WO2015050222A1 - 樹脂組成物、樹脂成形体及び多層構造体 - Google Patents
樹脂組成物、樹脂成形体及び多層構造体 Download PDFInfo
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- WO2015050222A1 WO2015050222A1 PCT/JP2014/076440 JP2014076440W WO2015050222A1 WO 2015050222 A1 WO2015050222 A1 WO 2015050222A1 JP 2014076440 W JP2014076440 W JP 2014076440W WO 2015050222 A1 WO2015050222 A1 WO 2015050222A1
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/10—Forming by pressure difference, e.g. vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
-
- 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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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
Definitions
- the present invention relates to a resin composition, a resin molded body, and a multilayer structure.
- melt molding using a resin composition is used for molding containers, films, sheets and the like.
- a resin composition has few defects such as streak and fish eye, and can form a molded product having excellent appearance, and long-term operation characteristics (long-run characteristics) in which the above-mentioned defects hardly occur even after long-time melt molding. It is required to have excellent properties. In particular, such defects not only impair the appearance of the molded product, but also cause performance deterioration, so it is important to suppress the occurrence of defects.
- an ethylene-vinyl alcohol copolymer (hereinafter also referred to as “EVOH”) is a polymer material having excellent gas shielding properties such as oxygen, oil resistance, non-charging property, mechanical strength, and the like. Therefore, the EVOH-containing resin composition is widely used as a molding material for molded articles such as containers.
- EVOH has a relatively active hydroxyl group in the molecule, oxidation and cross-linking reaction may occur in a high-temperature molten state even in an extruder with almost no oxygen, which may cause thermal degradation.
- a thermally deteriorated material accumulates inside the molding machine, and gel-like spots that cause fish eyes are likely to occur. For this reason, in the melt molding using the EVOH-containing resin composition, the long run property tends to be insufficient.
- an EVOH-containing resin composition (see Japanese Patent Application Laid-Open No. 11-60874) having improved long-run properties during melt molding by containing a boron compound, sodium acetate and magnesium acetate, and a conjugated polyene compound are melted.
- EVOH-containing resin composition (see Japanese Patent Application Laid-Open No. 9-71620) in which the generation of gel-like particles due to molding is suppressed, and a specific carboxylic acid metal salt and a hindered phenol-based antioxidant are included to improve thermal stability.
- An EVOH-containing resin composition (see Japanese Patent Application Laid-Open No. 4-227744) that is excellent in suppressing the formation of an oxidizing gel at high temperatures has been developed.
- the present invention has been made based on the circumstances as described above, and its purpose is excellent in the long run property of melt molding, and generation of defects such as streaks and fish eyes and coloring are suppressed, and the appearance is excellent. It is to provide a resin composition, a resin molded body, and a multilayer structure that can form a molded product while suppressing generation of odor.
- the invention made to solve the above-mentioned problems includes an ethylene-vinyl alcohol copolymer (A) and a saturated carbonyl compound (B) having 3 to 8 carbon atoms, wherein the saturated carbonyl compound (B)
- the resin composition is a saturated aldehyde (B-1), a saturated ketone (B-2) or a combination thereof, and the content of the saturated carbonyl compound (B) is 0.01 ppm or more and 100 ppm or less.
- the resin composition contains EVOH (A) and a specific amount of a saturated carbonyl compound (B), thereby suppressing the occurrence of defects such as streak and fisheye due to melt molding and coloring, and improving the appearance of the molded product. Excellent. Thereby, it can respond to the request
- the saturated aldehyde (B-1) is preferably propanal, butanal, hexanal or a combination thereof.
- the saturated ketone (B-2) is preferably acetone, methyl ethyl ketone, 2-hexanone or a combination thereof.
- the resin composition may further contain a boron compound.
- the boron compound content is preferably 100 ppm or more and 5,000 ppm or less.
- the resin composition may further contain a conjugated polyene compound.
- the content of the conjugated polyene compound is preferably 0.01 ppm or more and 1,000 ppm or less.
- the oxidation deterioration at the time of melt molding can be suppressed by further containing a specific amount of the conjugated polyene compound.
- production and coloring of a defect can be suppressed more, while being able to form the molded article which is excellent in external appearance property, long run property can be improved more.
- the conjugated polyene compound is preferably sorbic acid, sorbate or a combination thereof.
- sorbic acid, sorbate, or a combination thereof oxidative degradation during melt molding can be more effectively suppressed.
- production and coloring of a defect can be suppressed further, while being able to improve the external appearance property of a molded article, long run property can be improved more.
- the resin composition may further contain at least one of acetic acid and acetate.
- the total content of acetic acid and acetate is preferably 50 ppm to 1,000 ppm.
- coloring of a molded article can be prevented more by further containing a specific amount of acetic acid.
- the resin composition may further contain a phosphorus compound.
- the phosphorus compound content is preferably 1 ppm or more and 200 ppm or less.
- the present invention includes a resin molded body and a multilayer structure formed from the resin composition. Since these resin molded bodies and multilayer structures are formed from the resin composition, generation and accumulation of thermally deteriorated products during melt molding are suppressed. Therefore, when the resin molded body and the multilayer structure are formed, the thermally deteriorated material is prevented from staying and adhering inside and outside the die, so that the resin molded body and the multilayer structure formed during a long continuous operation can be obtained. Even the appearance is excellent.
- the resin composition of the present invention can suppress generation of defects and coloration during melt molding, it can provide a molded product having excellent appearance. Further, the resin composition is excellent in long-run property because defects and odor are hardly generated even after long-time melt molding. Therefore, the said resin composition is shape
- the resin composition contains EVOH (A) and a saturated carbonyl compound (B).
- the saturated carbonyl compound (B) is a saturated aldehyde (B-1), a saturated ketone (B-2) or a combination thereof.
- the said resin composition may further contain a boron compound, a conjugated polyene compound, acetic acid, and a phosphorus compound as a suitable component.
- the resin composition may contain other optional components as long as the effects of the present invention are not impaired.
- EVOH (A), saturated carbonyl compound (B), boron compound, conjugated polyene compound, acetic acid, phosphorus compound and other optional components will be described in detail.
- ppm is a mass ratio of the corresponding component in the resin composition, and 1 ppm is 0.0001 mass%.
- Content of boron compound is the content as boric acid equivalent mass.
- acetate content is the content as acetic acid equivalent mass.
- content of phosphorus compound is the content as phosphorus element equivalent mass.
- EVOH (A) is an ethylene-vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl ester.
- vinyl ester examples include vinyl acetate, vinyl propionate, vinyl pivalate and the like, and vinyl acetate is preferable. These vinyl esters may be used alone or in combination of two or more.
- EVOH (A) may contain other structural units derived from monomers other than ethylene and vinyl ester.
- monomers include vinylsilane compounds; unsaturated hydrocarbons such as propylene and butylene; unsaturated carboxylic acids such as (meth) acrylic acid; and polymerizable compounds such as vinylpyrrolidone such as N-vinylpyrrolidone.
- content of said other structural unit 0.0002 mol% or more and 0.2 mol% or less are preferable with respect to all the structural units of EVOH (A).
- the lower limit of the ethylene content of EVOH (A) is usually 20 mol%, preferably 24 mol%, more preferably 27 mol%.
- the upper limit of the ethylene content of EVOH (A) is usually 60 mol%, preferably 55 mol%, more preferably 45 mol%, still more preferably 42 mol%, and particularly preferably 38 mol%.
- the ethylene content is less than the above lower limit, the thermal stability at the time of melt extrusion is lowered and gelation tends to occur, and defects such as streak and fish eye are likely to occur. In particular, if the operation is performed for a long time at a higher temperature or at a higher speed than the general melt extrusion conditions, the possibility of gelation increases.
