WO2015163437A1 - エチレン-ビニルアルコール樹脂組成物、成形体および多層構造体 - Google Patents
エチレン-ビニルアルコール樹脂組成物、成形体および多層構造体 Download PDFInfo
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- WO2015163437A1 WO2015163437A1 PCT/JP2015/062482 JP2015062482W WO2015163437A1 WO 2015163437 A1 WO2015163437 A1 WO 2015163437A1 JP 2015062482 W JP2015062482 W JP 2015062482W WO 2015163437 A1 WO2015163437 A1 WO 2015163437A1
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- resin composition
- containing compound
- hydroxyl group
- molecular weight
- evoh
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Classifications
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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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
Definitions
- the present invention provides a resin composition having a high oxygen barrier property, a low glass transition temperature, and a high flexibility without bleeding out of a hydroxyl group-containing compound, a molded body using the same, and a layer comprising the resin composition. It is related with the multilayer structure containing.
- Ethylene-vinyl alcohol copolymer is a crystalline polymer that combines the excellent gas barrier properties and organic solvent resistance of polyvinyl alcohol with the hot melt moldability and water resistance characteristic of polyethylene.
- EP2 286 658 discloses an example in which a plurality of types of EVOH resins are blended and applied to a film.
- the film disclosed in Patent Document 1 is considered to have poor elongation and is inferior in transparency.
- Patent Document 2 discloses a film having a barrier layer based on EVOH resin and added with a plasticizer.
- plasticizers used in EVOH resins are propanediol, butanediol, pentanediol, propanetriol, glycerol, etc., and bleedout occurs at high temperature and high humidity due to its low melting point. (Normally, the mobility of the EVOH resin chain increases under high humidity, so that the plasticizer can move easily and bleed out.) There is a disadvantage that the performance decreases during storage.
- the present invention has been made in order to solve the above-mentioned problems.
- the object of the present invention is to prevent bleed out, high oxygen barrier properties (low oxygen permeability), and a glass transition temperature. It is to provide a low and highly flexible resin molded article and a resin composition therefor.
- the present invention is a resin composition
- a resin composition comprising an ethylene-vinyl alcohol copolymer (A) and a hydroxyl group-containing compound (B), wherein the hydroxyl group-containing compound (B) has a molecular weight of 200 or less,
- the ratio of the number of hydroxyl groups is in the range of 0.02 to 0.03, the melting point is 23 ° C. or higher, and the content of the hydroxyl group-containing compound (B) is 3 to 15% by mass with respect to the resin composition. It is characterized by.
- the hydroxyl group-containing compound (B) preferably has a melting point of 23 ° C. or higher and 200 ° C. or lower.
- the ratio of the number of hydroxyl groups in one molecule to the molecular weight of the hydroxyl group-containing compound (B) is preferably in the range of 0.021 to 0.025.
- the hydroxyl group-containing compound (B) is preferably 1,1,1-trimethylolpropane.
- the content of the hydroxyl group-containing compound (B) is preferably 5 to 10% by mass with respect to the resin composition.
- the ethylene content of the ethylene-vinyl alcohol copolymer (A) is preferably in the range of 20 to 60 mol%.
- the present invention also provides a molded body comprising the above-described resin composition of the present invention.
- the present invention further provides a multilayer structure including at least one layer comprising the above-described resin composition of the present invention.
- a resin that does not cause bleed out has a high oxygen barrier property (low oxygen permeability), a low glass transition temperature, and a highly flexible resin molded product (molded product).
- a multilayer structure including a composition, a molded body using the composition, and a layer composed of the resin composition can be provided.
- the resin composition of the present invention basically comprises an ethylene-vinyl alcohol copolymer (EVOH resin) (A) and a hydroxyl group-containing compound (B).
- EVOH resin ethylene-vinyl alcohol copolymer
- B hydroxyl group-containing compound
- EVOH resin ethylene-vinyl alcohol copolymer (A)
- the ethylene-vinyl alcohol copolymer (EVOH resin) (A) as the main component of the resin composition of the present invention is a copolymer mainly having ethylene units and vinyl alcohol units.
- EVOH (A) is obtained, for example, by saponifying a copolymer composed of ethylene and vinyl ester using an alkali catalyst or the like.
- a typical vinyl ester is vinyl acetate, but other fatty acid vinyl esters (such as vinyl propionate and vinyl pivalate) can also be used.
- EVOH (A) may contain other comonomers such as propylene, butylene, unsaturated carboxylic acid or ester thereof, vinylsilane compounds, and N-vinylpyrrolidone as long as the object of the present invention is not hindered. It can also be copolymerized.
