JP2013001770A - Polyamide sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide sheet having excellent rigidity after water absorption and high temperature rigidity and further excellent sheet moldability.SOLUTION: The polyamide sheet comprises (A) a polyamide copolymer containing a dicarboxylic acid component unit containing (a-p) an adipic acid unit, (b-p) an isophthalic acid unit and (c-p) a 1,4-cyclohexane dicarboxylic acid unit and a diamine component unit, wherein the relation of the (b-p) content (mol%) and the (c-p) content (mol%) when the total of the dicarboxylic acid component unit containing the (a-p), (b-p) and (c-p) which constitute the polyamide copolymer is 100 mol% satisfies following formula (1):(the content of (c-p))>(the content of (b-p))≥0.1.

Description

  The present invention relates to a polyamide sheet.

  Conventionally, polyamide resins are widely used as various parts materials for clothing, industrial materials, automobiles, electrical / electronics, and industrial use because of their excellent molding processability, mechanical properties and chemical resistance. It has been.

  In recent years, the use environment of polyamide resins has become severer in terms of heat and dynamics, and changes in physical properties in every environment that have improved mechanical properties, especially the rigidity after water absorption and the rigidity under high temperature use. There is a demand for a polyamide resin material having a low dependence on molding conditions and a polyamide resin material having a low dependence on molding conditions, which can provide a stable product under all molding conditions.

  In order to meet the above-described requirements, as a method for improving mechanical properties, polyamide containing 1 to 80 mol% of 1,4-cyclohexanedicarboxylic acid having a trans isomer / cis isomer ratio of 50/50 to 97/3 ( For example, refer to Patent Document 1.), polyamide comprising 1 to 40% of 1,4-cyclohexanedicarboxylic acid and aliphatic diamine (see, for example, Patent Document 2), 85 to 100 mol of dicarboxylic acid units. A polyamide (see, for example, Patent Document 3) in which% is composed of 1,4-cyclohexanedicarboxylic acid units and 60 to 100 mol% of diamine units is composed of aliphatic diamine units having 6 to 18 carbon atoms is disclosed. Further, as a method for improving the rigidity after water absorption, polyamide composed of 30 to 95% by mass of hexamethylene adipamide units, 0 to 40% by mass of hexamethylene terephthalamide units, and 5 to 30% by mass of hexamethylene isophthalamide units. Is disclosed (for example, see Patent Document 4).

International Publication No. 2002/048239 Pamphlet International Publication No. 1997/011108 Pamphlet Japanese Patent Laid-Open No. 9-12868 JP-A-6-32980

However, in the techniques disclosed in Patent Documents 1, 2, and 3, although the rigidity under normal use conditions is improved, the rigidity after water absorption and the rigidity under high temperature use are not sufficiently improved, and the use environment There is a problem that the physical property change due to the bottom becomes large.
Moreover, in the technique disclosed in Patent Document 4, since the rigidity after water absorption is not sufficiently improved, there is a problem that the physical property change due to the use environment becomes large as described above.

  As described above, according to the conventionally disclosed technology, a polyamide copolymer has been proposed that has excellent rigidity after water absorption and rigidity under high-temperature use, and has little change in physical properties under use in any environment. There is no actual situation. In addition, it is difficult to suppress a decrease in rigidity after water absorption and under high temperature use while maintaining a balance between mechanical strength and rigidity, which is a characteristic of polyamide copolymers, and a polyamide sheet having such physical properties is obtained. It is requested.

  The present invention has been made in view of the above-mentioned problems of the prior art, and has excellent rigidity after water absorption (water absorption rigidity), rigidity under high temperature use (heat rigidity), and sheet formability. The main object is to provide a polyamide sheet.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that (ap) adipic acid units, (bp) isophthalic acid units, and (cp) 1,4-cyclohexanedicarboxylic acid units. A polyamide copolymer comprising a dicarboxylic acid component unit comprising: and a diamine component unit, the (ap), (bp), and (cp) constituting the polyamide copolymer. The relationship between the content (mol%) of (bp) and the content (mol%) of (cp) in a total of 100 mol% of the dicarboxylic acid component units containing The present inventors have found that a polyamide sheet containing a polyamide copolymer (A) satisfying the above requirements can solve the above problems, and have completed the present invention.
Content of (cp)> Content of (bp) ≧ 0.1 (1)
That is, the present invention is as follows.

[1]
(A): a dicarboxylic acid component unit comprising (ap) an adipic acid unit, (bp) isophthalic acid unit, and (cp) 1,4-cyclohexanedicarboxylic acid unit; and a diamine component unit. A polyamide copolymer comprising:
The total amount of the dicarboxylic acid component units including the (ap), the (bp), and the (cp) constituting the polyamide copolymer is 100 mol%. A polyamide sheet comprising a polyamide copolymer in which the relationship between the content (mol%) and the content (mol%) of (cp) satisfies the following formula (1).
Content of (cp)> Content of (bp) ≧ 0.1 (1)
[2]
With respect to a total of 100 mol% of the dicarboxylic acid component units including the (ap), the (bp), and the (cp),
The content of the (ap) adipic acid unit is 40 to 80 mol%,
The content of the (bp) isophthalic acid unit is 0.1 to 25 mol%,
The content of the (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 40 mol%,
The polyamide sheet according to [1].
[3]
The polyamide sheet according to any one of [1] or [2], wherein the diamine component unit is an aliphatic diamine component unit.
[4]
The polyamide sheet according to [3], wherein the diamine component unit is a hexamethylenediamine unit.
[5]
Content (mol%) of (bp) isophthalic acid unit and content of trans isomer unit of (c-1-p) 1,4-cyclodicarboxylic acid unit in the polyamide copolymer (mol%) The polyamide sheet containing the polyamide copolymer according to claim 1, wherein the relationship with (1) satisfies the following formula (2).
(C-1-p) Content of trans isomer unit of 1,4-cyclodicarboxylic acid unit> (bp) Content of isophthalic acid unit ≧ 0.1 (2)
[6]
Trans isomer (c) to cis isomer (c-2-m) in (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclodicarboxylic acid −1-m) molar ratio ((c-1-m) / (c-2-m)) is from the above (cm) 1,4-cyclohexanedicarboxylic acid comprising 50/50 to 10/90. The manufacturing method of the polyamide sheet using the polyamide copolymer of Claim 5 obtained by copolymerizing the dicarboxylic acid component and diamine component which become the final ultimate temperature of 270 degreeC or more.
[7]
The method for producing a polyamide sheet according to [5] or [6], wherein the diamine component is an aliphatic diamine component.
[8]
The method for producing a polyamide sheet according to [7], wherein the aliphatic diamine component is hexamethylenediamine.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide sheet excellent also in the rigidity (water absorption rigidity) after water absorption, the rigidity under high temperature use (rigidity at the time of heat), and sheet moldability can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Polyamide sheet]
The polyamide sheet of this embodiment is
(A): a dicarboxylic acid component unit comprising (ap) adipic acid units, (bp) isophthalic acid units, and (cp) 1,4-cyclohexanedicarboxylic acid units;
A diamine component unit, and a polyamide copolymer comprising:
The total amount of the dicarboxylic acid component units including the (ap), the (bp), and the (cp) constituting the polyamide copolymer is 100 mol%. It is a polyamide sheet containing a polyamide copolymer in which the relationship between the content (mol%) and the content (mol%) of (cp) satisfies the following formula (1).

