WO2015133447A1 - ポリアミド樹脂組成物 - Google Patents
ポリアミド樹脂組成物 Download PDFInfo
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- WO2015133447A1 WO2015133447A1 PCT/JP2015/056142 JP2015056142W WO2015133447A1 WO 2015133447 A1 WO2015133447 A1 WO 2015133447A1 JP 2015056142 W JP2015056142 W JP 2015056142W WO 2015133447 A1 WO2015133447 A1 WO 2015133447A1
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
Definitions
- the present invention relates to a polyamide resin composition, and more particularly to a polyamide resin composition containing a swellable layered silicate, having toughness and low specific gravity, and excellent in strength, rigidity and hot rigidity.
- polyamide resins such as polyamide 6 and polyamide 66 are excellent in mechanical properties, impact resistance, chemical resistance, etc., and thus are reinforced with inorganic fillers and widely used in automobile parts, electrical parts, electronic parts, and the like. .
- the mechanical strength and heat resistance of the reinforced polyamide resin are improved, since the inorganic filler has poor affinity with polyamide, the inherent toughness of the polyamide resin is often impaired.
- nanocomposites have been proposed in which layered silicates such as montmorillonite are contained in a raw material monomer of a polyamide resin and polymerized, and the layered silicates are dispersed in the nano order (Patent Documents 1 and 2).
- this nanocomposite can give a higher elastic modulus and heat resistance with a small amount of inorganic filler, and can be reduced in weight. Relatively high elastic modulus and heat resistance can be expressed with the inorganic filler content.
- the toughness is significantly lowered, and depending on the application, the mechanical strength may be insufficient due to insufficient toughness, and there is room for improvement.
- An object of the present invention is to provide a polyamide resin composition that has toughness not found in conventional nanocomposites and has excellent strength, rigidity, and hot rigidity while having a low inorganic filler content and low specific gravity.
- the present inventors have reached the present invention as a result of earnest research.
- the polyamide resin composition of the present invention has a toughness not found in conventional nanocomposites and is a molded product that can increase the strength, rigidity and hot rigidity of polyamide resin while having a low inorganic filler content and low specific gravity. Can be provided.
- the polyamide resin (A 1 and A 2 ) used in the present invention means a polymer having an amide bond formed from an amino acid, a lactam or a diamine and a dicarboxylic acid.
- monomers that form such a polyamide include the following.
- amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid and the like.
- Examples of the lactam include ⁇ -caprolactam and ⁇ -laurolactam.
- Diamines include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4- / 2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, and 2,4-dimethyl.
- Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.
- Preferable polyamide resins used in the present invention are polycaproamide (polyamide 6), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sebacamide (polyamide 610).
- Polyhexamethylene dodecamide polyamide 612
- polyundecane methylene adipamide polyamide 116
- polyundecanamide polyamide 11
- polydodecanamide polyamide 12
- polytrimethylhexamethylene terephthalamide polyamide TMHT
- Polyhexamethylene isophthalamide polyamide 6I
- polyhexamethylene terephthalamide / isophthalamide polyamide 6T / 6I
- polybis (4-aminocyclohexyl) methane dodecamide poly Polyamide PACM12
- polybis (3-methyl-4-aminocyclohexyl) methane dodecamide polyamide dimethyl PACM12
- polymetaxylylene adipamide polyamide MXD6
- polyundecamethylene terephthalamide polyamide 11T
- polyundecamethylene examples include hexahydroterephthalamide (polyamide 11T (H)), copo
- the polyamide resin used here is usually produced by a known melt polymerization method or further using a solid phase polymerization method, and the polyamide resin preferably has a relative viscosity of 1.5 to 4.0.
- the relative viscosity of the polyamide resin in the present invention is measured under the conditions of a temperature of 25 ° C. and a concentration of 1 g / dl using 96 mass% concentrated sulfuric acid as a solvent.
- the relative viscosity of the polyamide resin A 1 3.0 to 4.0 using a polyamide resin relative viscosity of a mixture of a polyamide resin A 2 of 1.5 or more and less than 3.0.
- the relative viscosity of the polyamide resin A 1 is preferably 3.2 to 3.8, the relative viscosity of the polyamide resin A 2 is preferably 1.7 or more 2.8 or less.
