WO2000012630A1

WO2000012630A1 - Polyamide resin composition and process for the preparation thereof

Info

Publication number: WO2000012630A1
Application number: PCT/JP1998/003797
Authority: WO
Inventors: Hideho Tanaka; Kunio Watanabe
Original assignee: Ube Industries, Ltd.
Priority date: 1998-08-27
Filing date: 1998-08-27
Publication date: 2000-03-09

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

Description Polyamide resin composition and method for producing the same

The present invention relates to a polyamide resin composition and a method for producing the same, and more particularly, to a polyamide resin composition having an increased crystallization rate and a method for producing the same. Background art

A resin composition comprising 5 to 75% by weight of fibrous zonolite having a BET specific surface area of 21 m ² / g or more by nitrogen adsorption and 25 to 95% by weight of a polyamide resin is already known (see Kaihei 7—2 16 13 The above publication discloses that this resin composition has a high strength, high rigidity, and a good balance of heat resistance and impact resistance as compared with the conventional fibrous inorganic substance Z organic polymer substance composite material. It is disclosed that a molecular composite is provided. However, the above publication does not disclose the crystallization speed of a thermoplastic resin such as a polyamide resin used at all.

An object of the present invention is to provide a polyamide resin composition which has an increased crystallization rate and gives a molded article of a polyamide resin having improved crystallinity. The present inventors have conducted intensive studies in order to solve the above-described problems, and as a result, have found that a specific amount of fibrous zonolite having a specific property (that is, having a specific specific surface area and a specific shape). And the polyamide resin, and the heat of crystal fusion (ΔΗ) (ca 1 / g) of the polyamide resin and the heat of fusion (ΔΔ) of the polyamide resin composition observed under specific conditions. _{Ω ω} ) (ca 1 / g) and the volume of the polyamide resin in the polyamide resin composition obtained by the above formula (I) is within a specific range. The present inventors have found that the above objects can be achieved by providing a glove composition, and have completed the present invention. Disclosure of the invention

The first invention of the present invention comprises a polyamide resin and a fibrous zonolite. A polyamide resin composition containing 1% by weight or more and less than 10% by weight of fibrous zonolite, wherein the fibrous zonolite is at least 21 m ² / g or more. It has a specific surface area (however, measured by the BET method using nitrogen adsorption) and 0.1 m ≤ D <0.5 μm, 1 m ≤ L く 5 m and 10 ≤ LZD 2 20 However, D and L respectively indicate the average fiber diameter and the average fiber length of the fibrous zonolite, and the present invention relates to a polyamide resin composition characterized in that it satisfies at the same time.

In the second invention of the present invention, the polyamide resin composition is heated from room temperature at a rate of 10 ° C.Z to 30 ° C. higher than the equilibrium melting point of the polyamide resin constituting the resin composition. After heating at this temperature for 5 minutes to completely melt the resin composition, it is cooled at a constant cooling rate to 30 ° C. and held for 5 minutes. From the heat of fusion observed when the temperature is raised in step and the heat of crystal fusion of the polyamide resin, the 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, it is cooled to a constant speed of 30 ° C., held for 5 minutes, and then heat of fusion observed when the temperature is raised at a speed of 10 ° C.Z ( cal Zg)

Delta Eta _0: made of Polyamide Resin crystal heat of fusion (ca 1 / g)

W _f : the first invention, wherein the crystallinity of the polyamide resin determined by the weight fraction (1) of the fibrous zonolite in the polyamide resin composition is 0.40 or more. The present invention relates to a polyimide resin composition according to

The third invention of the present invention provides the polyamide resin composition at a temperature of at least 10 ° C higher than the equilibrium melting point of the polyamide resin constituting the resin composition and at a temperature higher by 60 ° C than the melting point. After completely melting and kneading the resin composition, the polyimide resin is cooled to room temperature at a constant cooling rate determined within a range of 5 ° C / min to 100 ° C / min. The present invention relates to a method for producing the 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 ₆ 〇 ₁₇ (OH) _2, formula: 6 C a 0 · 6 S i 0 2 · H 2 0) Needle crystalline material. In the present invention, the value of the specific surface area is very important and must be 2 lm ² Zg or more, preferably 30 m ² Zg or more (however, measured by the BET method by nitrogen adsorption). If the value is less than 30 m ² / g, the fibrous zono light has poor wettability with the polyamide resin, and particularly has a specific surface area of less than 21 m ² / g. In the case of (1), since the wettability deteriorates remarkably, the above-mentioned object of the present invention cannot be achieved.

