JP3356133B2 - Polyamide film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide film, and more particularly, to strength, elastic modulus, gas barrier properties, and the like.
The present invention relates to a polyamide film having excellent pinhole resistance.

[0002]

2. Description of the Related Art Polyamide films are mainly used in the field of food packaging because of their excellent properties such as transparency, pinhole resistance, gas barrier properties, heat resistance and oil resistance.

[0003] The polyamide film, especially nylon 6
Because the film is inferior in gas barrier property under high humidity, water vapor barrier property and rigidity, it is used as a film laminated with polyolefin by means such as co-extrusion or lamination, or using a special aromatic polyamide,
A film in which a layered silicate mineral is finely dispersed and blended with polyamide has been proposed and implemented.

[0004] However, in the lamination method, ethylene-vinyl alcohol copolymer and polyvinylidene chloride, which are excellent in gas barrier properties used for lamination and coating, are expensive. Due to poor stability, the cost of equipment is increased due to the installation of new equipment, etc., and there are many practical problems.

In the case of a polyamide film in which a layered silicate mineral is finely dispersed, a film in which the layered silicate mineral is finely and uniformly dispersed cannot be obtained depending on the kind of polyamide, and the toughness and impact resistance of the film are reduced. Drastically decrease,
In order to uniformly disperse the layered silicate mineral in the polyamide, there is a need for a pretreatment step in which the layered silicate is brought into contact with a swelling agent in advance to increase the layer interval. is there.

[0006]

DISCLOSURE OF THE INVENTION The present invention has excellent gas barrier properties and slipperiness, and has rigidity required for post-processing such as lamination, printing, bag making, and has a pinhole-resistant property. An object is to provide a polyamide film having excellent strength.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems of the present invention, and as a result,
The inventors have found that the above problem can be solved by a polyamide film made of a specific polyamide composition containing a specific amount of an apatite compound, and have completed the present invention.

That is, the present invention relates to (1) an apatite compound containing 70 to 99.9% by weight of a polyamide and an organic substance insoluble in a phenol solvent;
A polyamide film comprising 1 to 30% by weight, wherein the organic substance is 0.5 to 100 parts by weight per 100 parts by weight of the apatite compound; (2) 70 to 99.9% by weight of a polyamide-forming component; Po
Apatite-type compounds can be formed under the polymerization conditions of lamide
And a polyamide resin composition obtained by blending 0.1 to 30% by weight of an apatite-type compound-forming component and advancing a polymerization reaction of a polyamide and a synthesis reaction of an apatite-type compound. ,

(3) The polyamide film according to the above (1), wherein at least a part of the organic substance is a polyamide, and (4) the polyamide has a weight average molecular weight of 1 to 100.
(5) The polyamide film according to (1) or (2), wherein the average particle size of the apatite type compound is 1 μm or less, (6) apatite Molar ratio of the metal element to phosphorus constituting the type compound is 0.9 to 1
The polyamide film according to the above 1 or 2, wherein the polyamide film is 0.0.

(7) ASTM D-3958-81 (2
(8) The polyamide film as described in (1) or ( ² ) above, wherein the oxygen permeability measured under a condition of 3 ° C. and 0% RH is 35 (cc / m ² · 24 hr · atm) or less. The water vapor transmission rate measured according to JIS Z-208 (under conditions of 40 ° C. and 90% RH: cup method) is as follows:
The polyamide film according to 1 or 2, wherein the polyamide film is 150 (g / m ² · 24 hr) or less,

(9) A laminated polyamide film characterized by being a laminate of the polyamide film described in (1) or (2) above and a polymer film other than the above, and (10) an apatite type compound comprising a wide-angle X-ray (CuKα : Wavelength λ =
1.542 °) Diffraction angle (2θ) due to scattering is 25.5 to
1 or 2 above, which is a crystalline apatite compound having a (002) plane peak at 26.5 degrees and a (300) plane peak having a diffraction angle (2θ) of 32.5 to 33.5 degrees. (11) The polyamide film as described in (1) or (2) above, wherein the apatite compound is represented by the following general formula: (A) _10-z (HPO ₄ ) _z (PO ₄ ) _6-z (X) _2-z · nH ₂
O (where 0 ≦ z <2, 0 ≦ n ≦ 16, and A
Is a metal element, and X is an anion or an anion compound. )

(12) The polyamide film as described in (6) above, wherein the metal element is at least one element from Group 2A of the Periodic Table of the Elements. (13) The above-mentioned polyamide film, wherein the metal element is calcium. 6. The polyamide film according to 6,
(14) The above-mentioned item (2), wherein the polyamide-forming component is at least one selected from the group consisting of a polymerizable amino acid, a polymerizable lactam, a polymerizable diamine / dicarboxylate, and an oligomer group of the polymerizable compound. The polyamide film according to claim 2, wherein the component for forming an apatite type compound is a phosphate metal compound or a mixture of a phosphate metal compound and a non-phosphate metal compound. Yes,

(16) The polyamide film as described in (2) above, wherein the molar ratio of the metal element to phosphorus in the apatite type compound-forming component is 0.9 to 10.0.
(17) The polyamide film as described in (15) or (16) above, wherein the metal element of the phosphate metal compound and the non-phosphate metal compound is at least one element of Group 2A of the periodic table. The polyamide film according to the above 15 or 16, wherein the metal element of the acid-based metal compound and the non-phosphate metal compound is calcium.
(19) The polyamide film as described in (2) above, wherein the polymerization reaction of the polyamide and the synthesis reaction of the apatite compound are performed at a temperature of 40 to 300 ° C.

Hereinafter, the present invention will be described in detail. The present invention relates to a polyamide film containing an apatite compound in a polyamide. The polyamide used in the present invention is a polymer having an amide bond (—NHCO—) in the main chain.

Polyamides preferably used in the present invention include polycaprolactam (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and 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 (9
T), polyhexamethylene terephthalamide (6T),
Polybis (4-aminocyclohexyl) methandodecamide (nylon PACM12), polybis (3-methyl-
Aminocyclohexyl) methandodecamide (nylon dimethyl PACM12), polymethaxylylene adipamide (nylon MXD6), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)), and at least two different polyamides Polyamide copolymers containing components, and mixtures thereof.

Among these polyamides, more preferred polyamides for achieving the object of the present invention are polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene dodecamide (nylon 612), Hexamethylene isophthalamide (nylon 6I), and a polyamide copolymer containing at least two different polyamide components among them;
And mixtures thereof.

Examples of the polyamide-forming component (raw material) include a polymerizable amino acid, a polymerizable lactam, a polymerizable diamine / dicarboxylate, and a polymerizable oligomer of the compound.

As the polymerizable amino acid, for example, 6-
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Aminododecanoic acid and p-aminomethylbenzoic acid can be more specifically exemplified. In the present invention, these polymerizable amino acids may be used alone or in combination of two or more.

Examples of the polymerizable lactam include butyl lactam, pivalolactam, caprolactam, caprylactam, enantholactam, undecanolactam,
Dodecanolactam and the like can be more specifically mentioned. In the present invention, these polymerizable lactams may be used alone or in combination of two or more.

Examples of the diamine of the polymerizable diamine dicarboxylate include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, nonamethylene diamine, 2,2,4 -Trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-
Bis (aminomethyl) 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) piperazine, aminoethylpiperazine and the like can be mentioned. In the present invention, these polymerizable diamines may be used alone or in combination of two or more.

Examples of the dicarboxylic acid of the polymerizable diamine / dicarboxylic acid salt include, for example, 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-sodium sulfoisophthalic acid, hexahydroterephthalic acid,
Hexahydroterephthalic acid, diglycolic acid and the like can be mentioned. In the present invention, these polymerizable dicarboxylic acids may be used alone or in combination of two or more.

The polyamide-forming component (raw material) of the present invention may further contain a known terminal blocking agent for controlling the molecular weight or improving the hot water resistance. As the terminal blocking agent, a monocarboxylic acid or a monoamine is preferable.
Other examples include acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols.

The monocarboxylic acid which can be used as a terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid,
Aliphatic monocarboxylic acids such as pivalic acid and isobutylic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid And other aromatic monocarboxylic acids. 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. Examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine, and the like.
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic 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 molecular weight of the polyamide of the present invention is preferably 10,000 to 1,000,000 in terms of weight average molecular weight (Mw), and more preferably 30,000 to 200,000, because the moldability and physical properties are more excellent. Is particularly preferred. The weight average molecular weight can be determined by, for example, gel permeation chromatography (GPC) using hexafluoroisopropanol (HFIP) as a solvent and polymethyl methacrylate (PMMA) as a molecular weight standard sample.

The apatite type compound preferably used in the present invention is represented by the following general formula. (A) _10-z (HPO ₄ ) _z (PO ₄ ) _6-z (X) _2-z · nH ₂
O where 0 ≦ z <2, 0 ≦ n ≦ 16, A is a metal element, and X is an anion or an anion compound.
From the viewpoint of moldability and physical properties, it is more preferable that 0 ≦ z <1, and 0 ≦ n ≦ 4.

Preferred metal elements A include 1A, 2A, 3A, 4A, 5A, 6A, 7A, 8,
Group 1B, 2B and 3B elements and tin and lead can be mentioned. These metal elements may be one kind or two or more kinds. In the present invention, from the viewpoints of economy, safety and physical properties of the obtained resin composition, magnesium, calcium, strontium which is a 2A group element,
Barium or a mixture of two or more thereof is particularly preferred.

Examples of the anion or anion compound represented by X in the above general formula include a hydroxyl ion (OH ⁻ ), a fluorine ion (F ⁻ ), and a chloride ion (Cl ⁻ ). These anionic elements or anionic compounds may be one kind or two or more kinds.
In the present invention, hydrogen phosphate ion (HPO ₄ ²⁻ ), phosphate ion (PO ₄ ³⁻ ), or part of X in the above general formula is replaced with carbonate ion (CO ₃ ²⁻ ). Carbonate-containing apatite may be used.

