WO2001096464A1 - Composition de resine constituee d'un copolymere ethylene/alcool vinylique - Google Patents

Composition de resine constituee d'un copolymere ethylene/alcool vinylique Download PDF

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Publication number
WO2001096464A1
WO2001096464A1 PCT/JP2001/004870 JP0104870W WO0196464A1 WO 2001096464 A1 WO2001096464 A1 WO 2001096464A1 JP 0104870 W JP0104870 W JP 0104870W WO 0196464 A1 WO0196464 A1 WO 0196464A1
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Prior art keywords
mfr
resin composition
content
acid
carboxylic acid
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PCT/JP2001/004870
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English (en)
Japanese (ja)
Inventor
Hiroyuki Shindome
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Kuraray Co. Ltd.
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Publication date
Application filed by Kuraray Co. Ltd. filed Critical Kuraray Co. Ltd.
Priority to AU2001264229A priority Critical patent/AU2001264229A1/en
Priority to JP2002510593A priority patent/JP5093959B2/ja
Publication of WO2001096464A1 publication Critical patent/WO2001096464A1/fr

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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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material

Definitions

  • the present invention has excellent color appearance, low unevenness of film surface, excellent appearance, long run and low odor even at the time of melt molding at a high temperature, such as during co-extrusion molding or co-injection molding with a resin having a high melting point.
  • TECHNICAL FIELD The present invention relates to an ethylene-vinyl alcohol copolymer resin composition excellent in water resistance and a multilayer structure using the same. Background art
  • Ethylene-Biel alcohol copolymer (hereinafter sometimes abbreviated as EVOH) is a useful polymer material with excellent oxygen-shielding properties, oil resistance, antistatic properties, mechanical strength, etc., and various types of films, sheets, containers, etc. Widely used as packaging material.
  • Such packaging materials are usually produced by melt molding, and have a long run property during melt molding (a molded article free of fish eyes is obtained even over a long period of time), and the appearance of the molded article ( (A molded product with little coloring and no generation of fish eyes) is required.
  • the discharge speed is at least up to 10 hours.
  • E styrene content of 20 to 80 mole 0/0, a saponification degree of 95 mol% or more E styrene monoacetate Bulle copolymer saponified composition acetate Bulle component is disclosed (JP-a-2 — 23 5952; USP 5194474).
  • EVOH is often used by being laminated with another thermoplastic resin, and there are many embodiments in which EVOH is laminated with polyolefin through an adhesive resin made of modified polyolefin.
  • both the polyolefin and the adhesive resin laminated with EVOH usually have a lower melting point than EVOH, and can be molded at the most desirable molding temperature for molding EVOH. Even when the EVOH resin compositions described in (1) and (2) were used, there were not many problems during molding.
  • polyamide, polyester, etc. are higher than EVOH!
  • a multi-layer structure is molded by co-injection molding with a resin having a melting point.
  • molding is performed at a high molding temperature suitable for molding polyamide or polyester.
  • EVOH tends to deteriorate due to heating.
  • the moldability may be insufficient because the polyamide or polyester is not sufficiently melted. Therefore, even when molding at a high molding temperature suitable for molding polyamide or polyester, there is a need for the development of EVOH with low thermal degradation.
  • the techniques disclosed in the above (1) and (2) do not dissolve at high temperatures. There is no description about melt molding, and the EVOH compositions described in (1) and (2) cannot provide sufficient performance at the time of melt molding at high temperatures. Specifically, the EVOH composition described in the prior art (1) has unsatisfactory coloring resistance and long-run property at the time of molding at a high temperature.
  • the prior art (2) aims to reduce the generation of odor components, but the effect of improving odor is not always satisfactory.
  • the composition described in the prior art (2) is not suitable for melt-molding at high temperatures. Things left room for improvement.
  • the problem described above is that the content of carboxylic acid (A) is 0.05 to 2.5 ⁇ / g and the content of alkaline earth metal salt (B) is 10 ppm or less (metal).
  • the problem is solved by providing an ethylene-butyl alcohol copolymer resin composition that is an element-converted value and satisfies the following formula (1).
  • a carboxylic acid having a molecular weight of 75 or more (a 1) is used.
  • a salt thereof is used.
  • the content of the phosphoric acid compound (C) in the resin composition of the present invention is 8 Oppm or less (in terms of phosphate radical).
  • the resin composition of the present invention contains the boron compound (E) in an amount of 50 to 2000 ppm in terms of elemental boron.
  • the MFR (MFR (6 min.); 270 ° C, 2160 g load) when the resin composition is maintained at 270 ° C for 6 minutes in a melt indexer; MFR when held at 270 ° C for 10 minutes, 20 minutes, and 30 minutes (MFR (10 min.), MFR (20 min.) ⁇ MFR (30 min.); Deviation is 270 ° (:, 2160 g load) satisfies all of the following equations (2) to (4).
  • the present invention relates to a multilayer structure obtained by laminating a thermoplastic resin on at least one surface of a layer made of the resin composition.
  • a thermoplastic resin is a polyamide or a polyester.
  • the above-mentioned multilayer structure is formed by co-extrusion or co-injection molding.
  • the present invention also relates to a method for producing a multilayer structure in which a die temperature or a nozzle temperature during melt molding is 250 ° C. or higher.
  • the content of the carboxylic acid (A) is 0.05 to 2.5 ⁇ ⁇ / g, and the content of the alkaline earth metal salt (B) is 10 ppm or less
  • An ethylene-butyl alcohol copolymer (EVOH) resin composition which is a metal element conversion value and satisfies the following formula (1).
  • the EVOH used in the present invention those obtained by saponifying an ethylene-bi-ester copolymer are preferable, and those obtained by saponifying an ethylene-bi-butyl acetate copolymer are particularly preferable.
