JP3111449B2 - Nylon resin composition with enhanced crystallization rate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a nylon resin composition having an increased crystallization rate. The nylon resin molded article molded using the nylon resin composition of the present invention is excellent in moldability due to rapid crystallization, and at the same time gives good physical properties because the crystallinity of the nylon resin is high. Therefore, automotive materials, electrical and electronic components,
It can be widely used as precision machine parts, packaging materials, etc.

[0002]

2. Description of the Related Art The BET specific surface area by nitrogen adsorption is 21 m.
^A nylon resin composition comprising 1 to 75% by weight of a ² / g or more fibrous zonotolite and 25 to 99% by weight of a nylon resin is already known (see JP-A-6-128412). Although this nylon resin composition certainly accelerates the crystallization rate of the constituent nylon resin, the effect of improving its crystallinity (usually expressed by the degree of crystallinity) was hardly observed in many cases. Therefore, the effect of improving the physical properties of the nylon resin in this nylon resin composition was not as large as expected.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a nylon resin composition which has an accelerated crystallization rate and gives a nylon resin molded article having improved crystallinity.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies to solve the above problems, it has been obtained from a specific amount of a fibrous zonotolite having a specific property (that is, having a specific specific surface area and a specific shape) and a nylon resin, and The heat of fusion (ΔH ₀ ) (cal / g) of the crystal of the nylon resin and the heat of fusion (ΔH _m ) (ca) of the nylon resin composition observed under specific conditions
1 / g), the above object can be achieved by providing a nylon resin / fibrous zonotolite composition in which the crystallinity of the nylon resin in the nylon resin composition determined by the formula (I) is within a specific range. And found that the present invention was completed.

[0005] That is, the first invention in the present invention is:
A nylon resin composition comprising a nylon resin and a fibrous zonotolite, wherein the fibrous zonotolite is contained in a range of 1% by weight or more and less than 10% by weight, wherein the fibrous zonotolite has an amount of 21 m ² / g or more. It has a specific surface area (however, measured by the BET method by nitrogen adsorption), and 0.1 μm ≦ D <0.5 μm, 1 μm ≦ L <5 μm
m and 10 ≦ L / D <20 (where D and L are
Respectively, indicating the average fiber diameter and average fiber length of the fibrous zonotolite).

In a second aspect of the present invention, the temperature of the nylon resin composition is raised from room temperature to a temperature 30 ° C. higher than the equilibrium melting point of the nylon resin constituting the resin composition at a rate of 10 ° C./min. This is observed when the resin composition is completely melted by holding at 5 ° C. for 5 minutes, cooled to 30 ° C. at a constant cooling rate, held for 5 minutes, and further heated at a rate of 10 ° C./min. From the heat of fusion of the nylon resin and the heat of fusion of the crystal of the nylon resin,

[0007]

(Equation 2)

[0008] The nylon resin composition according to the first aspect of the present invention is characterized in that the crystallinity of the nylon resin determined by the method is 0.40 or more.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
You. The fibrous zonotolite described in the present invention is zonotora
Ito (indicative formula: Ca₆Si ₆O₁₇(OH)_Two,Chemical formula:
6CaO.6SiO_Two・ H_TwoO) Needle-like crystalline substance
U. In the present invention, the value of the specific surface area is very important.
21m^Two/ G or more, preferably 30 m^Two/ G or more
(However, it is a measured value by the BET method by nitrogen adsorption)
Must. This value is 30m^TwoLess than / g
In the case of fibrous zonotolite, wettability with nylon resin
Worse, especially 21m^Two/ G specific surface area
In the case of fibrous zonotolite,
Because of the remarkable, it is possible to achieve the above-described object of the present invention.
I can't.

Further, in the present invention, the fiber shape of the fibrous zonotolite is, in particular, an average fiber length (L) of 1 μm ≦ L <5 μm and an average fiber diameter (D) of 0.1 μm ≦
D <0.5 μm, and the aspect ratio (L / D) is 1
It is necessary to simultaneously satisfy the condition of 0 ≦ L / D <20. When D is less than 0.1 μm or L is 5 μm or more, mixing of fibrous zonotolite and nylon resin
At the time of kneading, the fibrous zonotolite may be broken. On the other hand, when D is 0.5 μm or more or L is less than 1 μm, the resulting nylon resin composition has a low mechanical strength due to the fibrous zonotolite. The improvement effect is not enough. When the L / D is less than 10, sufficient mechanical strength cannot be obtained in the obtained nylon resin composition, and when the L / D is 20 or more, the bulk specific gravity of the fibrous zonotolite is large. Is so small that kneading becomes difficult during the production of the nylon resin composition of the present invention.

