WO2015159834A1 - 半芳香族ポリアミド樹脂組成物およびそれを成形してなる成形体 - Google Patents
半芳香族ポリアミド樹脂組成物およびそれを成形してなる成形体 Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/053—Polyhydroxylic alcohols
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- 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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- 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
- C08G69/28—Preparatory processes
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Definitions
- the present invention relates to a semi-aromatic polyamide resin composition.
- Semi-aromatic polyamide is widely used as a molding material because of its excellent heat resistance and mechanical properties.
- semi-aromatic polyamides having a melting point of 300 ° C. or higher are used for applications that require particularly high heat resistance, such as around automobile engines and LED lighting.
- Patent Document 1 discloses that fluidity during melt processing is improved by end-capping a semi-aromatic polyamide with a long-chain monocarboxylic acid.
- Patent Document 2 discloses that fluidity is improved by blending a polyhydric alcohol.
- Patent Documents 3 and 4 disclose that heat aging is suppressed by blending a polyhydric alcohol.
- the technique of blending these polyhydric alcohols relates to aliphatic polyamides and copolymerized semi-aromatic polyamides having a melting point of substantially less than 310 ° C.
- homo-type semi-aromatic polyamides which are superior in heat resistance compared to the above-mentioned copolymer-type semi-aromatic polyamides, have a higher heat of crystal melting, so they are melt-processed than the peak temperature of the melting point compared to the copolymer type. It is necessary to set the temperature higher by 10 to 20 ° C. Therefore, homo-type semi-aromatic polyamides suffer from deterioration of physical properties due to thermal decomposition and poor appearance of the molded product when retained at a melt processing temperature of 330 ° C. or higher for a long time. Problems that have not been made apparent with aromatic polyamides may occur.
- Patent Document 5 discloses that heat aging is suppressed by blending a copper compound with a homo-type semi-aromatic polyamide.
- the effect of suppressing heat aging due to the blending of the copper compound is not sufficient, and the resin composition containing the copper compound has a decrease in physical properties due to thermal decomposition when it is retained for a long time at a high melt processing temperature.
- the appearance of the molded body is poor. That is, in the molding process of a semi-aromatic polyamide having a melting point of 300 ° C. or more, particularly a highly crystalline semi-aromatic polyamide which is not copolymerized, in addition to the above-described problems of fluidity and heat aging during melt processing.
- retention stability that the physical properties are deteriorated due to thermal decomposition and the appearance is deteriorated in the molded body.
- the present invention solves the above-mentioned problem, and has improved fluidity during melt processing, and further reduced semi-aromatic polyamide resin composition in which reduction of residence stability and thermal aging are effectively suppressed.
- the purpose is to provide goods.
- the present inventors have found that the above problems can be solved by blending a specific amount of polyhydric alcohol with a semi-aromatic polyamide having a melting point of 300 to 350 ° C.
- the present invention has been reached. That is, the gist of the present invention is as follows.
- the mass ratio (A / B) of the semi-aromatic polyamide (A) and the polyhydric alcohol (B) is 99.95 / 0.05 to 90/10
- the semi-aromatic polyamide (A) contains an aromatic dicarboxylic acid component and an aliphatic diamine component as constituent components, and has a melting point of 300 to 350 ° C.
- the semi-aromatic polyamide (A) contains a monocarboxylic acid component as a constituent component, and the content thereof is 0.3 to 4. with respect to all monomer components constituting the semi-aromatic polyamide (A).
- the semi-aromatic polyamide resin composition according to (1) which is 0 mol%.
- the composition further comprises 5 to 200 parts by mass of a fibrous reinforcing material (C) with respect to a total of 100 parts by mass of the semiaromatic polyamide (A) and the polyhydric alcohol (B).
- the semi-aromatic polyamide resin composition of the present invention contains a semi-aromatic polyamide (A) and a polyhydric alcohol (B).
- the semi-aromatic polyamide (A) constituting the semi-aromatic polyamide resin composition of the present invention contains an aromatic dicarboxylic acid component and an aliphatic diamine component as constituent components.
- the semi-aromatic polyamide (A) may contain a copolymer component, but it is copolymerized from the viewpoints of heat resistance, mechanical strength, chemical resistance, crystallization is fast, and a molded product can be obtained with a low-temperature mold.
- it consists of a single aromatic dicarboxylic acid component and a single aliphatic diamine component.
- examples of the aromatic dicarboxylic acid component constituting the semiaromatic polyamide (A) include terephthalic acid, phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
- terephthalic acid is preferable because heat resistance can be improved.
- Examples of the acid component that is copolymerized in addition to the aromatic dicarboxylic acid component include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc.
- dicarboxylic acids such as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
- the amount of copolymerization of aromatic dicarboxylic acids other than terephthalic acid, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids does not decrease the melting point and heat resistance of the semi-aromatic polyamide (A). On the other hand, it is preferably 5 mol% or less, and more preferably substantially not contained.
- examples of the aliphatic diamine component constituting the semiaromatic polyamide (A) include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,5-pentanediamine. 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, -Methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine.
- the aliphatic diamine component it is preferable to use one kind of the aliphatic diamine component alone, in combination with a good balance between heat resistance and mechanical properties, and to obtain a molded article having excellent chemical resistance. Therefore, it is preferable to use 1,10-decanediamine alone.
- Examples of the diamine component that is copolymerized in addition to the aliphatic diamine component include alicyclic diamines such as cyclohexanediamine, and aromatic diamines such as xylylenediamine and benzenediamine.
- the copolymerization amount of the alicyclic diamine and aromatic diamine other than the aliphatic diamine component does not impair the above-mentioned characteristics brought about by the aliphatic diamine component, so that it is 5 mol% or less with respect to the total number of moles of raw material monomers. It is more preferable that it is not substantially contained.
- other copolymerization components constituting the semi-aromatic polyamide (A) include lactams such as caprolactam and laurolactam, and ⁇ -aminocarboxylic acids such as aminocaproic acid and 11-aminoundecanoic acid. These copolymerization amounts are preferably 5 mol% or less based on the total number of moles of raw material monomers so as not to lower the heat resistance, mechanical properties, and chemical resistance of the semi-aromatic polyamide (A). More preferably, it is not substantially contained.
- the semi-aromatic polyamide (A) in the present invention is preferably composed of a single aromatic dicarboxylic acid component and a single aliphatic diamine component as described above, but the semi-aromatic polyamide resin composition of the present invention. May contain two or more semi-aromatic polyamides (A) having different constituent monomer components.
- the semi-aromatic polyamide resin composition contains two or more semi-aromatic polyamides (A) having different constituent monomer components, thereby further improving the surface appearance and suppressing heat aging.
- the semi-aromatic polyamide (A) preferably contains a monocarboxylic acid component as a constituent component in order to improve fluidity and releasability.
- the content of the monocarboxylic acid component is preferably 0.3 to 4.0 mol%, and preferably 0.3 to 3.0 mol% with respect to all monomer components constituting the semiaromatic polyamide (A). More preferably, it is 0.3 to 2.5 mol%, more preferably 0.8 to 2.5 mol%.
- the molecular weight of the monocarboxylic acid is preferably 140 or more, and more preferably 170 or more.
- the fluidity and releasability of the semiaromatic polyamide (A) is further improved.
- the resin composition contains a semi-aromatic polyamide (A) containing a monocarboxylic acid component having a molecular weight of 140 or more together with the polyhydric alcohol (B), the crystallization rate during molding remains unchanged.
- the resulting molded body has improved crystallinity.
- a semi-aromatic polyamide (A) containing a monocarboxylic acid component having a molecular weight of 140 or more and a polyhydric alcohol (The resin composition containing B) is particularly useful for this application.
- Examples of the monocarboxylic acid component include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids, and aliphatic monocarboxylic acids are preferred from the viewpoint of fluidity and releasability.
- Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Of these, stearic acid is preferred because of its high versatility.
- Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid.
- aromatic monocarboxylic acids having a molecular weight of 140 or more examples include 4-ethylbenzoic acid, 4-hexylbenzoic acid, 4-laurylbenzoic acid, alkylbenzoic acids, 1-naphthoic acid, 2-naphthoic acid, and their Derivatives.
- the monocarboxylic acid component may be used alone or in combination.
- a monocarboxylic acid having a molecular weight of 140 or more and a monocarboxylic acid having a molecular weight of less than 140 may be used in combination.
- the molecular weight of the monocarboxylic acid refers to the molecular weight of the starting monocarboxylic acid.
- the semi-aromatic polyamide (A) needs to have a melting point of 300 to 350 ° C., preferably 310 to 350 ° C., and more preferably 315 to 350 ° C.
- the resulting semiaromatic polyamide resin composition has insufficient heat resistance.
- the melting point of the semi-aromatic polyamide (A) exceeds 350 ° C., the decomposition temperature of the polyamide bond is about 350 ° C., so that carbonization and decomposition proceed during melt processing.
- the melting point is set to the top of the endothermic peak when the temperature is increased at a temperature increase rate of 20 ° C./min with a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- the relative viscosity of the semi-aromatic polyamide (A) measured in 96% sulfuric acid at 25 ° C. and at a concentration of 1 g / dL is preferably 1.8 or more from the viewpoint of mechanical properties. 1.8 to 3.5 is more preferable, and 2.2 to 3.1 is still more preferable. If the relative viscosity of the semi-aromatic polyamide (A) exceeds 3.5, melt processing may be difficult.