- the lower limit of the ethylene content of EVOH (A) is preferably 20 mol%, more preferably 25 mol%, and particularly preferably 40 mol%.
- the upper limit value of the ethylene content of EVOH (A) is preferably 60 mol%, more preferably 55 mol%, and particularly preferably 50 mol%. If the ethylene content is less than 20 mol%, the melt moldability of the resin composition may deteriorate. On the other hand, when the ethylene content exceeds 60 mol%, the oxygen barrier property of the obtained molded article may be lowered.
- the saponification degree of EVOH (A) is preferably 90 mol% or more, more preferably 95 mol% or more, and more preferably 99 mol% or more from the viewpoint of maintaining the oxygen barrier property of the obtained molded article. It is particularly preferred that
- the amount of 1,2-glycol bonds in EVOH (A) is preferably less than 1.8 mol% and less than 1.5 mol% from the viewpoint of thermal stability during melt molding of the resin composition. Is more preferable, and it is further more preferable that it is less than 1.0 mol%.
- a method in which the amount of 1,2-glycol bond is controlled by the polymerization temperature is the simplest and preferable.
- the polymerization is preferably carried out at 40 to 120 ° C, more preferably 50 to 100 ° C.
- the 1,2-glycol bond amount is represented by the ratio of monomer units that contributed to the bond to all monomer units.
- the lower limit of the melt flow rate (MFR) under a load of 210 ° C. and 2160 g is preferably 1.0 g / 10 minutes, and preferably 2.0 g / 10 minutes. More preferably, the upper limit is preferably 100 g / 10 minutes, and more preferably 60 g / 10 minutes.
- EVOH (A) can be used alone or in combination of two or more.
- the resin composition of the present invention basically contains a hydroxyl group-containing compound (B), and this hydroxyl group-containing compound (B) has the following requirements.
- ⁇ Molecular weight is 200 or less, The ratio of the number of hydroxyl groups in one molecule to the molecular weight is in the range of 0.02 to 0.03, -Melting point is 23 ° C or higher -The content is 3 to 15 mass% with respect to the resin composition.
- the oxygen barrier property is high (the oxygen permeability is low) and the bleed is proved in Examples described later. It is possible to provide a resin composition capable of realizing a resin molded body (molded body) that does not cause out, has a low glass transition temperature, and has high flexibility. This is considered to be because the hydroxyl group-containing compound (B) having the above requirements acts as a plasticizer for EVOH (A).
- the hydroxyl group-containing compound is not generally used as a plasticizer, but in the case of EVOH (A), the hydroxyl group of the hydroxyl group-containing compound interacts with the hydroxyl group of EVOH (A), and the EVOH (A) chains It is considered that the hydroxyl group-containing compound (B) enters into the chain to facilitate the movement of the chain, thereby acting as a plasticizer. Therefore, the compound that acts as a plasticizer on EVOH (A) needs to contain a hydroxyl group.
- a hydroxyl group-containing compound (B) having a molecular weight of 200 or less is used as described above.
- Hydroxyl-containing compounds having a molecular weight exceeding 200 for example, 1,14-tetradecanediol (molecular weight: 230), 1,16-hexadecanediol (molecular weight: 258), ditrimethylolpropane (molecular weight: 250), dipentaerythritol (molecular weight: 254), tripentaerythritol (molecular weight: 372, etc.
- compatibility with EVOH (A) is deteriorated, phase separation occurs, and it does not function as a plasticizer.
- the molecular weight of the hydroxyl group-containing compound (B) is preferably 50, more preferably 75, as the lower limit because the compatibility with EVOH (A) is improved and it acts as a plasticizer.
- the upper limit value is preferably 180, more preferably 150.
- the molecular weight of a hydroxyl-containing compound (B) is calculated by adding the mass number of each component element.
- a hydroxyl group-containing compound (B) having a ratio of the number of hydroxyl groups in one molecule to the molecular weight (number of hydroxyl groups in one molecule / molecular weight) in the range of 0.02 to 0.03 is used.
- a hydroxyl group-containing compound having a ratio of (number of hydroxyl groups in one molecule / molecular weight) of less than 0.02 for example, ratio of 1,5-pentanediol ((number of hydroxyl groups in one molecule / molecular weight): 0.019), 1 , 6-hexanediol ((number of hydroxyl groups in one molecule / molecular weight) ratio: 0.017), 1,7-heptanediol (ratio of (number of hydroxyl groups in one molecule / molecular weight): 0.015), etc.
- the interaction between EVOH (A) and the hydroxyl group-containing compound (B) is lowered, and the effect as a plasticizer is not sufficient, so that the glass transition temperature of the obtained resin composition is increased. Or the tensile modulus of the obtained molded product is high. Further, in some cases, it is not sufficiently compatible with EVOH (A), so that it is inferior in tensile elongation at break or inferior in oxygen transmission rate (OTR: Oxygen Transmission Rate). There is a problem that can be done.