- the ethylene content exceeds the above upper limit, gas barrier properties and the like are lowered, and there is a possibility that the advantageous characteristics possessed by EVOH cannot be sufficiently exhibited.
- the lower limit of the saponification degree of the structural unit derived from the vinyl ester of EVOH (A) is usually 85%, preferably 90%, more preferably 98%, and further preferably 99%. If the degree of saponification is less than the above lower limit, the thermal stability may be insufficient.
- the lower limit of the EVOH (A) content in the resin composition is usually 95% by mass, preferably 98.0% by mass, more preferably 99.0% by mass, and still more preferably 99.5% by mass.
- the saturated carbonyl compound (B) is either or both of a saturated aldehyde (B-1) and a saturated ketone (B-2), which suppresses the occurrence of defects such as streaks and fish eyes due to melt molding and coloring, and is a long run. It improves the sex.
- the saturated carbonyl compound (B) refers to a compound containing no unsaturated bond in a portion other than the carbonyl group.
- Saturated aldehyde (B-1) has a ring structure in the molecule, whether it is a linear aldehyde or a branched aldehyde, as long as it contains no unsaturated bond in any part other than the aldehyde group. It may be an aldehyde.
- the number of aldehyde groups in the molecule of the saturated aldehyde (B-1) may be 1 or 2 or more.
- saturated aldehyde (B-1) examples include propanal, butanal, pentanal, hexanal, heptanal, octanal, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, methylcyclohexanecarbaldehyde, methylcyclopentylaldehyde and the like.
- the saturated ketone (B-2) does not contain an unsaturated bond in a portion other than the carbonyl group, a linear ketone or a branched ketone has a ring structure in the molecule. It may be a ketone.
- the number of carbonyl groups in the molecule of the saturated ketone (B-2) may be 1 or 2 or more.
- Examples of the saturated ketone (B-2) include saturated aliphatic ketones and saturated cyclic ketones.
- saturated aliphatic ketones include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 3-methyl-2-butanone, 2-hexanone, 3-hexanone, 4-methyl-2-pentanone, 2-methyl-3- Pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-hexanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, Examples include 2-octanone, 3-methyl-2-heptanone, 5-methyl-3-heptanone, 3-octanone, 6-methyl-2-heptanone, methylcyclopentyl ketone, and methylcyclohexyl ketone.
- saturated cyclic ketone include cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and the
- the carbon number of the saturated carbonyl compound (B) is preferably from 3 to 50, more preferably from 3 to 15, and even more preferably from 3 to 8 from the viewpoint of improving the water solubility of the saturated carbonyl compound (B).
- saturated ketone (B-2) among the exemplified examples, saturated aliphatic ketones are preferable from the viewpoint of suppressing generation of defects and coloring due to melt molding and improving long-run properties, and acetone, methyl ethyl ketone, 2-hexanone, or these Is more preferable, and acetone is more preferable.
- the saturated carbonyl compound (B) a part or all of the hydrogen atoms (excluding the hydrogen atom of the aldehyde group of the saturated aldehyde (B-1)) are substituted with a substituent as long as the effects of the present invention are not impaired. Also good.
- the substituent include a halogen atom, a hydroxy group, an amino group, an amide group, and a cyano group.
- the lower limit of the content of the saturated carbonyl compound (B) in the resin composition is 0.01 ppm, preferably 0.05 ppm, more preferably 0.1 ppm, still more preferably 0.15 ppm, particularly 0.2 ppm. preferable.
- the upper limit of the content of the saturated carbonyl compound (B) is 100 ppm, preferably 95 ppm, more preferably 50 ppm, still more preferably 30 ppm, and particularly preferably 20 ppm. If the content of the saturated carbonyl compound (B) is less than the above lower limit, the effect of containing the saturated carbonyl compound (B), for example, the occurrence of defects and the effect of suppressing coloring cannot be obtained sufficiently.
- the resin composition is easily oxidized and crosslinked by the saturated carbonyl compound (B) at the time of melt molding, thereby inducing the generation of gelled blisters.
- the resin composition is likely to be colored.
- the boron compound suppresses gelation during melt molding and suppresses torque fluctuations (viscosity change during heating) of an extruder or the like.
- the boron compound include boric acids such as orthoboric acid, metaboric acid, and tetraboric acid; Borate esters such as triethyl borate and trimethyl borate; Borate salts such as alkali metal salts and alkaline earth metal salts of borates and borax; Examples thereof include borohydrides.
- boric acids are preferable, and orthoboric acid (hereinafter also referred to as “boric acid”) is more preferable.
- the lower limit of the boron compound content in the resin composition is preferably 100 ppm, more preferably 150 ppm.
- the upper limit of the boron compound content is preferably 5,000 ppm, more preferably 4,000 ppm, and even more preferably 3,000 ppm. If the boron compound content is less than the above lower limit, torque fluctuations in an extruder or the like may not be sufficiently suppressed. On the other hand, if the content of the boron compound exceeds the above upper limit, gelation is likely to occur during melt molding, and the appearance of the molded product may be deteriorated.
- the conjugated polyene compound suppresses oxidative degradation during melt molding.
- the conjugated polyene compound has a structure in which carbon-carbon double bonds and carbon-carbon single bonds are alternately connected, and the number of carbon-carbon double bonds is two or more. It is a compound having a heavy bond.
- This conjugated polyene compound may be a conjugated diene having two conjugated double bonds, a conjugated triene having three, or a conjugated polyene having more than that number.
- a plurality of sets of the conjugated double bonds may be present in one molecule without being conjugated with each other.
- a compound having three conjugated triene structures in the same molecule such as tung oil is also included in the conjugated polyene compound.
- the number of conjugated double bonds in the conjugated polyene compound is preferably 7 or less.
- the resin composition contains a conjugated polyene compound having 8 or more conjugated double bonds, the molded product may be colored.
- the above conjugated polyene compounds may be used alone or in combination of two or more.
- the carbon number of the conjugated polyene compound is preferably 4 to 30, and more preferably 4 to 10.
- sorbic acid, sorbic acid ester, sorbate, myrcene and a mixture of two or more thereof are preferable, and sorbic acid, sorbate (sodium sorbate, potassium sorbate, etc.) and a mixture thereof. Is more preferable. Sorbic acid, sorbate and a mixture thereof are highly effective in suppressing oxidative degradation at high temperatures, and are also widely used industrially as food additives, and thus are preferable from the viewpoint of hygiene and availability.
- the upper limit of the molecular weight of the conjugated polyene compound is usually 1,000, preferably 500, and more preferably 300.
- the upper limit of the molecular weight of the conjugated polyene compound is usually 1,000, preferably 500, and more preferably 300.
- the molecular weight of the conjugated polyene compound exceeds the upper limit, the dispersion state of the conjugated polyene compound in EVOH (A) may be deteriorated, and the appearance after melt molding may be deteriorated.
- As a minimum of content of a conjugated polyene compound in the resin composition 0.01 ppm is preferred, 0.1 ppm is more preferred, 0.5 ppm is still more preferred, and 1 ppm is especially preferred.
- the upper limit of the content is preferably 1,000 ppm, more preferably 800 ppm, and even more preferably 500 ppm.
- the content of the conjugated polyene compound is less than the above lower limit, the effect of suppressing oxidative deterioration during melt molding may not be sufficiently obtained. On the other hand, when the content of the conjugated polyene compound exceeds the upper limit, gelation of the resin composition may be promoted.
- Acetic acids prevent coloring of the molded product and suppress gelation during melt molding.
- the acetic acids include acetic acid and acetate.
- acetic acid it is preferable to use acetic acid and acetate (sodium acetate, potassium acetate, etc.) together, and it is more preferable to use acetic acid and sodium acetate together.
