WO2015083819A1 - ポリアミド系熱可塑性エラストマー組成物及びその成形品 - Google Patents
ポリアミド系熱可塑性エラストマー組成物及びその成形品 Download PDFInfo
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- WO2015083819A1 WO2015083819A1 PCT/JP2014/082224 JP2014082224W WO2015083819A1 WO 2015083819 A1 WO2015083819 A1 WO 2015083819A1 JP 2014082224 W JP2014082224 W JP 2014082224W WO 2015083819 A1 WO2015083819 A1 WO 2015083819A1
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/24—1,3 - Benzenedicarboxylic acid
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D3/00—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive
- F16D3/84—Shrouds, e.g. casings, covers; Sealing means specially adapted therefor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/50—Sealings between relatively-movable members, by means of a sealing without relatively-moving surfaces, e.g. fluid-tight sealings for transmitting motion through a wall
- F16J15/52—Sealings between relatively-movable members, by means of a sealing without relatively-moving surfaces, e.g. fluid-tight sealings for transmitting motion through a wall by means of sealing bellows or diaphragms
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such 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
- C08L2312/00—Crosslinking
- C08L2312/04—Crosslinking with phenolic resin
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
Definitions
- the present invention relates to a polyamide-based thermoplastic elastomer composition excellent in rubber elasticity and moldability, and a molded article thereof.
- the present invention also relates to a polyamide-based thermoplastic elastomer composition having good high temperature elastic retention, oil resistance, and moldability, and a molded article obtained from the composition by injection molding or blow molding (for example, a constant velocity joint for automobiles). Boots).
- the present invention relates to a resin composition used for an industrial tube, which is a polyamide-based thermoplastic elastomer composition excellent in flexibility, impact resistance, fuel and solvent permeation prevention properties, and swelling resistance, and this composition.
- the present invention relates to an industrial tube having at least a layer containing an object.
- Thermoplastic elastomer is a recyclable rubber material and has been actively researched in recent years.
- rubber elasticity is exhibited at room temperature in the same manner as vulcanized rubber, but since the matrix phase is plasticized and flows at high temperature, it can be handled in the same manner as a thermoplastic resin.
- a thermoplastic elastomer does not require a vulcanization step, and has an advantage that it can be processed by a normal thermoplastic resin molding machine.
- polyester-based thermoplastic elastomers have excellent durability, oil resistance, and heat resistance, and because of their high elastic modulus, they can be made thinner, meeting the needs of weight reduction and cost reduction. Actively studied as a material.
- thermoplastic elastomer in applications requiring oil resistance and gas barrier properties, block copolymers containing a crystalline resin synthesized by a polycondensation reaction such as polyester or polyamide as a hard segment are mainly used.
- a polyester elastomer in which the hard segment is made of polyester and the soft segment is made of polyether, and a polyamide elastomer in which the hard segment is made of polyamide and the soft segment is made of polyether are known.
- these thermoplastic elastomers have poor flexibility, rubber elasticity is not sufficient, and in addition, since it is inevitable that soft segments are mixed in hard segments, there is a disadvantage that heat resistance is low. Therefore, applicable applications are limited.
- a method for improving the flexibility there is a method for increasing the content of the soft segment in the polymer.
- the content of the soft segment is large, the oil resistance deteriorates and the heat resistance further decreases, and further, the gas barrier property tends to be remarkably impaired.
- a method of adding a plasticizer made of an organic compound is also known.
- polyester-based elastomers and polyamide-based elastomers are crystalline resins, and are hardly compatible with plasticizers (does not absorb much), so their plasticizing effect is small.
- a bleed phenomenon of the plasticizer may occur during use of the product.
- the plasticizer when the product is kept in contact with the oil for a long time, the plasticizer may be dissolved in the oil and the flexibility may be lowered. Furthermore, when the product is placed at a high temperature, the plasticizer volatilizes, and the same problem may occur.
- Patent Document 1 and Patent Document 2 in order to solve such problems, core-shell type rubber particles are added to a resin such as a polyester-based elastomer or a polyamide-based elastomer to improve flexibility and compression set.
- a resin such as a polyester-based elastomer or a polyamide-based elastomer to improve flexibility and compression set.
- a thermoplastic elastomer composition is disclosed.
- Patent Document 3 discloses a group consisting of polyamide, acrylic rubber, nitrile rubber, and polyether rubber as a thermoplastic elastomer that has sufficient flexibility while maintaining excellent oil resistance and improved high-temperature compression set.
- Patent Document 4 discloses a dynamic cross-linkable thermoplastic elastomer containing an aromatic polyamide and an addition polymerization block copolymer as a thermoplastic elastomer having good oil resistance and excellent chemical resistance and gas barrier properties. It is disclosed.
- polyester thermoplastic elastomers whose applications are being developed in various fields such as automobile parts and machine parts, are excellent in durability, oil resistance and heat resistance, and can be thinned due to their high elastic modulus. Therefore, it is actively considered as a substitute material for oil-resistant rubber because it well meets the needs for weight reduction and cost reduction.
- a chloroprene rubber material has been mainly used as a material for resin flexible boots having a bellows shape because it is relatively inexpensive, has an appropriate flexibility, and has excellent creep characteristics.
- replacement with polyester-based thermoplastic elastomers has been promoted because of the advantages that the manufacturing process can be simplified, the heat resistance is excellent, and the durability life as a boot material is long (Patent Document 5). .
- polyamides represented by nylon 6, nylon 66, etc. have excellent physical properties such as molding processability, mechanical properties, chemical resistance, etc., so that they are for automobiles, industrial materials, clothing, electrical / electronics, industrial use, etc. It is widely used as a component material in various fields.
- Nylon 11 and nylon 12 which are particularly excellent in flexibility, have been widely used, including tubes and hose molded products such as fuel pipes for automobiles.
- molded articles using nylon 11 or nylon 12 are excellent in toughness, chemical resistance and flexibility, but are not sufficient in permeation-preventing properties against fuels and alcohols. Therefore, it has become difficult to respond to the fuel gas transpiration regulations surrounding automobiles in recent years.
- a plasticizer such as butylbenzenesulfonamide (BBSA) added for softening the tube is extracted into the fuel, which may clog the tube or reduce the flexibility of the tube itself. .
- BBSA butylbenzenesulfonamide
- Patent Document 6 proposes a multilayer tube in which the outer layer is made of aliphatic polyamide and the inner layer is laminated with 9T nylon. This multilayer tube improves chemical resistance and fuel gas permeation prevention.
- Patent Document 7 a composition in which an impact modifier (polyolefin elastomer) is added to 10T10.10 nylon is used for the outer layer, and a specific fluorinated polymer is used as a barrier layer for the inner layer. Structures have been proposed.
- an impact modifier polyolefin elastomer
- Patent Document 8 proposes a polyamide 62 using oxalic acid as an aliphatic polyamide having excellent gas permeation-preventing properties. This polyamide is excellent in fuel permeation prevention and tube formability.
- thermoplastic elastomers described in Patent Documents 1 to 4 each have insufficient specific characteristics.
- compositions described in Patent Document 1 and Patent Document 2 are not sufficiently improved in flexibility, and also have a problem in moldability (fluidity) of the composition. Furthermore, since it is difficult to sufficiently disperse the rubber component in the composition, the surface appearance of the molded product tends to be inferior when extrusion molding or blow molding is performed.
- composition described in Patent Document 3 has poor moldability and cannot be said to have sufficient compression set resistance.
- versatility is low.
- the melting point of the aromatic polyamide used in the composition described in Patent Document 4 is as high as 317 ° C., it is difficult to control the reaction in the dynamic crosslinking step. Moreover, since the molding temperature of the composition is high, extrusion molding and blow molding are difficult. Furthermore, as can be seen from the examples and comparative examples of Patent Document 4, the hardness (rubber hardness) is increased by crosslinking, and it is difficult to control flexibility, and dynamic crosslinking provides sufficient flexibility. It is hard to say that it is attached.
- a polyester thermoplastic elastomer has a problem that its high temperature elastic retention is low because its elastic modulus decreases with softening when used at high temperatures.
- the mechanical strength of the product is remarkably lowered at a high temperature especially by hydrolysis.
- boot materials are required to have higher heat resistance. This is considered to be caused by, for example, changes in engine specifications (introduction of a supercharging system or exhaust gas recirculation system) or changes in the design of the vehicle body (e.g., installation of a vehicle under cover) accompanying an improvement in fuel efficiency. Further, it is becoming difficult to satisfy further heat resistance requirements with polyester-based thermoplastic elastomers having a low high temperature elastic retention and poor hydrolysis resistance.
- the outer layer has both sufficient flexibility (flexibility) and zinc chloride resistance.
- the resin performance of the barrier layer (fluorinated polymer layer) on the inner side is not sufficient, and it is necessary to make the barrier layer a multilayer structure as in the case of conventional materials. As a result, the flexibility of the multilayer structure is not sufficient.
- an object of the present invention is to provide a polyamide-based thermoplastic elastomer composition having excellent rubber elasticity such as flexibility, compression set resistance and elongation, and excellent moldability such as extrusion moldability, and a molded product thereof. There is to do.
- Another object of the present invention is to provide a polyamide-based thermoplastic elastomer composition having good high temperature elastic retention, oil resistance, and moldability, and a molded product thereof.
- the object of the present invention is to provide various performances required for industrial tubes, that is, sufficient flexibility and impact resistance without using a large amount of plasticizer, and also prevents permeation and resistance to fuel and solvent. It is in providing the resin composition excellent in swelling property, and the industrial tube using this resin composition.
- the present invention includes the following aspects [1] to [19].
- Polyamide [I] having a structural unit derived from terephthalic acid in an amount of 30 to 100 mol% in all dicarboxylic acid structural units, and having a melting point (Tm) determined by differential scanning calorimetry (DSC) of 220 to 290 ° C .; Ethylene / ⁇ containing structural units derived from ethylene [a], ⁇ -olefin [b] having 3 to 20 carbon atoms, and non-conjugated polyene [c] having at least one carbon-carbon double bond in one molecule
- An olefin / non-conjugated polyene copolymer rubber [II] A rubber composition [X] containing an olefin polymer [III] containing 0.3 to 5.0% by mass of a functional group structural unit in the molecule is dynamically crosslinked with a phenol resin crosslinking agent [IV].
- the functional group structural unit of the olefin polymer [III] includes a functional group selected from the group consisting of a carboxylic acid group, an ester group, an ether group, an aldehyde group, and a ketone group.
- the polyamide [I] is a matrix component, and the dispersion component dispersed in the matrix component is the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] and the olefin polymer [III].
- the polyamide-based thermoplastic elastomer composition [Y] satisfying the following (1): (1) The cross-sectional area of the particle having a particle size of 5 ⁇ m or more of the dispersed component is measured, and the ratio of the total cross-sectional area of the area to the entire cross-sectional area analyzed is 10% or less.
- the mass ratio ([II] / [III]) of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] and the olefin polymer [III] is The polyamide-based thermoplastic elastomer composition [Y1] according to [8], which is 95/5 to 60/40.
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] is 10 to 45 mass%, and the olefin polymer [III] is 2 to 20 mass%.
- the industrial tube according to [13] which is a tube for automobile piping, a pneumatic tube, a hydraulic tube, a paint spray tube, or a medical tube.
- fluorine resin high density polyethylene resin, polybutylene naphthalate resin (PBN), aliphatic polyamide resin, aromatic polyamide resin, metaxylene group-containing polyamide resin, saponified ethylene-vinyl acetate copolymer (EVOH)
- PPS polyphenylene sulfide resins
- Polyamide [Z1] having a melting point (Tm) determined by differential scanning calorimetry (DSC) of 210 to 270 ° C. and a heat of fusion ( ⁇ H) determined by DSC of 45 to 80 mJ / mg of 10 to 35% by mass
- Tm melting point
- ⁇ H heat of fusion
- the polyamide-based thermoplastic elastomer composition [Z] wherein the polyamide-based resin composition [Z2] is the polyamide-based thermoplastic elastomer composition [Y2] according to [12].
- a constant velocity joint boot for an automobile comprising the polyamide-based thermoplastic elastomer composition [Z] according to [17].
- the polyamide-based thermoplastic elastomer composition [Y], [Y1], excellent in elasticity, compression set resistance, rubber elasticity such as elongation, and excellent in moldability such as extrusion moldability, [Y2] and [Z] and a molded product thereof can be provided.
- Polyamide [I] used in the present invention has a structural unit derived from terephthalic acid in an amount of 30 to 100 mol% in all dicarboxylic acid structural units, and has a melting point (Tm) determined by differential scanning calorimetry (DSC) of 220 to 290 ° C. Is a polyamide.
- the structural unit derived from terephthalic acid is a unit represented by the following formula [IA].
- Polyamide [I] is obtained by a polycondensation reaction of a dicarboxylic acid component and a diamine component, and the molecule contains a dicarboxylic acid structural unit and a diamine structural unit.
