JP2000063665A - Production of polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyamide resin compsn, improved in toughness and in the balance among elastic modulus, strength, and elongation by polymerizing raw polyamide materials in the presence of a specified amt. of an apatite-type compd. SOLUTION: Law polyamide materials of 50-99.5 wt.% and 0.5-50 wt.% apatite-type compd. are compounded and polymerized. The apatite-type compd. is a mixture of a phosphoric acid-type metal compd. and a nonphosphoric acid- type metal compd., pref. has an average particle size of 100 μm or lower, and has a molar ratio of metal element/phosphorus of 1.1-10.0. The metal element is pref. at least one element of the group 2A of the periodic table, such as Mg, Ca, or Ba. The phosphoric acid-type metal compd. is a metal oxide, metal carbonate or the like, an example being calcium monohydrogenphosphate dihydrate, The nonphosphoric acid-type metal compd. is a metal hydroxide, a metal carbonate, or the like, examples being calcium carbonate and barium carbonate, The apatite compd. is represented by the formula: A10-Z (HPO4)2(PO4)6-Z(X)2-Z [wherein 0<=Z<2; A is a metal element; and X is an anion (compd.)].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various mechanical industrial parts, strength suitable for industrial materials such as electric and electronic parts,
The present invention relates to a method for producing a polyamide resin composition comprising a polyamide and an apatite type compound, which has high rigidity and excellent toughness.

[0002]

Conventionally, various fillers such as inorganic fibers such as glass fibers and carbon fibers or inorganic compounds such as calcium carbonate, mica and talc, montmorillonite and swelling fluoromica for the purpose of increasing strength and rigidity of polyamide resins. Although layered compounds such as, for example, have been used, these methods are effective in increasing strength and rigidity, but the affinity between polyamide and filler is low, and the toughness characteristic of polyamide resin is There was a drawback that it markedly impaired the. On the other hand, Japanese Patent Application Laid-Open No. 03-217454 discloses a polyamide resin composition composed of 100 parts by weight of polyamide and 5 to 300 parts by weight of apatite for the purpose of providing a material having a feel close to that of ivory. Similar to the composition with other fillers added, the strength and rigidity can be improved, but because the affinity between the polyamide and the apatite interface is extremely low, the decrease in toughness, that is, the decrease in tensile elongation is extremely large. However, it was difficult to use as an industrial material.

As described above, various inorganic fillers have been proposed for the purpose of improving the strength and rigidity of polyamide, but in the prior art, the toughness, that is, the tensile elongation is remarkably lowered, and in reality, the The application was limited and was not entirely satisfactory. Therefore, a polyamide resin composition containing an inorganic filler that improves rigidity and strength without causing a decrease in toughness has been expected.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyamide resin composition having high strength and rigidity and excellent toughness, which can solve the above problems.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention blended a polyamide raw material and a raw material of an apatite type compound, and polymerized the polyamide to obtain the above-mentioned problems. It was found that a polyamide composition capable of solving the above problem can be obtained, and the present invention has been completed.

That is, according to the present invention, (1) a polyamide raw material of 50 to 99.5% by weight and an apatite-type compound raw material of 0.
A method for producing a polyamide resin composition, which comprises blending 5 to 50% by weight and polymerizing a polyamide, (2)
The method for producing a polyamide resin composition according to (1) above, wherein the ratio of the metal element of the apatite type compound raw material to phosphorus is 1.1 to 10.0 in terms of molar ratio,
(3) The method for producing a polyamide resin composition according to (1) above, wherein the apatite-type compound raw material is a mixture of a phosphoric acid-based metal compound and a non-phosphoric acid-based metal compound, (4) metal The method for producing a polyamide resin composition according to the above (2) or (3), wherein the element is one or more elements of Group 2A of the Periodic Table of Elements.
(5) The production of the polyamide resin composition according to the above (3), wherein the non-phosphoric acid type metal compound is one or more kinds of metal hydroxide, metal fluoride, metal chloride and metal carbonate. Method (6): 50 to 99.5% by weight of polyamide raw material and 0.5 to 50% by weight of apatite type compound raw material are blended to synthesize an apatite type compound and simultaneously polymerize polyamide. (2) ~
The method for producing a polyamide resin composition according to any one of (5).

The present invention will be described in detail below. The polyamide of the present invention means an amide bond (-NHC) in the main chain.
It is a polymer having O-). Preferred as the polyamide of the present invention is polycaprolactam (nylon 6),
Polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (Nylon 116), Polyundecalactam (Nylon 11), Polydodecalactam (Nylon 12), Polytrimethylhexamethylene terephthalamide (Nylon TMHT), Polyhexamethylene isophthalamide (Nylon 6I), Polynonane methylene terephthalamide (9T ), Polyhexamethylene terephthalamide (6T), polybis (4-aminocyclohexyl) methandodecamide (nylon PACM12), polybis (3-methyl-aminocyclohexyl) methandodecamide (nylon) Methyl PACM12), poly-m-xylylene adipamide (nylon MXD6), polyundecamethylene methylene hexahydroterephthalic (nylon 1
1T (H)) and polyamide copolymers containing at least two different polyamide-forming components, and mixtures thereof.

Examples of the raw material of the polyamide include amino acids, lactams or salts of diamine and dicarboxylic acid, and oligomers thereof. Examples of amino acids include 6-aminocaproic acid and 11-amino acid.
Amino undecanoic acid, 12-amino dodecanoic acid, para-aminomethyl benzoic acid, etc. can be mentioned. In the present invention, these polymerizable amino acids may be used alone or in combination of two or more.

