WO2023171792A1 - 変性ポリエステル系エラストマー及びその製造方法 - Google Patents

変性ポリエステル系エラストマー及びその製造方法 Download PDF

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Publication number
WO2023171792A1
WO2023171792A1 PCT/JP2023/009272 JP2023009272W WO2023171792A1 WO 2023171792 A1 WO2023171792 A1 WO 2023171792A1 JP 2023009272 W JP2023009272 W JP 2023009272W WO 2023171792 A1 WO2023171792 A1 WO 2023171792A1
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Prior art keywords
polyester elastomer
modified polyester
modified
mass
content
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English (en)
French (fr)
Japanese (ja)
Inventor
翔平 黒瀬
晶光 樋口
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MCPP Innovation LLC
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MCPP Innovation LLC
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Priority to KR1020247028137A priority Critical patent/KR20240159570A/ko
Priority to JP2024506424A priority patent/JPWO2023171792A1/ja
Priority to EP23766968.4A priority patent/EP4491654A4/en
Priority to CN202380022719.2A priority patent/CN118749005A/zh
Priority to CA3244801A priority patent/CA3244801A1/en
Publication of WO2023171792A1 publication Critical patent/WO2023171792A1/ja
Priority to US18/828,947 priority patent/US20240425667A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • B32B27/28—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
    • B32B27/285—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 polyethers
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0478—Copolymers from unsaturated polyesters and low molecular monomers characterised by the monomers used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09J167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2439/70—Food packaging
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0881—Titanium

Definitions

  • the present invention relates to a modified polyester elastomer with excellent color tone and heat-resistant adhesive properties, and a method for producing the same.
  • the present invention also relates to a laminate, a modifier, and a polar polymer composition using this modified polyester elastomer.
  • Laminates containing gas barrier materials such as polyamides and ethylene-vinyl alcohol copolymers are widely used in the food packaging field due to their excellent mechanical properties, safety in food applications, and barrier properties against gases such as water vapor and oxygen. Used for containers such as bottles and cups.
  • gas barrier materials such as polyamides and ethylene-vinyl alcohol copolymers
  • Used for containers such as bottles and cups.
  • non-food field it is widely used in industrial piping and hoses, tubes for conveying beverages and medicines, automobile parts, etc.
  • a technique of laminating a gas barrier material and an ester polymer is well known.
  • Patent Document 1 discloses that a saturated polyester thermoplastic elastomer having a polyalkylene ether glycol segment content of 58 to 73% by weight is modified with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator.
  • An adhesive polymer composition comprising a modified polyester elastomer obtained by
  • Patent Document 2 polar polymers such as polyamide and ethylene/vinyl alcohol copolymers used as gas barrier materials have poor flexibility, and particularly poor impact resistance.
  • Patent Document 2 a modified polyester elastomer to a polar polymer to impart appropriate flexibility and impact resistance while having high gas barrier properties.
  • an adhesive polymer composition with excellent color tone is desired.
  • the adhesive layer In non-food fields such as industrial piping and automobile parts, where the adhesive layer is exposed to high-temperature environments, the adhesive layer decomposes and deteriorates due to heat, and the adhesive layer and gas barrier layer, such as polyamide or ethylene-vinyl alcohol copolymer layer, deteriorate. Peeling may occur at the interface. Therefore, there is a need for an adhesive polymer composition that can suppress such thermal decomposition and deterioration. For this reason, adhesive polymer compositions with excellent color tone and heat-resistant adhesive properties are required.
  • the adhesive polymer composition described in Patent Document 1 has excellent initial adhesion, but there is room for improvement in heat-resistant adhesion, and the color tone is also poor. be.
  • the modified polyester elastomer described in Patent Document 2 has an excellent modification effect, that is, the softening performance of polar polymers, as shown in Comparative Examples 1-2 and 3 below. There is room for improvement in the hue of things.
  • Patent Document 1 and Patent Document 2 do not mention the titanium content of the modified polyester elastomer, but at the time of filing of Patent Document 1 and Patent Document 2, the polyester heat used for modification was
  • the only plastic elastomer produced on an industrial level is one using a titanium catalyst, and its titanium content is the same as Comparative Examples 1-1 to 1-3 listed below, and is 250 wtppm or more than 250 wtppm. It was something. Therefore, the titanium content of the modified polyester elastomer obtained by modifying such a polyester thermoplastic elastomer is also 250 wtppm or more.
  • the present inventor has discovered that by reducing the titanium content of the modified polyester elastomer to a predetermined value or less, a modified polyester elastomer with excellent color tone and heat-resistant adhesion can be obtained.
  • this modified polyester elastomer is effective as a modifier for polar polymers such as ethylene/vinyl alcohol copolymers and polyamide polymers, leading to the present invention.
  • the gist of the present invention is as follows.
  • a modified polyester elastomer obtained by modifying a polyester polyether block copolymer consisting of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol with an unsaturated carboxylic acid and/or its derivative.
  • a laminate comprising a base layer, a layer made of the modified polyester elastomer according to any one of [1] to [8] or an adhesive polymer composition containing the modified polyester elastomer, and a resin layer.
  • a method for producing a modified polyester elastomer comprising a step of modifying a polyester elastomer polymerized in the presence of a titanium compound with an unsaturated carboxylic acid and/or a derivative thereof,
  • the polyester elastomer is a polyester polyether block copolymer consisting of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol,
  • a modifier comprising the modified polyester elastomer according to any one of [1] to [8].
  • the content of the polymer is 70 to 99% by mass
  • the content of the modified polyester elastomer is 1 to 30% by mass
  • the polar polymer is selected from an ethylene/vinyl alcohol copolymer and a polyamide polymer.
  • a polar polymer composition comprising at least one of:
  • the modified polyester elastomer of the present invention has excellent color tone and heat-resistant adhesive properties. Therefore, by using this modified polyester elastomer as an adhesive layer between an ester polymer layer and a gas barrier layer, a laminate with excellent color tone and transparency can be provided in the food packaging field. Furthermore, in non-food fields such as industrial piping and automobile parts, it is possible to provide a laminate with excellent heat-resistant adhesive properties and no problem of interfacial peeling.
  • the modified polyester elastomer of the present invention is also effective as a modifier for imparting properties such as flexibility to polar polymers such as ethylene/vinyl alcohol copolymers and polyamide polymers. Therefore, the polar polymer composition containing the modified polyester elastomer and polar polymer of the present invention provides a polar polymer composition in which physical properties such as flexibility are improved with respect to the polar polymer.
  • the density, melting point, hardness, and melt flow rate (MFR) of the polyester elastomer and modified polyester elastomer are values measured as follows.
  • the density is measured by an underwater displacement method in accordance with JIS K7112.
  • ⁇ Melting point> Melting points are measured using differential scanning calorimetry (DSC). Specifically, once the temperature was raised to 300°C to erase the thermal history, the temperature was lowered to 40°C at a cooling rate of 10°C/min, and then raised again at a heating rate of 10°C/min. The temperature at the top of the endothermic peak during measurement is defined as the melting point. The unit is °C.
  • MFR melt flow rate
  • the MFR (melt flow rate) of the polyester elastomer and modified polyester elastomer described below is measured in accordance with JIS K7210 at a temperature of 230° C., a load of 2.16 kg, and 10 minutes. In the measurement, the polyester elastomer and the modified polyester elastomer are vacuum-dried in pellet form at 100° C. for 4 hours to remove the moisture content.
  • the modified polyester elastomer of the present invention is a polyester polyether block copolymer consisting of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol, which is modified with an unsaturated carboxylic acid and/or a derivative thereof.
  • the modified polyester elastomer contains titanium, and the modified polyester elastomer has a titanium content of less than 250 wtppm.