- the proportion of structural units derived from terephthalic acid in 100 mol% of all dicarboxylic acid structural units in the polyamide [I] molecule is 30 to 100 mol%, preferably 40 to 100 mol%, more preferably 50 to 50 mol%. 100 mol%.
- the polyamide [I] contains a structural unit derived from terephthalic acid, its crystallinity increases and physical properties such as heat resistance are improved.
- the polyamide [I] is preferably a semi-aromatic polyamide having a part of an aliphatic skeleton.
- dicarboxylic acid component constituting the polyamide [I] an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid other than terephthalic acid can be used in combination with terephthalic acid.
- aromatic dicarboxylic acids other than terephthalic acid examples include isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, Examples include 1,3-phenylenedioxydiacetic acid, diphenic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. Two or more of these can be used in combination. Among these, isophthalic acid is preferable from the viewpoint of increasing the melt tension.
- the content of structural units derived from aromatic dicarboxylic acids (such as isophthalic acid) other than terephthalic acid is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, based on all dicarboxylic acid structural units.
- the aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 4 to 12 carbon atoms such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. Two or more of these can be used in combination. Among these, adipic acid is particularly preferable from the viewpoint of cost and mechanical properties.
- the content of the structural unit derived from the aliphatic dicarboxylic acid is preferably 0 to 50 mol%, more preferably 0 to 40 mol% in the total dicarboxylic acid structural unit.
- an aliphatic diamine is preferable.
- the number of carbon atoms in the aliphatic diamine is preferably 4-12, more preferably 6-9.
- Specific examples of the aliphatic diamine include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, Linear aliphatic diamines such as 1,11-diaminoundecane and 1,12-diaminododecane; 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1, 7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-
- aminocarboxylic acid having both amine and carboxylic acid in the molecule may be used as a component constituting polyamide [I].
- Specific examples of aminocarboxylic acids include linear forms such as 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.
- Aminocarboxylic acid; Two or more of these can be used in combination. Of these, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred.
- Polyamide [I] can be produced according to conventionally known methods.
- a dicarboxylic acid component containing terephthalic acid and a diamine component may be subjected to a condensation polymerization reaction in a solution.
- the end group of at least a part of the molecular chain of the polyamide [I] is preferably sealed with an end-capping agent.
- the proportion of terminal groups sealed with a terminal blocking agent is preferably 10% or more, more preferably 40% or more, and particularly preferably 60. % Or more, most preferably 75% or more.
- the amount of terminal amino groups of the molecular chain is preferably 0.1 to 100 mmol / kg, more preferably 0.1 to 30 mmol / kg.
- the end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide.
- monocarboxylic acid is used.
- An acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling.
- acid anhydride monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used.
- the monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group.
- Specific examples thereof include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid;
- Examples include alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
- Two or more of these can be used in combination.
- acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, benzoic acid Acid is more preferred.
- the monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group.
- Specific examples thereof include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; cyclohexylamine, dicyclohexylamine and the like.
- aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine. Two or more of these can be used in combination.
- butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are more preferable from the viewpoints of reactivity, boiling point, stability of the sealing end and price.
- the amount of the end-capping agent used when producing the polyamide [I] is preferably determined from the relative viscosity of the finally obtained polyamide and the capping rate of the end groups.
- the specific amount used varies depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-capping agent used, but is usually 0.3 to 10 with respect to the total number of moles of dicarboxylic acid and diamine as raw materials. Used in the range of mol%.
- the melting point (Tm) determined by differential scanning calorimetry (DSC) of polyamide [I] is 220 to 290 ° C, preferably 230 to 280 ° C, more preferably 240 to 280 ° C.
- Tm melting point
- This melting point (Tm) is measured under the following conditions. First, polyamide [I] is heated and once held at 320 ° C. for 5 minutes, then the temperature is lowered to 23 ° C. at a rate of 10 ° C./minute, and then the temperature is increased at a rate of 10 ° C./minute. The endothermic peak based on melting at this time is defined as the melting point (Tm) of the polyamide [I].
- the heat of fusion ( ⁇ H) obtained from DSC of polyamide [I] is 10 to 44 mJ / mg, preferably 15 to 40 mJ / mg, more preferably 20 to 40 mJ / mg.
- the melt flow rate (T + 10 ° C., 2.16 kg) of polyamide [I] is preferably 1 to 300 g / 10 minutes, more preferably 5 to 250 g / 10 minutes.
- This melt flow rate is a value measured in accordance with ASTM D1238 procedure B.
- T here refers to the melting end temperature (T) determined by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- the melting end temperature (T) refers to a temperature at which the endotherm due to melting disappears in DSC similar to the measurement of the melting point. Specifically, it refers to the temperature at which the endothermic peak observed in DSC returns to the baseline.
- the intrinsic viscosity [ ⁇ ] of the polyamide [I] is preferably 0.5 to 1.6 dl / g, more preferably 0.6 to 1.4 dl / g, and particularly preferably 0.6 to 1.4 dl / g. is there.
- the intrinsic viscosity [ ⁇ ] is within the above range, the fluidity at the time of molding of the resin composition can be improved, and the mechanical properties of the obtained molded product are also improved.
- This intrinsic viscosity [ ⁇ ] is a value measured in a temperature of 25 ° C. and 96.5% sulfuric acid.
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] used in the present invention is composed of ethylene [a], ⁇ -olefin [b] having 3 to 20 carbon atoms, carbon / polymerizable with a metallocene catalyst. It is a copolymer rubber containing a structural unit derived from non-conjugated polyene [c] having one or more carbon double bonds in one molecule.
- ⁇ -olefin [b] having 3 to 20 carbon atoms Specific examples of the ⁇ -olefin [b] having 3 to 20 carbon atoms constituting the copolymer rubber [II] include propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene. 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene. Of these, ⁇ -olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferable.
- Copolymer rubber [II] may contain structural units derived from two or more ⁇ -olefins [b].
- the ⁇ -olefin [b] is preferable because the raw material cost is relatively low and the copolymerization is excellent, and the copolymer rubber [II] is imparted with excellent mechanical properties and good flexibility.
- Non-conjugated polyene [c] Non-conjugated polyenes [c] having at least one carbon / carbon double bond per molecule that can be polymerized by the metallocene catalyst constituting the copolymer rubber [II], for example, aliphatic polyenes and alicyclic polyenes Can be used.
- aliphatic polyene examples include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene, and 3-methyl.
- 1,4-hexadiene 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5 -Methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4 -Methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6 -Methyl- 1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-oc
- alicyclic polyene examples include 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB); 5-alkenyl-2-norbornene such as 5-allyl-2-norbornene; 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, tetracyclo [4,4,0,1 2.5 , 1 7.10 ] Deca-3,8-diene.
- ENB 5-ethylidene-2-norbornene
- ENB 5-ethylidene-2-norbornene
- copolymer rubber [II] may contain a structural unit derived from two or more kinds of non-conjugated polyenes [c].
- the copolymer rubber [II] can be synthesized, for example, by the method described in JP2010-241897A.
- the proportion of the structural unit derived from ethylene [a] in 100% by mass of all the structural units of the copolymer rubber [II] is preferably 50 to 89% by mass, more preferably 55 to 83% by mass.
- the proportion of the structural unit derived from the ⁇ -olefin [b] having 3 to 20 carbon atoms is preferably 10 to 49% by mass, more preferably 15 to 43% by mass.
- the proportion of the structural unit derived from non-conjugated polyene [c] is preferably 1 to 20% by mass, more preferably 2 to 15% by mass.
- the intrinsic viscosity [ ⁇ ] of the copolymer rubber [II] is preferably 0.5 to 5.0 dl / g, more preferably 1.0 to 4.5 dl / g, and particularly preferably 1.5 to 4.0 dl. / G.
- This intrinsic viscosity [ ⁇ ] is a value measured in decalin at a temperature of 135 ° C., and can be determined by measuring according to ASTM D 1601.
- the olefin polymer [III] used in the present invention is an olefin polymer containing 0.3 to 5.0% by mass of a functional group structural unit.
- the olefin polymer [III] include a modified polyolefin ([III] -1) in which a functional group is introduced into a polyolefin molecular chain by reacting a compound having a functional group, an olefin monomer and a monomer having a functional group. And a functional group-containing olefin copolymer ([III] -2) obtained by copolymerization of
- polyolefin constituting the modified polyolefin ([III] -1) include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-butene copolymer.
- an unsaturated carboxylic acid or a derivative thereof can be used as the compound having a functional group constituting the modified polyolefin ([III] -1).
- the unsaturated carboxylic acid or derivative thereof include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [ Unsaturated carboxylic acids such as 2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid [trademark]), and derivatives of these acid halides, amides, imides, acid anhydrides, esters, etc.
- maleic anhydride has a relatively high reactivity with the polyolefin before modification, is less likely to cause polymerization between maleic anhydrides, and tends to be stable as a basic structure. Therefore, there are various advantages such as obtaining a modified polyolefin ([III] -1) having a stable quality.
- modified polyolefin ([III] -1) is a modified ethylene / ⁇ -olefin copolymer.
- the density of the modified ethylene / ⁇ -olefin copolymer is preferably 0.80 to 0.95 g / cm 3 , more preferably 0.85 to 0.90 g / cm 3 .
- Examples of the functional group-containing olefin copolymer ([III] -2) include a copolymer of ethylene and a monomer having a functional group such as an acrylic monomer or a vinyl monomer. Specific examples include an ethylene / vinyl acetate / maleic anhydride copolymer (Orevac (registered trademark), etc., manufactured by Arkema), an ethylene / acrylic acid ester / functional acrylic acid ester (for example, glycidyl acrylate or glycidyl methacrylate) copolymer. (Lotader (registered trademark) manufactured by Arkema Co., Ltd.).
- the intrinsic viscosity [ ⁇ ] measured in a 135 ° C. decalin (decahydronaphthalene) solution of the olefin polymer [III] is preferably 0.5 to 4.0 dl / g, more preferably 0.7 to 3.0 dl. / G, particularly preferably 0.8 to 2.5 dl / g. If [ ⁇ ] is within the above range, the toughness and melt fluidity of the resin composition can be achieved at a high level.
- This intrinsic viscosity [ ⁇ ] is measured as follows based on a conventional method. 20 mg of a sample is dissolved in 15 ml of decalin, and the specific viscosity ( ⁇ sp) is measured in an atmosphere of 135 ° C.
- the content of the functional group structural unit of the olefin polymer [III] is 0.3 to 5.0% by mass, preferably 0.4 to 4.0% by mass. If there are too few functional group structural units, the dispersibility of the polyamide [I] and the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] is lowered, the extrusion design surface is remarkably deteriorated, and the mechanical strength is reduced. May cause decline. On the other hand, when there are too many functional group structural units, an abnormal reaction with polyamide [I] occurs and gelation occurs, so that melt flowability is lowered, and as a result, moldability may be lowered.
- the content of this functional group structural unit is the ratio (mass%) of the mass of the compound having a functional group to 100 mass% of the polymer of the monomer portion having no functional group of the olefin polymer [III] alone. .
- the content of the functional group structural unit of the olefin polymer [III] is determined by the charge ratio when reacting the olefin polymer before modification with the compound having a functional group, 13 C-NMR measurement or 1 H-NMR. It can be specified by a known means such as measurement. Specific conditions for NMR measurement include the following conditions.
- an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. is used as a measurement apparatus, a mixed solvent of orthodichlorobenzene / heavy benzene (80/20 vol%), a measurement temperature is 120 ° C., The observation nucleus is 13C (125 MHz), single pulse proton decoupling, 45 ° pulse, repetition time is 5.5 seconds, integration number is 10,000 times or more, and 27.50 ppm is a reference value for chemical shift. Assignment of various signals is performed based on a conventional method, and quantification can be performed based on an integrated value of signal intensity.
- the functional group content of polymers having different functional group contents is determined by NMR measurement, and infrared spectroscopy (IR) measurement is performed on the polymer whose functional group content is determined.
- IR infrared spectroscopy
- a calibration curve between the intensity ratio of a specific peak of the infrared spectroscopy (IR) spectrum and the functional group content is created. Based on the calibration curve, the functional group content of any polymer is determined.
- This method is simpler than the NMR measurement described above, but basically, it is necessary to prepare a corresponding calibration curve depending on the type of base resin and functional group. For this reason, this method is preferably used for process management in resin production at a commercial plant, for example.
- Examples of commercially available olefin polymers [III] include Mitsui Chemicals' Tuffmer series (maleic anhydride modified ethylene-propylene rubber, maleic anhydride modified ethylene-butene rubber, etc.), Admer (maleic anhydride maleate). Acid-modified polypropylene, maleic anhydride-modified polyethylene); Kuraray's Claprene (maleic anhydride-modified isoprene rubber, maleic acid monomethyl ester-modified isoprene rubber), Septon (maleic anhydride-modified SEPS); Mitsui DuPont Polychemical Co., Ltd.