- the method for producing the semi-aromatic polyamide (A) is not particularly limited, and conventionally known methods such as a heat polymerization method and a solution polymerization method can be used. Of these, the heat polymerization method is preferably used because it is industrially advantageous. Examples of the heat polymerization method include a method comprising a step (i) of obtaining a reaction product from an aromatic dicarboxylic acid component and an aliphatic diamine component, and a step (ii) of polymerizing the obtained reaction product. .
- the aromatic dicarboxylic acid powder is heated in advance to a temperature not lower than the melting point of the aliphatic diamine and not higher than the melting point of the aromatic dicarboxylic acid.
- a method of adding an aliphatic diamine without substantially containing water so as to maintain the state of the dicarboxylic acid powder can be mentioned.
- a suspension of a molten aliphatic diamine and a solid aromatic dicarboxylic acid is stirred and mixed to obtain a mixed solution, and then the melting point of the semi-aromatic polyamide finally produced
- a method of obtaining a mixture of a salt and a low polymer by performing a salt formation reaction by reaction of an aromatic dicarboxylic acid and an aliphatic diamine and a low polymer formation reaction by polymerization of the generated salt at a temperature of less than It is done. In this case, crushing may be performed while the reaction is performed, or crushing may be performed after the reaction is once taken out. In the step (i), the former is preferable because the shape of the reaction product can be easily controlled.
- the reaction product obtained in the step (i) is solid-phase polymerized at a temperature lower than the melting point of the semi-aromatic polyamide to be finally produced to increase the molecular weight to a predetermined molecular weight.
- a method for obtaining a semi-aromatic polyamide is preferably performed in a stream of inert gas such as nitrogen at a polymerization temperature of 180 to 270 ° C. and a reaction time of 0.5 to 10 hours.
- step (i) and step (ii) are not particularly limited, and a known apparatus may be used. Step (i) and step (ii) may be performed by the same device or may be performed by different devices.
- the heating method in the heat polymerization method is not particularly limited, but the method of heating the reaction vessel with a medium such as water, steam, heat transfer oil, the method of heating the reaction vessel with an electric heater, the stirring generated by stirring A method using frictional heat accompanying the movement of contents such as heat can be mentioned. Moreover, you may combine these methods.
- a polymerization catalyst may be used in order to increase the polymerization efficiency.
- the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid, and salts thereof.
- the addition amount of a polymerization catalyst is 2 mol% or less with respect to all the monomer components which comprise a semi-aromatic polyamide (A).
- the semi-aromatic polyamide resin composition of the present invention needs to contain a polyhydric alcohol (B).
- the mass ratio of the semiaromatic polyamide (A) to the polyhydric alcohol (B) is 99.95 / 0.05 to 90 / 10 is necessary, and it is preferably 99.9 / 0.1 to 92/8, and more preferably 99.8 / 0.2 to 95/5.
- the mass ratio of the polyhydric alcohol (B) to the total of the semi-aromatic polyamide (A) and the polyhydric alcohol (B) is less than 0.05% by mass, the effect of suppressing heat aging is small.
- the polyhydric alcohol (B) used in the present invention is a compound containing two or more hydroxyl groups.
- Examples of the polyhydric alcohol (B) include saturated aliphatic compounds, unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, and saccharides.
- the polyhydric alcohol may contain one or more heteroatoms such as oxygen, nitrogen and / or sulfur.
- the polyhydric alcohol (B) may contain a substituent other than a hydroxyl group, for example, an ether, carboxylic acid, amide or ester group.
- the polyhydric alcohol may be a low molecular weight compound or a polymer type high molecular weight compound in which a certain monomer unit repeats.
- a polyhydric alcohol (B) may be used individually by 1 type, and may use multiple types together.
- saturated aliphatic compound examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, and glycerin monomethacrylate.
- Low molecular weight alcohol glycerol, trimethylolpropane, hexane-1,2,6-triol, 1,1,1-tris- (hydroxymethyl) ethane, 3- (2'-hydroxyethoxy) -propane-1, 2-diol, 3- (2'-hydroxypropoxy) -propane-1,2-diol, 2- (2'-hydroxyethoxy) -hexane-1,2-diol, 6- (2'-hydroxypropoxy)- Hexane-1,2-diol, 1,1,1-tris-[(2'-hydroxyethyl 3) such as xyl) -methyl] -ethane, 1,1,1-tris-[(2'-hydroxypropoxy) -methyl] -propane, di-trimethylolpropane, trimethylolpropane ethoxylate, trimethylolpropane propoxylate
- Low molecular weight alcohols such as pentaerythritol, dipent
- Examples of the unsaturated aliphatic compound include ricinoleyl alcohol.
- Examples of alicyclic compounds include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3,5-cyclohexanetriol, 2,3-di- (2′-hydroxy Ethyl) -cyclohexane-1-ol.
- aromatic compound examples include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, hydrobenzoin, 1,1,2,2-tetraphenylethane-1,2 -Diol, 1,1,1-tris- (4'-hydroxyphenyl) -ethane, 1,1,1-tris- (hydroxyphenyl) -propane, 1,1,3-tris- (dihydroxy-3-methyl Phenyl) -propane, 1,1,4-tris- (dihydroxyphenyl) -butane, 1,1,5-tris- (hydroxyphenyl) -3-methylpentane, bisphenoxyethanol fluorene.
- saccharide examples include cyclodextrin, D-mannose, glucose, galactose, sucrose, fructose, xylose, arabinose, D-mannitol, D-sorbitol, D- or L-arabitol, xylitol, iditol, galactitol, taritol, Examples include allitol, altitol, giltor, erythritol, threitol, ribitol, and D-gulonic acid- ⁇ -lactone.
- Examples of the polyhydric alcohol having two or more hydroxyl groups and an ester group as the other substituent include esters composed of pentaerythritol and a fatty acid (for example, Unistar H series manufactured by NOF Corporation), dipentaerythritol, Examples thereof include polyhydric alcohols that are ester-bonded to a carboxylic acid leaving two or more hydroxyl groups, such as esters composed of dibasic acids (for example, Ajinomoto Fine Techno Co., Ltd., Pleniser Series).
- the semi-aromatic polyamide resin composition of the present invention preferably further contains a fibrous reinforcing material (C).
- a fibrous reinforcement for example, glass fiber, carbon fiber, boron fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polybenzoxazole fiber, polytetrafluoro Examples include ethylene fiber, kenaf fiber, bamboo fiber, hemp fiber, bagasse fiber, high-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, and basalt fiber.
- glass fiber and carbon fiber are preferable because they have a high effect of improving mechanical properties, have heat resistance that can withstand the heating temperature during melt kneading with a semi-aromatic polyamide resin, and are easily available.
- a fibrous reinforcement (C) may be used individually by 1 type, and may use multiple types together.
- the fiber reinforcement (C) such as glass fiber or carbon fiber is preferably treated with a surface treatment agent such as a sizing agent.
- the main component of the sizing agent is preferably a coupling agent or a film forming agent.
- the coupling agent include vinyl silane, acrylic silane, epoxy silane, amino silane, amino titanium, and the like. Of these, aminosilane coupling agents are preferred because they have a high adhesion effect between the semi-aromatic polyamide (A) and glass fibers or carbon fibers and are excellent in heat resistance.
- the film forming agent include urethane-based, epoxy-based, and acrylic resins.
- urethane-based resins are preferable because they have a high adhesion effect with glass fibers or carbon fibers and are excellent in heat resistance.
- the film-forming agent preferably contains an acid component because the hydrolysis resistance of the resin composition is improved.
- the acid component is preferably copolymerized with a resin which is a main component of the film forming agent.
- the acid component include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and cinnamic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and maleic anhydride.
- the fiber length and fiber diameter of the fibrous reinforcing material (C) are not particularly limited, but the fiber length is preferably 0.1 to 7 mm, and more preferably 0.5 to 6 mm.
- the resin composition can be reinforced without adversely affecting the moldability.
- the fiber diameter of the fibrous reinforcing material (C) is preferably 3 to 20 ⁇ m, more preferably 5 to 13 ⁇ m.
- the resin composition can be reinforced without breaking during melt-kneading.
- Examples of the cross-sectional shape of the fibrous reinforcing material (C) include a circular shape, a rectangular shape, an elliptical shape, and other irregular cross-sections. Among them, a circular shape is preferable.
- the fibrous reinforcing material (C) When the fibrous reinforcing material (C) is used, its content is preferably 5 to 200 parts by mass with respect to 100 parts by mass in total of the semi-aromatic polyamide (A) and the polyhydric alcohol (B). It is more preferably from 180 to 180 parts by mass, further preferably from 20 to 150 parts by mass, particularly preferably from 30 to 130 parts by mass. When the content of the fibrous reinforcing material (C) is less than 5 parts by mass, the effect of improving mechanical properties may be small.
- the improvement effect of mechanical properties is saturated and not only the improvement effect can be expected, but also the workability at the time of melt kneading is lowered, and the semi-aromatic polyamide resin composition It may be difficult to obtain product pellets.
- the resin temperature increases due to shear heat generation, or the resin temperature must be increased to improve the fluidity.
- the molecular weight, mechanical properties, and retention stability may be reduced.