  • polyester polyether block copolymer for producing the modified polyester elastomer of the present invention by modification will be referred to as "polyester elastomer", “raw material polyester elastomer”, or “component (A)".
  • component (B) unsaturated carboxylic acid and/or its derivative used for modifying the polyester elastomer
  • component (C) the radical generator used for modification treatment
  • Modification in the present invention refers to graft modification of a polyester elastomer with an unsaturated carboxylic acid and/or its derivative, modification by terminal modification and transesterification reaction, modification by decomposition reaction, etc.
  • the sites to which unsaturated carboxylic acids and/or their derivatives are bonded can be considered to be terminal functional groups or alkyl chain moieties, particularly terminal carboxyl groups, terminal hydroxyl groups, and ether bonds of polyalkylene ether glycol segments.
  • carbon atoms at the ⁇ -position and ⁇ -position can be mentioned.
  • the unsaturated carboxylic acid and/or its derivatives are mostly bound to the ⁇ -position with respect to the ether bond of the polyalkylene ether glycol segment.
  • the modified polyester elastomer modified with the polyester elastomer, the unmodified polyester elastomer, the unsaturated carboxylic acid used for modification, and/or A modified polyester elastomer is obtained as a composition containing the derivative thereof, a radical generator described below, and the like.
  • the modified polyester elastomer of the present invention means a modified polyester elastomer composition containing an unmodified polyester elastomer and residues such as unsaturated carboxylic acids and/or derivatives thereof, obtained by the modification reaction. .
  • the modified polyester elastomer of the present invention contains a polyester elastomer that satisfies the titanium content specified in the present invention, preferably the polyalkylene ether glycol segment content described below, and more preferably the suitable acid value described below. As long as this is possible, a mixture of a modified polyester elastomer obtained by modifying a polyester elastomer and an unmodified polyester elastomer may be used.
  • modified polyester elastomer of the present invention has polyester as its main skeleton, it has high compatibility with the ester polymer.
  • modified polyester elastomers can have sufficient adhesion with gas barrier materials, especially polyamide polymers and ethylene/vinyl alcohol copolymers, and can also have good adhesion with hard segments (aromatic polyesters).
  • the elastomer structure consisting of soft segments (polyalkylene ether glycol) strengthens the adhesion by alleviating the strain and residual stress that occurs between the layers of the laminate (between the gas barrier layer and the adhesive layer) during molding. .
  • the modified polyester elastomer of the present invention has a titanium content below a predetermined value.
  • a polyester elastomer containing titanium at a predetermined content or less is usually used as a raw material polyester elastomer to be subjected to modification.
  • hydrolysis during modification can be suppressed, and a modified polyester elastomer with excellent color tone and heat-resistant adhesion can be obtained.
  • the modified polyester elastomer has a titanium content below a predetermined value, hydrolysis during molding and processing will be suppressed, and the color tone and heat-resistant adhesive properties can be maintained.
  • the modified polyester elastomer of the present invention has excellent compatibility with polar polymers such as ethylene/vinyl alcohol copolymer and polyamide polymer
  • the modified polyester elastomer of the present invention can be added to these polar polymers.
  • the modified polyester elastomer and the polar polymer can be sufficiently made compatible.
  • properties such as flexibility can be improved. Therefore, the modified polyester elastomer of the present invention is also useful as a modifier for such polar polymers.
  • a polar polymer composition having excellent properties such as color tone and flexibility can be obtained.
  • Such a modified polyester elastomer of the present invention is a method for producing a modified polyester elastomer, which comprises a step of modifying a polyester elastomer polymerized in the presence of a titanium compound with an unsaturated carboxylic acid and/or a derivative thereof.
  • the polyester elastomer is a polyester polyether block copolymer consisting of a hard segment containing aromatic polyester and a soft segment containing polyalkylene ether glycol, and the titanium content of the polyester elastomer is 250 wtppm.
  • the method for producing a modified polyester elastomer of the present invention which is characterized in that the polyester elastomer is less than
  • the method for producing the modified polyester elastomer of the present invention is not limited to the method for producing the modified polyester elastomer of the present invention.
  • polyester elastomer The raw material polyester elastomer used in the method for producing a modified polyester elastomer of the present invention is a polyester polyether block copolymer consisting of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol. .
  • Polyester elastomers usually contain i) an aliphatic and/or alicyclic diol having 2 to 12 carbon atoms, ii) an aromatic dicarboxylic acid and/or an alkyl ester thereof, and iii) a number average molecular weight of 400 to 6. ,000 polyalkylene ether glycol as a raw material, and polycondensation of an oligomer obtained by esterification reaction or transesterification reaction in the presence of a titanium compound.
  • aliphatic and/or alicyclic diol having 2 to 12 carbon atoms those commonly used as raw materials for ester polymers, particularly polyester elastomers, can be used.
  • examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol, with 1,4-butanediol and ethylene glycol being preferred. Particularly preferred is 1,4-butanediol.
  • These diols can be used alone or in a mixture of two or more.
  • aromatic dicarboxylic acid those commonly used as raw materials for ester polymers, particularly polyester elastomers, can be used.
  • examples include terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalene dicarboxylic acid.
  • terephthalic acid and 2,6-naphthalene dicarboxylic acid are preferred, and terephthalic acid is particularly preferred.
  • Two or more of these dicarboxylic acids may be used in combination.
  • dimethyl ester, diethyl ester, etc. of the above-mentioned dicarboxylic acid are used.
  • Preferred are dimethyl terephthalate and 2,6-dimethylnaphthalate.
  • polyalkylene ether glycol examples include polyethylene glycol, poly(1,2 and 1,3-propylene ether) glycol, poly(tetramethylene ether) glycol, poly(hexamethylene ether) glycol, poly(decamethylene ether) ) glycols.
  • poly(tetramethylene ether) glycol is particularly preferably used.
  • polyalkylene ether glycol those having a number average molecular weight of 400 to 6,000 are usually used, preferably those having a number average molecular weight of 600 to 4,000, and more preferably 900 to 3,000.
  • the number average molecular weight is at least the lower limit of the above range, it becomes easier to control the degree of modification by the unsaturated carboxylic acid and/or its derivative within the desired range, and it exhibits sufficient adhesive properties and functions as a modifier. It tends to become easier.
  • the number average molecular weight is below the upper limit of the above range, phase separation within the system can be suppressed, and deterioration in the physical properties of the resulting modified polyester elastomer tends to be suppressed.
  • the "number average molecular weight” is measured by nuclear magnetic resonance (NMR) analysis.
  • the content of polyalkylene ether glycol segments in the polyester elastomer is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, and still more preferably 20 to 80% by mass. It is used as follows.
  • the polyester elastomer may also be made by copolymerizing a small amount of trifunctional triol, tricarboxylic acid, or their esters, and further copolymerizing aliphatic dicarboxylic acids such as adipic acid or their dialkyl esters. It may also be used as a polymerization component.
  • titanium compounds are sometimes used as polymerization catalysts.
  • the titanium compound include potassium oxalate titanate, alkoxy or aryloxy titanate compounds, titanium carbonate compounds, halogenated titanium compounds, and titanium acetylacenate.
  • potassium oxalate titanate, alkoxy or aryloxy titanate compounds are preferred, and alkoxy or aryloxy titanate compounds are particularly preferred.
  • tetraalkyl titanates tetraalkoxy titanium
  • tetraaryl titanates tetraaryloxy titanium
  • tetra-n-propyl titanate tetra-n-propyl titanate
  • tetraisopropyl titanate tetra-n- -butyl titanate
  • tetra-t-butyl titanate tetra-t-butyl titanate
  • tetraphenyl titanate tetracyclohexyl titanate
  • tetrabenzyl titanate or mixtures thereof.