Further, in the present invention, as the fiber shape of the fibrous zonolite, particularly, the average fiber length (L) is 1 m≤L <5 ^ m, and the average fiber diameter (D) is 0.1 l / m≤D <0.5, "m, and the condition that the aspect ratio (L / D) is 10≤L / D <20 at the same time.

If D is less than 0.1 m and the palm is 5 μm or more, the fibrous zonolite may be broken during mixing and kneading of the fibrous zonolite and the polyamide resin. On the other hand, when D is 0.5 μm or more and L is less than 1 m, the effect of improving the mechanical strength of the obtained polyamide resin composition by the fibrous zonolite is not sufficient.

When the LZD force is less than si0, sufficient mechanical strength cannot be obtained in the obtained polyamide resin composition. If the L / D is 20 or more, the bulk specific gravity of the fibrous zonolite is too small, and it becomes difficult to knead the material when producing the polyamide resin composition of the present invention.

As described in detail below, the fibrous zonolite of the present invention having the specific properties described above can be produced, for example, by the production method described in Japanese Patent Application Laid-Open No. 6-128412, that is, Manufactured by blending calcareous raw materials and siliceous raw materials at a specific ratio and conducting a hydrothermal synthesis reaction _c

Examples of calcareous raw materials include quick lime, slaked lime, and carbide slag, and those containing few impurities such as magnesium oxide are preferable. Silicic materials include crushed silica, silica sand and quartz, silica, silica, silica gel, diatomaceous earth, clay and And silicon dust. These siliceous raw materials are desirably in the form of fine powder having few impurities and an average particle diameter of 10 μm or less. The mixing ratio (C a / S 匕) of these two is slightly smaller than the theoretical equivalent, and is preferably 0.8 to 0.99. The ratio of water to be mixed is desirably 5 to 40 times, preferably 8 to 30 times the total weight of the calcareous raw material and the siliceous raw material.

The hydrothermal synthesis reaction is performed, for example, by charging the calcareous raw material, the siliceous raw material, and water in the above-mentioned predetermined ratio into an autoclave, and performing the reaction at 180 to 240 ° C. for 1 to 8 hours while stirring. Just do it. In this case, a predetermined ratio of the calcareous raw material, the siliceous raw material, and water may be previously mixed in a slurry state and then charged into the autoclave. The reaction temperature and the reaction time in the hydrothermal synthesis reaction are important factors. If the reaction temperature and the reaction time are out of the above ranges, the fibrous zonolite having the specific specific surface area used in the present invention as described above cannot be obtained.

In the present invention, the fibrous zonolite obtained by the above-mentioned production method further comprises a surfactant and a surfactant to further improve the reinforcing effect on the composition comprising the polyamide resin described below. Alternatively, it is desirable to be treated with a force pulling agent (hereinafter referred to as “surface treatment agent”).

That is, the surface treatment agent is used for the purpose of improving the affinity of the fibrous zonolite with the matrix resin, that is, the polyamide resin, and further enhancing the reinforcing effect, that is, the mechanical strength. Is what is done. Specifically, the following surface treatment agents can be used.

As the surfactant, any of anionic, cationic, amphoteric and nonionic surfactants can be used. Examples of anionic surfactants include alkyl ether sulfates, dodecylbenzenesulfonates and stearate salts, and examples of cationic surfactants include tetradecylamine acetate and alkyltrimethylammonium chloride. Examples of the amphoteric surfactant include dimethylalkyl lauryl betaine and the like, and examples of the nonionic surfactant include polyoxyethylene octadecylamine and polyoxyethylene lauryl ether. Examples of the silane coupling agent include silane-based silane coupling agents, in particular, araminopropyltrimethoxysilane, araminopropyltriethoxysilane, and N-phenyl acrylonitrile. Aminopropyl trimethoxysilane, N— (aminoethyl) aminopropyltrimethoxysilane, N— / 3 (aminoethyl) y—Aminopropyltriethoxysilane, N— /? (Aminopropyl) y—Aminopropylmethyl In addition to aminosilane coupling agents such as dimethoxysilane, y-dibutylaminopropyltrimethoxysilane and y-peridopropyltriethoxysilane, titanate-based coupling agents, aluminum-based coupling agents, chromium-based coupling agents, and hydrogen-based coupling agents Force coupling agents and the like.

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 .

If the added amount is less than 0.1% by weight, the above-mentioned strength improving effect is not sufficient, and if the added amount exceeds 10% by weight, the above-mentioned strength improving effect is hardly obtained even if the added amount is increased. It doesn't increase very much. 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 There is a tendency for the effect to be reduced.