In the present invention, among the apatite-type compounds, hydroxyapatite (X is a hydroxyl ion) in which the metal element A is calcium, fluorinated apatite (a part or all of X is a fluorine ion), chlorinated Apatite (part or all of X is chloride ion), carbonate-containing hydroxyapatite, carbonate-containing fluorinated apatite, carbonate-containing chlorinated apatite, and a mixture thereof are most preferably used.

The apatite-type compound-forming component (raw material) includes apatite-type compound under polyamide polymerization conditions.
Apatite-type compound-forming component capable of forming a compound.A phosphoric acid-based metal compound, a mixture of a phosphate-based metal compound and a non-phosphate-based metal compound, and the like. More preferably, it is a mixture of a phosphoric acid metal compound and a non-phosphoric acid metal compound.
In the present invention, the molar ratio of the metal element to phosphorus in the apatite type compound-forming component may be 0.9 to 10.0,
More preferably 1.2 to 5.0, even more preferably 1.
5 to 2.0.

As the phosphoric acids of the phosphoric acid metal compound,
Is orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, meta
Phosphoric acid, phosphorous acid, hypophosphorous acid, etc.
You. More specifically, as the phosphate metal compound,
Calcium hydrogen phosphate (CaHPO)_Four・ MH_TwoO, but 0
≦ m ≦ 2. ), Calcium dihydrogen diphosphate (Ca
H_TwoP_TwoO₇), Calcium dihydrogen phosphate monohydrate (Ca
(H_TwoPO_Four)_Two・ H_TwoO), calcium diphosphate (α-
And β-Ca_TwoP_TwoO₇), Tricalcium phosphate (α-
And β-Ca_Three(PO_Four)_Two), Tetracalcium phosphate (C
a_Four(PO_Four)_TwoO), octacalcium phosphate pentahydrate (C
a₈H_Two(PO_Four)₆・ 5H_TwoO), calcium phosphite
Hydrate (CaHPO_Three・ H_TwoO), calcium hypophosphite
(Ca (H _TwoPO_Two)_Two), Magnesium phosphate second and third
Hydrate (MgHPO_Four・ 3H_TwoO), magnesium phosphate
Tertiary octahydrate (Mg_Three(PO_Four)_Two・ 8H_TwoO), phosphoric acid
Barium second (BaHPO_Four) Etc.
You.

Among these, in the present invention, a compound of phosphoric acid and calcium is preferably used from the viewpoints of economy and physical properties, and particularly, calcium monohydrogen phosphate (CaHPO ₄ .mH ₂ O, where 0 ≦ m ≦ 2 in it.) are more preferably used, calcium hydrogen phosphate dihydrate (CaHPO ₄ · 2H ₂ O) is most preferably used in particular as calcium hydrogen phosphate anhydrous (CaHPO _4).
These phosphorus-based metal compounds may be one kind,
It may be a combination of two or more.

When two or more kinds are combined, for example,
Calcium hydrogen phosphate dihydrate (CaHPO ₄ · 2H ₂
O) and calcium dihydrogen phosphate (CaH ₂ P ₂ O ₇ ), such as a combination of compounds containing the same kind of metal element, or calcium monohydrogen phosphate dihydrate (CaH 2
Examples include a combination of compounds containing different types of metal elements, such as using PO ₄ .2H ₂ O) and magnesium phosphate dibasic trihydrate (MgHPO ₄ .3H ₂ O). But you can.

In the present invention, the phosphate metal compound is
Calcium hydrogen phosphate (CaHPO) _Four・ MH_TwoO, but 0
≦ m ≦ 2. ), Phosphoru
sand it Compounds, 1 (195
8) CaO- by VanWazer described in
H_TwoOP_TwoO_FiveAs the phase diagram of the system shows, in the presence of water,
By mixing phosphate compound and calcium compound
It can be obtained by a known method.

More specifically, for example, at 20 to 100 ° C.
At this temperature, an alkali phosphate solution and a calcium chloride solution are added dropwise to a potassium dihydrogen phosphate solution to cause a reaction, or a method of mixing calcium carbonate or calcium hydroxide with a phosphoric acid aqueous solution may be used.

By the way, the present inventors have obtained the same effect as the present invention by using a compound composed of arsenic (As) or vanadium (V), that is, arsenic acid or vanadium acid instead of the phosphoric acid. I guess it can be done. However, in the present invention, phosphoric acids are most preferably used because they are excellent in stability of raw material components, availability of forming components, and safety.

The non-phosphate metal compound in the present invention is not particularly limited as long as it forms a compound with a metal element other than the above-mentioned phosphoric acids. Metal hydroxides (calcium hydroxide, magnesium hydroxide, water Strontium oxide, barium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, iron hydroxide,
Manganese hydroxide, etc.), metal chlorides (calcium chloride,
Magnesium chloride, strontium chloride, barium chloride, lithium chloride, sodium chloride, potassium chloride, aluminum chloride, iron chloride, manganese chloride, etc., metal fluorides (calcium fluoride, magnesium fluoride, barium fluoride, strontium fluoride, fluoride) Lithium oxide,
Sodium fluoride, potassium fluoride, aluminum fluoride, etc.),

Metal bromide (eg, calcium bromide), metal iodide (eg, calcium iodide, potassium iodide, copper iodide), metal carbide (eg, calcium carbide), metal oxide (eg, calcium oxide, magnesium oxide), Metal carbonates (calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, aluminum carbonate, etc.), metal sulfates (calcium sulfate, etc.), metal nitrate salts (calcium nitrate, etc.), silicic acid Inorganic metal compounds such as metal salts (calcium silicate, sodium hexafluorosilicate, etc.), compounds of metal elements and monocarboxylic acids (calcium acetate, copper acetate, calcium benzoate, calcium stearate, etc.), metal elements and dicarboxylic acids Compounds with acids (calcium oxalate Tartaric acid calcium), compounds of a metal element and the tricarboxylic acid (calcium citrate, etc.) and the like.

In the present invention, these non-phosphate metal compounds may be used alone or in combination of two or more. When two or more kinds are combined, a compound containing the same kind of metal element may be combined, such as a mixture of calcium hydroxide and calcium carbonate, or a mixture of calcium carbonate and magnesium hydroxide, for example. May be combined with a compound containing a different metal element.

In the present invention, among these compounds, metal hydroxides, metal fluorides, metal chlorides, metal carbonates, metal oxides, or mixtures thereof are used because of their better economy and physical properties. It is preferably used. Particularly preferred are hydroxides, fluorides, chlorides, carbonates of calcium, magnesium, strontium and barium, which are Group 2A elements of the periodic table, and mixtures thereof, among which calcium hydroxide and fluoride. ,
Most preferably, chlorides, carbonates, oxides, or mixtures thereof are used.

The phosphate metal compound and the non-phosphate metal compound which are the apatite type compound-forming components of the present invention have a preferable average particle diameter of 100 μm or less, more preferably 50 μm or less.
μm or less, more preferably 25 μm or less. The average particle diameter is measured by dispersing an apatite-type compound-forming component in pure water or alcohol and measuring with a laser diffraction / scattering type particle size distribution apparatus, or by using a scanning electron microscope (S
A method of measuring using observation by EM) may be used.

The method for producing the polyamide resin composition of the present invention is a method in which an apatite-type compound-forming component (raw material) is blended with a polyamide-forming component (raw material), and then the polyamide is polymerized and the apatite-type compound is synthesized. Good.
A preferred method of polymerization of the polyamide and the apatite-type compound is to heat a blend of the polyamide-forming component and the apatite-type compound-forming component, polymerize the polyamide-forming component in the presence of the apatite-type compound-forming component, and then form the apatite-type compound. A method of synthesizing or reacting an apatite type compound forming component in the presence of a polyamide forming component,
Thereafter, the polyamide is polymerized.

A more preferred method is to advance the polymerization reaction of the polyamide and the synthesis reaction of the apatite type compound at a temperature of 40 to 300 ° C. with the mixture of the two forming components. This is a method in which a polyamide polymerization reaction and an apatite-type compound synthesis reaction are allowed to proceed simultaneously and in parallel at a temperature of 40 to 300 ° C. under a mixture of forming components under pressure.

The polyamide-forming component and the apatite-type compound-forming component may be compounded by directly mixing the solid polyamide-forming component and the apatite-type compound-forming component, or by mixing the aqueous solution of the polyamide-forming component with the apatite-type compound-forming component. And a method of blending with an aqueous solution or a suspension. Further, in order to improve the dispersibility of the apatite type compound, a compound such as a dispersant or a complexing agent may be added to the polyamide-forming component or the apatite-type compound forming component, if necessary.

In the present invention, the kind of the dispersant is not particularly limited, and a known dispersant can be used. For example, "Elucidation of dispersion and aggregation and applied technology, 1992
Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, nonionics, etc., as described on pages 232 to 237 of "Year" (supervised by Fumio Kitahara, published by Techno System Co., Ltd.) A system surfactant or the like can be used.

Of these, anionic surfactants and nonionic surfactants are preferably used. In particular, from the viewpoint of price and physical properties, sodium citrate, sodium polyacrylate, ammonium polyacrylate, and styrene-anhydrous surfactant are preferred. More preferably, maleic acid copolymers, olefin-maleic anhydride copolymers such as ethylene-maleic anhydride, and sucrose esters such as sucrose stearic acid ester are used.

The complexing agent is not particularly limited as long as it is a compound which forms a complex with a metal ion. Examples thereof include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and glycoletherdiaminetetraacetic acid. Acetic acid, diethylenetriaminepentaacetic acid, citric acid, gluconic acid, tartaric acid, malic acid, succinic acid, aliphatic amines such as ethylenediamine, and urea can be used. Among them, citric acid, ethylenediaminetetraacetic acid (EDTA),
Ethylenediamine (en) is particularly preferred.