- the ratio of the hydroxyl group-containing compound for example, 1,2,3-propanetriol ((number of hydroxyl groups in one molecule / molecular weight)): 0.033 (the number of hydroxyl groups in one molecule / molecular weight) exceeds 0.03. ), Erythritol ((number of hydroxyl groups in one molecule / molecular weight ratio: 0.033), etc.) is used, the hydroxyl group-containing compound (B) inhibits crystallization of EVOH (A).
- the molded body is inferior in oxygen permeability.
- the lower limit of the ratio of (number of hydroxyl groups in one molecule / molecular weight) is 0.021 because a molded article having low oxygen permeability, low glass transition temperature, and high flexibility can be obtained.
- the upper limit is preferably 0.025, and more preferably 0.023.
- a hydroxyl group-containing compound (B) having a melting point (Tm) of 23 ° C. or higher is used.
- Hydroxyl-containing compounds having a melting point of less than 23 ° C. for example, 1,2-propylene glycol (melting point: ⁇ 59 ° C.), 1,4-propylene glycol (melting point: ⁇ 27 ° C.), 1,4-butanediol (melting point: 20 ), 1,5-pentanediol (melting point: ⁇ 18 ° C.), etc.
- the upper limit of the melting point of the hydroxyl group-containing compound (B) The value is preferably 200 ° C., more preferably 100 ° C.
- fusing point of a hydroxyl-containing compound (B) points out the value measured by the method based on JISK0064.
- the content of the hydroxyl group-containing compound (B) in the present invention is in the range of 3 to 15% by mass with respect to the resin composition.
- the content of the hydroxyl group-containing compound (B) is less than 3% by mass with respect to the resin composition, the effect as a plasticizer is not sufficient, so that the glass transition temperature becomes high, or the obtained molded article There is a problem that the tensile modulus of elasticity at room temperature increases.
- the content of the hydroxyl group-containing compound (B) exceeds 15% by mass with respect to the resin composition, the obtained molded product is inferior in oxygen permeability, or in some cases, inferior in tensile elongation at break. There is a problem that.
- the hydroxyl group-containing compound (B) is obtained because the resin composition that sufficiently exhibits the effect as a plasticizer, a resin composition having a low glass transition temperature is obtained, and a molded article that has high flexibility and can maintain low oxygen permeability is obtained.
- Content is preferably 4% by mass with respect to the resin composition, more preferably 5% by mass, and the upper limit is 10% by mass with respect to the resin composition. It is preferably 8% by mass.
- Examples of the hydroxyl group-containing compound (B) having the molecular weight, the ratio of (number of hydroxyl groups in one molecule / molecular weight) and the melting point include 1,1,1-trimethylolpropane and 1,1,1-trimethylol.
- Examples include ethane, trimethylol methane, tetramethylol methane (pentaerythritol), and the like.
- 1,1,1-trimethylolpropane and 1,1,1-trimethylolethane are preferable because a molded article having a low glass transition temperature and high flexibility can be obtained and low oxygen permeability is maintained. 1,1,1-trimethylolpropane is more preferable.
- the resin composition of the present invention is a known additive that is generally blended in EVOH (A), for example, heat, to the extent that the effects of the present invention are not impaired.
- Stabilizer, antioxidant, antistatic agent, colorant, UV absorber, lubricant, plasticizer, light stabilizer, surfactant, antibacterial agent, desiccant, antiblocking agent, flame retardant, crosslinking agent, curing agent, A foaming agent, a crystal nucleating agent, an antifogging agent, an additive for biodegradation, a silane coupling agent, an oxygen absorbent and the like may be added.
- the lower limit value of the glass transition temperature (Tg) of the resin composition of the present invention is preferably 10 ° C, more preferably 20 ° C, and the upper limit value is preferably 50 ° C. More preferably, it is ° C.
- Tg glass transition temperature
- the melting point (Tm) of the resin composition of the present invention is preferably 100 ° C. as the lower limit, more preferably 120 ° C., and the upper limit because the melt molding becomes easy. 200 ° C is preferable, and 180 ° C is more preferable.
- the present invention also provides a molded body comprising the above-described resin composition.
- a molded article of the present invention has high oxygen barrier properties (low oxygen permeability), no bleeding out, low glass transition temperature, and high flexibility.
- the molded product of the present invention may be 100 MPa as the lower limit of the tensile modulus (23 ° C., 50% RH, MD / TD) in a 20 ⁇ m single-layer film measured in accordance with JIS K 7161.