- the relative viscosity difference of the polyamide resin A 1 and the polyamide resin A 2 is preferably 0.3-2.0, more preferably 0.5 to 1.6, and more preferably 0.7 to 1.4.
- a 1 / A 2 95/5 to 50/50.
- polyamide resin A 1 is more than 98 wt%, by insufficient flowability during molding, the surface smoothness of the molded article obtained from the polyamide resin composition, more undesirable because the decorative properties deteriorate. That's the polyamide resin A 1 is less than 5 mass% is not preferable because the tensile elongation at break can not be maintained.
- Polyamide resin A 1 and the polyamide resin A 2 is preferably a polyamide resin of the same type. In this case, the same type indicates that 90 mol% or more of the constituent monomer types are the same. By using two kinds of polyamide resins of the same kind having different relative viscosities, the tensile elongation at break (%) of the obtained molded product is increased, and the toughness of the molded product is further improved.
- the swellable layered silicate used in the present invention may be a naturally swellable layered silicate produced in nature or a synthetic swellable layered silicate obtained by synthesis.
- “Swellability” refers to a property of swelling when a solvent such as water, alcohol or ether enters between the crystal layers of the layered silicate.
- a single plate-like crystal layer is formed by overlapping a silicic acid tetrahedral sheet on top and bottom of an octahedral sheet containing a metal such as aluminum, magnesium, or lithium.
- a structure having a type 1 structure is preferable, and in this case, an exchangeable cation is provided between the plate crystal layers.
- the size of the single plate-like crystal is preferably 0.05 to 0.5 ⁇ m in width and 6 to 15 ⁇ in thickness.
- the cation exchange capacity of the exchangeable cation is preferably 0.2 to 3 meq / g, more preferably 0.8 to 1.5 meq / g.
- swellable layered silicate examples include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, and various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate.
- Swellable mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc., which may be natural or synthesized. .
- smectite clay minerals such as montmorillonite and hectorite
- swellable mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable, and montmorillonite is most preferable.
- a swellable layered silicate in which an organic onium ion in which exchangeable cations are exchanged exists between layers.
- swellable layered silicates include Somasif MEE (manufactured by Corp Chemical) and Nanoclay I.I. 30T (manufactured by nanocor) can be used.
- Organic onium ions include ammonium ions, phosphonium ions, sulfonium ions, and the like. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used.
- Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like. Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium. Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.
- Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium and benzyldimethyloctadecylammonium, and alkyltrimethyls such as trimethyloctylammonium, trimethyldodecylammonium and trimethyloctadecylammonium.
- benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium and benzyldimethyloctadecylammonium
- alkyltrimethyls such as trimethyloctylammonium, trimethyldo
- Examples thereof include ammonium ions, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium, and trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium.
- dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium
- trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium.
- aniline p-phenylenediamine, ⁇ -naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecano
- ammonium ions preferred are quaternary ammonium ions such as trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, and ammonium ions derived from 12-aminododecanoic acid. Most preferred are octylmethylammonium and benzyldimethyloctadecylammonium.
- the swellable layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is obtained by reacting the swellable layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method.
- the amount of the organic onium ion relative to the swellable layered silicate is determined from the viewpoint of the dispersibility of the swellable layered silicate, the thermal stability at the time of melting, the gas during molding, the suppression of the generation of odors, and the like. Usually, it is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents, relative to the cation exchange capacity of the silicate.
- the swellable layered silicate is contained in an amount of 1 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin. If it is less than 1 part by mass, the tensile strength and the heat distortion temperature are not sufficient, and if it exceeds 10 parts by mass, the tensile elongation at break and the impact strength are significantly reduced.
- the content is preferably 3 to 8 parts by mass, more preferably 3 to 6 parts by mass.
- Examples of the phosphorus-containing compound having a phosphorus oxidation number of 3 or less used in the present invention include disodium phosphite, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, trimethyl phosphite, and triethyl phosphite. , Triphenyl phosphite, sodium hypophosphite, calcium hypophosphite and the like. Among them, it is preferable to use a metal phosphite salt or a metal hypophosphite salt.