As described in detail below, the fibrous zonotolite of the present invention having the above-mentioned specific properties can be produced, for example, by the production method described in Japanese Patent Application Laid-Open No. 6-128412, It is manufactured by blending a high-quality raw material with a specific ratio and performing a hydrothermal synthesis reaction.
Examples of the calcareous raw materials include quick lime, slaked lime, carbide slag, and the like, and those containing few impurities such as magnesium oxide are preferable. Examples of the siliceous raw materials include pulverized silica, silica sand and quartz, silicic acid, silicic acid anhydride, silica gel, diatomaceous earth, clay and ferrosilicon dust, and the like. A fine powder having a diameter of 10 μm or less is desirable. The mixing ratio (Ca / Si ratio) of these two is slightly smaller than the theoretical equivalent, and is preferably 0.8 to 0.99. Also,
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.

In the hydrothermal synthesis reaction, for example, the calcareous raw material, the siliceous raw material and water in the above-mentioned predetermined proportions are charged into an autoclave, and usually stirred at 180 to 240 ° C. for 1 hour.
It may take up to 8 hours. 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 zonotolite having the specific specific surface area used in the present invention as described above cannot be obtained.

In the present invention, the fibrous zonotolite obtained by the above-mentioned production method further comprises a surfactant and / or a surface in order to further enhance the reinforcing effect on a composition comprising a nylon resin described later. It is desirable to be treated with a coupling 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 zonotolite with the matrix resin, that is, the nylon resin, and the reinforcing effect, that is, further increasing the mechanical strength. Specifically, the following 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 stearates, and examples of cationic surfactants include tetradecylamine acetate and alkyltrimethylammonium chloride. Examples of the agent include dimethylalkyl lauryl petaine, and examples of the nonionic surfactant include polyoxyethylene octadecylamine and polyoxyethylene lauryl ether. As the coupling agent, a silane coupling agent, particularly γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, N-phenyl-γ
-Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-
aminosilane coupling agents such as β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminopropyl) γ-aminopropylmethyldimethoxysilane, γ-dibutylaminopropyltrimethoxysilane and γ-ureidopropyltriethoxysilane Others,
Examples include titanate-based coupling agents, aluminum-based coupling agents, chromium-based coupling agents, and boron-based coupling agents.

The amount of the surface treating agent to be added should be 0.1 to 10% by weight, preferably 0.5 to 8% by weight, based on the fibrous zonotolite (dry matter basis). When the addition amount is less than 0.1% by weight, the above-mentioned strength improving effect is not sufficient, and when the addition amount exceeds 10% by weight,
Even if the addition amount is increased, the above-mentioned strength improving effect hardly increases. When the amount of addition is in the range of 0.1 to 0.5% by weight, the above-mentioned strength improving effect may not be sufficient, and when the amount of addition is in the range of 8 to 10% by weight, the above-mentioned strength improving effect is not increased. It tends to be unsatisfactory.

In the present invention, as described above, the fibrous zonotolite slurry obtained by the hydrothermal synthesis reaction is extracted from the autoclave, and the fibrous zonotolite is subjected to a surface treatment. The surface treatment method is not particularly limited,
For example, the surface treating agent is added to the fibrous zonotolite slurry as it is or after adding an appropriate amount of water, and the mixture is mixed and stirred in a slurry state using an appropriate device.
Subsequently, excess water is filtered and separated by a centrifugal dehydrator or a filter press to obtain a cake-like fibrous zonotolite. In addition, the surface treatment may be performed by drying the fibrous zonotolite slurry and then using the surface treatment agent dissolved in a small amount of water or a solvent, a so-called dry treatment method, but the operation becomes complicated, Further, the effect of the surface treatment is small and there is no particular merit.