  • tetra-n-propyl titanate tetra-isopropyl titanate
  • tetra-n-butyl titanate is particularly preferred, and tetra-n-butyl titanate is most preferred.
  • Two or more of these titanium compounds may be used in combination.
  • the titanium compound used as a catalyst causes the titanium compound to remain in the resulting polyester elastomer.
  • the titanium (titanium atom) content of the raw polyester elastomer subjected to modification in the present invention is less than 250 wtppm, preferably 245 wtppm or less, more preferably 240 wtppm or less, and still more preferably 238 wtppm or less.
  • the lower limit of the titanium content is preferably 10 wtppm or more, more preferably 30 wtppm or more, and even more preferably 50 wtppm or more.
  • the titanium (titanium atom) content of the polyester elastomer means the titanium content as the polyester elastomer.
  • the polyester elastomer is composed of a plurality of polyester polyether block copolymers with different titanium contents, the titanium content of the polyester polyether block copolymer as a whole should be less than 250 wtppm. means.
  • a low titanium content in a polyester elastomer mainly means that the amount of titanium compound as a catalyst in the polyester elastomer manufacturing process is low, and sufficient polymerization reactivity cannot be obtained, making it impossible to obtain a polyester elastomer. There are cases. If the titanium content of the polyester elastomer is high, the decomposition reaction will be accelerated, the amount of terminal carboxyl groups will increase, and hydrolysis will proceed, which will worsen the color tone of the modified polyester elastomer and the laminate containing the modified polyester elastomer. , their heat-resistant adhesive properties and functionality as modifiers also tend to be poor.
  • the titanium content of the polyester elastomer can be determined by the ashing-alkali melting-ICP/AES method. When a plurality of polyester elastomers are mixed, the titanium content of the mixture is determined by arithmetic averaging the titanium content of each polyester elastomer.
  • the titanium content of the polyester elastomer may be determined by using one or more polyester elastomers with a titanium content of less than 250 wtppm, or by using a polyester elastomer with a titanium content of 250 wtppm or more and a polyester with a titanium content of less than 250 wtppm. By using it in combination with a polyester-based elastomer, the titanium content of the entire polyester-based elastomer can be made less than 250 wtppm.
  • the titanium content of the polyester elastomer can be controlled by adjusting the amount of titanium compound catalyst, reaction temperature, reaction time, etc. during production.
  • the content of polyalkylene ether glycol segments in the polyester polyether block copolymer is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, More preferably, it is 20 to 80% by mass.
  • the overall polyester The alkylene ether glycol segment content may be within the range of 5 to 90% by mass.
  • the content of the polyalkylene ether glycol segment in the polyester elastomer acts to alleviate the strain and residual stress that occurs between the layers of the laminate, improves the adhesion, and can also be used as a modifier. It also has excellent functionality.
  • the content of the polyalkylene ether glycol segment below the above upper limit, the crystallinity of the polyester elastomer is suppressed from decreasing, and the fusion of the polyester elastomer and modified polyester elastomer is prevented. Improves handling.
  • the content of polyalkylene ether glycol segments in polyester elastomers can be determined by dissolving a sample in a mixed solvent of deuterated chloroform/hexafluoroisopropanol and measuring the 1 H NMR spectrum at room temperature using a nuclear magnetic resonance apparatus (AVANCE 400 spectrometer manufactured by Bruker). is measured and calculated based on the chemical shift of the hydrogen spectrum.
  • AVANCE 400 spectrometer manufactured by Bruker
  • the content of polyalkylene ether glycol segments in the modified polyester elastomer and the content of polyalkylene ether glycol segments in the polyester elastomer before modification are the same value. That is, it can be considered that there is no change in the content of polyalkylene ether glycol segments before and after modification.
  • the polyester elastomer preferably has a density of 1.00 to 1.35 g/cm 3 , more preferably 1.02 to 1.30 g/cm 3 , and more preferably 1.04 to 1.25 g/cm 3 is even more preferable.
  • the density of a polyester elastomer correlates with the content of polyalkylene ether glycol segments, and as the content of polyalkylene ether glycol segments increases, the density decreases.
  • the density of the polyester elastomer By setting the density of the polyester elastomer to be equal to or higher than the lower limit of the above range, it becomes easier to suppress a decrease in the heat-resistant adhesive properties of the modified polyester elastomer obtained.
  • By setting the density of the polyester elastomer to below the upper limit of the above range it becomes easier to improve the adhesion of the obtained modified polyester elastomer to the gas barrier material. It also has excellent effects as a modifier.
  • the polyester elastomer preferably has a melting point of 145 to 245°C, more preferably 150 to 230°C, and even more preferably 160 to 215°C.
  • a melting point 145 to 245°C, more preferably 150 to 230°C, and even more preferably 160 to 215°C.
  • the D hardness (JIS-D hardness) of the polyester elastomer is preferably from 10 to 80, more preferably from 20 to 70, even more preferably from 25 to 60.
  • JIS-D hardness is at least the lower limit of the above range, the heat-resistant adhesive properties of the resulting modified polyester elastomer tend to be excellent, and when it is below the upper limit of the above range, films, tubes, etc. of the obtained modified polyester elastomer tend to be excellent.
  • the MFR measured at a temperature of 230°C, a load of 2.16 kg, and 10 minutes is preferably 0.5 to 300 g/10 minutes, and 1 to 150 g/10 More preferably, the amount is 2 to 75 g/10 minutes.
  • the melt tension of the modified polyester elastomer can be increased and drawdown during molding can be easily suppressed
  • the modified polyester elastomer can be easily suppressed. This makes it easier to suppress deterioration in moldability such as uneven thickness caused by insufficient fluidity of the polyester elastomer.
  • polyester elastomer Commercially available products may be used as the polyester elastomer.
  • Commercially available products include, for example, "Tefa Block (registered trademark)” manufactured by Mitsubishi Chemical Corporation, “Pelprene (registered trademark)” manufactured by Toyobo Co., Ltd., and “Hytrel (registered trademark)” manufactured by DuPont-Toray Co., Ltd.
  • polyester elastomer One type of polyester elastomer may be used. Two or more types of monomers having different monomer compositions, physical properties, etc. may be subjected to modification with an unsaturated carboxylic acid and/or a derivative thereof.
  • the unsaturated carboxylic acid used for modifying the polyester elastomer is preferably ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid. , citraconic acid, crotonic acid, and isocrotonic acid.
  • Examples of derivatives of unsaturated carboxylic acids include acid anhydrides and carboxylic esters of these unsaturated carboxylic acids, and furthermore, derivatives of acid halides, amides, imides, and the like may be used. Among these derivatives, acid anhydrides are preferred.
  • maleic acid and/or its anhydride are particularly preferred as the unsaturated carboxylic acid and/or its derivative.
  • a plurality of these compounds may be used in combination.
  • so-called vinylsilanes such as vinyltrimethoxysilane can be used in combination with unsaturated carboxylic acids and/or derivatives thereof.
  • the modification treatment in producing the modified polyester elastomer of the present invention is preferably carried out in the presence of a radical generator.
  • a radical generator is used to carry out a radical reaction when a polyester elastomer is modified with an unsaturated carboxylic acid and/or a derivative thereof.
  • radical generator examples include peroxy esters, dialkyl peroxides, diacyl peroxides, hydroperoxides, ketone peroxides, and the like. Among these, dibenzoyl peroxide and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane are preferably used as diacyl peroxides.
  • These radical generators may be appropriately selected depending on the type of polyester elastomer, the type of unsaturated carboxylic acid and/or its derivative, and the modification conditions. Two or more radical generators may be used in combination. The radical generator can also be added after being dissolved in an organic solvent or the like.
