- B-2 EVOH [ethylene content 27 mol%, saponification degree 99.8%, density 1.20 g / cm 3 , melt index 1.7 g / 10 min (ASTM-D1238, 190 ° C., 2160 g load), solubility parameter 12.6 (cal / cm 3 ) 1/2 , terminal carboxylic acid and lactone ring amount 0.06 mol%]
- B-3 EVOH [ethylene content 44 mol%, saponification degree 99.7%, density 1.14 g / cm 3 , melt index 1.7 g / 10 min (ASTM-D1238, 190 ° C., 2160
- B-4 EVOH [ethylene content 32 mol%, saponification degree 99.7%, density 1.19 g / cm 3 , melt index 1.5 g / 10 min (ASTM-D1238, 190 ° C., 2160 g load), solubility parameter 12.3 (cal / cm 3 ) 1/2 , terminal carboxylic acid and lactone ring amount 0.02 mol%]
- B-5 EVOH [ethylene content 19 mol%, saponification degree 99.8%, density 1.24 g / cm 3 , melt index 1.8 g / 10 min (ASTM-D1238, 190 ° C., 2160 g load), solubility parameter 13.07 (cal / cm 3 ) 1/2 , terminal carboxylic acid and lactone ring amount 0.09 mol%]
- B-6 EVOH [ethylene content 61 mol%, saponification degree 99.7%, density 1.07 g / cm 3 , melt index 2.9 g / 10 min (ASTM-D1238, 190 ° C., 2160
- C-1 Maleic anhydride-modified ethylene-vinyl acetate copolymer [olefin content 89 mol%, acid modification amount 0.18 mmol / g, density 0.95 g / cm 3 , melt index 16.0 g / 10 min (ASTM -D1238, 190 ° C., 2160 g load), solubility parameter 9.8 (cal / cm 3 ) 1/2 ]
- C-2 Maleic anhydride modified ethylene-vinyl acetate copolymer [olefin content 93 mol%, acid modification amount 0.18 mmol / g, density 0.94 g / cm 3 , melt index 15.7 g / 10 min (ASTM -D1238, 190 ° C., 2160 g load), solubility parameter 9.41 (cal / cm 3 ) 1/2 ]
- C-3 Maleic anhydride-modified ethylene-vinyl acetate copolymer [olefin content 89 mol%, acid modification amount
- C-4 Maleic anhydride modified ethylene-vinyl acetate copolymer [olefin content 78 mol%, acid modification amount 0.18 mmol / g, density 0.98 g / cm 3 , melt index 14.5 g / 10 min (ASTM -D1238, 190 ° C., 2160 g load)], solubility parameter 10.63 (cal / cm 3 ) 1/2 ]
- C-5 Maleic anhydride-modified ethylene-vinyl acetate copolymer [olefin content 89 mol%, acid modification amount 0.33 mmol / g, density 0.95 g / cm 3 , melt index 18.2 g / 10 min (ASTM -D1238, 190 ° C., 2160 g load)], solubility parameter 10.26 (cal / cm 3 ) 1/2 ]
- C-6 Maleic anhydride-modified ethylene-vinyl acetate copolymer [olefin content 89 mol%, acid
- C-7 Maleic anhydride modified ethylene-vinyl acetate copolymer [olefin content 96 mol%, acid modification amount 0.18 mmol / g, density 0.93 g / cm 3 , melt index 12.4 g / 10 min (ASTM -D1238, 190 ° C., 2160 g load)], solubility parameter 9.09 (cal / cm 3 ) 1/2 ]
- EVAAc ethylene-vinyl acetate copolymer [olefin content 89 mol%, density 0.96 g / cm 3 , melt index 12.4 g / 10 min (ASTM-D1238, 190 ° C., 2160 g load)], solubility parameter 8.