- Nucleol ethylene-methacrylic acid copolymer
- HPR maleic anhydride modified EEA, maleic anhydride modified EVA
- Chemtura Royaltuf maleic anhydride modified EPDM
- Kraton kraton FG maleic anhydride Acid modified SEBS
- Nisseki polybutene maleic anhydride modified polybutene
- Bondaine maleic anhydride modified EEA
- Tuftec M maleic anhydride modified from Asahi Kasei
- Lexpearl ET maleic anhydride modified EEA of Nippon Polyethylene Co., Ltd .
- Modic maleic anhydride modified EVA, maleic anhydride modified polypropylene, maleic anhydride modified polyethylene
- Mitsubishi Chemical Corporation Sumitomo Chemical ( Bond First (E-GMA) from LANXESS
- Clinac carboxy-modified nit
- the rubber composition [X] used in the present invention is a composition containing the polyamide [I], the ethylene / ⁇ -olefin / nonconjugated polyene copolymer rubber [II] and the olefin polymer [III] described above. is there.
- the mass ratio ([II] / [III]) of the copolymer rubber [II] and the olefin polymer [III] is preferably 95/5 to 60/40, more preferably 90/10. To 65/35, particularly preferably 90/10 to 70/30.
- the crosslinking agent [IV] used in the present invention is a phenol resin-based crosslinking agent. Moreover, as long as it is a crosslinking agent capable of dynamic crosslinking with the rubber composition, it may be used in combination with a phenol resin crosslinking agent as long as the effects of the present invention are not impaired. For example, a sulfur crosslinking agent can be used. .
- the phenol resin-based crosslinking agent is typically a resole resin obtained by condensing an alkyl-substituted or unsubstituted phenol with an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst.
- the alkyl group of the alkyl-substituted phenol is preferably an alkyl group having 1 to about 10 carbon atoms. Further preferred are dimethylolphenols or phenolic resins substituted with an alkyl group having from 1 to about 10 carbon atoms in the p-position.
- n and m are integers of 0 to 20, R 1 is an organic group such as an alkyl group, and R 2 is —H or —CH 2 —OH.
- n and m are preferably integers of 0 to 15, more preferably integers of 0 to 10.
- R 1 is preferably an organic group having less than 20 carbon atoms, more preferably an organic group having 4 to 12 carbon atoms.
- phenol resin-based crosslinking agent for example, an alkylphenol formaldehyde resin, a methylolated alkylphenol resin, or a halogenated alkylphenol resin can be used. Of these, halogenated alkylphenol resins are preferred.
- the halogenated alkylphenol resin is an alkylphenol resin in which a hydroxyl group at the molecular chain terminal is substituted with a halogen atom such as bromine, and examples thereof include a compound represented by the following formula [IV-2].
- n and m are integers of 0 to 20, R 1 is an organic group such as an alkyl group, and R 3 is —H, —CH 3 or —CH 2 —Br).
- n and m are preferably integers of 0 to 15, more preferably integers of 0 to 10.
- R 1 is preferably an organic group having less than 20 carbon atoms, more preferably an organic group having 4 to 12 carbon atoms.
- the phenol resin-based crosslinking agent described above is available as a commercial product.
- Commercially available products include, for example, Takuro Chemical Industry Co., Ltd. Tackol 201, Tacchi Roll 250-I, Tacchi Roll 250-III; SI Group SP1045, SP1055, SP1056; Showa Denko Co., Ltd. Shounol CRM; Arakawa Chemical Industries, Ltd.
- Examples include Tamanoru 531 from Sumitomo Bakelite Co., Ltd .; Sumitrite Resin PR from Sumitomo Bakelite Co., Ltd .; Residue Top from Gunei Chemical Industry Co., Ltd. (all trade names). Two or more of these can be used in combination.
- Takiroll 250-III brominated alkylphenol formaldehyde resin
- SP1055 brominated alkylphenol formaldehyde resin
- the average particle diameter is preferably 0.1 ⁇ m to 3 mm, more preferably 1 ⁇ m to 1 mm, and particularly preferably 5 ⁇ m to 0.5 mm.
- the flaky curing agent is preferably used after being powdered by a pulverizer such as a jet mill or a pulverizer with a pulverizing blade.
- the melt kneading temperature suitable for the elastomer composition of the present invention is relatively high, so that the decomposition rate is too high with the organic peroxide.
- the crosslinking reaction of the rubber components ([II] and [III]) proceeds rapidly, and the polyamide [I] component cannot be sufficiently kneaded.
- distribution becomes inadequate the physical property of a polyamide-type thermoplastic elastomer composition will fall remarkably.
- the polyamide-based thermoplastic elastomer composition [Y] is a resin composition in which the rubber composition and the crosslinking agent [IV] are dynamically crosslinked.
- the polyamide-based thermoplastic elastomer composition [Y] is obtained by crosslinking the rubber composition [X] and the crosslinking agent [IV] in a melt flow state (dynamic state).
- a dynamic cross-linking reaction is usually performed by supplying the rubber composition [X] and the cross-linking agent [IV] to a melt-kneading apparatus, heating to a predetermined temperature, and melt-kneading.
- melt kneader examples include a twin screw extruder, a single screw extruder, a kneader, and a Banbury mixer.
- a twin screw extruder is preferable from the viewpoint of shearing force and continuous productivity.
- the melt kneading temperature is usually 200 to 320 ° C.
- the melt kneading time is usually 0.5 to 30 minutes.
- This dynamic cross-linking forms a dynamic cross-linked body in the polyamide-based thermoplastic elastomer composition [Y], and as a result, a sea-island structure is formed.
- the sea phase matrix component
- the island phase disersed component
- the sea phase is composed of a crosslinked rubber component and is a phase that exhibits rubber elasticity.
- the polyamide-based thermoplastic elastomer composition [Y] is a particle in which the polyamide [I] is a matrix component, and the dispersion component dispersed in the matrix component is a copolymer rubber [II] and an olefin polymer [III]. And satisfies the following (1).
- (1) The cross-sectional area of the particle having a particle size of 5 ⁇ m or more of the dispersed component is measured, and the ratio of the total cross-sectional area of the area to the entire cross-sectional area analyzed is 10% or less.
- the ratio of the total cross-sectional area of particles having a particle size of 5.0 ⁇ m or more to the total cross-sectional area is 5.0% or less, more preferably the total of cross-sectional areas of particles having a particle size of 5.0 ⁇ m or more is The proportion in the cross-sectional area is 2.5% or less. Most preferably, there is no total cross-sectional area of particles having a particle size of 5.0 ⁇ m or more in the above range.
- the average particle size of the dispersion component is 0.5 ⁇ m or more and 5.0 ⁇ m or less, preferably 0.5 ⁇ m or more and 4.0 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 2.5 ⁇ m or less.
- the fluidity of the entire composition is made uniform, and the discharge hole of the extrusion die is accompanied with pulsation during extrusion.
- a small amount of the composition adheres to the edge of the metal, so-called spear formation is suppressed, and the flow velocity (fluidity) of the part not in contact with the metal inner wall is stabilized, and the resin stays on the metal inner wall. Since (especially the rubber dispersion component) is hindered, the generation of the eyes is generally suppressed significantly.
- the control of the particle diameter of the dispersed component in the present invention is performed by, for example, blending order, kneading temperature, screw rotation speed, and screw arrangement.
- blending order kneading temperature
- screw rotation speed screw arrangement
- screw arrangement it is preferable to suppress the crosslinking rate under a high shear force.
- the sheet-like or tube-like molded body thus obtained is a crosslinked rubber component particle (dispersed phase) / polyamide resin comprising the copolymer rubber [II] and the olefin polymer [III] of this embodiment.
- the matrix phase has a phase structure that controls the morphology of the matrix phase and the polyamide-based thermoplastic elastomer composition is finely dispersed in the matrix phase. Has creep resistance.
- the area occupied by the particles of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] and the olefin polymer [III] containing the structural unit is specified.
- the area of each identified area occupied by the particle was calculated by image analysis. And the diameter of the perfect circle of the area equal to the area was calculated
- the average particle diameter in this embodiment is measured about the particle diameter of 0.5 micrometer or more.
- Particles having a particle size of 0.5 ⁇ m or more are defined as a particle group (A).
- particle group (B) particles having a particle diameter of less than 0.5 ⁇ m
- particle group (B) have an area ratio of less than 1% in all particles, and the particle groups of external additives that exist independently are also included. This is because a large number are included, and it is considered that there is no influence on the effects of eye stain suppression, pressure resistance, and creep resistance of the present embodiment.
- Embodiment Example 1 Polyamide-based thermoplastic elastomer composition [Y1]
- the polyamide-based thermoplastic elastomer composition [Y1] according to this embodiment is a total of 100 components [I], [II], [III] and [IV] in the polyamide-based thermoplastic elastomer composition [Y].
- the polyamide [I] is 10 to 60 mass%
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] is 30 to 86 mass%
- the olefin polymer [III] is 3 to 30
- the rubber composition [X] containing 10% by mass and the phenol resin crosslinking agent [IV] 1 to 10% by mass are dynamically crosslinked.
- the proportion of polyamide [I] is 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass.
- the proportion of the copolymer rubber [II] is 30 to 86% by mass, preferably 33 to 80% by mass, more preferably 33 to 70% by mass.
- the proportion of the olefin polymer [III] is 3 to 30% by mass, preferably 5 to 20% by mass, more preferably 5 to 15% by mass.
- the ratio of the crosslinking agent [IV] is 1 to 10% by mass, preferably 1 to 8% by mass, more preferably 2 to 6% by mass.
- additive component include a crosslinking aid, a plasticizer, a permanent filler, a lubricant, a light stabilizer, a pigment, a flame retardant, an antistatic agent, silicone oil, an antiblocking agent, an ultraviolet absorber, and an antioxidant. It is done.
- the molded product of the present embodiment is a molded product obtained from the polyamide-based thermoplastic elastomer composition [Y1]. Its use is not particularly limited. For example, it is very useful as a molded product for various uses such as automobile parts, building material parts, sporting goods, medical equipment parts, and industrial parts.
- Embodiment Example 2 Polyamide-based thermoplastic elastomer composition [Y2]
- the polyamide-based thermoplastic elastomer composition [Y2] according to this embodiment is a total of 100 components [I], [II], [III], and [IV] in the polyamide-based thermoplastic elastomer composition [Y].
- the polyamide [I] is 30 to 87.7 mass%
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubber [II] is 10 to 45 mass%
- the olefin polymer [III] 2 The rubber composition [X] containing ⁇ 20% by mass and the phenol resin-based crosslinking agent [IV] 0.3 ⁇ 5.0% by mass are dynamically crosslinked.
- the proportion of polyamide [I] is 30 to 87.7% by mass, preferably 40 to 86% by mass, more preferably 45 to 85% by mass.
- the proportion of the copolymer rubber [II] is 10 to 45% by mass, preferably 11 to 43% by mass, more preferably 11 to 42% by mass.
- the proportion of the olefin polymer [III] is 2 to 20% by mass, preferably 3 to 15% by mass, more preferably 3 to 12% by mass.
- the ratio of the cross-linking agent [IV] is 0.3 to 5.0% by mass, preferably 0.5 to 4.0% by mass, more preferably 1.0 to 4.0% by mass.
- additive component examples include a crosslinking aid, an inorganic filler, a lubricant, a light stabilizer, a pigment, a flame retardant, an antistatic agent, an antiblocking agent, an ultraviolet absorber, and an antioxidant.
- a plasticizer such as butylbenzenesulfonamide (BBSA) is not added to the polyamide-based thermoplastic elastomer composition [Y2] according to the present embodiment example, or a plasticizer is added in a small amount.
- the amount of the plasticizer added to 100 parts by mass of the resin is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass.
- the industrial tube of the present invention is an industrial tube having at least a layer containing the polyamide-based thermoplastic elastomer composition [Y2] according to this embodiment.
- An industrial tube means a tube used in particular for industrial equipment. Specific examples include tubes through which fluids (fuel, solvent, chemicals, gas, etc.) necessary for industrial equipment such as vehicles (for example, automobiles), pneumatic / hydraulic equipment, painting equipment, and medical equipment are passed. In particular, it is very useful in applications such as vehicle piping tubes (for example, fuel system tubes, intake system tubes, cooling system tubes), pneumatic tubes, hydraulic tubes, paint spray tubes, medical tubes (for example, catheters).
- the outer diameter of the industrial tube is preferably 2 mm to 50 mm, more preferably 6 mm to 30 mm.
- the wall thickness is preferably 0.2 mm to 10 mm, more preferably 0.5 to 7 mm.
- the industrial tube may be a single-layer tube or a multilayer tube such as a two-layer tube or a three-layer tube.
