WO2000012630A1 - Polyamide resin composition and process for the preparation thereof - Google Patents

Polyamide resin composition and process for the preparation thereof Download PDF

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Publication number
WO2000012630A1
WO2000012630A1 PCT/JP1998/003797 JP9803797W WO0012630A1 WO 2000012630 A1 WO2000012630 A1 WO 2000012630A1 JP 9803797 W JP9803797 W JP 9803797W WO 0012630 A1 WO0012630 A1 WO 0012630A1
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Prior art keywords
polyamide
resin composition
de
made
temperature
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PCT/JP1998/003797
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French (fr)
Japanese (ja)
Inventor
Hideho Tanaka
Kunio Watanabe
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Ube Industries, Ltd.
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/10Silicon-containing compounds

Abstract

A polyamide resin composition comprising a polyamide resin and fibrous xonotlite, characterized in that the xonotlite content is 1 wt.% or above but below 10 wt.%, that the xonotlite has a BET specific surface area of 21 m2/g or above as determined by the nitrogen adsorption method and a specific shape, and preferably that the crystallinity of the polyamide resin is 0.40 or above as represented by the formula: ΔH¿m?/{ΔH0(1-Wf)} wherein ΔHm is the heat of fusion of the polyamide resin composition as found under specific conditions; Wf is the weight fraction of the fibrous xonotlite in the composition; and ΔH0 is the heat of fusion of crystal of the polyamide resin. Moldings of the composition exhibit excellent physical properties by virtue of the speedy crystallization and excellent moldability of the composition and the high crystallinity of the polyamide resin, thus being widely usable as automobile materials, electrical and electronic components, parts of precision machines, wrapping materials and so on.

Description

Bright fine manual made of Polyamide resin composition and its production method art

The present invention relates to a made of Polyamide resin composition and a manufacturing method thereof, and more particularly, made of Polyamide resin composition having soon as possible was crystallization rate and a method of manufacturing the same. BACKGROUND

BET specific surface area by nitrogen adsorption 2 1 m 2 / g or more fibrous Zono tri preparative for 5-7 5 wt% and made of Polyamide resin 2 5-9 5% by weight of the resin composition is already known (JP see JP Hei 7- 2 1 6 1 3 3). The above publication, not the resin composition, as compared to conventional fibrous inorganic material Z organic polymeric material composites, high strength, in KoTsuyoshi resistance, heat resistance and impact resistance of the balanced organic high and this molecular composite material is provided is disclosed. However, the above publication does not describe at all about the rate of crystallization of a thermoplastic resin such as made of Polyamide resin used.

Object of the present invention has an early obtained crystallization rate is to provide a made of Polyamide resin composition which gives made of Polyamide resin molded article crystallinity is enhanced. Accordingly, the present inventors have found, after intensive studies to solve the above problems, have specific properties (i.e., having a particular specific surface area and a specific shape) specific amount of fibrous Zono Tri DOO and obtained from the polyamide-de resin and the polyamide de resins of crystalline heat of fusion (Δ Η) (ca 1 / g) and heat of fusion of Po Riami de resin composition observed in certain conditions (delta Η ω) (ca 1 / g ) crystallinity of made of polyamide resins made of polyamide resin composition obtained Te formula (I) Niyotsu from and is in a specific range Boriami de resin Z fibrous Zono Torai if providing bets compositions, find that the above objects can be achieved, thereby completing the present invention. Disclosure of the Invention

The first invention in the present invention, Ri Do and a made of Polyamide resin and a fibrous Zono tri DOO, and made of Polyamide resin fibrous Zono tri bets is that contained in a range of less than 1 0% by weight or more 1 wt% It shall apply in the object, which has the fibrous Zono tri solved ^ 2 1 m 2 / g or more on a specific surface area (but measured at B ET method by nitrogen adsorption), 0. 1 m≤D <0. 5 μ m, 1 m≤ L rather 5 m and 1 0≤ LZD twice as 0 (although, D and L, respectively, showing the average fiber diameter Oyobi average fiber 維長 fibrous Zono tri g) at the same time made of polyamide resin composition according to Toku徵 that thereby satisfying relates.

The second invention in the present invention is made of Polyamide resin composition 1 0 ° 3 than the equilibrium melting point of Poriami de 榭脂 constituting the resin composition in CZ minute rate from room temperature 0 ° C higher temperature until in temperature raised, the rate of the after temperature was maintained for 5 minutes to completely melt the resin composition, and held for 5 minutes and cooled to 3 0 ° C at a constant cooling rate, further, 1 0 ° CZ min in the heat of fusion observed when was heated, and a heat of crystal fusion of the polyamide-de resin, under following formula (I): crystallinity = (I)

ΔΗ. X (1 -W f)

Here delta Eta [pi: made of Polyamide resin composition 1 was heated from room temperature at 0 ° C / min up to 3 0 ° C higher temperature than the equilibrium melting point of the polyamide-de resin, held to the at this temperature for 5 minutes after the resin composition is completely melted, and held for 5 minutes and cooled to 3 0 ° C at a constant velocity, further, 1 0 ° the heat of fusion is observed when it was elevated CZ minute speed ( cal Zg)

Delta Eta 0: made of Polyamide Resin crystal heat of fusion (ca 1 / g)

W f: made of Polyamide weight fraction of fibrous Zono Tri bets in the resin composition of the first aspect of crystallinity of the polyamide-de resin obtained is characterized in that at 0.4 0 or by (one) about Poriami de resin composition according to the.