Examples of the lactam include butyllactam, pivalolalactam, caprolactam, capryllactam, enanthlactam, undecanolactam and dodecanolactam. In the present invention, these polymerizable lactams may be used alone or in combination of two or more. As a diamine,
For example, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, nonanemethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine. , 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine,
Paraxylylenediamine, 1,3-bis (aminemethyl) cyclohexane, 3,8-bis (aminomethyl) tricyclodecane, 1-amino-3-aminomethyl-3,
5,5, -Trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl)
Examples thereof include piperazine and aminoethylpiperazine. In the present invention, these polymerizable diamines may be used alone or in combination of two or more.

Examples of the dicarboxylic acid include malonic acid,
Dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid , Dodecanedioic acid, eicodioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydro Examples thereof include terephthalic acid and diglycolic acid. In the present invention, these polymerizable dicarboxylic acids may be used alone.
You may use it in combination of 2 or more types.

An end-capping agent may be added to the raw material of the polyamide of the present invention in order to control the molecular weight or improve hot water resistance. The endcapping agent is preferably monocarboxylic acid or monoamine. Other examples include acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters and monoalcohols.

The monocarboxylic acid that can be used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid,
Aliphatic monocarboxylic acids such as pivalic acid and isobutyric acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid And the like, such as aromatic monocarboxylic acid. In the present invention, these monocarboxylic acids may be used alone or in combination of two or more.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine,
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine, cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine, aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine Can be mentioned. In the present invention, these monoamines may be used alone or in combination of two or more.

The apatite type compound of the present invention is represented by the following general formula. A _10-z (HPO ₄ ) _z (PO ₄ ) _6-z (X) _2-z where 0 ≦ z <2, A is a metal element, and X is an anion or an anionic compound. Preferred metal elements A are 1A, 2A, 3A, 4A, 5 of the Periodic Table of the Elements.
Mention may be made of elements A, 6A, 7A, 8, 1B, 2B, 3B and tin, lead. These metal elements may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a Group 2A element such as magnesium, calcium, strontium, barium, or a mixture of two or more thereof, from the viewpoints of economy, safety and characteristics of the obtained resin composition. .

Examples of the anion and anionic compound represented by X in the above general formula include hydroxyl group (OH), fluorine (F), chlorine (Cl) and the like. These anionic elements and anionic compounds may be used alone or in combination of two or more. Further, in the present invention,
Carbonate-containing apatite in which a part of phosphate ion (PO ₄ ) and / or X in the general formula is replaced with carbonic acid (CO ₃ ) can also be used.

In the present invention, among the apatite type compounds, hydroxyapatite (X is a hydroxyl group) whose metal element is calcium, fluoroapatite (X is fluorine), chlorine apatite (X is chlorine), carbonic acid-containing hydroxide. Apatite,
Carbonate-containing fluoroapatite, Carbonate-containing chlorine apatite,
Furthermore, mixtures of these are most preferably used.
Examples of the raw material for the apatite-type compound include a phosphoric acid-based metal compound and a mixture of a phosphoric acid-based metal compound and a non-phosphoric acid-based metal compound. It is more preferable to use a mixture of a non-phosphate metal compound. In particular, the phosphoric acid-based metal compound and non-phosphoric acid having a molar ratio of the metal element to phosphorus of 1.1 to 10.0, preferably 1.2 to 5.0, and more preferably 1.3 to 2.5. Most preferably, a mixture of metal compounds is used. The molar ratio between the metal element and phosphorus can be calculated from the weight of the apatite-type compound raw material to be blended and its molecular weight. This ratio is 1.1
If it is less than the above range, it may be difficult to obtain a high-molecular-weight polyamide, and there may occur problems such as coloring of the reactor during the polymerization, foaming and inclusion of bubbles during the extrusion or molding process. On the other hand, if this ratio exceeds 10.0, the deterioration in toughness will be significantly increased.

As the phosphoric acid type of the phosphoric acid type metal compound,
Orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaline
Acid, phosphorous acid, hypophosphorous acid, etc. can be mentioned.
Calcium monohydrogen phosphate as a phosphoric metal compound
(CaHPO_Four), Calcium monohydrogen phosphate dihydrate
(CaHPO_Four・ 2H₂O), calcium dihydrogen phosphate
(CaH₂P₂O₇), Calcium dihydrogen phosphate monohydrate
(Ca (H₂PO_Four)₂・ H₂O), calcium diphosphate
(Α- and β-Ca₂P₂O₇), Tricalcium phosphate
(Α- and β-Ca₃(PO_Four)₂), Tetracalcium phosphate
Umm (Ca_Four(PO_Four)₂O), octacalcium phosphate pentahydrate
Japanese (Ca₈H₂(PO_Four)₆・ 5H₂O), calcium phosphite
Cium monohydrate (CaHPO₃・ H₂O), hypophosphorous acid
Lucium (Ca (H₂PO₂)₂), Magnesium phosphate
Secondary trihydrate (MgHPO_Four・ 3H₂O), phosphate mug
Nesium third octahydrate (Mg₃(PO_Four)₂・ 8H
₂O), barium phosphate second (BaHPO_Four) Etc.
You can Among these, is it more economical?
In the present invention, calcium monohydrogen phosphate (CaHPO
_Four) And calcium monohydrogen phosphate dihydrate (CaHP
O_Four・ 2H₂O) is particularly preferably used. These raw
The materials may be used alone or in combination of two or more.
You may stay. When combining two or more, for example,
For example, calcium monohydrogen phosphate dihydrate (CaHPO_Four・
2H₂O) and calcium dihydrogen diphosphate (CaH₂P
₂O₇) And are used to contain raw materials containing similar metal elements.
Combination of ingredients and calcium monohydrogen phosphate dihydrate
(CaHPO_Four・ 2H₂O) and magnesium phosphate second
Trihydrate (MgHPO_Four・ 3H₂O) and
Examples include combinations of raw materials containing different metal elements
However, either is acceptable.