  • Modification treatment method for modified polyester elastomer Any known method can be used for the process of modifying the polyester elastomer with an unsaturated carboxylic acid and/or its derivative, and a melt-kneading reaction method, a solution reaction method, and a suspension dispersion reaction method can be used. . Usually, a melt-kneading reaction method is preferred.
  • the components (A) and (B), and optionally the component (C) may be uniformly mixed at a predetermined mixing ratio and then melt-kneaded.
  • a Henschel mixer, a ribbon blender, a V-type blender, etc. are used.
  • melt-kneading a single-screw or twin-screw extruder, a roll, a Banbury mixer, a kneader, a Brabender mixer, etc. can usually be used.
  • a twin-screw extruder is particularly preferred.
  • Melt kneading is usually carried out at a temperature of 100°C or higher, preferably 120°C or higher, more preferably 150°C or higher, and usually 300°C or lower, preferably 280°C or lower, more preferably 250°C or lower, in order to prevent thermal deterioration of the resin. It will be held in
  • the amount of the unsaturated carboxylic acid and/or its derivative used in the modification (B) is usually 0.01 parts by mass or more, preferably 0.01 parts by mass or more, based on the total of 100 parts by mass of the polyester elastomer (A)
  • the amount is .05 parts by weight or more, more preferably 0.1 parts by weight or more, and usually 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 1 part by weight or less.
  • the amount of the radical generator (component (C)) is usually at least 0.001 parts by mass, preferably at least 0.005 parts by mass, and more preferably at least 0.00 parts by mass, per 100 parts by mass of the polyester elastomer (A).
  • the amount is .01 parts by mass or more, and usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2 parts by mass or less.
  • the amount of the radical generator is more than the above lower limit, the modification reaction is easily caused, and when it is less than the above lower limit, the material strength is significantly increased by promoting lowering of the molecular weight (viscosity reduction) of component (A). It is possible to suppress the decline.
  • Modified polyester elastomer [Titanium content]
  • the titanium compound remains in the produced polyester elastomer, and the raw material polyester elastomer used for modification contains titanium (titanium atoms). Become something to do.
  • the modified polyester elastomer also contains titanium.
  • the titanium content of the modified polyester elastomer of the present invention is less than 250 wtppm, preferably 248 wtppm or less, more preferably 245 wtppm or less, particularly preferably 240 wtppm or less.
  • the lower limit of the titanium content is preferably 20 wtppm or more, more preferably 40 wtppm or more, and even more preferably 60 wtppm or more.
  • the titanium (titanium atom) content of the modified polyester elastomer means the titanium content as a modified polyester elastomer.
  • the modified polyester elastomer is composed of multiple modified polyester elastomers with different titanium contents. If the titanium content is less than 250 wtppm, it means that the titanium content of the entire modified polyester elastomer is less than 250 wtppm.
  • the low titanium content of the modified polyester elastomer mainly means that the amount of titanium compound as a catalyst in the manufacturing process of the raw material polyester elastomer is low, and sufficient polymerization reactivity cannot be obtained and the raw material polyester elastomer You may not get it. If the titanium content of the modified polyester elastomer is high, the decomposition reaction will be accelerated, the amount of terminal carboxyl groups will increase, and hydrolysis will proceed, which will worsen the color tone of the modified polyester elastomer and the laminate containing the modified polyester elastomer. However, heat-resistant adhesion properties also tend to be poor. Furthermore, for the same reason, its function as a modifier also tends to be poor.
  • the titanium content of the modified polyester elastomer can also be determined by the ashing-alkali melting-ICP/AES method.
  • the titanium content of the mixture can be determined by averaging the titanium content of each modified polyester elastomer.
  • the titanium content of the modified polyester elastomer is such that a modified polyester elastomer with a titanium content of less than 250 wtppm is used alone or in combination, or a modified polyester elastomer with a titanium content of 250 wtppm or more and a titanium content of 250 wtppm are used.
  • a modified polyester elastomer of less than 250 wtppm in combination the titanium content of the modified polyester elastomer as a whole can be less than 250 wtppm.
  • the titanium content of the raw material polyester elastomer When the titanium content of the raw material polyester elastomer is low, the titanium content of the modified polyester elastomer obtained by modification tends to be low, and in order to obtain a modified polyester elastomer with a titanium content of less than 250 wtppm, it is necessary to subject it to modification. It is preferable to use a polyester elastomer having a titanium content of less than 250 wtppm as the raw material polyester elastomer. However, the titanium content of the raw material polyester elastomer and the titanium content of the modified polyester elastomer are not necessarily in a proportional relationship.
  • the titanium content of the modified polyester elastomer increases or decreases as it is mixed in from the extruder metal during the modification process or removed by the mesh filter.
  • the titanium content of the polyester elastomer can be controlled by adjusting the amount of titanium compound catalyst, reaction temperature, reaction time, etc. during the production of the polyester elastomer, but the titanium content of the modified polyester elastomer is It can be controlled by adjusting the titanium content of the polyester elastomer.
  • the titanium content of the modified polyester elastomer can also be controlled by the configuration of the mesh filter during the modification treatment, the selection of the metal type of the extruder, etc.
  • the lower limit of the acid value of the modified polyester elastomer of the present invention is preferably 1 eq/T (equivalent/ton) or more, more preferably 5 eq/T or more, from the viewpoint of suppressing by-products during heating during molding. , more preferably 10 eq/T or more.
  • the upper limit of the acid value of the modified polyester elastomer is preferably 70 eq/T or less, more preferably 68 eq/T or less, still more preferably 66 eq/T or less, from the viewpoint of color tone and heat-resistant adhesive properties.
  • the acid value of the modified polyester elastomer can be determined, for example, by heating and dissolving the modified polyester elastomer in a benzyl alcohol solvent and titrating it with an indicator using a 0.1 mol/L sodium hydroxide benzyl alcohol solution. It can be determined by quantifying the amount of carboxyl groups.
  • the acid value of the modified polyester elastomer can be adjusted within the above range by adjusting the temperature, time, degree of polymerization, etc. during production of the modified polyester elastomer.
  • the density of the modified polyester elastomer of the present invention is preferably 1.00 to 1.35 g/cm 3 , more preferably 1.02 to 1.30 g/cm 3 , even more preferably 1.04 to 1.25 g/cm 3 .
  • the density of the modified polyester elastomer correlates with the content of polyalkylene ether glycol segments, and as the content of polyalkylene ether glycol segments increases, the density decreases. In other words, by setting the density at or above the lower limit of the above range, it becomes easier to suppress the decrease in heat-resistant adhesion, and by setting the density at or below the upper limit of the above range, it improves the adhesion with gas barrier materials and the functionality as a modifier. It becomes easier to improve.
  • the melting point of the modified polyester elastomer of the present invention is preferably 145 to 245°C, more preferably 150 to 230°C, even more preferably 160 to 215°C.
  • the melting point is preferably 145 to 245°C, more preferably 150 to 230°C, even more preferably 160 to 215°C.
  • the D hardness (JIS-D hardness) of the modified polyester elastomer of the present invention is preferably from 10 to 80, more preferably from 20 to 70, even more preferably from 25 to 60.
  • JIS-D hardness is at least the lower limit of the above range, heat-resistant adhesive properties and functionality as a modifier tend to be excellent.
  • the JIS-D hardness is below the upper limit of the above range, it tends to maintain the flexibility required for a laminate such as a film or tube.
  • the modified polyester elastomer of the present invention preferably has an MFR of 0.5 to 300 g/10 minutes, measured at a temperature of 230°C, a load of 2.16 kg, and 10 minutes in accordance with JIS K7210, and is preferably 1 It is more preferably 300 g/10 minutes, even more preferably 1 to 150 g/10 minutes, and particularly preferably 2 to 75 g/10 minutes.
  • MFR of the modified polyester elastomer is below the upper limit of the above range, the melt tension is increased and drawdown during molding is easily suppressed.