The third invention in the present invention, the polyamide-de resin composition, 1 0 ° C higher temperature than the equilibrium melting point of the polyamide-de resin constituting the resin composition, said at 6 0 ° C higher temperature than the melting point after the resin composition is completely melted and kneaded, 5 ° C / min ~ 1 0 0 ° C / min in a constant cooling rate determined by the range, characterized in that cooling to room temperature Poria Mi de resin the method for producing a composition. BEST MODE FOR CARRYING OUT THE INVENTION

The fibrous Zono tri preparative described the present invention, Zono tri Doo (rational formula: C a 6 S i 617 (OH) 2, formula: 6 C a 0 · 6 S i 0 2 · H 2 0) It refers to a needle-like crystal substance. In the present invention, the value of the specific surface area is very important, 2 lm 2 Zg above, preferred properly is 30 m 2 Zg above (provided that a is measured in the BET method by nitrogen adsorption) must be. This value is 30 m 2 / g less fibrous Zono tri bets cases, worsens wettability and made of Polyamide resin, in particular, fibrous Zono tri bets with 2 1 m 2 / g ratio of less than table area for, this because wettability deteriorating significant, it is impossible to achieve the object of the present invention which was pre-mentioned.

Further, in the present invention, the shape of the fibers of the fibrous Zono tri DOO, particularly, the average fiber length (L) is 1 m≤L <5 ^ m, average fiber diameter (D) is 0. l / m≤D <0. 5, "m, and it is necessary to Asupeku Doo ratio (L / D) satisfies simultaneously the condition of 1 0≤L / D <20.

D is intended palm is more than 5 mu m of less than 0. 1 m, in mixing and kneading of the fibrous Zono tri preparative and Poriami de resin, there is a possibility that the fibrous Zono tri bets is broken. On the other hand, those D is the 0.5 5〃 m or more objects or L is less than 1 m, the made of Polyamide resin composition obtained, the effect of improving the mechanical strength due to the fibrous Zono tri bets are not sufficient.

In the case of less than LZD force si 0, in made of Polyamide resin composition obtained, it is impossible to obtain sufficient mechanical strength. When L / D is 20 or more, a bulk density of fibrous Zono tri bets becomes too small, kneading becomes difficult, etc. made of Polyamide resin composition during manufacture of the present invention.

Fibrous Zono Tri bets of the present invention having the specific properties as described above, so as to more predicates below, for example, JP-A-6-1 284 1 2 No. process as described in Japanese, ie, the calcareous material and a siliceous material mixed in a specific ratio, c is produced by hydrothermal synthesis reaction

The calcareous material, quick lime, slaked lime, include Carbide de debris, with less impurities such as oxide magnetic Shiumu are preferred. As the siliceous material, silica, silica sand and quartz ground product, silicic acid, silicic anhydride, silica gel, Keisou earth, such as clay and off We opening silicon Dust and the like. These siliceous materials are low without and an average particle diameter of impurities is desirable that the 1 0 mu m or less pulverulent. Mixing ratio of these two (C a / S spoon) is slightly less than the theoretical equivalent, from 0.8 to 0. Preferably 9 9. The ratio of mixing water, the total weight of 5-4 0 times the siliceous material and the calcareous material, it is desirable that preferably 8-3 0 times.

The hydrothermal synthesis reaction, for example, the predetermined proportion of calcareous material, a siliceous material Contact and water was poured into Otokurebu, with stirring 1 8 0~ 2 4 0 ° C over a period of usually 1 to 8 hours row Ebayoi. In this case, a predetermined proportion of the calcareous material, was pre-mixed to the slurry one form the siliceous material and water, it may be charged to the autoclave. The reaction temperature Contact Yopi reaction time in hydrothermal synthesis reaction is an important factor, if outside the above range is not obtained fibrous zone Roh tri preparative having a particular specific surface area used in the present invention as described above.

In the present invention, the resulting fibrous Zono tri metropolitan by the above-described method, the order to be more its reinforcing effect for compositions comprising the described below Poriami de resin improved, further, the surface of the surfactant and 7 or force coupling agent (hereinafter referred to as "surface treatment agent") by it is desirable process.

That is, the surface treatment agent, the fibrous Zono tri DOO, matrix resin, that is, to improve the affinity with polyamide de 榭脂, its reinforcing effect, that is, used in further enhancing purpose mechanical-strength it is intended to be. As such a surface treatment agent, specifically, it may be as follows force 吏用.

As the surfactant, anionic, cationic, none of the amphoteric and nonionic surfactants may be used. The anionic surfactants include alkyl ether sulphates, dodecyl benzene sulfonate, such as stearic phosphate salt, the cationic boundary surface active agents, Tetoradeshiruami down acetates, alkyl trimethyl ammonium Niu Mukurorai Donado, the amphoteric surface active agents, such as dimethyl alkyl lauryl betaine, and, as a nonionic surfactant, polyoxyethylene O Kuta Deshiruamin, such as polyoxyethylene lauryl ether. As the force coupling agent, silane force Ppuri ring agent, in particular § one Aminopuropiruto Increment Tokishishiran, § one § amino propyl triethoxy silane, N- phenyl Ichia one § Mino Pro built Increment Tokishishiran, N- (aminoethyl) § one aminopropyl Rutori main Tokishishiran, N- / 3 (aminoethyl) y - § amino propyl triethoxysilane Toki Shishiran, N-/ (Aminopuropiru) y -? § amino propyl methyl dimethyl Tokishishira down, y - Jibuchiruami Nopurobirutorime Tokishishiran and y- Urei other amino silane coupling-rings such as Dopuropi Le triethoxysilane, titanate force Ppuri ring agents, aluminum-based couplings agents, chromium-based couplings agents, and e © arsenide-based power coupling agent.

The addition amount of these surface treating agents, 0 to said fibrous Zono tri preparative (dry basis). 1 to 0 weight 0/0, should preferably be from 0.5 to 8 wt 0/0 .

The amount added is 0. Less than 1 wt%, insufficient strength improving effect of the above, also when the added pressure weight exceeds 1 0% by weight, even if increasing the amount added strength improving effect of the aforementioned ho Tondo Takamara not. In the range the amount added is from 0.1 to 0.5 wt 0/0, may-strength improving effect of the above is not sufficient, in the range the amount added is 8-1 0% by weight, strength of the above increase of the effect tends to be not be expected.