((A) polyamide copolymer)
(A) Polyamide copolymer (in this specification, (A): may be described as a polyamide copolymer or a polyamide copolymer (A)) is (ap) an adipic acid unit, (b -P) a polyamide copolymer containing a dicarboxylic acid component unit containing an isophthalic acid unit and a (cp) 1,4-cyclohexanedicarboxylic acid unit, and a diamine component unit, the polyamide copolymer constituting the polyamide copolymer Content (mol%) of (bp) in a total of 100 mol% of the dicarboxylic acid component units including (ap), (bp), and (cp) The relation of the content (mol%) of (cp) is a polyamide copolymer satisfying the following formula (1).
Thereby, it can be set as the polyamide sheet which is not only excellent in water absorption rigidity and the rigidity at the time of heat | fever but is excellent also in sheet moldability.
Content of (cp)> Content of (bp) ≧ 0.1 (1)

<Dicarboxylic acid component>
The composition ratio of the dicarboxylic acid component unit in the (A) polyamide copolymer is the (ap) adipic acid unit, (bp) isophthalic acid unit, and (cp) 1,4-cyclohexane. Preferably, the content of (ap) adipic acid unit is 35 to 80 mol%, and the content of (bp) isophthalic acid unit is 100 mol% in total of dicarboxylic acid component units including dicarboxylic acid units. The content of 0.1 to 25 mol% and (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 45 mol%, and a more preferable composition ratio is the content of (ap) adipic acid unit Is 40 to 80 mol%, (bp) the content of isophthalic acid units is 1 to 25 mol%, and (cp) the content of 1,4-cyclohexanedicarboxylic acid units is 20 to 40 mol% And (bp) (C-p) relation is a polyamide copolymer which satisfies the above formula (1).
By setting the composition ratio within the above range and satisfying the relationship of the formula (1), it is possible to obtain a polyamide resin composition having further excellent water absorption rigidity and thermal rigidity without impairing sheet formability.
In addition, the ratio of each composition which comprises a polyamide copolymer can be calculated | required with a nuclear magnetic resonance apparatus (NMR).

<Diamine component>
The diamine component unit in the (A) polyamide copolymer is not particularly limited, and examples thereof include aliphatic diamines, aromatic diamines, and diamines having substituents branched from the main chain. Among these, aliphatic Diamine is preferred.

  Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, heptamethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, And straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as tridecamethylenediamine. Among these aliphatic diamine components, hexamethylene diamine is preferable from the viewpoint of rigidity.

  Examples of the aromatic diamine include metaxylylenediamine.

  Examples of the diamine having a substituent branched from the main chain include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine.

  One of these diamine components may be used alone, or two or more of these diamine components may be used in combination.

<Other copolymer components>
(A) The polyamide copolymer has (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid as long as the object of the present embodiment is not impaired. Other aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, polycondensable amino acids, lactams, and the like can be used as copolymerization components.

  Examples of aliphatic dicarboxylic acids other than (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyl C3-C20 straight chain such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid Examples include branched saturated aliphatic dicarboxylic acids.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid. An alicyclic dicarboxylic acid etc. whose number is 5-10 are mentioned. The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.

Examples of the aromatic dicarboxylic acid include unsubstituted or various substitutions such as terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with a group.
Examples of the various substituents include halogen groups such as alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, chloro groups and bromo groups, and carbon numbers. Examples thereof include 3 to 10 alkylsilyl groups, and sulfonic acid groups and groups such as sodium salts thereof.

  Examples of the polycondensable amino acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid and the like.

  Examples of the lactam include butyl lactam, pivalolactam, caprolactam, capryl lactam, enantolactam, undecanolactam, dodecanolactam and the like.

  These dicarboxylic acid components, amino acid components, and lactam components may be used alone or in combination of two or more.

  The (A) polyamide copolymer comprises (a′-p) a unit composed of adipic acid and hexamethylene diamine, (b′-p) a unit composed of isophthalic acid and hexamethylene diamine, and (c′-p). It is preferable that a unit comprising 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine is included. By including such a unit, it is possible to obtain a polyamide sheet that is further excellent in water absorption rigidity and high-temperature rigidity.

<End sealant>
As a raw material for the (A) polyamide copolymer, an end-capping agent can be further added in order to adjust the molecular weight or improve hot water resistance. For example, when polymerizing the (A) polyamide copolymer, a known end-capping agent can be further added.

  The terminal blocking agent is not particularly limited, and examples thereof include acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Among them, monocarboxylic acids and monoamines are preferable from the viewpoint of production cost. These terminal blocking agents may be used alone or in combination of two or more.

  The monocarboxylic acid used as a terminal blocking agent is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Aliphatic monocarboxylic acids such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalene And aromatic monocarboxylic acids such as carboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. These monocarboxylic acids may be used alone or in combination of two or more.

  The monoamine used as the end-capping agent is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine Aliphatic monoamines such as dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; These monoamines may be used alone or in combination of two or more.