In the present invention, as described above, the fibrous zonolite slurry obtained by the hydrothermal synthesis reaction is extracted from the autoclave, and the fibrous zonolite is subjected to a surface treatment. The surface treatment method is not particularly limited. For example, the surface treatment agent is added to the fibrous zonolite slurry as it is, or after adding an appropriate amount of water, and mixed in a slurry state with an appropriate device. Stir. Subsequently, the excess water is filtered and separated by a centrifugal dehydrator or a filter press to obtain a cake-like fibrous zonolite.

In addition, the surface treatment may be performed by a so-called dry treatment method in which the fibrous zonotrit slurry is dried and then used with the surface treatment agent dissolved in a small amount of water or a solvent. The operation becomes complicated, and the effect of the surface treatment is small, so there is no particular advantage.

Next, the cake-like fibrous zonolite to which the surface treatment agent is adhered as described above is dried and, if a coupling agent is used as the surface treatment agent, further heat-treated and used in the present invention. The resulting fibrous zonolite is obtained.

The drying is performed using a known drying device such as a hot air circulation type drying device or an infrared heating type drying device. It is preferred that the heating is carried out at a temperature of 100 to 150 ° C. for 20 to 30 hours until the water content of the fibrous zonolite becomes 1% by weight or less. Further, the heat treatment when a coupling agent is used as the surface treatment agent is preferably performed following the drying of the water under heating at 100 to 150 ° C. and 20 to 30 hours. .

Furthermore, the fibrous zonolite used in the present invention may be granulated for the purpose of easily mixing and kneading with a polyamide resin described later.

Granular fibrous zonolite is obtained by forming a cake-like fibrous zonolite to which the above surface treatment agent is attached into granules having a diameter of 1 to 8 mm by a granulator, and then drying the granulated fibrous zonolite. And, when a coupling agent is used as the surface treatment agent, it can be obtained by further performing a heat treatment. In this case, the granulator is not particularly limited, and may be a rotating vertical granulator, a rotating drum granulator, a rotating flat granulator, a screw extrusion granulator, a roll extrusion granulator. A known granulator such as a granulator can be used. Further, when the diameter of the granular fibrous zonolite is out of the above range, mixing and kneading with a polyamide resin during mixing and kneading with a single-screw extruder or a twin-screw extruder becomes difficult. And mixing and kneading must be successively performed using a mixer or a Banbury mixer, and the fibrous zonolite may be significantly broken, resulting in a decrease in the mechanical strength of the resin composition obtained.

In the present invention, in the production of granular fibrous zonolite, the above-mentioned cake-like fibrous zonolite is dried and heat-treated as necessary, and granulated to a particle size of about 5 mm. It may be formed into a shape. However, powder is likely to be produced, and the bulk is rather large, making it somewhat difficult to handle.

As the polyamide resin used in the present invention, a known resin can be used as long as it is a crystalline polyamide resin. For example, crystalline polyamides obtained by ring-opening polymerization of a cyclic aliphatic lactam having three or more rings, crystalline polyamides obtained by polycondensing diamine and dicarboxylic acid, and diamines and dicarboxylic acids Crystalline polyamides obtained by polycondensation of salts, crystalline polyamides obtained by polycondensation of _ω -aminocarboxylic acid, or copolymerization of two or more of these polyamide-forming monomer components Crystalline copolymerized polyamides. Alternatively, these crystalline polyamides or crystalline copolymer polyamides Mixtures of two or more can also be used.

Examples of the diamine include hydrazine, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, and octamethylene diamine. , Nonamethylene diamine, decamethylene diamine, pendecamethylene diamine, dodecamethylene diamine, 2,2,4 trimethylhexamethylene diamine, 2,4,4-trime Tylhexamethylene diamine, 2-methylhexamethylene diamine, 3-methylhexamethylene diamine, 2-ethylhexamethylene diamine, and 3-t-butylhexamethylene diamine Aliphatic diamins such as amines, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclo 1,4-bis (aminomethyl) cyclohexane, isophoronediamin, piperazine, N-aminoethylpiperazine, 2,5-dimethylbiperazine, bis (p-aminocyclohexyl) methane and 2,2bis Alicyclic diamines such as 1- (4,1-aminocyclohexyl) propane; and aromatic diamines such as m-xylylenediamine and p-xylylenediamine.