In the present invention, as described above, extracted fibrous zone Roh tri Tosurari obtained by hydrothermal synthesis reaction from Otokurebu, the surface treatment of fibrous Zono Tri bets. Surface treatment method is not particularly limited, for example, as the fibrous Zono tri preparative slurry, or after adding an appropriate amount of water, and added pressure to the surface treatment agent, mixed in a slurry state, by a suitable device and stirred. Subsequently, the excess water is filtered off by a centrifugal dehydrator or filter press is to obtain a cake-like fiber 維状 Zono tri bets.

As for the surface treatment, after drying the fibrous Zono tri Tosurari one, it carried out using the surface treatment agent dissolved in a small amount of water or solvent, may be the so-called Ru dry treatment method, operation is complicated, also, the effect of the surface treatment small fence, no particular benefits.

Then, the cake-like fibrous Zono tri bets adhering a surface treatment agent as described above is dried and, when using a coupling agent as the surface treatment agent is heat-treated to further use in the present invention fibrous Zono tri-door to be obtained.

The drying, hot-air circulation type dryer, using a known dryer such as an infrared heating dryer over 2 0-3 0 hours at a temperature of 1 0 0~ 1 5 0 ° C, the fibrous Zono Tri DOO water is preferably performed to the extent that less than 1 wt%. The heat treatment in the case of using an active coupling agent as a surface treatment agent is preferably carried out subsequent to the drying of water with heating at above 1 0 0~ 1 5 0 ° C and 2 0-3 0 hours .

Furthermore, fibrous Zono tri bets to be used in the present invention may be granulated into granules with easily perform object mixing and kneading with the later-described made of Polyamide resin.

Granular fibrous Zono tri DOO is a fiber-like Zono tri bets cake adhering the surface treatment agent, the diameter granulating machine was molded into granules of. 1 to 8 mm, followed by the drying and, when using a coupling agent as the surface treatment agent is obtained by performing a heat treatment to further. In this case, as the granulator, the present invention is not particularly restricted, rotation vertical granulator, rotating drum granulator, rotating further granulator, a screw extruding granulator, a roll extrusion granulator It may be a known granulator such machine. Further, if the diameter of the granular fibrous Zono trie bets are departing from the scope of the, when mixed 'kneading with Poriami de resin, mixing in such a uniaxial extruder or a biaxial extruder - kneading becomes difficult, roll and Banbury was successively filled with such as single mixer, mixing - must be carried out kneading, may result in lowering of the mechanical strength of the resin composition obtained fibrous Zono tri bets are significantly destroyed.

In the present invention, granular in the production of fibrous Zono tri DOO, heat treated in accordance with the cake-like fibrous Zono Tri bets intact drying and optionally, granules in a manner to crush to about particle diameter 5 mm it may be molded to Jo. However, powder tends to occur, and, somewhat a difficulty somewhat larger handling bulky.

The made of Polyamide resins for use in the present invention, if the crystallinity of the polyamide-de resin may be a known. For example, that obtained three or more-membered ring cyclic aliphatic lactam ring-opening polymerization obtained crystalline polyamide earth, crystalline polyamide earth obtained by Jiamin and dicarboxylic acids by polycondensation, from Jiamin dicarboxylic acid crystalline polyamide earth obtained salt polycondensation, omega - crystallinity obtained by polycondensation Aminokarubon acid polyamide earth, or by copolymerizing two or more of these polyamide-de-forming monomers Ingredient give such is crystalline copolymers made of polyamide acids and the like. Alternatively, it is also possible to use these crystalline polyamide earth or a mixture of two or more crystalline copolymers made of Polyamide acids.

As the Jiami down, for example, hydrazine, Echirenjiami down, propylene Jiami down, tetramethylene § Mi emissions, pentamethylene di § Mi emissions, to Kisamechiren Jiami down, heptamethylene di § Mi emissions, O Kuta methylenedioxy § Mi emissions, Nonamechirenji § Mi emissions, decamethylenedicarboxylic § Mi emissions, © down decamethylenedicarboxylic § Min, dodecamethylene di § Mi emissions, 2, 2, 4 hexamethylene di § Mi down to trimethyl, 2, 4, 4-trimethyl hexamethylene di § Mi down to chill, to 2-methyl hexamethylene di § Mi emissions, 3-methyl hexamethylene di Amin, to 2-E chill O Kuta methylenedioxy Amin and 3-t chromatography Bed chill Kisamechirenji aliphatic Jiami emissions such as § Mi emissions, 1, to 3-Jiaminoshikuro hexane, 1, 4-diamino cyclo hexane, to 1, 3-bis (aminomethyl) consequent opening key Emissions, 1, 4-bis (aminomethyl) cyclohexane, Isohoronjiami down, piperidines Rajin, N-aminoethyl piperazine, 2, 5-dimethyl-bi prochlorperazine, bis (p-aminocyclohexyl) methane and 2, 2-bis one (4, to single Amino cyclo hexyl) alicyclic Jiami emissions such as propane, and include aromatic diamines such as m-xylylene Renjia Mi emissions and p-xylylenediamine.