<Number average molecular weight>
The molecular weight of the (A) polyamide copolymer is not particularly limited, but from the viewpoint of moldability and mechanical properties, the number average molecular weight (Mn) is preferably 7000 to 100,000, more preferably 7500 to 50,000. Yes, more preferably from 10,000 to 40,000.
The number average molecular weight (Mn) is determined by gel permeation using, for example, hexafluoroisopropanol (HFIP) in which 0.1 mol% of sodium trifluoroacetate is dissolved as a solvent and polymethyl methacrylate (PMMA) as a standard sample. It can be determined by chromatography (GPC).
When the number average molecular weight (Mn) of the (A) polyamide copolymer is 7000 or more, there is a tendency that a decrease in toughness can be further suppressed. Tend.

<Melting point>
The melting point of the (A) polyamide copolymer is preferably 210 to 340 ° C, more preferably 230 to 330 ° C, still more preferably 240 to 320 ° C, and still more preferably 240 to 300 ° C. is there.
The melting point can be measured according to JIS K7121. More specifically, for example, measurement can be performed using “DSC-7” manufactured by PERKIN-ELMER.
Specifically, using 8 mg of the sample, the temperature is raised to 400 ° C. under a temperature rising rate of 20 ° C./min, and the peak temperature of the obtained melting curve is taken as the melting point.
When the melting point is 210 ° C. or higher, the chemical resistance and the heat resistance tend to be further suppressed, and when it is 340 ° C. or lower, the thermal decomposition during molding tends to be further suppressed.

<Glass transition temperature>
The glass transition temperature of said (A) polyamide copolymer becomes like this. Preferably it is 50-110 degreeC, More preferably, it is 50-100 degreeC, More preferably, it is 50-90 degreeC.
The glass transition temperature can be measured according to JIS K7121. More specifically, for example, measurement can be performed using “DSC-7” manufactured by PERKIN-ELMER.
First, the sample is melted on a hot stage (for example, “EP80” manufactured by Mettler Co.), and the molten sample is rapidly cooled in liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the measurement sample, the glass transition temperature can be measured by raising the temperature in the range of 30 to 300 ° C. under a temperature rising rate of 20 ° C./min.
When the glass transition temperature is 50 ° C. or higher, it is difficult to cause a decrease in heat resistance and chemical resistance, and an increase in water absorption can be effectively prevented. In addition, when the glass transition temperature is 110 ° C. or lower, a product having a more excellent molded appearance can be obtained.

((A) Polyamide copolymer production method)
(A) It does not specifically limit as a manufacturing method of a polyamide copolymer, A well-known method can be used.
For example, a solution of adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, and a mixture of other components as necessary, or an aqueous suspension is heated and polymerized while maintaining the molten state. Method (thermal melt polymerization method); Method of increasing the degree of polymerization of the polyamide copolymer obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (thermal melt polymerization / solid phase polymerization method); An extruder such as a kneader is further heated with an aqueous solution or water suspension of a mixture of acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, and other components as necessary, and water. Method of increasing the degree of polymerization by re-melting with (a prepolymer / extrusion polymerization method); adipic acid, isophthalic acid, 1,4-cyclohexanedicarbo Heat the aqueous solution of the mixture of acid, hexamethylenediamine, and other components as necessary, or a suspension of water, and the degree of polymerization while maintaining the solid state at a temperature below the melting point of the polyamide. Method of raising (prepolymer / solid phase polymerization method); adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, if necessary, a mixture with other components, solid salt or polycondensate, Examples thereof include a method of polymerizing (solid phase polymerization method) while maintaining a solid state.

(A) It does not specifically limit as a polymerization form of a polyamide copolymer, A batch type or a continuous type may be sufficient.
The polymerization apparatus is not particularly limited, and a known apparatus such as an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like can be used.

Among the above production methods, the hot melt polymerization method is preferable from the viewpoint of productivity. Examples of the hot melt polymerization method include a batch type hot melt polymerization method. The polymerization temperature condition of the batch-type hot melt polymerization method is not particularly limited, but is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 170 ° C. or higher from the viewpoint of productivity.
For example, a mixture of adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and hexamethylenediamine, a solid salt, an aqueous solution, or the like is stirred at a temperature of 110 to 200 ° C., and water vapor is increased to about 60 to 90%. Is gradually removed and concentrated by heating. Subsequently, heating is continued until the internal pressure becomes about 1.5 to 5.0 MPa (gauge pressure). Thereafter, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure) while removing water and / or gas components, and the internal temperature is preferably 250 ° C. or higher, more preferably 260 ° C. or higher, more preferably 270 ° C. or higher. At this point, a hot melt polymerization method can be used in which water and / or gas components are removed and the pressure is gradually released and polycondensation is performed under normal pressure or reduced pressure.
Furthermore, a solid phase polymerization method in which a mixture, a solid salt, or a polycondensate of adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and hexamethylenediamine is subjected to thermal polycondensation at a temperature below the melting point is used. Can do.
These methods may be combined as necessary.

For example, as described above, (a′-p) a unit composed of adipic acid and hexamethylenediamine, (b′-p) a unit composed of isophthalic acid and hexamethylenediamine, and (c′-p) 1,4- A polyamide copolymer containing units composed of cyclohexanedicarboxylic acid and hexamethylenediamine can be produced by a hot melt polymerization method.
The structural unit of the polyamide copolymer can be confirmed by a nuclear magnetic resonance apparatus (NMR).

(A) In the polymerization step of the polyamide copolymer, a dicarboxylic acid component consisting of (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, and a diamine Derived from each of the dicarboxylic acid components, including (cm) 1,4-cyclodicarboxylic acid, (am) adipic acid, and (bm) isophthalic acid The total content of the units to be 100 mol%, (A) the content (mol%) of units derived from the (bp) isophthalic acid constituting the polyamide copolymer and (c-1-p) 1, It is preferable to obtain a polyamide copolymer satisfying the following formula (2) in relation to the content (mol%) of a trans isomer unit of a unit derived from 4-cyclodicarboxylic acid.
(A) By satisfy | filling following formula (2), a polyamide copolymer can further improve water absorption rigidity and high temperature rigidity, without impairing shaping | molding external appearance property.
(C-1-p) Content of trans isomer unit of 1,4-cyclodicarboxylic acid unit> (bp) Content of isophthalic acid unit ≧ 0.1 (2)
In addition, the content of the unit of the trans isomer of the (c-1-p) 1,4-cyclodicarboxylic acid unit and the content of the unit derived from the (bp) isophthalic acid are respectively determined by NMR.