As a method for synthesizing the phosphoric acid metal compound,
Taking calcium monohydrogen phosphate and its hydrate as an example, Phosphorus and its Comp
Vans described in Sounds, 1 (1958)
As the _{CaO-H 2 O-P 2} O 5 system phase diagram of the by Wazer, the presence of water, can be obtained by mixing the phosphoric acid compound and a calcium compound. For example,
An alkali phosphate solution and a calcium chloride solution may be added dropwise to the potassium dihydrogen phosphate solution and reacted at about 100 ° C. for synthesis, or a method of mixing calcium carbonate or calcium hydroxide with an aqueous phosphoric acid solution may be used.

By the way, the inventors of the present invention can obtain the same effect as the present invention by using a compound consisting of arsenic (As) or vanadium (V), that is, arsenate or vanadate instead of the phosphoric acid. It is estimated that it will be obtained. However, in the present invention, it is most preferable to use the phosphoric acid type because it is excellent in stability of the compound, availability of raw materials, and safety.

The non-phosphoric acid type metal compound in the present invention is not particularly limited as long as it forms a compound with a metal element other than the phosphoric acid type, and metal hydroxides (calcium hydroxide, magnesium hydroxide, water Strontium oxide, barium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, etc., metal chlorides (calcium chloride, magnesium chloride, strontium chloride, barium chloride, lithium chloride, sodium chloride,
Potassium chloride, aluminum chloride, etc.), metal fluoride (calcium fluoride, magnesium fluoride, barium fluoride, strontium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, aluminum fluoride, etc.), metal bromide (odor Calcium iodide), metal iodide (calcium iodide, etc.), metal carbide (calcium carbide, etc.), metal oxide (calcium oxide, etc.), metal carbonate (calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, lithium carbonate) , Sodium carbonate, potassium carbonate, aluminum carbonate, etc.), inorganic metal compounds such as metal sulfates (calcium sulfate etc.), metal nitrates (calcium nitrate etc.), metal silicates (calcium silicate etc.) and metal elements Compounds with monocarboxylic acids (calcium acetate Beam, calcium benzoate, calcium stearate, etc.), a compound of a metal element and a dicarboxylic acid (calcium oxalate, tartaric acid, calcium), compounds of a metal element and the tricarboxylic acid (calcium citrate, etc.) and the like. These raw materials may be used alone or in combination of two or more. When two or more kinds are combined, for example, like a mixture of calcium hydroxide and calcium carbonate,
A compound containing the same kind of metal element may be combined, or a compound containing different kinds of metal elements may be combined, such as a mixture of calcium carbonate and magnesium hydroxide. In the present invention, among these compounds, metal hydroxides, metal fluorides, metal chlorides and metal carbonates, or a mixture thereof are preferably used because they are more economical and physical properties. In particular, hydroxides, fluorides, chlorides and carbonates of 2A group elements calcium, magnesium, strontium and barium, or a mixture thereof are more preferable, and among them, hydroxides, fluorides, chlorides and carbonates of calcium are preferable. Most preferably, a salt or a mixture thereof is used.

The phosphoric acid type metal compound or non-phosphoric acid type metal compound which is the raw material for the apatite type compound of the present invention has an average particle size of 100 μm or less, preferably 50 μm or less, more preferably 25 μm or less. good. The average particle diameter may be measured by a method of deriving a raw material dispersed in pure water using a laser diffraction / scattering type particle size distribution device or the like.

The compounding amount of the apatite type compound raw material of the present invention is 0.5 to 50% by weight. When the compounding amount of the apatite-type compound raw material is less than 0.5% by weight, the rigidity and strength of the obtained polyamide resin composition are not significantly improved, while when it exceeds 50% by weight, extrusion or molding is performed. Problems occur. In the polymerization method of the present invention, it is preferable that the polyamide raw material and the apatite type compound raw material are first mixed and then the polyamide is polymerized.

The polyamide raw material and the apatite type compound raw material may be blended by directly mixing the solid polyamide raw material and the apatite type compound raw material, the polyamide raw material aqueous solution and the apatite type compound raw material aqueous solution or suspension. May be used. In the present invention, the method for polymerizing the polyamide is not particularly limited, and a known method can be used. For example, 11-
Made from ingredients that are poorly soluble in water, such as aminoundecanoic acid,
A method of polycondensation by heating at 200 to 290 ° C., using an ε-caprolactam aqueous solution as a raw material, adding a terminal blocking agent such as a monocarboxylic acid or a reaction accelerator such as ε-aminocaproic acid, if necessary, and an inert gas. , A ring-opening polycondensation method of lactams in which polycondensation is carried out by heating to 200 to 290 ° C., a salt aqueous solution of a diamine component such as an aqueous solution of hexamethylene adipamide and a dicarboxylic acid component is used as a raw material, and 200 to 290 ° C. It is possible to use a hot-melt polycondensation method or the like in which the polycondensation is carried out by condensing by heating and condensing and maintaining the generated water vapor pressure at an appropriate pressure between 10 and 20 atm, and finally releasing the pressure to carry out polycondensation under normal pressure or reduced pressure. . Furthermore, a solid-state polymerization method performed at a temperature below the melting point of a solid salt or polycondensate of a diamine component and a dicarboxylic acid component, a solution method of polycondensing a dicarboxylic acid halide component and a diamine component in a solution, and the like can also be used. You can These methods may be combined if necessary. The polymerization form may be batch type or continuous type. The polymerization apparatus is also not particularly limited, and known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader can be used.