On the other hand, examples of the dicarboxylic acids, e.g., oxalic acid, succinic acid, glutaric acid, adipic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-t-Buchirua adipic acid, Pimeri phosphate, slip phosphate, Azerain acid, sebacic acid, nonanedione acid, Dekanjion acid, Undekanjion acid, dodecanedioic acid, Toridekanjio phosphate, Te tiger decane dioic acid, pentadecane dione acid, to Kisa decane dioic acid, Aikosan dioic acid, dimer of Li Nderu acid aliphatic dicarboxylic acids such as dimer dicarboxylic acid dicarboxylic acids and Orein acid, 1, 2-cycloheteroalkyl Kisanjika carboxylic acid, 1, 3-cyclohexane to Cyclohexanedicarboxylic acid and 1, 4 Shikuro hexane such as dicarboxylic acid alicyclic dicarboxylic acids, and, terephthalic acid, isophthalic acid, 5 - t - Butyl isophthalic acid, 1, 2-naphthalene dicarboxylic acid, 1, 3-naphthoquinone evening dicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, 1, 6-naphthalene dicarboxylic acid, 1, 7-naphthalene dicarboxylic acid, 1, 8-naphthyl evening dicarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 1, 3-anthrahydroquinone Senjikarubon acid, 1, 4 one anthranilamide Sen dicarboxylic acid, 1, 5 - an anthracene dicarboxylic acid, 1, 9 - anthracite Sen dicarboxylic acid, 2, 3 - an Torasenjika carboxylic acid, 9, 1 0 - anthracite Sen dicarboxylic acid, Bifue two Lou 2, 2 '- deer carboxylic acid , Bifue two Lou 2, 3, one dicarboxylic acid and 3 - (4-Karubokishifue sulfonyl) 1, 1, 3 - Fang such indane carboxylic acid Include the aromatic dicarboxylic acid. And Salts derived from said Jiami down and dicarboxylic acids, for example, E Ji range ammonium Niu arm adipate, tetramethylene diammine monitor © beam adipate, Te tiger methylene Jian monitor © arm pin melee DOO, Te tiger methylene Jian Moniumuaze rate, pentamethylene Jian monitor © beam sebacate gate, hexamethylene diammine monitor Umuajipeto, hexamethylene diammine monitor © beam sebacate gate, to Kisamechirenji ammonium Niu musk glycinate, O Kuta methylene Jian monitor © Mua di Bae over preparative , Okuta methylene Jian monitor ©-time sebacate, nona methylene Jian monitor ©-time adipate, nona methylene Jian monitor ©-time sebacate, decamethylene Jian monitor © Mua di adipate, © down decamethylene Jian monitor ©-time sebacate, dodecamethylene Jian monitor ©-time It may be mentioned xylylene Jian monitor © Muse bucket over the diamines and equimolar salt obtained from the above dicarboxylic acids, such as bets - Jipe DOO, dodecamethylene Jian monitor © beam sebacate and p.

Further, as the ω- § Mi Nokarubon acids, e.g., epsilon - aminocaproic acid, w - aminoheptanoic acid, omega - aminononanoic acid, omega - like can be illustrated aminoundecanoic acid and ω- Amino dodecanoic acid, the three the membered ring or cycloaliphatic easy evening-time, for example, epsilon - force caprolactam, omega - Enan Torakutamu, alpha-pyrrolidone, O, one Mechirupirori Don, shed Piperi Don, .omega. © down decane lactam and omega - or the like can be mentioned dodecalactam.

Thus, specific examples, Borisukushin'ami de (nylon 4), Porikabu Rami de (nylon), poly one omega - amino Nononan acid (nylon 9), polytetra Mechiren'ajipami de (nylon 4 6), hexamethylene adipaldehyde Ami de poly - (nylon 6 6), hexamethylene sebacate kami de (nylon 6 1 0) to poly, poly to Kisame styrene Dodekanoami de (nylon 6 1 2), poly © down decane ami de (nylon 1 1), poly Dodekan'ami de ( nylon 1 2) aliphatic Homoporiami de such as, hexamethylene terephthalate Tarami de (nylon 6 T (T represents a terephthalic acid component unit. hereinafter the same) to poly), poly-m-xylylene azide Pami de (nylon MX D 6 (M XD is, m- xylylene represent § Min component units. hereinafter the same)), Po Rimeta Xylylene Reference base Rami de (nylon MXD 8), Porimetakishiri Renseba force Mi-de (nylon MXD 10), Poriparakishiri Ren'ajipami de (nylon PXD 6 (P XD is, p- xylylene represent amine unit. The same hereinafter)), Poriparakishiri Renpimerami de (nylon PXD7), Poriparakishiri Renaze Rami de (nylon PXD9), semi-aromatic, such as polyparaxylylene sebacic kami de (nylon PXD 10) Homoporiami Donado, and, as a copolymer made of polyamide compounds, nylon 6 / 66, nylon 6Z1 1, nylon 6/12, nylon 6/610, nylon 6 Bruno 612, nylon 66/610, nylon 66/612, nylon 6/66/610, nylon 6/667612, nylon 6 / 66Zl l, Nai Ron 6Z66Z12, nylon 6/6 T, nylon 6/61 (I is the same in the representative. below isophthalic acid component unit ), Nylon 66/6 T, nylon 66/61, nylon 6Tauzeta6 iota, nylon 6/1 1 / 6T, nylon 6 / 12Zeta6tau, nylon 6/11/6 I, nylon 6/12/6 I, nylon 66/1 1/6 T, nylon 66 / 12Ζ6Τ, nylon 66/1 1/61, nylon 66 / 12Ζ 61, nylon 6Zeta6tauzeta6 iota, nylon 66 / 6ΤΖ6 Ι, nylon 1 1Z 6 Τ / 6 I, nylon 12/6 T / 6 I, nylon 6 ZMX D 6, nylon 66 / MXD6, nylon MXD 6 PXD 6, nylon MX D 7 ZPXD 7, and the like Nai port emissions MXD9 Roh PXD9 and nylon MXD 10 / P XD 10.

Also, mixtures of these Homoporiami earth Ya copolymer made of Polyamide compounds may be mentioned as specific examples.

In the present invention, it may be mentioned as examples particularly good suitable nylon 6, nylon 66, nylon 12, nylon 6Z66, nylon 6 Roh 66/12, nylon 66/6 T etc. Among them.