- the single-layer tube is a tube composed of only one type of composition including at least the thermoplastic elastomer composition [Y2] according to this embodiment.
- a multilayer tube is a tube which consists of a laminated structure of the layer of the polyamide-type thermoplastic elastomer composition [Y2] which concerns on this embodiment example, and one or more layers (other layers) other than that, for example. Since the layer of the polyamide-based thermoplastic elastomer composition [Y2] according to the present embodiment has both sufficient barrier properties and flexibility, there is no need for a multilayer structure as in the conventional barrier layer, and in terms of manufacturing cost. Very advantageous.
- the material constituting the other layer of the multilayer tube may be appropriately determined as necessary.
- the material include fluorine resin, high density polyethylene resin, polybutylene naphthalate resin (PBN), aliphatic polyamide resin, aromatic polyamide resin, metaxylene group-containing polyamide resin, and saponified ethylene-vinyl acetate copolymer.
- an adhesive layer may be provided to improve the adhesion between the layers.
- the fluororesin include polytetrafluoroethylene (PTEF), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). Further, it may be a resin partially containing chlorine such as polychlorofluoroethylene (PCTFE), or a copolymer with ethylene or the like.
- PTEF polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- PCTFE polychlorofluoroethylene
- the polyamide-based thermoplastic elastomer composition [Z] includes the following polyamide [Z1] and polyamide-based resin composition [Z2].
- the polyamide [Z1] functions as a highly crystalline component
- the polyamide-based resin composition [Z2] functions as a flexible component.
- the polyamide [Z1] used in this embodiment example has a melting point (Tm) determined by differential scanning calorimetry (DSC) of 210 to 270 ° C. and a melting heat amount ( ⁇ H) determined by DSC of 45 to 80 mJ / mg. It is.
- polyamide [Z1] examples include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyundecamethylene adipamide (nylon 116).
- Polymetaxylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polytetramethylene sebacamide (nylon 410), polyhexamethylene sebacamide (nylon 610), polydecamethylene Adipamide (nylon 106), polydecamethylene sebamide (nylon 1010), polyhexamethylene dodecamide (nylon 612), polydecamethylene dodecamide (nylon 1012), polyhexamethylene isophthalamide (nylon 6I), poly Tetramethyle Terephthalamide (nylon 4T), polypentamethylene terephthalamide (nylon 5T), poly-2-methylpentamethylene terephthalamide (nylon M-5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene hexahydroterephthalamide (Nylon 6T (H)), Polynonamethylene terephthalamide (Nylon 9T), Polyundecamethylene terephthalamide (N
- the melting point (Tm) determined by differential scanning calorimetry (DSC) of polyamide [Z1] is 210 to 270 ° C., preferably 215 to 265 ° C., more preferably 220 to 260 ° C.
- Tm melting point
- This melting point (Tm) is measured under the following conditions. First, the polyamide [Z1] is heated and once held at 320 ° C. for 5 minutes, then the temperature is decreased to 23 ° C. at a rate of 10 ° C./min, and then the temperature is increased at a rate of 10 ° C./min. The endothermic peak based on melting at this time is defined as the melting point (Tm) of the polyamide.
- the heat of fusion ( ⁇ H) obtained by DSC of polyamide [Z1] is 45 to 80 mJ / mg, preferably 45 to 75 mJ / mg, more preferably 50 to 70 mJ / mg.
- the polyamide [Z1] has an appropriate degree of crystallinity, thereby exhibiting excellent high-temperature rigidity.
- This heat of fusion ( ⁇ H) is measured under the following conditions. First, the polyamide [Z1] is heated and once held at 320 ° C. for 5 minutes, then the temperature is decreased to 23 ° C. at a rate of 10 ° C./min, and then the temperature is increased at a rate of 10 ° C./min. The heat of fusion was calculated from the integrated value of the endothermic peak based on the melting at this time.
- the polyamide-based thermoplastic elastomer composition [Z] includes the above-described polyamide-based thermoplastic elastomer composition [Y2] as the polyamide [Z1] and the polyamide-based resin composition [Z2] described above. It is a thing.
- the ratio of polyamide [Z1] is 10 to 35% by mass, preferably 15 to 35% by mass, more preferably 100% by mass in total of 100% by mass of components [Z1] and [Z2] in the polyamide-based thermoplastic elastomer composition. 15 to 30% by mass.
- the proportion of the polyamide resin composition [Z2] is 65 to 90% by mass, preferably 65 to 85% by mass, more preferably 70 to 85% by mass.
- the polyamide-based thermoplastic elastomer composition [Z] of the present invention can be obtained by mixing polyamide [Z1] and polyamide-based resin composition [Z2] (polyamide-based thermoplastic elastomer composition [Y2]).
- the mixing method is not particularly limited, and may be mixed using a known apparatus.
- a melt-kneading apparatus such as the above-described twin-screw extruder, single-screw extruder, kneader, or Banbury mixer can be used.
- additive component in the polyamide-based thermoplastic elastomer composition [Z] of the present invention, various additive components may be added as necessary in addition to the components described above as long as the object of the present invention is not impaired.
- the additive component include a crosslinking aid, a plasticizer, a permanent filler, a lubricant, a light stabilizer, a pigment, a flame retardant, an antistatic agent, silicone oil, an antiblocking agent, an ultraviolet absorber, and an antioxidant. It is done.
- a specific high crystal component polyamide [Z1]
- a specific soft component polyamide thermoplastic elastomer composition [Y2]
- the polyamide-based thermoplastic elastomer composition [Z] of this embodiment is very useful as a material for various molded articles produced by such a molding method, for example, a resin flexible boot such as a constant velocity joint boot for automobiles. Useful.
- the molded product of the present embodiment is a molded product obtained by injection molding or blow molding from the polyamide-based thermoplastic elastomer composition [Z] of the present embodiment.
- the polyamide-based thermoplastic elastomer composition [Z] of this embodiment example has a good high temperature elastic retention, oil resistance, and moldability, various uses requiring such physical properties (for example, automobiles and electrical products). ) Widely available.
- Specific examples of the molded product of this embodiment include boot parts such as constant velocity joint boots, oil seals, gaskets, packings, dust covers, valves, stoppers, precision seal rubbers, weather strips, and the like.
- the constant velocity joint boot for motor vehicles containing the polyamide-type thermoplastic elastomer composition [Z] of this embodiment example is preferable.
- a known method such as an injection molding method or a blow molding method (an injection blow molding method or a press blow molding method) can be used.
- the bellows shape of the boot is not particularly limited, and is usually 2 mountain 2 valley 15 mountain 15 valley, preferably 3 mountain 3 valley 8 mountain 8 valley.
- Polyamide [I-1]: (6T6I66 50/35/15)
- Dicarboxylic acid component terephthalic acid 50% by mass, isophthalic acid 35% by mass, adipic acid 15% by mass
- Percentage of end groups sealed with end-capping agent (benzoic acid) 79%
- Molecular chain terminal amino group content 21 mmol / kg
- This polyamide [I-1] was synthesized as follows. 1986 g (12.0 mol) of terephthalic acid, 2800 g (24.1 mol) of 1,6-hexanediamine, 1390 g (8.4 mol) of isophthalic acid, 524 g (3.6 mol) of adipic acid, 36.5 g of benzoic acid ( 0.3 mol), 5.7 g of sodium hypophosphite-hydrate (0.08% by mass with respect to the raw material) and 545 g of distilled water were placed in an autoclave having an internal volume of 13.6 L and purged with nitrogen. Stirring was started from 190 ° C., and the internal temperature was raised to 250 ° C. over 3 hours.
- the internal pressure of the autoclave was increased to 3.03 MPa.
- the reaction was continued for 1 hour as it was, and then discharged from the spray nozzle installed at the bottom of the autoclave to extract the low condensate. Then, it cooled to room temperature, grind
- the obtained low condensate had a water content of 4100 ppm and an intrinsic viscosity [ ⁇ ] of 0.14 dl / g.
- this low condensate was put into a shelf type solid phase polymerization apparatus, and after nitrogen substitution, the temperature was raised to 180 ° C. over about 1 hour and 30 minutes.
- the reaction was performed for 1 hour 30 minutes, and the temperature was lowered to room temperature.
- the intrinsic viscosity [ ⁇ ] of the obtained polyamide was 0.18 dl / g.
- Polyamide [I-2]: (6T6I66 44/36/20)
- Dicarboxylic acid component terephthalic acid 44% by mass, isophthalic acid 36% by mass, adipic acid 20% by mass
- This polyamide [I-2] was obtained in the same manner as the polyamide [I-1] except that the amounts of terephthalic acid, isophthalic acid and adipic acid were changed.
- This polyamide [I-3] was used with 3971 g (23.9 mol) of terephthalic acid, 1899 g (12.0 mol) of 1,9-nonanediamine, and 1900 g (12.1 g) of 2-methyl-1,8-octanediamine.
- Dicarboxylic acid component terephthalic acid
- Diamine component Decamethylenediamine
- Percentage of terminal groups sealed with terminal blocker (benzoic acid) 81% Molecular chain terminal amino group content 17 mmol / kg
- Polyamide [I-5]: (6T6I66 65/20/15)
- Dicarboxylic acid component 65% by mass of terephthalic acid, 20% by mass of isophthalic acid, 15% by mass of adipic acid
- Percentage of end groups sealed with end-capping agent 79% Molecular chain terminal amino group content 23 mmol / kg
- This polyamide [I-5] was obtained in the same manner as polyamide [I-1] except that the amounts of terephthalic acid, isophthalic acid and adipic acid were changed.
- Example A Polyamide-based thermoplastic elastomer composition [Y1]> ⁇ Example A1> Polyamide [I-1] was prepared as polyamide [I].
- olefin polymer [III-1] As the olefin polymer [III-1], a modified polyolefin (maleic anhydride-modified ethylene / 1-butene copolymer, maleic anhydride graft modification amount (functional group structural unit content) of 0.97 was synthesized as follows. The intrinsic viscosity [ ⁇ ] (1.98 dl / g) measured in a mass%, 135 ° C. decalin solution was prepared.
- the polymerization was started by injecting 0.9 mmol of triisobutylaluminum and 2.0 ml of the above catalyst solution (0.0005 mmol as Zr) with ethylene.
- the total pressure was maintained at 8.0 kg / cm 2 -G, and polymerization was performed at 80 ° C. for 30 minutes.
- a small amount of ethanol was introduced into the system to stop the polymerization, and then unreacted ethylene was purged.
- the obtained solution was poured into a large excess of methanol to precipitate a white solid.
- the white solid was collected by filtration and dried overnight under reduced pressure to obtain a white solid ethylene / 1-butene copolymer.
- the ethylene / 1-butene copolymer has a density of 0.862 g / cm 3 , MFR (ASTM D1238 standard, 190 ° C., 2160 g load) is 0.5 g / 10 min, and 1-butene structural unit content is 4 mol%.
- Met. 100 parts by mass of this ethylene / 1-butene copolymer was mixed with 1.0 part by mass of maleic anhydride and 0.04 parts by mass of peroxide (trade name Perhexin 25B, manufactured by NOF Corporation). The obtained mixture was melt-grafted with a single screw extruder set at 230 ° C. to obtain the maleic anhydride-modified ethylene / 1-butene copolymer.
- cross-linking agent [IV] a flaky brominated alkylphenol formaldehyde resin (manufactured by Taoka Chemical Industry Co., Ltd., trade name Tackol 250-III) was stirred with a Henschel mixer for 10 seconds to prepare a powder.
- the polyamide [I-1] is 40% by mass, the copolymer rubber [II] is 45% by mass, the olefinic polymer [III-1] is 12% by mass, the crosslinking agent [IV] is 3% by mass, and a small amount of crosslinking aid.
- Agent Haux Itec Co., Ltd., 2 types of zinc oxide
- a twin screw extruder Nahon Steel Works, TEX-30
- cylinder temperature 280 ° C screw rotation speed 300 rpm was melt kneaded. Strands extruded from this twin-screw extruder were cut to obtain polyamide thermoplastic elastomer composition pellets.
- Examples A2 to A12 Pellets were prepared and evaluated in the same manner as in Example A1 except that the types of polyamide [I] and olefin polymer [III] used and the compounding ratio of each component were changed as shown in Table 1. The results are shown in Table 1.
- the olefin polymers [III-2] and [III-3] are as follows.
- the physical property evaluation in each example was performed according to the following method.
- [Tensile properties] Using a 50-ton press machine (280 ° C.), a sheet sample of 20 cm ⁇ 20 cm ⁇ 2 mm prepared from the pellets of the thermoplastic elastomer composition was used as a test piece, in accordance with JIS6251 at a measurement temperature of 25 degrees and a tensile speed of 500 mm / min. A tensile test was conducted to measure 100% tensile modulus (MPa), strength TB at break (MPa), and elongation EB (%).