(A) In the polymerization step of the polyamide copolymer, a dicarboxylic acid component containing (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, and a diamine The final internal temperature in copolymerization with the components is preferably 270 ° C. or higher, more preferably 280 ° C. or higher, and further preferably 290 ° C. or higher. As a result, the content of the trans isomer unit (c-1) of 1,4-cyclohexanedicarboxylic acid in the polyamide copolymer can be increased, and the water absorption rigidity and thermal rigidity can be increased without impairing the molding appearance. A more excellent polyamide resin composition can be obtained.
For example, when employing the above-described hot melt polymerization method, it is preferable to carry out polycondensation at normal pressure or reduced pressure while keeping the final internal temperature within the above temperature range.

(A) In the polymerization step of the polyamide copolymer, when an extrusion type reactor such as a kneader is used, the conditions for extrusion are not particularly limited, but the degree of vacuum is preferably about 0 to 0.07 MPa.
The extrusion temperature is preferably about 1 to 100 ° C. higher than the melting point determined by differential scanning calorimetry (DSC) measurement according to JIS K7121. The shear rate is preferably about 100 (sec ⁻¹ ) or more, and the average residence time is preferably about 0.1 to 15 minutes. By setting it as said extrusion conditions, generation | occurrence | production of problems, such as coloring and high molecular weight being unable to be suppressed, can be suppressed effectively.

(A) In the polymerization step of the polyamide copolymer, a predetermined polymerization catalyst may be used.
The catalyst is not particularly limited as long as it is a known one used for the production of polyamide. For example, phosphoric acid, phosphorous acid, hypophosphorous acid, orthophosphorous acid, pyrophosphorous acid, phenylphosphinic acid, phenylphosphonic acid. Examples include acid, 2-methoxyphenylphosphonic acid, 2- (2′-pyridyl) ethylphosphonic acid, and metal salts thereof.
Examples of the metal of the metal salt include metal salts such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony, and ammonium salts.
Further, phosphate esters such as ethyl ester, isopropyl ester, butyl ester, hexyl ester, decyl ester, isodecyl ester, octadecyl ester, stearyl ester, and phenyl ester can also be used.

As described above, (cm) 1,4-cyclohexanedicarboxylic acid used as a raw material monomer in the polymerization step of the (A) polyamide copolymer has a trans isomer and a cis geometric isomer.
(Cm) 1,4-cyclohexanedicarboxylic acid used as a raw material monomer may use either the trans isomer or the cis isomer, or may be used as a mixture in various ratios of the trans isomer and the cis isomer. Good.
(Cm) 1,4-cyclodicarboxylic acid is isomerized at a high temperature to have a certain ratio, and the cis isomer is higher in water solubility of an equivalent salt with diamine than the trans isomer. The molar ratio of the trans isomer (c-1-m) to the cis isomer (c-2-m) in the (cm) 1,4-cyclodicarboxylic acid used ((c-1-m) / (c -2-m)) is preferably 50/50 to 10/90, more preferably 40/60 to 10/90, and even more preferably 35/65 to 15/85.
By setting the trans isomer / cis isomer ratio in the above range, it is possible to obtain a polyamide resin composition that is further excellent in water absorption rigidity and thermal rigidity without impairing the molding appearance. The trans isomer / cis isomer ratio can be measured using a nuclear magnetic resonance apparatus (NMR).

The material of the sheet (film) of the present embodiment includes additives commonly used for polyamides, for example, colorants such as pigments and dyes (colored master batches), as long as the object of the present embodiment is not impaired. ), Flame retardant, fibrillating agent, lubricant, fluorescent bleaching agent, plasticizer, antioxidant, stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, It can also contain nucleating agents, rubber, reinforcing agents as well as other polymers.
The sheet (film) of the present embodiment contains a polyamide copolymer, but the content of polyamide in the sheet is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and 95 to 100% by mass. % Is more preferable, and 98 to 100% by mass is even more preferable.

[Inorganic filler]
For example, the filler such as inorganic filler is not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, Hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, aluminosilicate Sodium, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable fluorine mica and Apatite, and the like.
The inorganic filler may be surface treated with a silane coupling agent or the like. Although it does not restrict | limit especially as said silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane. And the like; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Especially, it is preferable that it is 1 or more types selected from said enumeration component, and aminosilanes are more preferable.

[Thermal stabilizer]
For example, as a stabilizer such as a heat stabilizer, for example, a phenol-based heat stabilizer, a phosphorus-based heat stabilizer, an amine-based heat stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb of the periodic table Group, Group IVa and Group IVb element metal salts, and alkali and alkaline earth metal halides.
Among these, from the viewpoint of thermal aging properties, metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table, and alkali and alkaline earth metals The halides are preferred. The above-mentioned heat stabilizers may be used alone or in combination of two or more.

[Phenolic heat stabilizer]
Although it does not restrict | limit as a phenol type heat stabilizer below, For example, a hindered phenol compound is mentioned. Phenol-based heat stabilizers, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.
Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5-di t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3 , 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type. Among these, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.
When using a phenol-based heat stabilizer, the blending amount of the phenol-based heat stabilizer in the polyamide copolymer is preferably 0.01 to 1 part by weight, more preferably 100 parts by weight of the polyamide copolymer. Is 0.1 to 1 part by mass. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

[Phosphorus heat stabilizer]
Examples of the phosphorus-based heat stabilizer include, but are not limited to, for example, pentaerythritol type phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, phenyl Diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di -T-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4'-butylidene-bis (3- Til-6-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-tert-butyl) Phenyl) .di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite , Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono , Dimixed nonylphenyl) phosphite, 4,4′-isopropylidenebis (2- -Butylphenyl) .di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t -Butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenyl polyphosphite, bis (octylphenyl) bis (4,4'-butylidenebis (3-methyl-6-tert-butyl) Phenyl)) · 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphite, tris (4,4′-isopropyl Redenbis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2, 2 Methylene bis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylene bis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4- And di-t-butyl-5-methylphenyl) -4,4′-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type.