  • the MFR of the modified polyester elastomer By setting the MFR of the modified polyester elastomer to be equal to or higher than the lower limit of the above range, deterioration in moldability such as uneven thickness caused by insufficient fluidity can be easily suppressed.
  • the content of polyalkylene ether glycol segments in the modified polyester elastomer and the content of polyalkylene ether glycol segments in the raw material polyester elastomer before modification are theoretically the same value.
  • the content of polyalkylene ether glycol segments in 100% by mass of the modified polyester elastomer of the present invention is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, and even more preferably 20 to 80% by mass.
  • the handleability is good, and when this is used as an adhesive layer, good adhesion can be achieved. can. Furthermore, it has excellent functionality as a modifier.
  • the content of polyalkylene ether glycol segments in the modified polyester elastomer is the content of polyalkylene ether glycol segments in the entire modified polyester elastomer. That is, for example, when using a mixture of two or more modified polyester elastomers, even if one of them deviates from the polyalkylene ether glycol segment content of 5 to 90% by mass, the modified polyester elastomer as a mixture
  • the polyalkylene ether glycol segment content of the polyalkylene ether glycol segment may be in the range of 5 to 90% by mass.
  • the acid modification rate of the modified polyester elastomer of the present invention is not particularly limited, but is preferably from 0.01 to 10. If the acid modification rate is at least the lower limit of the above range, sufficient adhesiveness with the gas barrier layer can be obtained. Furthermore, it has excellent functionality as a modifier. If the acid modification rate is below the upper limit of the above range, it is possible to suppress discoloration due to unsaturated carboxylic acids and/or derivatives thereof.
  • the lower limit of the acid modification rate is more preferably 0.1 or more, even more preferably 0.15 or more, and particularly preferably 0.16 or more.
  • the upper limit of the acid modification rate is more preferably 4 or less, and even more preferably 0.8 or less.
  • the acid modification rate of the modified polyester elastomer is measured and calculated by the method described in the Examples section below.
  • Adhesive polymer composition containing modified polyester elastomer An adhesive polymer composition can be made using the modified polyester elasmer of the present invention. This adhesive polymer composition can be used for the adhesive layer of the laminate of the present invention, which will be described later.
  • the content of the modified polyester elastomer of the present invention in the adhesive polymer composition is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. If the content of the modified polyester elastomer of the present invention in the adhesive polymer composition is at least the above lower limit, the adhesiveness with the gas barrier layer and other layers such as the ester polymer layer can be sufficiently increased. .
  • the upper limit of the content of the modified polyester elastomer of the present invention in the adhesive polymer composition is not particularly limited and is less than 100% by mass.
  • the adhesive polymer composition contains any components (hereinafter sometimes referred to as other components) depending on the purpose.
  • other components only one type may be used, or two or more types may be used in combination in any combination and ratio.
  • other components include polymers other than the modified polyester elastomer of the present invention and rubber components (ester polymers such as polyethylene terephthalate and polybutylene terephthalate, styrene (co)polymers such as polystyrene, and polyolefins).
  • acrylic/methacrylic copolymers such as polymethyl methacrylate), heat stabilizers, weather stabilizers (antioxidants, light stabilizers, ultraviolet absorbers, etc.), flame retardants, antiblocking agents, slip agents, electrostatic charges Inhibitors, fillers (inorganic and/or organic fillers, etc.), processing aids, plasticizers such as paraffin oil, crystal nucleating agents, impact modifiers, compatibilizers, catalyst residue neutralizers, carbon black, colorants. (pigments, dyes, etc.), antifogging agents, crosslinking agents, crosslinking aids, chain extenders, dispersants, antibacterial agents, antiviral agents, optical brighteners, and other additives.
  • heat stabilizers weather stabilizers (antioxidants, light stabilizers, ultraviolet absorbers, etc.), flame retardants, antiblocking agents, slip agents, electrostatic charges Inhibitors, fillers (inorganic and/or organic fillers, etc.), processing aids, plasticizers such as paraffin oil, crystal nucleating agents
  • the content thereof is not limited, but the content in 100% by mass of the adhesive polymer composition constituting the adhesive layer is usually 0.01% by mass or more, preferably 0.05% by mass. % or more, and usually 5% by mass or less, preferably 2% by mass or less.
  • An adhesive layer made of the modified polyester elastomer of the present invention or an adhesive polymer composition containing the modified polyester elastomer can be laminated with a gas barrier layer to form a laminate. That is, the modified polyester elastomer of the present invention or the adhesive polymer composition containing the modified polyester elastomer can be used to form an adhesive layer of a laminate.
  • the laminate using the modified polyester elastomer of the present invention is preferably a laminate having two or three or more layers.
  • this laminate includes a base material layer, a layer made of the modified polyester elastomer of the present invention or an adhesive polymer composition containing the modified polyester elastomer of the present invention as an adhesive layer, and a resin layer such as a gas barrier layer. It is preferable that the laminate of the present invention has the following.
  • the gas barrier layer is preferably made of a polyamide polymer and/or an ethylene/vinyl alcohol copolymer, and preferably has an ester polymer layer if necessary.
  • the gas barrier layer is made of a polyamide polymer and/or an ethylene/vinyl alcohol copolymer
  • the adhesive layer is the modified polyester elastomer of the present invention or an adhesive polymer composition containing the modified polyester elastomer. It is more preferable that the adhesive layer is made of a material and the base material layer is a laminate made of an ester polymer.
  • a laminate in which two or more of some layers are laminated, such as base material layer/adhesive layer/gas barrier layer/adhesive layer/base material layer, may be used.
  • the adhesive layer made of the modified polyester elastomer of the present invention or the adhesive polymer composition containing the modified polyester elastomer preferably contains the modified polyester elastomer of the present invention in an amount of 50% by mass or more based on the entire constituent components of the adhesive layer.
  • the content is more preferably 55% by mass or more, still more preferably 60% by mass or more. If the content of the modified polyester elastomer is at least the above lower limit, the adhesiveness with the gas barrier layer, the ester polymer layer serving as the base layer, etc. can be sufficiently improved. Note that there is no particular upper limit to the content of the modified polyester elastomer of the present invention, and it may be 100% by mass.
  • the gas barrier layer according to the present invention includes a polyamide polymer layer, an ethylene-vinyl alcohol copolymer layer, a polyvinyl alcohol layer, a metal foil such as aluminum, an aluminum vapor-deposited film, a transparent vapor-deposited film such as alumina vapor-deposited film or silica vapor-deposited film, Examples include gas barrier layers such as polyvinylidene chloride layers. Among these, a layer mainly composed of polyamide or ethylene/vinyl alcohol copolymer is preferable.
  • Polyamide polymers are usually produced by a polycondensation reaction of diamines and dicarboxylic acids, but they can also be obtained by ring-opening polymerization of lactams. Specific examples of these polyamide polymers include polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 4,6, polyamide 6, polyamide 12, polyamide 11, and the like. Also, polyamide 6/6, 6, polyamide 6/6, 10, polyamide 6/12, polyamide 6/6, 12, polyamide 6/6, 6/6, 10, polyamide 6/6, 6/12, etc. Polymeric polyamides can also be used.
  • semi-aromatic polyamides such as polyamide 6/6,T (T: terephthalic acid component), polyamide 6,T/6,I (I: isophthalic acid component), and polyamide MXD6 can also be used.
  • the dicarboxylic acid is replaced with an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid (in this case, the diamine may also be replaced with an alicyclic diamine), or the diamine is replaced with meta-xylene. It is produced by substitution with aromatic diamines such as diamines.
  • Polyesteramides in which part of the diamine is substituted with a diol can also be used.