- MPa tensile modulus
- MPa strength TB at break
- EB elongation EB
- Example A8 since the melting point (Tm) of the polyamide [I-5] used was too high, extrusion molding could not be performed and each physical property could not be measured.
- Example A9 since the crosslinking agent [IV] was not used, the elongation (%) and the breaking strength (MPa) were small, the compression set was large, and the extrusion moldability was also poor.
- Example A10 and A11 since the amount of polyamide [I] was large and the amount of copolymer rubber [II] was small, the elongation (%) was small and the compression set was large.
- Example A12 since the unmodified olefin polymer [III-3] was used, the elongation (%) was small, the compression set was large, and the extrusion design surface state was also deteriorated.
- Example B Polyamide-based thermoplastic elastomer composition
- Y2 Industrial tube>
- Example B1> Polyamide-based thermoplastic elastomer composition
- polyamide [I] is polyamide [I-1]
- modified polyolefin maleic anhydride modified ethylene / 1-butene copolymer [III] synthesized in Example A1 as olefin polymer [III] -1]
- maleic anhydride graft modification amount maleic anhydride graft modification amount (functional group structural unit content) 0.97% by mass
- crosslinking agent [IV] Flour-like brominated alkylphenol formaldehyde resin (product name: Takkol 250-III, manufactured by Taoka Chemical Co., Ltd.) was stirred for 10 seconds with a Henschel mixer and powdered I was prepared that was.
- the physical property evaluation in each example was performed according to the following method.
- [Bending elastic modulus] Using an injection molding machine (manufactured by Sodick Plustech Co., Ltd., apparatus name Tupal TR40S3A), injection molding was performed under conditions of cylinder temperature [melting end temperature (T) +10] ° C. and mold temperature 40 ° C. A test piece was prepared, and the test piece was further allowed to stand for 24 hours in a nitrogen atmosphere at a temperature of 23 ° C. Next, the test piece was bent under the conditions of a span of 51 mm and a bending speed of 1.4 mm / min using a bending tester (manufactured by NTECCO, apparatus name AB5) in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. The test was performed and the flexural modulus (MPa) was measured.
- MPa flexural modulus
- Test piece of ASTM-1 (dumbbell piece) having a thickness of 3 mm was prepared using the same apparatus and molding conditions as the above-described test piece for measuring the flexural modulus, and left for 24 hours under the same conditions. Next, a tensile test was performed on the test piece under the same temperature and humidity conditions, and tensile elongation (%) and tensile strength (MPa) were measured.
- Fuel permeation coefficient ⁇ [decreasing mass (g)] ⁇ [sheet thickness (mm)] ⁇ / ⁇ open area 1.26 ⁇ 10 ⁇ 3 (m 2 )] ⁇ [measurement interval (day)] ⁇ The fuel permeation coefficient (g ⁇ mm / m 2 ⁇ day) was calculated.
- M15 mass change rate (W 1 ⁇ W 0 ) / W 0 ⁇ 100 M15 mass change rate (%) was calculated.
- Example B6 since the melting point (Tm) of the polyamide [I-5] used was too high, extrusion molding could not be performed and each physical property could not be measured.
- the crosslinking agent [IV] is not used, so that it is harder than the corresponding examples (that is, examples where the ratio of the rubber component and the type of resin are the same), the M15 mass change rate is high, and the CE10 fuel The permeability coefficient and ethanol permeability were also high.
- Example B10 an unmodified olefin polymer [III-3] is used, so that the tensile elongation is decreased and the M15 mass change rate is lower than that of Examples B2, B4, and B5 in which the ratio of the rubber component is the same.
- the CE10 fuel permeability coefficient and ethanol permeability were also high.
- the polyamide [I-1] 47% by mass, the copolymer rubber [II] 40% by mass, the olefin polymer [III] 10% by mass, the crosslinking agent [IV] 3% by mass and a small amount of crosslinking aid Huxuitec Co., Ltd., 2 types of zinc oxide
- Huxuitec Co., Ltd., 2 types of zinc oxide Huxuitec Co., Ltd., 2 types of zinc oxide
- Pellets P2 to P5 were obtained in the same manner as the pellet P1, except that the screw rotation speed N or the cylinder temperature of the extruder was changed as shown in Table 3. Each characteristic of the elastomer composition thus pelletized was evaluated. The results are shown in Table 3.
- a crack with a size of 1 mm or more occurs over the entire periphery of the die hole within 5 minutes after the start of sheet extrusion.
- the pellets P1 to P3 in which the ratio of the total cross-sectional area of the area to the analyzed cross-sectional area with the particle size of the dispersed component (particle group (A)) of 5 ⁇ m or more is 10% or less are good, and the extruder has little discoloration. Met. On the other hand, a lot of eyes were generated in the pellets P4 and P5 whose ratio exceeded 10%. If the cumulative cross-sectional area ratio is 5% or less, and further 2.5% or less, it is excellent in tensile creep resistance and tube pressure resistance. In particular, the pellet P1 has a cumulative cross-sectional area ratio of 0%, that is, 5 ⁇ m. When the above large particle group did not exist, it was excellent in all of tensile creep property, suppression of eyes and tube pressure resistance.
- Modified polyolefin maleic anhydride modified ethylene / 1-butene copolymer, maleic anhydride graft modified amount (functional group structural unit content) 0.97% by mass as olefin polymer [III] synthesized as follows Intrinsic viscosity [ ⁇ ] (1.98 dl / g) measured in a 135 ° C. decalin solution was prepared.
- the polymerization was started by injecting 0.9 mmol of triisobutylaluminum and 2.0 ml of the above catalyst solution (0.0005 mmol as Zr) with ethylene.
- the total pressure was kept at 8.0 kg / cm 2 -G by continuously supplying ethylene, and polymerization was carried out at 80 ° C. for 30 minutes.
- a small amount of ethanol was introduced into the system to stop the polymerization, and then unreacted ethylene was purged.
- the obtained solution was poured into a large excess of methanol to precipitate a white solid.
- the white solid was collected by filtration and dried overnight under reduced pressure to obtain a white solid ethylene / 1-butene copolymer.
- the density of this ethylene / 1-butene copolymer is 0.862 g / cm 3
- the MFR ASTM D1238 standard, 190 ° C., 2160 g load
- the 1-butene structural unit content is 4 mol%.
- 100 parts by mass of this ethylene / 1-butene copolymer was mixed with 1.0 part by mass of maleic anhydride and 0.04 parts by mass of peroxide (trade name Perhexin 25B, manufactured by NOF Corporation).
- the obtained mixture was melt-grafted with a single screw extruder set at 230 ° C. to obtain the maleic anhydride-modified ethylene / 1-butene copolymer.
- cross-linking agent [IV] a flaky brominated alkylphenol formaldehyde resin (manufactured by Taoka Chemical Industry Co., Ltd., trade name Tackol 250-III) was stirred with a Henschel mixer for 10 seconds to prepare a powder.
- the polyamide [I-2] is 40% by mass, the copolymer rubber [II] is 45% by mass, the olefin polymer [III] is 12% by mass, the crosslinking agent [IV] is 3% by mass, and a small amount of a crosslinking aid ( Hux Itec Co., Ltd., zinc oxide (2 types) is premixed and supplied to a twin-screw extruder (Nihon Steel Works, TEX-30), and melted at a cylinder temperature of 280 ° C and a screw speed of 300 rpm. Kneaded. The strand extruded from the twin-screw extruder was cut to obtain a polyamide-based resin composition [Y-1] pellet.
- a crosslinking aid Hux Itec Co., Ltd., zinc oxide (2 types
- test piece [Tensile rupture strength, elongation between marked rupture marks]
- a test piece having a shape of 2 (1/3) shape and a thickness of about 2 mm was used.
- the test was conducted at 23 ° C. and a test speed of 500 mm / min. In principle, the test piece was conditioned at a temperature of 23 ° C. ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5% for 48 hours or more before the test.
- blow moldability The drawdown property in blow molding was evaluated as follows. Using a large blow molding machine (direct blow molding machine, manufactured by Becum), a cylindrical (pipe-shaped) parison was extruded in a continuous manner without using an accumulator with a die ⁇ 70 mm and a mandrel ⁇ 60 mm. The parison shapeability (solidification, elongation state) and the drawdown state were evaluated according to the following criteria. The molding conditions were such that the cylinder temperature was (melting end temperature (T) +10) ° C. and the mold temperature was 40 ° C. The air was sprayed immediately after the mold was clamped for 10 spray times.
- T melting end temperature
- A Parison shapeability is stable, and a molded product can be obtained without drawing down.
- B Parison shaping is possible, but the drawdown is severe, and the thickness unevenness is noticeable in the molded product.
- C Parison shaping is not stable and draws down, and remarkable molding defects (perforated, torn) are observed.
- polyamides [Z1-1] to [Z1-3] and the polyester elastomer in Table 5 are specifically the following commercially available products.
- [Z1-3]: A copolymer of a salt of hexamethylenediamine and isophthalic acid / a salt of hexamethylenediamine and terephthalic acid (trade name polyamide MXD6 Reny “# 6002”, manufactured by Mitsubishi Engineering Plastics Co., Ltd., melting point 243) ° C
- Example D8 since the polyamide resin composition [Y-4] containing polyamide [I-5] having a too high melting point was used, the high temperature elastic retention was inferior and blow molding could not be performed.
- Example D9 the polyamide resin composition [Y-5] which does not use the crosslinking agent [IV] and is not dynamically crosslinked was used. Therefore, the high temperature elastic retention and oil resistance were inferior, and blow molding could not be performed.
- Example D10 since the amount of polyamide [Z1] was too small, the high temperature elastic retention, oil resistance, and blow moldability were inferior.
- Example D11 since the amount of polyamide [Z1] was too large, the high temperature elastic retention and blow moldability were inferior.
- Example D12 a commercially available polyester elastomer was used alone, and the high temperature elastic retention and oil resistance were inferior.
- Example D13 since the polyamide resin composition [Y-7] containing the unmodified olefin polymer [III-3] was used, the oil resistance was poor, the water absorption rate was high, and the high temperature elastic retention was inferior. Blow molding was not possible.
- the polyamide-based thermoplastic elastomer composition [Y] of the present invention is divided into two elastomer compositions [Y1] and [Y2] according to the composition range of the components [I], [II], [III], and [IV].
- the elastomer composition [Y1] can be used as the polyamide resin composition [Z2] of the polyamide thermoplastic elastomer composition [Z].