Next, the cake-like fibrous zonotolite to which the surface treatment agent is attached as described above is dried, and when a coupling agent is used as the surface treatment agent,
After further heat treatment, the fibrous zonotolite used in the present invention is obtained. The drying is performed by using a known dryer such as a hot air circulation dryer or an infrared heating dryer, and the drying is performed for 100 to 15 days.
It is preferable to carry out at a temperature of 0 ° C. for 20 to 30 hours until the water content of the fibrous zonotolite becomes 1% by weight or less. In addition, the heat treatment when a coupling agent is used as the surface treatment agent is performed at 100 to 150 ° C. and 20 ° C.
It is preferred to carry out the drying following the drying of the water under heating for up to 30 hours. Furthermore, the fibrous zonotolite used in the present invention may be granulated for the purpose of easily mixing and kneading with a nylon resin described later. Granular fibrous zonotolite is a cake-like fibrous zonotolite to which the above-mentioned surface treatment agent is attached, and has a diameter of 1 to 3
When molded into 8 mm granules, followed by drying and using a coupling agent as the surface treatment agent,
It is obtained by further performing a heat treatment. in this case,
The granulator is not particularly limited, and may be a known type such as a rotary vertical granulator, a rotary drum granulator, a rotary flat granulator, a screw extrusion granulator, and a roll extrusion granulator. A granulator can be used. Further, when the diameter of the granular fibrous zonotolite is out of the above range, mixing and kneading with a single-screw extruder or a twin-screw extruder becomes difficult when mixing and kneading with the nylon resin, and the roll or the Banbury mixer is used. The resin composition must be sequentially filled and mixed and kneaded, for example, so that the fibrous zonotolite is remarkably destroyed, resulting in a decrease in the mechanical strength of the resin composition obtained. In the present invention, in the production of granular fibrous zonotolite, the above-mentioned cake-like fibrous zonotolite is dried as it is and heat-treated as necessary to obtain a particle size of 5%.
It may be formed into granules by a method of crushing to about mm, but powder is likely to be generated and the bulk is somewhat large, which makes handling somewhat difficult.

As the nylon resin used in the present invention, known nylon resins can be used as long as they are crystalline nylon resins. For example, crystalline polyamides obtained by ring-opening polymerization of a cyclic aliphatic lactam having three or more rings,
Crystalline polyamides obtained by polycondensation of diamine and dicarboxylic acid, crystalline polyamides obtained by polycondensation of salt obtained from diamine and dicarboxylic acid, crystallinity obtained by polycondensation of ω-aminocarboxylic acid Examples thereof include polyamides and crystalline copolymerized polyamides obtained by copolymerizing two or more of these polyamide-forming monomer components. Alternatively, a mixture of two or more of these crystalline polyamides or crystalline copolymerized polyamides can also be used.

Examples of the diamine include hydrazine, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and the like. Dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine,
Aliphatic diamines such as 2-methylhexamethylenediamine, 3-methylhexamethylenediamine, 2-ethyloctamethylenediamine and 3-t-butylhexamethylenediamine; 1,3-diaminocyclohexane;
4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl)
Cyclohexane, isophoronediamine, piperazine, N
Alicyclic diamines such as -aminoethylpiperazine, 2,5-dimethylpiperazine, bis (p-aminocyclohexyl) methane and 2,2-bis- (4'-aminocyclohexyl) propane, and m-xylylenediamine and and aromatic diamines such as p-xylylenediamine.

On the other hand, the dicarboxylic acids include, for example, oxalic acid, succinic acid, glutaric acid, adipic acid,
-Methyladipic acid, 3-methyladipic acid, 3-t-
Butyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonandioic acid, decanedioic acid,
Undecandioic acid, dodecandionic acid, tridecandionic acid, tetradecandionic acid, pentadecandionic acid, hexadecandionic acid, eicosandioic acid, dimeric dicarboxylic acid of lindelic acid and dicarboxylic acid of dimeric oleic acid, etc. Aliphatic dicarboxylic acid, 1,2-
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic 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 Acid, 2,3-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3-anthracenedicarboxylic acid,
1,4-anthracene dicarboxylic acid, 1,5-anthracene dicarboxylic acid, 1,9-anthracene dicarboxylic acid, 2,3-anthracene dicarboxylic acid, 9,10-anthracene dicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, Aromatic dicarboxylic acids such as biphenyl-2,3'-dicarboxylic acid and 3- (4-carboxyphenyl) 1,1,3-indanecarboxylic acid. And, as the salt obtained from the diamine and dicarboxylic acid, for example, ethylene diammonium adipate, tetramethylene diammonium adipate, tetramethylene diammonium pimerate, tetramethylene diammonium azelate, pentamethylene diammonium sebacate, hexamethylene Methylene diammonium adipate, hexamethylene diammonium sebacate, hexamethylene diammonium succinate, octamethylene diammonium adipate, octamethylene diammonium sebacate, nonamethylene diammonium adipate, nonamethylene diammonium sebacate, decamethylene diammonium Adipate, undecamethylene diammonium sebacate, dodecamethylene diammonium adipate, dodecame It can be mentioned the diamine and equimolar salt obtained from the above dicarboxylic acids, such as oven ammonium sebacate and p- xylylene ammonium sebacate.