- the lower limit of the acetic acid content in the resin composition is preferably 50 ppm, more preferably 100 ppm, still more preferably 150 ppm, and particularly preferably 200 ppm.
- the upper limit of the acetic acid content is preferably 1,000 ppm, more preferably 500 ppm, and still more preferably 400 ppm. If the acetic acid content is less than the above lower limit, a sufficient anti-coloring effect cannot be obtained, and the molded product may be yellowed. On the other hand, if the content of acetic acid exceeds the above upper limit, gelation tends to occur during melt molding, particularly during long melt molding, and the appearance of the molded product may be deteriorated.
- the phosphorus compound suppresses generation and coloring of defects such as streaks and fish eyes and improves long run properties.
- the phosphorus compound include phosphates such as phosphoric acid and phosphorous acid.
- any form of a primary phosphate, a secondary phosphate, and a tertiary phosphate may be sufficient.
- the cation species of the phosphate are not particularly limited, but alkali metal salts and alkaline earth metal salts are preferable. Among these, sodium dihydrogen phosphate, potassium dihydrogen phosphate, dihydrogen phosphate are preferable.
- Sodium and dipotassium hydrogen phosphate are more preferable, and sodium dihydrogen phosphate and dipotassium hydrogen phosphate are more preferable.
- As a minimum of content of a phosphorus compound in the resin composition 1 ppm is preferred, 2 ppm is more preferred, 3 ppm is still more preferred, and 5 ppm is especially preferred.
- As an upper limit of content of a phosphorus compound 200 ppm is preferable, 150 ppm is more preferable, and 100 ppm is further more preferable. When the content of the phosphorus compound is less than the above lower limit or exceeds the above upper limit, the thermal stability is reduced, and there is a risk that gelled spots and coloration are likely to occur during long-time melt molding. .
- the resin composition may contain other optional components as long as the effects of the present invention are not impaired.
- Other optional components include, for example, alkali metals, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, heat stabilizers, other resins, and metal salts of higher aliphatic carboxylic acids. Etc.
- the resin composition may contain two or more of these optional components, and the total content of the optional components is preferably 1% by mass or less in the resin composition.
- a hindered phenol compound and a hindered amine compound for example, a metal salt of a higher aliphatic carboxylic acid, a hydrotalcite compound, or the like may be added. These may be used alone or in combination of two or more.
- the addition amount of the compound for preventing gelation is usually 0.01% by mass or more and 1% by mass or less.
- the saturated carbonyl compound (B) can be uniformly blended in EVOH (A), and the final carbonyl compound (B) is added in an amount of 0.01 ppm to 100 ppm. If it is a method made to contain, it will not specifically limit.
- the resin composition includes, for example, a step of copolymerizing ethylene and vinyl ester (hereinafter also referred to as “step (1)”), and a step of saponifying the copolymer obtained by this step (1) (hereinafter referred to as “step”). (Also referred to as “step (2)”).
- the method for containing the specific amount of the saturated carbonyl compound (B) in the resin composition is not particularly limited.
- a method of adding a specific amount of a saturated carbonyl compound (B) to the EVOH (A) obtained in step (2) is not particularly limited.
- the resulting resin In order to contain a desired amount of the saturated carbonyl compound (B) in the composition, the amount added is increased in consideration of the amount consumed in the polymerization reaction in step (1) or the saponification reaction in step (2). There is a need. However, if the amount of the saturated carbonyl compound (B) is large, these reactions may be inhibited.
- the saturated carbonyl compound (B) consumed varies depending on the polymerization reaction in step (1) and the saponification reaction in step (2), the saturated carbonyl compound (B) in the resin composition It is difficult to adjust the content of. Therefore, a method of adding a specific amount of the saturated carbonyl compound (B) to the EVOH (A) obtained by the step (2) after the step (2) is preferable.
- a method for adding a specific amount of the saturated carbonyl compound (B) to EVOH (A) for example, a method in which the saturated carbonyl compound (B) is previously blended in EVOH (A) and pellets are formed, an ethylene-vinyl ester copolymer is used.
- a method of impregnating a saturated carbonyl compound (B) into a strand to be precipitated after saponification of a polymer, a method of impregnating a saturated carbonyl compound (B) after cutting off the strand to be precipitated, and a redissolved chip of a dry resin composition A method of adding a saturated carbonyl compound (B) to a slab, a method of melt kneading EVOH (A) and a saturated carbonyl compound (B), and supplying a saturated carbonyl compound (B) to a melt of EVOH (A) from the middle of an extruder And a method in which a saturated carbonyl compound (B) is blended with a part of EVOH (A) at a high concentration and granulated.
- the Batchi the EVOH (A) and a method of melt-kneading the dry blend.
- the saturated carbonyl compound (B) is prepared in advance.
- a method of granulating pellets by blending with EVOH (A) is preferred.
- the saturated carbonyl compound (B) is added by adding the saturated carbonyl compound (B) to a solution obtained by dissolving EVOH (A) in a good solvent such as a water / methanol mixed solvent, and then adding the mixed solution.
- the resin composition is obtained as pellets in which the saturated carbonyl compound (B) is uniformly mixed with EVOH (A).
- Examples of a method of adding each component other than the saturated carbonyl compound (B) to the resin composition include, for example, a method of mixing and melting and kneading the pellets together with the components, and a saturated carbonyl compound (B ) And a method of mixing each component, a method of immersing the pellet in a solution containing each component, and the like.
- a ribbon blender, a high speed mixer kneader, a mixing roll, an extruder, an intensive mixer, etc. can be used for mixing a pellet and another component.
- the resin molded body is formed from the resin composition.
- seat, a container, a pipe, a hose, a fiber, a packaging material etc. are mentioned, for example.
- a film usually has a thickness of less than 300 ⁇ m
- a sheet usually has a thickness of 300 ⁇ m or more.
- the resin molded body is formed by, for example, melt molding, and is formed by performing secondary processing molding as necessary.
- the melt molding method include extrusion molding, inflation extrusion, blow molding, melt spinning, injection molding, and injection blow molding.
- the melt molding temperature varies depending on the melting point of EVOH (A) and the like, but is preferably 150 ° C. or higher and 270 ° C. or lower.
- the secondary processing molding include bending, vacuum molding, blow molding, and press molding.
- the multilayer structure includes a layer formed from the resin composition (hereinafter also referred to as “resin composition layer”).
- the layer structure of the multilayer structure is not particularly limited, but preferably includes a layer formed from a thermoplastic resin (hereinafter, also referred to as “thermoplastic resin layer”). More preferably, it is adjacent to the resin composition layer.
- the thermoplastic resin layer can also be configured as an adhesive resin layer. This adhesive resin layer adheres the other resin layers to each other, and is a layer having a lower melting point or softening point than the other resin layers.
- thermoplastic resin forming the thermoplastic resin layer High density, medium density or low density polyethylene; Polyethylene copolymerized with vinyl acetate, acrylic acid ester, or ⁇ -olefins such as butene and hexene; Ionomer resin; Polypropylene homopolymer; Polypropylene copolymerized with ⁇ -olefins such as ethylene, butene and hexene; Polyolefins such as modified polypropylene blended with rubber polymers; Resins obtained by adding or grafting maleic anhydride to these resins; Polyester is preferred.
- thermoplastic resin examples include polyamide, polystyrene, polyvinyl chloride, acrylic resin, polyurethane, polycarbonate, and polyvinyl acetate.