- the semi-aromatic polyamide resin composition of the present invention can further improve the melt stability and effectively suppress the heat aging by containing various stabilizers such as an antioxidant, a light stabilizer and a heat stabilizer.
- various stabilizers such as an antioxidant, a light stabilizer and a heat stabilizer.
- the antioxidant include a hindered phenol antioxidant, a sulfur antioxidant, and a phosphorus antioxidant
- the light stabilizer include a hindered amine light stabilizer.
- a phosphorus-based antioxidant is preferable for suppressing heat aging
- a hindered phenol-based antioxidant and a hindered amine-based light stabilizer are preferable for improving retention stability.
- hindered phenol antioxidant examples include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′- Methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6- Hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl -4-hydroxyphenyl) -propionate], 2,2'-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl)
- a dophenol antioxidant may be used independently and may be used together.
- examples of commercially available hindered phenol antioxidants include ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, AO-330, manufactured by Adeka Corporation.
- sulfur-based antioxidants include distearyl 3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole, didodecyl 3,3′-thiodiprote. Pionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,4'-thiodipropionate, 2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3 Mention may be made of propanediyl esters.
- Sulfur-based antioxidants may be used alone or in combination.
- examples of commercially available sulfur-based antioxidants include Sumitizer TP-D and MB manufactured by Sumitomo Chemical Co., Ltd.
- the phosphorus antioxidant may be either an inorganic compound or an organic compound.
- examples of the phosphorus antioxidant include inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite; Phenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonyl phenyl phosphite, diphenyl isodecyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl)
- hindered amine light stabilizers include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, tetrakis (2,2,6,6- Tetramethyl-1-4-piperidyl) butane-1,2,3,4-tetracarboxylate, dimethyl succinate 1- (2hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl- 4-piperidine polycondensate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [(6-morpholino-S-triazine-2,4-diyl) [2,2, 6,6-tetramethyl-4-piperidyl] imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino].
- the hindered amine light stabilizers may be used alone or in combination.
- Examples of commercially available stabilizers include Nylothtab S-EED manufactured by Clariant Japan, Biosorb 04 manufactured by Kyodo Yakuhin, Siasorb UV-3346 manufactured by Cytec, Adeka Stub LA-57, LA-63P, LA-68 manufactured by Adeka, and BASF. Cimasorb 119, 944 and Tinuvin 622, 765 manufactured by the company are listed.
- the content of the stabilizer is preferably 0.005 to 3 parts by mass with respect to 100 parts by mass in total of the semi-aromatic polyamide (A) and the polyhydric alcohol (B), preferably 0.1 to 1 part by mass. More preferably it is.
- the semi-aromatic polyamide resin composition of the present invention contains a polyamide other than the semi-aromatic polyamide (A), the fluidity and retention stability are further improved, and the surface appearance is excellent. It can also suppress heat aging.
- the polyamide other than the semi-aromatic polyamide (A) (hereinafter sometimes abbreviated as “other polyamide”) is not particularly limited, but it is amorphous or has a melting point of less than 300 ° C. Examples thereof include polyamide and aliphatic polyamide.
- Examples of the semi-aromatic polyamide other than the semi-aromatic polyamide (A) include a copolymer of terephthalic acid, isophthalic acid, and aliphatic diamine.
- Examples of the aliphatic polyamide other than the semi-aromatic polyamide (A) include polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 410, polyamide 412, polyamide 510, polyamide 512, polyamide 66, polyamide 610, polyamide 612, Examples thereof include polyamide 1010, polyamide 1012, polyamide 6/66, polyamide 66/1010, polyamide 66/612, polyamide 2Me5C, polyamide 6C, polyamide 8C, polyamide 9C, polyamide 10C, and polyamide 12C.
- C represents 1,4-cyclohexanedicarboxylic acid
- 2Me5 represents 2-methylpentamethylenediamine.
- the content thereof is 1 to 100 parts by mass with respect to 100 parts by mass in total of the semi-aromatic polyamide (A) and the polyhydric alcohol (B). It is preferably 3 to 50 parts by mass, more preferably 3 to 30 parts by mass.
- the semi-aromatic polyamide resin composition of the present invention has improved fluidity during melt processing by containing 1 to 100 parts by mass of another polyamide with respect to 100 parts by mass in total of (A) and (B). In addition, the surface appearance of the obtained molded body is also improved. Furthermore, because of the high fluidity, it is possible to lower the temperature of the melt processing, and the residence stability during the melt processing is further improved. Moreover, heat aging is also suppressed. The said effect may not be acquired as content is less than 1 mass part. On the other hand, if the content exceeds 100 parts by mass, the heat resistance and mechanical properties of the semi-aromatic polyamide (A) may be impaired.
- the filler include talc, swellable clay mineral, silica, alumina, glass beads, and graphite.
- the colorant include pigments such as titanium oxide and carbon black, and dyes such as nigrosine. In particular, by containing nigrosine, the fluidity at the time of melt processing of the semi-aromatic polyamide resin composition can be improved, the melt processing temperature can be lowered and the retention stability can be improved. The surface appearance is improved.
- a semi-aromatic polyamide (A), a polyhydric alcohol (B), a fibrous reinforcing material (C) added as necessary, other additives, and the like are blended, and the resin composition of the present invention.
- the method for producing is not particularly limited, but the melt-kneading method is preferred.
- the melt-kneading method include a method using a batch kneader such as Brabender, a Banbury mixer, a Henschel mixer, a helical rotor, a roll, a single screw extruder, a twin screw extruder and the like.
- the melt kneading temperature is not particularly limited as long as the semi-aromatic polyamide (A) melts and does not decompose, but if it is too high, the semi-aromatic polyamide (A) is decomposed.
- the melting point is preferably ⁇ 20 ° C. or higher and (the melting point of semi-aromatic polyamide + 40 ° C.) or lower.
- the melted resin composition can be extruded into strands to form pellets, hot cut, underwater cut into pellets, extruded into sheets, cut into blocks, or extruded and ground into blocks It can be processed into various shapes depending on the powder shape method.
- the molded product of the present invention is formed by molding the semi-aromatic polyamide resin composition.
- the molding method include an injection molding method, an extrusion molding method, a blow molding method, and a sintering molding method, and the injection molding method is preferable because it has a great effect of improving mechanical properties and moldability.
- the injection molding machine is not particularly limited, and examples thereof include a screw in-line type injection molding machine and a plunger type injection molding machine.
- a semi-aromatic polyamide resin composition heated and melted in a cylinder of an injection molding machine is weighed for each shot, injected into a mold in a molten state, cooled to a predetermined shape, solidified, and then formed into a molded body. Removed from the mold.
- the resin temperature during injection molding is more preferably (melting point of semi-aromatic polyamide ⁇ 20 ° C.) or more and less than (melting point of semi-aromatic polyamide + 40 ° C.). Since the resin composition of the present invention is excellent in fluidity at the time of melt processing, it is not necessary to increase the resin temperature at the time of molding more than necessary. Therefore, the residence stability during melt processing is not impaired.
- the semi-aromatic polyamide resin composition When the semi-aromatic polyamide resin composition is melt-processed, it is preferable to use semi-aromatic polyamide resin composition pellets that have been sufficiently dried. If a semi-aromatic polyamide resin composition containing a large amount of water is used, the resin may foam in the cylinder of the injection molding machine, making it difficult to obtain an optimal molded product.
- the water content of the semi-aromatic polyamide resin composition pellets used for injection molding is preferably less than 0.3 parts by mass and less than 0.1 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide resin composition. More preferably.
- the semi-aromatic polyamide resin composition of the present invention has good fluidity and retention stability at the time of melt processing, and further effectively suppresses heat aging. Therefore, the semi-aromatic polyamide resin composition of the present invention can be suitably used as a molded body molding resin for a wide range of applications such as automobile parts, electrical and electronic parts, general merchandise, and civil engineering and building articles. It can be used as a modeling resin. Examples of automobile parts include a thermostat cover, an IGBT module member of an inverter, an insulator member, an intercooler member, an exhaust finisher, a power device housing, an ECU housing, an ECU connector, an insulating material for motors and coils, and a cable covering material. It is done.
- Electrical and electronic parts include, for example, connectors, LED reflectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, breakers, electromagnetic switches, holders, plugs, casings for electrical devices such as portable personal computers.
- Examples include components, resistors, ICs, and LED housings.
- the semi-aromatic polyamide resin composition of the present invention is to be used for a long time while being exposed to various chemicals in a high temperature environment because heat aging is effectively suppressed and chemical resistance is excellent.
- the present invention can be particularly suitably used for molding automobile parts.
- the semi-aromatic polyamide resin composition of this invention and the semi-aromatic polyamide (A) which comprises it can be used as modeling resin of 3D printer.
- the 3D printer modeling method include an ink jet method, a hot melt lamination method, and a powder fixing method.
- the heat melting lamination method includes laser irradiation, infrared ray irradiation, a method of melting by heating, and the like
- the powder fixing method includes a method of spraying an adhesive onto a powder resin.
- the physical properties of the semi-aromatic polyamide and the semi-aromatic polyamide resin composition were measured by the following methods.