- Acid-modified PE maleic anhydride-modified high-density polyethylene [acid modification amount 0.18 mmol / g, density 0.95 g / cm 3 , melt index 12.3 g / 10 min (ASTM-D1238, 190 ° C., 2160 g load), solubility Parameter 7.96 (cal / cm 3 ) 1/2 ]
- D-1 “Evaflex EV260” manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene-vinyl acetate copolymer [olefin content 89 mol%, melt index 6.0 g / 10 min (ASTM-D1238, 190 ° C., 2160g load)]
- D-2 “Evaflex P1107” manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene-vinyl acetate copolymer [olefin content 97 mol%, melt index 9.0 g / 10 min (ASTM-D1238, 190 ° C., 2160g load)]
- D-3 “Evaflex EV40LX” manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene-vinyl acetate copolymer [olefin content 82 mol%, melt index 2.0 g /
- E-1 Stearic acid amide
- E-2 Ethylene bis stearic acid amide
- E-3 Calcium stearate
- Adhesive resin manufactured by Mitsubishi Chemical Corporation, “Modic AP P604V”, grade for polypropylene [density 0.90 g / cm 3 , melt index 3.2 g / 10 min (ASTM-D1238, 230 ° C., 2160 g load)]
- Pigment “EPONY L-11268MPT” manufactured by DIC Corporation, white inorganic pigment, derived from TiO 2
- the integral value (I 1 ) is derived from hydrogen of all CH 2 units contained in the ethylene unit (III), the vinyl alcohol unit (IV), and the vinyl ester unit (V).
- the integral value (I 2 ) is derived from the hydrogen of the CH 2 unit adjacent to the carboxyl group of the terminal carboxylic acid unit (I).
- the integral value (I 3 ) is derived from the hydrogen of the CH 2 unit adjacent to the carbonyl group of the terminal lactone ring unit (II).
- the integral values (I 1 ) and (I 3 ) are derived from the same hydrogen as the integral value (I 1 ) of FIG. 1, and the integral value (I 2 ) is the vinyl alcohol unit (IV).
- the integral value (I 4 ) is methine hydrogen of vinyl alcohol unit (IV) (when both sides of the unit are ethylene and ethylene-vinyl alcohol)
- the integral value (I 5 ) is derived from methine hydrogen having a 1,2-glycol structure
- the integral value (I 6 ) is a vinyl ester unit (V).
- the integral value (I 7) is derived from the hydrogens of the methyl group in -CH 2 CH 3 group present in the EVOH terminus.
- a line of 10 cm ⁇ 10 cm is drawn around the center of the single-layer film obtained by the above-mentioned streak and streak evaluations so that it is perpendicular to each of the TD and MD directions at a distance of 5 cm in each of the MD and TD directions.
- a sample of was cut out.
- the number of fish eyes was counted visually while applying a fluorescent lamp to the cut sample.
- the number of fish eyes is preferably 200 or less, and more preferably 150 or less.
- Example 1 [Manufacture of collected materials]
- the outermost layer is A-1 as the polyolefin (A)
- the innermost layer is B-1 as the EVOH (B)
- “Modic APP P604V” is used as the adhesive resin layer.
- the polyolefin layer / adhesive resin layer / EVOH layer / adhesive resin layer / polyolefin layer 200 ⁇ / 20 ⁇ / 20 ⁇ / 20 ⁇ / 200 ⁇ 3 kinds of five layers were co-extruded to prepare a multilayer film.
- Each resin is supplied to the feed block using a 32 mm ⁇ extruder for the polyolefin layer, a 25 mm ⁇ extruder for the adhesive resin layer, and a 20 mm ⁇ extruder for the EVOH layer, and the extrusion temperature is 220 ° C. for each resin.
- the part and the feed block part were also performed at 220 ° C.
- the obtained multilayer film was pulverized with a pulverizer having a diameter of 8 mm ⁇ mesh to obtain a recovered material.
- Examples 2 to 11 A mixed resin was obtained in the same manner as in Example 1 except that EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) were used in the same manner as in Example 1 except that EVOH and the copolymer described in Table 1 were used. Each evaluation was implemented using the obtained mixed resin. The results are summarized in Table 1.
- Comparative Example 1 A mixed resin was obtained in the same manner as in Example 1 except that the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) was not blended, and each evaluation was performed using the obtained mixed resin. The results are summarized in Table 1.
- Comparative Examples 2-4 A mixed resin was obtained in the same manner as in Example 1 except that EVOH (B) and the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) were each EVOH and a copolymer listed in Table 1. Each evaluation was implemented using the obtained mixed resin. The results are summarized in Table 1.
- Comparative Example 5 A mixed resin was obtained in the same manner as in Example 1 except that EVAc was used instead of C-1, and each evaluation was performed using the obtained mixed resin. The results are summarized in Table 1.