  • the ethylene content Ri preferably 2 0-6 5 mol% der, more preferably 2 5-5 5 mol 0/0 , and the ones optimally 2 5-5 0 mole 0/0 are preferred.
  • the saponification degree of the butyl acetate component is preferably at least 80%, and from the viewpoint of obtaining a molded article having excellent gas barrier properties, is more preferably at least 95%, further preferably at least 98%. Particularly preferably, it is 99%.
  • the ethylene content exceeds 65 mol%, there is a possibility that the barrier property, printability and the like may be insufficient.
  • the saponification degree is less than 80%, noriability, thermal stability and moisture resistance may be deteriorated. '
  • EVOH may contain Bierushiran compound 0. 0 0 0 2 to 0.2 moles 0/0 as a copolymer component.
  • examples of the butylsilane-based compound include vinyltrimethoxysilane, butyltriethoxysilane, vinyltri (] 3-methoxy-1-ethoxy) silane, and ⁇ -methacryloxypropylmethoxysilane. Among them, biertrimethoxysilane and burtriethoxysilane are preferably used.
  • the polymerization of ethylene and butyl acetate is not limited to solution polymerization, but may be any of solution polymerization, suspension polymerization, chemical polymerization, and Balta polymerization, and may be any of continuous type and batch type.
  • the polymerization conditions for batch solution polymerization are as follows.
  • Alcohols are preferred, but other organic solvents (such as dimethyl sulfoxide) that can dissolve ethylene, biel acetate, and ethylene-butyl acetate copolymer Can be used.
  • organic solvents such as dimethyl sulfoxide
  • methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol, t-butyl alcohol and the like can be used, and methyl alcohol is particularly preferable.
  • Cumyl peroxy cineeodecanoate disopropyl peroxy carbonate, di-n-propyl peroxy dicarbonate, t-butyl peroxy neo decanoate, lauper peroxide, benzoyl peroxide, t- An organic peroxide initiator such as butynole hydroperoxide can be used.
  • Time 2 to: 15 hours, preferably 3 to: 11 hours.
  • Polymerization rate 10 to 90%, preferably 30 to 80% based on the charged vinyl ester.
  • Resin content in the solution after polymerization 5 to 85%, preferably 20 to 70%.
  • Ethylene content of the copolymer preferably 2 0-6 5 mol 0/0, further preferably 2 5-6 0 mole percent, and optimally 2 5-5 0 mol 0/0.
  • ⁇ -olefins such as pyrene pyrene, isobutylene, ⁇ -otaten, and a-dodecene
  • nitriles such as atarilonitrile and methacrylonitrile
  • amides such as acrylyl amide and methacrylamide
  • ethylene Olefin sulfonic acids such as sulfonic acid, arylsulfonic acid, and metharylsulfonic acid or salts thereof
  • alkyl vinyl ethers, vinyl ketone, ⁇ -butylpyrrolidone, butyl chloride, chloridylidene, and the like coexist in small amounts. It is also possible
  • the copolymer solution is continuously supplied at a constant rate from the upper part of a tower filled with Raschig rings.
  • An organic solvent vapor such as methanol is blown from the bottom of the tower, and a mixed vapor of an organic solvent such as methanol and unreacted vinyl acetate is distilled out from the section of the tower, and the copolymer solution from which unreacted vinyl acetate is removed is removed from the bottom of the tower.
  • a method is adopted.
  • the saponification method can be either continuous or batch.
  • the alkali catalyst include sodium hydroxide, hydroxylated lime, and alkali metal alkoxide.
  • the saponification conditions for the batch system are as follows.
  • Amount of catalyst used 0.02 to 0.6 equivalents (per butyl acetate component).
  • the degree of saponification after the saponification reaction varies depending on the purpose, it is preferably at least 80%, more preferably at least 95%, still more preferably at least 98%, particularly preferably at least 99% of the butyl acetate component. is there.
  • the saponification degree can be arbitrarily adjusted depending on the conditions.
  • the ethylene-butyl alcohol copolymer after the reaction contains an alkali catalyst, by-product salts, and other impurities, it is preferable to remove these by neutralizing and washing as necessary.
  • Examples of the carboxylic acid (A) used in the resin composition of the present invention include: saturated aliphatic carboxylic acids such as acetic acid and propionic acid; unsaturated aliphatic carboxylic acids such as oleic acid; Examples thereof include hydroxycarboxylic acids such as glycolic acid and lactic acid, and aromatic carboxylic acids such as benzoic acid.
  • Their pKa at 25 ° C. is preferably 3.5 or more. If the pKa at 25 ° C is less than 3.5, it may be difficult to control the pH of the resin composition composed of EVOH, and the color resistance and interlayer adhesion may be unsatisfactory. .
  • the upper limit of the pKa of the carboxylic acid (A) at 25 ° C. is preferably 5 or less, more preferably 4.5 or less, and still more preferably 4 or less.
  • Examples of the carboxylic acid having a molecular weight of 75 or more (a1) used in the present invention include succinic acid, adipic acid, benzoic acid, acetic acid, lauric acid, glycolic acid, lactic acid and the like, and include succinic acid, adipic acid and the like.
  • the dicarboxylic acid of the above is used, gel-bubbles may easily occur during molding.
  • the use of hydroxycarboxylic acids such as dalicholic acid and lactic acid does not cause the above-mentioned problems and is preferable from the viewpoint of excellent water solubility. Among them, lactic acid is particularly preferable.
  • carboxylic acid (al) having a molecular weight of 75 or more used in the present invention a carboxylic acid having a molecular weight of 80 or more is more preferable, a molecular weight of 85 or more is more preferable, and a molecular weight of 90 or more is particularly preferable. It is.