- thermoplastic resin layer / resin composition layer / thermoplastic resin layer As the layer structure of the multilayer structure, from the viewpoint of moldability and cost, for example, thermoplastic resin layer / resin composition layer / thermoplastic resin layer; Resin composition layer / thermoplastic resin layer (adhesive resin layer) / thermoplastic resin layer; Examples include thermoplastic resin layer / thermoplastic resin layer (adhesive resin layer) / resin composition layer / thermoplastic resin layer (adhesive resin layer) / thermoplastic resin layer.
- the multilayer structure includes a plurality of thermoplastic resin layers, the plurality of thermoplastic resin layers may be layers made of different resins or layers made of the same resin.
- thermoplastic resin layer / resin composition layer / thermoplastic resin layer is preferable, and the layer structure in which a thermoplastic resin layer made of a polyester resin composition is laminated on both sides of the resin composition layer. More preferred.
- the method for obtaining the multilayer structure is not particularly limited.
- extrusion lamination, dry lamination, extrusion blow molding, coextrusion lamination, coextrusion sheet molding, coextrusion pipe molding examples include a coextrusion blow molding method, a co-injection molding method, and a solution coating method.
- the multilayer structure obtained by such a method may be subjected to secondary processing by vacuum-pressure-air deep drawing, blow molding, or the like after reheating within the range below the melting point of EVOH (A). .
- scrap generated during the formation of the multilayer structure may be reused by blending with the thermoplastic resin layer or may be used separately.
- Moisture content of hydrous EVOH pellets Using METTLER TOLEDO Halogen Moisture Analyzer “HR73”, the moisture content of hydrous EVOH pellets was measured under the conditions of a drying temperature of 180 ° C., a drying time of 20 minutes, and a sample amount of about 10 g. It was measured.
- the moisture content of the water-containing EVOH shown below is mass% based on the dry mass of EVOH.
- the amount of acetic acid and acetate ions was calculated by quantifying the amount of acetate ions according to the following measurement conditions using ion chromatography “ICS-1500” manufactured by Yokogawa Electric Corporation. Is the content of acetic acid and acetate. A calibration curve prepared using acetic acid was used for quantification. (Measurement condition) Column: “IonPAC ICE-AS1 (9 ⁇ ⁇ 250 mm, electrical conductivity detector)” manufactured by DIONEX Eluent: 1.0 mmol / L Octanesulfonic acid aqueous solution Measurement temperature: 35 ° C Eluent flow rate: 1 mL / min Analytical volume: 50 ⁇ L
- the obtained decomposition product solution is quantitatively analyzed at each observation wavelength shown below, and the amounts of metal ions, phosphorus compounds and boron compounds was quantified.
- the amount of the phosphorus compound was calculated as the phosphorus element equivalent mass by quantifying the phosphorus element.
- the boron compound content was calculated as boric acid equivalent mass.
- the amount of the saturated carbonyl compound (B) (saturated aldehyde (B-1) or saturated ketone (B-2)) was quantified by quantitative analysis of the extracted sample by high performance liquid chromatography. For quantification, a calibration curve prepared using a sample obtained by reacting each saturated carbonyl compound (B) with a DNPH preparation solution was used.
- Detector Photodiode array detector (360 nm), TOF-MS
- the polymerization rate of vinyl acetate in the obtained copolymer was about 40%.
- the sorbic acid is supplied to an extraction tower, unreacted vinyl acetate is removed from the top of the tower by introduction of methanol vapor from the bottom of the tower, and ethylene-vinyl acetate copolymer 41 A mass% methanol solution was obtained.
- the ethylene content of this ethylene-vinyl acetate copolymer was 32 mol%.
- This methanol solution of ethylene-vinyl acetate copolymer is charged into a saponification reactor, and caustic soda / methanol solution (80 g / L) is added so as to be 0.4 equivalent to the vinyl ester component in the copolymer. Then, methanol was added to adjust the copolymer concentration to 20% by mass. This solution was heated to 60 ° C. and reacted for about 4 hours while blowing nitrogen gas into the reactor. This solution was extruded into water from a metal plate having a circular opening, precipitated, and cut to obtain pellets having a diameter of about 3 mm and a length of about 5 mm. The obtained pellets were drained with a centrifuge, and the operation of adding a large amount of water and draining was repeated.
- This strand was introduced into a pelletizer to obtain a porous resin composition chip.
- the obtained porous resin composition chip was washed with an aqueous acetic acid solution and ion-exchanged water, and then immersed in an aqueous solution containing acetic acid, sodium acetate, potassium dihydrogen phosphate and boric acid.
- the aqueous solution for immersion treatment and the resin composition chip were separated and drained, and then placed in a hot air dryer, dried at 80 ° C.
- Example 10 Resin composition pellets were prepared in the same manner as in Example 1 except that myrcene was used in place of sorbic acid as the conjugated polyene compound.
- Example 11 Resin composition pellets were prepared in the same manner as in Example 1 except that potassium sorbate was used in place of sorbic acid as the conjugated polyene compound.
- Example 19 Resin composition pellets were prepared in the same manner as in Example 1 except that butanal was used as the saturated aldehyde instead of propanal.
- Example 20 Resin composition pellets were prepared in the same manner as in Example 1 except that hexanal was used in place of propanal as a saturated aldehyde.
- This strand was introduced into a pelletizer to obtain a porous resin composition chip.
- the obtained porous resin composition chip was washed with an aqueous acetic acid solution and ion-exchanged water, and then immersed in an aqueous solution containing acetic acid, sodium acetate, potassium dihydrogen phosphate and boric acid.
- the aqueous solution for immersion treatment and the resin composition chip are separated and drained, and then placed in a hot air dryer, dried at 80 ° C. for 4 hours, and further dried at 100 ° C. for 16 hours to obtain a resin composition (dried Resin composition pellets) were obtained.
- the content of each component in the obtained resin composition was quantified using the above quantification method.
- the resin composition of Comparative Examples 1, 3, and 4 was prepared so that content of each component might become as the description of Table 2 by adjusting the density
- the saturated aldehyde (B-1) was below the lower limit of detection.
- This strand was introduced into a pelletizer to obtain a porous resin composition chip.
- the obtained porous resin composition chip was washed with an aqueous acetic acid solution and ion-exchanged water, and then immersed in an aqueous solution containing acetic acid, sodium acetate, potassium dihydrogen phosphate and boric acid.
- the aqueous solution for immersion treatment and the resin composition chip were separated and drained, and then placed in a hot air dryer, dried at 80 ° C.
- Example 32 Resin composition pellets were prepared in the same manner as in Example 23 except that myrcene was used in place of sorbic acid as the conjugated polyene compound.
- Example 33 Resin composition pellets were prepared in the same manner as in Example 23 except that potassium sorbate was used in place of sorbic acid as the conjugated polyene compound.
- Example 41 Resin composition pellets were prepared in the same manner as in Example 23 except that methyl ethyl ketone was used instead of acetone as the saturated ketone.
- Example 42 Resin composition pellets were prepared in the same manner as in Example 23 except that 2-hexanone was used instead of acetone as the saturated ketone.
- This strand was introduced into a pelletizer to obtain a porous resin composition chip.
- the obtained porous resin composition chip was washed with an aqueous acetic acid solution and ion-exchanged water, and then immersed in an aqueous solution containing acetic acid, sodium acetate, potassium dihydrogen phosphate and boric acid.
- the aqueous solution for immersion treatment and the resin composition chip are separated and drained, and then placed in a hot air dryer, dried at 80 ° C. for 4 hours, and further dried at 100 ° C. for 16 hours to obtain a resin composition (dried Resin composition pellets) were obtained.
- the content of each component in the obtained resin composition was quantified using the above quantification method.
- the resin composition of Comparative Examples 7, 9, and 10 was prepared so that the content of each component was as described in Table 4 by adjusting the concentration of each component in the aqueous solution for immersion treatment.