- Comparative Example 6 A mixed resin was obtained in the same manner as in Example 1 except that acid-modified PE was used instead of C-1, and each evaluation was performed using the obtained mixed resin. The results are summarized in Table 1.
- Example 1 the olefin content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) and the ethylene content of EVOH (B) and the olefin content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C)
- Example 1 in which any difference from the amount was within the scope of the claims, a molded article with little screw adhesion, little streak and streak, and little fish eye was obtained.
- Comparative Example 3 where the difference between the ethylene content of EVOH (B) and the olefin content of the acid-modified olefin-carboxylic acid vinyl ester copolymer (C) is large, and in Comparative Example 4 where the difference is small, the screw adhesion amount , Streaks, streaks, and fish eyes were insufficiently improved.
- Examples 12-15 A mixed resin was obtained in the same manner as in Example 1 except that the blending amount of C-1 was changed to the mass ratio described in Table 2, and each evaluation was performed using the obtained mixed resin. The results are summarized in Table 2.
- a master batch (MB) was obtained by melt-kneading at a extrusion temperature of 200 ° C. with a 30 mm ⁇ co-directional twin-screw extruder (manufactured by Nippon Steel Works, TEX-30N) to a mass ratio of 45 / 2.55. .
- Examples 19 and 20 A mixed resin was obtained in the same manner as in Example 18 except that the copolymers described in Table 3 were used as the unmodified olefin-carboxylic acid vinyl ester copolymer (D), and the obtained mixed resin was used. Each evaluation was performed. The results are summarized in Table 3.
- a master batch (MB) was obtained by melt-kneading at an extrusion temperature of 200 ° C. with a 30 mm ⁇ co-directional twin-screw extruder (manufactured by Nippon Steel Works, TEX-30N) so as to obtain a mass ratio of 45 / 0.2. .
- a master batch (MB) was obtained by melt-kneading at a extrusion temperature of 200 ° C. with a 30 mm ⁇ co-axial twin-screw extruder (manufactured by Nippon Steel Works, TEX-30N) so as to obtain a mass ratio of 45 / 9.5. .
- MB master batch
- Each evaluation was implemented by said method using the obtained mixed resin. The results are summarized in Table 3.
- a master batch (MB) was obtained by melt-kneading at an extrusion temperature of 200 ° C. with Nippon Steel Works, TEX-30N).
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Abstract