Examples of the ω-aminocarboxylic acid include ε-aminocaproic acid, ω-aminoheptanoic acid, ω-aminononanoic acid, ω-aminoundecanoic acid and ω-aminododecanoic acid. As the cyclic aliphatic lactam having three or more members, for example,
ε-caprolactam, ω-enantholactam, α-pyrrolidone, δ-methylpyrrolidone, α-piperidone, ω-
Undecanelactam and ω-dodecalactam can be mentioned.

Therefore, specific examples include polysuccinamide (nylon 4), polycapramide (nylon 6), poly-ω-aminononanoic acid (nylon 9), polytetramethylene adipamide (nylon 46), and polyhexamethylene adzide. Aliphatic homopolyamides such as poamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanoamide (nylon 612), polyundecaneamide (nylon 11), polydodecaneamide (nylon 12) , Polyhexamethylene terephthalamide (nylon 6T (T represents terephthalic acid component unit; the same applies hereinafter)), polymethaxylylene adipamide (nylon MXD6 (MXD
Represents an m-xylylenediamine component unit. The same applies to the following)), polymethaxylylene veramide (nylon MXD8), polymetaxylylene sebacamide (nylon MXD10), polyparaxylylene adipamide (nylon PXD6 (PXD is a p-xylylenediamine component unit) The same applies hereinafter)), semi-aromatic homopolyamides such as polyparaxylylene pimeramide (nylon PXD7), polyparaxylylene azeramide (nylon PXD9), polyparaxylylene sebacamide (nylon PXD10), etc. And as copolymerized polyamides, nylon 6/66, nylon 6/11, nylon 6/12, nylon 6/610, nylon 6/612,
Nylon 66/610, Nylon 66/612, Nylon 6/66/610, Nylon 6/66/612, Nylon 6/66/11, Nylon 6/66/12, Nylon 6 / 6T, Nylon 6 / 6I (I , Isophthalic acid component unit, the same applies hereinafter), nylon 66 /
6T, nylon 66 / 6I, nylon 6T / 6I, nylon 6/11 / 6T, nylon 6/12 / 6T, nylon 6/11 / 6I, nylon 6/12 / 6I, nylon 66/11 / 6T, nylon 66 / 12 / 6T, nylon 66/11 / 6I, nylon 66/12 / 6I, nylon 6 / 6T / 6I, nylon 66 / 6T / 6I, nylon 11 / 6T / 6I, nylon 12 / 6T / 6I, nylon 6 / MXD6 , Nylon 66 / MXD6, nylon MXD6 / PXD6, nylon MXD7 / PXD7,
Nylon MXD9 / PXD9 and Nylon MXD10
/ PXD10 and the like. In addition, a mixture of these homopolyamides and copolymerized polyamides is also a specific example. In the present invention, among these, nylon 6, nylon 66, nylon 12, nylon 6/66, nylon 6/66/12, nylon 6
6 / 6T can be mentioned as a particularly suitable example. The nylon 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, within the range where the effects of the present invention are not impaired, various sub-materials usually blended with the resin in order to improve the properties and production of the nylon resin composition comprising the nylon resin and the fibrous zonotolite, That is, heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, antiblocking agents, tackifiers, sealability improvers, antifogging agents, crystal nucleating agents, release agents, In addition to additives and modifiers such as impact modifiers, plasticizers, crosslinking agents, foaming agents, flame retardants, flame retardant aids, pigments, dyes, and fragrances, fillers and reinforcing materials can also be added. it can. As the filler or reinforcing material, for example, wood flour as an organic substance, pulp, and iron as an inorganic substance, whisker such as copper, gold, silver, aluminum, flakes, fiber or powdered metal, carbon black, graphite, Carbon fiber, activated carbon, carbon materials such as hollow spheres, silica, alumina, silica-alumina, titanium oxide, iron oxide, zinc oxide, magnesia, calcia, potassium titanate, various ferrites, basic magnesium sulfate, basic magnesium carbonate Oxides including other complex oxides, silicates such as talc, clay, mica, asbestos and zinc silicate, hydroxides, carbonates, sulfates, phosphates, borates and borosilicates of various metals , Aluminosilicates, titanates, basic sulfates, basic carbonates and other basic salts, Scan hollow spheres, glass materials such as glass flake, silicon carbide, silicon nitride, aluminum nitride, mullite, ceramic, such as cordierite, waste such as fly ash and micro silica, 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, and they can also be crosslinked.