  • polyamide polymers produced using diamines or dicarboxylic acids synthesized from plant-derived raw materials can also be used. Particularly preferred polyamide polymers are polyamide 6, polyamide 6,6, polyamide 12, polyamide 11, and polyamide MXD6.
  • polyamide polymers Commercial products of such polyamide polymers include, for example, “Novamid (registered trademark)” manufactured by DSM Japan Engineering Plastics, “Xencor (registered trademark)” manufactured by Solvay, “Amodel (registered trademark)", and “Amodel (registered trademark)” manufactured by Arkema. Examples include “Rilsan (registered trademark)” manufactured by Mitsubishi Gas Chemical Co., Ltd., “MX Nylon (registered trademark)” manufactured by Mitsubishi Engineering Plastics, and “Reny (registered trademark)” manufactured by Mitsubishi Engineering Plastics.
  • the gas barrier layer according to the present invention may contain only one type of polyamide-based polymer, or may contain two or more types of polyamide-based polymers having different monomer compositions, etc. It is preferable that the main component is usually 50% by mass or more, particularly 65 to 100% by mass, especially 75 to 100% by mass. If the polyamide polymer content in the gas barrier layer is at least the above lower limit, excellent mechanical strength and gas barrier properties can be obtained.
  • Ethylene/vinyl alcohol copolymer is produced by saponifying ethylene/vinyl acetate copolymer in the presence of alcohol.
  • the ethylene/vinyl alcohol copolymer constituting the gas barrier layer an ethylene/vinyl acetate copolymer having an ethylene content of preferably 15 to 65 mol%, more preferably 20 to 50 mol% is used, depending on its degree of saponification. It is preferably used that has been saponified so that the amount is preferably 50% or more, more preferably 90% or more.
  • ethylene-vinyl alcohol copolymers Commercial products of such ethylene-vinyl alcohol copolymers include, for example, "Soarnol (registered trademark)” manufactured by Mitsubishi Chemical Corporation, “Eval (registered trademark)” manufactured by Kuraray Co., Ltd., and “Evasin (registered trademark)” manufactured by Changchun Group. registered trademark).
  • the gas barrier layer according to the present invention may contain only one kind of ethylene/vinyl alcohol copolymer, or may contain two or more kinds having different saponification degrees, monomer compositions, etc.
  • the gas barrier layer preferably contains an ethylene/vinyl alcohol copolymer as a main component, usually 50% by mass or more, particularly 65 to 100% by mass, particularly 75 to 100% by mass. If the ethylene/vinyl alcohol copolymer content in the gas barrier layer is at least the above lower limit, excellent gas barrier properties can be obtained.
  • Components other than polyamide polymers and ethylene/vinyl alcohol copolymers that may be included in the gas barrier layer are not particularly limited, but include polyolefins, styrene (co)polymers such as polystyrene, and acrylic/methacrylic copolymers.
  • polymer components such as coalescence, heat-resistant stabilizers, weather-resistant stabilizers (antioxidants, light stabilizers, ultraviolet absorbers, etc.), flame retardants, anti-blocking agents, slip agents, fillers (inorganic and/or organic fillers, etc.) ), processing aids, plasticizers such as paraffin oil, crystal nucleating agents, impact modifiers, compatibilizers, catalyst residue neutralizing agents, coloring agents (pigments, dyes, etc.), and various other additives.
  • plasticizers such as paraffin oil, crystal nucleating agents, impact modifiers, compatibilizers, catalyst residue neutralizing agents, coloring agents (pigments, dyes, etc.), and various other additives.
  • Base material layer Components constituting the base layer according to the present invention include ester polymers, styrene (co)polymers such as polystyrene, polyolefins, acrylic/methacrylic copolymers such as polymethyl methacrylate, polyvinyl chloride, ABS, etc. , thermoplastic polymers such as polycarbonates.
  • ester polymers such as polystyrene, polyolefins, acrylic/methacrylic copolymers such as polymethyl methacrylate, polyvinyl chloride, ABS, etc.
  • thermoplastic polymers such as polycarbonates.
  • a layer made of an ester polymer is preferred in order to impart functionality such as aroma preservability, rigidity, heat resistance, cold resistance, and surface printability.
  • Ester polymers are produced by dehydration condensation of polyhydric carboxylic acids and polyalcohols. For example, those obtained by polycondensing a dicarboxylic acid and a diol can be mentioned.
  • carboxylic acids are not particularly limited, but include, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4- or 2,6-dicarboxylic acid, oxalic acid, Examples include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and undecadicarboxylic acid, and alicyclic dicarboxylic acids such as hexahydroterephtheric acid.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4- or 2,6-dicarboxylic acid, oxalic acid
  • aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and undecadicarboxylic acid
  • diols are not particularly limited, but include, for example, aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, and neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic dihydroxy glycols such as bisphenol A. Examples include compounds.
  • ester polymer examples include polyethylene terephthalate (PET), copolymerized PET, polybutylene terephthalate, polyethylene naphthalate, polycyclohexine terephthalate, and polyester elastomer. These ester polymers can be used alone or in a mixture with a plurality of ester polymers.
  • Polyamide, ethylene/vinyl alcohol copolymers, and ester copolymers are chemically recycled polymers that are polymerized using biomass-derived components and recycled monomers and oligomers obtained by depolymerizing plastic waste materials as starting materials. Any component such as a combined component, a material recycling component obtained by crushing edge trimming waste, slit waste, etc. generated during film manufacturing, or remelting and pelletizing the waste waste or defective film, or It may contain a plurality of these components.
  • the form of the gas barrier layer and the base material layer is not limited to a film or a sheet, but may be a woven fabric or a nonwoven fabric.
  • the gas barrier layer and the base material layer may have a single layer structure or a multilayer structure.
  • the method for creating a base material having a multilayer structure is not particularly limited, and examples thereof include a co-extrusion film method, a dry lamination method, a wet lamination method, a hot melt lamination method, an extrusion lamination method, a thermal lamination method, and the like.
  • the laminate of the present invention may include any layer. can be provided.
  • the laminate of the present invention can also be a laminate in which three or four or more layers are laminated, further comprising a resin layer and/or a base material layer such as the adhesive layer and gas barrier layer described above.
  • Examples of the form of the laminate of the present invention include a laminate film, a laminate sheet, and a laminate tube.
  • film and sheet both mean a planar molded article and have the same meaning.
  • the overall thickness of the laminate of the present invention is not particularly limited, and can be adjusted as appropriate depending on the application.
  • the overall thickness of the laminate of the present invention is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, even more preferably 100 ⁇ m or more, and preferably 10 mm or less, more preferably 6 mm or less, and even more preferably 1 mm or less.
  • the thickness is within the above range, it becomes easy to manufacture a laminate without wrinkles or cracks.
  • the thickness of the adhesive layer made of the modified polyester elastomer of the present invention or the adhesive polymer composition containing the modified polyester elastomer of the present invention is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 10 ⁇ m or more, and preferably is 1 mm or less, more preferably 0.5 mm or less, even more preferably 0.1 mm or less.
  • the thickness of the gas barrier layer is generally 0.002 to 1 mm.
  • the thickness of the base material layer is generally 0.01 to 5 mm.
  • Method for manufacturing laminate As a method for manufacturing the laminate of the present invention, various conventionally known methods can be employed. For example, blown films, cast films, sheets, tubes, pipes, bottles, etc., produced by co-extrusion methods in which individual molten polymers melted in an extruder are supplied to a multilayer die and laminated in the die, and blown films, cast films, sheets, tubes, pipes, bottles, etc. Co-injection molding, in which the polymers are sequentially injected into the same mold, may be used, or co-extrusion lamination, such as an unstretched test tube-shaped parison, may be performed.