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Abstract
Description
また、本発明は、良好な高温弾性保持率、耐油性、成形性を併せ持つポリアミド系熱可塑性エラストマー組成物、及びこの組成物から射出成形又はブロー成形により得られる成形品(例えば自動車用等速ジョイントブーツ)に関する。
さらに、本発明は、産業用チューブに用いる樹脂組成物であって、柔軟性、耐衝撃性、燃料や溶媒の透過防止性、耐膨潤性に優れたポリアミド系熱可塑性エラストマー組成物、及びこの組成物を含む層を少なくとも有する産業用チューブに関する。
また、熱可塑性エラストマーは加硫ゴムと異なり加硫工程が不要であり、通常の熱可塑性樹脂の成形機で加工が可能という利点がある。特に、ポリエステル系熱可塑性エラストマーは、耐久性、耐油性、耐熱性に優れ、しかも高弾性率ゆえに部材の薄肉化が可能で、軽量化や低コスト化のニーズに良く合致するので、耐油ゴム代替材料として活発に検討されている。
柔軟性を改良する方法として、ポリマー中のソフトセグメントの含有量を多くする方法がある。しかし、ソフトセグメントの含有量が多いと、耐油性が悪化すると共に耐熱性がさらに低下し、さらにはガスバリア性が著しく損なわれる傾向がある。また、他の方法として、有機化合物からなる可塑剤を添加する方法も知られている。しかし、ポリエステル系エラストマー及びポリアミド系エラストマーは結晶性樹脂であり、可塑剤と馴染み難い(あまり吸わない)ので、その可塑化効果は小さい。また、製品の使用中に可塑剤のブリード現象が起こる場合もある。例えば、製品をオイルに長期間接触し続けた場合は可塑剤がオイル中に溶け出してしまい、柔軟性が低下する場合がある。さらに、製品が高温下に置かれた場合は可塑剤が揮発してしまい、同様の不具合が生じる場合もある。
例えば、蛇腹形状を有する樹脂製フレキシブルブーツ類の材料としては、比較的安価で適度な柔軟性を有し、クリープ特性に優れる点から、クロロプレンゴム材料が主に使用されていた。しかし近年は、製造工程の簡素化が可能であり、耐熱性が優れ、さらにブーツ材としての耐久寿命が長いという利点から、ポリエステル系熱可塑性エラストマーへの代替が進められている(特許文献5)。
また、本発明の目的は、良好な高温弾性保持率、耐油性、成形性を併せ持つポリアミド系熱可塑性エラストマー組成物及びその成形品を提供することにある。
〔1〕 テレフタル酸由来の構造単位を全ジカルボン酸構造単位中30~100モル%有し、示差走査熱量測定(DSC)より求まる融点(Tm)が220~290℃であるポリアミド[I]と、
エチレン[a]、炭素原子数3~20のα-オレフィン[b]、炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]に由来する構造単位を含むエチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]と、
分子中に官能基構造単位を0.3~5.0質量%含むオレフィン系重合体[III]と
を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]とが動的に架橋されているポリアミド系熱可塑性エラストマー[Y]。
(1) 前記分散成分の粒径が5μm以上の上記粒子の断面積を計測し、かつ解析した断面積全体に対する前記面積の累計断面積の割合が10%以下である。
前記エチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]30~86質量%、及び
前記オレフィン系重合体[III]3~30質量%
を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]1~10質量%が動的に架橋されているポリアミド系熱可塑性エラストマー組成物[Y1](ただし、[I]、[II]、[III]及び[IV]の合計量を100質量%とする)。
前記エチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]10~45質量%、及び
前記オレフィン系重合体[III]2~20質量%
を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]0.3~5.0質量%が動的に架橋されているポリアミド系熱可塑性エラストマー組成物[Y2](ただし、[I]、[II]、[III]及び[IV]の合計量を100質量%とする)。
前記ポリアミド系樹脂組成物[Z2]が、〔12〕に記載のポリアミド系熱可塑性エラストマー組成物[Y2]であることを特徴とするポリアミド系熱可塑性エラストマー組成物[Z]。
本発明に用いるポリアミド系熱可塑性エラストマー組成物[Y]は、以下に説明する成分[I]、[II]及び[III]を含有するゴム組成物[X]と架橋剤[IV]が動的に架橋されている組成物である。
本発明に用いるポリアミド[I]は、テレフタル酸由来の構造単位を全ジカルボン酸構造単位中30~100モル%を有し、示差走査熱量測定(DSC)により求まる融点(Tm)が220~290℃であるポリアミドである。
本発明に用いるエチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]は、エチレン[a]、炭素原子数3~20のα-オレフィン[b]、メタロセン系触媒により重合可能な炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]に由来する構造単位を含む共重合体ゴムである。
共重合体ゴム[II]を構成する炭素原子数3~20のα-オレフィン[b]の具体例としては、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、4-メチル-1-ペンテン、1-ヘプテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-エイコセンが挙げられる。中でも、プロピレン、1-ブテン、1-ヘキセン、1-オクテンなどの炭素原子数3~8のα-オレフィンが好ましい。共重合体ゴム[II]は、2種以上のα-オレフィン[b]に由来する構造単位を含んでいてもよい。以上のα-オレフィン[b]は、原料コストが比較的安価で共重合性に優れると共に、共重合体ゴム[II]に優れた機械的性質と良好な柔軟性を付与するので好ましい。
共重合体ゴム[II]を構成するメタロセン系触媒により重合可能な炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]として、例えば、脂肪族ポリエン、脂環族ポリエンを使用できる。
本発明に用いるオレフィン系重合体[III]は、官能基構造単位を0.3~5.0質量%含むオレフィン系重合体である。このオレフィン系重合体[III]としては、例えば、官能基を有する化合物を反応させることによりポリオレフィン分子鎖に官能基を導入した変性ポリオレフィン([III]-1)、オレフィンモノマーと官能基を有するモノマーを共重合することにより得られる官能基含有オレフィン系共重合体([III]-2)が挙げられる。
本発明に用いるゴム組成物[X]は、以上説明したポリアミド[I]、エチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]及びオレフィン系重合体[III]を含有する組成物である。
本発明に用いる架橋剤[IV]は、フェノール樹脂系架橋剤である。また、ゴム組成物と動的架橋が可能な架橋剤であれば、本発明の効果を損なわない範囲でフェノール樹脂系架橋剤と組み合わせて使用しても良く、例えば、硫黄系架橋剤を使用できる。
式[IV-1]において、n、mは、好ましくは0~15の整数、より好ましくは0~10の整数である。R1は、好ましくは20未満の炭素原子を有する有機基、より好ましくは4~12の炭素原子を有する有機基である。
式[IV-2]において、n、mは、好ましくは0~15の整数、より好ましくは0~10の整数である。R1は、好ましくは20未満の炭素原子を有する有機基、より好ましくは4~12の炭素原子を有する有機基である。
ポリアミド系熱可塑性エラストマー組成物[Y]は、ゴム組成物と架橋剤[IV]が動的に架橋されている樹脂組成物である。
(1) 前記分散成分の粒径が5μm以上の上記粒子の断面積を計測し、かつ解析した断面積全体に対する前記面積の累計断面積の割合が10%以下である。
前記分散成分の平均粒子径は0.5μm以上5.0μm以下であり、好ましくは0.5μm以上4.0μm以下、さらに好ましくは0.5μm以上2.5μm以下である。
小粒子であるためには、高せん断力下で、かつ架橋速度を抑制することが好ましい。具体的には、押出機の混練部前半では低せん断で高分配混合であり、混練部後半では高せん断となるようにスクリューアレンジを組むことにより達成される。スクリューセグメントを適切に設計しても混練部前半から高温、高せん断となるような条件は、架橋ゴム成分の凝集が発生し、累計断面積の割合が10%以下とする要件を満足しない。
このようにして得られるシート状又はチューブ状の成形体は、本実施形態の共重合体ゴム[II]とオレフィン系重合体[III]からなる架橋ゴム成分の粒子(分散相)/ポリアミド樹脂(マトリックス相)のモルフォロジーを制御し、かつマトリックス相にポリアミド系熱可塑性エラストマー組成物が微細に分散した状態の相構造を有する組成物から成っているため、その特性として、目ヤニ抑制や耐圧性、耐クリープ性能を有する。
上記のようにして押出成形した各試験片の任意の断面約45μm×75μm以上の範囲を透過型電子顕微鏡(測定装置:株式会社日立ハイテクノロジー社製H-7650)を用いて解析した(3000倍に拡大)。
解析は画像解析ソフト ImageJを用いて二値化処理をし、解析した。この画像中(図1)、ポリアミド樹脂(図1の、他部より色が白い部位、マトリックス)と、炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]に由来する構造単位を含むエチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]とオレフィン系重合体[III]の粒子の占有域を特定した。
特定された粒子の占有域の一つ毎を画像解析により、その面積を算出した。
そして、その面積と等しい面積の真円の直径を求め、それぞれの占有域について求めた値を算術平均したものを粒子の平均測定粒径とした。
すなわち、各粒子の粒子径は各粒子の面積Sを求め、Sを用いて、(4S/π)0.5を各粒子の粒子径とする。
その理由は、0.5μm未満の粒子径のもの(粒子群(B)とする)は、全粒子中に占める面積比率が1%未満であり、独立して存在する外部添加剤の粒子群も多数含まれ、本実施形態の目ヤニ抑制や耐圧性、耐クリープの効果に与える影響が無いと考えられるからである。
本実施形態例に係るポリアミド系熱可塑性エラストマー組成物[Y1]は、上記ポリアミド系熱可塑性エラストマー組成物[Y]中の成分[I]、[II]、[III]および[IV]の合計100質量%中、前記ポリアミド[I]10~60質量%、前記エチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]30~86質量%、及び前記オレフィン系重合体[III]3~30質量%を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]1~10質量%が動的に架橋されているものである。
ポリアミド[I]の割合は10~60質量%であり、好ましくは15~50質量%、より好ましくは20~45質量%である。共重合体ゴム[II]の割合は30~86質量%であり、好ましくは33~80質量%、より好ましくは33~70質量%である。オレフィン系重合体[III]の割合は3~30質量%であり、好ましくは5~20質量%、より好ましくは5~15質量%である。架橋剤[IV]の割合は1~10質量%であり、好ましくは1~8質量%、より好ましくは2~6質量%である。
本実施形態例の成形品は、ポリアミド系熱可塑性エラストマー組成物[Y1]から得られる成形品である。その用途は特に限定されない。例えば、自動車部品、建材部品、スポーツ用品、医療器具部品、工業部品など、各種用途の成形品として非常に有用である。
本実施形態例に係るポリアミド系熱可塑性エラストマー組成物[Y2]は、上記ポリアミド系熱可塑性エラストマー組成物[Y]中の成分[I]、[II]、[III]および[IV]の合計100質量%中、前記ポリアミド[I]30~87.7質量%、前記エチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]10~45質量%、及び前記オレフィン系重合体[III]2~20質量%を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]0.3~5.0質量%が動的に架橋されている。
ポリアミド[I]の割合は30~87.7質量%であり、好ましくは40~86質量%、より好ましくは45~85質量%である。共重合体ゴム[II]の割合は10~45質量%であり、好ましくは11~43質量%、より好ましくは11~42質量%である。オレフィン系重合体[III]の割合は2~20質量%であり、好ましくは3~15質量%、より好ましくは3~12質量%である。架橋剤[IV]の割合は0.3~5.0質量%であり、好ましくは0.5~4.0質量%、より好ましくは1.0~4.0質量%である。
本発明の産業用チューブは、本実施形態例に係るポリアミド系熱可塑性エラストマー組成物[Y2]を含む層を少なくとも有する産業用チューブである。産業用チューブとは、特に産業機器に使用されるチューブを意味する。具体例としては、車両(例えば自動車)、空圧・油圧機器、塗装機器、医療機器などの産業機器に必要な流体(燃料、溶剤、薬品、ガス等)を通すチューブが挙げられる。特に、車両配管用チューブ(例えば燃料系チューブ、吸気系チューブ、冷却系チューブ)、空圧チューブ、油圧チューブ、ペイントスプレーチューブ、医療用チューブ(例えばカテーテル)等の用途において非常に有用である。
本実施形態例に係るポリアミド系熱可塑性エラストマー組成物[Z]は、下記のポリアミド[Z1]とポリアミド系樹脂組成物[Z2]とを含む。本実施形態例に係るポリアミド系熱可塑性エラストマー組成物[Z]において、ポリアミド[Z1]は高結晶成分として機能し、ポリアミド系樹脂組成物[Z2]は柔軟成分として機能する。
<ポリアミド[Z1]>