Description
上記各単位(I)~(V)は以下の式のとおりである。
MxAly(OH)2x+3y-2z(A)z・aH2O
(MはMg、Ca、Sr、Ba、Zn、Cd、Pb、Snの1つ以上を表わし、AはCO3またはHPO4を表わし、x、y、zは正数であり、aは0または正数であり、2x+3y-2z>0である)
で示される複塩であるハイドロタルサイト(G)を好適なものとして挙げることができる。
Mg6Al2(OH)16CO3・4H2O
Mg8Al2(OH)20CO3・5H2O
Mg5Al2(OH)14CO3・4H2O
Mg10Al2(OH)22(CO3)2・4H2O
Mg6Al2(OH)16HPO4・4H2O
Ca6Al2(OH)16CO3・4H2O
Zn6Al2(OH)16CO3・4H2O
Mg3ZnAl2(OH)12CO3・2.7H2O
Mg6Zn2Al2(OH)20CO3・1.6H2O
Mg5Zn1.7Al3.3(OH)20(CO3)1.65・4.5H2O
可塑剤:ジメチルフタレート、ジエチルフタレート、ジオクチルフタレート、ワックス、流動パラフィン、リン酸エステルなど。
充填剤:グラスファイバー、アスベスト、バラストナイト、ケイ酸カルシウムなど。
3層 c/ad/b
4層 a/c/ad/b
5層 c/ad/b/ad/c、a/ad/b/ad/c
6層 a/c/ad/b/ad/a、c/a/ad/b/ad/a、c/a/ad/b/
ad/c、a/c/ad/b/ad/c
7層 a/c/ad/b/ad/c/a
<ポリオレフィン(A)>
A-1:日本ポリプロ株式会社製、「ノバテックPP EA7A」、ポリプロピレン[密度0.90g/cm3、メルトインデックス1.4g/10分(ASTM-D1238、230℃、2160g荷重)]
B-1:EVOH[エチレン含有量32モル%、けん化度99.7%、密度1.19g/cm3、メルトインデックス1.6g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター12.3(cal/cm3)1/2、末端カルボン酸及びラクトン環量0.07モル%]
B-2:EVOH[エチレン含有量27モル%、けん化度99.8%、密度1.20g/cm3、メルトインデックス1.7g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター12.6(cal/cm3)1/2、末端カルボン酸及びラクトン環量0.06モル%]
B-3:EVOH[エチレン含有量44モル%、けん化度99.7%、密度1.14g/cm3、メルトインデックス1.7g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター11.58(cal/cm3)1/2、末端カルボン酸及びラクトン環量0.09モル%]
B-5:EVOH[エチレン含有量19モル%、けん化度99.8%、密度1.24g/cm3、メルトインデックス1.8g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター13.07(cal/cm3)1/2、末端カルボン酸及びラクトン環量0.09モル%]
B-6:EVOH[エチレン含有量61モル%、けん化度99.7%、密度1.07g/cm3、メルトインデックス2.9g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター10.5(cal/cm3)1/2、末端カルボン酸及びラクトン環量0.09モル%]
C-1:無水マレイン酸変性エチレン-酢酸ビニル共重合体[オレフィン含有量89モル%、酸変性量0.18mmol/g、密度0.95g/cm3、メルトインデックス16.0g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター9.8(cal/cm3)1/2]
C-2:無水マレイン酸変性エチレン-酢酸ビニル共重合体[オレフィン含有量93モル%、酸変性量0.18mmol/g、密度0.94g/cm3、メルトインデックス15.7g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター9.41(cal/cm3)1/2]
C-3:無水マレイン酸変性エチレン-酢酸ビニル共重合体[オレフィン含有量82モル%、酸変性量0.18mmol/g、密度0.97g/cm3、メルトインデックス15.0g/10分(ASTM-D1238、190℃、2160g荷重)]、溶解度パラメーター9.41(cal/cm3)1/2]
C-5:無水マレイン酸変性エチレン-酢酸ビニル共重合体[オレフィン含有量89モル%、酸変性量0.33mmol/g、密度0.95g/cm3、メルトインデックス18.2g/10分(ASTM-D1238、190℃、2160g荷重)]、溶解度パラメーター10.26(cal/cm3)1/2]
C-6:無水マレイン酸変性エチレン-酢酸ビニル共重合体[オレフィン含有量89モル%、酸変性量0.03mmol/g、密度0.95g/cm3、メルトインデックス14.0g/10分(ASTM-D1238、190℃、2160g荷重)]、溶解度パラメーター9.04(cal/cm3)1/2]
EVAc:エチレン-酢酸ビニル共重合体[オレフィン含有量89モル%、密度0.96g/cm3、メルトインデックス12.4g/10分(ASTM-D1238、190℃、2160g荷重)]、溶解度パラメーター8.84(cal/cm3)1/2]
酸変性PE:無水マレイン酸変性高密度ポリエチレン[酸変性量0.18mmol/g、密度0.95g/cm3、メルトインデックス12.3g/10分(ASTM-D1238、190℃、2160g荷重)、溶解度パラメーター7.96(cal/cm3)1/2]