  • the modifier of the present invention contains the above-mentioned modified polyester elastomer of the present invention, and particularly modifies properties such as flexibility of polar polymers such as ethylene/vinyl alcohol copolymers and polyamide polymers. It is useful as a modifier for
  • the modified polyester elastomer of the present invention is used as a modifier for these polar polymers, there is no particular restriction on the mixing ratio of the modified polyester elastomer of the present invention to the polar polymer;
  • the amount of the modified polyester elastomer of the present invention is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or more, based on the total amount with the elastomer. It is preferable to use it in an amount of not more than 23% by mass, more preferably not more than 20% by mass, particularly preferably not more than 20% by mass. If the proportion of the modified polyester elastomer of the present invention is within the above range, the modification effect of the modified polyester elastomer of the present invention can be sufficiently obtained without impairing the properties as a polar polymer.
  • the polar polymer composition of the present invention is a polar polymer composition containing 1 to 30% by mass of the above-mentioned modified polyester elastomer of the present invention based on the total of the polar polymer and the modified polyester elastomer of the present invention.
  • the polar polymer contains at least one selected from an ethylene/vinyl alcohol copolymer and a polyamide polymer.
  • ethylene/vinyl alcohol copolymer and polyamide polymer contained in the polar polymer composition of the present invention include the ethylene/vinyl alcohol copolymer and polyamide contained in the gas barrier layer in the laminate of the present invention described above.
  • system polymer examples include those listed above, and preferred ones are also the same.
  • the ethylene/vinyl alcohol copolymer and the polyamide polymer may each be used alone or in a mixture of two or more.
  • One or more ethylene/vinyl alcohol copolymers and one or more polyamide polymers may be used as a mixture.
  • the modified polyester elastomer of the present invention in the polar polymer composition of the present invention, if the content of the modified polyester elastomer of the present invention is 1% by mass or more based on the total of the polar polymer and the modified polyester elastomer of the present invention, the modified polyester elastomer of the present invention can be used. By containing it, a sufficient modification effect can be obtained. When the content of the modified polyester elastomer of the present invention is 30% by mass or less with respect to the total of the polar polymer and the modified polyester elastomer of the present invention, the characteristics inherent to the polar polymer can be sufficiently obtained.
  • the content of the modified polyester elastomer of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total of the polar polymer and the modified polyester elastomer of the present invention. On the other hand, it is preferably 25% by mass or less, more preferably 23% by mass or less, and even more preferably 20% by mass or less. From the same viewpoint, the content of the polar polymer is 70% by mass or more, preferably 75% by mass or more, more preferably 77% by mass or more, and 80% by mass based on the total of the polar polymer and the modified polyester elastomer. % is more preferable. On the other hand, it is 99% by mass or less, preferably 97% by mass or less, and more preferably 95% by mass or less.
  • the polar polymer composition of the present invention may contain polymers other than the polar polymer and the modified polyester elastomer of the present invention, arbitrary additives, etc. (hereinafter referred to as These are referred to as "other ingredients"). As for the other components, only one type may be used, or two or more types may be used in combination in any combination and ratio.
  • additives include antioxidants, ultraviolet absorbers, plasticizers, lubricants, fillers, and antistatic agents.
  • the total content of these additives in the polar polymer composition of the present invention is usually 50% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less.
  • Method for producing polar polymer composition There is no particular restriction on the method of mixing each component to obtain the polar polymer composition of the present invention, and the polar polymer, the modified polyester elastomer of the present invention, and other components used as necessary may be dry blended at once.
  • a method of melt-kneading the polar polymer, the modified polyester elastomer of the present invention, and some of the other components used as necessary, and then blending the other components and melt-kneading. can be mentioned.
  • a specific method for melt-kneading is to uniformly mix each component at a predetermined blending ratio using a Henschel mixer, ribbon blender, V-type blender, etc., and then mix the components using a multi-screw kneading extruder, such as Ikegai.
  • An example of this method is a method of kneading using PCM30, a twin-screw kneading extruder manufactured by Co., Ltd.
  • the temperature for melt-kneading each component is generally 100 to 300°C, preferably 120 to 280°C, similar to the temperature during the modification treatment with an unsaturated carboxylic acid and/or its derivative in the modified polyester elastomer of the present invention described above. Preferably it is 150 to 250°C.
  • a molded article (hereinafter sometimes referred to as a "polar polymer molded article") can be obtained by molding the polar polymer composition of the present invention.
  • Examples of the shape of the polar polymer molded product include films, sheets, tapes, cups, trays, tubes, bottles, pipes, filaments, irregular cross-section extrudates, and various irregularly shaped products.
  • heating and stretching processing refers to a film, sheet, or parison-shaped molded product that has been uniformly heated to a cup, tray, tube, bottle, film, etc. using a chuck, plug, vacuum force, pneumatic force, blow, etc.
  • the stretching method include a roll stretching method, a tenter stretching method, a tubular stretching method, a stretch blowing method, a vacuum forming method, a pressure forming method, a vacuum pressure forming method, and the like.
  • the stretching may be either uniaxial stretching or biaxial stretching, but in the case of biaxial stretching, either a simultaneous biaxial stretching method or a sequential biaxial stretching method can be adopted.
  • the stretching temperature is usually 60 to 170°C, more preferably 80 to 160°C.
  • A-1 Polyester elastomer A polyester polyether block copolymer having polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment, in which Using a polyester elastomer with a polytetramethylene ether glycol segment content of 73% by mass (density: 1.07 g/cm 3 , melting point: 160.1°C, JIS-D hardness: 24, MFR: 20 g/10 min) there was.
  • A-2 Polyester elastomer A polyester polyether block copolymer having polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment, in which A polyester elastomer with a content of polytetramethylene ether glycol segments of 64% by mass (density: 1.10 g/cm 3 , melting point: 186.1°C, JIS-D hardness: 31, MFR: 21 g/10 min) was used. there was.
  • A-3 Polyester elastomer A polyester polyether block copolymer having polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 1,000 as a soft segment, in which Using a polyester elastomer with a polytetramethylene ether glycol segment content of 61% by mass (density: 1.10 g/cm 3 , melting point: 160.6°C, JIS-D hardness: 38, MFR: 17 g/10 min) there was.
  • A-4 Polyester elastomer A polyester polyether block copolymer having polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment, in which A polyester elastomer with a content of polytetramethylene ether glycol segments of 64% by mass (density: 1.09 g/cm 3 , melting point: 184.8°C, JIS-D hardness: 31, MFR: 26 g/10 min) was used. there was.
  • Polyester elastomer A polyester polyether block copolymer having polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment, in which Polyester elastomer with a polytetramethylene ether glycol segment content of 75% by mass (density: 1.06 g/cm 3 , melting point: 147.2.0°C, JIS-D hardness: 22, MFR: 25 g/10 min) was used.
  • A-6 Polyester elastomer A polyester polyether block copolymer having polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 1,000 as a soft segment, in which A polyester elastomer (density: 1.12 g/cm 3 , melting point: 165° C., JIS-D hardness: 33, MFR: 29 g/10 min) having a polytetramethylene ether glycol segment content of 58% by mass was used.
  • Example 1-3 and Comparative Example 1-3 the physical properties were evaluated for the modified polyester elastomer, and for the other Examples and Comparative Examples, the adhesive polymer composition containing the modified polyester elastomer was evaluated. Physical properties were evaluated.
  • the content of additives (antiblocking agents) other than the modified polyester elastomers was very small; Since the evaluation results can be regarded as evaluation results for the modified polyester elastomer, they are shown as values for the modified polyester elastomer.
  • titanium content The titanium content of the adhesive polymer composition containing the polyester elastomer and modified polyester elastomer/modified polyester elastomer was measured according to the method described above.
  • Polyalkylene ether glycol segment content The polyalkylene ether glycol content in the adhesive polymer composition containing the polyester elastomer and modified polyester elastomer/modified polyester elastomer was measured according to the method described above.