- Tensile strength, tensile strength retention rate Tensile strength was measured in accordance with ISO178 using test pieces 1 to 4 prepared by the following method. Obtain the tensile strength retention rate (%) of the test piece 2 relative to the test piece 1, evaluate the retention stability, determine the tensile strength retention rate (%) of the test piece 3 relative to the test piece 1, evaluate the thermal aging, Furthermore, the tensile strength retention (%) of the test piece 4 with respect to the test piece 1 was calculated
- ⁇ Test piece 1> (Test piece prepared under standard conditions) Using the injection molding machine S2000i-100B type (manufactured by FANUC), the semi-aromatic polyamide resin composition was subjected to cylinder temperature (melting point of semi-aromatic polyamide + 15 ° C.), mold temperature (melting point of semi-aromatic polyamide ⁇ 175 And test piece 1 (ISO multi-purpose test piece). In Examples 24 to 28 and 35, the cylinder temperature was (melting point of semi-aromatic polyamide + 5 ° C.), and in Examples 33 to 34, the cylinder temperature was (melting point of semi-aromatic polyamide + 10 ° C.). In No. 3, the cylinder temperature was (polyamide melting point + 20 ° C.).
- ⁇ Test piece 2> (Retention stability evaluation test piece, 600-second retention treatment) Except that the residence time in the cylinder was set to 600 seconds, injection molding was performed under the same conditions as for the test piece 1 to prepare a test piece 2 (ISO multipurpose test piece). The residence time in the cylinder was set to 600 seconds by adjusting the cooling time.
- ⁇ Test piece 3> (Test piece for thermal aging evaluation, heat treatment at 200 ° C. for 1000 hours)
- the test piece 1 was heat-treated at 200 ° C. for 1000 hours in a hot stove to produce a test piece 3.
- ⁇ Test piece 4> (Test piece for hydrolyzability evaluation, 130 ° C.
- Specimen 1 was immersed in a 2-fold diluted solution of LLC liquid (Castle, Long Life Coolant V9230-0102, red) in an autoclave and treated at 130 ° C. for 100 hours to produce Specimen 4 did.
- the surface appearance of the test piece 1 was visually observed and evaluated according to the following criteria.
- Crystallinity index at low temperature molding Test piece 5 obtained by injection molding under the same conditions as test piece 1 except that the mold temperature is (melting point of semi-aromatic polyamide-255 ° C),
- the ratio of the heat of crystal fusion was calculated from the following formula and used as an index of crystallinity.
- the heat of crystal fusion of the test pieces 1 and 5 is the endothermic peak when the temperature is increased to 370 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer). And from the exothermic peak, it calculated
- Heat of crystal fusion (endothermic peak [J / g]) ⁇ (exothermic peak [J / g])
- Crystallinity index (%) (heat of crystal fusion of test piece 5 [J / g]) / (heat of crystal fusion of test piece 1 [J / g]) ⁇ 100
- Aromatic dicarboxylic acid component / TPA terephthalic acid / IPA: isophthalic acid
- B-1 Dipentaerythritol (Guangei Chemical Industry Co., Ltd., dipentalit)
- B-2 Bisphenoxyethanol fluorene (Osaka Gas Chemical Co., BPEF)
- B-3 ester composed of dipentaerythritol and adipic acid (manufactured by Ajinomoto Fine-Techno Co., Ltd., Plenizer ST-210)
- B-4 Polyvinyl butyral (Kuraray, Mowital B75H)
- Monoalcohol B-5 Stearyl alcohol (manufactured by Shin Nippon Chemical Co., Ltd., Conol 30SS)
- Fibrous reinforcing material C-1: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., T-262H, average fiber diameter 10.5 ⁇ m, average fiber length 3 mm, using a film forming agent containing an acid copolymer)
- C-3 Carbon fiber (manufactured by Toho Tenax Co., Ltd., HTA-C6-NR, average fiber diameter 7 ⁇ m, average fiber length 6 mm)
- the internal temperature was kept at 215 ° C., and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2 MPa.
- the pressure was reduced to 1.2 MPa over 30 minutes to obtain a prepolymer.
- the prepolymer was pulverized to a size of 1 mm or less and dried at 120 ° C. under reduced pressure for 12 hours. This was subjected to solid phase polymerization at 230 ° C. and 13.3 Pa for 10 hours to obtain polyamide (P-4) (polyamide 10C) having a melting point of 312 ° C.
- AO-1 bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (phosphorus antioxidant, manufactured by Adeka, Adeka Stub PEP-36)
- AO-2 3,9-bis [2- ⁇ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ -1,1-dimethylethyl] 2,4,8,10 -Tetraoxaspiro (5,5) undecane (hindered phenol antioxidant, manufactured by Adeka, Adeka Stub AO-80)
- S-1 2-ethyl-2-ethoxy-oxalanilide (hindered amine light stabilizer, manufactured by Clariant Japan, Nyrostab S-EED)
- ⁇ H-1 Copper iodide (special grade reagent)
- H-2 Potassium iodide
- Colorant / N-1 Nigrosine (Orient Chemical Industries, NUBIAN BLACK TH-807, Solvent Black 7)
- A-1 Semi-aromatic polyamide (A-1) 4.70 kg of powdered terephthalic acid (TPA) as an aromatic dicarboxylic acid component, 0.32 kg of stearic acid (STA) as a monocarboxylic acid component, and 9.3 g of sodium hypophosphite monohydrate as a polymerization catalyst, was put into a ribbon blender reactor and heated to 170 ° C. with stirring at a rotation speed of 30 rpm under nitrogen sealing. Thereafter, while maintaining the temperature at 170 ° C. and maintaining the rotation speed at 30 rpm, 4.98 kg of 1,10-decanediamine (DDA) heated to 100 ° C. as an aliphatic diamine component was added using a liquid injection device.
- TPA powdered terephthalic acid
- STA stearic acid
- DDA 1,10-decanediamine
- reaction product was polymerized by heating at 250 ° C. and a rotation speed of 30 rpm for 8 hours under a nitrogen stream in the same reaction apparatus to prepare a semi-aromatic polyamide powder.
- the obtained semi-aromatic polyamide powder is formed into a strand shape using a twin-screw kneader, and the strand is cooled and solidified by passing it through a water tank, which is then cut with a pelletizer to obtain a semi-aromatic polyamide (A-1). Pellets were obtained.
- Table 1 shows the resin composition and characteristic values of the obtained semi-aromatic polyamide.
- Example 1 99 parts by mass of semi-aromatic polyamide (A-1) and 1 part by mass of polyhydric alcohol (B-1) are dry blended, and a loss-in-weight continuous quantitative supply device CE-W-1 type (manufactured by Kubota) is used. Then, the mixture was supplied to the main supply port of the TEM26SS type (Toshiba Machine Co., Ltd.) twin screw extruder with a screw diameter of 26 mm and L / D50, and melt kneading was performed. On the way, 45 parts by mass of fibrous reinforcing material (C-1) was supplied from the side feeder and further kneaded.
- TEM26SS type Toshiba Machine Co., Ltd.
- the barrel temperature settings of the extruder were (melting point of semi-aromatic polyamide + 5 ° C.) to (melting point of semi-aromatic polyamide + 15 ° C.), screw rotation speed 250 rpm, discharge rate 25 kg / h.
- the resin compositions of Examples 1 to 35 have the heat resistance and mechanical properties inherent to the semi-aromatic polyamide, and are suppressed in heat aging, and further have fluidity during melt processing. It was excellent in retention stability and surface appearance.
- the lower the relative viscosity of the semi-aromatic polyamide (Examples 1 and 4) the better the fluidity during melt processing, while the higher the relative viscosity of the semi-aromatic polyamide (Example 2). 3)
- the retention stability was excellent.
- Example 1 since the monocarboxylic acid component of the semi-aromatic polyamide resin is an aliphatic monocarboxylic acid, compared with Example 5 in which the monocarboxylic acid component is an aromatic monocarboxylic acid, the flow during melt processing The property was excellent.
- the aliphatic diamine component of the semi-aromatic polyamide resin is 1,10-decanediamine, the mechanical properties are higher than in Example 6 in which the aliphatic diamine component is 1,9-nonanediamine. Due to the high crystallinity, the deflection temperature under load was high and the heat resistance was high.
- Example 7 the aliphatic diamine component is 1,6-hexanediamine.
- Example 1 Although the deflection temperature under load is higher than that in Example 1, since the melting point is high, the processing temperature becomes high and the residence stability is high. It was inferior.
- Example 1 since the semi-aromatic polyamide resin is a homo-type, the crystallinity index at the time of low-temperature molding is higher than that of copolymer type Example 8 and Comparative Example 2, and crystallization is also performed in a low-temperature mold. A molded product having a high degree was obtained.
- Example 9 since the resin composition contains two types of semi-aromatic polyamides (A) having different constituent monomer components, Examples 1 and 6 each containing semi-aromatic polyamides (A) alone are included. In comparison, heat aging was suppressed and the surface appearance was excellent.
- Example 1 contains the glass fiber surface-treated with the film forming agent copolymerized with the acid component, the hydrolysis resistance is excellent as compared with Example 22 in which the acid component is not copolymerized. It was.
- the resin compositions containing other polyamides were superior to Example 1 in fluidity during melt processing, suppressed heat aging, and excellent in surface appearance.
- the resin composition containing the stabilizer was superior in retention stability and suppressed heat aging compared to Example 1.