  • a strong carboxylic acid having a high molecular weight volatile components can be effectively reduced. Specifically, it exhibits excellent low odor and long run properties even at high temperatures such as co-extrusion molding or co-injection molding with a high melting point thermoplastic resin such as polyamide or polyester. be able to.
  • lactic acid when lactic acid is used as the carboxylic acid (al) having a molecular weight of 75 or more, it is preferable because it has excellent water solubility as described above and has extremely low volatility as compared with acetic acid.
  • a pellet made of EVOH resin yarn When a pellet made of EVOH resin yarn is produced, it is usually necessary to dry the water-containing pellet, and lactic acid must be used in the drying step. As a result, the volatilization of the acid component is greatly suppressed, and a more stable quality product can be produced.
  • acetic acid pKa at 4.75 ° C
  • the content of the carboxylic acid (A) in the resin composition of the present invention is 0.05 to 2.5 ⁇ / g.
  • the content of the carboxylic acid (A) is less than 0.05 ⁇ / g, the coloring at the time of melting is remarkable, particularly at the time of molding at a high temperature. Also, 2.5 Even when the temperature exceeds the above range, coloring of the resin becomes remarkable during molding at a high temperature.
  • the content of the carboxylic acid (A) is more than 2.5 zmol / g, the tangling property at the time of molding at a high temperature is significantly reduced, and the effect of improving the low odor property and the coloring resistance, and The effect of improving the adhesive force with the adhesive resin in the coextrusion molding becomes insufficient, and a sufficient long-run property cannot be obtained.
  • the lower limit of the content of the carboxylic acid (A) is preferably at least 0.1 AtmolZg, and more preferably at least 0.2 fflolZg. Further, the upper limit of the content of the carboxylic acid (A) is more preferably 2 ⁇ / g or less, still more preferably 1. S ⁇ umol / g or less, and most preferably 1.0 ⁇ umol / g or less. g or less.
  • a carboxylic acid such as acetic acid
  • a salt thereof having a molecular weight of less than 75 it is preferable that the content of the carboxylic acid having a molecular weight of less than 75 is small.
  • the resin composition of the present invention satisfies the following formula (1).
  • the resin composition of the present invention has an alkaline earth metal salt (B) content of 10 ppm or less (in terms of metal element).
  • the content of the alkaline earth metal salt (B) is more preferably 5 ppm or less (in terms of a metal element), and particularly preferably substantially no content.
  • Such an alkaline earth metal salt (B) is not particularly limited, and examples thereof include a magnesium salt, a calcium salt, a barium salt, a beryllium salt and the like.
  • the anion species of the alkaline earth metal salt (B) is not particularly limited, and examples thereof include aion acetate, aion lactate, and anion phosphate.
  • the content of alkaline earth metal salt (B) is 10 ppm (metal element conversion). Values) tend to improve the long-run property during melt molding.
  • the melting point of polyamide or polyester is high! /
  • the Al-Li earth metal salt (B) If the content exceeds l Op p pm (converted to metal element), the formability will be unsatisfactory. Specifically, the state of the film surface between the EVOH and other thermoplastic resin to be laminated becomes extremely poor, and the EVOH layer is markedly colored, and the long run property is also observed. It becomes bad.
  • the content of the carboxylic acid (A) is 0.05 to 2.5 ⁇ mol / g
  • the content of the alkaline earth metal salt (B) is 10 ppm or less (in terms of metal element).
  • the present inventors have found for the first time that the use of an ethylene-vinyl alcohol copolymer resin composition that satisfies the following formula (1) significantly improves moldability at high temperatures. From this viewpoint, the present invention is significant.
  • the content of the phosphoric acid compound (C) is 80 ppm or less (in terms of phosphate radical).
  • the phosphate compound (C) include, but are not limited to, various acids such as phosphoric acid and phosphorous acid, and salts thereof. May be contained in any form of a first phosphate, a second phosphate, and a third phosphate, and the cation species is not particularly limited.
  • sodium dihydrogen phosphate examples include potassium dihydrogen phosphate, disodium hydrogen phosphate, and dihydrogen phosphate.
  • Example 3 of the above-mentioned prior art (2) discloses an EVOH composition containing acetic acid, sodium acetate and potassium dihydrogen phosphate and having a calcium content of 5 ppm.
  • a composition in which the carboxylic acid is composed of only acetic acid and (al) Z (A) is less than 0.7 provides a sufficiently low odor.
  • Example 3 of this specification containing lactic acid, sodium lactate and dihydrogen phosphate phosphate, and having a content of alkaline earth metal salt of less than 10 ppm in terms of metal element. Although the low odor property was greatly improved, there was room for improvement in the long-run property during melt molding at high temperatures.
  • the content of carboxylic acid (A) was 0.05 to 2.5 ⁇ / g, and the content of alkaline earth metal salt (B) was 10 ppm or less.
  • the content of the phosphoric acid compound (C) was 8 Opm or less, it has been clarified that the long-run property at the time of melt molding at a high temperature is further improved, and the effect of the present invention can be more remarkably exhibited.
  • the content of the carboxylic acid (A) is 0.05 to 2.5 molZg
  • the content of the alkaline earth metal salt (B) is 10 ppm or less (in terms of metal element)
  • ( al) / In the case of the EVOH resin composition of the present invention in which (A) is 0.7 or more and 1.0 or less, there is a tendency that the long-run property is adversely reduced by the addition of the phosphoric acid compound (C). Was first discovered by the present inventors.
  • the upper limit of the phosphate compound (C) is preferably 80 ppm or less.
  • Such an EVOH resin composition has excellent coloring, low unevenness on the film surface, excellent appearance and excellent odor and low odor even at the time of melt molding at a high temperature. Benefits can be obtained.