For the polymerization of the polyamide, a known method can be used. For example, a component that is hardly soluble in water such as 11-aminoundecanoic acid is used as a forming component, and 40 to 300 ° C.
A polycondensation method by heating with ε-caprolactam as a forming component, and adding an inert gas to the aqueous solution by adding a terminal blocking agent such as a monocarboxylic acid or a reaction accelerator such as ε-aminocaproic acid as needed. While distributing,
A ring-opening polycondensation method for lactams which is polycondensed by heating to 300 ° C., and a diamine / dicarboxylic acid such as hexamethylene adipamide is used as a forming component, and an aqueous solution thereof is concentrated by heating at a temperature of 40 to 300 ° C. A hot-melt polycondensation method in which the steam pressure is maintained at a pressure between normal pressure and 20 atm and finally the pressure is released and the polycondensation is performed at normal pressure or reduced pressure can be used.

Further, a solid phase polymerization method carried out at a temperature equal to or lower than the melting point of the diamine / dicarboxylic acid solid salt or polycondensate, a solution method in which a dicarboxylic acid halide component and a diamine component are polycondensed in a solution, and the like can also be used. it can. These methods may be combined as needed. Further, the polymerization form may be a batch type or a continuous type. The polymerization apparatus is not particularly limited, and a known apparatus, for example, an extruder-type reactor such as an autoclave-type reactor, a tumbler-type reactor, or a kneader can be used.

The apatite type compound of the present invention can be confirmed, for example, by a method of directly confirming by wide-angle X-ray diffraction or infrared absorption spectrum using a pellet or a film, or by using a polyamide resin composition or a film made of a polyamide such as phenol. A method in which the polyamide resin is immersed in a soluble solvent, eluted and separated, and the remaining components are confirmed by wide-angle X-ray diffraction, infrared absorption spectrum, or the like may be used. The apatite type compound contained in the polyamide film of the present invention may be a crystalline apatite type compound or an amorphous apatite type compound, but from the viewpoint of physical properties, a crystalline apatite type compound may be used. More preferably, there is. Whether the apatite type compound is crystalline can be confirmed by measuring wide-angle X-ray diffraction of a polyamide resin composition, a film, or the like.

Further, the polyamide resin composition or film is immersed in a solvent in which polyamide such as phenol is soluble,
The polyamide resin is eluted, and the remaining separated components can be confirmed by measuring wide-angle X-ray diffraction. More specifically, as an X-ray source, copper Kα (wavelength λ = 1.54
Using 2Å), the wide-angle X-ray diffraction of the separated component was measured, and the diffraction angle (2θ) became (00) at 25.5 to 26.5 degrees.
2) A plane peak exists, and the diffraction angle (2θ) is 32.
What is necessary is just to confirm that the (300) plane peak exists at 5 to 33.5 degrees. In the present invention, the crystalline apatite-type compound confirmed as described above is particularly preferable.

The content of the apatite type compound of the present invention is
It is necessary to be 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. The content of the apatite type compound can be determined, for example, by measuring the loss on ignition (Ig.loss) of a polyamide resin composition or a film according to JIS R3420, and determining the weight loss.

Specifically, after the polyamide resin composition and the film are sufficiently dried, about 1 g is weighed on a platinum dish, and 650 g is weighed.
Ashed in an electric furnace at ± 20 ° C, cooled, weighed,
The content of the apatite type compound is determined. When the content of the apatite type compound is less than 0.1% by weight, the improvement in gas barrier properties, slipperiness, and rigidity is not so remarkable as to achieve the object of the present invention, while exceeding 30% by weight. In such a case, the mechanical strength of the film may be reduced.

The molar ratio of the metal element to phosphorus in the apatite type compound of the present invention is preferably 0.9 to 10.0, more preferably 1.2 to 5.0, and particularly preferably, 1.3 to 2.0. The quantitative determination of the metal element will be specifically described for the case of calcium as the metal element. First, the polyamide resin composition or the film 0.1.
5 g is weighed on a platinum dish and carbonized at 500 ° C. using an electric furnace.

After cooling the carbide, 5 ml of hydrochloric acid and 5 ml of pure water are added thereto and dissolved by boiling on a heater. It is cooled again, pure water is added to make 500 ml, and calcium in this sample may be quantified by high frequency inductively coupled plasma (ICP) emission analysis (characteristic wavelength: 317.933 nm). Other metal elements can be quantified in a similar manner by selecting a characteristic wavelength.

On the other hand, for the determination of phosphorus, 0.5 g of a polyamide resin composition was weighed, 20 ml of concentrated sulfuric acid was added thereto, and the mixture was wet-decomposed on a heater. After cooling, 5 ml of hydrogen peroxide was added, and the mixture was heated on a heater. And concentrate until the total volume is 2-3 ml. This was cooled again and made up to 500 ml with pure water.
The determination may be made by high frequency inductively coupled plasma (ICP) emission analysis (characteristic wavelength: 213.618 nm).

Based on the quantitative results thus obtained,
The molar ratio of the metal element to phosphorus can be calculated. If the ratio is less than 0.9, air bubbles are likely to be mixed or foamed during extrusion or molding, and the yield of the film may be reduced. If this ratio exceeds 10.0, the toughness may be significantly reduced.

The polyamide resin composition of the present invention contains 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.

In the synthesis of apatite type compounds, for example, taking hydroxyapatite as an example, generally, a wet method in which calcium hydroxide and phosphoric acid are reacted in an aqueous solution of about PH8, calcium monohydrogen phosphate, About 200 ° C, 15
Although a hydrothermal method performed under high pressure and high temperature conditions is used, the conditions for synthesizing this apatite compound are very similar to the conditions for polymerizing polyamide. The present inventors have paid attention to this point.

That is, the polyamide composition used for the polyamide film of the present invention is obtained by mixing a polyamide-forming component and an apatite-forming component and synthesizing an apatite-type compound at any stage of the polyamide polymerization process. It was done. By doing so, a physical and chemical interaction such as an ionic bonding reaction, an adsorption reaction or a grafting reaction occurs between the polyamide to be polymerized and the apatite type compound to be synthesized, and the apatite type A polyamide-forming component (raw material) and a polyamide component are incorporated into the inside and the surface of the compound particles.

The apatite type compound synthesized via these reaction products (organic substances) is uniformly and finely dispersed in the matrix polyamide, and the interface between the polyamide and the apatite type compound is surprisingly good. Adhere to and adhere to For this reason, the obtained polyamide film exhibits excellent gas barrier properties, rigidity and puncture resistance.

The polyamide, which is the matrix of the polyamide resin composition of the present invention, has the property that the polyamide elutes in a phenol solvent, whereas the reaction product (organic substance) does not elute or dissolve in the phenol solvent. That is, even when the organic substance is eluted / dissolved with a phenol solvent, the organic substance does not elute / dissolve and the organic substance remains together with the apatite type compound. In the present invention, the organic matter insoluble in the phenol solvent remaining in the apatite type compound needs to be 0.5 to 100 parts by weight per 100 parts by weight of the apatite type compound.

The amount is more preferably 1 to 100 parts by weight, further preferably 3 to 100 parts by weight, particularly preferably 4 to 50 parts by weight. When the amount of the organic substance is less than 1 part by weight per 100 parts by weight of the apatite type compound, the toughness of the obtained film may be greatly reduced. On the other hand, when the amount exceeds 100 parts by weight, there is a concern that molding workability may be deteriorated.

The organic substance of the present invention is formed by a polyamide-forming component and / or a polyamide as a result of physical and chemical interaction with apatite, and has a property that it cannot be eluted into a phenol solvent. It is preferable that at least a part of the organic substance is a polyamide from the viewpoint of further improving adhesion and adhesion to the polyamide as the matrix. Further, the organic substance may contain water.

The organic substance can be confirmed by analyzing the separated apatite type compound by, for example, pyrolysis gas chromatography and mass spectrum (MS) of the pyrolysis component. It can also be confirmed by infrared absorption spectrum and nuclear magnetic resonance (NMR) of the separated apatite type compound. According to the study by the present inventors, the organic matter in the present invention is obtained from a pyrolysis gas chromatography and a measurement result of mass spectrometry (MS) or infrared absorption spectrum of the decomposition component. Is the reaction product of

The identity of the organic substance is determined by eluting the polyamide resin composition or film with a 90% by weight aqueous phenol solution and then separating the thermally decomposed components of the separated apatite type compound with those of the polyamide-forming component or the polyamide. This can be done by confirming the presence of a characteristic component.

For example, in the case where adipic acid / hexamethylenediamine salt is used as the polyamide-forming component, the obtained polyamide resin composition or film is eluted with a 90% by weight aqueous phenol solution and then separated from the apatite type. If cyclopentanone can be confirmed as a thermal decomposition component at 550 ° C. of the compound, the organic substance contains adipic acid, and if adiponitrile can be confirmed, it indicates that the organic substance contains hexamethylenediamine. Further, if cyclopentanone and adiponitrile can be simultaneously confirmed as the thermal decomposition components, it indicates that the organic substance contains polyhexamethylene adipamide (nylon 66).

The amount of the organic substance of the present invention is, specifically,
(A) separation operation of apatite type compound as follows,
(B) measurement of the heat loss rate of the separated apatite type compound,
(C) It can be determined by quantifying an organic substance by measuring a thermal decomposition component.

(A) Separation operation of apatite type compound: 10 g of a polyamide resin composition or a film is weighed,
Mix with 200 ml of 90% by weight phenol and add
After stirring for an hour, a separating operation is performed using a centrifuge, and the supernatant solvent is removed. Further, 200 ml of phenol was added, and the same dissolving operation and separation operation using a centrifuge were repeated four times. Subsequently, 200 ml of 99.5% by weight of ethanol is added, the mixture is stirred at 23 ° C. for 2 hours, and a separating operation is performed using a centrifuge to remove a supernatant solvent. After repeating this operation four more times, drying is performed in a vacuum dryer to obtain an apatite type compound.