- the upper limit value is preferably 2000 MPa, and more preferably 1000 MPa.
- the molded product of the present invention may have a lower limit value of 20 MPa as a tensile breaking strength (23 ° C., 50% RH, MD / TD) in a 100 ⁇ m single layer film measured in accordance with JIS K 7161.
- the upper limit is 40 MPa.
- the molded product of the present invention has a lower limit value of tensile elongation at break (23 ° C., 50% RH, MD / TD) in a 100 ⁇ m single layer film measured in accordance with JIS K 7161.
- the upper limit is preferably 500%.
- the molded object of this invention is 3N as a lower limit of the puncture strength (23 degreeC, 50% RH) in the 20 micrometer single layer film measured based on prescription
- the value is preferably 5.0N.
- OTR oxygen transmission rate
- the molded body of the present invention can be produced by mixing each component by a known method such as a melt mixing method, a solution mixing method, or a mechanical mixing method, and molding the mixture by a known method.
- a melt mixing method each component is dry blended and then melted and mixed, for example, using a known melt kneading apparatus such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer, or a plast mill.
- a known melt kneading apparatus such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer, or a plast mill.
- it is industrially preferable to use a single-screw or twin-screw extruder and it is also preferable to provide a vent suction device, a gear pump device, a screen device, or the like, if necessary.
- the solution mixing method examples include a method in which each component is dissolved and mixed in a common good solvent and precipitated in a common poor solvent.
- the resin mixed by the melt mixing method or the solution mixing method can be used, for example, in a powder form, a spherical or cylindrical pellet form, a flake form, or the like.
- the present invention also provides a multilayer structure including at least one layer comprising the above-described resin composition of the present invention.
- the layer composed of the resin composition of the present invention in such a multilayer structure of the present invention preferably has the same tensile elastic modulus, tensile rupture strength, tensile rupture elongation, puncture strength as the above-described molded product of the present invention, Has oxygen permeability.
- the resin used as a layer other than the resin composition layer constituting the multilayer structure is not particularly limited, and a hydrophobic thermoplastic resin may be mentioned for the purpose of preventing the gas barrier performance of the resin composition from being lowered by moisture.
- polyolefin resins linear low density polyethylene, low density polyethylene, ultra low density polyethylene, ultra low density linear polyethylene, medium density polyethylene, polyethylene such as high density polyethylene, and ethylene- ⁇ -Polyethylene resins such as olefin copolymers, polypropylene resins such as polypropylene, ethylene-propylene (block and random) copolymers, propylene- ⁇ -olefin ( ⁇ -olefins having 4 to 20 carbon atoms) copolymers, Polybutene, polypentene, etc .; grafted polyolefin obtained by graft-modifying these polyolefins with unsaturated carboxylic acid or ester thereof, cyclic polyolefin resin; ion
- a multilayer structure combined with paper, metal foil, uniaxial or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metal strip, wood surface, aluminum or silica deposition Good.
- a layer obtained from the resin composition of the present invention is F
- a layer obtained from a hydrophobic thermoplastic resin is A
- a hydrophobic thermoplastic modified with an unsaturated carboxylic acid or a derivative thereof is represented by MA
- the following layer structure can be illustrated.
- the layer structure indicates that the left layer is the outer layer (side exposed to the external environment).
- the layer MA made of a hydrophobic thermoplastic resin modified with an unsaturated carboxylic acid or derivative thereof is used as an adhesive resin layer and also as an outer layer.
- Tm melting point
- Tg glass transition temperature
- Oxygen permeability (OTR) The obtained monolayer film having a thickness of 20 ⁇ m was conditioned under the condition of 20 ° C./85% RH, and then an oxygen permeability measuring device (OX-Tran 2/20 manufactured by Modern Control) was used in accordance with ISO 14663-2. The oxygen transmission rate (OTR) was measured under the conditions of 20 ° C./85% RH.
- EVOH resin having an ethylene content of 44 mol%, a saponification degree of 99 mol% or more, an MFR of 5.7 g / 10 min (210 ° C., 2160 g load), and a 1,2-glycol bond content of 0.46 mol% ( A ratio of 90% by mass (also referred to as “A1”) and 1,1,1-trimethylolpropane (molecular weight: 134, hydroxyl number: 3, (number of hydroxyl groups in one molecule / molecular weight)) as a hydroxyl group-containing compound: 022, melting point: 58 ° C.) (also referred to as “TMP”) 10% by mass, melt-kneaded and pelletized using a twin screw extruder by the above-described method, and heated at 80 ° C.
- a ratio of 90% by mass also referred to as “A1”
- 1,1,1-trimethylolpropane molecular weight
- TMP melting point: 58 ° C.