  • the upper limit of the phosphoric compound (C) is more preferably 60 ppm or less, still more preferably 40 ppm or less, particularly preferably 20 ppm or less, and it is not substantially contained! /, That is optimal.
  • the resin composition of the present invention preferably contains an alkali metal salt (D) from the viewpoint of improving adhesiveness.
  • An example of a preferred embodiment using the EVOH resin composition of the present invention is, for example, laminating polyamide or polyester on one surface of an EVOH resin composition layer, and laminating with polyolefin or the like via an adhesive resin on the other surface. And a laminated multilayer structure. In such embodiments, it is particularly preferred that the EVOH resin composition exhibit good adhesion.
  • the upper limit of the content of the alkali metal salt (D) is preferably 500 ppm or less, It is more preferably less than 500 ppm, even more preferably 400 ppm or less, particularly preferably 300 ppm or less.
  • the lower limit of the content of the alkali metal salt (D) is preferably at least 10 ppm, more preferably at least 3 ppm, even more preferably at least 50 ppm. It is particularly preferred that it is p or more.
  • by blending the alkali metal salt (D) it is possible to improve the adhesive strength between the resin composition of the present invention and the adhesive resin.
  • the alkali metal salt (D) is not particularly limited, but preferred examples thereof include a sodium salt and a potassium salt.
  • the aeon species of the alkali metal salt (D) is not particularly limited, but preferred examples include anion acetate, aion lactate, and anion phosphate, with aion lactate being particularly preferred.
  • the resin composition of the present invention contains the boron compound (E) in an amount of 50 to 2000 ppm in terms of a boron element.
  • the boron compound (E) include, but are not limited to, boric acids, borate esters, borates, and borohydrides.
  • the boric acids include orthoboric acid, metaboric acid, tetraboric acid, and the like.
  • the borate esters include triethyl borate, trimethyl borate, and the like.
  • orthoboric acid hereinafter sometimes simply referred to as boric acid is preferable.
  • the lower limit of the content of the boron compound (E) is preferably at least 50 ppm, more preferably at least 100 ppm, and even more preferably at least 15 ppm in terms of boron element.
  • the upper limit of the content of the boron compound (E) is preferably 1500 ppm or less in terms of a boron element, and more preferably 1 OOOppm or less. If the content of the boron compound (E) is less than 50 ppm, the generation of gel and pop may increase as the molding time becomes longer. May worsen. On the other hand, if the content of the boron compound (E) exceeds 2000 ppm, there is a possibility that Görich will be chewy and the moldability will be poor.
  • Suitable melt flow rate (MFR) of the resin composition comprising EVOH of the present invention (measured at 190 ° C under a load of 2160 g; if the melting point is around 190 ° C or exceeds 190 ° C, the load is 2160 g
  • MFR melt flow rate
  • the lower limit of the MFR is more preferably not less than 0.2 g / l 0 min., More preferably not less than 0.5 gZl 0 min., And most preferably not less than l gZl Omin. It is.
  • the upper limit of the MFR is more preferably 50 g / 1 Omin. Or less, still more preferably 10 g / 1 Omin. Or less, and most preferably 7 g / 10 min. Or less. If the melt flow rate is smaller than the above range, the inside of the extruder will be in a high torque state at the time of molding and extrusion processing will be difficult, and if it is larger than this range, the mechanical strength of the molded product will be insufficient. Not preferred.
  • the resin composition of the present invention may be blended with an ethylene-vinyl alcohol copolymer having a different degree of polymerization, an ethylene content, and a different degree of saponification within a range that does not impair the object of the present invention, and melt-molded.
  • an ethylene-vinyl alcohol copolymer having a different degree of polymerization, an ethylene content, and a different degree of saponification within a range that does not impair the object of the present invention, and melt-molded.
  • other various plasticizers, stabilizers, surfactants, coloring agents, ultraviolet absorbers, slip agents, antistatic agents, drying agents, and crosslinking agents may be added to the resin composition as long as the object of the present invention is not impaired. It is also possible to add appropriate amounts of metal salts, fillers, reinforcing agents for various fibers, and the like.
  • thermoplastic resins include various polyolefins (polyethylene, polypropylene, poly 1-butene, poly 4-methylenol 1-pentene, ethylene-propylene copolymer, copolymer of ethylene and ct-olefin with 4 or more carbon atoms, polyolefin and anhydrous Copolymers with maleic acid, ethylene-polyester copolymers, ethylene-acrylate copolymers, or modified polyolefins obtained by graft-modifying these with unsaturated carboxylic acids or derivatives thereof, and various nylons (nylon 6, Nylon-6,6, Nylon-6 / 6,6 copolymer), Polychlorinated vinyl, Polyvinylidene chloride, Polyester, Polystyrene, Polyacrylonitrile, Polyurethane, Polyacetal-modified polyvinyl alcohol resin Is used.
  • polyolefins polyethylene, polypropylene, poly 1-butene, poly 4-methylenol 1-pentene,
  • an ethylene-butyl alcohol copolymer contains a carboxylic acid (A) and, if necessary, an alkali metal salt (D) and a boron compound (E).
  • the law is not particularly limited. For example, there are a method of immersing the EVOH in a solution in which the compound is dissolved, a method of melting the EVOH and mixing the compound, a method of dissolving the EVOH in an appropriate solvent and mixing the compound, and the like. .
  • a method of immersing EVOH in a solution of the above compound is desirable.
  • This processing can be performed by either the patch method or the continuous method.
  • the shape of the EVOH may be any shape such as powder, granule, sphere, and columnar pellet.