The polyamide resin composition obtained by the production method of the present invention comprises polyamide and an apatite type compound, and is characterized in that the interface between the polyamide and the apatite type compound is extremely well fixed and adhered. For example, when hydroxyapatite is taken as an example, synthesis of an apatite-type compound is generally carried out by a wet method in which calcium hydroxide and phosphoric acid are reacted in an aqueous solution of about PH8, and calcium monohydrogen phosphate is used. A hydrothermal method or the like, which is performed under conditions of high temperature and high pressure of 200 ° C. and 15 atmospheres, is used, and the synthesis conditions of this apatite type compound are very similar to the polymerization conditions of polyamide. The present inventors have paid attention to this point. That is, the present invention also synthesizes the apatite type compound at any stage of the polyamide polymerization process. In the present invention, in particular, it is preferable to carry out the polymerization of the polyamide and the synthesis of the apatite type compound almost at the same time, and by doing so, between the polyamide to be polymerized and the apatite type compound to be synthesized, both, Physical,
A chemical interaction occurs, and the polyamide is incorporated and reacted inside and on the surface of the apatite-type compound particles, whereby the apatite-type compound grafted with the polyamide can be synthesized. As a result, the interface between the polyamide and the apatite-type compound is surprisingly satisfactorily fixed and adhered.

Specifically, the polyamide resin composition obtained by the production method of the present invention has a content of the apatite type compound of 0.5 to 50% by weight, and the ratio of the metal element of the apatite type compound to phosphorus. Is 1.1-10.
0 and the grafted polyamide is present in the apatite type compound in the composition, and the amount of the grafted polyamide is 3 to 100 parts by weight of the apatite type compound.
The polyamide resin composition is 100 parts by weight. Grafted polyamide present in the apatite-type compound in the present invention, the polyamide resin composition is immersed in a polyamide-soluble solvent such as phenol, after the polyamide is sufficiently eluted to deposit the apatite-type compound, it is eluted in the solvent It refers to an organic substance containing polyamide as a main component which remains in the apatite type compound without being present. By the presence of a specific amount of this grafted polyamide, the polyamide and the apatite type compound are surprisingly excellently adhered and adhered. Of.

The polyamide in the polyamide resin composition obtained by the production method of the present invention has a number average molecular weight (Mn) which is excellent in moldability and physical properties.
Then, 10,000 to 1,000,000 are preferable, and those in the range of 20,000 to 200,000 are particularly preferable. The number average molecular weight can be measured, for example, by using hexafluoroisopropanol (HF) as a solvent.
IP), using polymethylmethacrylate (PMMA) as a molecular weight standard sample, it can be determined by gel permeation chromatography (GPC).

Confirmation of formation of the apatite type compound in the polyamide resin composition obtained by the production method of the present invention is as follows.
For example, a method of directly confirming with wide-angle X-ray diffraction using pellets or molded products, or by immersing the pellets or molded products in a solvent in which polyamide such as phenol is soluble to remove the polyamide resin, the remaining components are wide-angled. A method such as confirmation by X-ray diffraction or infrared absorption spectrum may be used. Wide angle X
In the case of line diffraction, taking hydroxyapatite whose metallic element is calcium as an example, it is observed at 2θ of about 25.9, 31.7 and 32.6 (degrees) (002), (21).
The presence of peaks due to the 1) and (300) planes confirms the formation of apatite.

The content of the apatite type compound is 0.5 to
It is 50% by weight, preferably 2.5-40% by weight, more preferably 5-30% by weight. The content of the apatite-type compound is, for example, JIS R
Ignition loss (Ig.loss) is measured according to 3420 and can be determined from the weight loss. Specifically, after thoroughly drying the polyamide resin composition, about 1 g was weighed in a platinum dish, ashed in an electric furnace at 650 ± 20 ° C., cooled, and then weighed to determine the content of the apatite-type compound. Quantify.

The ratio of the metal element of the apatite type compound to phosphorus is 1.1 to 10.0, preferably 1.
2 to 5.0, more preferably 1.3 to 2.5. Specifically, the quantitative determination of the metal element will be described in the case of using calcium as the metal element. 0.5 g of the polyamide resin composition is weighed in a platinum dish and carbonized in a 500 ° C. electric furnace. After cooling, 5 ml of hydrochloric acid and 5 ml of pure water are added and the mixture is boiled and dissolved on a heater. Cool again and add pure water to 50
The volume is set to 0 ml and quantified at a wavelength of 317.933 nm by high frequency inductively coupled plasma (ICP) emission analysis. For other metallic elements, by selecting the characteristic wavelength,
It can be quantified by the same method. On the other hand, the amount of phosphorus is determined by weighing 0.5 g of the polyamide resin composition, adding 20 ml of concentrated sulfuric acid, wet decomposing on a heater, cooling, and then measuring 5 m of hydrogen peroxide.
Add 1 liter, heat on a heater and concentrate until the total volume is 2-3 ml. Cool it again, bring it to 500 ml with pure water,
It is quantified at a wavelength of 213.618 (nm) by high frequency inductively coupled plasma (ICP) emission analysis. The molar ratio between the metal element and phosphorus can be calculated based on the quantitative result thus obtained.