  • MFR MFR is determined by vacuum drying an adhesive polymer composition containing a modified polyester elastomer in pellet form at 100°C for 4 hours to remove the moisture content, and then drying it at a temperature of 230°C and under a load of 2.5 hours in accordance with JIS K7210. Measurement was carried out under the conditions of 16 kg and 10 minutes.
  • Acid value was measured by neutralization titration method. Specifically, a sample was poured into a benzyl alcohol solvent, heated and dissolved in an oil bath at 195°C, cooled by adding a chloroform solvent, and dissolved in benzyl alcohol sodium hydroxide with a known titer of 0.1 mol/L. Indicator titration was performed using the solution, and the end point was when the sample solution changed color from yellow to red, and the acid (carboxyl group) value was calculated from the following formula.
  • the melting point was measured using a differential scanning calorimeter (DSC). Specifically, once the temperature was raised to 300°C to erase the thermal history, the temperature was lowered to 40°C at a cooling rate of 10°C/min, and then raised again at a heating rate of 10°C/min. The temperature at the top of the endothermic peak during measurement is defined as the melting point. The unit is °C.
  • Hardness was measured using a durometer in accordance with JIS K6253 (D hardness).
  • the acid modification rate means the content rate of the unsaturated carboxylic acid component in the modified polyester elastomer as measured with an infrared spectrometer (JASCOFT/IR610, manufactured by JASCO Corporation).
  • the acid modification rate is determined by the rate of unsaturated carboxylic acid and/or its derivatives in a sample obtained by press-molding pellets of an adhesive polymer composition containing a modified polyester elastomer into a sheet with a thickness of 20 to 50 ⁇ m at 230°C. It was determined by measuring the ratio of absorption (1900 to 1600 cm -1 ) and absorption (1000 to 800 cm -1 ) specific to the aromatic ring in the hard segment.
  • the interlaminar strength of the laminate is 2 N/15 mm or more, it is considered to be a strength sufficient for practical use, and those with an adhesive retention rate of more than 80% after the heat resistance test were considered to be passed.
  • the 5-layer film obtained in each example was cut into test pieces with a width of 15 mm parallel to the molding direction, and a T-peel peel test was performed at a constant temperature of 23°C at a speed of 300 mm/min to determine the adhesive strength. was measured.
  • the adhesive strength of Examples 1 to 6 and Comparative Examples 1 to 3 is the adhesive strength at the interface between the PA6 layer and the adhesive layer.
  • Izod impact strength was measured under four temperature conditions (23°C, 0°C, -30°C, -50°C) in accordance with ISO 180/1A.
  • a laminate was manufactured using the adhesive polymer composition containing the modified polyester elastomer obtained above as the adhesive layer material.
  • a multilayer film molding machine (Labtech Engineering Co.) having a three-type, five-layer feedblock type T-die with a width of 350 mm, an ester polymer layer/an adhesive layer made of an adhesive polymer composition containing a modified polyester elastomer/ A five-layer film was produced as a laminate of a polyamide (PA6) layer/an adhesive layer made of an adhesive polymer composition containing a modified polyester elastomer/an ester polymer layer.
  • the temperature of the T die was set at 240° C., the molding speed was 6 m/min., the cast roll temperature was 80° C., and a film having a total thickness of 120 ⁇ m with each layer having a thickness of 40 ⁇ m/10 ⁇ m/20 ⁇ m/10 ⁇ m/40 ⁇ m was obtained.
  • the adhesive strength of the obtained five-layer film was measured.
  • Examples 1-2 to 1-6, Comparative Examples 1-1 to 1-3 In producing an adhesive polymer composition containing a modified polyester elastomer, pellets of an adhesive polymer composition containing a modified polyester elastomer were prepared in the same manner as in Example 1-1 except that the formulations listed in Table 1 were used. A laminate was produced in the same manner, and measurements were taken on each. The results are shown in Table 1.
  • Table 1 shows the polyalkylene ether glycol segment content and titanium content of the polyester elastomer used to produce the modified polyester elastomer, and the polyalkylene ether glycol segment content and titanium content of the modified polyester elastomer. Acid value, melt flow rate, density, melting point, hardness, and acid modification rate are also listed.
  • Example 2-1 ⁇ Production of modified ethylene/vinyl alcohol copolymer (EVOH) composition and production of test pieces> 20 parts by mass of pellets of the adhesive polymer composition containing the modified polyester elastomer obtained in Example 1-1 and ethylene-vinyl alcohol copolymer (EVOH) "Soarnol (registered trademark) DC3203RB” manufactured by Mitsubishi Chemical Corporation. 80 parts by mass were dry blended and mixed, kneaded and molded at a set temperature of 230°C using a multi-purpose small molding machine (Micro 15cc Twin Screw Compounder manufactured by Leo Lab Co., Ltd.) to form a 4 mm thick x 10 mm wide x 80 mm long piece.
  • a multi-purpose small molding machine Micro 15cc Twin Screw Compounder manufactured by Leo Lab Co., Ltd.
  • Test pieces for Izod impact strength and flexural modulus measurements were obtained. Thereafter, a notch was made in the test piece for Izod impact strength measurement using a notching tool (refer to JIS K7110 for the dimensions of the notch). The flexural modulus and Izod impact strength of the obtained test piece were measured. The above measurement results are shown in Table 2.
  • PA modified polyamide polymer
  • Pellets were obtained by kneading and strand cutting.
  • modified polyamide polymer (PA) composition obtained above was kneaded and molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS130GN-5A) at an injection temperature of 260°C and a mold temperature of 80°C.
  • a test piece was prepared in the same manner as Example 2-1.
  • the flexural modulus and Izod impact strength of the obtained test piece were measured. The above measurement results are shown in Table 2.
  • Example 2-2 Comparative Examples 2-1 to 2-3
  • EVOH modified ethylene/vinyl alcohol copolymer
  • Table 2 also lists the color tone (pellet YI) measured for each modified polyester elastomer.
  • the modified ethylene-vinyl alcohol copolymer (EVOH) compositions of Examples 2-1 and 2-2 containing the modified polyester elastomer of the present invention having a titanium content of less than 250 wtppm did not contain the modified polyester elastomer.
  • the flexibility is improved compared to Comparative Example 2-3.
  • the modified polyamide polymer (PA) composition of Example 3-1 containing the modified polyester elastomer of the present invention having a titanium content of less than 250 wtppm was different from that of Comparative Example 3-2 containing no modified polyester elastomer. Flexibility is improved in comparison.
  • the modified ethylene-vinyl alcohol copolymer (EVOH) compositions of Comparative Examples 2-1 and 2-2 which were blended with a modified polyester elastomer having a titanium content of 250 wtppm or more, and the modified ethylene-vinyl alcohol copolymer (EVOH) compositions of Comparative Example 3-1.
  • the flexibility of the polyamide-based polymer (PA) composition was improved, the color tone of the modified polyester-based elastomer was inferior to that of Examples 2-1 to 2-2 and Example 3-1.
  • the color tone of the vinyl alcohol copolymer composition and the modified polyamide polymer (PA) composition seems to be inferior.

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PCT/JP2023/009272 2022-03-11 2023-03-10 変性ポリエステル系エラストマー及びその製造方法 Ceased WO2023171792A1 (ja)

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CA3244801A CA3244801A1 (en) 2022-03-11 2023-03-10 MODIFIED POLYESTER-BASED ELASTOMER AND ITS PRODUCTION PROCESS
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JP2022038261A (ja) 2020-08-26 2022-03-10 日本車輌製造株式会社 杭打機の作業装置取付用治具
JP2022099720A (ja) 2020-12-23 2022-07-05 株式会社デンソー 半導体パッケージおよびこれを用いた電子装置

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