  Among those listed above, pentaerythritol phosphite compounds and tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the generated gas. Examples of the pentaerythritol phosphite compound include, but are not limited to, for example, 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-di-t-butyl. -4-methylphenyl methyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2-ethylhexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4 -Methylphenyl isodecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl Isotridecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4 Methylphenyl stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl benzyl Pentaerythritol diphosphite, 2, _6-di-t-butyl-4-methylphenyl ethyl cellosolve Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl butyl carbitol Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl nonylphenyl pentaerythritol Diphosphite, bis (2,6-di-t- Til-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl, 2,4-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2,4-di-t-octylphenyl · pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2-cyclohexyl Phenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol Diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight is mentioned. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) Pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

  When using a phosphorus heat stabilizer, the compounding quantity of the phosphorus heat stabilizer in a polyamide copolymer is 0.01-1 mass part with respect to 100 mass parts of polyamide copolymers, More preferably, it is 0. .1 to 1 part by mass. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

[Amine heat stabilizer]
Examples of amine heat stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4 -Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethyl Piperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethyl Piperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2, 2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, Bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6- Tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6) Tetramethyl-4-piperyl__dioxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6) -Tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2 , 6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4 -Tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl) -4-hydroxyphenyl) Pionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′ , Β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type.

  When an amine heat stabilizer is used, the compounding amount of the amine heat stabilizer in the polyamide copolymer is preferably 0.01 to 1 part by mass, more preferably 100 parts by mass of the polyamide copolymer. Is 0.1 to 1 part by mass. When it is within the above range, the heat aging resistance can be further improved, and the amount of generated gas can be further reduced.

[Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table]
The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table is not particularly limited, but is preferably a copper salt. is there. Examples of such copper salts include, but are not limited to, copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid. Examples thereof include copper, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. These may be used alone or in combination of two or more.

Among the copper salts listed above, one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate are preferred, and copper iodide is more preferred. And / or copper acetate. When such a preferable copper salt is used, a polyamide having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter also simply referred to as “metal corrosion”) of a screw or a cylinder during extrusion is obtained.
When using a copper salt, the compounding amount of the copper salt in the polyamide copolymer is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 parts per 100 parts by mass of the polyamide copolymer. It is -0.15 mass part. When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.
Further, from the viewpoint of improving the heat aging resistance, the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, still more preferably 50 to 300 ppm, based on the total amount of the polyamide copolymer. .

[Alkali metal and alkaline earth metal halides]
Examples of alkali metal and alkaline earth metal halides include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Can be mentioned. In particular, from the viewpoint of improvement in heat aging resistance and suppression of metal corrosion, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable.
When alkali metal and alkaline earth metal halides are used, the blending amount of the alkali metal and alkaline earth metal halides in the polyamide copolymer is preferably 0.000 with respect to 100 parts by mass of the polyamide copolymer. It is 05-5 mass parts, More preferably, it is 0.2-2 mass parts. Within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

The component of the heat stabilizer mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type. Particularly preferred are mixtures of copper salts with alkali metal and alkaline earth metal halides.
The ratio of the copper salt to the alkali metal and alkaline earth metal halide is included in the polyamide copolymer so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. It is preferably 5/1 to 30/1. In the above range, the heat aging resistance can be further improved.
When the halogen / copper is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed.
On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw of the molding machine can be prevented without substantially impairing mechanical properties such as toughness.

(A) As a manufacturing method of the material of the sheet | seat (film) of this Embodiment in the case of making a polyamide copolymer contain another component, what is the method of mixing a (A) polyamide copolymer and another component? For example, there is no particular limitation.
As a method for mixing the polyamide and the inorganic filler, for example, a method in which the polyamide and other components are mixed using a Henschel mixer, and supplied to a melt kneader and kneaded, or in a molten state with a single or twin screw extruder. The method of mix | blending other components with polyamide from a side feeder is mentioned. Moreover, the method of pellet-blending the thing which made the other component the masterbatch and / or a raw material is mention | raise | lifted.

  In the method of supplying polyamide and other components to the melt-kneader, all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports. The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature. The melt kneading time is preferably about 0.25 to 5 minutes. The apparatus for performing the melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a mixing roll, or the like can be used.

  The polyamide sheet of the present embodiment has a thickness of 0.01 to 2.0 mm, preferably 0.01 to 0.5 mm, and more preferably 0.01 to 0.2 mm. The polyamide sheet of the present embodiment can be manufactured by a conventionally known method using the above-mentioned (A) polyamide, mixing with the above-mentioned other materials, and using this as a raw material.

  The polyamide sheet of the present embodiment can be prepared by mixing constituent materials in advance and molding the extruded sheet. In addition, the constituent components are directly fed into an extruded sheet molding machine, and blending and sheet molding are performed simultaneously. It can also be made. Moreover, you may manufacture the polyamide sheet of this Embodiment by the extrusion tubular method (method also called the inflation method). Furthermore, the polyamide sheet of the present embodiment can also be manufactured by a T-die extrusion method. In this case, it may be used without stretching, may be uniaxially stretched, or may be biaxially stretched. When it is desired to increase the strength of the sheet, it can be achieved by stretching.

  The polyamide sheet of the present embodiment may have a surface laminated with a paint, a metal layer, various polymers, or the like.

[Use]
The polyamide sheet of the present embodiment is excellent in heat resistance, strength, toughness, low water absorption, moldability, and has an excellent color tone, so it is for automobiles, electric and electronic, industrial materials It can be suitably used as various parts materials for daily use and household goods. There are no particular limitations on the electrical and electronic use, and for example, it is used for electrical insulating materials such as motors, transformers, and cables, dielectric materials such as capacitors, printed circuit boards, and electronic board materials such as flat cables.
There is no particular limitation for industrial equipment, and for example, it is used for magnetic materials such as sheet magnets.
It is not specifically limited as for daily use and household goods, for example, it is used for buttons, food containers, office furniture and the like.

Hereinafter, the present embodiment will be described more specifically by way of examples. However, the present embodiment is not limited to these examples.
The structures of the materials used in the examples and comparative examples, the methods for measuring physical properties, the molding methods, and the evaluation methods are shown below.