Grafting present in apatite type compounds
Polyamide is per 100 parts by weight of apatite type compound
3 to 100 parts by weight, preferably 3.5 to 75 parts by weight,
It is preferably 4 to 50 parts by weight. Grafted poly
The presence of amide can be confirmed by infrared absorption spectrum and thermal decomposition gas.
It can be performed by chromatography. concrete
The amount of this grafted polyamide is determined as follows.
Do it like this. First, weigh 10 g of polyamide resin composition
Weigh and mix with 200 ml of 90% phenol at 40 ° C
Stir for 2 hours, separate using a centrifuge,
Remove the clear solvent. Add another 200 ml of phenol
In addition, the same dissolution operation and separation operation using a centrifuge
Repeat the work 4 times. Continued, 99.5% ethanol
200 ml, and stir at 23 ° C for 2 hours, centrifuge
Separation operation is performed using a separator to remove the supernatant solvent.
After repeating this operation four more times,
It is dried at 0 ° C. for 12 hours to obtain an apatite type compound. Profit
Weigh 5 to 15 mg of the obtained apatite type compound, and
The amount of grafted polyamide can be measured with a quantitative analysis (TGA) device.
You can ask. The temperature condition is from 30 ° C to 5
Raise the temperature to 00 ° C at 99.9 ° C / min, and then increase to 1 at 500 ° C.
Hold for time. Initial weight at 30 ° C (W ₀) And 5
Final weight (W₁) Is used
Can be calculated by the following formula. Amount of grafted polyamide (parts by weight / apatite) = (W
₀-W₁) × 100 / W₁ In the polyamide resin composition obtained by the production method of the present invention
Is usually within a range not impairing the object of the present invention, if necessary.
Fillers used in polyamide resins such as glass fiber
Inorganic fibers such as fiber and carbon fiber, mica, talc, clay ore
Substances, inorganic fillers such as alumina and silica, ammonium trioxide
Zimon, aluminum hydroxide, magnesium hydroxide, e
Zinc oxalate, zinc stannate, zinc hydroxystannate, poly
Ammonium acid salt, melamine cyanurate, succinogua
Namin, melamine polyphosphate, melamine sulfate, phthalic acid
Melamine, aromatic polyphosphate, composite glass powder
Flame retardants such as powder, pigments and colorants such as titanium white,
Heat represented by sodium phosphite and hindered phenol
Stabilizers, lubricants such as stearic acid and paraffin wax
Agents, various plasticizers, weather resistance improvers, antistatic agents, etc.
Seed additives can be added.

Further, if necessary, a thermoplastic resin or elastomer usually blended with a polyamide resin within a range not impairing the object of the present invention, such as polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-
Propylene copolymer, ethylene-propylene-diene copolymer, natural rubber and acid-modified products of these with maleic anhydride, styrene-maleic anhydride copolymer, styrene-phenylmaleimide copolymer, polyethylene,
Polypropylene, butadiene-acrylonitrile copolymer, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, other polyamide resins, aromatic polyester resins, polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, epoxy resins and the like may be added.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the examples below. The physical properties were evaluated by the following methods. 1. Properties of Polyamide and Apatite-Type Compound Raw Material (1-1) Content of Apatite-Type Compound Raw Material (% by Weight) It was calculated from the blending amounts of the polyamide raw material and the apatite-type compound raw material. (1-2) Molar ratio of metal element to phosphorus of apatite type compound raw material The molar ratio of metal element to phosphorus was calculated from the compounding amount of the apatite type compound raw material and its molecular weight. 2. Observation of colored state during polymerization A mirror-finished SUS304 test piece was put together with the raw material, and the surface state of the test piece after the polymerization was visually observed. 3. Characteristic (3-1) Number average molecular weight (Mn) of the obtained polyamide resin composition It was determined by gel permeation chromatography (GPC). The device is HLC-8020 manufactured by Tosoh Corporation, the detector is a differential refractometer (RI), the solvent is hexafluoroisopropanol (HFIP), and the column is TS manufactured by Tosoh Corporation.
Two Kgel-GMHHR-H and one G1000HHR were used. The solvent flow rate was 0.6 ml / min, the sample concentration was 1 to 3 (mg sample) / 1 (ml solvent), and the insoluble matter was removed by filtration with a filter to obtain a measurement sample. The number average molecular weight was calculated by polymethylmethacrylate (PMMA) conversion based on the obtained elution curve. (3-2) Quantification of content of apatite type compound (% by weight) The polyamide resin composition is dried at 100 ± 20 ° C for 8 hours and cooled. 1 g of the composition is weighed in a platinum dish and 650 ± 20
After ashing in an electric furnace at ℃, after cooling, the weight was weighed to quantify the content of the apatite type compound. (3-3) Molar Ratio of Metal Element to Phosphorus (a) Quantification of Metal Element: Hereinafter, the case where calcium is used as the metal element will be described, but other metal elements can be similarly determined. 0.5 g of the polyamide resin composition is weighed in a platinum dish and carbonized in an electric furnace at 500 ° C. After cooling, 5 ml of hydrochloric acid and 5 ml of pure water are added and the mixture is boiled and dissolved on a heater. Cool again, add pure water, 500m
It was set to l. The device is Thermo Jarrell As
Quantification was performed at a wavelength of 317.933 nm by high frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by h. (B) Quantification of phosphorus: 0.5 g of the polyamide resin composition was weighed, 20 ml of concentrated sulfuric acid was added, and wet decomposition was performed on a heater. After cooling, 5 ml of hydrogen peroxide was added, and the mixture was heated on a heater and concentrated until the total amount became 2-3 ml. It was cooled again and made up to 500 ml with pure water. The device is Thermo J
Using IRIS / IP manufactured by arrell Ash, high-frequency inductively coupled plasma (ICP) emission analysis was performed to obtain a wavelength of 2
It quantified at 13.618 (nm). (3-4) Amount of grafted polyamide (parts by weight / apatite) (a) Separation operation of apatite-type compound: 10 g of polyamide resin composition was weighed, mixed with 200 ml of 90% phenol, and stirred at 40 ° C. for 2 hours, Using a centrifuge [H103N manufactured by Kokusan Co., Ltd.], separation operation was performed at 3500 rpm for 1 hour to remove the supernatant solvent. 2 more
00 ml of phenol was added, and thereafter, the same dissolution operation and separation operation using a centrifugal separator were repeated 4 times. Then, add 200 ml of 99.5% ethanol, and add 23
Stir for 2 hours at ℃, use a centrifuge to 3500 rpm
The separation operation is performed for 1 hour to remove the supernatant solvent. After repeating this operation four more times,
It was dried at ℃ for 12 hours to obtain the desired apatite type compound. (B) Quantification of grafted polyamide amount: 5 to 15 mg of the obtained apatite-type compound was weighed, and thermogravimetric analysis (T
The amount of grafted polyamide was determined with a (GA) device. The equipment is Shimadzu TGA-50, and the temperature condition is 3
After raising the temperature from 0 ℃ to 500 ℃ at 99.9 ℃ / min, 5
Hold at 00 ° C for 1 hour. Initial weight at 30 ° C (W
₀ ) and the final weight (W ₁ ) after holding at 500 ° C. for 1 hour
Was used to calculate the amount of grafted polyamide by the following formula. Amount of grafted polyamide (parts by weight / apatite) = (W
₀ −W ₁ ) × 100 / W ₁ (3-5) Confirmation of formation of apatite-type compound by X-ray diffraction The X-ray diffraction of the apatite-type compound obtained in (a) of (3-4) was measured. The measurement conditions are as follows. X-ray: Copper Kα Wave number: 1.542Å Tube voltage: 40 KV Tube current: 200 mA Scanning speed: 4 deg. / Min Divergence slit: 1 deg. Scattering slit: 1 deg. Light receiving slit: 0.15 mm (3-6) Preparation of injection molded product A molded product was prepared using an injection molding machine. The apparatus was PS40E manufactured by Nissei Plastic Co., Ltd., the cylinder temperature was 280 ° C., the mold temperature was 80 ° C., and the cycle was 17 seconds for injection and 20 seconds for cooling. (3-7) Flexural modulus and flexural strength (Kg / cm ² ) The flexural modulus and flexural strength were measured according to ASTM D790. (3-8) Tensile Strength (Kg / cm ² ) and Tensile Elongation (%) The tensile strength (Kg / cm ² ) was measured according to ASTM D638.