  • the ethylene-vinyl alcohol copolymer When the ethylene-vinyl alcohol copolymer is immersed in a solution containing the carboxylic acid (A) and, if necessary, the alkali metal salt (D) and the boron compound (E), the carboxylic acid (A) in the above solution,
  • the respective concentrations of the alkali metal salt (D) and the boron compound (E) added as necessary are not particularly limited.
  • the solvent of the solution is not particularly limited, but is preferably an aqueous solution for reasons of handling.
  • the suitable range of the immersion time varies depending on the form of the ethylene-butyl alcohol copolymer, but is preferably 1 hour or more, and more preferably 2 hours or more in the case of a pellet of about 1 to 10 mm.
  • the immersion treatment of the above-mentioned various compounds in a solution may be carried out by dividing into a plurality of solutions and immersion at once. Above all, it is preferable from the viewpoint of simplification of the process that the treatment is carried out with a solution containing the carboxylic acid (A), and further the alkali metal salt (D) and the boron compound (E) which are added as necessary.
  • the treatment is performed by immersion in the solution as described above, the final drying is performed to obtain the desired ethylene-butyl alcohol copolymer composition.
  • the MFR (MFR (10 min .;), MFR (20 min.), MFR (30 min.), Respectively; 270. C, 2160 g load) when held for 30 minutes is calculated by the following formulas (2) to (4 It is preferable that all of the above conditions are satisfied from the viewpoint of moldability of the resin composition. 0.5 ⁇ MFR (lOmin.) MFR (6min.) ⁇ 1.5 (2)
  • the lower limit is more preferably 0.6 or more, and even more preferably 0.8 or more.
  • the upper limits of MF R (lOmin.), MF R (6 min.), MFR (20 min.), Z MF R (6 min.) And MF R (30 min.) Z MFR (6 min.) Are more preferably 1. 4 or less, more preferably 1.2 or less.
  • the resin composition of the present invention is a resin composition which has not been subjected to a heat treatment.
  • FR (0) and the resin composition heated at 220 ° C in a nitrogen atmosphere, the resin I and the MF of the resin I, 50 hours after 8 hours, 16 hours, and 24 hours from the start of heating R (respectively, MFR (8hr), MFR (16hr), MFR (24hr), MFR (50hr); all at 230 ° C, 10.9 kg load) is the total of the following formulas (5) to (8) It is preferable to satisfy
  • the resin composition of the present invention is preferably subjected to co-extrusion molding or co-injection molding with a resin having a high melting point such as polyamide or polyester, and the die temperature or the nozzle temperature during molding is preferably 250 °. C or more.
  • the change in the melting behavior of the resin composition over a long period of time at a heating temperature of 220 ° C. satisfies all of the above formulas (5) to (8). It is preferred that It is not clear why the melting behavior of the resin composition at a heating temperature of 220 ° C affects the moldability at high temperatures, but it satisfies all of the above equations (5) to (8) and increases slowly. Due to the tendency to stick, it is possible to effectively suppress the generation of gel / bubbles in the EVOH resin composition layer at the time of molding at a high temperature, and to improve the coloring resistance.
  • the obtained resin composition of the present invention is formed into various molded articles such as films, sheets, containers, pipes, and fibers by melt molding. These molded products can be pulverized for re-use and molded again. It is also possible to uniaxially or biaxially stretch films, sheets, fibers and the like.
  • melt molding method extrusion molding, inflation extrusion, blow molding, melt spinning, injection molding and the like are possible.
  • the melting temperature varies depending on the melting point of the copolymer and the like, but is preferably about 150 to 270 ° C.
  • the resin composition of the present invention is, as described above, a multilayer structure having at least one layer of a molded product such as a composition film or sheet of the present invention, in addition to the production of a resin molded product having only a single layer of the resin composition. Often used for practical use.
  • the layer composition of the multilayer structure is represented by E for the resin composition of the present invention, Ad for the adhesive resin, and T for the thermoplastic resin, E / T, T / EZT, E / Ad / T, T / AdZE / Ad / T, etc., but are not limited thereto.
  • Each layer may be a single layer or, in some cases, a multilayer.
  • the method for producing the above-described multilayer structure is not particularly limited. For example, a method of melt-extruding a thermoplastic resin into the molded article (film, sheet, etc.), a method of co-extruding the resin composition and another thermoplastic resin on a base material such as a thermoplastic resin, Plastic resin And a method of co-injecting a resin composition comprising EVOH and an organic titanium compound, an isocyanate compound, a polyester compound, and a molded product obtained from the resin composition of the present invention and a film or sheet of another substrate. And laminating using a known adhesive.
  • the thermoplastic resin used includes linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polypropylene, and propylene- ⁇ Polyolefins such as olefin copolymers (polyolefins having 4 to 20 carbon atoms), polybutene, polypentene, etc.
  • polyesters such as polyethylene terephthalate, polyester elastomers, nylon-16, nylon-16 And 6 etc., polystyrene, polychlorinated polyvinyl chloride, polychlorinated polyvinylidene, acrylic resin, vinyl ester resin, polyurethane elastomer, polycarbonate, chlorinated polyethylene, chlorinated polypropylene, etc. .
  • polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-butyl acetate copolymer, polyamide, polystyrene and polyester are preferably used.
  • an adhesive resin When laminating the resin composition of the present invention and a thermoplastic resin, an adhesive resin may be used, and in this case, an adhesive resin made of a carboxylic acid-modified polyolefin is preferable.
  • the carboxylic acid-modified polyolefin is a modified resin containing a carboxyl group obtained by chemically (for example, adding or grafting) an ethylenically unsaturated carboxylic acid or an anhydride thereof to an olefin polymer. This refers to an olefin polymer.