(B) Measurement of heat loss rate (X (parts by weight / 100 parts by weight of apatite type compound)) of the separated apatite type compound: 5 to 15 m of the obtained apatite type compound
g at 30 ° C. by thermogravimetric analysis (TGA).
To 550 ° C at a rate of 99.9 ° C / min.
Hold at C for 1 hour. Initial weight at 30 ° C. (W ₀ )
Using the final weight (W ₁ ) after holding at 550 ° C. for one hour, the heat loss rate X can be calculated by the following equation. Heat loss rate X (parts by weight / 100 parts by weight of apatite compound) = (W ₀ −W ₁ ) × 100 / W ₁

(C) Quantification of organic substances by measurement of pyrolysis components: The apatite type compound obtained in (a) was
Weigh 10 mg, pyrolysis gas chromatography, pyrolysis temperature 550 ° C, column temperature 50-320 ° C
(Measurement rate is 20 ° C./min). The pyrolysis gas chromatography pyrogram obtained is
The peak area is calculated by dividing the retention time into less than 2 min and 2 min or more. Since the components of 2 min or less are low molecular weight components such as carbon dioxide, these low molecular weight components were subtracted from the whole to obtain the amount of organic substances. Specifically, the respective areas Sa (less than 2 min) and Sb (more than 2 min) are calculated, and the amount of organic matter is calculated by the following equation using the heat loss rate X of (b). Amount of organic substance (parts by weight / 100 parts by weight of apatite type compound) = X · Sb / (Sa + Sb)

The average particle size of the apatite type compound of the present invention is preferably 1 μm or less, more preferably 0.1 μm
It is as follows. The average particle diameter in the present invention can be determined by an electron micrograph, and the average particle diameter can be calculated as follows. That is, the polyamide resin composition or a transmission electron microscope of ultra-thin sections were cut from the film: shooting (TEM photograph magnification 25,000 times), the particle size d _i of the apatite type compound, the number of particles n _i determined, The average particle diameter is calculated by the following equation. Average particle size = Σ
d _i · n _i / Σn _{i In} this case, if the particle diameter cannot be regarded as spherical, the minor axis and the major axis are measured, and の of the sum of both is measured.
Is the particle size. In addition, a minimum of 20
The particle size of 00 particles is measured.

The polyamide film of the present invention may be an unstretched film or a stretched film. The method of forming the unstretched film is not particularly limited.
It is melt-kneaded by an extruder at an extrusion temperature of 0 ° C., extruded into a film by a T-die, and cooled by a T-die method in which a film cast on a casting roll surface is cooled. Water-cooled tubular molding methods can be used. On this occasion,
The polyamide resin composition comprising the polyamide and the apatite type compound may be diluted with the above-mentioned polyamide not containing the apatite type compound and then subjected to film formation.

The method for forming the stretched film is not particularly limited, and the unstretched film formed by the casting method or the tubular method as described above may be used in the form of 50 to 18%.
A method in which uniaxial stretching or biaxial stretching is performed at a stretching temperature of 0 ° C., and heat fixing is performed at a temperature of 120 ° C. or higher and lower than the melting point, if necessary, can be used. In the case of biaxial stretching, a known method such as a tenter biaxial stretching method or a tubular biaxial stretching method can be used. There is no particular limitation on the thickness of the polyamide film of the present invention.
It is used in the range of 0 to 800 μm.

The polyamide film of the present invention can also be used as a laminate by laminating it with another polymer film, paper, metal foil such as aluminum, or the like. Other polymer films include, for example, low-density polyethylene films, medium-density polyethylene, high-density polyethylene films, polypropylene films, polybutene films, copolymer films thereof, and modified polyolefin resins obtained by modifying these with maleic anhydride or the like. Further, there may be mentioned ethylene-ethylene acrylate copolymer, ethylene-acrylic acid copolymer film, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer film, ionomer resin film, polyester and the like.

The method for laminating is not particularly limited. For example, the polyamide resin composition of the present invention and one or more polymer compounds constituting another polymer film may be bonded via an adhesive resin. A method of melt co-extrusion from a multilayer die or a method of bonding the polyamide film of the present invention to another polymer film, paper, metal foil, or the like with an adhesive can be applied.

The oxygen permeability of the polyamide film of the present invention is 35 (cc / m ² · 24 hr · atm) or less, more preferably 30 (cc / m ² · 24 hr · atm) or less, particularly preferably 25 (cc / m ² · 24 hr · atm). / m ² · 24hr · at
m) Oxygen permeability is, for example, 23 ° C. and 0%
It can be carried out according to ASTM D-3985-81 under RH conditions.

The water vapor permeability of the polyamide film of the present invention is 150 (g / m ² · 24 hr) or less, preferably 120 (g / m ² · 24 hr) or less, particularly preferably 1 (g / m ² · 24 hr).
00 (g / m ² · 24 hr) or less. The water vapor permeability is measured, for example, under the conditions of 40 ° C. and 90% RH under JISZ-
It can be measured by the cup method according to the method described in No. 208.

The polyamide resin composition of the present invention may contain, if necessary, fillers used in ordinary polyamide resins within the range not impairing the object of the present invention, for example, inorganic fibers such as glass fiber and carbon fiber, mica, talc, and the like. Clay minerals, inorganic fillers such as alumina and silica, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate,
Zinc stannate, zinc hydroxystannate, ammonium polyphosphate, melamine cyanurate, succinoguanamine, melamine polyphosphate, melamine sulfate, melamine phthalate,
Flame retardants such as aromatic polyphosphates and composite glass powder, pigments and colorants such as titanium white, heat stabilizers such as sodium phosphite and hindered phenol, lubricants such as stearic acid and paraffin wax, various And various additives such as a plasticizer, a weather resistance improver and an antistatic agent.

Further, if necessary, a thermoplastic resin or an elastomer, such as polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene rubber, which is usually blended with a polyamide resin within a range not to impair the object of the present invention.
Propylene copolymer, ethylene-propylene-diene copolymer, natural rubber and their acid-modified products such as 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, and epoxy resins may be contained. .

[0082]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below with reference to Examples, but the present invention is not limited to the following Examples as long as the gist is not exceeded. In addition, the physical property evaluation described in the following Examples and Comparative Examples was performed as follows. 1. Characteristics of polyamide-forming component and apatite-type compound-forming component (1-1) Content of apatite-type compound-forming component (% by weight) Calculated from the blending amount of polyamide-forming component and apatite-type compound-forming component. (1-2) Molar ratio of metal element to phosphorus of apatite type compound-forming component The molar ratio of metal component to phosphorus was calculated from the blending amount of the apatite type compound-forming component and its molecular weight.

2. Characteristics of polyamide resin composition (2-1) Weight average molecular weight (Mw) Determined by gel permeation chromatography (GPC). The apparatus 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 mixture was filtered with a filter to remove insolubles, and used as a measurement sample. Based on the obtained elution curve, the weight average molecular weight (Mw) was calculated in terms of polymethyl methacrylate (PMMA).
Was calculated.

(2-2) Determination of the content of the 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 was weighed on a platinum dish and 650 ± 20.
After incineration in an electric furnace at a temperature of ° C., after cooling, the weight was weighed to determine the content of the apatite type compound.

(2-3) Molar Ratio of Metal Element to Phosphorus (a) Determination of Metal Element: The case where calcium is used as the metal element will be described below, 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 a 500 ° C. electric furnace. After cooling, 5 ml of hydrochloric acid and 5 ml of pure water are added and dissolved by boiling on a heater. Cool again, add pure water and 500m
l. The equipment is Thermo Jarrel Ash
It was quantified at a wavelength of 317.933 nm by high frequency inductively coupled plasma (ICP) emission spectrometry using IRIS / IP manufactured by KK.

(B) Determination of phosphorus: 0.5 g of the polyamide resin composition was weighed, 20 ml of concentrated sulfuric acid was added, and the mixture was wet-decomposed 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 to 3 ml. It was cooled again and made up to 500 ml with pure water. The device is Th
Quantification was performed at a wavelength of 213.618 (nm) by high frequency inductively coupled plasma (ICP) emission spectrometry using IRIS / IP manufactured by thermo Jarrel Ash.

(2-4) Amount of organic substance (parts by weight / 100 parts by weight of apatite type compound) a) Separation operation of apatite type compound: 10 g of polyamide resin composition was weighed and 200 ml of 90% by weight phenol was prepared.
And stirred at 40 ° C. for 2 hours, using a centrifuge [H103RLH manufactured by Domestic Centrifuge Co., Ltd.] at 20,000 rpm.
m for 1 hour to remove the supernatant solvent.
Further, 200 ml of phenol was added, and the same dissolving operation and separation operation using a centrifugal separator were repeated four times. Subsequently, 200 ml of 99.5% by weight of ethanol was added, the mixture was stirred at 23 ° C. for 2 hours, and centrifuged for 2 hours.
The separation operation is performed at 0000 rpm for 1 hour, and the supernatant solvent is removed. After repeating this operation four more times, the resultant was dried at 80 ° C. for 12 hours in a vacuum dryer to obtain a target apatite compound.

(B) Measurement of heat loss rate (X (parts by weight / apatite type compound)) of the separated apatite type compound: (2
-4) 10 mg of the apatite compound obtained in (a)
Is weighed, and the weight loss rate X is measured by a thermogravimetric analysis (TGA) device.
I asked. The equipment is TGA-50 manufactured by Shimadzu Corporation. The temperature condition is 99.9 ° C / min from 30 ° C to 550 ° C.
And then kept at 550 ° C. for 1 hour. Using the initial weight (W ₀ ) at 30 ° C. and the final weight (W ₁ ) after holding at 550 ° C. for 1 hour, the amount of organic matter was calculated by the following equation. Heat loss rate X (parts by weight / 100 parts by weight of apatite compound) = (W ₀ −W ₁ ) × 100 / W ₁

(C) Determination of organic substance: (a) of (2-4)
3 mg of the apatite type compound obtained in the above was weighed, and subjected to pyrolysis chromatography (GC) and pyrolysis GC under the following conditions.
/ MS pyrogram was obtained.・ Pyrolysis device: Frontier Double Shot Pyrolyzer P
Y-2010D Thermal decomposition temperature: 550 ° C

Gas chromatography (GC) device: HP-58 manufactured by HEWLETT PACKARD
90 column: DURABOND DB-1 (0.
25 mmI. D. × 30 m, film thickness 0.25 μm) Column temperature: 50 ° C. → 320 ° C. (heating rate 20 ° C./mi)
n) Inlet temperature: 320 ° C Detector temperature: 320 ° C

Mass spectrum (MS) Apparatus: AutoMS System II manufactured by JEOL Ionization: EI (70 V) Measurement mass range: m / z = 10-400 Temperature: 200 ° C.