On the other hand, the dicarboxylic acids include, for example, oxalic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, 3-methyladipic acid, 3-t-butyladipic acid, pimelic acid, suberic acid, Dimer of azelaic acid, sebacic acid, nonandionic acid, decanedioic acid, pendecanedioic acid, dodecanedioic acid, tridecandioic acid, tetradecandioic acid, pentadecandionic acid, hexadecanedioic acid, eicosandioic acid and lindelic acid Dicarboxylic acids such as dicarboxylic acids and dimeric dicarboxylic acids of oleic acid; 1,2-cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid; and 1,4-cyclohexanedicarboxylic acid Alicyclic dicarboxylic acid, and terephthalic acid, isophthalic acid, 5-t- Butylisophthalic acid, 1,2 naphthalenedicarboxylic acid, 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, 1,6 naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3-anthra Sendicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,5-anthracenedicarboxylic acid, 1,9-anthracenedicarboxylic acid, 2,3-anthracenedicarboxylic acid, 9,10-anthracenedicarboxylic acid, Aromatic dicarboxylic acids such as biphenyl 2,2'-dicarbonic acid, biphenyl 2,3,1-dicarboxylic acid and 3- (4-carboxyphenyl) 1,1,3, indanecarboxylic acid . Examples of the salt obtained from the diamine and the dicarboxylic acid include, for example, ethylene diammonium adipate, tetramethylene diammonium adipate, tetramethylene diammonium pimelate, and tetramethylene dianme Monumizelate, pentamethylene diammonium sebagate, hexamethylene diammonium adipate, hexamethylene diammonium sebagate, hexamethylene diammonium succinate, octamethylene diammonium acetate Octa methylene diammonium sebacate, nonamethylene diammonium acetate, nonamethylene methylene diammonium acetate, decamethylene diammonium acetate, decamethylene methylene diammonium sebacate, Dodecamethylene diammonium 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 Examples of cycloaliphatic lactams having at least two-membered rings include _ε- caprolactam, _ω- enantholactam, α-pyrrolidone, ό, monomethylpyrrolidone, hipiperidone, ω-ndecanelactam and ω — Dodecalactam and the like can be mentioned.

Therefore, specific examples include borsk cinamide (nylon 4), polycarbamide (nylon), poly- _ω- aminononanoic acid (nylon 9), polytetramethylene adipamide (nylon 46), and polyhexamethylene adipamide. (Nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanoamide (nylon 612), polydecaneamide (nylon 11), polydodecane amide ( Aliphatic homopolyamides such as nylon 12), polyhexa Methylene terephthalamide (nylon 6 T (T stands for terephthalic acid component unit; the same applies hereinafter)), polymethaxylylene adipamide (nylon MX D 6 (MXD is m-xylylenediamine component unit) The same applies to the following.)), Polymethyxylene velamide (nylon MXD 8), polymethaxylylene selenium force mid (nylon MXD 10), polyparaxylylene adipamide (nylon PXD 6 (PXD: p-xylylenediamine component unit) The same applies to the following.)), Semi-aromatic homopolyamides such as polyparaxylylene piramamide (nylon PXD7), polyparaxylylene azelamide (nylon PXD9), and polyparaxylylene sebacamide (nylon PXD10) As polymerized polyamides, nylon 6/66, nylon 6Z11, Iron 6/12, Nylon 6/610, Nylon 6-612, Nylon 66/610, Nylon 66/612, Nylon 6/66/610, Nylon 6/667612, Nylon 6 / 66Zl l, Nylon 6Z66Z12, Nylon 6 / 6 T, nylon 6/61 (I represents isophthalic acid component unit; the same applies hereinafter), nylon 66/6 66, nylon 66/61, nylon 6ΤΖ6Ι, nylon 6/1 1 / 6T, nylon 6 / 12Ζ6Τ , Nylon 6/11/6 I, Nylon 6/12/6 I, Nylon 66/1 1/6 Τ, Nylon 66 / 12Ζ6Τ, Nylon 66/1 1/61, Nylon 66 / 12Ζ61, Nylon 6Ζ6ΤΖ6 Ι, Nylon 66 / 6ΤΖ6 Ι, nylon 1 1Z 6 Τ / 6 I, nylon 12/6 Τ / 6 I, nylon 6 ZMX D 6, nylon 66 / MXD6, nylon MXD 6 PXD 6, nylon MX D 7 ZPXD 7, MXD9 PXD9 and nylon MXD10 / P XD10.

Further, specific examples thereof include a mixture of these homopolyamides and copolymerized polyamides.

In the present invention, among these, nylon 6, nylon 66, nylon 12, nylon 6Z66, nylon 6/66/12, nylon 66 / 6T and the like can be mentioned as particularly preferred examples.

In addition, the polyamide resin used in the present invention is not particularly limited in the type and concentration of the terminal group, or in the molecular weight and molecular weight distribution. Further, various sub-materials usually added to the resin to improve the properties and the production of the polyamide resin composition comprising the polyamide resin and the fibrous zonolite, as long as the effects of the present invention are not impaired. That is, heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, antiblocking agents, tackifiers, sealant improvers, antifogging agents, crystal nucleating agents, mold release Additives, impact modifiers, plasticizers, crosslinkers, foaming agents, flame retardants, flame retardant aids, additives such as pigments, dyes, fragrances, etc. You can also.