In the present invention, it is necessary that the content of the fibrous zonotolite in the nylon resin composition comprising the nylon resin and the fibrous zonotolite is 1% by weight or more and less than 10% by weight. is there. If the content of the fibrous zonotolite is less than 1% by weight, the reinforcing effect of the fibrous zonotolite on the nylon resin, which is the original object of the present invention, is not sufficient. On the other hand, when the content of the fibrous zonotolite is 10% by weight or more, the effect of improving the crystallinity of the nylon resin is not exhibited, and the effect of increasing the crystallization rate is also undesirably saturated.

The nylon resin composition of the present invention
It is necessary that the composition be composed of the above components, that is, the nylon resin and the fibrous zonotolite, and the above-mentioned composition of these components, and further have the following properties. That is, the nylon resin composition of the present invention was cooled at room temperature (23 ° C.) at a rate of 10 ° C./min.
° C) to a temperature higher by 30 ° C than the equilibrium melting point of the nylon resin constituting the nylon resin composition, and kept at this temperature for 5 minutes to completely melt the nylon resin composition. / Minute to 200 ° C./min., Cooled to 30 ° C. at a fixed cooling rate and held for 5 minutes,
Further, from the heat of fusion (ΔH _m ) (cal / g) observed when the temperature was raised at a rate of 10 ° C./min and the heat of crystal fusion (ΔH ₀ ) (cal / g) of the nylon resin, Formula (I)

[0025]

(Equation 3)

It is necessary that the crystallinity of the nylon resin determined by the above is 0.40 or more. For example, when the nylon resin composition of the present invention comprises a nylon 6 resin and the fibrous zonotolite, the heat of fusion (ΔH _m )
After the temperature of the nylon resin composition was raised from room temperature (23 ° C.) to 255 ° C. at a rate of 10 ° C./min, and kept at 255 ° C. for 5 minutes to completely melt the nylon resin composition,
At a constant cooling rate determined in the range of 100 ° C./min to 100 ° C./min, and kept for 5 minutes.
Heat of fusion observed when the temperature is increased at a rate of
1 / g) and the heat of crystal fusion (ΔH ₀ ) of the nylon 6 resin is 45 cal / g (see “Solid Structure of Polymer II”, edited by The Society of Polymer Science, Kyoritsu Shuppan (1984)). The crystallinity of the nylon 6 resin determined by (I) needs to be 0.40 or more. When the crystallinity of the nylon resin determined by the formula (I) is less than 0.40, it is not possible to obtain a nylon resin molded article having an increased crystallization rate and improved crystallinity. The object of the invention cannot be achieved.

Next, the nylon resin composition of the present invention can be produced as follows. That is, the nylon resin composition comprising the nylon resin and the fibrous zonotolite is produced by a known method. Generally, the above-mentioned predetermined amount of the nylon resin and the fibrous zonotolite are melt-kneaded using a kneader to obtain the nylon resin composition of the present invention. At this time, the melting and kneading temperature is 10 ° C. higher than the melting point of the nylon resin used.
Higher temperature, not higher than 60 ° C higher than the melting point, preferably higher than 10 ° C higher than the melting point, 40 ° C higher than the melting point.
It is preferable that the temperature is not higher than the high temperature. When a mixture of the nylon resins is used, a nylon resin having a high melting point may be selected from the nylon resins to be used. If the melt-kneading temperature is lower than the melting point of the nylon resin + 10 ° C., the melt viscosity of the nylon resin becomes too high in the kneading machine, and a portion having a temperature lower than the melting point of the resin is formed. Do
Poor kneading may occur. On the other hand, if the melting and kneading temperature is higher than the melting point of the nylon resin + 60 ° C., the resin is thermally decomposed or thermally degraded, which results in discoloration or deterioration in physical properties of the obtained nylon resin composition. In order to reliably prevent the occurrence of these undesired 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 roll,
Examples thereof include a kneader and a Brabender plastograph, and the nylon 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.