[0033]

EXAMPLE 1 1.5 kg of equimolar solid salt of adipic acid and hexamethylenediamine, 1.5 kg of pure water, calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O) 150
g, calcium carbonate suspended in 200 g of pure water (CaC
58 g of O ₃ ) was placed in a 5 L autoclave and well stirred. After that, mirror-finished SUS for coloring evaluation
A 304 test piece was put in. The content of the apatite-type compound raw material was calculated to be 12.2 (% by weight), and the molar ratio of the metal element and phosphorus was calculated to be 1.66. After sufficiently replacing with nitrogen, the temperature was raised from room temperature to 220 ° C. At this time, the pressure inside the autoclave is 18 Kg / c as a gauge pressure.
Heating was continued for 1 hour while removing water to the outside of the system so that the pressure became 18 kg / cm ² or more although the pressure became m ² . After that, stop heating, cool to room temperature, open the autoclave,
About 1.5 Kg of polymer was taken out and pulverized by a pulverizer. No coloring was observed on the surface of the SUS304 test piece for coloring evaluation taken out at the same time. The obtained pulverized polymer was charged into a 5 L autoclave and sufficiently replaced with nitrogen, and then the pressure was set to a gauge pressure and set to 5 kg / cm ² .
The temperature was raised from room temperature to 240 ° C., and the state was maintained for 4 hours. In this series of operations, the pressure was adjusted so that the pressure did not exceed 5 Kg / cm ² , and the produced water was removed by the partial condenser. After cooling, open the autoclave,
The polymer was taken out and dried in a nitrogen stream at 80 ° C. for 24 hours. The obtained polymer was pelletized using a small twin-screw extruder (Labo Plastomill ME type manufactured by Toyo Seiki Co., Ltd.) under conditions of a cylinder temperature of 280 ° C., a screw rotation speed of 70 rpm, and an extrusion rate of 4 Kg / hr. The obtained pellets were dried in a nitrogen stream at 80 ° C. for 24 hours. The number average molecular weight (Mn) of the obtained pellets was 43,000. From the result of measurement by ashing, the content of the apatite type compound was 10.2 (% by weight). Calcium (Ca) by high frequency inductively coupled plasma (ICP) emission spectrometry
As a result of quantification of phosphorus and phosphorus, the molar ratio was calculated to be 1.67. The X-ray diffraction result of the apatite type compound obtained by the separation operation is shown in FIG. From this figure, formation of apatite type compound can be confirmed. The amount of grafted polyamide of the apatite-type compound obtained by the separation operation was 4.5 (parts by weight / apatite) as a result of thermogravimetric analysis (TGA). Injection molding could be performed very stably without any problems. Table 1 shows the results of measuring the physical properties of the obtained molded product.