Examples of the fillers and reinforcing materials include wood flour, pulp, and whiskers such as iron, copper, gold, silver, and aluminum as inorganic substances, flakes, fibers or powdered metals, carbon black, and graphite. Carbon materials such as Ait, carbon fiber, activated carbon, hollow spheres, etc., silica, alumina, silica / alumina, titanium oxide, iron oxide, zinc oxide, magnesia, potassium, potassium titanate, various types of fluorides and bases Oxides including basic magnesium sulfate, basic magnesium carbonate and other complex oxides, talc, clay, mai, asbestos, silicates such as zinc silicate, hydroxides, carbonates, sulfates of various metals, Phosphates, borates, borosilicates, aminosilicates, titanates, basic sulfates, basic carbonates and Other basic salts, such as glass fiber, glass hollow spheres, glass flakes, and other glass materials, silicon carbide, silicon nitride, aluminum nitride, ceramics such as mullite, kojierite, fly ash and microsilica, etc. Waste and the like.

Furthermore, other thermoplastic resins, thermoplastic elastomers, rubbers, and the like can be blended, if necessary, in an amount that does not impair the effects of the present invention. it can.

Incidentally, in the present invention, the content of the fibrous zonolite in the polyamide resin composition comprising the polyamide resin and the fibrous zonolite is 1% by weight or more and less than 10% by weight. And preferably in the range of 1 to 7% by weight, more preferably in the range of 3 to 7% by weight.

If the content of the fibrous zonolite is less than 1% by weight, the reinforcing effect of the fibrous zonolite on the polyamide resin, which is the original object of the present invention, is not sufficient. Further, when the content of the fibrous zonolite is 10% by weight or more, the polyamide resin The effect of improving the crystallinity is not exhibited, and the effect of increasing the crystallization rate is saturated, which is preferable.

The polyamide resin composition of the present invention comprises the above components, that is, the polyamide resin and the fibrous zonolite, and the above-described blend of these components. It must have the characteristics shown below.

That is, the polyamide resin composition of the present invention is heated at a rate of 10 ° C./min from room temperature (23 ° C.) to 30 ° C. higher than the equilibrium melting point of the polyamide resin constituting the polyamide resin composition. After the temperature is raised to the temperature and maintained at this temperature for 5 minutes to completely melt the polyamide resin composition, a predetermined cooling determined within a range of 5 ° CZ min to 100 ° C / min. The heat of fusion (ΔΗ _Π ) (ca 1 / g) observed when cooling at a rate of 30 ° C and holding for 5 minutes, and then heating at a rate of 10 ° C / min, From the heat of crystallization of the resin (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 the material is completely melted, cool at a constant rate to 30 ° C, hold for 5 minutes, and further observe the heat of fusion observed when the temperature is increased at a rate of 10 ° C / min (cal Zg)

ΔH. : Heat of crystal fusion of polyamide resin (ca1 / g)

W _f : It is necessary that the crystallinity of the polyamide resin determined by the weight fraction (1) of the fibrous zonolite in the polyamide resin composition is 0.40 or more. For example, when the polyamide resin composition of the present invention comprises a nylon 6 resin and the fibrous zonolite, the polyamide resin composition may be heated at room temperature (AH _ra ) at a rate of 10 ° CZ minute. (23 ° C) to 255 ° C, hold at 255 ° C for 5 minutes to completely melt the polyamide resin composition, and then range from 5 ° C / min to 100 ° C / min. The heat of fusion (ca 1 / g) observed when cooling to 30 ° C at a constant cooling rate determined within and holding for 5 minutes, and then heating at a rate of 10 ° C / min. ) The heat of crystal fusion (Δ Η ₀ ) of Nymouth 6 resin is 45 ca 1 Zg (see “Solid Structure of Polymer II” edited by the Society of Polymer Science, Kyoritsu Shuppan (1989)). It is necessary that the crystallinity of the nylon 6 resin determined by the above formula (I) is 0.40 or more.

When the crystallinity of the polyamide resin determined by the formula (I) is less than 0.40, it is possible to obtain a polyamide resin molded article having an increased crystallization rate and an increased crystallinity. Cannot achieve the object of the present invention.

Next, the method for producing the polyamide resin composition of the present invention can be performed as follows.