Further, the addition and mixing order of these components at the time of melt-kneading the nylon resin and the fibrous zonotolite can be arbitrarily selected. For example,
Prior to melt kneading, using a Henschel mixer, ribbon blender, tumbler blender, or the like, after mixing the nylon resin and the fibrous zonotolite, the mixture may be supplied to a hopper of an extruder. May be supplied with only the nylon resin, and the fibrous zonotolite may be supplied from the middle of the extruder. In the production of the nylon resin composition, the above-mentioned various auxiliary materials can be simultaneously added, if necessary, from the hopper of the extruder or in the middle of the extruder.

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

[0031]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited by these Examples and Comparative Examples unless it exceeds the gist thereof. Absent.

The methods for evaluating the physical properties of nylon resin molded articles described in the following Examples and Comparative Examples are as follows.
It carried out according to the following method. That is, using a differential scanning calorimeter (manufactured by PerkinElmer, model: DSC 7),
The crystallization temperature was determined as a measure of the crystallization rate, and the degree of crystallinity was determined as an index of crystallinity by the following methods. The measurement was performed in a helium atmosphere using liquid nitrogen as a cooling medium using a 10 mg sample of a nylon 6 resin composition.

(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. Thereafter, a crystallization peak temperature observed when cooling was performed at a predetermined constant cooling rate was determined and defined as a crystallization temperature.

(2) Crystallinity The sample was cooled to 30 ° C. in the same manner as in the above item (1), held for 5 minutes, and then heat of fusion observed when the temperature was increased at a rate of 10 ° C./min. (ΔH _m ) (cal / g) was determined.
Therefore, the heat of crystal fusion (ΔH ₀ ) of nylon 6 resin is 45
cal / g, and the crystallinity of the nylon 6 resin is expressed by the following formula (I
It was calculated in I).

[0035]

(Equation 4)

Reference Example 1 As a calcareous raw material, quicklime (manufactured by Calceed Co., Ltd., Ca
430 g of siliceous raw material for agricultural use (a product of Japan General Co., Ltd., Blaine specific surface area: 7,000 cm ² / g, SiO ₂ purity: 97%) 4
70 g and 18 liters of tap water were charged into a 30 liter SUS316 autoclave equipped with a stirrer. Then, while stirring at a rotation speed of a stirrer of 80 rpm, the temperature was raised to a holding temperature of 220 ° C. at a rate of 2 ° C./min, and held at a holding temperature of 220 ° C. for 5 hours to perform a hydrothermal synthesis reaction. Thereafter, the mixture was allowed to cool over 10 hours or more with stirring to obtain a fibrous zonotolite slurry. When the X-ray diffraction of this slurry was measured, only zonotolite was identified.

Then, about 920 g (based on solid content) of the fibrous zonotolite slurry and about 18 liters of tap water and a nonionic surfactant (polyoxyethylene octadecylamine, a product of Nippon Yushi Co., Ltd., trade name: Nimeen 204) ) 46 g (5% based on fibrous zonotolite solids)
% By weight) and surface-treated while dispersing with a homogenizer. The slurry was dehydrated with a nutschet to form a cake, and then formed into a diameter of φ3 mm using a granulator.
By drying at 0 ° C., a surface-treated granular fibrous zonotolite was obtained. The BET specific surface area of this granular fibrous zonotolite was measured by nitrogen adsorption, and the average fiber length and average fiber diameter were measured by a scanning electron micrograph. As a result, 39 m ² /
g, 3 μm and 0.2 μm (hence the aspect ratio: 15).