本実施形態例に用いるポリアミド[Z1]は、示差走査熱量測定(DSC)により求まる融点(Tm)が210~270℃であり、DSCにより求まる溶融熱量(ΔH)が45~80mJ/mgであるポリアミドである。
本実施形態例の成形品は、本実施形態例のポリアミド系熱可塑性エラストマー組成物[Z]から射出成形又はブロー成形により得られる成形品である。特に、本実施形態例のポリアミド系熱可塑性エラストマー組成物[Z]は良好な高温弾性保持率、耐油性、成形性を併せ持つので、そのような物性が要求される各種用途(例えば自動車、電気製品)に広く利用可能である。本実施形態例の成形品の具体例としては、等速ジョイントブーツ等のブーツ部品、オイルシール、ガスケット、パッキン、ダストカバー、バルブ、ストッパ、精密シールゴム、ウェザストリップ等が挙げられる。中でも、本実施形態例のポリアミド系熱可塑性エラストマー組成物[Z]を含む自動車用等速ジョイントブーツが好ましい。
ポリアミド[I-1]:(6T6I66=50/35/15)
ジカルボン酸成分=テレフタル酸50質量%、イソフタル酸35質量%、アジピン酸15質量%
ジアミン成分=1,6-ヘキサンジアミン
融点(Tm)=276℃
末端封止剤(安息香酸)によって封止されている末端基の割合=79%
分子鎖の末端アミノ基量=21mmol/kg
ジカルボン酸成分=テレフタル酸44質量%、イソフタル酸36質量%、アジピン酸20質量%
ジアミン成分=1,6-ヘキサンジアミン
融点(Tm)=264℃
末端封止剤(安息香酸)によって封止されている末端基の割合=80%
分子鎖の末端アミノ基量=19mmol/kg
ジカルボン酸成分=テレフタル酸、
アミン成分=1,9-ノナンジアミン50質量%、2-メチル-1,8-オクタンジアミン50質量%
融点(Tm)=265℃
末端封止剤(安息香酸)によって封止されている末端基の割合76%
分子鎖の末端アミノ基量=18mmol/kg
ジカルボン酸成分=テレフタル酸
ジアミン成分=デカメチレンジアミン
アミノカルボン酸成分=11-アミノウンデカン酸
融点(Tm)=260℃
末端封止剤(安息香酸)によって封止されている末端基の割合=81%
分子鎖の末端アミノ基量17mmol/kg
ジカルボン酸成分=テレフタル酸65質量%、イソフタル酸20質量%、アジピン酸15質量%
ジアミン成分=ヘキサメチレンジアミン
融点(Tm)=295℃
末端封止剤によって封止されている末端基の割合=79%
分子鎖の末端アミノ基量23mmol/kg
<例A1>
ポリアミド[I]として、ポリアミド[I-1]を用意した。
使用するポリアミド[I]及びオレフィン系重合体[III]の種類及び各成分の配合比を表1に示すように変更したこと以外は、例A1と同様にしてペレットを作製し、評価した。結果を表1に示す。オレフィン系重合体[III-2]、[III-3]は以下の通り。
オレフィン重合体(III-1)の製造における変性処理前のエチレン・1-ブテン共重合体を変性する時に添加する無水マレイン酸の量を、0.5重量部に変更した以外はオレフィン重合体(A)と同様にして調製した。無水マレイン酸グラフト変性量は0.50重量%であった。また135℃デカリン溶液中で測定した極限粘度[η]は1.79dl/gであった。
オレフィン重合体(III-1)の製造における変性処理前のエチレン・1-ブテン共重合体をそのまま使用した。
[引張特性]
50tプレス機(280℃)を用いて、熱可塑性エラストマー組成物のペレットから調製した20cm×20cm×2mmのシートサンプルを試験片とし、JIS6251に従って、測定温度25度、引張速度500mm/分の条件で引張り試験を行い、100%引張りモジュラス(MPa)、破断時の強度TB(MPa)および伸びEB(%)を測定した。
上記の引張り物性の測定の場合と同じシートサンプルを試験片とし、JIS6253に準拠し、デュロメーターA硬度計により、JIS A硬度を測定した。具体的には試験片を3枚重ね、これに1.0kgの荷重をかけ、荷重が試験片の加圧面に密着してから1秒以内の標準硬さを読み取り、これをShore-A硬度(度)とした。
上記の引張り物性の測定の場合と同じシートサンプルを試験片とし、この試験片を6枚重ねることでブロック状サンプルを調製し、圧縮永久歪み測定金型に取り付けた。試験片の高さが荷重をかける前の高さの1/4になるよう圧縮し、金型ごと100℃のギヤーオーブン中にセットして22時間熱処理した。次いで、試験片を金型から取出し、30分間放冷後、試験片の高さを測定し、以下の計算式から圧縮永久歪み〔CS〕(%)を算出した。
圧縮永久歪み〔CS〕(%)={(t0-t1)/(t0-t2)}×100
t0:試験片の試験前の高さ。
t1:試験片を熱処理し30分間放冷した後の高さ。
t2:試験片の測定金型に取り付けた状態での高さ。
熱可塑性エラストマー組成物のペレットをL/D=30、スクリュー径50mmの単軸押出機を用いて、窒素雰囲気中、280℃で押出し、幅1.5cm、厚み2mmの口金形状にて所定の形状に成形した。得られた平板試料(1.5cm幅×2mm厚み×長さ2m)の押出し意匠面状態を以下の基準により3段階で評価をした。
「A」:平滑性に優れ、良好な外観を示す。
「B」:若干の凹凸が見られ、表面光沢が乏しい。
「C」:細かな凹凸が多数見られ、平滑性に乏しい。
例A1~A7では、100%モジュラス(MPa)が適度に低く、伸び(%)が大きく、しかも破断強度(MPa)が大きいので、引張り特性に優れていることが分かる。またShore-A硬度が適度な値なので、柔軟性も充分であることが分かる。さらに圧縮永久歪みも小さい。したがって、例A1~A7では総合的に優れたゴム弾性が得られていると言える。しかも、押出成形性も良好である。
<例B1>
例A1と同様にして、 ポリアミド[I]としてポリアミド[I-1]、共重合体ゴム[II]として、エチレン・プロピレン・5-エチリデン-2-ノルボルネン共重合体ゴム([η]=2.4dl/g、エチレン含量65質量%、ジエン含量4.6質量%)、オレフィン系重合体[III]として、例A1で合成した変性ポリオレフィン(無水マレイン酸変性エチレン・1-ブテン共重合体[III-1]、無水マレイン酸グラフト変性量(官能基構造単位含有率)0.97質量%、135℃デカリン溶液中で測定した極限粘度[η]1.98dl/g)、架橋剤[IV]として、フレーク状の臭素化アルキルフェノールホルムアルデヒド樹脂(田岡化学工業(株)製、商品名タッキロール250-III)をヘンシェルミキサーにて10秒間攪拌し粉状にしたものを用意した。
そして、このポリアミド[I-1]83質量%、共重合体ゴム[II]12質量%、オレフィン系重合体[III-1]3質量%、架橋剤[IV]2質量%及び少量の架橋助剤(ハクスイテック(株)製、酸化亜鉛2種)を予備混合し、これを二軸押出機((株)日本製鋼所製、TEX-30)に供給し、シリンダー温度280℃、スクリュー回転数300rpmで溶融混練した。この二軸押出機から押出されたストランドを切断して、ポリアミド系熱可塑性エラストマー組成物のペレットを得た。
使用するポリアミド[I]及びオレフィン系重合体[III]の種類及び各成分の配合比を表2に示すように変更したこと以外は、例B1と同様にしてペレットを作製し、評価した。結果を表2に示す。
[曲げ弾性率]
射出成形機((株)ソディックプラステック製、装置名ツパールTR40S3A)を用い、シリンダー温度[融解終了温度(T)+10]℃、金型温度40℃の条件で射出成形を行って厚さ3mmの試験片を作製し、さらにこの試験片を温度23℃、窒素雰囲気下で24時間放置した。次いで、この試験片に対して温度23℃、相対湿度50%の雰囲気下で、曲げ試験機(NTESCO社製、装置名AB5)を用い、スパン51mm、曲げ速度1.4mm/分の条件で曲げ試験を行い、曲げ弾性率(MPa)を測定した。
上記の曲げ弾性率測定の試験片と同じ装置及び成形条件を用いて、厚さ3mmのASTM-1(ダンベル片)の試験片を作製し、同じ条件で24時間放置した。次いで、この試験片に対して同じ温度及び湿度条件で引張試験を行い、引張伸び(%)及び引張強度(MPa)を測定した。
ヒートプレス機を用い、プレス温度[融解終了温度(T)+5]℃、プレス圧力3MPaの条件で圧縮成形を行って厚さ0.5mmのシートを作製し、このシートから直径100mmの円盤状試験片を切り出した。この円盤状試験片を、模擬燃料であるCE10(トルエン/イソオクタン/エタノール=45/45/10容量%)18mLが入っているSUS製容器(容積20mL、開放部面積1.26×10-3m2)の開放部にセットし、密閉して試験体とした。この試験体を恒温装置(60℃)に入れ、試験体の質量を測定し、単位時間当たりの質量減少が一定となった時点で、下記式:
燃料透過係数={[減少質量(g)]×[シート厚(mm)]}/{開放部面積1.26×10-3(m2)]×[測定間隔(day)]}
により燃料透過係数(g・mm/m2・day)を算出した。
上記の曲げ弾性率測定の試験片と同じ装置及び成形条件を用いて、長さ35mm、幅25mm、厚さ0.5mmの試験片を作製し、さらにこの試験片を窒素雰囲気下、温度150℃で1時間放置した。この試験片を、オートクレーブ内に入れた疑似燃料であるM15(トルエン/イソオクタン/メタノール=42.5/42.5/15容量%)0.5L中に浸漬し、蓋を閉めた。オートクレーブを60℃の水槽で加温し、定期的に試験片をオートクレーブから取り出して試験片の質量変化を測定し、試験片の質量変化が無くなる(飽和状態)まで、浸漬を継続した。浸漬前の質量(W0)と飽和状態の質量(W1)との差から下記式:
M15質量変化率=(W1-W0)/W0×100
によりM15質量変化率(%)を算出した。
実施例及び比較例で得た単層チューブを長さ30cmにカットし、一方の端部を密栓し、内部にエタノールを入れ、他方の端部を密栓し、全体の重量を測定した。次いで、このチューブを60℃のオーブンに入れ、24時間後の重量変化(g)を測定し、その測定値によりエタノール透過性(g/24hr)を評価した。
例B1~B5では、可塑剤を使用しなかったにもかかわらず、各物性[曲げ弾性率、引張伸び、引張強度]の値から十分な柔軟性を有することが分かる。またM15質量変化率が低いので燃料による膨潤が少なく、CE10燃料透過係数及びエタノール透過性が低いので燃料や溶媒が透過し難いことも分かる。したがって、例B1~B5では、産業用チューブ用樹脂組成物として総合的に優れた特性を有する樹脂組成物が得られたと言える。
例A1と同様にして、ポリアミド[I]としてポリアミド[I-2]、共重合体ゴム[II]として、エチレン・プロピレン・5-エチリデン-2-ノルボルネン共重合体ゴム([η]=2.4dl/g、エチレン含量65質量%、ジエン含量4.6質量%)、オレフィン系重合体[III]として、例A1で合成した変性ポリオレフィン(無水マレイン酸変性エチレン・1-ブテン共重合体、無水マレイン酸グラフト変性量(官能基構造単位含有率)0.97質量%、135℃デカリン溶液中で測定した極限粘度[η]1.98dl/g)、架橋剤[IV]として、フレーク状の臭素化アルキルフェノールホルムアルデヒド樹脂(田岡化学工業(株)製、商品名タッキロール250-III)をヘンシェルミキサーにて10秒間攪拌し粉状にしたものを用意した。
そして、このポリアミド[I-1]47質量%、共重合体ゴム[II]40質量%、オレフィン系重合体[III]10質量%、架橋剤[IV]3質量%及び少量の架橋助剤(ハクスイテック(株)製、酸化亜鉛2種)を予備混合し、これを二軸押出機((株)日本製鋼所製、TEX-30)に供給し、下記溶融条件(基準溶融条件とする)にて溶融混練した。この二軸押出機から押出されたストランドを切断して、ポリアミド系熱可塑性エラストマー組成物のペレットP1を得た。
1)押出機のシリンダー温度=280℃
2)押出機 バレル内径D=32mm
3)スクリュー回転数N=350rpm
このようにしてペレット化したエラストマー組成物の各特性を評価した。
その結果を表3に示した。
各ペレットの断面を、マイクロトームにて研削しフィルム断面の超薄切片をトリミングした後、四酸化ルテニウムの蒸気に一定時間晒して一方を選択的に染色させた。それぞれ透過電子顕微鏡(TEM、株式会社日立ハイテクノロジー社製H-7650)を用いて、3000倍率でそれぞれ観察した。TEM像から、染色された粒子(粒子群(A))の平均粒径、画像解析面積、粒径5μm以上の面積の合計を求め、粒径5μm以上の粒子が解析面積中に占める比率を算出した。
上記の曲げ弾性率測定の試験片を同様の方法で各ペレットから試験片を作製し、JIS K7162-1BA型のダンベル試験片に打ち抜いた。次いで、このダンベル試験片に対して温度23℃、相対湿度50%の雰囲気下において、引張応力を15MPa、30minのクリープ試験を行った。また、クリープ特性は以下の評価基準に基づき評価した。
A:クリープ歪みが10%未満
B:クリープ歪みが10%以上
C:クリープ歪みが破断
幅15mm、厚み1mmの長方形のダイを取り付けた押出成形機(サーモ・プラスティックス工業(株)製、スクリュー径20mm)を用い、シリンダー温度290℃で各ペレットの押出成形を行い、シート状の成形品を得た。この時、ダイ付近への目ヤニの生成状況を確認した。
尚、目ヤニの発生状況は以下の評価基準に基づき評価した。
A:シート押出開始後30分を経過しても1辺の長さが1mm以上の大きさの目ヤニの発生が確認されない。
B:シート押出開始後5分~30分経過後に、1辺の長さが1mm以上の大きさの目ヤニの発生が極微量認められる。
C:シート押出開始後5分~30分経過後に、1辺の長さが1mm以上の大きさの目ヤニの発生が少量認められる。
D:シート押出開始後、5分以内に1mm以上の大きさの目ヤニがダイ穴周辺全体に渡って発生する。
外径8mm、肉厚1mmのチューブ状成形体を、50cm長にカットしたチューブを40℃に調整した水槽内にて状態調節を行った。その後、片側の端部を密栓し、もう片方の端部に加圧装置を連結してエア抜きを行った。その後、初期圧力0.5MPaの試験応力にて3分間加圧を行い、破壊しなかった場合には圧力を0.5MPaずつ段階的に上昇させ、その圧力で3分間保持するテストを連続的に行って、チューブが破壊した時の試験応力から内圧P(kg/cm2)を算出した。また、耐圧性は以下の評価基準に基づき評価した。
A:破壊時の内圧Pが、10kg/cm2以上
B:破壊時の内圧Pが5kg/cm2以上10kg/cm2未満
C:破壊時の内圧Pが5kg/cm2未満