- saturated ketone (B-2) was less than the lower limit of detection.
- a single layer film is produced by continuous operation under the above conditions, 20 g of each film produced after 8 hours and 15 hours from the start of operation is sampled, put into a 100 mL glass sample tube, and a lid is put on the mouth with aluminum foil. Then, it was heated in a hot air dryer at 220 ° C. for 30 minutes. After removing from the dryer and allowing to cool at room temperature for 30 minutes, the sample tube was shaken 2-3 times, and then the lid of the aluminum foil was removed to confirm the odor. The odor intensity of the film was evaluated according to the following criteria. A: Do not feel odor B: Feel weak odor C: Clearly feel odor
- Example 22 Using a seven-layer coextrusion cast film forming facility equipped with the following four types of extruders, a coextrusion film forming test of a multilayer film as a multilayer structure was performed.
- Extruder for outer layer polyolefin (1): single screw, screw diameter 65 mm, L / D 22
- Extruder for polyolefin (2): single screw, screw diameter 40mm, L / D 26
- Polypropylene (hereinafter referred to as “PP”) is supplied to the extruder (1) and the extruder (2), and a maleic anhydride-modified polypropylene adhesive resin (“ADMER QF-” manufactured by Mitsui Chemicals, Inc.) is supplied to the extruder (3).
- ADMER QF- maleic anhydride-modified polypropylene adhesive resin
- 500 the resin composition obtained in Example 1 was supplied to the extruder (4), and co-extrusion film formation was performed to obtain a multilayer film having a seven-layer structure with a total thickness of 100 ⁇ m.
- the extrusion temperature is 200 to 250 ° C. for the extruder (1), 200 to 250 ° C. for the extruder (2), 160 to 250 ° C. for the extruder (3), and 170 to 250 for the extruder (4).
- the temperature was set to 250 ° C. for the feed block and the die.
- Example 6 A multilayer film was prepared in the same manner as in Example 22 except that the resin composition of Comparative Example 5 was used instead of the resin composition of Example 1, and the multilayer film 10 hours after the start of film formation was sampled. When the appearance of this multilayer film was observed, many appearance marks due to EVOH aggregation and many flow marks due to flow abnormalities were observed.
- Example 44 A multilayer film was prepared in the same manner as in Example 22 except that the resin composition of Example 23 was used instead of the resin composition of Example 1, and the multilayer film 10 hours after the start of film formation was sampled. When the appearance of this multilayer film was observed, the appearance defect due to aggregation of EVOH and the flow mark due to flow abnormality were hardly observed, and a multilayer film having no practical problem was obtained.
- Example 12 A multilayer film was prepared in the same manner as in Example 22 except that the resin composition of Comparative Example 11 was used instead of the resin composition of Example 1, and the multilayer film 10 hours after the start of film formation was sampled. When the appearance of this multilayer film was observed, many appearance marks due to EVOH aggregation and many flow marks due to flow abnormalities were observed.
- the resin composition of the present invention can suppress generation of defects and coloration during melt molding, it can provide a molded product having excellent appearance. Further, the resin composition is excellent in long-run property because defects and odor are hardly generated even after long-time melt molding. Therefore, the said resin composition is shape
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Abstract
Description