D-1:三井・デュポンポリケミカル株式会社製、「エバフレックス EV260」、エチレン-酢酸ビニル共重合体[オレフィン含有量89モル%、メルトインデックス6.0g/10分(ASTM-D1238、190℃、2160g荷重)]
D-2:三井・デュポンポリケミカル株式会社製、「エバフレックス P1107」、エチレン-酢酸ビニル共重合体[オレフィン含有量97モル%、メルトインデックス9.0g/10分(ASTM-D1238、190℃、2160g荷重)]
D-3:三井・デュポンポリケミカル株式会社製、「エバフレックス EV40LX」、エチレン-酢酸ビニル共重合体[オレフィン含有量82モル%、メルトインデックス2.0g/10分(ASTM-D1238、190℃、2160g荷重)]
E-1:ステアリン酸アミド
E-2:エチレンビスステアリン酸アミド
E-3:ステアリン酸カルシウム
接着性樹脂:三菱化学株式会社製、「モディックAP P604V」、ポリプロピレン用銘柄[密度0.90g/cm3、メルトインデックス3.2g/10分(ASTM-D1238、230℃、2160g荷重)]
顔料:DIC株式会社製、「EPONY L-11268MPT」、白色無機顔料、TiO2由来
・測定条件
装置名:日本電子製 超伝導核磁気共鳴装置Lambda500
観測周波数:500MHz(1H)
溶媒:DMSO-d6、水/メタノール(4/6)
ポリマー濃度:4wt%
測定温度:95℃、40℃
積算回数:600回
パルス繰り返し時間:4秒
サンプル回転速度:10~12Hz
重合体末端におけるカルボン酸類単位(I)及びラクトン環単位(II)の合計の、エチレン単位(III)、ビニルアルコール単位(IV)及びビニルエステル単位(V)の合計に対する比率((I+II)/(III+IV+V)、末端カルボン酸及びラクトン環量)は、H-NMR測定(水/メタノール溶媒、80℃で測定)を用いて算出した(化学シフト値はTMSのピーク0ppmを基準とした)。図1のチャートに示すように0.7~2.0ppmのメチレン水素の積分値(I1)、2.2~2.5ppmのピークの積分値(I2)、2.5~2.65ppmのピークの積分値(I3)を用いて、下記の式1により末端カルボン酸およびラクトン環量の算出を行った。下記式にあるEtとはエチレン含有量である。
エチレン含有量はH-NMR測定(DMSO溶媒、40℃と95℃で測定)を用いて算出した(化学シフト値は溶媒のピーク2.5ppmを基準とした)。図2,3のチャートに示すように0.7~1.8ppmのメチレン水素の積分値(I1),(I3)を基準として、それぞれの積分値をもとめた。図2,3の積分値(I1),(I2),(I3),(I4),(I5),(I6)を用いて、下記の式2によりエチレン含有量の算出を行った。
JIS規格K2501に基づいて、酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)並びに下記の実施例及び比較例で得られた混合樹脂に配合される各成分の酸価を測定し、酸価から酸変性量(mmol/g)を算出した。混合樹脂の酸変性量は各成分の酸変性量を合計することにより算出した。
下記の実施例及び比較例で得られた混合樹脂を凍結粉砕により粉砕した。得られた粉末0.15gに65質量%硫酸3mL、97質量%硫酸3mLを加え、湿式分解装置(アクタック製スピードウェーブ(MWS-2)にて樹脂を分解した。得られた分解液を0.45μmのフィルターに通した後、イオン交換水で100倍にメスアップした後、株式会社パーキンエルマージャパン社製ICP発光分光分析装置「Optima 4300 DV」を用いて、各観測波長(Na:589.592nm、K:766.490nm)で定量分析することで、アルカリ金属イオンの量を定量した。
押出機を用いて、下記の実施例及び比較例で得られた混合樹脂を20kg溶融混練した後、得られたペレットを再度溶融混練する操作を繰り返し、計5回溶融混練した。それから、2kgの低密度ポリエチレンを溶融混練した後、さらに2kgの高密度ポリエチレンを高密度ポリエチレンが押出機からでなくなるまで溶融混練した。次にスクリューを取り外してスクリュー付着物を採取し、秤量した。スクリュー付着量は3000mg以下であることが好ましく、2000mg以下であることがより好ましい。使用した押出機と溶融混練条件を以下に示す。
押出機:株式会社東洋精機製作所製2軸押出機「ラボプラストミル」
スクリュー径:25mmφ
スクリュー回転数:100rpm
フィーダー回転数:100rpm
シリンダー、ダイ温度設定:C1/C2/C3/C4/C5/D=180℃/210℃/230℃/230℃/230℃/230℃
上記スクリュー付着量の評価において、5回溶融混練して得られたペレットを用いて、300mm幅のフレキシブルダイを取り付けた20mmφの一軸押出機(株式会社東洋精機製作所製、ラボプラストミル)を用いて230℃の押出温度、80℃の冷却温度にて厚さ60μの単層フィルムを作成した。
得られた単層フィルムを目視で以下の4段階に評価した。
A:スジ、厚みムラが殆どない。
B:スジ、厚みムラがところどころで発見できる。
C:スジ、厚みムラが多く見られる。
D:穴が空いている。
上記スジ、ストリークの評価で得られた単層フィルムの中央を中心としてMD、TD方向それぞれ5cmずつ離れた箇所にTD、MD方向それぞれに垂直になるように線を枠取り、10cm×10cmの正方形のサンプルを切り出した。続いて、切り出したサンプルに蛍光灯を当てながら目視でフィッシュアイの個数をカウントした。フィッシュアイの個数は200個以下であることが好ましく、150個以下であることがより好ましい。
[回収物の製造]