[Measuring method of material structure and physical properties]
(Number average molecular weight (Mn) of polyamide copolymer)
The number average molecular weight of the polyamide copolymer was 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) in which 0.1 mol% of sodium trifluoroacetate is dissolved, the column Used 2 pieces of “TSKgel-GMHHR-H” and 1 piece of “G1000HHR” manufactured by Tosoh Corporation.
The solvent flow rate was 0.6 mL / min, and the sample concentration was 1 to 3 (mg sample) / 1 (mL solvent), which was filtered through a filter to remove insolubles, thereby obtaining a measurement sample.
Based on the obtained elution curve, the number average molecular weight (Mn) was calculated in terms of polymethyl methacrylate (PMMA).

(Trans isomer ratio of 1,4-cyclohexanedicarboxylic acid unit in polyamide copolymer, and constitutional unit in polyamide copolymer)
The trans isomer ratio of 1,4-cyclohexanedicarboxylic acid units in the polyamide copolymer was measured by ¹ H-NMR after dissolving 30 to 40 mg of the polyamide copolymer in 1.2 g of hexafluoroisopropanol deuteride.
As a device, “JNM ECA-500” manufactured by JEOL Ltd. was used. In the case of 1,4-cyclohexanedicarboxylic acid, the trans isomer ratio (trans isomer / cis isomer) was determined from the ratio between the peak area derived from the trans isomer and the peak area derived from the cis isomer.
Moreover, the ratio of the structural unit in a polyamide copolymer was measured by < ¹ > H-NMR, and it calculated | required from the ratio of the peak area originating in each component.
The peaks used for the ratio calculation are shown below.

<Trans / cis ratio of 1,4-cyclohexanedicarboxylic acid in polyamide copolymer>
Transpeak: 1.98 ppm
Cis peak: 1.77 ppm, 1.86 ppm
<Ratio of structural units in polyamide copolymer>
1,4-cyclohexanedicarboxylic acid: peak used for the above trans / cis ratio Adipic acid: 2.3 ppm, 2.4 ppm
Isophthalic acid: 3.5ppm
Hexamethylenediamine: 3.28 ppm, 3.5 ppm

(Mole ratio of trans / cis of raw material 1,4-cyclohexanedicarboxylic acid)
Using a HPLC (high performance liquid chromatography) apparatus, the molar ratio of trans / cis in 1,4-cyclohexanedicarboxylic acid as a raw material monomer was measured.
As an HPLC apparatus, LC-10A manufactured by Shimadzu Corporation was used. The 1,4-cyclohexanedicarboxylic acid monomer is separated into a trans component (elution time of about 11 minutes) and a cis component (elution time of about 14.5 minutes) by a gradient elution method using a reverse phase column. It calculated | required by ratio of peak area.
Details of the HPLC analysis conditions are shown below.

Equipment: Shimadzu Corporation LC-10A vp
Reversed phase (C30) column: Nomura Chemical Co., Ltd. Develosil PRAQUEUS
Temperature: 40 ° C
Flow rate: 1.0 mL / min
Detection: UV214nm
Mobile phase A: water (containing 0.1% by mass of trifluoroacetic acid)
Mobile phase B: water / acetonitrile = 10/90 (containing 0.1% by mass of trifluoroacetic acid)
Mobile phase mixing ratio: B = 0 → 100% (15 minutes)
Sample concentration: 10 mg / mL
(Solvent: (water / acetonitrile = 50/50)
Sample solution injection volume: 20 mL

(Melting point (℃))
The melting point was measured using “DSC-7” manufactured by PERKIN-ELMER according to JIS K7121.
The measurement conditions are as follows. The temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample is heated at a rate of temperature increase of 20 ° C./min in a nitrogen atmosphere is Tm 1 (° C.). The temperature is lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held for 2 minutes, held for 2 minutes, and then the peak temperature of the endothermic peak (melting peak) that appears when the temperature is raised at a temperature rise rate of 20 ° C./min (° C.)).

(Glass transition temperature (℃))
The glass transition temperature was measured using “DSC-7” manufactured by PERKIN-ELMER according to JIS K7121.
First, the sample was melted on a hot stage (“EP80” manufactured by Mettler), and the molten sample was quenched in liquid nitrogen and solidified to obtain a measurement sample.
A 10 mg sample for measurement was heated in the range of 30 to 300 ° C. under a temperature rising rate of 20 ° C./min, and the glass transition temperature was measured.

(Sheet formability)
“Formability” when the sheet-like molded body shown below was produced was evaluated by thickness unevenness. The thickness of the central part of the sheet was measured at 30 points every 30 seconds in the flow direction, and evaluated based on the occurrence of thickness unevenness.
A: The thickness unevenness measured at 20 points is less than 10% of the set thickness, and the thickness of the sheet is fairly stable.
Δ: The thickness unevenness of the 20-point measurement is less than 20% of the set thickness, but the sheet feels slightly wavy, but the thickness is stable.
X: Thickness unevenness measured at 20 points, there are 20% or more of the set thickness, and the sheet is considerably wavy. Or, a film having a stable thickness cannot be obtained.

(Measurement of tensile modulus)
The tensile elastic modulus was measured according to ISO527 using the sheet-like molded body shown below.

(Measurement of tensile modulus after water absorption)
Using the sheet-like molded body shown below, after being immersed in warm water at 80 ° C. for 24 hours, the tensile elastic modulus was measured according to ISO 527.
Wet retention was determined using the following formula.
Wet retention (%) = after water absorption (Wet) tensile modulus / before water absorption (Dry) tensile modulus × 100

(Measurement of tensile modulus at 100 ° C)
The tensile modulus of elasticity was measured according to ISO 527 in an atmosphere of 100 ° C. as shown below. The 100 ° C. retention was determined using the following formula.
100 ° C. retention (%) = 100 ° C. tensile modulus / before water absorption (Dry) tensile modulus × 100

[Polyamide sheet]
(material)
The following compounds were used in the production of polyamide copolymers in Examples and Comparative Examples.
(1) Adipic acid Wako Pure Chemical Industries, Ltd. Product name: Adipic acid (2) 1,4-cyclohexanedicarboxylic acid, Eastman Chemical product name: 1,4-CHDA HP grade (trans isomer / cis isomer (mol) Ratio) = 25/75)
(3) Isophthalic acid Product name: Isophthalic acid, manufactured by Wako Pure Chemical Industries, Ltd.
(4) Hexamethylenediamine Product name: Hexamethylenediamine, manufactured by Wako Pure Chemical Industries, Ltd.