Further, the made of Polyamide resin used in the present invention, the type and concentration of the terminal groups, or is no particular restriction on the molecular weight and molecular weight distribution. Further, in effect is not inhibited scope of the present invention, for improving characteristics and manufacturing improvements made of Polyamide resin composition consisting of the polyamide-de resin and the fiber-like Zono tri DOO, various auxiliary materials that are commonly incorporated in the resin , namely, a heat stabilizer, an ultraviolet absorber, a light stabilizer asymmetric L antioxidants, antistatic agents, lubricants, antiblocking agents, tackifiers, seals modifiers, anti-fogging agents, crystal nucleating agents, release agents, impact modifiers, plasticizers, crosslinking agents, foaming agents, flame retardants, flame retardant aids, pigments, dyes, other additives Ya modifiers such as flavors, additives such as fillers and reinforcing materials it is also possible to.

Examples of the fillers or reinforcing materials, for example, wood flour as organic, pulp, and iron as minerals, copper, gold, silver, whiskers such as aluminum, flakes, textiles or powdered metal, carbon black, graph Ai DOO, carbon materials such as carbon fiber, activated carbon, hollow spheres, silica, alumina, silica-alumina, Sani匕 titanium, acid iron, zinc oxide, magnesia, force Lucia, potassium titanate, various Fuwerai preparative acids and bases sex sulfate Maguneshiumu, basic carbonate Maguneshiumu other composite oxides of including oxides, talc, clay, My power, silicates such as asbestos and zinc silicate, hydroxides of various metals, carbonates, sulfates, phosphate, borate, borosilicate, Al Mino silicates, titanates, basic sulfate, basic carbonates and Etc. Other basic salts, glass fibers, hollow glass spheres, glass materials such as glass flake, silicon carbide, silicon nitride, aluminum nitride, mullite DOO, ceramic box, such as co-one Jierai bets, such as fly ash and micro silica such as waste, and the like.

Furthermore, other thermoplastic resins, thermoplastic elastomers and foremost, and rubbers as needed, the effect of the present invention may be formulated in an amount of from not inhibited, also be such a crosslinking formulation it can.

Incidentally, in the present invention, the polyamide-de 榭脂 the content of the fibrous Zono tri DOO in made of Polyamide resin composition consisting of the fibrous Zono tri bets is 1 wt% or more and less than 1 0% by weight it is necessary that there, preferably in the range of 1-7 by weight%, more preferably in the range of 3-7 wt%.

The fibrous When Zono content of tri bets is less than 1 wt%, fibrous Zono tri preparative les reinforcing effect is sufficient in the made of Polyamide resin is the invention intended purpose. Also, when the content of the fibrous Zono trie Bok is more than 1 0% by weight, to crystalline effect of improving made of Polyamide resin is not exhibited, good because increasing effect of crystallization speed becomes saturated Mashikuna Les,.

Then, made of Polyamide resin composition of the present invention, the components described above, i.e., the polyamide-de resin and the fibrous Zono tri bets, and is constituted from the above such formulations of these components, further, then it is necessary and has a characteristic as shown.

That is, made of Polyamide resin composition 1 0 ° C / min rate at room temperature (23 ° C) the polyamide de 30 ° C higher Ri by equilibrium melting point of the resin constituting the polyamide-de 榭脂 compositions from the present invention temperature to a temperature was raised, and thereafter the temperature was held 5 minutes to completely melt the polyamide de resin composition, a constant cooling that is determined in the range of 5 ° CZ min ~ 1 00 ° C / min and held and cooled at a rate up to 30 ° C 5 minutes, further, 1 0 ° C / min heat of fusion observed when was heated at a rate between (ΔΗ Π) (ca 1 / g), the polyamic because of de resin crystal heat of fusion and (ΔΗ 0) (cal Zg) , the following formula (I): crystallinity: (I)

ΔΗ. X (1 -W f)

Here AH m: made of Polyamide resin composition 1 0 ° was heated from room temperature at a C / min up to 30 ° C higher temperature than the equilibrium melting point of the polyamide-de resin, the resin composition was held at this temperature for 5 minutes after things was completely melted, cooled to 3 0 ° C at a constant velocity was held for 5 minutes, further, 1 0 ° C / min heat of fusion observed when the temperature was raised at a rate of (cal Zg)

Δ H. : A polyamide-de resin crystal heat of fusion (ca 1 / g)

W f: crystallinity of the polyamide-de resin obtained by Poriami de weight fraction of the fibrous Zono Tri bets in the resin composition (I) is required to be 0.40 or more. For example, if made of Polyamide resin composition of the present invention consists of the fiber維状Zono tri preparative nylon 6 resin, as the heat of fusion (AH ra), the made of Polyamide resin composition 1 0 ° CZ component of velocity at room temperature ( the temperature was raised from 23 ° C) to 255 ° C, after completely melting the polyamide de resin composition was held for 5 minutes at 255 ° C, of ​​5 ° C / min ~ 1 00 ° C / min range was cooled to 30 ° C at a constant cooling rate determined by the inner and held for 5 minutes, to the et, 1 0 ° C / min heat of fusion observed when the temperature was raised at a rate (ca 1 / g ) as well as the adoption of, Nai port emissions of 6 resin crystal melting heat (delta Eta 0) a 4 5 ca 1 Z g ( "solid structure II polymer" high molecular Gakkai, Kyoritsu Shuppan (1 9 8 4 ) as a reference), the expression degree of crystallization of nylon 6 resin obtained by (I) is 0.4 is required to be 0 or more.

When crystallinity of the polyamide-de resin obtained by the formula (I) is 0.4 0 less than, to obtain a made of Polyamide resin molded article crystallinity is enhanced and having an early obtained crystallization rate It can not, can not achieve the object of the present invention.

A method of manufacturing made of Polyamide resin composition of the present invention can and this carried out as follows.

That is, polyamide Mi de resin composition comprising the polyamide-de resin and the fibrous Zono tri DOO is produced in a manner described below. In general, the polyamide-de 榭脂 and the fibrous Zono tri bets a predetermined amount of the foregoing, 1 0 ° C higher temperature than the equilibrium melting point of the Poriami de resins that make up the resin composition, from the melting point 6 0 after ° C shall high temperature below the temperature to completely melt kneaded by using a kneader the resin composition, 5 ° C / min to 1 0 0 ° CZ fraction constant which is determined in the range at a cooling rate cooling to room temperature, it is the onset Ming made of polyamide resin composition.