Example 1 Using a co-rotating twin-screw extruder having a cylinder diameter of φ30 mm (model: PCM30, manufactured by Ikegai Iron Works Co., Ltd.), the temperature was 250 ° C. Same), nylon 6 (Ube Industries, Ltd.)
(Product name: UBE nylon 1013B) and 3 parts by weight of the fibrous zonotolite obtained in Reference Example 1 were melt-kneaded to prepare pellets of a nylon 6 resin composition. However, at this time, the fibrous zonotolite was supplied from the first vent of the extruder using a screw feeder, and deaeration was performed from the second vent of the extruder.

Then, the pellets of the nylon 6 resin composition thus obtained are placed in a heating oven at 120 ° C.
After that, vacuum drying was performed in a vacuum dryer at 80 ° C. overnight.
Then, the crystallization temperature and the degree of crystallization when the cooling rate was set to 100 ° C./min using the pellets were determined. Table 1 shows the results.

Examples 2 to 4 In Examples 2 to 4, instead of 97 parts by weight of nylon 6 and 3 parts by weight of fibrous zonotolite, nylon 6 and fibrous zonotolite were mixed as shown in Table 1, respectively. The same operation as in Example 1 was performed, except that the ratio was used. Table 1 shows the obtained results of the crystallization temperature and the degree of crystallinity of the obtained pellets.

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

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

Example 9 Except that the amount of nylon 6 was changed to 97 parts by weight to 93 parts by weight, and the amount of fibrous zonotolite was changed to 3 parts by weight to 7 parts by weight. The same operation as in Example 6 was performed. Table 1 shows the obtained results of the crystallization temperature and crystallinity of the obtained pellets.

Example 10 Except that the amount of nylon 6 was changed to 97 parts by weight to 93 parts by weight, and the amount of fibrous zonotolite was changed to 3 parts by weight to 7 parts by weight. The same operation as in Example 7 was performed. Table 1 shows the obtained results of the crystallization temperature and crystallinity of the obtained pellets.

Comparative Examples 1 to 4 In each of Comparative Examples 1 to 4, 97 parts by weight of nylon 6 and 3 parts by weight of fibrous zonotolite were replaced by nylon 6 and fibrous zonotolite, respectively, as shown in Table 1. The same operation as in Example 1 was performed, except that the ratio was used. Table 1 shows the obtained results of the crystallization temperature and the degree of crystallinity of the obtained pellets. In Comparative Example 1, the crystallization temperature was 155 ° C., and the crystallinity was 0.32. In each case, the case of Example (crystallization temperature: 165 to 198 ° C., crystallinity: 0.41 to 0) .4
It was considerably lower than 9). Further, in Comparative Examples 2 to 4, the crystallinity was 0.30, which was significantly lower than that in the example (0.41 to 0.49).

[0046]

[Table 1]

[0047]

As is clear from the examples and comparative examples described above, the nylon resin composition provided by the present invention has a high crystallization temperature (this is because crystallization occurs quickly, that is, The crystallization rate is high), and the crystallinity of the crystallized product is high. Therefore, it can be widely used as automotive materials, electric / electronic parts, precision machine parts, packaging materials and the like.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 C08K 3/00-3/40

Claims (2)

(57) [Claims] 1. A nylon resin composition comprising a nylon resin and a fibrous zonotolite, wherein the fibrous zonotolite is contained in a range of 1% by weight or more and less than 10% by weight, wherein the fibrous zonotolite comprises: 1) 21 m ² / g
It has the above specific surface area (however, a value measured by the BET method by nitrogen adsorption) and (2) 0.1 μm ≦ D <
0.5 μm, (3) 1 μm ≦ L <5 μm and (4) 1
0 ≦ L / D <20 (where D and L are respectively
(Indicating the average fiber diameter and average fiber length of the fibrous zonotolite) at the same time. 2. The temperature of the nylon resin composition is increased from room temperature to a temperature 30 ° C. higher than the equilibrium melting point of the nylon resin constituting the resin composition at a rate of 10 ° C./min, and maintained at this temperature for 5 minutes. After the resin composition was completely melted, it was cooled to 30 ° C. at a constant cooling rate and held for 5 minutes.
The heat of fusion observed when heating at a rate of 0 ° C./min;
From the heat of crystal fusion of the nylon resin, the following formula (I) is obtained. Crystallinity of nylon resin determined by
The nylon resin composition according to claim 1, wherein the composition has an accelerated crystallization rate.