- Example 33 the resin composition containing nigrosine as a black dye had excellent fluidity during melt processing and excellent surface appearance.
- the resin composition using other polyamide and nigrosine in combination was more excellent in fluidity during melt processing than Examples 24 and 34 containing each independently.
- the molecular weight of the monocarboxylic acid component of the semi-aromatic polyamide resin is 140 or more, and since it contains a polyhydric alcohol, the molecular weight is less than 140 and the comparison does not contain a polyhydric alcohol.
- the chemical resistance was synergistically improved.
- the resin composition of Comparative Example 1 contains a semi-aromatic polyamide resin having no melting point, the deflection temperature under load was low. Further, since the resin composition of Comparative Example 2 contains a copolymer type semi-aromatic polyamide having a melting point of less than 300 ° C., the deflection temperature under load was low and the crystallinity index during low-temperature molding was low. Since the resin composition of Comparative Example 3 contained polyamide 66 having a melting point of 265 ° C. as the polyamide resin, heat aging was large and the deflection temperature under load was low. Since the resin composition of Comparative Example 4 did not contain a polyhydric alcohol, heat aging was large.
Abstract
Description
特許文献1には、半芳香族ポリアミドを長鎖モノカルボン酸で末端封鎖することにより、溶融加工時の流動性が向上することが開示されている。
また特許文献2には、多価アルコールを配合することにより、流動性が向上することが開示されている。また、特許文献3、4には、多価アルコールを配合することにより、熱老化を抑制することが開示されている。また、しかしながら、これらの多価アルコールを配合する技術は、脂肪族ポリアミドや実質的には融点が310℃未満の共重合型の半芳香族ポリアミドに関するものであった。
また、特許文献5には、ホモ型の半芳香族ポリアミドに銅化合物を配合することにより、熱老化を抑制することが開示されている。しかしながら、銅化合物の配合による熱老化の抑制効果は十分なものではなく、また銅化合物を含有する樹脂組成物は、高温の溶融加工温度で長時間滞留させたときに、熱分解による物性低下や、成形体外観不良の問題が発生することがあった。
すなわち、融点が300℃以上の半芳香族ポリアミド、特に共重合をしていない高結晶性の半芳香族ポリアミドの成形加工においては、上記した溶融加工時の流動性不良や熱老化の問題に加えて、装置内に溶融状態で滞留すると、熱分解による物性低下や、成形体に外観不良を引き起こすという、いわゆる滞留安定性の問題があった。
(1)半芳香族ポリアミド(A)と多価アルコール(B)を含有する半芳香族ポリアミド樹脂組成物であって、
半芳香族ポリアミド(A)と多価アルコール(B)の質量比(A/B)が、99.95/0.05~90/10であり、
半芳香族ポリアミド(A)は、構成成分として芳香族ジカルボン酸成分と脂肪族ジアミン成分を含有し、融点が300~350℃であることを特徴とする半芳香族ポリアミド樹脂組成物。
(2)半芳香族ポリアミド(A)が、構成成分としてモノカルボン酸成分を含有し、その含有量が、半芳香族ポリアミド(A)を構成する全モノマー成分に対して0.3~4.0モル%であることを特徴とする(1)記載の半芳香族ポリアミド樹脂組成物。
(3)多価アルコール(B)が、ジペンタエリスリトールであることを特徴とする(1)または(2)記載の半芳香族ポリアミド樹脂組成物。
(4)多価アルコール(B)が、2個以上の水酸基を残してカルボン酸とエステル結合していることを特徴とする(1)~(3)のいずれかに記載の半芳香族ポリアミド樹脂組成物。
(5)半芳香族ポリアミド(A)と多価アルコール(B)の合計100質量部に対し、さらに繊維状強化材(C)を5~200質量部含有することを特徴とする(1)~(4)のいずれかに記載の半芳香族ポリアミド樹脂組成物。
(6)繊維状強化材(C)が、酸成分を含有する表面処理剤で処理されていることを特徴とする(5)記載の半芳香族ポリアミド樹脂組成物。
(7)繊維状強化材(C)が、ガラス繊維および/または炭素繊維であることを特徴とする(5)または(6)記載の半芳香族ポリアミド樹脂組成物。
(8)さらに半芳香族ポリアミド(A)以外のポリアミドを含有することを特徴とする(1)~(7)のいずれかに記載の半芳香族ポリアミド樹脂組成物。
(9)上記(1)~(8)のいずれかに記載の半芳香族ポリアミド樹脂組成物を成形してなることを特徴とする成形体。
本発明の半芳香族ポリアミド樹脂組成物は、半芳香族ポリアミド(A)と多価アルコール(B)を含有する。
分子量が140以上の脂環族モノカルボン酸としては、例えば、4-エチルシクロヘキサンカルボン酸、4-へキシルシクロヘキサンカルボン酸、4-ラウリルシクロヘキサンカルボン酸が挙げられる。
分子量が140以上の芳香族モノカルボン酸としては、例えば、4-エチル安息香酸、4-へキシル安息香酸、4-ラウリル安息香酸、アルキル安息香酸類、1-ナフトエ酸、2-ナフトエ酸およびそれらの誘導体が挙げられる。
本発明において、半芳香族ポリアミド(A)と多価アルコール(B)との質量比(半芳香族ポリアミド(A)/多価アルコール(B))は、99.95/0.05~90/10であることが必要であり、99.9/0.1~92/8であることが好ましく、99.8/0.2~95/5であることがさらに好ましい。半芳香族ポリアミド(A)と多価アルコール(B)の合計に対する多価アルコール(B)の質量比率が、0.05質量%未満の場合、熱老化の抑制効果が小さい。一方、半芳香族ポリアミド(A)と多価アルコール(B)の合計に対する多価アルコール(B)の質量比率が、10質量%を超えると、熱老化の抑制効果が飽和し、それ以上の効果発現が見込めない。また、成形体の機械的特性が不十分となったり、溶融加工時に多価アルコールが気化してガスが大量に発生したり、滞留安定性が不良になったり、成形体表面に多価アルコールがブリードアウトして外観が損なわれたりする。
脂環式化合物としては、例えば、1,2-シクロヘキサンジオール、1,3-シクロヘキサンジオール、1,4-シクロヘキサンジオール、1,3,5-シクロヘキサントリオール、2,3-ジ-(2′-ヒドロキシエチル)-シクロヘキサン-1-オールが挙げられる。
芳香族化合物としては、例えば、1,2-ベンゼンジメタノール、1,3-ベンゼンジメタノール、1,4-ベンゼンジメタノール、ヒドロベンゾイン、1,1,2,2-テトラフェニルエタン-1,2-ジオール、1,1,1-トリス-(4′-ヒドロキシフェニル)-エタン、1,1,1-トリス-(ヒドロキシフェニル)-プロパン、1,1,3-トリス-(ジヒドロキシ-3-メチルフェニル)-プロパン、1,1,4-トリス-(ジヒドロキシフェニル)-ブタン、1,1,5-トリス-(ヒドロキシフェニル)-3-メチルペンタン、ビスフェノキシエタノールフルオレンが挙げられる。
糖類としては、例えば、シクロデキストリン、D-マンノース、グルコース、ガラクトース、ショ糖、フルクトース、キシロース、アラビノース、D-マンニトール、D-ソルビトール、D-またはL-アラビトール、キシリトール、イジトール、ガラクチトール、タリトール、アリトール、アルトリトール、ギルトール、エリスリトール、トレイトール、リビトール、D-グロン酸-γ-ラクトンが挙げられる。
カップリング剤としては、例えば、ビニルシラン系、アクリルシラン系、エポキシシラン系、アミノシラン系、アミノチタン系などのカップリング剤が挙げられる。中でも、半芳香族ポリアミド(A)とガラス繊維または炭素繊維との密着効果が高く、耐熱性に優れることから、アミノシラン系カップリング剤が好ましい。
被膜形成剤としては、例えば、ウレタン系、エポキシ系、アクリル系の樹脂が挙げられ、中でも、ガラス繊維または炭素繊維との密着効果が高く、耐熱性に優れることから、ウレタン系樹脂が好ましい。被膜形成剤は、樹脂組成物の耐加水分解性が向上することから、酸成分を含有することが好ましい。酸成分は、被膜形成剤の主成分である樹脂に共重合していることが好ましい。酸成分としては、例えば、アクリル酸、メタクリル酸、ケイ皮酸等の不飽和モノカルボン酸や、マレイン酸、フマル酸、イタコン酸等の不飽和ジカルボン酸や、無水マレイン酸が挙げられる。
中でも、トリエチレングリコール-ビス-[3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)-プロピオネート]、テトラキス[メチレン-3-(3′,5′-ジ-t-ブチル-4′-ヒドロキシフェニル)プロピオネート]メタン、1,6-ヘキサンジオール-ビス-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)-プロピオネート]、ペンタエリスリチル-テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、N,N′-ヘキサメチレンビス-(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシンナマイドが好ましい。ヒンダードフェノール系酸化防止剤は単独で用いてもよいし、併用してもよい。