In this case, the melt kneading temperature is made of Polyamide 1 than the melting point of the resin 0 ° C higher temperatures than used, 6 0 ° C higher temperature or lower than the melting point, preferably 1 0 ° C higher temperature than the than the melting point, the it is 4 0 ° C higher temperature or lower than the melting point. When using the mixture of the polyamide-de resin, of polyamide de resin used may be selected based on the made of Polyamide resin having a high melting point.

If the melt kneading temperature is lower than the melting point + 1 0 ° C of polyamide-de resin, Te kneader smell, together with the melt viscosity of Poriami de 榭脂 becomes too high, the temperature and become part below the melting point of the resin occurs, and such the resin is solidified during manufacture and may cause the kneading failure. Moreover, not preferable melt kneading temperature is higher than the melting point + 6 0 ° C of polyamide-de resin, it occurs thermal decomposition and thermal deterioration of the resin, because it provides a coloration or deterioration in properties of made of Polyamide resin composition obtained.

In order to reliably prevent the occurrence of these undesirable phenomena according to the melt-kneading temperature, kneading temperature should be a temperature within the preferred ranges mentioned above. As the kneading machine, e.g., an extruder such as a single screw extruder or twin screw extruder, a twin-screw continuous mixer, a Banbury one mixer, super one mixer, mixing port Ichiru, two one da one, Brabender Plastograph, etc. It can be mentioned, made of polyamide resin composition of the present invention is generally to obtain a Perez bets like is usual.

As the kneading machine, preferably an extruder Among the above, particularly preferred arbitrariness biaxial extruder.

Furthermore, addition of these components that put upon melt-kneading of the fibrous Zono tri preparative and the made of Polyamide resin, the mixing order may be arbitrarily selected. For example, prior to melt-kneading, using a Henschel mixer, a ribbon-flop render tumbler Bed render the like, after mixing the said fibrous Zono tri preparative and the made of Polyamide resin, supplying the mixture to the hopper of an extruder at best, also in the hopper of the extruder supply only the made of polyamide resin, it may be supplied to the fibrous Zono tri bets from the middle of the extruder. Incidentally, Te Atatsu in producing the made of Polyamide resin composition, from the middle of the extruder hopper or extruder, may be added to the seed sub-materials mentioned above at the same time if necessary.

Then, holding the composition at this temperature, after completely melting and kneading the resin composition at room temperature with constant cooling rate determined in the range of 5 ° CZ min ~ 1 0 0 ° C / min until cooling. The cooling rate is required to be constant across, it is preferably 5 ° C / min ~ 5 0 ° C / min range, in the range of 5 ° CZ min ~ 2 0 ° CZ min especially preferred les this cooling rate is 1 0 0 ° C / min good Ri fast, might crystallinity made of polyamide resin 0. lower than 4, it is impossible to achieve the object of the present invention. On the other hand, when slower than 5 ° C / min, too much time for the molten resin composition is solidified, it is not preferable from the industrial point of view.

For made of Polyamide resin composition thus obtained, 1 0 ° C / min heat of fusion observed when the temperature was raised at a rate between (AH ra) (ca 1 / g), of the made of Polyamide resin since the crystal melting heat (Δ Η 0) (ca 1 / g), when determining the crystallinity of the polyamide-de resin by the formula (I), 0. 4 0 or one is obtained.

Thus made of Polyamide resin composition of the present invention obtained by injection molding, extrusion forming shape, compression molding, such as blow molding, is molded into a desired shape by various known molding methods, made of Polyamide Resin the molded article can be obtained.

Example

Hereinafter, the present invention will be described by way of Examples and Comparative Examples more specifically, the onset Akira, unless exceeding the gist thereof does not undergo these Examples and Comparative Examples in any way limiting.

Note that the made of Polyamide property evaluation method of a resin molded article described in the following examples and comparative examples were carried out according to the following methods. That is, a differential scanning calorimeter (Parr Kin'eruma one company, Ltd., Model: DSC 7) used, the crystallization temperature as a measure of the crystallization rate and the crystallization degree as an index of crystallinity, respectively, by the following method I asked meta. Measurements using samples 1 Omg nylon 6 resin composition was subjected to liquid nitrogen in Heriumu atmosphere as a cooling medium body.

(1) crystallization temperature

Heated from room temperature to 255 ° C in sample 1 0 ° C / min, was completely melted for 5 minutes hold at this temperature. Then, the peak temperature of crystallization that is observed when cooled at a constant cooling rate determined was determined and a crystallization temperature.

(2) the degree of crystallinity

After the sample was held the paragraph (1) and a similar manner 3 0 ° C until cooled for 5 minutes, 1 0 ° CZ minute speed heat of fusion is observed when it was elevated (.DELTA..eta ") (cal / g) was determined. Therefore, Nai port emissions of 6 resin crystal heat of fusion (.DELTA..eta 0) and 4 5 ca 1 / g, was calculated crystallinity of nylon 6 resin by the following formula (II). crystallized degree: (II)

45 (1 -W f)

In 厶 Eta,: a nylon 6 resin composition sample from room temperature at 1 0 ° CZ min speed

25 the temperature was raised to 5 ° C, after completely melted and held for 5 minutes at 255 ° C the resin composition was cooled to 30 ° C at a constant that is determined cooling rate and held for 5 minutes, further , 1 0 ° C / min heat of fusion observed when the temperature was raised at a rate of (cal / g)

W, -: made of Polyamide resin composition weight fraction of the fibrous Zono Tri bets in (1) Reference Example 1 quicklime as calcareous material (Karushido Corp. product, C a O Purity: 9 8%) 4 3 0 g , agricultural silica powder as siliceous material (Japan General Corporation products, the Blaine specific surface area: 7, 0 0 0 c mV g, S i 0 2 purity: 9 7%) 4 7 0 g, and tap water 1 8 was charged with Li Tsu torr SUS 3 1 with a 6-steel stirrer Otokurebu having an inner volume of 3 0 liters. Then, with stirring at a rotation number 8 0 r pm the stirrer, the holding temperature 2 2 0 ° C until the temperature was raised at a rate of 2 ° C / min, holding temperature 2 2 0 ° C for 5 hours retention to hydrothermal the synthesis reaction was carried out. Then, to obtain a fibrous Zono try Tosurari was allowed to cool under stirring over 1 0 hours or more. Incidentally, the measured X-ray diffraction of the slurry, Zono tri Tonomi were identified.