  • the olefin polymer is defined as polyethylene (low pressure, medium pressure, high pressure), linear low density polyethylene, polyolefin such as propylene, boreptene, or a comonomer capable of copolymerizing olefin and the olefin.
  • polyethylene low pressure, medium pressure, high pressure
  • polyolefin such as propylene, boreptene
  • a comonomer capable of copolymerizing olefin and the olefin.
  • unsaturated carboxylic acid esters such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate It means a stele copolymer or the like.
  • linear low density polyethylene ethylene monoacetate Bulle copolymer (content of acetic Bulle 5-5 5 weight 0 /.), Echirenaku acrylic acid Echiruesuteru copolymer (content of Akuriru acid Echiruesuteru 8-3 5 The weight is preferably 0 /.), And linear low-density polyethylene and ethylene monoacetate copolymer are particularly preferred.
  • Ethylenically unsaturated carboxylic acids or anhydrides include ethylenically unsaturated monocarboxylic acids, their esters, ethylenically unsaturated dicarboxylic acids, their mono- or diesters, and their anhydrides, of which ethylenically unsaturated Dicarboxylic anhydrides are preferred.
  • Maleic anhydride is particularly preferred.
  • the amount of addition or grafting (degree of modification) of the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer is 0.0001 to 15% by weight, preferably 0.0%, based on the olefin polymer. 0 to 10% by weight.
  • the addition reaction and the graft reaction of the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer are obtained by, for example, a radical polymerization method in the presence of a solvent (such as xylene) or a catalyst (such as peroxide).
  • melt flow rate (MFR) of the carboxylic acid-modified polyolefin thus obtained measured at 190 ° C under a load of 210 g should be 0.2 to 30 g / 10 minutes. And more preferably 0.5 to :! O g Z l O minutes.
  • MFR melt flow rate
  • These adhesive resins may be used alone or as a mixture of two or more.
  • a high melting point thermoplastic resin such as polyamide or polyester and the resin composition of the present invention are bonded from the viewpoint that the effect of the present invention, which is excellent in moldability at high temperatures, can be particularly effectively exerted.
  • An embodiment in which the layers are directly laminated without the intervention of a conductive resin or the like is preferable.
  • a high melting point thermoplastic resin such as polyamide or polyester and the resin composition of the present invention are co-extruded or co-injected to form a multilayer structure. are particularly preferred.
  • the method of coextrusion molding of the composition of the present invention and a thermoplastic resin is not particularly limited, and examples thereof include a multi-manifold merging method T-die method, a feedblock merging method T-die method, and an infusion method. Is done.
  • the method of coinjection molding is not particularly limited, and a general method can be used. From the viewpoint that the effect of the present invention, which is excellent in moldability at high temperatures, can be particularly effectively exerted, a multilayer structure composed of the resin composition of the present invention and another thermoplastic resin is produced by co-extrusion molding or co-injection molding. In this case, it is particularly preferable to use a production method in which the die temperature or the nozzle temperature is 250 ° C. or higher.
  • Multi-layer co-stretched sheet or film obtained by uniaxially or biaxially stretching or biaxially stretching a multilayer structure (such as a sheet or film) and heat-treating it.
  • Multi-layered structure sheet or film, etc.
  • Multi-layer tray cup-shaped container formed by thermoforming, vacuum forming, pressure forming, vacuum forming, etc.
  • Multilayer structure (such as parison) Bottle-shaped container made by biaxial stretching blow molding of force
  • the co-extruded multilayer structure and co-injection multilayer structure obtained in this way have excellent low odor, low fish eyes, and are transparent and have few streaks, so they can be used as food container materials, such as deep drawn containers and cups. It is suitably used as a material for shaped containers and bottles.
  • the MFR (MFR (20 min.)) For a retention time of 10 minutes, the MFR (MFR (20 min.)) For 20 minutes, and the MFR (MFR (30 min.)) For 30 minutes ).
  • X At least one of MFR (lOmin.) / MFR (6rain.), MFR (20min.) / MFR (6rain.) And MFR (30min.) / MFR (6min.) Is 0.5 to: I Not included in range 5.
  • MFR (8hr) / MFR (0), MFR (16hr) / MFR (0), MFR (24hr) / MFR (0) and MFR (50hr) ZMFR (0) are all in the range of 0.02 to 1. Included in the box.
  • X at least one of MFR (8hr) / MFR (0), MFR (16hr) / MFR (0), MFR (24hr) / MFR (0) and MFR (50hr) / MFR (0) is 0.02 Not included in the range of ⁇ 1.
  • T die 300 arm width coat hanger die (Plastic Engineering Laboratory)
  • the state of the interface between the EVOH layer and the polyamide layer of the multilayer film produced by the above method was visually observed and determined as follows.
  • the multilayer film produced by the above method is wound around a paper tube, Was visually determined and determined as follows.
  • the film was sampled, the polyimide layer was swollen with trifluoroethanol, peeled off, and only the EVOH layer was taken out.
  • the gel-like bulk in the EVOH layer (approximately 100 ⁇ visible to the naked eye) Above).
  • a 5 mm chip was obtained, and the obtained chip was washed with 1 g ZL of an aqueous acetic acid solution, and the operation of adding a large amount of water and removing water was repeated, and the obtained EVOH chip had a water content of 110%. (Dry base).
  • the EVOH thus obtained (ethylene content 38 mol%, saponification degree 99.4%, 10 kg of a water-containing chip having an intrinsic viscosity of 0.085 1 / g) was immersed in 18 L of an aqueous solution containing 0.53 g / L of boric acid at 25 ° C for 5 hours, and then immersed.