市販のヒンダードフェノール系酸化防止剤としては、例えば、アデカ社製アデカスタブAO-20、AO-30、AO-40、AO-50、AO-60、AO-70、AO-80、AO-330、チバスペシャリティケミカル社製イルガノックス245、259、565、1010、1035、1076、1098、1222、1330、1425、1520、3114、5057、住友化学工業社製スミライザーBHT-R、MDP-S、BBM-S、WX-R、NW、BP-76、BP-101、GA-80、GM、GS、サイアナミド社製サイアノックスCY-1790が挙げられる。
溶融混練法としては、ブラベンダー等のバッチ式ニーダー、バンバリーミキサー、ヘンシェルミキサー、ヘリカルローター、ロール、一軸押出機、二軸押出機等を用いる方法が挙げられる。溶融混練温度は、半芳香族ポリアミド(A)が溶融し、分解しない温度であれば特に限定されないが、高すぎると、半芳香族ポリアミド(A)が分解することから、(半芳香族ポリアミドの融点-20℃)以上、(半芳香族ポリアミドの融点+40℃)以下であることが好ましい。
自動車部品としては、例えば、サーモスタットカバー、インバータのIGBTモジュール部材、インシュレーター部材、インタークーラー部材、エキゾーストフィニッシャー、パワーデバイス筐体、ECU筐体、ECUコネクタ、モーターやコイルの絶縁材、ケーブルの被覆材が挙げられる。電気電子部品としては、例えば、コネクタ、LEDリフレクタ、スイッチ、センサー、ソケット、コンデンサー、ジャック、ヒューズホルダー、リレー、コイルボビン、ブレーカー、電磁開閉器、ホルダー、プラグ、携帯用パソコン等の電気機器の筐体部品、抵抗器、IC、LEDのハウジングが挙げられる。中でも、本発明の半芳香族ポリアミド樹脂組成物は、熱老化が効果的に抑制され、かつ耐薬品性に優れることから、高温環境下かつ様々な薬品に晒されながら長期間使用されることになる自動車部品の成形に特に好適に用いることができる。
また、本発明の半芳香族ポリアミド樹脂組成物やそれを構成する半芳香族ポリアミド(A)は、3Dプリンタの造形用樹脂として使用することができる。3Dプリンタの造形方式としては、インクジェット方式、熱溶解積層方式、粉末固着方式が挙げられる。熱溶解積層方式には、レーザー照射、赤外線線照射、加熱により溶解する方式等、粉末固着方式には、粉末の樹脂に接着剤を吹き付ける方式等が含まれる。
半芳香族ポリアミドおよび半芳香族ポリアミド樹脂組成物の物性測定は以下の方法によりおこなった。
(1)融点
示差走査熱量計DSC-7型(パーキンエルマー社製)用い、窒素雰囲気下にて昇温速度20℃/分で370℃まで昇温した後、370℃で5分間保持し、降温速度20℃/分で25℃まで降温し、さらに25℃で5分間保持後、再び昇温速度20℃/分で昇温測定した際の吸熱ピークのトップを融点とした。
96質量%硫酸を溶媒とし、濃度1g/dL、25℃で測定した。
下記の方法で作製した試験片1~4を用いて、ISO178に準拠して引張強度を測定した。試験片1に対する試験片2の引張強度保持率(%)を求め、滞留安定性を評価し、また試験片1に対する試験片3の引張強度保持率(%)を求め、熱老化を評価し、さらに試験片1に対する試験片4の引張強度保持率(%)を求め、加水分解性を評価した。
<試験片1>(標準条件で作製した試験片)
半芳香族ポリアミド樹脂組成物を、射出成形機S2000i-100B型(ファナック社製)を用いて、シリンダー温度(半芳香族ポリアミドの融点+15℃)、金型温度(半芳香族ポリアミドの融点-175℃)、シリンダー内滞留時間10秒の条件で射出成形し、試験片1(ISO多目的試験片)を作製した。なお、実施例24~28、35においては、シリンダー温度を(半芳香族ポリアミドの融点+5℃)、実施例33~34においては、シリンダー温度を(半芳香族ポリアミドの融点+10℃)、比較例3においては、シリンダー温度を(ポリアミドの融点+20℃)とした。
<試験片2>(滞留安定性評価用試験片、600秒滞留処理)
シリンダー内滞留時間を600秒とした以外は、試験片1と同様の条件で射出成形し、試験片2(ISO多目的試験片)を作製した。シリンダー内滞留時間は、冷却時間を調整することにより600秒とした。
<試験片3>(熱老化評価用試験片、200℃×1000時間熱処理)
試験片1を、熱風炉の中で、200℃で1000時間熱処理して、試験片3を作製した。
<試験片4>(加水分解性評価用試験片、130℃×100時間オートクレーブ処理)
試験片1を、オートクレーブの中で、LLC液(キャッスル社製、ロングライフクーラント V9230-0102、赤色)の水2倍希釈液に浸漬し、130℃で100時間処理して、試験片4を作製した。
JIS K7210に従い、半芳香族ポリアミドの融点+20℃の温度、1.2kgfの荷重で測定した。
試験片1を用いて、ISO75-1、2に従って、荷重1.8MPaで測定した。
試験片1の表面外観を目視で観察し、以下の基準により評価した。
◎:繊維状強化材の浮きがなく、表面にざらつきがない。
○:繊維状強化材の浮きがあるか、表面にざらつきがあるかのいずれかである。
×:繊維状強化材の浮きがあり、かつ、表面にざらつきがある。
金型温度を(半芳香族ポリアミドの融点-255℃)とする以外は試験片1と同様の条件で射出成形して得られた試験片5と、試験片1について、下記式から、結晶融解熱量の比を算出し、結晶化度の指標とした。
試験片1、5の結晶融解熱量は、示差走査熱量計DSC-7型(パーキンエルマー社製)用い、窒素雰囲気下にて昇温速度20℃/分で370℃まで昇温した時の吸熱ピークおよび発熱ピークから、下記式にもとづいて、それぞれ求めた。
結晶融解熱量=(吸熱ピーク[J/g])-(発熱ピーク[J/g])
結晶化度指標(%)=(試験片5の結晶融解熱量[J/g])/(試験片1の結晶融解熱量[J/g])×100
試験片5を、20℃の薬品中に1週間浸漬し、大きな変形や消失が生じないか確認した。また、大きな変形や消失が生じない場合、処理後の重量変化率を下記式から算出した。試験に使用した薬品は、60%硫酸、メタクレゾール、エチレングリコールである。
浸漬後の試験片5に大きな変形や消失が生じた場合、「×」と評価し、大きな変形や消失が生じなかった場合は、重量変化率を記載した。
重量変化率(%)=(浸漬前の重量-浸漬後の重量)/浸漬前の重量×100
実施例および比較例で用いた原料を以下に示す。
(1)芳香族ジカルボン酸成分
・TPA:テレフタル酸
・IPA:イソフタル酸
・DDA:1,10-デカンジアミン
・NDA:1,9-ノナンジアミン
・HDA:1,6-ヘキサンジアミン
・STA:ステアリン酸(分子量:284)
・BA:安息香酸(分子量:122)
・B-1:ジペンタエリスリトール(広栄化学工業社製、ジ・ペンタリット)
・B-2:ビスフェノキシエタノールフルオレン(大阪ガスケミカル社製、BPEF)
・B-3:ジペンタエリスリトールとアジピン酸からなるエステル(味の素ファインテクノ社製、プレンライザーST-210)
・B-4:ポリビニルブチラール(クラレ社製、Mowital B75H)
・B-5:ステアリルアルコール(新日本理化社製、コノール30SS)
・C-1:ガラス繊維(日本電気硝子社製、T-262H、平均繊維径10.5μm、平均繊維長3mm、酸共重合物を含んだ被膜形成剤を使用)
・C-2:ガラス繊維(日本電気硝子社製、T-249H、平均繊維径10.5μm、平均繊維長3mm、ウレタン系樹脂を含んだ被膜形成剤を使用)
・C-3:炭素繊維(東邦テナックス社製、HTA-C6-NR、平均繊維径7μm、平均繊維長6mm)
・P-1:ポリアミド66(ユニチカ社製、A125J、融点265℃)
・P-2:ポリアミド6(ユニチカ社製、A1030BRL、融点225℃)
・P-3:ポリアミド6T/6I(エムスケミージャパン社製、Grivory G21、非晶性)
・P-4:ポリアミド10Cとして、下記の方法で製造したものを使用した。
シス:トランス比が70:30の1,4-シクロヘキサンジカルボン酸5111.2g(29.7モル)、1,10-デカンジアミン5271.0g(30.59モル)、末端封止剤としての安息香酸224.2g(1.84モル)、次亜リン酸ナトリウム一水和物10g、および蒸留水2.5Lを、内容積40Lのオートクレーブに入れ、窒素置換した。2時間かけて内部温度を200℃に昇温した。この時、オートクレーブは2MPaまで昇圧した。その後2時間、内部温度を215℃に保ち、水蒸気を徐々に抜いて圧力を2MPaに保ちながら反応させた。次いで、30分かけて圧力を1.2MPaまで下げ、プレポリマーを得た。このプレポリマーを1mm以下の大きさまで粉砕し、120℃、減圧下で12時間乾燥した。これを230℃、13.3Paの条件で10時間固相重合し、融点312℃のポリアミド(P-4)(ポリアミド10C)を得た。
[酸化防止剤]
・AO-1:ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト(リン系酸化防止剤、アデカ社製、アデカスタブPEP-36)
・AO-2:3,9-ビス[2-{3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}-1,1-ジメチルエチル]2,4,8,10-テトラオキサスピロ(5,5)ウンデカン(ヒンダードフェノール系酸化防止剤、アデカ社製、アデカスタブAO-80)
[光安定剤]
・S-1:2-エチル-2-エトキシ-オキザルアニリド(ヒンダートアミン系光安定剤、クラリアントジャパン社製、ナイロスタブS-EED)
[熱安定剤]
・H-1:ヨウ化銅(試薬特級)
・H-2:ヨウ化カリウム(試薬特級)
・N-1:ニグロシン(オリエント化学工業社製、NUBIAN BLACK TH-807、ソルベントブラック7)
・半芳香族ポリアミド(A-1)
芳香族ジカルボン酸成分として粉末状のテレフタル酸(TPA)4.70kgと、モノカルボン酸成分としてステアリン酸(STA)0.32kgと、重合触媒として次亜リン酸ナトリウム一水和物9.3gとを、リボンブレンダー式の反応装置に入れ、窒素密閉下、回転数30rpmで撹拌しながら170℃に加熱した。その後、温度を170℃に保ち、かつ回転数を30rpmに保ったまま、液注装置を用いて、脂肪族ジアミン成分として100℃に加温した1,10-デカンジアミン(DDA)4.98kgを、2.5時間かけて連続的(連続液注方式)に添加し反応生成物を得た。なお、原料モノマーのモル比は、TPA:DDA:STA=48.5:49.6:1.9(原料モノマーの官能基の当量比率は、TPA:DDA:STA=49.0:50.0:1.0)であった。
続いて、得られた反応生成物を、同じ反応装置で、窒素気流下、250℃、回転数30rpmで8時間加熱して重合し、半芳香族ポリアミドの粉末を作製した。
その後、得られた半芳香族ポリアミドの粉末を、二軸混練機を用いてストランド状とし、ストランドを水槽に通して冷却固化し、それをペレタイザーでカッティングして半芳香族ポリアミド(A-1)ペレットを得た。