Subsequently, the fibrous Zono tri Tosurari 9 2 0 g (solids) of tap water to about 1 8 rate Torr and non-ionic surfactants (polyoxyethylene O Kuta decyl Amin, NOF Corporation product, product name: Nymeen 2 0 4) 4 6 g (5% by weight relative to the fibrous Zono tri preparative solids) was added, and the surface treated while dispersing with a homogenizer. After the cake was dehydrated slurry by Nutsche, and molded to the diameter of 3 mm Ri by the granulator and dried in about 1 0 0 ° C, granulated fibrous Zono surface treated to obtain a tri door. This granular fibrous Zono tri preparative was measured for the average fiber維長and average fiber diameter by the measurement and scanning electron micrograph of the BET specific surface area by nitrogen adsorption, respectively, 3 9 m 2 / g , 3 μ πι and 0.5 (hence, aspect ratio: 1 5) was.

Example 1

Siri Nda diameter: 3 0 mm co-rotating type twin-screw extruder (Ikegai Tekko Co., Ltd., Model: P CM3 0) using, 2 5 0 ° C (provided that the temperature of the nozzle portion, in the same) in the following, nylon 6 (Ube Industries, Ltd., trade name: UBE nylon 1 0 1 3 B) and 9 7 wt%, and 3 wt% resulting fibrous Zono tiger I bets in reference example 1 the melt-kneaded, to prepare a Perez bets nylon 6 resin composition. However, this time, to supply the pre-Symbol fibrous Zono tri preparative than the first vent port of the extruder using a screw feeder primary, and were Datsukimisao operation from the second vent port of the extruder .

Therefore, overnight vacuum dried in this manner for 6 hours in a heating oven 1 2 0 ° C to Perez bets of the resulting nylon 6 resin composition, further 8 0 ° C in a vacuum dryer. And it was determined the crystallization temperature and the crystallinity of the case of the 1 0 0 ° CZ min cooling rate using the Perez bets. The results are shown in Table 1.

Example 2-4

In Example 2-4, instead of fibrous Zono tiger I bets 9 7 wt% of Nai port emissions 6 3 wt 0/0, nylon 6 and a fibrous Zono tri DOO, respectively, shown in Table 1 except for using the proportions Does it I was conducted in exactly the same manner as in example 1. Crystallization temperature and crystallinity of the resulting the Perez bets, the results obtained, respectively, shown in Table 1.

Example 5-7

In Example 5-7, the cooling rate is changed to 1 0 0 ° C / min, respectively, except that the values ​​shown in Table 1, was conducted in exactly the same manner as in Example 1. Crystallization temperature and crystallinity of the resulting Perez bets, the results obtained, respectively, shown in Table 1.

That the amount of Example 8 Nylon 6 9 7% by weight to vary 9 3 wt%, Contact and, except for the usage of the fibrous Zono tri preparative 3% by weight to vary 7 wt% It was conducted in exactly the same manner as in example 5. Crystallization temperature and crystallinity of the resulting Perez bets, the results obtained are shown in Table 1.

Example 9

The amount of nylon 6 9 7 wt 0/0 to varied 9 3 wt 0/0 to the fact, and, except that the fiber維状Zono usage tri preparative 3% by weight to vary 7 wt% It was conducted in exactly the same manner as in example 6. Crystallization temperature and crystallinity of the resulting Perez bets, the results obtained are shown in Table 1.

Example 1 0

The amount of nylon 6 9 7 wt 0/0 to varied 9 3 wt 0/0 to the fact, and, except that the fiber維状Zono usage tri preparative 3% by weight to vary 7 wt% It was conducted in exactly the same manner as in example 7. Crystallization temperature and crystallinity of the resulting Perez bets, the results obtained are shown in Table 1.

In Comparative Examples 1-4 Comparative Examples 1-4, 9 7 weight 0/0 nylon 6 and changed to 3% by weight of the fibrous Zono tiger wells, nylon 6 and a fibrous Zono tri DOO, respectively, first except for using the proportions Does it'll shown in Table was conducted in exactly the same manner as in example 1. Crystallization temperature and crystallinity of the resulting the Perez bets, the results obtained, respectively, shown in Table 1.

In Comparative Example 1, the crystallization temperature is 1 5 5 ° C, crystallinity is 0 3 2, both in the case of Example (crystallization temperature:. 1 6 5~ 1 9 8 ° C, the degree of crystallinity:. 0 was significantly lower than in 4 1-0 4 9).. In Comparative Example 2-4, the degree of crystallinity 0.3 0, it was significantly lower and compared to the case of Example (0. 4.sub.1 to 0. 4 to 9).

Table 1

Note * 1: In the measurement of crystallization temperature and the crystallinity of the nylon 6 resin composition, sample 1 0 ° C / min rate and heating from room temperature to 2 5 5 ° C for 5 minutes hold and, after complete melting, representing the cooling rate during cooling. As is clear from the examples and comparative examples described above, made of Polyamide resin composition provided by the present invention, the crystallization temperature is high (this is that crystallization occurs quickly, namely, the crystallization rate is It shows earliness), and high crystallinity of the crystalline product. Industrial Applicability

Made of Polyamide resin molded article is molded by using a made of Polyamide resin composition of the present invention, the crystallization is faster at the same time is excellent in moldability, due to the high crystallinity of the polyamide-de resins, which provide good physical properties it is.