- the resin composition was obtained by drying for 6 hours. Subsequently, by using the obtained resin composition, single-layer extruders (molded bodies) having a thickness of 20 ⁇ m and 100 ⁇ m were prepared by the above-described method using a single screw extruder. The glass transition temperature of the obtained resin composition was measured by the method described above. Further, the obtained molded article was measured for the tensile elastic modulus, tensile breaking strength, tensile breaking elongation, puncture strength, oxygen permeability (OTR), and presence / absence of bleed-out by the methods described above. The results are shown in Table 1.
- Example 2> ethylene content is 32 mol%, saponification degree is 99 mol% or more, MFR is 4.4 g / 10 min (210 ° C, 2160 g load), 1,2-glycol bond content is 0.73 mol%
- a resin composition and a molded body were obtained in the same manner as in Example 1 except that EVOH resin (also referred to as “A2”) was used.
- Table 1 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 3 A resin composition and a molded body were obtained in the same manner as in Example 1 except that the mixture was 85% by mass of EVOH resin and 15% by mass of the hydroxyl group-containing compound. Table 1 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 4 A resin composition and a molded body were obtained in the same manner as in Example 1 except that the EVOH resin was mixed at a ratio of 93% by mass and the hydroxyl group-containing compound was 7% by mass. Table 1 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 5 A resin composition and a molded body were obtained in the same manner as in Example 1 except that the EVOH resin was mixed in a ratio of 97% by mass and the hydroxyl group-containing compound was 3% by mass. Table 1 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 6 1,1,1-trimethylolethane (molecular weight: 120, number of hydroxyl groups: 3, (number of hydroxyl groups in one molecule / molecular weight) ratio: 0.025, melting point: 193 ° C.) instead of TMP
- TMP 1,1,1-trimethylolethane
- Example 7 Instead of TMP, tetramethylolmethane (pentaerythritol) (molecular weight: 136, number of hydroxyl groups: 4, (number of hydroxyl groups in one molecule / molecular weight) ratio: 0.029, melting point: 261 ° C.) (“ A resin composition and a molded body were obtained in the same manner as in Example 1 except that the material was also referred to as “TeMM”. Table 1 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 8> ethylene content is 44 mol%, saponification degree is 99 mol% or more, MFR is 3.3 g / 10 min (210 ° C., 2160 g load), 1,2-glycol bond content is 0.49 mol%
- a resin composition and a molded body were obtained in the same manner as in Example 1 except that EVOH resin (also referred to as “A3”) was used.
- Table 2 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 9> ethylene content is 32 mol%, saponification degree is 99 mol% or more, MFR is 3.7 g / 10 min (210 ° C, 2160 g load), 1,2-glycol bond content is 0.71 mol%
- a resin composition and a molded body were obtained in the same manner as in Example 1 except that EVOH resin (also referred to as “A4”) was used.
- Table 2 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 10 A resin composition and a molded body were obtained in the same manner as in Example 8, except that 85% by mass of EVOH resin and 15% by mass of the hydroxyl group-containing compound were mixed. Table 2 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 11 A resin composition and a molded body were obtained in the same manner as in Example 8 except that the EVOH resin was mixed at a ratio of 93% by mass and the hydroxyl group-containing compound was 7% by mass.
- Table 2 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 12 A resin composition and a molded body were obtained in the same manner as in Example 8 except that the EVOH resin was mixed in a ratio of 97% by mass and the hydroxyl group-containing compound was 3% by mass.
- Table 2 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 13 A resin composition and a molded body were obtained in the same manner as in Example 8 except that TME was used as the hydroxyl group-containing compound instead of TMP.
- Table 2 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 14 A resin composition and a molded body were obtained in the same manner as in Example 8 except that TeMM was used as the hydroxyl group-containing compound instead of TMP.
- Table 2 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
- Example 1 A resin composition and a molded body were obtained in the same manner as in Example 1 except that the hydroxyl group-containing compound was not mixed. The obtained resin composition and molded product were evaluated in the same manner as in Example 1 except for the presence or absence of bleeding out.
- Example 3 A resin composition and a molded body were obtained in the same manner as in Example 1 except that 80% by mass of EVOH resin and 20% by mass of the hydroxyl group-containing compound were mixed. Table 3 shows the results of evaluating the obtained resin composition and molded product in the same manner as in Example 1.