[0034]

[Example 2] 3.0 Kg of equimolar solid salt of adipic acid and hexamethylenediamine and 200 g of calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O) were well stirred with a Henschel mixer and placed in a 5 L autoclave. I put it in. After that, mirror-finished SUS304 for coloring evaluation
A test piece was put in. The content of the apatite-type compound raw material was calculated to be 6.3 (% by weight), and the molar ratio of the metal element and phosphorus was calculated to be 1.00. After sufficiently purging with nitrogen, the pressure was set to a gauge pressure of 5 Kg / cm ² , the temperature was raised from room temperature to 190 ° C., and the state was maintained for 2 hours. At this time, the pressure inside the autoclave should be 15 gauge pressure.
It becomes Kg / cm ² . Subsequently, the pressure was reduced to 5 Kg / cm ² , the temperature was raised to 240 ° C., and the state was maintained for 4 hours. In this series of operations, the pressure was 5 Kg / cm ²
The pressure was adjusted so as not to exceed the above, and the produced water was removed by a partial condenser. After cooling, the autoclave was opened, and the polymer was taken out and pulverized. A part of the surface of the SUS304 test piece for color evaluation that was taken out at the same time was observed to have a part colored in brown. The crushed polymer was dried in a nitrogen stream at 80 ° C. for 24 hours. Then, using a small twin-screw extruder (Labo Plastomill ME type manufactured by Toyo Seiki Co., Ltd.), a cylinder temperature of 280 ° C. and a screw rotation speed of 70 r
Pelletized under the conditions of pm and extrusion rate of 4 kg / hr. The obtained pellets were dried in a nitrogen stream at 80 ° C. for 24 hours. The number average molecular weight (Mn) of the obtained pellets was 60,000. From the result of measurement by ashing, the content of apatite was 5.2 (% by weight). Calcium (C) by high frequency inductively coupled plasma (ICP) emission spectrometry
As a result of quantification of a) and phosphorus (P), the molar ratio was 1.01.
Was calculated. The X-ray diffraction result of the apatite type compound obtained by the separation operation is shown in FIG. From this figure, formation of apatite type compound can be confirmed. The amount of grafted polyamide of the apatite-type compound obtained by the separation operation was 5.0 (parts by weight / apatite) as a result of thermogravimetric analysis (TGA). During injection molding, it was easy for air bubbles to enter the molded product. Therefore, by visually observing the molded articles free of air bubbles, the physical properties were evaluated. The results are shown in Table 1.

[0035]

Example 3 1.2 kg of equimolar solid salt of adipic acid and hexamethylenediamine, 1.2 kg of pure water, calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O) 300
g, calcium carbonate suspended in 500 g of pure water (CaC
O ₃ ) 60 g and barium carbonate (BaCO ₃ ) 109 g
Was charged in a 5 L autoclave and well stirred. The content of the apatite raw material was 28.1 (% by weight), and the molar ratio of the metal element and phosphorus was calculated to be 1.66. The subsequent polymerization operation, extrusion operation and polymerization operation were performed in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained pellets was 35,000. The content of apatite was 25.3 (% by weight) based on the measurement result by ashing. As a result of quantitative determination of calcium (Ca), barium (Ba) and phosphorus (P) by high frequency inductively coupled plasma (ICP) emission analysis, the molar ratio of metal element and phosphorus was calculated to be 1.67. The amount of grafted polyamide of the apatite-type compound obtained by the separation operation was 4.2 (parts by weight / apatite) as a result of thermogravimetric analysis (TGA). Injection molding could be performed very stably without any problems. Table 1 shows the results of measuring the physical properties of the obtained molded product.

[0036]

Comparative Example 1 1.5 Kg of equimolar solid salt of adipic acid and hexamethylene diamine, 1.5 Kg of pure water, and 300 g of hydroxyapatite manufactured by Taihei Chemical Industry Co., Ltd. were charged in a 5 L autoclave and well stirred. Then, a mirror-finished SUS304 test piece for coloring evaluation was put in. The content of the apatite-type compound raw material was calculated to be 16.7 (wt%), and the molar ratio of the metal element and phosphorus was calculated to be 1.66. The subsequent polymerization operation, extrusion operation and drying operation were performed in the same manner as in Example 1. After the first-stage polymerization, no coloring was observed on the surface of the taken out SUS304 test piece for color evaluation. The number average molecular weight (Mn) was 32,000. From the measurement result by ashing, the content of the apatite type compound was 20.5 (% by weight). As a result of quantification of calcium (Ca) and phosphorus (P) by high frequency inductively coupled plasma (ICP) emission spectrometry, the molar ratio was calculated to be 1.66. The X-ray diffraction result of the apatite type compound obtained by the separation operation is shown in FIG. The amount of grafted polyamide of the apatite-type compound obtained by the separation operation was 2.5 (parts by weight / apatite) as a result of thermogravimetric analysis (TGA).
Met. Table 1 shows the results of measuring the physical properties of the obtained molded product.

[0037]

Comparative Example 2 0.7 Kg of equimolar solid salt of adipic acid and hexamethylene diamine, 0.7 Kg of pure water, calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O) 1050
g, calcium carbonate suspended in 1000 g of pure water (Ca
407 g of CO ₃ ) was charged into a 5 L autoclave and well stirred. The content of apatite type raw material is 67.5
(Wt%), the ratio of metal element to phosphorus is 1.
Calculated as 66. The subsequent polymerization operation was performed in the same manner as in Example 1. An attempt was made to pelletize the resulting polymerized polymer using an extruder, but it could not be done. When the polymerized polymer was pulverized and evaluated, the number average molecular weight (Mn) was 15
It was 000. The content of apatite was 63.8 (% by weight) from the measurement result by ashing. Calcium (C) by high frequency inductively coupled plasma (ICP) emission spectrometry
As a result of quantification of a) and phosphorus (P), the molar ratio was 1.67.
Was calculated. The amount of grafted polyamide of apatite obtained by the separation operation was 3.5 (parts by weight / apatite) as a result of thermogravimetric analysis (TGA). An attempt was made to mold using the crushed polymer, but molding failed.