当該樹脂組成物は、EVOH(A)及び飽和カルボニル化合物(B)を含有する。この飽和カルボニル化合物(B)は、飽和アルデヒド(B-1)、飽和ケトン(B-2)又はこれらの組み合わせである。また、当該樹脂組成物は、好適成分として、ホウ素化合物、共役ポリエン化合物、酢酸類及びリン化合物をさらに含有していてもよい。当該樹脂組成物は、本発明の効果を損なわない限り、その他の任意成分を含有していてもよい。以下、EVOH(A)、飽和カルボニル化合物(B)、ホウ素化合物、共役ポリエン化合物、酢酸類、リン化合物及びその他の任意成分について詳述する。
EVOH(A)は、エチレンとビニルエステルとの共重合体をケン化したエチレン-ビニルアルコール共重合体である。
飽和カルボニル化合物(B)は、飽和アルデヒド(B-1)及び飽和ケトン(B-2)のいずれか又は両方であり、溶融成形によるストリーク、フィッシュアイ等の欠陥の発生及び着色を抑制すると共にロングラン性を改善するものである。ここで飽和カルボニル化合物(B)とは、カルボニル基以外の部分に不飽和結合を含まない化合物のことをいう。
飽和環状ケトンとしては、例えばシクロブタノン、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、シクロオクタノン等が挙げられる。
ホウ素化合物は、溶融成形時のゲル化を抑制すると共に押出成形機等のトルク変動(加熱時の粘度変化)を抑制するものである。上記ホウ素化合物としては、例えば
オルトホウ酸、メタホウ酸、四ホウ酸等のホウ酸類;
ホウ酸トリエチル、ホウ酸トリメチル等のホウ酸エステル;
上記ホウ酸類のアルカリ金属塩及びアルカリ土類金属塩、ホウ砂等のホウ酸塩;
水素化ホウ素類などが挙げられる。これらの中でも、ホウ酸類が好ましく、オルトホウ酸(以下、「ホウ酸」ともいう)がより好ましい。当該樹脂組成物におけるホウ素化合物の含有量の下限としては、100ppmが好ましく、150ppmがより好ましい。ホウ素化合物の含有量の上限としては、5,000ppmが好ましく、4,000ppmがより好ましく、3,000ppmがさらに好ましい。ホウ素化合物の含有量が上記下限未満であると、押出成形機等のトルク変動を十分に抑制することができないおそれがある。一方、ホウ素化合物の含有量が上記上限を超えると、溶融成形時にゲル化を起こし易くなり成形品の外観が悪化するおそれがある。
共役ポリエン化合物は、溶融成形時の酸化劣化を抑制するものである。ここで、共役ポリエン化合物とは、炭素-炭素二重結合と炭素-炭素単結合が交互に繋がってなる構造を有し、炭素-炭素二重結合の数が2個以上である、いわゆる共役二重結合を有する化合物である。この共役ポリエン化合物は、共役二重結合を2個有する共役ジエン、3個有する共役トリエン、又はそれ以上の数を有する共役ポリエンであってもよい。また、上記共役二重結合が互いに共役せずに1分子中に複数組あってもよい。例えば桐油のように共役トリエン構造が同一分子内に3個ある化合物も上記共役ポリエン化合物に含まれる。
酢酸類は、成形品の着色を防止すると共に溶融成形時のゲル化を抑制するものである。この酢酸類は、酢酸及び酢酸塩を含む。酢酸類としては、酢酸及び酢酸塩(酢酸ナトリウム、酢酸カリウム等)を併用することが好ましく、酢酸及び酢酸ナトリウムを併用することがより好ましい。
リン化合物は、ストリーク、フィッシュアイ等の欠陥の発生及び着色を抑制すると共に、ロングラン性を向上させるものである。このリン化合物としては、例えばリン酸、亜リン酸等のリン酸塩などが挙げられる。上記リン酸塩としては、第一リン酸塩、第二リン酸塩及び第三リン酸塩のいずれの形でもよい。また、リン酸塩のカチオン種についても特に限定されるものではないが、アルカリ金属塩及びアルカリ土類金属塩が好ましく、これらのうちリン酸二水素ナトリウム、リン酸二水素カリウム、リン酸水素二ナトリウム及びリン酸水素二カリウムがより好ましく、リン酸二水素ナトリウム及びリン酸水素二カリウムがさらに好ましい。当該樹脂組成物におけるリン化合物の含有量の下限としては、1ppmが好ましく、2ppmがより好ましく、3ppmがさらに好ましく、5ppmが特に好ましい。リン化合物の含有量の上限としては、200ppmが好ましく、150ppmがより好ましく、100ppmがさらに好ましい。リン化合物の含有量が上記下限未満である場合、又は上記上限を超える場合、熱安定性が低減し、長時間にわたる溶融成形を行なう際のゲル状ブツの発生、着色が生じ易くなるおそれがある。
当該樹脂組成物は、本発明の効果を損なわない範囲で、その他の任意成分を含有していてもよい。その他の任意成分としては、例えばアルカリ金属、酸化防止剤、紫外線吸収剤、可塑剤、帯電防止剤、滑剤、着色剤、充填剤、熱安定剤、他の樹脂、高級脂肪族カルボン酸の金属塩等が挙げられる。当該樹脂組成物は、これらの任意成分を2種以上含有してもよく、任意成分の合計含有量としては、当該樹脂組成物中の1質量%以下が好ましい。
当該樹脂組成物の製造方法としては、EVOH(A)中に飽和カルボニル化合物(B)を均一にブレンドでき、最終的に得られる樹脂組成物に飽和カルボニル化合物(B)を0.01ppm以上100ppm以下含有させられる方法であれば特に限定されない。当該樹脂組成物は、例えばエチレンとビニルエステルとを共重合させる工程(以下、「工程(1)」ともいう)、及びこの工程(1)により得られる共重合体をケン化する工程(以下、「工程(2)」ともいう)を備える製造方法により得ることができる。
当該樹脂成形体は、当該樹脂組成物から形成される。この樹脂成形体としては、例えばフィルム、シート、容器、パイプ、ホース、繊維、包装材等が挙げられる。フィルムとは、通常300μm未満の厚みを有するものをいい、シートとは、通常300μm以上の厚みを有するものをいう。当該樹脂成形体は、例えば溶融成形により形成され、必要に応じて、二次加工成形を行うことで形成される。この溶融成形の方法としては、例えば押出成形、インフレーション押出、ブロー成形、溶融紡糸、射出成形、射出ブロー成形等が挙げられる。溶融成形温度としては、EVOH(A)の融点等により異なるが、150℃以上270℃以下が好ましい。上記二次加工成形としては、例えば曲げ加工、真空成形、ブロー成形、プレス成形等が挙げられる。
当該多層構造体は、当該樹脂組成物から形成される層(以下、「樹脂組成物層」ともいう)を含む。当該多層構造体の層構成は、特に限定されるものではないが、熱可塑性樹脂から形成される層(以下、「熱可塑性樹脂層」ともいう)を含むことが好ましく、この熱可塑性樹脂層が上記樹脂組成物層に隣接することがより好ましい。熱可塑性樹脂層は、接着性樹脂層として構成することもできる。この接着性樹脂層は、他の樹脂層同士を接着するものであり、他の樹脂層よりも融点又は軟化点が低い層である。
高密度、中密度又は低密度のポリエチレン;
酢酸ビニル、アクリル酸エステル、又はブテン、ヘキセン等のα-オレフィン類を共重合したポリエチレン;
アイオノマー樹脂;
ポリプロピレンホモポリマー;
エチレン、ブテン、ヘキセン等のα-オレフィン類を共重合したポリプロピレン;
ゴム系ポリマーをブレンドした変性ポリプロピレン等のポリオレフィン類;
これらの樹脂に無水マレイン酸を付加又はグラフトした樹脂;
ポリエステルが好ましい。
熱可塑性樹脂層/樹脂組成物層/熱可塑性樹脂層;
樹脂組成物層/熱可塑性樹脂層(接着性樹脂層)/熱可塑性樹脂層;
熱可塑性樹脂層/熱可塑性樹脂層(接着性樹脂層)/樹脂組成物層/熱可塑性樹脂層(接着性樹脂層)/熱可塑性樹脂層等が挙げられる。当該多層構造体が複数の熱可塑性樹脂層を含む場合、複数の熱可塑性樹脂層は互いに異なる樹脂からなる層であってもよいし、同一の樹脂からなる層であってもよい。
メトラー・トレド社のハロゲン水分率分析装置「HR73」を用い、乾燥温度180℃、乾燥時間20分、サンプル量約10gの条件で、含水EVOHペレットの含水率を測定した。以下に示す含水EVOHの含水率は、EVOHの乾燥質量基準の質量%である。
核磁気共鳴装置(日本電子社の「超伝導核磁気共鳴装置 Lambda500」)を用い、DMSO-d6を測定溶媒として、1H-NMRにより求めた。
乾燥EVOHペレットを凍結粉砕により粉砕した。得られた粉砕EVOHを、呼び寸法1mmのふるい(JIS規格Z8801-1~3準拠)で分けた。上記ふるいを通過したEVOH粉末10gとイオン交換水50mLを共栓付き100mL三角フラスコに投入し、冷却コンデンサーを付けて、95℃で10時間撹拌した。得られた溶液2mLを、イオン交換水8mLで希釈した。この希釈溶液について、横河電機社のイオンクロマトグラフィー「ICS-1500」を用い、下記測定条件に従って酢酸イオンの量を定量することで、酢酸及び酢酸イオンの量を算出し、得られた算出値を酢酸及び酢酸塩の含有量とした。なお、定量に際しては酢酸を用いて作成した検量線を用いた。