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Abstract
Description
本発明はさらに、上述した本発明の樹脂組成物からなる層を少なくとも1層含む多層構造体についても提供する。
本発明の樹脂組成物は、エチレン-ビニルアルコール共重合体(EVOH樹脂)(A)および水酸基含有化合物(B)を基本的に含む。
本発明の樹脂組成物の主成分となるエチレン-ビニルアルコール共重合体(EVOH樹脂)(A)は、主にエチレン単位とビニルアルコール単位とを有する共重合体である。EVOH(A)は、たとえば、エチレンとビニルエステルとからなる共重合体をアルカリ触媒などを用いてケン化して得られる。ビニルエステルとしては、酢酸ビニルが代表的なものとして挙げられるが、その他の脂肪酸ビニルエステル(プロピオン酸ビニル、ピバリン酸ビニルなど)も使用できる。
本発明の樹脂組成物は、水酸基含有化合物(B)を基本的に含み、この水酸基含有化合物(B)が以下の要件を兼ね備えることを特徴とする。
・分子量に対する1分子中の水酸基数の比が0.02~0.03の範囲、
・融点が23℃以上、
・含有量が樹脂組成物に対して3~15質量%。
本発明はまた、上述した樹脂組成物からなる成形体についても提供する。このような本発明の成形体は、酸素バリア性が高く(酸素透過度が低く)、ブリードアウトが生じることがなく、ガラス転移温度が低く、かつ、柔軟性の高い性質を有するものである。
本発明は、上述した本発明の樹脂組成物からなる層を少なくとも1層含む多層構造体についても提供する。このような本発明の多層構造体における本発明の樹脂組成物からなる層は、好ましくは、上述した本発明の成形体と同様の引張弾性率、引張破断強度、引張破断伸度、突刺強度、酸素透過度を有する。
3層 A/MA/F、MA/F/MA、F/MA/F
4層 A/MA/F/MA、MA/F/MA/F
5層 F/MA/A/MA/F、A/MA/F/MA/A
MA/F/MA/F/MA、A/MA/F/MA/F
6層 A/MA/F/MA/A/MA
7層 A/MA/F/MA/F/MA/A
本発明の多層構造体の製造方法としては、樹脂組成物を溶融した状態で成形する方法(溶融成形法)と、樹脂組成物を溶媒に溶解して成形する方法(たとえば溶液コート法)などに大別される。中でも生産性の観点から、溶融成形法が好ましい。
DMSO-d6を溶媒とした1H-NMR測定(測定装置:日本電子製JNM-GX-500型)により求めた。
DMSO-d6を溶媒とした1H-NMR測定(測定装置:日本電子製JNM-GX-500型)により求めた。
メルトインデクサ(宝工業製L244)を用い、温度210℃、荷重2160gの条件下で、試料の流出速度(g/10分)を測定し求めた。
JIS K 7121に準拠し、示差走査熱量計(DSC)(TAインスツルメント製Q2000)を用い、融点(Tm)およびガラス転移温度(Tg)を求めた。
EVOH(A)と水酸基含有化合物(B)を混合した後、以下の条件で溶融混練、ペレット化、乾燥し、当該樹脂組成物のペレットを得た。
・L/D:25
・スクリュー:同方向完全噛合型
・ダイスホール数:2ホール(3mmφ)
・押出温度(℃):C1=200、C2~C5=230、Die=230
・回転数:100rpm
・吐出量:約5kg/hr
・乾燥:熱風乾燥80℃/6hr
[単層フィルム(成形体)作製条件]
得られた樹脂組成物を以下の条件で製膜し、厚み20μmおよび100μmの単層フィルム(成形体)を得た。
・L/D:20
・スクリュー:フルフライト
・ダイ:300mmコートハンガーダイ
・押出温度(℃):C1=180、C2~C3=200、Die=200
・スクリーン:50/100/50
・冷却ロール温度:20℃
・回転数:(厚み20μmのフィルム製膜時)40rpm、
(厚み100μmのフィルム製膜時)100rpm
・引取り速度:(厚み20μmのフィルム製膜時)3.0~3.5m/分、
(厚み100μmのフィルム製膜時)1.5~1.75m/分
[引張弾性率]
JIS K 7161に準拠し、得られた20μmの単層フィルムを23℃/50%RHの条件下で調湿した後、幅15mm、長さ12cmにカットし短冊を作製し、AUTOGRAPH AGS-H(島津製作所製)を用い、チャック間距離50mm、引張り速度5mm/分でMD、TDそれぞれについて測定を行ない、柔軟性の指標とした。
JIS K 7161に準拠し、得られた100μmの単層フィルムを23℃/50%RHの条件下で調湿した後、幅15mm、長さ12cmにカットし短冊を作製し、AUTOGRAPH AGS-H(島津製作所製)を用い、チャック間距離50mm、引張り速度500mm/分でMD、TDそれぞれについて測定を行なった。
JIS Z 1707に準拠し、得られた20μmの単層フィルムを23℃/50%RHの条件下で調湿した後、直径10cmの円形にカットし、治具を用い試験片を固定し、AUTOGRAPH AGS-H(島津製作所製)を用い、直径1.0mm、先端形状半径0.5mmの半円形の針を50mm/分の速度で突き刺し、針が貫通するまでの最大応力を測定した。
得られた厚み20μmの単層フィルムを20℃/85%RHの条件下で調湿した後、ISO14663-2に準拠し、酸素透過度測定装置(Modern Control製OX-Tran2/20)を使用し、20℃/85%RHの条件下で酸素透過度(OTR)を測定した。
得られた厚み20μmの単層フィルムを40℃/100%RHの条件下に7日間保管し、目視およびフーリエ変換赤外分光光度計(Perkin Elmer製、Spectrum One)を用いてATR(全反射測定)のモードで赤外吸収スペクトルを測定することにより、水酸基含有化合物(B)のブリードアウトを確認し、以下のX,Yのように判定した。