樹脂組成を表1に示すように変更した以外は、半芳香族ポリアミド(A-1)と同様にして、半芳香族ポリアミド(A-2)~(A-10)を得た。
半芳香族ポリアミド(A-1)99質量部、多価アルコール(B-1)1質量部をドライブレンドし、ロスインウェイト式連続定量供給装置CE-W-1型(クボタ社製)を用いて計量し、スクリュー径26mm、L/D50の同方向二軸押出機TEM26SS型(東芝機械社製)の主供給口に供給して、溶融混練をおこなった。途中、サイドフィーダーより繊維状強化材(C-1)45質量部を供給し、さらに混練をおこなった。ダイスからストランド状に引き取った後、水槽に通して冷却固化し、それをペレタイザーでカッティングして半芳香族ポリアミド樹脂組成物ペレットを得た。押出機のバレル温度設定は、(半芳香族ポリアミドの融点+5℃)~(半芳香族ポリアミドの融点+15℃)、スクリュー回転数250rpm、吐出量25kg/hとした。
半芳香族ポリアミド樹脂組成物の組成を表2、3に示すように変更した以外は、実施例1と同様の操作をおこなって半芳香族ポリアミド樹脂組成物ペレットを得た。
比較例1においては、バレル温度設定を300℃とした。
実施例1~4において、半芳香族ポリアミドの相対粘度が低いほど(実施例1、4)、溶融加工時の流動性が優れ、一方、半芳香族ポリアミドの相対粘度が高いほど(実施例2、3)、滞留安定性が優れていた。
実施例1は、半芳香族ポリアミド樹脂のモノカルボン酸成分が脂肪族モノカルボン酸であるため、モノカルボン酸成分が芳香族モノカルボン酸である実施例5に比較して、溶融加工時の流動性が優れていた。
実施例1は、半芳香族ポリアミド樹脂の脂肪族ジアミン成分が1,10-デカンジアミンであるため、脂肪族ジアミン成分が1,9-ノナンジアミンである実施例6に比較して、機械的特性が高く、また高結晶性のため、荷重たわみ温度が高く、耐熱性が高いものであった。実施例7は、脂肪族ジアミン成分が1,6-ヘキサンジアミンであり、実施例1に比較して、荷重たわみ温度が高いものの、融点が高いために、加工温度が高くなり、滞留安定性が劣っていた。実施例1は、半芳香族ポリアミド樹脂がホモ型であるため、共重合型の実施例8や比較例2に比較して、低温成形時の結晶化度指標が高く、低温金型でも結晶化度の高い成形体が得られた。
実施例9は、樹脂組成物が、構成モノマー成分が異なる半芳香族ポリアミド(A)を2種含有するため、半芳香族ポリアミド(A)をそれぞれ単独で含有する実施例1および実施例6に比べて、熱老化が抑制され、表面外観が優れていた。
実施例1、10~15において、多価アルコールの含有量が多いほど、樹脂組成物は、熱老化が抑制されるが、高濃度領域ではその効果が飽和しており、また、多価アルコールの含有量が多いほど、樹脂組成物は、やや滞留安定性が劣っていた。
実施例1は、酸成分が共重合した被膜形成剤にて表面処理されたガラス繊維を含有するため、酸成分が共重合されていない実施例22に比較して、耐加水分解性が優れていた。
実施例24~28において、他のポリアミドを含有する樹脂組成物は、実施例1に比較して、溶融加工時の流動性に優れ、熱老化が抑制され、表面外観が優れていた。
実施例29~32において、安定剤を含有する樹脂組成物は、実施例1に比較して、滞留安定性が優れ、熱老化が抑制されていた。実施例33~34において、黒色染料としてニグロシンを含有する樹脂組成物は、溶融加工時の流動性が優れ、表面外観が優れていた。実施例35において、他のポリアミドとニグロシンを併用した樹脂組成物は、それぞれ単独で含有する実施例24、34に比較して、溶融加工時の流動性がより優れていた。
実施例1は、半芳香族ポリアミド樹脂のモノカルボン酸成分の分子量が140以上であり、また多価アルコールを含有するため、分子量が140未満である実施例5や、多価アルコールを含有しない比較例4、5に比較して、耐薬品性が相乗的に向上していた。
比較例4の樹脂組成物は、多価アルコールを含有しないため、熱老化が大きかった。比較例5の樹脂組成物は、多価アルコールを含有せず、ヨウ化銅やヨウ化カリウムを含有するため、熱老化が大きく、また滞留安定性も不良であった。比較例6の樹脂組成物は、多価アルコールを含有せず、モノアルコールを含有するため、熱老化が大きかった。比較例7の樹脂組成物は、多価アルコールの含有量が多かったため、溶融加工時に多価アルコールのガスが多量に発生し、また、滞留安定性が不良であり、得られた成形体は、表面に多価アルコールがブリードアウトして外観が劣っていた。
Claims (9)
- 半芳香族ポリアミド(A)と多価アルコール(B)を含有する半芳香族ポリアミド樹脂組成物であって、
半芳香族ポリアミド(A)と多価アルコール(B)の質量比(A/B)が、99.95/0.05~90/10であり、
半芳香族ポリアミド(A)は、構成成分として芳香族ジカルボン酸成分と脂肪族ジアミン成分を含有し、融点が300~350℃であることを特徴とする半芳香族ポリアミド樹脂組成物。 - 半芳香族ポリアミド(A)が、構成成分としてモノカルボン酸成分を含有し、その含有量が、半芳香族ポリアミド(A)を構成する全モノマー成分に対して0.3~4.0モル%であることを特徴とする請求項1記載の半芳香族ポリアミド樹脂組成物。
- 多価アルコール(B)が、ジペンタエリスリトールであることを特徴とする請求項1または2記載の半芳香族ポリアミド樹脂組成物。
- 多価アルコール(B)が、2個以上の水酸基を残してカルボン酸とエステル結合していることを特徴とする請求項1~3のいずれかに記載の半芳香族ポリアミド樹脂組成物。
- 半芳香族ポリアミド(A)と多価アルコール(B)の合計100質量部に対し、さらに繊維状強化材(C)を5~200質量部含有することを特徴とする請求項1~4のいずれかに記載の半芳香族ポリアミド樹脂組成物。
- 繊維状強化材(C)が、酸成分を含有する表面処理剤で処理されていることを特徴とする請求項5記載の半芳香族ポリアミド樹脂組成物。
- 繊維状強化材(C)が、ガラス繊維および/または炭素繊維であることを特徴とする請求項5または6記載の半芳香族ポリアミド樹脂組成物。
- さらに半芳香族ポリアミド(A)以外のポリアミドを含有することを特徴とする請求項1~7のいずれかに記載の半芳香族ポリアミド樹脂組成物。
- 請求項1~8のいずれかに記載の半芳香族ポリアミド樹脂組成物を成形してなることを特徴とする成形体。
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6138321B1 (ja) * | 2016-06-30 | 2017-05-31 | ユニチカ株式会社 | 熱可塑性樹脂組成物およびそれを成形してなる成形体 |
WO2017130469A1 (ja) * | 2016-01-26 | 2017-08-03 | 鉦則 藤田 | 3次元造形物の製造方法、及び3次元造形物製造用のフィラメント |
JPWO2016098812A1 (ja) * | 2014-12-16 | 2017-09-21 | 株式会社クラレ | ポリアミド樹脂組成物およびその成形品 |
WO2018003512A1 (ja) * | 2016-06-30 | 2018-01-04 | ユニチカ株式会社 | 熱可塑性樹脂組成物およびそれを成形してなる成形体 |
EP3312224A1 (en) | 2016-10-21 | 2018-04-25 | Ems-Patent Ag | Polyamide moulding composition and multi-layered structure made herefrom |
WO2018088471A1 (ja) * | 2016-11-11 | 2018-05-17 | 株式会社イハラ合成 | 炭素繊維強化樹脂押出材及びその製造方法 |
JP2018193437A (ja) * | 2017-05-15 | 2018-12-06 | ユニチカ株式会社 | 熱可塑性樹脂組成物およびそれを成形してなる成形体 |
EP3415563A1 (en) | 2017-06-13 | 2018-12-19 | Ricoh Company, Limited | Resin powder for solid freeform fabrication, device for fabricating solid freeform fabrication object, and resin powder |
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JP2019507196A (ja) * | 2017-01-20 | 2019-03-14 | 金発科技股▲ふん▼有限公司 | 半芳香族ポリアミド樹脂、その製造方法及びそれで製造されるポリアミド成形組成物 |
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JPWO2019160117A1 (ja) * | 2018-02-16 | 2020-12-03 | 三井化学株式会社 | ポリアミド樹脂組成物およびその成形体、レーザー溶着体の製造方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170037217A1 (en) * | 2014-04-30 | 2017-02-09 | Unitika Ltd. | Semi-aromatic polyamide resin composition and formed article obtained by forming same |
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JP2022178259A (ja) * | 2021-05-19 | 2022-12-02 | 旭化成株式会社 | 樹脂組成物及び成形品 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5365341A (en) * | 1976-11-25 | 1978-06-10 | Toray Ind Inc | Gas barrier films |
JP2007154110A (ja) * | 2005-12-07 | 2007-06-21 | Asahi Kasei Chemicals Corp | 耐熱性に優れる樹脂組成物 |
JP2007182551A (ja) * | 2005-11-15 | 2007-07-19 | Asahi Kasei Chemicals Corp | 耐熱性に優れる樹脂組成物 |
JP2008019440A (ja) * | 2006-07-11 | 2008-01-31 | Ems-Chemie Ag | ポリアミド成形組成物及びその使用 |
JP2011529993A (ja) * | 2008-07-30 | 2011-12-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 長期熱老化耐性ポリアミド組成物 |