分散成分(粒子群(A))の粒径が5μm以上の解析した断面積全体に対する前記面積の累計断面積の割合が10%以下であるペレットP1~P3では押出機の目ヤニが少なく、良好であった。一方、その割合が10%を超えるペレットP4,P5では目ヤニが多く発生した。また、累計断面積の割合が5%以下、さらに2.5%以下であれば、引張クリープ性及びチューブ耐圧性にも優れ、特に累計断面積の割合が0%であるペレットP1、すなわち、5μm以上の大きな粒子群が存在しない場合には、引張クリープ性、目ヤニ抑制及びチューブ耐圧性のいずれにも優れたものとなった。
ポリアミド[I]として、ポリアミド[I-2]を用意した。
使用するポリアミド[I]の種類及び各成分の配合比を表4に示すように変更したこと以外は、製造例Y-1と同様にしてペレットを作製し、曲げ弾性率の測定を実施した。結果を表4に示す。
射出成形機((株)ソディックプラステック製、装置名ツパールTR40S3A)を用い、シリンダー温度[融解終了温度(T)+10]℃、金型温度40℃の条件で射出成形を行って厚さ3mmの試験片を作製し、さらにこの試験片を温度23℃、窒素雰囲気下で24時間放置した。次いで、この試験片に対して温度23℃、相対湿度50%の雰囲気下で、曲げ試験機(NTESCO社製、装置名AB5)を用い、スパン51mm、曲げ速度1.4mm/分の条件で曲げ試験を行い、曲げ弾性率(MPa)を測定した。
JIS K7215に準拠し、デュロメーターDスケールで測定した。
JIS K6251に記載の方法に準じて、測定はn=3で行い、試験片が破断したときの強度(MPa)、および伸び(%)の平均値を採用した。試験片は、2(1/3)号形の形状で、厚さが約2mmのものを用いた。試験は、23℃、500mm/分の試験速度で行った。試験片は、原則として、試験前に温度23℃±2℃、相対湿度50±5%で48時間以上、状態調節したものを用いた。
上述の曲げ弾性率の測定を120℃にて行い、以下の式1より算出した。
(式1) 曲げ弾性率(120℃)/曲げ弾性率(23℃)×100
[耐油性(重量変化率/%)]
JIS K6258に準拠し、140℃に保持したIRM903オイル中に組成物の成形体を72時間浸し、重量変化率(重量%)を求めた。
ASTM D570に準拠し、23℃、24時間の条件にて測定した。
ブロー成形におけるドローダウン性の評価を次のように行った。大型のブロー成形機(ベクム社製、ダイレクトブロー成形機)を用い、ダイスφ70mm、マンドレルφ60mmでアキュムレーターを使用せずに連続方式で円筒状(パイプ状)のパリソンを押出した。パリソンの賦形性(固化、伸び状態)とドローダウンの状態を以下の基準で評価した。なお、成形条件は、シリンダー温度を(融解終了温度(T)+10)℃とし、金型温度は40℃とした。エアーの吹き付けは、型締め直後に、吹き付け時間10条間で行った。
「A」;パリソン賦形性が安定し、ドローダウンすることなく成形品が得られる。
「B」;パリソン賦形は可能もドローダウンが激しく、成形品に顕著な厚みムラが見られる。
「C」;パリソン賦形が安定せずドローダウンしてしまい、また著しい成形不良(穴あき、破れ)が見られる。
表5に示すポリアミド[Z1]、ポリアミド系樹脂組成物[Z2]、並びに、その他の添加剤として安定剤(住友化学社製、スミライザー#GA80)1.0質量部、結晶核剤(松村産業社製、#ET-5)0.7質量部を、35φ二軸押出機(東芝機械社製)に供給し、シリンダー温度280℃、スクリュー回転数300rpmで溶融混練した。この二軸押出機から押出されたストランドを切断して、ポリアミド系熱可塑性エラストマー組成物[Z]のペレットを得た。このペレットを使用して前記の各評価試験を実施した。結果を表5に示す。
[Z1-1]:ポリカプロアミド(ナイロン6)(東レ社製、商品名アミラン「CM1046」、融点=225℃、溶融熱量(ΔH)=64mJ/mg)
[Z1-2]:ポリヘキサメチレンアジパミド(ナイロン66)(東レ社製、商品名アミラン「CM3001-N」、融点=265℃、溶融熱量(ΔH)=66mJ/mg)
[Z1-3]:ヘキサメチレンジアミンとイソフタル酸との塩/ヘキサメチレンジアミンとテレフタル酸との塩の共重合体(三菱エンジニアリングプラスチックス社製、商品名ポリアミドMXD6レニー「#6002」、融点=243℃、溶融熱量(ΔH)=52mJ/mg)
「ポリエステルエラストマー」:熱可塑性ポリエーテルエステルエラストマー(TPEE)(東レ・デュポン株式会社製、商品名ハイトレル「HTR-4275」、融点=202℃、溶融熱量(ΔH)=36.2mJ/mg)
例D1~D7は、何れの評価項目においても優れていた。したがって、このような物性が求められる成形品(例えば自動車用等速ジョイントブーツ)の材料として総合的に優れた特性を有する組成物が得られたと言える。
Claims (19)
- テレフタル酸由来の構造単位を全ジカルボン酸構造単位中30~100モル%有し、示差走査熱量測定(DSC)より求まる融点(Tm)が220~290℃であるポリアミド[I]と、
エチレン[a]、炭素原子数3~20のα-オレフィン[b]、炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]に由来する構造単位を含むエチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]と、
分子中に官能基構造単位を0.3~5.0質量%含むオレフィン系重合体[III]と
を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]とが動的に架橋されているポリアミド系熱可塑性エラストマー組成物[Y]。 - 前記ポリアミド[I]が、ジカルボン酸成分としてイソフタル酸由来の構造単位を含み、ジアミン成分として炭素原子数4~15の脂肪族ジアミン由来の構造単位を含む、請求項1に記載のポリアミド系熱可塑性エラストマー組成物[Y]。
- 前記ポリアミド[I]のイソフタル酸由来の構造単位/テレフタル酸由来の構造単位のモル比が65/35~50/50である請求項2に記載のポリアミド系熱可塑性エラストマー組成物[Y]。
- 前記ポリアミド[I]に含まれる全ジアミン成分のうち、40~100モル%が1,6-ヘキサンジアミン由来の構造単位である請求項1に記載のポリアミド系熱可塑性エラストマー組成物[Y]。
- 前記オレフィン系重合体[III]の官能基構造単位が、カルボン酸基、エステル基、エーテル基、アルデヒド基およびケトン基からなる群から選ばれる官能基を含む、請求項1に記載のポリアミド系熱可塑性エラストマー組成物[Y]。
- 前記オレフィン系重合体[III]の官能基構造単位が、無水マレイン酸構造単位である、請求項5に記載のポリアミド系熱可塑性エラストマー組成物[Y]。
- テレフタル酸由来の構造単位を全ジカルボン酸構造単位中30~100モル%を有し、示差走査熱量測定(DSC)より求まる融点(Tm)が220~290℃であるポリアミド[I]をマトリックス成分とし、そのマトリックス成分に分散する分散成分がエチレン[a]、炭素原子数3~20のα-オレフィン[b]、炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]に由来する構造単位を含むエチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]と、分子中に官能基構造単位を0.3~5.0質量%含むオレフィン系重合体[III]からなる粒子であり、下記(1)を満たすポリアミド系熱可塑性エラストマー組成物:
(1) 前記分散成分の粒径が5μm以上の上記粒子の断面積を計測し、かつ解析した断面積全体に対する前記面積の累計断面積の割合が10%以下である。 - テレフタル酸由来の構造単位を全ジカルボン酸構造単位中30~100モル%有し、示差走査熱量測定(DSC)より求まる融点(Tm)が220~290℃であるポリアミド[I]10~60質量%、
エチレン[a]、炭素原子数3~20のα-オレフィン[b]、炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]に由来する構造単位を含むエチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]30~86質量%、及び
分子中に官能基構造単位を0.3~5.0質量%含むオレフィン系重合体[III]3~30質量%
を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]1~10質量%が動的に架橋されているポリアミド系熱可塑性エラストマー組成物[Y1](ただし、[I]、[II]、[III]及び[IV]の合計量を100質量%とする)。 - 前記ゴム組成物[X]中、エチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]とオレフィン系重合体[III]の質量比([II]/[III])が、95/5~60/40である請求項8に記載のポリアミド系熱可塑性エラストマー組成物[Y1]。
- ポリアミド[I]の分子鎖の末端基の10%以上が末端封止剤によって封止されており、その分子鎖の末端アミノ基量が0.1~100mmol/kgである請求項8記載のポリアミド系熱可塑性エラストマー組成物[Y1]。
- 請求項8に記載のポリアミド系熱可塑性エラストマー組成物[Y1]から得られる成形品。
- テレフタル酸由来の構造単位を全ジカルボン酸構造単位中30~100モル%有し、示差走査熱量測定(DSC)より求まる融点(Tm)が220~290℃であるポリアミド[I]30~87.7質量%、
エチレン[a]、炭素原子数3~20のα-オレフィン[b]、炭素・炭素二重結合を1分子内に1個以上有する非共役ポリエン[c]に由来する構造単位を含むエチレン・α-オレフィン・非共役ポリエン共重合体ゴム[II]10~45質量%、及び
分子中に官能基構造単位を0.3~5.0質量%含むオレフィン系重合体[III]2~20質量%
を含有するゴム組成物[X]とフェノール樹脂系架橋剤[IV]0.3~5.0質量%が動的に架橋されているポリアミド系熱可塑性エラストマー組成物[Y2](ただし、[I]、[II]、[III]及び[IV]の合計量を100質量%とする)。 - 請求項12に記載のポリアミド系熱可塑性エラストマー組成物[Y2]を含む層を少なくとも有する産業用チューブ。
- 自動車配管用チューブ、空圧チューブ、油圧チューブ、ペイントスプレーチューブ、又は医療用チューブである請求項13に記載の産業用チューブ。
- 外径が2mm~50mm、肉厚が0.2mm~10mmである請求項13に記載の産業用チューブ。
- さらに、フッ素樹脂、高密度ポリエチレン樹脂、ポリブチレンナフタレート樹脂(PBN)、脂肪族ポリアミド樹脂、芳香族ポリアミド樹脂、メタキシレン基含有ポリアミド樹脂、エチレン-酢酸ビニル共重合体鹸化物(EVOH)及びポリフェニレンサルファイド樹脂(PPS)からなる群より選ばれる少なくとも1種の樹脂からなる層を含む請求項13から請求項15のいずれかに記載の産業用チューブ。
- 示差走査熱量測定(DSC)により求まる融点(Tm)が210~270℃であり、DSCにより求まる溶融熱量(ΔH)が45~80mJ/mgであるポリアミド[Z1]10~35質量%と、ポリアミド系樹脂組成物[Z2]65~90質量%とを含むポリアミド系熱可塑性エラストマー組成物(ただし[Z1]及び[Z2]の合計量を100質量%とする)であって、
前記ポリアミド系樹脂組成物[Z2]が、請求項12に記載のポリアミド系熱可塑性エラストマー組成物[Y2]であることを特徴とするポリアミド系熱可塑性エラストマー組成物[Z]。 - 請求項17記載のポリアミド系熱可塑性エラストマー組成物[Z]から射出成形又はブロー成形により得られる成形品。
- 請求項17記載のポリアミド系熱可塑性エラストマー組成物[Z]を含む自動車用等速ジョイントブーツ。
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CN201480072354.5A CN105899586B (zh) | 2013-12-06 | 2014-12-05 | 聚酰胺系热塑性弹性体组合物及其成型品 |
EP14867983.0A EP3078701B1 (en) | 2013-12-06 | 2014-12-05 | Polyamide thermoplastic elastomer composition and molded article thereof |
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WO2017217447A1 (ja) * | 2016-06-17 | 2017-12-21 | 東洋紡株式会社 | 半芳香族ポリアミド樹脂 |
JPWO2017217447A1 (ja) * | 2016-06-17 | 2019-04-04 | 東洋紡株式会社 | 半芳香族ポリアミド樹脂 |
JP7081152B2 (ja) | 2016-06-17 | 2022-06-07 | 東洋紡株式会社 | 半芳香族ポリアミド樹脂 |
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JP2019172829A (ja) * | 2018-03-28 | 2019-10-10 | 三井化学株式会社 | ポリアミド系熱可塑性エラストマー組成物、成形体および中空成形体 |
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JP7336858B2 (ja) | 2019-03-18 | 2023-09-01 | 三井化学株式会社 | 樹脂組成物および成形体、ならびに樹脂組成物の製造方法 |
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JPWO2015083819A1 (ja) | 2017-03-16 |
EP3078701A4 (en) | 2017-10-11 |
EP3078701A1 (en) | 2016-10-12 |
CN105899586A (zh) | 2016-08-24 |
EP3078701B1 (en) | 2019-01-30 |
CN105899586B (zh) | 2018-02-13 |
KR20160094402A (ko) | 2016-08-09 |
US20170283556A1 (en) | 2017-10-05 |
JP6654045B2 (ja) | 2020-02-26 |
KR101777985B1 (ko) | 2017-09-12 |
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