Y:ブリードアウトが発生した。
エチレン含有率が44モル%、ケン化度が99モル%以上、MFRが5.7g/10分(210℃、2160g荷重)、1,2-グリコール結合量が0.46モル%のEVOH樹脂(「A1」とも呼称する)90質量%と、水酸基含有化合物として1,1,1-トリメチロールプロパン(分子量:134、水酸基数:3、(1分子中の水酸基数/分子量)の比:0.022、融点:58℃)(「TMP」とも呼称する)10質量%とを混合し、上述した方法により、二軸押出機を使用して溶融混練、ペレット化し、熱風乾燥機にて80℃/6hr乾燥させ、樹脂組成物を得た。続いて、得られた樹脂組成物を用い、上述した方法により、単軸押出機を使用し、20μmおよび100μmの単層フィルム(成形体)を作製した。得られた樹脂組成物のガラス転移温度を上述した方法により測定した。また得られた成形体の引張弾性率、引張破断強度、引張破断伸度、突刺強度、酸素透過度(OTR)、ブリードアウトの有無を上述した方法により測定した。結果を表1に示す。
A1の代わりにエチレン含有率が32モル%、ケン化度が99モル%以上、MFRが4.4g/10分(210℃、2160g荷重)、1,2-グリコール結合量が0.73モル%のEVOH樹脂(「A2」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表1に示す。
EVOH樹脂85質量%、水酸基含有化合物15質量%の比率で混合したこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表1に示す。
EVOH樹脂93質量%、水酸基含有化合物7質量%の比率で混合したこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表1に示す。
EVOH樹脂97質量%、水酸基含有化合物3質量%の比率で混合したこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表1に示す。
TMPの代わりに、水酸基含有化合物として1,1,1-トリメチロールエタン(分子量:120、水酸基数:3、(1分子中の水酸基数/分子量)の比:0.025、融点:193℃)(「TME」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表1に示す。
TMPの代わりに、水酸基含有化合物としてテトラメチロールメタン(ペンタエリスリトール)(分子量:136、水酸基数:4、(1分子中の水酸基数/分子量)の比:0.029、融点:261℃)(「TeMM」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表1に示す。
A1の代わりにエチレン含有率が44モル%、ケン化度が99モル%以上、MFRが3.3g/10分(210℃、2160g荷重)、1,2-グリコール結合量が0.49モル%のEVOH樹脂(「A3」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表2に示す。
A1の代わりにエチレン含有率が32モル%、ケン化度が99モル%以上、MFRが3.7g/10分(210℃、2160g荷重)、1,2-グリコール結合量が0.71モル%のEVOH樹脂(「A4」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表2に示す。
EVOH樹脂85質量%、水酸基含有化合物15質量%の比率で混合したこと以外は実施例8と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表2に示す。
EVOH樹脂93質量%、水酸基含有化合物7質量%の比率で混合したこと以外は実施例8と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表2に示す。
EVOH樹脂97質量%、水酸基含有化合物3質量%の比率で混合したこと以外は実施例8と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表2に示す。
TMPの代わりに、水酸基含有化合物としてTMEを用いたこと以外は実施例8と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表2に示す。
TMPの代わりに、水酸基含有化合物としてTeMMを用いたこと以外は実施例8と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表2に示す。
水酸基含有化合物を混合しなかったこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、ブリードアウトの有無以外について実施例1と同様に評価を行なった結果を表3に示す。
水酸基含有化合物を混合しなかったこと以外は実施例2と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、ブリードアウトの有無以外について実施例1と同様に評価を行なった結果を表3に示す。
EVOH樹脂80質量%、水酸基含有化合物20質量%の比率で混合したこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表3に示す。
EVOH樹脂98質量%、水酸基含有化合物2質量%の比率で混合したこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表3に示す。