- the metal of the phosphite metal salt or the hypophosphite metal salt is preferably selected from alkali metals, alkaline earth metals and zinc groups, more preferably alkali metals.
- the phosphorus-containing compound having an oxidation number of phosphorus of 3 or less sodium hypophosphite is particularly preferable.
- the compounding amount of the phosphorus-containing compound having a phosphorus oxidation number of 3 or less is 0.01 to 0.3 parts by mass, preferably 0.05 to 0.2 parts by mass with respect to 100 parts by mass of the polyamide. . If the amount is less than 0.01 parts by mass, the melt viscosity is not increased. On the other hand, if the amount exceeds 0.3 parts by mass, the melt viscosity is excessively increased and molding becomes difficult.
- the reinforced polyamide resin composition of the present invention has a tensile elongation at break (%) of 3.0% or more.
- the tensile elongation at break is a value measured by the method described in the Examples section below.
- the upper limit of the tensile elongation at break of the polyamide resin composition is not particularly defined, it may be about 100%. Since it has such a tensile elongation at break, it is preferable because the toughness and impact resistance of a molded article made of the polyamide resin composition are increased.
- the reinforced polyamide resin composition of the present invention includes a light or heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a lubricant, and a crystal nucleating agent within a known range as necessary.
- Mold release agents, antistatic agents, combinations of halogen flame retardants and antimony trioxide, various phosphate flame retardants, melamine flame retardants, inorganic pigments, organic pigments, dyes, or other polymers I can do it.
- the polyamide resin composition of the present invention preferably occupies 90% by mass or more of the polyamide resin, which is an essential component, the swellable layered silicate, and the phosphorus-containing compound having an oxidation number of phosphorus of 3 or less, and 95% by mass. It is more preferable to occupy% or more.
- the above-described components and other blends are blended in an arbitrary blending sequence in the blending composition, then mixed with a tumbler or a Henschel mixer, etc., and melt mixed. Smelted. Any method known to those skilled in the art can be used as the melt kneading method, and a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a roll, etc. can be used. Among them, a twin screw extruder is used. It is preferable to do.
- the polyamide resin composition of the present invention a relative viscosity 3.0 to 4.0 of the polyamide resin A 1, less than a relative viscosity of 1.5 or more 3.0 polyamide resin A 2, swellable layered silicate, and phosphorus It can be produced by a very simple method in which a phosphorus-containing compound having an oxidation number of 3 or less is melt-kneaded at the above blending ratio.
- Relative viscosity The measurement was performed using a Ubbelohde viscosity tube at a temperature of 25 ° C. and a concentration of 1 g / dl using 96% by mass concentrated sulfuric acid as a solvent. density: The measurement was performed according to ISO 1183. Tensile strength, tensile modulus, tensile elongation at break: Using a Toshiba Machine Co., Ltd. IS-100, a cylinder was set at 250 ° C., and a molded product was obtained according to ISO 527-1 under conditions of a mold temperature of 130 ° C., and then measured according to ISO-178. The measurement was performed at five levels, and the average value was adopted.
- HDT Thermal deformation temperature
- Comparative Example 6 Polyamide having a relative viscosity of 2.5 by adding a swellable fluoromica ME-100 (manufactured by Co-op Chemical Co., Ltd.) as a swellable layered silicate during polymerization of ⁇ -caprolactam. A polyamide resin composition having a swellable fluorine mica content of 4.0 mass% in 6 resins was obtained. The evaluation results are shown in Table 1.
- Examples 1 to 8 although the density is 1.16 g / cm 3 or less and the specific gravity is low, HDT under a high load is 80 ° C. or more, and the tensile elongation at break is 3% or more. Excellent heat resistance and toughness.
- Comparative Examples 1 and 2 although the tensile elongation at break is as high as 200% or higher, HDT is 55 ° C. and heat resistance is low.
- Comparative Examples 3 to 6 although the HDT is high, the tensile elongation at break is lower than 3%.
- the polyamide resin composition of the present invention has toughness, low specific gravity, and can provide a molded product having excellent strength, rigidity, and hot rigidity. It is suitable for such applications.