The pyrogram of the obtained pyrolyzed GC was divided into a retention time of less than 2 min and a retention time of 2 min or more, and the respective peak areas Sa (less than 2 min) and Sb (2 min or more) were calculated. Heat loss rate X obtained in (b)
Was used to calculate the amount of the organic substance by the following equation. Amount of organic substance (parts by weight / 100 parts by weight of apatite type compound) = X · Sb / (Sa + Sb) Further, a thermal decomposition component was identified from a mass spectrum (MS).

(2-5) Infrared absorption spectrum The infrared absorption spectrum of the apatite type compound obtained in (2-4) (a) was measured. The device is Perkin Elm
er 1640, resolution was measured at 4 cm ^-1 .

(2-6) Confirmation of generation of apatite type compound by X-ray diffraction X-ray diffraction of the apatite type compound obtained in (2-4) (a) 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: 0.15mm

3. Film properties (3-1) Tensile properties Tensile properties were measured according to ASTM D-882. As a method for evaluating the rigidity of the film, a tensile modulus was used.
In addition, each measured value in the table indicates an average value in the MD direction and the TD direction.

(3-2) Pinhole Resistance A sample film is fixed to a cylindrical form having an inner diameter of 100 mm by tension, and the tip of the sample has a radius of curvature of 0.5 m at the center of the sample.
The needle was pierced perpendicularly to the sample surface at a speed of 50 mm / min, and the strength was measured when the film was broken.

(3-3) Oxygen permeability OX-TRAN10 / 50 manufactured by US Modern Control Co.
Using H, it measured according to ASTM D-3985-81. The measurement conditions are 23 ° C. and 0% RH.

(3-4) Water Vapor Permeability Measured by a cup method according to JISZ-208. The measurement conditions are 40 ° C. and 90% RH.

[0099]

Example 1 1.5 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used as a polyamide-forming component. The solid salt was dissolved in 1.5 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite type compound forming component, an average particle diameter of 10 μm calcium monohydrogen phosphate dihydrate (CaHPO
₄ · 2H ₂ O) of 25 wt.% Suspension of 600 g (calcium monophosphate dihydrate: pure water = 150 g: 450
g), and 232 g of a 25% by weight suspension of heavy calcium carbonate (CaCO ₃ ) having an average particle diameter of 1.5 μm (calcium carbonate: pure water = 58 g: 174 g) were used.

The aqueous solution of the polyamide-forming component and the suspension of the apatite-type compound-forming component were charged into a 5-liter autoclave, and stirred well at a temperature of 50 ° C.
From the amounts of the components used, the content of the apatite-type compound-forming component is calculated as 12.2% by weight, and the ratio of the metal element to phosphorus is calculated as 1.67 in terms of molar ratio. After sufficient replacement with nitrogen, the temperature was raised from 50 ° C to 270 ° C. On this occasion,
The pressure in the autoclave was 1.77 M in gauge pressure.
It becomes Pa, but the pressure and heating was continued for 1 h while removing out of the system the water so as not to over 1.77MPa.

Thereafter, the heating was stopped, the mixture was cooled to room temperature, the autoclave was opened, and about 1.5 kg of the polymer was taken out.
It was pulverized by a pulverizer and dried in a nitrogen stream at 80 ° C. for 24 hours. The pulverized polymer was kneaded with an extruder having a diameter of 40 mm at a cylinder temperature of 280 ° C.
It was extruded into a film by a T-die having a width of mm, and solidified on a cooling roll at 30 ° C. to produce a film having a thickness of 40 μm.
The weight average molecular weight (Mw) determined using the film is 3
It was 6000, and the content of the apatite type compound was 10.2% by weight as measured by incineration.

Further, as a result of quantification of calcium and phosphorus by high frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.67. From the result of observation with a transmission microscope, the average particle size of the apatite compound was 0.32 μm. FIG. 1 shows the results of wide-angle X-ray diffraction measurement of the apatite-type compound obtained by the elution / separation operation using a 90% by weight aqueous phenol solution. As can be seen from this figure, formation of a crystalline apatite type compound can be confirmed.

The apatite type compound obtained by the elution / separation operation has a thermal weight loss rate X by thermogravimetric analysis of 6.
38 (parts by weight / 100 parts by weight of apatite type compound), Sb / (S) determined by pyrolysis gas chromatography (GC)
a + Sb) = 0.80, and the amount of organic matter was calculated to be 5.1 (parts by weight / 100 parts by weight of apatite). Also,
From the analysis result of the thermal decomposition GC / mass spectrum, cyclopentanone was confirmed as one of the thermal decomposition components of the organic substance remaining in the apatite type compound.

Further, from the observation of the infrared absorption spectrum,
A peak indicating the presence of an organic substance was observed at 1548 cm ^-1 which was not observed in Comparative Example 1. By the way, in the infrared absorption spectrum, peaks at 1416 cm ^-1 and 1455 cm indicating a carbonate-containing apatite compound were simultaneously confirmed. Table 1 shows the measurement results of the physical properties of the obtained film.
Shown in

Comparative Example 1 9 K of Leona 1300 (nylon 66) manufactured by Asahi Kasei Corporation
g, and 1 kg of hydroxyapatite manufactured by Taihei Chemical Industry Co., Ltd. having an average particle diameter of 25 μm, and melt-kneaded at a temperature of 280 ° C. with a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.). The kneaded material taken out in a shape was cooled with water and cut to obtain a polyamide resin composition. Using this polyamide resin composition, a film was produced in the same manner as in Example 1. The weight average molecular weight determined using the film was 36,000.

From the result of the measurement by incineration, the content of the apatite type compound was 10.1% by weight. As a result of quantifying phosphorus and calcium by high-frequency inductively coupled plasma emission spectrometry, the molar ratio of calcium to phosphorus was calculated to be 1.66. From the result of observation with a transmission microscope, the average particle size of the apatite compound was 3.2 μm. 90% by weight
FIG. 3 shows the wide-angle X-ray diffraction results of the apatite type compound obtained by the elution / separation operation using phenol.

The apatite type compound had a thermal weight loss rate X by thermogravimetric analysis of 2.50 (parts by weight / apatite type compound 100 parts by weight), and Sb / (Sa) by pyrolysis GC / MS.
+ Sb) = 0.06, and the amount of the organic substance was calculated to be 0.15 (parts by weight / 100 parts by weight of the apatite compound).

From the results of the analysis of the pyrolysis GC / mass spectrum, the pyrolysis components of the organic substances present in the apatite type compound were the same as those of the polyamide-forming component (hexamethylenediamine and adipic acid) and the polyhexamethyleneadipamide. No match could be found. In addition, the infrared absorption spectrum was almost the same as that of hydroxyapatite manufactured by Taihei Kagaku Sangyo Co., Ltd., which was a compounded apatite compound, and a peak indicating the presence of an organic substance could not be confirmed. Table 1 shows the measurement results of the physical properties of the obtained film.

Reference Example 1 Hydroxyapatite manufactured by Taihei Chemical Industry Co. (molar ratio of calcium to phosphorus: 1.67) used in Comparative Example 1 was dried at 80 ° C. under reduced pressure, and the result of thermogravimetric analysis was as follows.
The heat loss rate X was 2.23 (weight / apatite type compound 10).
0 parts by weight). No peak was detected in the pyrogram of pyrolysis GC for 2 minutes or more, and Sb / (Sa + S
b) = 0.0, and the amount of the organic matter was calculated to be 0.0 (parts by weight / 100 parts by weight of the apatite compound).

Example 2 As a polyamide-forming component, hexamethylenediamine
1.2 kg of equimolar solid salt of adipic acid and 0.3 kg of equimolar solid salt of hexamethylenediamine / isophthalic acid were used. The procedure was performed in the same manner as in Example 1 except that 1.5 kg of pure water was added to and dissolved in the solid salt and used as an aqueous solution. Table 1 shows the measurement results of the physical properties of the obtained film.

Example 3 As a polyamide-forming component, hexamethylenediamine
1.5 kg of an equimolar solid salt of dodecanoic acid was used. A pulverized polymer was obtained in the same manner as in Example 1 except that 1.5 kg of pure water was added to and dissolved in the solid salt and used as an aqueous solution. Using the pulverized polymer, the mixture was kneaded with an extruder having a diameter of 40 mm at a cylinder temperature of 260 ° C., extruded into a film with a T-die having a width of 300 mm, and solidified on a cooling roll at 30 ° C. to obtain a film having a thickness of 40 μm. Was prepared. Table 1 shows the measurement results of the physical properties of the obtained film.

Example 4 As a polyamide-forming component, hexamethylenediamine
1.2 kg of an equimolar adipic acid solid salt and 0.3 kg of ε-caprolactam were used. 1.5 kg of pure water in the solid salt
And used in the same manner as in Example 3 except that it was dissolved in water and used as an aqueous solution. Table 1 shows the measurement results of the physical properties of the obtained film.

Example 5 As a polyamide-forming component, ε-caprolactam 2.0
Kg was used. It was dissolved in 1.0 kg of pure water and used as an aqueous solution. As an apatite type compound-forming component, 600 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g) and an average A 25% by weight suspension of heavy calcium carbonate having a particle size of 1.5 μm
32 g (calcium carbonate: pure water = 58 g: 174 g) was used. The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave,
The mixture was stirred well at a temperature of 0 ° C.

Next, the temperature was raised to 260 ° C., and 1.4
The mixture was stirred for 1 hour under a pressure of 7 MPa . Thereafter, the pressure was released, and while removing water from the autoclave, the pressure was reduced to 260
The reaction was carried out at a temperature of 2 ° C. for 2 hours, and further under a reduced pressure of 400 mmHg for 1 hour. After the completion of the reaction, the product was taken out from the bottom nozzle in a strand form, cooled with water and cut to obtain pellets. The obtained pellet was dried in a nitrogen stream at 80 ° C. for 24 hours. Using the pellets, a diameter of 4
The mixture was kneaded with a 0 mm extruder at a cylinder temperature of 260 ° C., extruded into a film with a 300 mm width T-die, and extruded.
The film was solidified on a cooling roll at 0 ° C. to produce a film having a thickness of 40 μm. Table 1 shows the measurement results of the physical properties of the obtained film.