最外層にポリオレフィン(A)としてA-1、最内層にEVOH(B)としてB-1、接着性樹脂層に「モディックAP P604V」を用い、フィードブロックダイにてポリオレフィン層/接着性樹脂層/EVOH層/接着性樹脂層/ポリオレフィン層=200μ/20μ/20μ/20μ/200μの3種5層共押出を行い、多層フィルムを作成した。フィードブロックへのそれぞれの樹脂の供給は、ポリオレフィン層は32mmφ押出機、接着性樹脂層は25mmφ押出機、EVOH層は20mmφ押出機をそれぞれ使用し、また押出の温度は各樹脂とも220℃、ダイス部、フィードブロック部も220℃で行った。
EVOH(B)及び酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)としてそれぞれ表1に記載されたEVOH及び共重合体を用いた以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表1に纏めて記載する。
酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)を配合しなかった以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表1に纏めて記載する。
EVOH(B)及び酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)としてそれぞれ表1に記載されたEVOH及び共重合体を用いた以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表1に纏めて記載する。
C-1の代わりにEVAcを用いた以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表1に纏めて記載する。
C-1の代わりに酸変性PEを用いた以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表1に纏めて記載する。
C-1の配合量をそれぞれ表2に記載された質量比に変更した以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表2に纏めて記載する。
多層フィルムの各層厚みを、ポリオレフィン層/接着性樹脂層/EVOH層/接着性樹脂層/ポリオレフィン層=200μ/20μ/4μ/20μ/200μに変更し、C-1の配合量を回収物/C-1/顔料=100/0.02/0.3の質量比になるようにドライブレンドした以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表2に纏めて記載する。
多層フィルムの各層厚みを、ポリオレフィン層/接着性樹脂層/EVOH層/接着性樹脂層/ポリオレフィン層=200μ/20μ/150μ/20μ/200μに変更した以外は実施例1と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表2に纏めて記載する。
酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)としてC-1を、未変性オレフィン-カルボン酸ビニルエステル共重合体(D)としてD-1を、C-1/D-1=0.45/2.55の質量比になるように30mmφの同方向二軸押出機(日本製鋼所製、TEX-30N)にて200℃の押出温度で溶融混練してマスターバッチ(MB)を得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/3/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
未変性オレフィン-カルボン酸ビニルエステル共重合体(D)としてそれぞれ表3に記載された共重合体を用いた以外は実施例18と同様にして混合樹脂を得、得られた混合樹脂を用いて各評価を実施した。結果を表3に纏めて記載する。
酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)としてC-1を、未変性オレフィン-カルボン酸ビニルエステル共重合体(D)としてD-1を、C-1/D-1=0.45/0.2の質量比になるように30mmφの同方向二軸押出機(日本製鋼所製、TEX-30N)にて200℃の押出温度で溶融混練してマスターバッチ(MB)を得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/0.64/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)としてC-1を、未変性オレフィン-カルボン酸ビニルエステル共重合体(D)としてD-1を、C-1/D-1=0.45/9.5の質量比になるように30mmφの同方向二軸押出機(日本製鋼所製、TEX-30N)にて200℃の押出温度で溶融混練してマスターバッチ(MB)を得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/9.55/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)としてC-1を、未変性オレフィン-カルボン酸ビニルエステル共重合体(D)としてD-1を、滑材(E)としてE-1を、C-1/D-1/E-1=0.45/2.55/0.005の質量比になるように30mmφの同方向二軸押出機(日本製鋼所製、TEX-30N)にて200℃の押出温度で溶融混練してマスターバッチ(MB)を得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/3.005/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
C-1/D-1/E-1=0.45/2.55/0.03の質量比になるようにした以外は実施例23と同様にしてMBを得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/3.03/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