<Production Example 1: Production of polyamide copolymer (A1)>
Adipic acid 517.0 g (3.54 mol), isophthalic acid 55.1 g (0.33 mol), and trans-cis / cis-isomer molar ratio 25/75 285.5 g (1 .66 mol) and 642.3 g (5.53 mol) of hexamethylenediamine were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomer.
This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to concentrate the solution concentration to 70% by mass. Thereafter, the internal temperature was raised to 218 ° C. At this time, the autoclave was pressurized to 1.8 MPa. Then, until the internal temperature reached 270 ° C., the reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa.
Next, the pressure was reduced to 1 MPa over 1 hour, and the polymerization was further continued for 15 minutes while flowing nitrogen into the autoclave to obtain a polyamide copolymer. At this time, the final internal temperature of the polymerization was 290 ° C.
The obtained polyamide copolymer was pulverized to a size of 2 mm or less and dried at 100 ° C. in a nitrogen atmosphere for 12 hours. The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 69.8 mol%.
The composition of the obtained polyamide copolymer (A1) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A1) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 2: Production of polyamide copolymer (A2)>
440.6 g (3.02 mol) of adipic acid, 91.1 g (0.55 mol) of isophthalic acid, 330.6 g (1) of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 .92 mol), and the polyamide copolymer was polymerized by the method described in Production Example 1 except that 637.4 g (5.49 mol) of hexamethylenediamine was used.
At this time, the final internal temperature of the polymerization was 291 ° C. The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 71.4 mol%.
The composition of the obtained polyamide copolymer (A2) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A2) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 3: Production of polyamide copolymer (A3)>
Adipic acid 509.4 g (3.49 mole), isophthalic acid 128.7 g (0.77 mole), and trans-cis / cis mole ratio 25/75, 219.1 g (1 .27 mol) and 642.9 g (5.53 mol) of hexamethylenediamine were used to polymerize the polyamide copolymer by the method described in Production Example 1. At this time, the final internal temperature of the polymerization was 292 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 71.8 mol%.
The composition of the obtained polyamide copolymer (A3) is shown in Table 1 below. The proportion of the structural unit of the polyamide copolymer shown in Table 1, the obtained copolymer was determined by analyzing by ^{1 H-NMR.}
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A3) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 4: Production of polyamide copolymer (A4)>
Adipic acid 433.3 g (2.97 mol), isophthalic acid 173.3 g (1.04 mol), and trans-cis / cis-isomer molar ratio 25/75 255.3 g (1 .48 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 638.1 g (5.49 mol) of hexamethylenediamine was used. At this time, the final internal temperature of the polymerization was 293 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.0 mol%.
The composition of the obtained polyamide copolymer (A4) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A4) was evaluated for molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 5: Production of polyamide copolymer (A5)>
Adipic acid 595.3 g (4.07 mol), isophthalic acid 83.4 g (0.50 mol), 172.9 g (1 mol) of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 0.0000 mol) and 648.4 g (5.58 mol) of hexamethylenediamine, the polyamide copolymer was polymerized by the method described in Production Example 1. At this time, the final internal temperature of the polymerization was 290 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.2 mol%.
The composition of the obtained polyamide copolymer (A5) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A5) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 6: Production of polyamide copolymer (A6)>
337.5 g (2.28 mol) of adipic acid, 207.6 g (1.25 mol) of isophthalic acid, 327.5 g of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 (1 .90 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 631.4 g (5.43 mol) of hexamethylenediamine was used. At this time, the final internal temperature of the polymerization was 290 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 70.2 mol%.
The composition of the obtained polyamide copolymer (A6) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A6) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 7: Production of polyamide copolymer (A7)>
331.6 g (2.28 mol) of adipic acid, 135.2 g (0.81 mol) of isophthalic acid, 401.6 g (2 of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 .33 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 630.3 g (5.42 mol) of hexamethylenediamine was used. At this time, the final internal temperature of the polymerization was 292 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.1 mol%.
The composition of the obtained polyamide copolymer (A7) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A7) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 8: Production of polyamide copolymer (A8)>
Adipic acid 268.1g (1.83mol), isophthalic acid 233.1g (1.40mol), 1,4-cyclohexanedicarboxylic acid 371.7g (2 .16 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 627.1 g (5.40 mol) of hexamethylenediamine was used. At this time, the final internal temperature of the polymerization was 291 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.3 mol%.
The composition of the obtained polyamide copolymer (A8) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A8) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Comparative Production Example 1: Polyamide copolymer (A9)>
692.2 g (4.74 mol) of adipic acid, 74.9 g (0.45 mol) of isophthalic acid, 77.7 g of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 80/20 (0 .45 mol) and 655.2 g (5.64 mol) of hexamethylenediamine were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomer. This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen. While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 218 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the temperature reached 253 ° C. for 1 hour.
Next, the pressure was reduced to 1 MPa over 1 hour, and the polymerization was further continued for 15 minutes while flowing nitrogen into the autoclave to obtain a polyamide copolymer.
This was pulverized to a size of 2 mm or less and dried in a nitrogen atmosphere at 100 ° C. for 12 hours.
The composition of the obtained polyamide copolymer (A9) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A9) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Comparative Production Example 2: Polyamide copolymer (A10)>
Adipic acid 595.9 g (4.08 mol), isophthalic acid 129.9 g (0.78 mol), 125.0 g of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 80/20 (0 .73 mol), and the polyamide copolymer was polymerized by the method described in Comparative Production Example 1 except that the hexamethylenediamine was 649.1 g (5.59 mol).
The composition of the obtained polyamide copolymer (A10) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A10) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Comparative Production Example 3: Polyamide copolymer (A11)>
Adipic acid 317.5 g (2.17 mol), isophthalic acid 270.7 g (1.63 mol), 1,4-cyclohexanedicarboxylic acid 280.6 g (1 mole ratio of trans / cis isomer) is 80/20 0.663 mol), and a polyamide copolymer was polymerized by the method described in Comparative Production Example 1 except that 631.2 g (5.43 mol) of hexamethylenediamine was used.
The composition of the obtained polyamide copolymer (A11) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A11) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Comparative Production Example 4: Polyamide copolymer (A12)>
Adipic acid 509.9 g (3.49 mol), isophthalic acid 174.8 g (1.05 mol), 1,4-cyclohexanedicarboxylic acid 171.7 g (1 mole ratio of trans / cis isomer) is 80/20 (1 0.0000 mole) and 643.6 g (5.54 mole) of hexamethylenediamine, the polyamide copolymer was polymerized by the method described in Comparative Production Example 1.
The composition of the obtained polyamide copolymer (A12) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A12) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 9: Polyamide copolymer (A13)>
Adipic acid 509.4 g (3.49 mole), isophthalic acid 128.7 g (0.77 mole), and trans-cis / cis mole ratio 25/75, 219.1 g (1 .27 mol) and 642.9 g (5.53 mol) of hexamethylenediamine were dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass aqueous solution of the raw material monomer.
This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen. While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 218 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the temperature reached 253 ° C. for 1 hour.
Next, the pressure was reduced to 1 MPa over 1 hour, and the polymerization was further continued for 15 minutes while flowing nitrogen into the autoclave to obtain a polyamide copolymer. At this time, the final internal temperature of the polymerization was 275 ° C.
This was pulverized to a size of 2 mm or less and dried in a nitrogen atmosphere at 100 ° C. for 12 hours.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 56.7 mol%.
The composition of the obtained polyamide copolymer (A13) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A13) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