(測定条件)
カラム :DIONEX社の「IonPAC ICE-AS1(9φ×250mm、電気伝導度検出器)」
溶離液 :1.0mmol/L オクタンスルホン酸水溶液
測定温度 :35℃
溶離液流速 :1mL/min
分析量 :50μL
乾燥EVOHペレット0.5gをアクタック社のポリテトラフルオロエチレン製耐圧容器に仕込み、和光純薬工業社の精密分析用硝酸5mLをさらに加えた。30分放置後、ラプチャーディスク付きキャップリップにて容器に蓋をし、アクタック社のマイクロウェーブ高速分解システム「スピードウェーブ MWS-2」にて150℃10分、次いで180℃10分処理し、乾燥EVOHペレットを分解させた。乾燥EVOHペレットの分解が完了できていない場合は、処理条件を適宜調節した。得られた分解物を10mLのイオン交換水で希釈し、すべての液を50mLのメスフラスコに移し取り、イオン交換水で定容し、分解物溶液を得た。
Na :589.592nm
K :766.490nm
Mg :285.213nm
Ca :317.933nm
P :214.914nm
B :249.667nm
Si :251.611nm
Al :396.153nm
Zr :343.823nm
Ce :413.764nm
W :207.912nm
Mo :202.031nm
50質量%の2,4-ジニトロフェニルヒドラジン(DNPH)溶液200mgに、1,1,1,3,3,3-ヘキサフルオロイソプロパノール(HFIP)50mL、酢酸11.5mL及びイオン交換水8mLを添加し、DNPH調整溶液を作製した。その後、乾燥樹脂組成物ペレット1gをDNPH調整溶液20mLに添加し、35℃にて1時間攪拌溶解させた。この溶液にアセトニトリルを添加してEVOH(A)を沈降させ、溶液を濾過、濃縮し、抽出サンプルを得た。この抽出サンプルを高速液体クロマトグラフィーにて定量分析することで飽和カルボニル化合物(B)(飽和アルデヒド(B-1)又は飽和ケトン(B-2))の量を定量した。なお、定量に際しては、それぞれの飽和カルボニル化合物(B)をDNPH調製溶液と反応させて得た標品を用いて作成した検量線を使用した。
カラム:TSKgel ODS-80Ts(東ソー社)
移動相:水/アセトニトリル=52:48(体積比)
検出器:フォトダイオードアレイ検出器(360nm)、TOF-MS
乾燥樹脂組成物ペレットを凍結粉砕により粉砕し、呼び寸法0.150mm(100メッシュ)のふるい(JIS規格Z8801-1~3準拠)によって粗大粒子を除去して得た粉砕物10gをソックスレー抽出器に充填し、クロロホルム100mLを用いて48時間抽出処理した。この抽出液中の共役ポリエン化合物の量を高速液体クロマトグラフィーにて定量分析することで、共役ポリエン化合物の量を定量した。なお、定量に際しては、それぞれの共役ポリエン化合物の標品を用いて作成した検量線を使用した。
[合成例1]
250Lの加圧反応槽を用いて以下の条件で重合を実施し、エチレン-酢酸ビニル共重合体を合成した。
(仕込み量)
酢酸ビニル83.0kg
メタノール26.6kg
2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)(2.5g/Lメタノール溶液)の供給量 1119.5mL/hr
(重合条件)
重合温度 60℃
重合槽エチレン圧力 3.6MPa
重合時間 5.0時間
重合時にプロパナール濃度が0.5ppmとなるようにプロパナールを供給した以外は合成例1と同様にして重合、ケン化、ペレット化及び洗浄を行ってペレットを得た。
重合時にアセトン濃度が0.5ppmとなるようにアセトンを供給した以外は合成例1と同様にして重合、ケン化、ペレット化及び洗浄を行ってペレットを得た。
[実施例1~9、12~18、21及び比較例2]
上記合成例1で脱液して得られたペレット20kgを、180kgの水/メタノール=40/60(質量比)の混合溶媒に入れ、60℃で6時間攪拌し完全に溶解させた。得られた溶液に飽和アルデヒド(B-1)、及び共役ポリエン化合物を添加し、さらに1時間攪拌して飽和アルデヒド(B-1)及び共役ポリエン化合物を完全に溶解させ、樹脂組成物溶液を得た。この樹脂組成物溶液を直径4mmのノズルより、0℃に調整した水/メタノール=90/10(質量比)の凝固浴中に連続的に押出してストランド状に凝固させた。このストランドをペレタイザーに導入して多孔質の樹脂組成物チップを得た。得られた多孔質の樹脂組成物チップを酢酸水溶液及びイオン交換水を用いて洗浄した後、酢酸、酢酸ナトリウム、リン酸二水素カリウム及びホウ酸を含む水溶液で浸漬処理を行った。この浸漬処理用水溶液と樹脂組成物チップとを分離して脱液した後、熱風乾燥機に入れて80℃で4時間乾燥を行い、さらに100℃で16時間乾燥を行って、樹脂組成物(乾燥樹脂組成物ペレット)を得た。得られた樹脂組成物における各成分の含有量は、上記定量方法を用いて定量した。なお、飽和アルデヒド(B-1)の添加量、浸漬処理用水溶液の各成分の濃度を調節することにより、各成分の含有量が表1及び表2に記載の通りとなるように樹脂組成物を調製した。
共役ポリエン化合物としてソルビン酸に代えてミルセンを用いた以外は実施例1と同様とし、樹脂組成物ペレットを調製した。
共役ポリエン化合物としてソルビン酸に代えてソルビン酸カリウムを用いた以外は実施例1と同様とし、樹脂組成物ペレットを調製した。
飽和アルデヒドとしてプロパナールに代えてブタナールを用いた以外は実施例1と同様とし、樹脂組成物ペレットを調製した。
飽和アルデヒドとしてプロパナールに代えてヘキサナールを用いた以外は実施例1と同様とし、樹脂組成物ペレットを調製した。
上記合成例2で得られたペレット20kgを180kgの水/メタノール=40/60(質量比)の混合溶媒に入れ、60℃で6時間攪拌し完全に溶解させた。得られた溶液に共役ポリエン化合物としてソルビン酸を添加し、さらに1時間攪拌してソルビン酸を完全に溶解させ、樹脂組成物溶液を得た。この樹脂組成物溶液を直径4mmのノズルより、0℃に調整した水/メタノール=90/10(質量比)の凝固浴中に連続的に押出してストランド状に凝固させた。このストランドをペレタイザーに導入して多孔質の樹脂組成物チップを得た。得られた多孔質の樹脂組成物チップを酢酸水溶液及びイオン交換水を用いて洗浄した後、酢酸、酢酸ナトリウム、リン酸二水素カリウム及びホウ酸を含む水溶液で浸漬処理を行った。この浸漬処理用水溶液と樹脂組成物チップを分離して脱液した後、熱風乾燥機に入れて80℃で4時間乾燥を行い、さらに100℃で16時間乾燥を行って、樹脂組成物(乾燥樹脂組成物ペレット)を得た。得られた樹脂組成物における各成分の含有量は、上記定量方法を用いて定量した。なお、浸漬処理用水溶液の各成分の濃度を調節することにより、各成分の含有量が表2に記載の通りとなるように比較例1,3,4の樹脂組成物を調製した。ここで、飽和アルデヒド(B-1)は検出下限未満であった。
飽和アルデヒドを用いなかった以外は実施例1と同様とし、樹脂組成物ペレットを調製した。
上記合成例1で脱液して得られたペレット20kgを、180kgの水/メタノール=40/60(質量比)の混合溶媒に入れ、60℃で6時間攪拌し完全に溶解させた。得られた溶液に飽和ケトン(B-2)、及び共役ポリエン化合物を添加し、さらに1時間攪拌して飽和ケトン(B-2)及び共役ポリエン化合物を完全に溶解させ、樹脂組成物溶液を得た。この樹脂組成物溶液を直径4mmのノズルより、0℃に調整した水/メタノール=90/10(質量比)の凝固浴中に連続的に押出してストランド状に凝固させた。このストランドをペレタイザーに導入して多孔質の樹脂組成物チップを得た。得られた多孔質の樹脂組成物チップを酢酸水溶液及びイオン交換水を用いて洗浄した後、酢酸、酢酸ナトリウム、リン酸二水素カリウム及びホウ酸を含む水溶液で浸漬処理を行った。この浸漬処理用水溶液と樹脂組成物チップとを分離して脱液した後、熱風乾燥機に入れて80℃で4時間乾燥を行い、さらに100℃で16時間乾燥を行って、樹脂組成物(乾燥樹脂組成物ペレット)を得た。得られた樹脂組成物における各成分の含有量は、上記定量方法を用いて定量した。なお、飽和ケトン(B-2)の添加量、浸漬処理用水溶液の各成分の濃度を調節することにより、各成分の含有量が表3及び表4に記載の通りとなるように樹脂組成物を調製した。
共役ポリエン化合物としてソルビン酸に代えてミルセンを用いた以外は実施例23と同様とし、樹脂組成物ペレットを調製した。