JP2012107217A (ja) * | 2010-10-20 | 2012-06-07 | Ube Industries Ltd | ポリアミド樹脂組成物及びそれよりなるフィルム |
JP2012122066A (ja) * | 2010-11-19 | 2012-06-28 | Ube Industries Ltd | ポリアミド樹脂組成物及びそれよりなるフィルム |
JP2013500883A (ja) * | 2009-07-30 | 2013-01-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | オーバーモールドされた耐熱性ポリアミド複合構造およびその作製方法 |
WO2013163012A1 (en) * | 2012-04-23 | 2013-10-31 | E. I. Du Pont De Nemours And Company | Thermoplastic polyamide composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010084111A (ja) * | 2008-10-03 | 2010-04-15 | Kuraray Co Ltd | 長繊維強化ポリアミド組成物 |
CN102093706B (zh) * | 2011-02-24 | 2012-09-19 | 金发科技股份有限公司 | 高流动性聚酰胺组合物 |
WO2013042541A1 (ja) * | 2011-09-22 | 2013-03-28 | ユニチカ株式会社 | 半芳香族ポリアミドおよびそれからなる成形体 |
-
2015
- 2015-04-13 CN CN201580010947.3A patent/CN106029782B/zh active Active
- 2015-04-13 EP EP15780540.9A patent/EP3133123B1/en active Active
- 2015-04-13 JP JP2015545561A patent/JP5911651B2/ja active Active
- 2015-04-13 US US15/301,729 patent/US20170022349A1/en not_active Abandoned
- 2015-04-13 WO PCT/JP2015/061305 patent/WO2015159834A1/ja active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5365341A (en) * | 1976-11-25 | 1978-06-10 | Toray Ind Inc | Gas barrier films |
JP2007182551A (ja) * | 2005-11-15 | 2007-07-19 | Asahi Kasei Chemicals Corp | 耐熱性に優れる樹脂組成物 |
JP2007154110A (ja) * | 2005-12-07 | 2007-06-21 | Asahi Kasei Chemicals Corp | 耐熱性に優れる樹脂組成物 |
JP2008019440A (ja) * | 2006-07-11 | 2008-01-31 | Ems-Chemie Ag | ポリアミド成形組成物及びその使用 |
JP2011529993A (ja) * | 2008-07-30 | 2011-12-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 長期熱老化耐性ポリアミド組成物 |
JP2011529986A (ja) * | 2008-07-30 | 2011-12-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 補助安定剤を含む耐熱性熱可塑性物品 |
JP2013500883A (ja) * | 2009-07-30 | 2013-01-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | オーバーモールドされた耐熱性ポリアミド複合構造およびその作製方法 |
JP2012107217A (ja) * | 2010-10-20 | 2012-06-07 | Ube Industries Ltd | ポリアミド樹脂組成物及びそれよりなるフィルム |
JP2012122066A (ja) * | 2010-11-19 | 2012-06-28 | Ube Industries Ltd | ポリアミド樹脂組成物及びそれよりなるフィルム |
WO2013163012A1 (en) * | 2012-04-23 | 2013-10-31 | E. I. Du Pont De Nemours And Company | Thermoplastic polyamide composition |
Non-Patent Citations (1)
Title |
---|
See also references of EP3133123A4 * |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2016098812A1 (ja) * | 2014-12-16 | 2017-09-21 | 株式会社クラレ | ポリアミド樹脂組成物およびその成形品 |
US10995197B2 (en) * | 2014-12-16 | 2021-05-04 | Kuraray Co., Ltd. | Polyamide resin composition and molded article thereof |
US20180009965A1 (en) * | 2014-12-16 | 2018-01-11 | Kuraray Co., Ltd. | Polyamide resin composition and molded article thereof |
JPWO2017130469A1 (ja) * | 2016-01-26 | 2018-02-01 | 鉦則 藤田 | 3次元造形物の製造方法、及び3次元造形物製造用のフィラメント |
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JP6255141B2 (ja) * | 2016-01-26 | 2017-12-27 | 鉦則 藤田 | 3次元造形物の製造方法、及び3次元造形物製造用のフィラメント |
KR102057468B1 (ko) | 2016-01-26 | 2019-12-19 | 마사노리 후지타 | 3차원 조형물의 제조방법 및 3차원 조형물 제조용 필라멘트 |
CN109071941A (zh) * | 2016-05-04 | 2018-12-21 | Ems专利股份公司 | 聚酰胺模塑组合物和由此制成的模塑品 |
JP2019515099A (ja) * | 2016-05-04 | 2019-06-06 | エーエムエス−パテント アクチェンゲゼルシャフト | ポリアミド成形材料及びそれからなる成形品 |
JP7042752B2 (ja) | 2016-05-04 | 2022-03-28 | エムス ヒェミー アーゲー | ポリアミド成形材料及びそれからなる成形品 |
JP2018002818A (ja) * | 2016-06-30 | 2018-01-11 | ユニチカ株式会社 | 熱可塑性樹脂組成物およびそれを成形してなる成形体 |
JP6138321B1 (ja) * | 2016-06-30 | 2017-05-31 | ユニチカ株式会社 | 熱可塑性樹脂組成物およびそれを成形してなる成形体 |
WO2018003512A1 (ja) * | 2016-06-30 | 2018-01-04 | ユニチカ株式会社 | 熱可塑性樹脂組成物およびそれを成形してなる成形体 |
EP3312224A1 (en) | 2016-10-21 | 2018-04-25 | Ems-Patent Ag | Polyamide moulding composition and multi-layered structure made herefrom |
JP2018095838A (ja) * | 2016-10-21 | 2018-06-21 | エムス−パテント アクチエンゲゼルシャフト | ポリアミド成形組成物及びポリアミド成形組成物から形成された多層構造体 |
US10577478B2 (en) | 2016-10-21 | 2020-03-03 | Ems-Patent Ag | Polyamide moulding composition and multi-layered structure made therefrom |
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US11673341B2 (en) | 2018-02-16 | 2023-06-13 | Mitsui Chemicals, Inc. | Polyamide resin composition, molded body thereof, and method for manufacturing laser-welded body |
WO2020230805A1 (ja) | 2019-05-16 | 2020-11-19 | ユニチカ株式会社 | ポリアミド樹脂組成物 |
EP3738749A1 (en) | 2019-05-17 | 2020-11-18 | Ricoh Company, Ltd. | Thermoplastic resin powder, resin powder, resin powder for producing three-dimensional object, three-dimensional object and three-dimensional object producing method |
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EP3133123B1 (en) | 2022-12-28 |
US20170022349A1 (en) | 2017-01-26 |
CN106029782B (zh) | 2019-07-05 |
EP3133123A4 (en) | 2018-01-24 |
JP5911651B2 (ja) | 2016-04-27 |
EP3133123A1 (en) | 2017-02-22 |
JPWO2015159834A1 (ja) | 2017-04-13 |
CN106029782A (zh) | 2016-10-12 |
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