That is, a polyamide resin composition comprising the polyamide resin and the fibrous zonolite is produced by the method described below. Generally, the above-mentioned predetermined amounts of the polyamide resin and the fibrous zonolite are brought to a temperature higher than or equal to 10 ° C higher than the equilibrium melting point of the polyamide resin constituting the resin composition, and higher than the melting point. After the resin composition is completely melt-kneaded using a kneader at a temperature of 60 ° C. or higher, a fixed temperature determined within a range of 5 ° C./min to 100 ° C.Z. After cooling to room temperature at a cooling rate, the polyamide resin composition of the present invention is obtained.

At this time, the melt-kneading temperature is at least 10 ° C higher than the melting point of the polyamide resin used, at most 60 ° C higher than the melting point, preferably at least 10 ° C higher than the melting point. The temperature is 40 ° C higher than the melting point. When a mixture of the above-mentioned polyamide resins is used, a polyamide resin having a high melting point may be selected from the polyamide resins to be used.

If the melt-kneading temperature is lower than the melting point of the polyamide resin + 10 ° C, the melt viscosity of the polyamide resin becomes too high in the kneader, and a portion having a temperature equal to or lower than the melting point of the resin occurs. Poor kneading may occur due to solidification of the resin during production. On the other hand, if the melt-kneading temperature is higher than the melting point of the polyamide resin + 60 ° C, the resin is thermally decomposed or thermally degraded, resulting in coloration of the resulting polyamide resin composition and deterioration of physical properties, which is not preferable.

In order to surely prevent the occurrence of these undesirable phenomena related to the melt-kneading temperature, the melt-kneading temperature should be within the above-mentioned preferable range. Examples of the kneading machine include extruders such as a single-screw extruder and a twin-screw extruder, a twin-screw continuous mixer, a Banbury mixer, a super-mixer, a mixing port, a Ni-Da, a Brabender plastograph, and the like. The polyamide resin composition of the present invention is generally obtained as a pellet.

As the kneader, an extruder is preferable among the above, and a twin-screw extruder is particularly preferable.

Furthermore, the order of addition and mixing of these components during melt-kneading of the polyamide resin and the fibrous zonolite can be arbitrarily selected. For example, prior to melt kneading, the polyamide resin and the fibrous zonolite are mixed using a Henschel mixer, a ribbon blender, a tumbler blender, or the like, and then the mixture is supplied to a hopper of an extruder. Alternatively, only the polyamide resin may be supplied to the hopper of the extruder, and the fibrous zonolite may be supplied from the middle of the extruder. In the production of the polyamide resin composition, the above-mentioned various sub-materials can be simultaneously added, if necessary, from the hopper of the extruder or in the middle of the extruder.

Next, the composition is held at this temperature, and the resin composition is completely melt-kneaded, and then cooled to room temperature at a constant cooling rate determined in the range of 5 ° C.Z to 100 ° C./min. Cool down to The cooling rate needs to be constant and is preferably in the range of 5 ° C / min to 50 ° C / min, and more preferably in the range of 5 ° CZ to 20 ° CZ. If the cooling rate is higher than 100 ° C./min, the crystallinity of the polyamide resin may be lower than 0.4, and the object of the present invention cannot be achieved. On the other hand, when the temperature is lower than 5 ° C / min, it takes too much time for the molten resin composition to solidify, which is not preferable from an industrial viewpoint.

For the polyamide resin composition thus obtained, the heat of fusion (AH _ra ) (ca 1 / g) observed when the temperature was increased at a rate of 10 ° C./min, and the amount of the 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.

The polyamide resin composition of the present invention thus obtained is molded into a desired shape by various known molding methods such as injection molding, extrusion molding, compression molding, and hollow molding. Thus, a polyamide resin molded product is obtained.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited at all by the Examples and Comparative Examples unless it exceeds the gist thereof.

The methods for evaluating the physical properties of the polyamide resin molded articles described in the following Examples and Comparative Examples were performed according to the following methods. That is, using a differential scanning calorimeter (Perkin Elmer Co., Ltd., model: DSC 7), the crystallization temperature is used as a measure of the crystallization rate, and the degree of crystallinity is used as an index of crystallinity. I asked. The measurement was performed using a 1 Omg sample of a nylon 6 resin composition in a helium atmosphere using liquid nitrogen as a cooling medium.

(1) Crystallization temperature

The sample was heated from room temperature to 255 ° C at a rate of 10 ° C / min and kept at this temperature for 5 minutes to completely melt. Then, the peak temperature of crystallization observed when cooling was performed at a fixed constant cooling rate was determined and defined as the crystallization temperature.