Example 6 As a polyamide-forming component, 3.0 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used. 200 g of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm was used as an apatite type compound-forming component. The polyamide-forming component and the apatite-type compound-forming component were thoroughly stirred with a Henschel mixer, and charged in a 5-liter autoclave. The content of the apatite-type compound-forming component is calculated to be 6.3 (% by weight), and the ratio of the metal element to phosphorus is calculated to be 1.00 in molar ratio. After replacing with enough nitrogen,
The pressure was set to a gauge pressure of 0.49 MPa , the temperature was raised from room temperature to 190 ° C., and the state was maintained for 2 hours. At this time, the pressure in the autoclave becomes a gauge pressure of 1.47 MPa . Continue increasing pressure to 0.049M
The pressure was reduced to Pa , the temperature was raised to 240 ° C., and the state was maintained for 8 hours.

In this series of operations, the pressure was set to 0.04
In order to keep the pressure at 9 MPa , generated water was removed by a decomposer. After cooling, the autoclave was opened, and the polymer was taken out and pulverized. The ground polymer was dried in a nitrogen stream at 80 ° C. for 24 hours. Thereafter, using a small twin-screw extruder (Labo Plastmill ME type manufactured by Toyo Seiki Co., Ltd.), pellets were formed under the conditions of a cylinder temperature of 280 ° C., a screw rotation speed of 70 rpm, and an extrusion rate of 4 kg / hr. Using the pellets, a film was produced in the same manner as in Example 1.

The obtained pellets were dried in a nitrogen stream at 80 ° C. for 24 hours. The weight average molecular weight of the obtained pellet was 210,000. From the result of measurement by incineration, the content of the apatite type compound was 5.2% by weight. As a result of quantification of calcium and phosphorus by high frequency inductively coupled plasma emission spectrometry, the molar ratio of calcium to phosphorus was 1.
01 was calculated. The average particle diameter of the apatite type compound was 0.25 μm from the result of observation with a transmission microscope. 9
FIG. 2 shows the results of X-ray diffraction of an apatite type compound obtained by elution and separation using a 0% by weight phenol aqueous solution.
Shown in

From this figure, the formation of the apatite type compound can be confirmed. The thermal weight loss rate X by thermogravimetric analysis is 5.67 (parts by weight / 100 parts by weight of apatite), and S by pyrolysis GC
b / (Sa + Sb) was 0.72, and the amount of organic matter was calculated to be 4.1 (parts by weight / 100 parts by weight of apatite). From the analysis result of the thermal decomposition GC / mass spectrum, adiponitrile was confirmed as a thermal decomposition component of the apatite type compound. From the observation of the infrared absorption spectrum, 165
A peak indicating the presence of an organic substance was observed at 0 cm ^-1 . Table 2 shows the measurement results of the physical properties of the obtained film.

Example 7 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m was performed in the same manner as in Example 6 except that 100 g of calcium hydrogen phosphate dihydrate was used. The weight average molecular weight of the obtained film was 520000. From the measurement results by incineration, the content of the apatite type compound was 2.5
% By weight. Table 2 shows the measurement results of the physical properties of the obtained film.

Example 8 As a polyamide-forming component, 1.0 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used. The solid salt was dissolved in 1.0 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite type compound-forming component, 25% by weight of an average particle diameter of 10 μm calcium monohydrogen phosphate dihydrate
1.0 Kg of the suspension (calcium monohydrogen phosphate dihydrate: pure water = 250 g: 750 g) and 25 wt% suspension of heavy calcium carbonate having an average particle size of 1.5 μm were added to 3
87 g (calcium carbonate: pure water = 97 g: 290 g) was used.

The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave and stirred well at a temperature of 50 ° C. The content of the apatite-type compound-forming component is calculated to be 25.8% by weight, and the ratio of the metal element to phosphorus is calculated to be 1.67 in molar ratio. After sufficient replacement with nitrogen, the temperature was raised from 50 ° C to 270 ° C. At this time, the pressure in the autoclave became 1.77 MPa in terms of gauge pressure, and heating was continued for 1 hour while removing water from the system so that the pressure did not become 1.77 MPa or more. Thereafter, the heating was stopped, the temperature was cooled to room temperature, the autoclave was opened, the polymer was taken out, pulverized by a pulverizer, and dried in a nitrogen stream at 80 ° C. for 24 hours.

A film was produced in the same manner as in Example 1 using the obtained polymer. The weight average molecular weight of the film was 35,000. From the result of measurement by incineration, the content of the apatite type compound was 22.3% by weight.
As a result of quantification of calcium and phosphorus by high-frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.67. Table 2 shows the measurement results of the physical properties of the obtained film.

Comparative Example 2 As an apatite type compound-forming component, the average particle diameter was 10 μm.
The procedure was performed in the same manner as in Example 6, except that 2.5 g of calcium monohydrogen phosphate dihydrate was used. The content of the apatite compound forming component is calculated to be 0.08% by weight, and the molar ratio of calcium to phosphorus is calculated to be 1.00. The weight average molecular weight of the obtained film was 70,000. From the result of measurement by incineration, the content of apatite was 0.05% by weight. As a result of quantifying calcium and phosphorus by high-frequency inductively coupled plasma emission spectrometry, the molar ratio of calcium to phosphorus was calculated to be 0.95. Table 2 shows the measurement results of the physical properties of the obtained film.

Comparative Example 3 A nylon resin (SF1022 manufactured by Ube Industries, Ltd .: SF1022) was used as the polyamide resin, and the diameter was 40 m.
k, kneading at a cylinder temperature of 260 ° C. and extruding into a film with a 300 mm wide T-die.
The film was solidified on a cooling roll at a temperature of 0 ° C. to produce a film having a thickness of 40 μm. Table 2 shows the measurement results of the physical properties of the obtained film.

Reference Example 2 Hexamethylenediamine / adipic acid equimolar solid salt
Only 3 kg of an aqueous solution in which 5 kg was dissolved in 1.5 kg of pure water, that is, only the polyamide-forming component was charged in a 5-liter autoclave. Thereafter, the operation was performed in the same manner as in Example 1. The weight average molecular weight of the obtained film was 35,000. Table 2 shows the measurement results of the physical properties of the obtained film.

Example 9 As a polyamide-forming component, 1.5 kg of hexamethylenediamine / adipic acid equimolar solid salt was used. The solid salt was dissolved in 1.5 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite type compound-forming component, 600 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g) and an average A 25% by weight suspension of heavy calcium carbonate having a particle size of 1.5 μm
32 g (calcium carbonate: pure water = 58 g: 174 g) was used.

The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave, and acetic acid (CH ₃ COO) was used as a molecular weight regulator.
H) 4.5 g was added and stirred well at a temperature of 50 ° C. After replacing with sufficient nitrogen, raise the temperature from 50 ° C to 270 ° C.
Temperature. At this time, the pressure in the autoclave is made to 1.77MPa in the gauge pressure, the pressure 1.77
Heating was continued for 1 hour while removing water outside the system so as not to exceed MPa . After that, over 1 hour, the pressure was reduced to atmospheric pressure, and the polymer was extracted in a strand form from the bottom,
Water cooling, cutting, and pelletization.

The weight average molecular weight of the obtained polymer was 12
500. This polymer was placed in a 10-liter tumbler-type reactor and kept at 200 ° C. for 8 hours while constantly flowing nitrogen at 5 liter / min.
After cooling, the polymer was removed. The weight average molecular weight of the obtained polymer was 42,000. Using the polymer, a film was produced in the same manner as in Example 1. Table 3 shows the measurement results of physical properties of the obtained film.

Example 10 As a polyamide-forming component, 1.5 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used. The solid salt was dissolved in 1.5 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite type compound-forming component, 25% by weight of an average particle diameter of 10 μm calcium monohydrogen phosphate dihydrate
600 g of the suspension (calcium monohydrogen phosphate dihydrate:
Pure water = 150 g: 450 g), and an average particle size of 1.5
232 g of a 25% by weight suspension of μm heavy calcium carbonate
(Calcium carbonate: pure water = 58 g: 174 g) was used.
The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave, and adipic acid (COOH (CH ₂ ) ₄ C) was further added as a molecular weight regulator.
OOH) was added, and the mixture was stirred well at a temperature of 50 ° C. After replacing with sufficient nitrogen, the temperature is raised from 50 ° C to 270 ° C.
The temperature was raised to ° C.

At this time, the pressure in the autoclave becomes 1.77 MPa in gauge pressure, but the pressure is 1.77 M
Heating was continued for 1 hour while removing water outside the system so as not to exceed Pa . Then, over 1 hour, the pressure was reduced to atmospheric pressure, the polymer was drawn out in a strand form from the bottom, cooled with water, cut, and formed into pellets. The weight average molecule of the obtained polymer was 14,500. Kneader type reactor (Plastic BT-30 manufactured by Plastic Engineering Laboratory)
-S2-60-L (L / D = 60))
It was extruded at a temperature of ° C. at a discharge rate of 4 kg / hr. The weight average molecular weight of the obtained polymer was 37000. Using the polymer, a film was produced in the same manner as in Example 1. Table 3 shows the measurement results of physical properties of the obtained film.

Example 11 The procedure of Example 8 was repeated, except that 20 g of stearylamine (CH ₃ (CH ₂ ) ₁₆ CH ₂ NH ₂ ) was used instead of acetic acid as a molecular weight regulator. Table 3 shows the measurement results of physical properties of the obtained film.

Example 12 As a molecular weight regulator, aniline (C ₆
Except for using H ₅ NH ₂₎ 14g was carried out in the same manner as in Example 9. Table 3 shows the measurement results of physical properties of the obtained film.