  • the content of carboxylic acid (A) in the obtained dried chips is 0.33 / zmolZg, and the total content of carboxylic acid (A) and its salt is 7.9 ⁇ 1 / g (molecular weight in The content of 75 or more carboxylic acids (a 1) and its salts is 7.9 ⁇ 1 / g), the content of metal salts is 20 ppm in terms of metal elements, and the content of boron compounds is boron elements The converted value was 280 ppm.
  • MFR is 1.7 gZl O
  • FIG. 1 is a graph showing the relationship between the heating time and the MFR (270 ° C, 2160 g load) when the resin composition composed of EVOH is maintained at 270 ° C in a melt indexer.
  • the odor test result was A.
  • a dried pellet was prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 1, and evaluation was performed in the same manner as in Example 1. Table 3 shows the evaluation results.
  • Example 3 shows the evaluation results.
  • Table 1 shows the composition of the liquid used to immerse the water-containing EVOH chip using a water-containing chip of EVOH (water content: 110%: dry base) with a saponification degree of 99.5% and an intrinsic viscosity of 0.097 lZg.
  • a dried pellet was prepared in the same manner as in Example 1 except that the composition was changed to, and the evaluation was performed in the same manner as in Example 1.
  • Table 3 shows the evaluation results.
  • Example 1 Using the water-containing EVOH chip obtained in Example 1 before immersion treatment (ethylene content 38 mol%, saponification degree 99.4%, intrinsic viscosity 0.085 1 / g), the water-containing EVOH chip is immersed A dried pellet was produced in the same manner as in Example 1 except that the composition of the solution to be used was changed as shown in Table 1.
  • the obtained dried chips are held in a melt indexer at 270 ° C., and the MFR (270 ° C., 2160 g load) of each resin composition at the holding time of 6, 10, 20, and 30 minutes was measured.
  • the measurement results are shown below and are also shown in Figure 1.
  • the obtained dried chips were placed in a stainless steel metal container under a nitrogen atmosphere and sealed.
  • the MFR when this sample container was heated at 220 ° C for 8, 16, 24, and 50 hours and the MFR (MFR (O)) of the resin not subjected to the heat treatment were measured.
  • the measurement results are shown below and are also shown in Figure 2.
  • Example 2 Using hydrous EVOH chips before immersion treatment obtained in Example 2 (ethylene content 38 molar 0/0, saponification degree 99.4%, intrinsic viscosity 0. 1 12 1 / g), the water EV OH A dried bellet was produced in the same manner as in Example 1 except that the composition of the liquid in which the chip was immersed was changed as shown in Table 1.
  • the obtained dried chips are held in a melt indexer at 270 ° C., and the MFR (270 ° C., 2160 g load) of each resin composition at the holding time of 6, 10, 20, and 30 minutes is measured. It was measured.
  • the measurement results are as follows, which is also shown in Figure 1. Show.
  • the obtained dried chips were placed in a stainless steel metal container under a nitrogen atmosphere and sealed.
  • the MFR when the sample container was heated at 220 for 8, 16, 24, and 50 hours and the MFR (MFR (O)) of the resin not subjected to the heat treatment were as follows. The measurement results are shown below and are also shown in Figure 2.
  • Example 2 Using the water-containing EVOH chip (ethylene content 38 mol%, saponification degree 99.4%, intrinsic viscosity 0.085 1 / g) obtained in Example 1 before immersion treatment, 10 kg of the OH chip was immersed in 18 L of an aqueous solution containing 0.53 g / L of boric acid at 25 ° C for 5 hours.
  • the content of carboxylic acid (A) in the obtained dried chips was 2.2 ⁇ 1 / g, and the total content of carboxylic acid (A) and its salts was 5.5 mo 1 / g (of which The content of carboxylic acid (al) with a molecular weight of 75 or more (al) and its salt is 0 ⁇ 1 Zg), the content of alkali metal salt is 200 ppm in metal element conversion, and the content of boron compound is boron element conversion value At 280 ppm.
  • the MFR was 1.9 gZlO content (190 ° C, 2160 g load).
  • Example 1 Using the water-containing EVOH chip obtained in Example 1 before immersion treatment (ethylene content 38 mol%, saponification degree 99.4%, intrinsic viscosity 0.085 1 / g), the water-containing EVOH chip was immersed. A dried pellet was prepared in the same manner as in Example 1 except that the composition of the solution to be used was changed as shown in Table 1, and evaluation was performed in the same manner as in Example 1. Table 3 shows the evaluation results. table 1
  • X is the concentration of aqueous solution containing only boric acid
  • Y is the concentration of aqueous solution containing boric acid and metal salt
  • X at least any of MFR (8hr) / MFR (0), MFR (16hr) / MFR (0), MFR (24hr) / FR (0), MFR (50hr) / MFR (0) is 0 2 to 1 Out of range.
  • Example 3 In Example 3 in which the content of the phosphoric acid compound (C) exceeds 80 ppm (in terms of phosphate radical), the long-run property was further reduced.
  • Example 4 in which the content of the alkali metal salt (D) was more than 30 Oppm (in terms of metal element), the surface of the film was slightly uneven at the time of multilayer film formation, and the color resistance and the long run property were slightly inferior. .
  • Example 5 in which (& 1) da () is less than 0.98 (provided that (A): the total content of carboxylic acid (A) and its salts ( ⁇ / g), (a 1): The content of the carboxylic acid (a1) having a molecular weight of 75 or more (a1) and its salt (mol / g)) was slightly inferior in the effect of improving the low odor.
  • Comparative Example 1 in which the content of the carboxylic acid was more than 2.5 / molZg, the long run property and the coloring resistance during the multilayer film formation were remarkably inferior.
  • Comparative Example 2 in which the content of the alkaline earth metal salt (B) exceeds l Op pm (converted to a metal element), severe film surface unevenness occurs during coextrusion molding with polyamide, and the color resistance is remarkably high. Dropped.