C-1/D-1/E-1=0.45/2.55/0.3の質量比になるようにした以外は実施例23と同様にしてMBを得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/3.3/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
滑材(E)としてE-2を用い、C-1/D-1/E-2=0.45/2.55/0.03の質量比になるようにした以外は実施例23と同様にしてMBを得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/3.03/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
滑材(E)としてE-3を用い、C-1/D-1/E-3=0.45/2.55/0.15の質量比になるようにした以外は実施例23と同様にしてMBを得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/3.15/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)としてC-1、未変性オレフィン-カルボン酸ビニルエステル共重合体(D)としてD-1、滑材(E)としてE-1及びハイドロタルサイトを、C-1/D-1/E-1/ハイドロタルサイト=0.45/2.55/0.03/0.15の質量比になるように30mmφの同方向二軸押出機(日本製鋼所製、TEX-30N)にて200℃の押出温度で溶融混練してマスターバッチ(MB)を得た。
実施例1と同様にして得られた回収物を用いて、回収物/MB/顔料=100/3.18/0.3の質量比になるようにドライブレンドし、混合樹脂を得た。得られた混合樹脂を用いて上記の方法で各評価を実施した。結果を表3に纏めて記載する。
Claims (13)
- ポリオレフィン(A)、エチレン-酢酸ビニル共重合体けん化物(B)、酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)を含有し、前記酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)のオレフィン含有量が50~95モル%であり、前記エチレン-酢酸ビニル共重合体けん化物(B)のエチレン含有量と前記酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)のオレフィン含有量との差が20~70モル%の範囲である混合樹脂。
- 前記酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)の酸変性量が0.01~2mmol/gである請求項1に記載の混合樹脂。
- 前記エチレン-酢酸ビニル共重合体けん化物(B)のエチレン含有量が20~60モル%であり、けん化度が80%以上である請求項1または2のいずれか1項に記載の混合樹脂。
- 前記エチレン-酢酸ビニル共重合体けん化物(B)の重合体末端におけるカルボン酸類単位(I)及びラクトン環単位(II)の合計の、エチレン単位(III)、ビニルアルコール単位(IV)及びビニルエステル単位(V)の合計に対する比率((I+II)/(III+IV+V))が0.03モル%以上である請求項1~3のいずれか1項に記載の混合樹脂。
- 前記酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)の含有量が前記エチレン-酢酸ビニル共重合体けん化物(B)の質量に対して0.1~30質量%である請求項1~4のいずれか1項に記載の混合樹脂。
- 前記エチレン-酢酸ビニル共重合体けん化物(B)の含有量が混合樹脂の総質量に対して0.1~30質量%である請求項1~5のいずれか1項に記載の混合樹脂。
- 前記酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)の溶解度パラメーターと前記エチレン-酢酸ビニル共重合体けん化物(B)の溶解度パラメーターとの差が0.5~4.0(cal/cm3)1/2の範囲である請求項1~6のいずれか1項に記載の混合樹脂。
- さらに、アルカリ金属を含有し、前記アルカリ金属含有量と混合樹脂の酸変性量とのモル比が0.05~75の範囲である請求項1~7のいずれか1項に記載の混合樹脂。
- さらに、未変性オレフィン-カルボン酸ビニルエステル共重合体(D)を含有し、前記未変性オレフィン-カルボン酸ビニルエステル共重合体(D)のオレフィン含有量が50~98モル%であり、前記未変性オレフィン-カルボン酸ビニルエステル共重合体(D)の含有量が混合樹脂の総質量に対し0.01~20質量%である請求項1~8のいずれか1項に記載の混合樹脂。
- さらに、滑剤(E)を含有し、前記滑剤(E)の含有量が混合樹脂の総質量に対し0.005~1.0質量%である請求項1~9のいずれか1項に記載の混合樹脂。
- さらに、顔料を含有し、前記顔料の含有量が混合樹脂の総質量に対し0.0001~10質量%である請求項1~10のいずれか1項に記載の混合樹脂。
- 請求項1~11のいずれか1項に記載の混合樹脂を溶融成形して得られた層を有する多層構造体。
- ポリオレフィン(A)を含有する樹脂組成物からなる層及びエチレン-酢酸ビニル共重合体けん化物(B)からなる層を有する多層構造体の回収物と、酸変性オレフィン-カルボン酸ビニルエステル共重合体(C)を含有する樹脂組成物からなる回収助剤とを混合する工程を含む、請求項1~11のいずれか1項に記載の混合樹脂の製造方法。
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