(2) Crystallinity

The heat of fusion (ΔΗ „) (cal) observed when the sample was cooled to 30 ° C and held for 5 minutes in the same manner as in (1) above, and then heated at a rate of 10 ° CZ Therefore, the heat of crystal fusion (ΔΗ ₀ ) of the Nymouth 6 resin was set to 45 ca 1 / g, and the crystallinity of the Nylon 6 resin was calculated by the following formula (II). Degree: (II)

45 (1 -W _f )

In room temperature, a sample of the nylon 6 resin composition is taken from room temperature at a rate of 10 ° CZ min.

After the temperature was raised to 255 ° C and kept at 255 ° C for 5 minutes to completely melt the resin composition, it was cooled to 30 ° C at a fixed cooling rate and held for 5 minutes. Heat of fusion observed when heating at a rate of 10 ° C / min (cal / g)

W,-: Weight fraction of fibrous zonolite in polyamide resin composition (1) Reference Example 1 Lime as a calcareous raw material (Calcide Co., Ltd., CaO purity: 98%) 43 g, siliceous silica powder for agriculture as a siliceous raw material (Japan General Co., Ltd. product, Brain specific surface area: 7,000) 0 c mV g, S i 0 2 purity: 9 7%) 4 7 0 g, and the tap water 1 8 Li Tsu torr was charged to SUS 3 1 with 6 made agitator Otokurebu having an inner volume of 3 0 l. Then, while stirring at a rotation speed of the stirrer of 80 rpm, the temperature was raised at a rate of 2 ° C / min to a holding temperature of 220 ° C, and the liquid was held at the holding temperature of 220 ° C for 5 hours to obtain hydrothermal heat A synthesis reaction was performed. Thereafter, the mixture was allowed to cool over 10 hours or more with stirring to obtain a fibrous zonolite slurry. When X-ray diffraction of this slurry was measured, only zonotrite was identified.

Then, about 90 liters of tap water and about 90 liters of tap water and a nonionic surfactant (polyoxyethylene octadecylamine, Nippon Oil & Fats Co., Ltd.) Trade name: Nymein 204) 46 g (5% by weight based on the solid content of fibrous zonolite) was added, and the surface was treated while being dispersed with a homogenizer. This slurry is dehydrated with a nutschet to form a cake, then formed into a diameter of 3 mm by a granulator, and dried at about 100 ° C to obtain a surface-treated granular fibrous zono. Got a try. 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 μπι and 0. (Thus, the aspect ratio: 15).

Example 1

Using a co-rotating twin-screw extruder with a cylinder diameter of 30 mm (Ikegai Iron Works Co., Ltd., model: PCM30), at 250 ° C (however, the temperature at the nozzle is 97% by weight of nylon 6 (manufactured by Ube Industries, Ltd., trade name: UBE nylon 103B) and 3% by weight of the fibrous zonotralite obtained in Reference Example 1. Was melt-kneaded to produce a pellet of a nylon 6 resin composition. However, at this time, the fibrous zonolite was supplied from the first vent of the extruder using a screw feeder, and the deaeration operation was performed from the second vent of the extruder. .

Therefore, the pellets of the nylon 6 resin composition thus obtained were heated at 120 ° C. For 6 hours in a heating oven and overnight in a vacuum dryer at 80 ° C. overnight. Then, using this pellet, the crystallization temperature and the degree of crystallinity when the cooling rate was set to 100 ° C. CZ minutes were determined. The results are shown in Table 1.

Examples 2 to 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 such a mixing ratio, the same operation as in Example 1 was performed. Table 1 shows the obtained results of the crystallization temperature and crystallinity of the obtained pellets.

Examples 5 to 7

In Examples 5 to 7, the same operation as in Example 1 was performed except that the cooling rate was changed to 100 ° C./min and the values were as shown in Table 1, respectively. Table 1 shows the obtained results of the crystallization temperature and crystallinity of the obtained pellets.

Example 8 Except that the amount of nylon 6 was changed to 97% by weight to 93% by weight, and the amount of fibrous zonolite was changed to 3% by weight to 7% by weight. The same operation as in Example 5 was performed. Table 1 shows the obtained results on the crystallization temperature and crystallinity of the obtained pellets.

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% Performed exactly the same operation as in Example 6. Table 1 shows the obtained results of the crystallization temperature and crystallinity of the obtained pellets.

Example 10

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% Was performed in exactly the same manner as in Example 7. Table 1 shows the obtained results of the crystallization temperature and crystallinity of the obtained pellets.

Comparative Examples 1 to 4 In 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, Una by shown in Table 1 Except for using the compounding ratio, the same operation as in Example 1 was performed. Table 1 shows the obtained results of the crystallization temperature and crystallinity of the obtained pellets.

In Comparative Example 1, the crystallization temperature was 155 ° C. and the crystallinity was 0.32, and both were the case of the examples (crystallization temperature: 165 to 198 ° C., Crystallinity: considerably lower than 0.41 to 0.49). Further, in Comparative Examples 2 to 4, the crystallinity was 0.30, which was remarkably lower than that in Examples (0.41 to 0.49).