[0038]

Comparative Example 3 1.5 Kg of equimolar solid salt of adipic acid and hexamethylene diamine, 1.5 Kg of pure water, 50 g of calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O),
Calcium carbonate suspended in 500 g of pure water (CaC
300 g of O ₃ ) was placed in a 5 L autoclave and well stirred. The content of the apatite-type compound raw material is 18.
9 (wt%), the molar ratio of metal element to phosphorus is 1
Calculated as 1.3. The subsequent polymerization operation, extrusion operation and drying operation were performed in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained pellets was 25,000.
From the result of measurement by ashing, the content of apatite was 16.
It was 5 (% by weight). High frequency inductively coupled plasma (IC
As a result of quantification of calcium (Ca) and phosphorus (P) by P) emission analysis, the molar ratio was calculated to be 11.5. The amount of grafted polyamide of the apatite-type compound obtained by the separation operation was 3.1 as a result of thermogravimetric analysis (TGA).
(Parts by weight / apatite). Table 1 shows the results of measuring the physical properties of the obtained molded product.

[0039]

Comparative Example 4 3.0 Kg of equimolar solid salt of adipic acid and hexamethylene diamine and 10.5 g of calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O) were well stirred with a Henschel mixer and 5 L Charged in the autoclave. The content of the apatite-type compound raw material was calculated to be 0.35 (% by weight), and the molar ratio of the metal element to phosphorus was calculated to be 1.00. The subsequent polymerization operation, extrusion operation and drying operation were performed in the same manner as in Example 2. The number average molecular weight (Mn) of the obtained pellets was 70,000. The content of apatite was 0.21 (% by weight) from the measurement result by ashing. As a result of quantitative determination of calcium (Ca) and phosphorus (P) by high frequency inductively coupled plasma (ICP) emission analysis, the molar ratio was calculated to be 1.01. The amount of grafted polyamide of the apatite-type compound obtained by the separation operation was 4.8 (parts by weight / weight) as a result of thermogravimetric analysis (TGA).
Apatite). Table 1 shows the results of measuring the physical properties of the obtained molded product.

[0040]

Reference Example 2.0 kg of equimolar solid salt of adipic acid and hexamethylenediamine and 2.0 kg of pure water were charged in a 5 L autoclave. The subsequent polymerization operation, extrusion operation and drying operation were performed in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained pellets was 36000. Table 1 shows the results of measuring the physical properties of the obtained molded product.

As is apparent from Table 1, the polyamide resin composition obtained by the production method of this example according to the present invention is a material having a better balance of elastic modulus, strength and elongation than the comparative example. It can be confirmed that there is.

[0042]

[Table 1]

[0043]

EFFECT OF THE INVENTION The method for producing a polyamide resin composition of the present invention is a method in which a polyamide raw material and an apatite type compound raw material are allowed to coexist, and both are polymerized and synthesized to obtain an apatite type compound having a very strong affinity with polyamide. Including,
A polyamide resin composition comprising a polyamide and an apatite type compound can be obtained. Therefore, according to the present invention, it is possible to stably obtain a polyamide resin composition having a significantly improved balance of rigidity, strength and toughness, and the polyamide resin composition according to the present invention can be used as a mechanical industrial component, an electric / electronic component or the like. It is expected to be very useful as an industrial material for.

[Brief description of drawings]

1 is an X-ray diffraction measurement result of an apatite-type compound separated from the composition of Example 1. FIG.

2 is an X-ray diffraction measurement result of an apatite-type compound separated from the composition of Example 2. FIG.

3 is an X-ray diffraction measurement result of an apatite-type compound separated from the composition of Comparative Example 1. FIG.

4 is an X-ray diffraction measurement result of hydroxyapatite used as a raw material in Comparative Example 1. FIG.

Continued front page    F-term (reference) 4J001 DA01 DB01 DB02 EA02 EA06                       EA07 EA08 EA16 EA17 EB05                       EB06 EB07 EB08 EB09 EB13                       EB14 EB26 EB28 EB36 EB37                       EB46 EC07 EC08 EC09 EC13                       EC14 EC16 EC47 EC48 EE16E                       GA12 JA01                 4J002 CL011 CL031 DH006 GM00                       GQ00

Claims (6)

[Claims] 1. Polyamide raw material 50 to 99.5% by weight
And 0.5 to 50% by weight of the apatite-type compound raw material, and polymerizing the polyamide to produce a polyamide resin composition. 2. The method for producing a polyamide resin composition according to claim 1, wherein the ratio of the metal element of the apatite-type compound raw material to phosphorus is in the range of 1.1 to 10.0 in terms of molar ratio. . 3. The method for producing a polyamide resin composition according to claim 1, wherein the apatite-type compound raw material is a mixture of a phosphoric acid-based metal compound and a non-phosphoric acid-based metal compound. 4. The method for producing a polyamide resin composition according to claim 2, wherein the metal element is one or more elements of Group 2A of the Periodic Table of the Elements. 5. The polyamide resin composition according to claim 3, wherein the non-phosphoric metal compound is one or more of metal hydroxide, metal fluoride, metal chloride and metal carbonate. Production method. 6. Polyamide raw material 50 to 99.5% by weight
And 0.5 to 50% by weight of the apatite-type compound raw material are mixed to synthesize the apatite-type compound and simultaneously polymerize the polyamide, and the polyamide resin according to any one of claims 2 to 5. A method for producing a composition.