Accordingly, automobile materials, electric, electronic parts, precision machine parts, can be widely used as such packaging materials.

Claims

The scope of the claims
1. consists of a made of Polyamide resin and a fibrous Zono tri DOO, and a Poriami de resin composition fibrous Zono tri bets are included in a range of less than 1 0% by weight 1% by weight or more, the fibrous Zono tri-door is,
(1) 2 1 m 2 / g or more specific surface area (but measured at B ET method by nitrogen adsorption) and having a,
(2) 0. 1 μ m≤D <0. 5 / m,
(3) 1 / m≤ L <5 m and
(4) 1 0≤L / D <2 0
However, D and L, respectively, showing the average fiber diameter Oyo beauty average fiber length of the fibrous Zono Tri bets,
Made of Polyamide resin composition, characterized in that to satisfy simultaneously.
2. made of Polyamide resin composition was heated from room temperature at 1 0 ° C / min up to 3 0 ° C higher temperature than the equilibrium melting point of the polyamide-de resin constituting the resin composition, 5 minutes at this temperature after complete melting the resin composition was held, and cooling to 3 (TC at a constant cooling rate and held for 5 minutes, further, observed when the temperature was raised at a 1 0 ° C / min rate a fusion fever that is, from the crystal melting heat of the polyamide de resin, the following formula (I):
^ KuchiAkira degree: (I)
ΔΗ 0 X (1 one W f)
In AH ": Poriami de resin composition 3 0 ° C higher temperature to heated than the equilibrium melting point of the polyamide-de resin from room 1 o ° c / min, the resin composition was held at this temperature for 5 minutes after things was completely melted, cooled to 3 0 ° C at a constant velocity was held for 5 minutes, further, 1 0 ° C / min heat of fusion observed when the temperature was increased at a rate (ca 1 / g)
: A polyamide-de resin crystal heat of fusion (ca 1 / g)
W f: made of Polyamide weight fraction of fibrous Zono Tri bets in the resin composition according to claim 1, wherein the crystallinity of the polyamide-de resin obtained is 0.4 0 or by (one) Poriami de resin composition
3. Poriami de resin composition ranging first claim of claim, 1 0 ° C higher temperature than the equilibrium melting point of the polyamide-de resins that make up the resin composition, the following 60 ° C higher temperature than the melting point in after complete melting and kneading the resin composition, 5 ° C / min ~ 1 00 ° C / min constant cooling rate determined by the within range of characterized in that to cool to room temperature made of polyamide resin Processes for making compositions.
4. The resin composition constituting Poriami de 1 than the equilibrium melting point of the resin 0 ° C higher temperature than on, Poriami de ranging third claim of claim melt-kneading at 40 ° C higher temperature below the temperature above the melting point method for producing a resin composition.
5. a manufacturing method of the cooling rate is 5 ° CZ min ~ 50 ° Poriami de resin composition ranging third claim of claim is C / min.
6. The resulting made of Polyamide resin composition, from 1 0 ° and heat of fusion observation seen when it was elevated C / min, and crystal heat of fusion made of Polyamide resin used, the following formula (I ): the degree of crystallinity = one (I)
ΔΗ. X (1 -W f)
In 厶 Η- made of Polyamide 榭脂 composition 1 0 ° was heated from room temperature at a C / min up to 30 ° C higher temperature than the equilibrium melting point of the polyamide-de resin, at this temperature
And held for 5 minutes after complete melting the resin composition, and held for 5 minutes and cooled to 3 0 ° C at a constant velocity, further, when temperature was raised at 1 0 ° C / min the heat of fusion is observed (ca 1 / g)
Delta H Q: Poriami de resin crystal melting heat (ca 1 Z g)
W f: made of Polyamide range third preceding claims, wherein the crystallinity of the polyamide-de resin obtained by the weight fraction of the fibrous Zono Tri bets in the resin composition (I) is 0.40 or more method for producing a made of polyamide resin composition according to.
PCT/JP1998/003797 1998-08-27 1998-08-27 Polyamide resin composition and process for the preparation thereof WO2000012630A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2904240A1 (en) * 2006-07-26 2008-02-01 Air Liquide Packing structure of a container, useful for storing acetylene, comprises crystal structure of xonotlite, tobermorite and/or crystallized foshagite in the form of needles
US8628708B2 (en) 2008-07-02 2014-01-14 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for producing a packing structure with control over the drying step

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02500917A (en) * 1986-10-20 1990-03-29
JPH07216133A (en) * 1994-02-04 1995-08-15 Ube Ind Ltd Reinforced organic polymer composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02500917A (en) * 1986-10-20 1990-03-29
JPH07216133A (en) * 1994-02-04 1995-08-15 Ube Ind Ltd Reinforced organic polymer composition

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* Cited by examiner, † Cited by third party
Title
"POLYAMIDE RESIN HANDBOOK, PASSAGE", POLYAMIDE RESIN HANDBOOK, XX, XX, 30 January 1988 (1988-01-30), XX, pages 79 + 102, XP002926666 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2904240A1 (en) * 2006-07-26 2008-02-01 Air Liquide Packing structure of a container, useful for storing acetylene, comprises crystal structure of xonotlite, tobermorite and/or crystallized foshagite in the form of needles
EP1887275A1 (en) * 2006-07-26 2008-02-13 L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Packing structure for gas container with needle-shaped crystallised material
US7972667B2 (en) 2006-07-26 2011-07-05 L'Air Liquide Societe Anonyme pour l'Etude et l'Exploitation des Procedes G eorges Claude Gas container packing structure having a material crystallized in needle form
US8628708B2 (en) 2008-07-02 2014-01-14 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for producing a packing structure with control over the drying step

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