Example 13 Example 13 was carried out in the same manner as in Example 8, except that 20 g of acetic acid was used as a molecular weight regulator. The weight average molecular weight (Mw) of the obtained film was 18,000. Table 3 shows the measurement results of physical properties of the obtained film.

Example 14 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g) and 104 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 26 g: 78 g). The content of the apatite-type compound-forming component is calculated to be 10.4% by weight, and the ratio of the metal element to phosphorus is calculated to be 1.30 in terms of molar ratio. The weight average molecular weight of the obtained film was 38,000, and the content of the apatite type compound was 9.2% by weight as measured by incineration. Further, as a result of quantifying calcium and phosphorus by high frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.28. Table 4 shows the measurement results of physical properties of the obtained film.

Example 15 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 469 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
117 g: 351 g), and 232 g (calcium carbonate: pure water = 58 g: 174 g) of a 25% by weight suspension of heavy calcium carbonate having an average particle diameter of 1.5 μm was carried out in the same manner as in Example 1. The content of the apatite-type compound-forming component is calculated to be 10.4% by weight, and the ratio of the metal element to phosphorus is calculated to be 1.85 in molar ratio. The weight average molecular weight of the obtained film was 32,000, and the content of the apatite type compound was determined to be 9.3% by weight based on measurement by incineration.
Met. Further, as a result of quantification of calcium and phosphorus by high frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.88. Table 4 shows the measurement results of physical properties of the obtained film.

Example 16 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
100 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
25 g: 75 g) and 232 g (calcium carbonate: pure water = 58 g: 174 g) of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm was used in the same manner as in Example 1. The content of the apatite type compound-forming component is calculated to be 5.2% by weight, and the ratio of the metal element to phosphorus is calculated to be 5.0 in terms of molar ratio. The weight average molecular weight of the obtained film was 26000, and the content of the apatite type compound was 4.3% by weight as measured by incineration. Further, as a result of quantifying calcium and phosphorus by high-frequency inductively coupled plasma emission spectrometry, the molar ratio of calcium to phosphorus was calculated to be 5.2. Table 4 shows the measurement results of physical properties of the obtained film.

Example 17 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
80 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water = 2
0 g: 60 g) and 464 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 116 g: 348 g), and the same procedure as in Example 1 was carried out. The content of the apatite type compound-forming component is calculated to be 8.3% by weight, and the ratio of the metal element to phosphorus is calculated to be 11.0 in molar ratio. The weight average molecular weight of the obtained film was 22,000, and the content of the apatite type compound was 6.5% by weight as measured by incineration. Further, as a result of quantifying calcium and phosphorus by high frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 11.2. Table 4 shows the measurement results of physical properties of the obtained film.

Example 18 As a polyamide-forming component, 3.0 kg of an equimolar solid salt of hexamethylenediamine / adipic acid was used. As an apatite type compound-forming component, 200 g of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm, and phosphoric acid 28.
The procedure was performed in the same manner as in Example 7 except that 5 g was used. The polyamide-forming component and the apatite-type compound-forming component were thoroughly stirred with a Henschel mixer, and charged in a 5-liter autoclave. The content of the apatite type compound-forming component is calculated to be 7.1% by weight, and the ratio of the metal element to phosphorus is calculated to be 0.8 in molar ratio. The weight average molecular weight of the obtained film is 12000, and from the measurement by incineration,
The content of the apatite type compound was 6.0% by weight.
Further, as a result of quantifying calcium and phosphorus by high-frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 0.79. Table 4 shows the measurement results of physical properties of the obtained film.

Example 19 As an apatite type forming component, 600 g of a 25% by weight suspension of anhydrous calcium monohydrogen phosphate (CaHPO ₄ ) having an average particle size of 1.0 μm (anhydrous calcium hydrogen phosphate: pure water = 150 g: 450 g), and an average particle diameter of 10 μm
216 g of a 25% by weight suspension of calcium hydroxide (Ca (OH) ₂ ) (calcium hydroxide: pure water = 54 g: 16
2g) The procedure was the same as in Example 1 except that 2g) was used. Table 5 shows the measurement results of physical properties of the obtained film.

Example 20 As an apatite type forming component, phosphorus having an average particle diameter of 10 μm was used.
Tricalcium acid (Ca _Three(PO_Four)_Two25% suspension by weight)
600 g of the liquid (tricalcium phosphate: pure water = 150 g:
450 g), and an average particle diameter of 10 μm calcium hydroxide
60 g of a 25% by weight suspension of calcium hydroxide (calcium hydroxide: pure
Water = 12 g: 48 g) Except for using the same procedure as in Example 1.
I went. Table 5 shows the measurement results of the physical properties of the obtained film.
You.

[0141] As Example 21 apatite type forming component, 25 weight% of the average grain size 10μm diphosphate dihydrogen calcium (CaH ₂ P ₂ O ₇₎
600 g of the suspension (calcium dihydrogen diphosphate: pure water =
150 g: 450 g) and 400 g of a 25% by weight suspension of calcium hydroxide having an average particle size of 10 μm (calcium hydroxide: pure water = 100 g: 300 g) were used in the same manner as in Example 1. Table 5 shows the measurement results of physical properties of the obtained film.

Example 22 As an apatite type forming component, calcium dihydrogen phosphate monohydrate (Ca (HPO ₄ ) ₂ .H ₂
300 g of a 25% by weight suspension of O) (calcium dihydrogen phosphate monohydrate: pure water = 75 g: 225 g), and 288 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm. (Calcium carbonate: pure water = 72 g: 21
6g) The same procedure as in Example 1 was carried out except that the composition was used. Table 5 shows the measurement results of physical properties of the obtained film.

[0143] As Example 23 apatite type forming component, a 25 wt% suspension having an average particle diameter of 10μm dicalcium phosphate _{(Ca 2 P 2 O 7)} 600g ( diphosphate calcium: pure water = 150 g: 45
0g) and 320 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 µm (calcium carbonate: pure water = 80 g: 240 g) were used in the same manner as in Example 1. Table 5 shows the measurement results of physical properties of the obtained film.

Example 24 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 220 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 55 g: 165 g), and an average particle size of 5.
10 g of a 25% by weight suspension of 0 μm calcium fluoride (CaF ₂ ) (calcium fluoride: pure water = 2.5 g: 7.
The procedure was performed in the same manner as in Example 1 except that 5 g) was used. Table 6 shows the measurement results of physical properties of the obtained film.

Example 25 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 176 g of a 25% by weight suspension of heavy calcium carbonate having an average particle diameter of 1.5 μm (calcium carbonate: pure water = 44 g: 132 g), and an average particle diameter of 5.
44 g of a 25% by weight suspension of 0 μm calcium fluoride (CaF ₂ ) (calcium fluoride: pure water = 11 g: 33)
Except using g), it carried out similarly to Example 1. Table 6 shows the measurement results of physical properties of the obtained film.

Example 26 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 200 g of a 25% by weight suspension of heavy calcium carbonate having an average particle diameter of 1.5 μm (calcium carbonate: pure water = 50 g: 150 g), and an average particle diameter of 5.
The procedure was performed in the same manner as in Example 1 except that 36 g of a 25% by weight suspension of 0 μm calcium chloride (CaCl ₂ ) was used (calcium chloride: pure water = 9 g: 27 g). Table 6 shows the measurement results of physical properties of the obtained film.

Example 27 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 200 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 50 g: 150 g), and an average particle size of 10
248 g of a 25% by weight suspension of μm strontium carbonate (SrCO ₃ ) (strontium carbonate: pure water = 12 g:
The procedure was performed in the same manner as in Example 1 except that 36 g) was used.
Table 6 shows the measurement results of physical properties of the obtained film.

Example 28 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 200 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 50 g: 150 g), and an average particle size of 10
The procedure was performed in the same manner as in Example 1 except that 64 g (barium carbonate: pure water = 16 g: 48 g) of a 25% by weight suspension of μm barium carbonate (BaCO ₃ ) was used. Table 6 shows the measurement results of physical properties of the obtained film.

Example 29 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
540 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
135 g: 405 g), 60 g of a 25% by weight suspension of magnesium phosphate dibasic trihydrate (MgHPO ₄ .3H ₂ O) having an average particle size of 5.0 μm (magnesium phosphate
Trihydrate: pure water = 15 g: 45 g), average particle diameter 10 μm
172 g of a 25% by weight suspension of heavy calcium hydroxide
(Calcium hydroxide: pure water = 43 g: 129 g) was used in the same manner as in Example 1. Table 6 shows the measurement results of physical properties of the obtained film.

Example 30 As an apatite type compound-forming component, an average particle size of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 160 g of a 25% by weight suspension of calcium hydroxide having an average particle diameter of 10 μm (calcium hydroxide: pure water = 40 g: 120 g), and an average particle diameter of 10 μm
m of iron (II) chloride tetrahydrate (FeCl ₂ .4H ₂ O)
32 g of a weight% suspension (iron (II) chloride tetrahydrate: pure water =
8 g: 24 g) was used in the same manner as in Example 1. Table 7 shows the measurement results of physical properties of the obtained film.

Example 31 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 160 g of a 25% by weight suspension of calcium hydroxide having an average particle diameter of 10 μm (calcium hydroxide: pure water = 40 g: 120 g), and an average particle diameter of 10 μm
m iron (III) chloride hexahydrate (FeCl ₃ · 6H ₂ O) of 2
The procedure was performed in the same manner as in Example 1 except that 44 g of a 5% by weight suspension (iron (III) chloride hexahydrate: pure water = 11 g: 33 g) was used. Table 7 shows the measurement results of physical properties of the obtained film.

Example 32 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 160 g of a 25% by weight suspension of calcium hydroxide having an average particle diameter of 10 μm (calcium hydroxide: pure water = 40 g: 120 g), and an average particle diameter of 10 μm
m Example 1 except that 32 g of a 25% by weight suspension of copper iodide (CuI) (copper iodide: pure water = 8 g: 24 g) was used.
Was performed in the same manner as described above. Table 7 shows the measurement results of physical properties of the obtained film.