[Production example of polyamide sheet]
<Examples 1-9, Comparative Examples 1-4>
The polyamides of Production Examples 1 to 8 and 13 Comparative Production Examples 9 to 12 were further dried in a nitrogen stream, and the moisture content was adjusted to 0.05% by mass or less. Extrusion sheet molding was performed at a screw rotation speed of 30 rpm and a discharge rate of 6 kg / h using a single-screw extruder with a screw diameter of 40 mm, in which the temperature of the cylinder and the temperature of the T dice (width: 40 cm) were set to melting point Tm2 + 20 ° C. .
At this time, the clearance of the T dice and the sheet take-up speed were adjusted so that the sheet had a thickness of 0.10 mm.
Using the prepared sheet, the above-described tensile elastic modulus and sheet formability were evaluated. The evaluation and measurement results are shown in Table 1 below.

As shown in Table 1, it was confirmed that the polyami sheet of each example had excellent water absorption rigidity and hot rigidity, and further excellent sheet formability.
On the other hand, the relationship between the content (mol%) of (bp) isophthalic acid units and the content (mol%) of (cp) 1,4-cyclohexanedicarboxylic acid units is (b−p) = (c -P) from Comparative Examples 1 and 3, and the polyamide copolymer of Comparative Examples 2 and 4 in which the relationship between (bp) and (cp) is (bp)> (cp) It was confirmed that the obtained molded product was greatly reduced in water absorption rigidity and heat rigidity at 100 ° C.
Furthermore, the relationship between the (bp) isophthalic acid unit and the (cp) 1,4-cyclohexanedicarboxylic acid unit is (cp)> (bp), and (c-1-p) Content of trans isomer unit of 1,4-cyclodicarboxylic acid unit> (bp) Content of isophthalic acid unit ≧ 0.1 Molded article obtained from the polyamide copolymer of Example 3 As compared with the molded product of Example 9, it was confirmed that the water absorption rigidity, the thermal rigidity, and the sheet formability were further excellent.

  The polyamide sheet of the present invention has industrial applicability as a molding material for various parts in the automotive field, electrical / electronic field, portable device field, machine / industrial field, office equipment field, aerospace field. .

Claims (8)

(A): a dicarboxylic acid component unit comprising (ap) adipic acid units, (bp) isophthalic acid units, and (cp) 1,4-cyclohexanedicarboxylic acid units, a diamine component unit, A polyamide copolymer comprising:
The total amount of the dicarboxylic acid component units including the (ap), the (bp), and the (cp) constituting the polyamide copolymer is 100 mol%. A polyamide sheet comprising a polyamide copolymer in which the relationship between the content (mol%) and the content (mol%) of (cp) satisfies the following formula (1).
Content of (cp)> Content of (bp) ≧ 0.1 (1) With respect to a total of 100 mol% of the dicarboxylic acid component units including the (ap), the (bp), and the (cp),
The content of the (ap) adipic acid unit is 40 to 80 mol%,
The content of the (bp) isophthalic acid unit is 0.1 to 25 mol%,
The polyamide sheet according to claim 1, wherein the content of the (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 40 mol%.   The polyamide sheet according to claim 1, wherein the diamine component unit is an aliphatic diamine component unit.   The polyamide sheet according to claim 3, wherein the aliphatic diamine component unit is a hexamethylenediamine unit. Content (mol%) of (bp) isophthalic acid unit and content of trans isomer unit of (c-1-p) 1,4-cyclodicarboxylic acid unit in the polyamide copolymer (mol%) The polyamide sheet containing the polyamide copolymer according to claim 1, wherein the relationship with (1) satisfies the following formula (2).
(C-1-p) Content of trans isomer unit of 1,4-cyclodicarboxylic acid unit> (bp) Content of isophthalic acid unit ≧ 0.1 (2)   Trans isomer (c) to cis isomer (c-2-m) in (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclodicarboxylic acid −1-m) molar ratio ((c-1-m) / (c-2-m)) is from the above (cm) 1,4-cyclohexanedicarboxylic acid comprising 50/50 to 10/90. The manufacturing method of the polyamide sheet using the polyamide copolymer of Claim 5 obtained by copolymerizing the dicarboxylic acid component and diamine component which become the final ultimate temperature of 270 degreeC or more.   The method for producing a polyamide sheet according to claim 5 or 6, wherein the diamine component is an aliphatic diamine component.   The method for producing a polyamide sheet according to claim 7, wherein the aliphatic diamine component is hexamethylenediamine.