Table 1

(Note) * 1: In the measurement of crystallization temperature and crystallinity of nylon 6 resin composition, the sample was heated from room temperature to 255 ° C at a rate of 10 ° C / min and held for 5 minutes. It indicates the cooling rate when cooling after complete melting. As is clear from the examples and comparative examples described above, the polyamide resin composition provided by the present invention has a high crystallization temperature (this is because crystallization occurs early. That is, the crystallization rate is high), and the crystallinity of the crystallized product is high. Industrial applicability

Polyamide resin molded articles molded using the polyamide resin composition of the present invention are excellent in moldability because of rapid crystallization, and at the same time, provide good physical properties due to high crystallinity of the polyamide resin. It is.

Therefore, it can be widely used as automotive materials, electric and electronic parts, precision machine parts, packaging materials, etc.

Claims

The scope of the claims

1. A polyamide resin composition comprising a polyamide resin and fibrous zonolite, and containing the fibrous zonolite in a range of 1% by weight or more and less than 10% by weight, wherein the fibrous Zono light,

(1) It has a specific surface area of 21 m ² / g or more (however, measured by the BET method by nitrogen adsorption) and

(2) 0.1 μm≤D <0.5 / m,

(3) 1 / m≤L <5m and

(4) 1 0≤L / D <2 0

Here, D and L indicate the average fiber diameter and average fiber length of the fibrous zonolite, respectively.

A polyamide resin composition characterized by simultaneously satisfying the following.

2. The polyamide resin composition is heated at a rate of 10 ° C / min from room temperature to a temperature 30 ° C higher than the equilibrium melting point of the polyamide resin constituting the resin composition, and the temperature is maintained at this temperature for 5 minutes. After holding and completely melting the resin composition, observe at a constant cooling rate of 3 (cooling to TC, holding for 5 minutes, and then heating at a rate of 10 ° C / min. From the heat of fusion to be melted and the heat of crystal fusion of the polyamide resin, the following formula (I):

^ Vitrification degree ^: (I)

ΔΗ ₀ X (1-1 W _f )

AH „: The temperature of the polyamide resin composition is raised from room temperature to a temperature 30 ° C higher than the equilibrium melting point of the polyamide resin at a rate of 1 ° C / min, and held at this temperature for 5 minutes. After the material is completely melted, it is cooled at a constant rate to 30 ° C, held for 5 minutes, and the heat of fusion observed when the temperature is increased at a rate of 10 ° C / min (ca 1 / g)

: Heat of crystal fusion of polyamide resin (c a 1 / g)

W _f : The crystallinity of the polyamide resin determined by the weight fraction (1) of the fibrous zonolite in the polyamide resin composition is 0.40 or more. The polyamide resin composition described in paragraph 1

3. The polyamide resin composition according to claim 1 is subjected to a temperature not lower than 10 ° C higher than the equilibrium melting point of the polyamide resin constituting the resin composition and not higher than 60 ° C higher than the melting point. After completely melting and kneading the resin composition in (1), the polyamide resin is cooled to room temperature at a constant cooling rate determined in the range of 5 ° C / min to 100 ° C / min. A method for producing the composition.

4. The polyamide according to claim 3, which is melt-kneaded at a temperature not lower than 10 ° C higher than the equilibrium melting point of the polyamide resin constituting the resin composition and not higher than 40 ° C higher than the melting point. A method for producing a resin composition.

5. The method for producing a polyamide resin composition according to claim 3, wherein the cooling rate is 5 ° CZ to 50 ° C / min.

6. From the heat of fusion observed when the obtained polyamide resin composition is heated at a rate of 10 ° C./min and the heat of crystal fusion of the polyamide resin used, the following formula (I ): Crystallinity = 1 (I)

ΔΗ. X (1 -W _f )

The polyamide resin composition is heated from room temperature to a temperature 30 ° C higher than the equilibrium melting point of the polyamide resin at a rate of 10 ° C / min.

When the resin composition is completely melted by holding for 5 minutes, cooled to a constant rate of 30 ° C, held for 5 minutes, and then heated at a rate of 10 ° C / min. Heat of fusion observed in (ca 1 / g)

ΔH _Q : Heat of crystal fusion of the polyimide resin (ca 1 Zg)

W _f : The crystallinity of the polyamide resin determined by the weight fraction (1) of the fibrous zonolite in the polyamide resin composition is 0.40 or more, wherein the crystallinity is 0.40 or more. 3. The method for producing a polyamide resin composition according to claim 1.