  • the present invention can provide an ethylene-vinyl alcohol copolymer resin composition having excellent properties and low odor, and a multilayer structure using the same.
  • the multilayer structure of the present invention is useful as various food containers, for example, deep drawing containers, cup-shaped containers, bottles and the like.

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  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une composition de résine constituée d'un copolymère éthylène/alcool vinylique, présentant une teneur en acides carboxyliques (A) comprise entre 0,05 et 2, 5 νmoles/g et une teneur en sels de métaux alcalinoterreux (B) inférieure ou égale à 10 ppm (en termes d'éléments métalliques) et satisfaisant à la relation suivante (1). L'invention concerne également des structures multicouches utilisant ladite composition. Dans la formule (1), (A) représente la teneur totale (νmoles/g) en acides carboxyliques (A) et leur sels ; et (a1) représente la teneur (νmoles/g) en acides carboxyliques (a1) présentant des poids moléculaires supérieurs ou égaux à 75, et leurs sels.
PCT/JP2001/004870 2000-06-14 2001-06-08 Composition de resine constituee d'un copolymere ethylene/alcool vinylique WO2001096464A1 (fr)

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JP2008189940A (ja) * 2002-02-18 2008-08-21 Kuraray Co Ltd エチレン−ビニルアルコール共重合体樹脂組成物およびそれからなるペレット
US7473735B2 (en) 2003-08-01 2009-01-06 Kuraray Co., Ltd. Resin composition and method for producing the same
US8137775B2 (en) 2003-08-11 2012-03-20 Kuraray Co., Ltd. Blow molded container and method for producing the same
WO2013005807A1 (fr) * 2011-07-07 2013-01-10 株式会社クラレ Composition de résine de copolymère éthylène-alcool vinylique et son procédé de fabrication
US11407880B2 (en) 2014-12-24 2022-08-09 Kuraray Co., Ltd. Polymethallyl alcohol resin composition and molding containing same
US11865815B2 (en) 2014-12-24 2024-01-09 Kuraray Co., Ltd. Polymethallyl alcohol resin composition and molding containing same

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JPH07329253A (ja) * 1994-06-07 1995-12-19 Kuraray Co Ltd 積層フィルム、積層体およびその用途
JPH1121320A (ja) * 1997-05-09 1999-01-26 Kuraray Co Ltd エチレン−ビニルアルコール共重合体からなる成形物
EP1067152A1 (fr) * 1999-07-07 2001-01-10 Kuraray Co., Ltd. Composition de résine contenant d'un copolymère de l'éthylène et de l'alcool vinylique ayant une bonne adhésion interlaminaire

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JP3523679B2 (ja) * 1993-02-22 2004-04-26 日本合成化学工業株式会社 ポリビニルアルコール系樹脂組成物、ホットメルト接着剤及びその製造方法
JP4722270B2 (ja) * 1999-09-07 2011-07-13 株式会社クラレ 低臭性および層間接着性に優れたエチレン−ビニルアルコール共重合体からなる樹脂組成物およびそれを用いた多層構造体
JP5307960B2 (ja) * 1999-12-16 2013-10-02 株式会社クラレ ロングラン性の改善されたエチレン−ビニルアルコール共重合体樹脂組成物およびその成形物

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Publication number Priority date Publication date Assignee Title
US5430090A (en) * 1993-02-22 1995-07-04 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Hot-melt adhesive
JPH07329253A (ja) * 1994-06-07 1995-12-19 Kuraray Co Ltd 積層フィルム、積層体およびその用途
JPH1121320A (ja) * 1997-05-09 1999-01-26 Kuraray Co Ltd エチレン−ビニルアルコール共重合体からなる成形物
EP1067152A1 (fr) * 1999-07-07 2001-01-10 Kuraray Co., Ltd. Composition de résine contenant d'un copolymère de l'éthylène et de l'alcool vinylique ayant une bonne adhésion interlaminaire

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008189940A (ja) * 2002-02-18 2008-08-21 Kuraray Co Ltd エチレン−ビニルアルコール共重合体樹脂組成物およびそれからなるペレット
JP2008189941A (ja) * 2002-02-18 2008-08-21 Kuraray Co Ltd エチレン−ビニルアルコール共重合体樹脂組成物からなる溶融成形品
US7473735B2 (en) 2003-08-01 2009-01-06 Kuraray Co., Ltd. Resin composition and method for producing the same
KR101132962B1 (ko) * 2003-08-01 2012-04-10 가부시키가이샤 구라레 수지 조성물 및 이의 제조방법
US8137775B2 (en) 2003-08-11 2012-03-20 Kuraray Co., Ltd. Blow molded container and method for producing the same
KR101132963B1 (ko) * 2003-08-11 2012-04-09 가부시키가이샤 구라레 취입성형 용기 및 이의 제조방법
WO2013005807A1 (fr) * 2011-07-07 2013-01-10 株式会社クラレ Composition de résine de copolymère éthylène-alcool vinylique et son procédé de fabrication
JPWO2013005807A1 (ja) * 2011-07-07 2015-02-23 株式会社クラレ エチレン−ビニルアルコール共重合体樹脂組成物及びその製造方法
US9951199B2 (en) 2011-07-07 2018-04-24 Kuraray Co., Ltd. Ethylene-vinyl alcohol copolymer resin composition and method for producing same
US11407880B2 (en) 2014-12-24 2022-08-09 Kuraray Co., Ltd. Polymethallyl alcohol resin composition and molding containing same
US11865815B2 (en) 2014-12-24 2024-01-09 Kuraray Co., Ltd. Polymethallyl alcohol resin composition and molding containing same

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