Example 33 As an apatite type compound-forming component, an average particle size of 25.
600 g of a 25% by weight suspension of 0 μm calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g), and an average particle size of 1.5 μm The procedure was performed in the same manner as in Example 1 except that 232 g (calcium carbonate: pure water = 58 g: 174 g) of the weight% suspension was used. From the result of observation of the film with a transmission type microscope, the average particle size of the apatite type compound was found to be 0.1%.
It was 52 μm. Table 8 shows the measurement results of physical properties of the obtained film.

Example 34 As an apatite type compound-forming component, an average particle diameter of 75.
600 g of a 25% by weight suspension of 0 μm calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g), and an average particle size of 1.5 μm The procedure was performed in the same manner as in Example 1 except that 232 g (calcium carbonate: pure water = 58 g: 174 g) of the weight% suspension was used. From the result of observation of the film with a transmission type microscope, the average particle size of the apatite type compound was found to be 0.1%.
It was 88 μm. Table 8 shows the measurement results of physical properties of the obtained film.

Example 35 As an apatite type compound-forming component, an average particle diameter of 200
600 g (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g) of a 25% by weight suspension of μm calcium monohydrogen phosphate dihydrate, 25 μg of heavy calcium carbonate having an average particle size of 1.5 μm The procedure was performed in the same manner as in Example 1 except that 232 g (calcium carbonate: pure water = 58 g: 174 g) of the weight% suspension was used. From the results of observation of the film with a transmission microscope, the average particle size of the apatite compound was 1.8.
It was 3 μm. Table 8 shows the measurement results of physical properties of the obtained film.

Example 36 The average particle diameter of the component forming the apatite type compound was 3.0 μm.
25% by weight of calcium monohydrogen phosphate dihydrate and 25% of heavy calcium carbonate having an average particle size of 0.25 μm.
Each of the weight% suspensions was performed in the same manner as in Example 1 except that ultrasonic treatment was performed at a temperature of 40 ° C. for 30 minutes. Table 9 shows the measurement results of physical properties of the obtained film.

Example 37 The average particle size of the apatite type compound-forming component was 3.0 μm.
25% by weight of calcium monohydrogen phosphate dihydrate and 25% of heavy calcium carbonate having an average particle size of 0.25 μm.
Each of the weight% suspensions was performed in the same manner as in Example 1 except that the suspensions were each subjected to a treatment with a homogenizer at a temperature of 60 ° C. for 10 minutes. Table 9 shows the measurement results of physical properties of the obtained film.

Example 38 The average particle size of the apatite type compound-forming component was 3.0 μm.
6 g of ammonium polyacrylate (Ceramo D-134, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added as a dispersant to a 25% by weight suspension of calcium monohydrogen phosphate dihydrate. After adding 2.32 g of ammonium polyacrylate to a 25% by weight suspension of 0.25 μm heavy calcium carbonate, each was subjected to ultrasonic treatment at 40 ° C. for 30 minutes.
The procedure was performed in the same manner as in Example 1 except that the procedure was performed for one minute.

An apatite type compound obtained by eluting and separating the obtained film using a 90% by weight aqueous phenol solution had a thermal weight loss X of 12.7 by thermogravimetric analysis.
(Parts by weight / 100 parts by weight of apatite), Sb / (Sa + Sb) by pyrolysis GC was 0.75, and the amount of organic matter was calculated to be 9.5 (parts by weight / 100 parts by weight of apatite). From the results of the analysis of the pyrolysis GC / mass spectrum, both the pyrolysis components of cyclopentanone and adiponitrile were confirmed as the pyrolysis components of the apatite type compound. In addition, from the observation of the infrared absorption spectrum, 1550 cm ⁻¹ and 165 cm
A peak indicating the presence of an organic substance was observed at 0 cm ^-1 . Table 9 shows the measurement results of physical properties of the obtained film.

Example 39 The average particle diameter of the apatite type compound-forming component was 3.0 μm.
6 g of sodium polyacrylate (Sharol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added as a dispersant to a 25% by weight suspension of calcium monohydrogen phosphate dihydrate. Sodium polyacrylate 2.3 in a 25% by weight suspension of .25 μm heavy calcium carbonate 2.3
After the addition of 2 g, each was carried out in the same manner as in Example 1 except that ultrasonic treatment was performed at a temperature of 40 ° C. for 30 minutes. Table 9 shows the measurement results of physical properties of the obtained film.

Example 40 The average particle size of the apatite type compound-forming component was 3.0 μm.
sodium citrate as a dispersant in a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (Showa Kako Co., Ltd.)
1.2 g) and 0.46 g of sodium citrate to a 25% by weight suspension of heavy calcium carbonate having an average particle size of 0.25 μm, and then subjected to ultrasonic treatment at a temperature of 40 ° C. Was performed in the same manner as in Example 1 except that the measurement was performed for 30 minutes. Table 9 shows the measurement results of physical properties of the obtained film.

Example 41 The average particle size of the apatite type compound-forming component was 3.0 μm.
6 g of sucrose stearic acid ester (DK ester, Daiichi Kogyo Seiyaku Co., Ltd.) as a dispersant was added to a 25% by weight suspension of calcium monohydrogen phosphate dihydrate, and the average particle diameter was 0.25 μm weight. 2.32 g of sucrose stearic acid ester was added to a 25% by weight suspension of porous calcium carbonate, and each was subjected to ultrasonic treatment at a temperature of 40 ° C. for 30 minutes, except that each was performed in the same manner as in Example 1. Was. Table 9 shows the measurement results of physical properties of the obtained film.

Example 42 An aqueous solution obtained by dissolving 1.5 kg of a hexamethylenediamine / adipic acid equimolar solid salt in 1.5 kg of pure water at 50 ° C. was used as a polyamide-forming component. 600 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle diameter of 3.0 μm as an apatite type compound-forming component
(Calcium monohydrogen phosphate dihydrate: pure water = 150 g:
450 g) and 232 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 58 g: 174 g). The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave, and 6 g of ethylenediaminetetraacetic acid (EDTA) was added as a complexing agent.
Stir well at a temperature of ° C. Subsequent operations were performed in the same manner as in Example 1. Table 10 shows the measurement results of physical properties of the obtained film.

Example 43 Ethylenediaminetetraacetic acid (EDTA) 6 was used as a complexing agent.
In the same manner as in Example 42 except that 1.3 g of ethylenediamine (en) was used instead of g. Table 10 shows the measurement results of physical properties of the obtained film.

Example 44 A film obtained in the same manner as in Example 1 was stretched at a stretching temperature of 120 using a biaxial stretching apparatus (BIX-702S, manufactured by Iwamoto Seisakusho KK).
The film was simultaneously biaxially stretched at a stretching ratio of 2.0 ° C and longitudinal and transverse stretching ratios of 2.0 times, and heat-set at 150 ° C to obtain a biaxially stretched film having a thickness of 10 µm. Table 11 shows the physical property measurement results of the obtained film.

Comparative Example 4 A film obtained in the same manner as in Comparative Example 1 was biaxially stretched in the same manner as in Example 44. Table 11 shows the physical property measurement results of the obtained film.

Example 45 To a polymer obtained in the same manner as in Example 1 was added 0.08% by weight of ethylenebisstearylamide, and nylon 66 (outer layer) was added using a water-cooled three-layer blown film apparatus (Placo Co., Ltd.). ) / Adhesive resin (intermediate layer) / low density polyethylene (interior) (20/20 / 30μ)
A film having a layer structure was produced. Adhesive resin is UBE-B
OND F1100 (Ube Industries, Ltd.), and the low-density polyethylene is UBE polyethylene F023 (Ube Industries, Ltd.).

The molding conditions are as follows. Die diameter: diameter 100 mm Film folding diameter: 200 mm (BUR = 1.27) Tensile speed: 10 m / min Cooling water temperature: 20 ° C. Molding temperature (setting): Nylon 66 (280 ° C.), adhesive resin ( 200 ° C.), low-density polyethylene (200 ° C.) Table 11 shows the physical property measurement results of the obtained three-layer structure film.

Comparative Example 5 To a polymer obtained in the same manner as in Comparative Example 1, 0.08% by weight of ethylenebisstearylamide was added, and a three-layer structure film was produced in the same manner as in Example 45. Table 11 shows the physical property measurement results of the obtained film.

[0170]

[Table 1]

[0171]

[Table 2]

[0172]

[Table 3]

[0173]

[Table 4]

[0174]

[Table 5]

[0175]

[Table 6]

[0176]

[Table 7]

[0177]

[Table 8]

[0178]

[Table 9]

[0179]

[Table 10]

[0180]

[Table 11]

[0181]

The polyamide film of the present invention is a film obtained by using a polyamide resin composition containing an apatite-type compound, which is uniformly and finely fixed and adhered very well to a polyamide as a matrix. . Accordingly, the polyamide film of the present invention has excellent gas barrier properties, rigidity, and puncture resistance, and is used for non-food use such as mechanical part packaging and futon packaging, or
It is very useful as a film material for food such as noodles and pet food.

[Brief description of the drawings]

FIG. 1 shows the results of wide-angle X-ray diffraction measurement of an apatite compound separated from the film of Example 1.

FIG. 2 shows the results of wide-angle X-ray diffraction measurement of an apatite compound separated from the film of Example 6.

FIG. 3 shows the results of wide-angle X-ray diffraction measurement of an apatite compound separated from the film of Comparative Example 1.

FIG. 4 shows the results of wide-angle X-ray diffraction measurement of the commercially available hydroxyapatite used in Reference Example 1.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 C08K 3/32 WPI (DIALOG)

Claims (2)

(57) [Claims] 1. An apatite type compound containing an organic substance insoluble in a phenol solvent in an amount of 0.5 to 99.9% by weight per 100 parts by weight of an apatite type compound. A polyamide film, wherein the amount is from 100 to 100 parts by weight. 2. An apatite compound under the polymerization conditions of a polyamide, comprising 70 to 99.9% by weight of a polyamide-forming component.
A polyamide film characterized by using a polyamide resin composition obtained by blending an apatite-type compound-forming component that can be formed with 0.1 to 30% by weight and proceeding a polymerization reaction of a polyamide and a synthesis reaction of an apatite-type compound. .