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Abstract
Description
近年、ポリアミド樹脂の原料モノマー中にモンモリロナイトなどの層状珪酸塩類を含有させて重合し、層状珪酸塩類をナノオーダーで分散させた、いわゆるナノコンポジットが提案されている(特許文献1、2など)。
このナノコンポジットは、従来の無機フィラーを充填した複合材料に比較して、少量の無機フィラーによって、より高い弾性率や耐熱性を付与し得る上、軽量化が可能であるとされ、確かに少ない無機フィラー含有量で比較的高い弾性率や耐熱性を発現可能である。
しかしながら、無機フィラーを含有しないナチュラル品と比較すると、靭性の低下は著しく、用途によっては靭性不足に起因する機械的強度不足になることがあり、改善の余地がある。
(1) ポリアミド樹脂100質量部に対し、膨潤性層状珪酸塩を1~10質量部、及びリンの酸化数が3以下のリン含有化合物を0.01~0.3質量部含有するポリアミド樹脂組成物であって、前記ポリアミド樹脂が、相対粘度3.0以上4.0以下のポリアミド樹脂A1と相対粘度1.5以上3.0未満のポリアミド樹脂A2からなり、その混合割合(質量比)が、A1/A2=98/2~5/95であり、該ポリアミド樹脂組成物の引張破断伸度が3.0%以上であること特徴とするポリアミド樹脂組成物。
(2) リンの酸化数が3以下のリン含有化合物が、次亜リン酸塩である(1)に記載のポリアミド樹脂組成物。
本発明で用いるポリアミド樹脂(A1及びA2)とは、アミノ酸、ラクタムあるいはジアミンとジカルボン酸とから形成されるアミド結合を有する重合体を意味する。このようなポリアミドを形成するモノマーの例としては次のようなものがある。
アミノ酸としては6-アミノカプロン酸、11-アミノウンデカン酸、12-アミノドデカン酸、パラアミノメチル安息香酸などがある。
ラクタムとしてはε-カプロラクタム、ω-ラウロラクタムなどがある。
本発明におけるポリアミド樹脂の相対粘度は、溶媒として96質量%濃硫酸を用い、温度25℃、濃度1g/dlの条件で測定したものである。
本発明においては、相対粘度が3.0以上4.0以下のポリアミド樹脂A1と、相対粘度が1.5以上3.0未満のポリアミド樹脂A2とを混合したポリアミド樹脂を用いる。ポリアミド樹脂A1の相対粘度は、3.2以上3.8以下が好ましく、ポリアミド樹脂A2の相対粘度は、1.7以上2.8以下が好ましい。ポリアミド樹脂A1とポリアミド樹脂A2とは、相対粘度が異なっていることが必要である。ポリアミド樹脂A1とポリアミド樹脂A2の相対粘度差は、0.3~2.0が好ましく、0.5~1.6がより好ましく、0.7~1.4がさらに好ましい。
ポリアミド樹脂A1とポリアミド樹脂A2との混合割合(質量比)は、A1/A2=98/2~5/95であり、好ましくはA1/A2=95/5~40/60、より好ましくはA1/A2=95/5~50/50である。ポリアミド樹脂A1が98質量%を超えると、成形時の流動性が不足することで、ポリアミド樹脂組成物から得られる成形品の表面平滑性、さらには加飾性が悪くなるため好ましくない。ポリアミド樹脂A1が5質量%未満だと、引張破断伸度が保てなくなるため好ましくない。
ポリアミド樹脂A1とポリアミド樹脂A2は、同種のポリアミド樹脂であることが好ましい。この場合、同種とは構成するモノマー種の90モル%以上が同じであることを指す。
そのような相対粘度が異なる同種の2種類のポリアミド樹脂を用いることにより、得られる成形品の引張破断伸度(%)が高くなり、成形品の靭性がより向上することになる。
本発明において使用される膨潤性層状珪酸塩としては、アルミニウム、マグネシウム、リチウム等の金属を含む8面体シートの上下に珪酸4面体シートが重なって1枚の板状結晶層を形成している2:1型の構造を持つものが好ましく、その場合、その板状結晶層の層間に交換性の陽イオンを有している。
そのような膨潤性層状珪酸塩としては、ソマシフMEE(コープケミカル社製)やナノクレイI.30T(nanocor社製)が使用可能である。
2級アンモニウムイオンとしてはメチルドデシルアンモニウム、メチルオクタデシルアンモニウムなどが挙げられる。
3級アンモニウムイオンとしてはジメチルドデシルアンモニウム、ジメチルオクタデシルアンモニウムなどが挙げられる。
また、これらの他にもアニリン、p-フェニレンジアミン、α-ナフチルアミン、p-アミノジメチルアニリン、ベンジジン、ピリジン、ピペリジン、6-アミノカプロン酸、11-アミノウンデカン酸、12-アミノドデカン酸などから誘導されるアンモニウムイオンなども挙げられる。