共役ポリエン化合物としてソルビン酸に代えてソルビン酸カリウムを用いた以外は実施例23と同様とし、樹脂組成物ペレットを調製した。
飽和ケトンとしてアセトンに代えてメチルエチルケトンを用いた以外は実施例23と同様とし、樹脂組成物ペレットを調製した。
飽和ケトンとしてアセトンに代えて2-ヘキサノンを用いた以外は実施例23と同様とし、樹脂組成物ペレットを調製した。
上記合成例3で得られたペレット20kgを180kgの水/メタノール=40/60(質量比)の混合溶媒に入れ、60℃で6時間攪拌し完全に溶解させた。得られた溶液に共役ポリエン化合物としてソルビン酸を添加し、さらに1時間攪拌してソルビン酸を完全に溶解させ、樹脂組成物溶液を得た。この樹脂組成物溶液を直径4mmのノズルより、0℃に調整した水/メタノール=90/10(質量比)の凝固浴中に連続的に押出してストランド状に凝固させた。このストランドをペレタイザーに導入して多孔質の樹脂組成物チップを得た。得られた多孔質の樹脂組成物チップを酢酸水溶液及びイオン交換水を用いて洗浄した後、酢酸、酢酸ナトリウム、リン酸二水素カリウム及びホウ酸を含む水溶液で浸漬処理を行った。この浸漬処理用水溶液と樹脂組成物チップを分離して脱液した後、熱風乾燥機に入れて80℃で4時間乾燥を行い、さらに100℃で16時間乾燥を行って、樹脂組成物(乾燥樹脂組成物ペレット)を得た。得られた樹脂組成物における各成分の含有量は、上記定量方法を用いて定量した。なお、浸漬処理用水溶液の各成分の濃度を調節することにより、各成分の含有量が表4に記載の通りとなるように比較例7、9、10の樹脂組成物を調製した。ここで、飽和ケトン(B-2)は検出下限未満であった。
飽和ケトンを用いなかった以外は実施例23と同様とし樹脂組成物ペレットを調製した。
上記得られた樹脂組成物について、成形時の臭気、ロングラン性、フィルム外観、溶液外観及びモータートルク変動を以下の方法に従い評価した。評価結果を表1~表4に示す。
単軸押出装置(東洋精機製作所社の「D2020」;D(mm)=20、L/D=20、圧縮比=2.0、スクリュー:フルフライト)を用い、下記条件に従い、各乾燥樹脂組成物ペレットから厚さ20μmの単層フィルムを作製した。
(試験条件)
押出温度:220℃
スクリュー回転数:40rpm
ダイス幅:30cm
引取りロール温度:80℃
引取りロール速度:3.1m/分
A: 臭気を感じない
B: 弱い臭気を感じる
C: 明らかに臭気を感じる
成形時の臭気の評価と同様にして運転開始から8時間後及び15時間後に作製された各フィルムについて、フィルム長17cm当たりの欠点数をカウントした。上記欠点数のカウントは、フィルム欠点検査装置(フロンティアシステム社の「AI-10」)を用いて行った。なお、上記装置における検出カメラは、そのレンズ位置がフィルム面より195mmの距離となるように設置した。各樹脂組成物のロングラン性は、以下の基準で評価した。
A(良好):欠点数が50個未満
B(やや良好):欠陥数が50個以上200個未満
C(不良):欠陥数が200個以上
成形時の臭気の評価と同様にして運転開始から8時間後及び15時間後に作製された各フィルムをロール状とし、このロールの端部の着色を確認した。各樹脂組成物のロール端部の着色は、以下の基準で評価した。
A(良好):ロール端部に着色が認められない
B(やや良好):ロール端部に着色が認められるが、製品として問題がない
C(不良):ロール端部に明らかな着色が認められる
成形時の臭気の評価と同様にして運転開始から15時間後に作製されたフィルムについて、目視にて外観を確認した。フィルム外観は、以下の基準でストリーク及び着色のそれぞれについて評価した。
A(良好):ストリークは認められなかった
B(やや良好):ストリークが確認された
C(不良):多数のストリークが確認された
A(良好):無色
B(やや良好):黄変
C(不良):著しく黄変
乾燥樹脂組成物ペレットを空気中120℃で15時間熱処理したペレット10gを300mLの三角フラスコに取り、水/プロパノール混合溶液(質量比:水/プロパノール=45/55)100mLを加え、75℃で3時間攪拌し、目視にて溶液を確認した。溶液外観は、以下の基準で溶液の透明性及び着色のそれぞれについて評価した。
A(良好):透明(目視で確認できる浮遊物なし)
B(やや良好):やや白濁(目視で確認できる浮遊物あり)
C(不良):白濁(浮遊物あり)
A(良好):無色
B(やや良好):やや着色
C(不良):著しく着色
乾燥樹脂組成物ペレット60gをラボプラストミル(東洋精機製作所社の「20R200」;二軸異方向)100rpm、260℃で混練し、混練開始から5分後のトルク値が1.5倍になるまでの所要時間を測定することで行った。モータートルク変動は、以下の基準で評価した。なお、加熱状態での樹脂組成物の粘度は、二次加工時のロングラン性に影響する要因である。
A(良好):60分以上
B(やや良好):40分以上60分未満
C(不良):40分未満
[実施例22]
下記4種の押出機を備える7層共押出キャスト製膜設備を用いて、多層構造体としての多層フィルムの共押出製膜試験を実施した。
ポリオレフィン用押出機(2) :単軸、スクリュー直径40mm、L/D=26
接着性樹脂用押出機(3) :単軸、スクリュー直径40mm、L/D=22
EVOH用押出機(4) :単軸、スクリュー直径40mm、L/D=26
実施例1の樹脂組成物に代えて比較例5の樹脂組成物を用いた以外は実施例22と同様にして多層フィルムを作成し、製膜開始から10時間後の多層フィルムをサンプリングした。この多層フィルムについて外観を観察したところ、EVOHの凝集による外観不良及び流動異常によるフローマークが多数観察された。
実施例1の樹脂組成物に代えて実施例23の樹脂組成物を用いた以外は実施例22と同様にして多層フィルムを作成し、製膜開始から10時間後の多層フィルムをサンプリングした。この多層フィルムについて外観を観察したところ、EVOHの凝集による外観不良及び流動異常によるフローマークがほとんど認められず、実用上問題のない多層フィルムが得られた。
実施例1の樹脂組成物に代えて比較例11の樹脂組成物を用いた以外は実施例22と同様にして多層フィルムを作成し、製膜開始から10時間後の多層フィルムをサンプリングした。この多層フィルムについて外観を観察したところ、EVOHの凝集による外観不良及び流動異常によるフローマークが多数観察された。
Claims (10)
- エチレン-ビニルアルコール共重合体(A)及び炭素数が3以上8以下である飽和カルボニル化合物(B)を含有し、
上記飽和カルボニル化合物(B)が飽和アルデヒド(B-1)、飽和ケトン(B-2)又はこれらの組み合わせであり、
上記飽和カルボニル化合物(B)の含有量が0.01ppm以上100ppm以下である樹脂組成物。 - 上記飽和カルボニル化合物(B)が上記飽和アルデヒド(B-1)であり、上記飽和アルデヒド(B-1)がプロパナール、ブタナール、ヘキサナール又はこれらの組み合わせである請求項1に記載の樹脂組成物。
- 上記飽和カルボニル化合物(B)が上記飽和ケトン(B-2)であり、上記飽和ケトン(B-2)がアセトン、メチルエチルケトン、2-ヘキサノン又はこれらの組み合わせである請求項1に記載の樹脂組成物。
- ホウ素化合物をさらに含有し、
上記ホウ素化合物の含有量が100ppm以上5,000ppm以下である請求項1に記載の樹脂組成物。 - 共役ポリエン化合物をさらに含有し、
上記共役ポリエン化合物の含有量が0.01ppm以上1,000ppm以下である請求項1に記載の樹脂組成物。 - 上記共役ポリエン化合物がソルビン酸、ソルビン酸塩又はこれらの組み合わせである請求項5に記載の樹脂組成物。
- 酢酸及び酢酸塩のうちの少なくとも一方をさらに含有し、
上記酢酸及び酢酸塩の合計含有量が50ppm以上1,000ppm以下である請求項1に記載の樹脂組成物。 - リン化合物をさらに含有し、
上記リン化合物の含有量が1ppm以上200ppm以下である請求項1に記載の樹脂組成物。 - 請求項1から請求項8のいずれか1項に記載の樹脂組成物から形成される樹脂成形体。
- 請求項1から請求項8のいずれか1項に記載の樹脂組成物から形成される層を含む多層構造体。
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CN201480054584.9A CN105579525B (zh) | 2013-10-02 | 2014-10-02 | 树脂组合物、树脂成型体和多层结构体 |
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