TMPの代わりに、水酸基含有化合物として1,2-プロピレングリコール(分子量:76、水酸基数:2、(1分子中の水酸基数/分子量)の比:0.026、融点:-59℃)(「PPG」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表3に示す。
TMPの代わりに、水酸基含有化合物として1,5-ペンタンジオール(分子量:104、水酸基数:2、(1分子中の水酸基数/分子量)の比:0.019、融点:-18℃)(「PeDO」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表3に示す。
TMPの代わりに、水酸基含有化合物として1,6-ヘキサンジオール(分子量:118、水酸基数:2、(1分子中の水酸基数/分子量)の比:0.017、融点:42℃)(「HDO」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表3に示す。
TMPの代わりに、水酸基含有化合物として1,2,3-プロパントリオール(分子量:92、水酸基数:3、(1分子中の水酸基数/分子量)の比:0.033、融点:18℃)(「PrTO」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表3に示す。
TMPの代わりに、水酸基含有化合物として1,4-ブタンジオール(分子量:90、水酸基数:2、(1分子中の水酸基数/分子量)の比:0.022、融点:20℃)(「BDO」とも呼称する)を用いたこと以外は実施例1と同様にして樹脂組成物および成形体を得た。得られた樹脂組成物および成形体について、実施例1と同様に評価を行なった結果を表3に示す。
Claims (8)
- エチレン-ビニルアルコール共重合体(A)および水酸基含有化合物(B)を含む樹脂組成物であって、
前記水酸基含有化合物(B)の分子量が200以下であり、分子量に対する1分子中の水酸基数の比が0.02~0.03の範囲であり、融点が23℃以上であり、
水酸基含有化合物(B)の含有量が樹脂組成物に対して3~15質量%である樹脂組成物。 - 前記水酸基含有化合物の(B)の融点が23℃以上200℃以下である請求項1に記載の樹脂組成物。
- 前記水酸基含有化合物(B)の分子量に対する1分子中の水酸基数の比が0.021~0.025の範囲である請求項1または2に記載の樹脂組成物。
- 前記水酸基含有化合物(B)が1,1,1-トリメチロールプロパンである請求項1~3のいずれか1項に記載の樹脂組成物。
- 前記水酸基含有化合物(B)の含有量が前記樹脂組成物に対して5~10質量%である請求項1~3のいずれか1項に記載の樹脂組成物。
- 前記エチレン-ビニルアルコール共重合体(A)のエチレン含有率が20~60モル%の範囲である請求項1~5のいずれか1項に記載の樹脂組成物。
- 請求項1~6のいずれか1項に記載の樹脂組成物からなる成形体。
- 請求項1~6のいずれか1項に記載の樹脂組成物からなる層を少なくとも1層含む多層構造体。
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JP2020196790A (ja) * | 2019-05-31 | 2020-12-10 | 公立大学法人 滋賀県立大学 | エチレン−ビニルアルコール樹脂組成物、及びそれを用いた成形体並びに多層構造体 |
WO2022034876A1 (ja) * | 2020-08-11 | 2022-02-17 | 三菱ケミカル株式会社 | ポリビニルアルコール系樹脂組成物及び当該樹脂組成物を用いた溶融成形体 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US10814596B2 (en) | 2014-11-28 | 2020-10-27 | Kuraray Co., Ltd. | Silage film, wrapped fodder, and storage method of fodder |
JP2020196790A (ja) * | 2019-05-31 | 2020-12-10 | 公立大学法人 滋賀県立大学 | エチレン−ビニルアルコール樹脂組成物、及びそれを用いた成形体並びに多層構造体 |
JP7312983B2 (ja) | 2019-05-31 | 2023-07-24 | 公立大学法人 滋賀県立大学 | エチレン-ビニルアルコール樹脂組成物、及びそれを用いた成形体並びに多層構造体 |
WO2022034876A1 (ja) * | 2020-08-11 | 2022-02-17 | 三菱ケミカル株式会社 | ポリビニルアルコール系樹脂組成物及び当該樹脂組成物を用いた溶融成形体 |
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CN106459547B (zh) | 2019-12-17 |
MY171762A (en) | 2019-10-28 |
EP3135724A1 (en) | 2017-03-01 |
JPWO2015163437A1 (ja) | 2017-04-20 |
EP3135724B1 (en) | 2019-04-10 |
US20170044350A1 (en) | 2017-02-16 |
CN106459547A (zh) | 2017-02-22 |
EP3135724A4 (en) | 2017-09-13 |
US10053551B2 (en) | 2018-08-21 |
JP6214760B2 (ja) | 2017-10-18 |
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