本発明のポリアミド樹脂組成物は、必須成分であるポリアミド樹脂、膨潤性層状珪酸塩、及びリンの酸化数が3以下のリン含有化合物の合計で、90質量%以上を占めることが好ましく、95質量%以上を占めることがより好ましい。
また、加工時の揮発成分、分解低分子成分を除去するため、サイド口と押し出し機先端のダイヘッドとの間で真空ポンプによる吸引を行うことが望ましい。
本発明のポリアミド樹脂組成物は、相対粘度3.0以上4.0以下のポリアミド樹脂A1、相対粘度1.5以上3.0未満のポリアミド樹脂A2、膨潤性層状珪酸塩、及びリンの酸化数が3以下のリン含有化合物を上記した配合比で溶融混練するという、非常に簡便な方法により、製造することが可能である。
[ポリアミド樹脂]
・ポリアミド(1):ポリアミド6(相対粘度:3.5)、TP-6603(集成社製)
・ポリアミド(2):ポリアミド6(相対粘度:2.5)、TP-4208(集成社製)
・ポリアミド(3):ポリアミド6(相対粘度:3.7)、T-850(東洋紡社製)
・ポリアミド(4):ポリアミド6(相対粘度:1.9)、T-860(東洋紡社製)
[膨潤性層状珪酸塩]
・膨潤性層状珪酸塩(1):ソマシフMEE(コープケミカル社製);親水性膨潤性雲母のカチオン交換能を利用し、層間に有機カチオンを担持させ、有機変性した親油性膨潤性雲母
・膨潤性層状珪酸塩(2):ナノクレイI.30T(nanocor社製);層間に交換性陽イオンが交換された有機オニウムイオンが存在する膨潤性層状珪酸塩
・膨潤性層状珪酸塩(3):膨潤性フッ素雲母ME-100(コープケミカル社製)
[非膨潤性珪酸塩]
・非膨潤性珪酸塩:ミクロマイカMK-100(コープケミカル社製)
[リンの酸化数が3以下のリン含有化合物]
・次亜リン酸ナトリウム
相対粘度(RV):
溶媒として96質量%濃硫酸を用い、温度25℃、濃度1g/dlの条件で、ウーベローデ粘度管を用いて測定した。
密度:
ISO1183に準拠して測定した。
引張強度、引張弾性率、引張破断伸度:
東芝機械社IS-100を用い、シリンダー250℃に設定し、金型温度130℃の条件でISO527-1に準じて成形品を得た後、ISO-178に準じて測定した。測定は5水準行い、その平均値を採用した。
熱変形温度(HDT):
東芝機械社IS-100を用い、シリンダー250℃に設定し、金型温度130℃の条件でISO527-1に準じて成形品を得た後、ISO-75-1,2に準じて測定した。
評価サンプルの製造は、表1に示した質量割合で各原料を計量してタンブラーで混合した後、L/D=32の二軸押出機を用い、二軸押出機の混錬温度250℃で溶融混練を行い、ペレットとした。得られたポリアミド樹脂組成物のペレットは射出成形機で各種の評価用試料を成形した。評価結果は表1に示した。
ε-カプロラクタムの重合時に膨潤性層状珪酸塩として膨潤性フッ素雲母ME-100(コープケミカル社製)を添加し、特開2007-231076号公報に記載された方法で、相対粘度2.5のポリアミド6樹脂に膨潤性フッ素雲母の含有量が4.0質量%であるポリアミド樹脂組成物を得た。評価結果は表1に示した。
Claims (2)
- ポリアミド樹脂100質量部に対し、膨潤性層状珪酸塩を1~10質量部、及びリンの酸化数が3以下のリン含有化合物を0.01~0.3質量部含有するポリアミド樹脂組成物であって、前記ポリアミド樹脂が、相対粘度3.0以上4.0以下のポリアミド樹脂A1と相対粘度1.5以上3.0未満のポリアミド樹脂A2からなり、その混合割合(質量比)が、A1/A2=98/2~5/95であり、該ポリアミド樹脂組成物の引張破断伸度が3.0%以上であること特徴とするポリアミド樹脂組成物。
- リンの酸化数が3以下のリン含有化合物が、次亜リン酸塩である請求項1に記載のポリアミド樹脂組成物。
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CN201580010436.1A CN106029780B (zh) | 2014-03-05 | 2015-03-03 | 聚酰胺树脂组合物 |
JP2015516340A JP6160691B2 (ja) | 2014-03-05 | 2015-03-03 | ポリアミド樹脂組成物 |
US15/122,434 US20170066922A1 (en) | 2014-03-05 | 2015-03-03 | Polyamide resin composition |
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KR20200117385A (ko) * | 2019-04-04 | 2020-10-14 | 현대모비스 주식회사 | 내구성 및 내마모성이 우수한 웜휠용 조성물 및 이를 이용하여 제조된 웜휠 |
CN112708267B (zh) * | 2020-12-07 | 2022-12-06 | 金发科技股份有限公司 | 一种断路器用聚酰胺组合物及其制备方法和应用 |
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JP2002088239A (ja) * | 2000-09-12 | 2002-03-27 | Toray Ind Inc | ポリアミド樹脂組成物およびそれからなる成形品 |
JP2004250562A (ja) * | 2003-02-20 | 2004-09-09 | Toray Ind Inc | ポリアミド樹脂組成物及びそれからなる成形品 |
JP2007112915A (ja) * | 2005-10-21 | 2007-05-10 | Toray Ind Inc | 高強度ポリアミド樹脂組成物およびその製造方法 |
WO2007058170A1 (ja) * | 2005-11-15 | 2007-05-24 | Asahi Kasei Chemicals Corporation | 耐熱性に優れる樹脂組成物 |
JP2009263460A (ja) * | 2008-04-24 | 2009-11-12 | Asahi Kasei Chemicals Corp | チューブ成形に適した樹脂組成物およびそれからなるチューブ |
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JP4033362B2 (ja) * | 1997-11-11 | 2008-01-16 | 旭化成ケミカルズ株式会社 | ポリアミド樹脂複合材料及びその製造方法 |
JPWO2002085984A1 (ja) * | 2001-04-19 | 2004-08-12 | ユニチカ株式会社 | ヒューズ素子用ポリアミド樹脂組成物およびヒューズ素子 |
JP2004091586A (ja) * | 2002-08-30 | 2004-03-25 | Toray Ind Inc | 自動車用フューズ |
EP1405874B1 (en) * | 2002-10-03 | 2014-03-26 | Mitsubishi Gas Chemical Company, Inc. | Process for production of polyamide composite material |
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JP2002088239A (ja) * | 2000-09-12 | 2002-03-27 | Toray Ind Inc | ポリアミド樹脂組成物およびそれからなる成形品 |
JP2004250562A (ja) * | 2003-02-20 | 2004-09-09 | Toray Ind Inc | ポリアミド樹脂組成物及びそれからなる成形品 |
JP2007112915A (ja) * | 2005-10-21 | 2007-05-10 | Toray Ind Inc | 高強度ポリアミド樹脂組成物およびその製造方法 |
WO2007058170A1 (ja) * | 2005-11-15 | 2007-05-24 | Asahi Kasei Chemicals Corporation | 耐熱性に優れる樹脂組成物 |
JP2009263460A (ja) * | 2008-04-24 | 2009-11-12 | Asahi Kasei Chemicals Corp | チューブ成形に適した樹脂組成物およびそれからなるチューブ |
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TWI649377B (zh) | 2019-02-01 |
CN106029780B (zh) | 2020-05-12 |
TW201609963A (zh) | 2016-03-16 |
US20170066922A1 (en) | 2017-03-09 |
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