WO2016208272A1 - ポリアミド樹脂および成形品 - Google Patents
ポリアミド樹脂および成形品 Download PDFInfo
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- WO2016208272A1 WO2016208272A1 PCT/JP2016/063270 JP2016063270W WO2016208272A1 WO 2016208272 A1 WO2016208272 A1 WO 2016208272A1 JP 2016063270 W JP2016063270 W JP 2016063270W WO 2016208272 A1 WO2016208272 A1 WO 2016208272A1
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- dicarboxylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Definitions
- the present invention relates to a novel polyamide resin and a molded product.
- it relates to a polyamide resin excellent in transparency and heat aging resistance and a molded product thereof.
- Patent Document 1 discloses a heat-resistant polyamide resin comprising a diamine component containing 40 mol% or more of bis (aminomethyl) cyclohexane and a dicarboxylic acid component containing 50 mol% or more of isophthalic acid and / or terephthalic acid.
- Patent Document 1 a polyamide resin that is a polycondensate of 1,3-bis (aminomethyl) cyclohexane, isophthalic acid, and terephthalic acid is described.
- Patent Document 2 discloses a mixture of cis-1,3-bis (aminomethyl) cyclohexane 60 to 100 mol% and trans-1,3-bis (aminomethyl) cyclohexane 40 to 0 mol% in the diamine component ( A diamine containing 70 mol% or more) and a dicarboxylic acid containing an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms in the dicarboxylic acid component and 70 mol% or more.
- the object of the present invention is to provide a polyamide resin having high transparency and excellent heat aging resistance.
- ⁇ 1> a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, wherein 70 mol% or more of the structural unit derived from the diamine is derived from 1,3-bis (aminomethyl) cyclohexane, Of the structural units derived from the dicarboxylic acid, 10 to 90 mol% is derived from isophthalic acid, 90 to 10 mol% is derived from a linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms, and derived from terephthalic acid.
- Polyamide resin substantially free of structural units ⁇ 2> 30 to 70 mol% of the structural unit derived from the dicarboxylic acid is derived from isophthalic acid, and 70 to 30 mol% is derived from a linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms.
- ⁇ 4> The polyamide resin according to any one of ⁇ 1> to ⁇ 3>, wherein the polyamide resin has a melt viscosity of 200 to 1200 Pa ⁇ s at a shear rate of 122 sec ⁇ 1 , 280 ° C. and a holding time of 6 minutes.
- ⁇ 5> The polyamide resin according to any one of ⁇ 1> to ⁇ 4>, wherein the polyamide resin has a number average molecular weight of 8000 to 25000.
- ⁇ 6> The polyamide resin according to any one of ⁇ 1> to ⁇ 5>, wherein the polyamide resin has a glass transition temperature of 100 to 190 ° C.
- the 1,3-bis (aminomethyl) cyclohexane constituting the structural unit derived from the diamine has a cis / trans molar ratio (cis / trans) of 100/0 to 50/50,
- the present invention makes it possible to provide a polyamide resin having high transparency and excellent heat aging resistance.
- the polyamide resin of the present invention includes a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from 1,3-bis (aminomethyl) cyclohexane, 10 to 90 mol% of the structural unit derived from dicarboxylic acid is derived from isophthalic acid, 90 to 10 mol% is derived from linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms, and derived from terephthalic acid It is characterized by substantially not including units.
- permeability and excellent heat aging resistance is obtained. Furthermore, a polyamide resin having a low melt viscosity and a high glass transition temperature (Tg) can be obtained.
- 70 mol% or more of the structural unit derived from diamine is derived from 1,3-bis (aminomethyl) cyclohexane.
- the structural unit derived from diamine is preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more, Derived from 3-bis (aminomethyl) cyclohexane.
- diamines other than 1,3-bis (aminomethyl) cyclohexane include aliphatic groups such as 1,4-bis (aminomethyl) cyclohexane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, and nonamethylenediamine.
- aromatic diamines such as diamine, paraphenylenediamine, metaxylylenediamine, and paraxylylenediamine. These other diamines may be one type or two or more types.
- 1,3-bis (aminomethyl) cyclohexane which is a raw material diamine for polyamide resin, has a cis isomer and a trans isomer.
- the isomer molar ratio (cis / trans) is preferably 100/0 to 50 / 50, more preferably 90/10 to 60/40, and still more preferably 80/20 to 70/30.
- 10 to 90 mol% of the structural units derived from dicarboxylic acid are derived from isophthalic acid
- 90 to 10 mol% are derived from linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms
- terephthalic acid The structural unit derived from is substantially not included.
- substantially free of structural units derived from terephthalic acid means that, for example, among all the dicarboxylic acids constituting the structural units derived from dicarboxylic acid, terephthalic acid is 10 mol% or less, and 5 moles. % Or less, more preferably 3 mol% or less, and even more preferably 1 mol% or less.
- the lower limit of the proportion of isophthalic acid is preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, more preferably 50 mol. % Or more is more preferable and can also be 51 mol% or more.
- the upper limit of the proportion of isophthalic acid is preferably 80 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less, still more preferably 68 mol% or less, and even more preferably 65 mol% or less. By setting it as such a range, there exists a tendency for the transparency of a polyamide resin to improve more, and it is preferable.
- the lower limit of the proportion of the linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms is preferably 20 mol% or more, more preferably 25 mol% or more, 30 mol% or more is more preferable, 32 mol% or more is more preferable, and 35 mol% or more is still more preferable.
- the upper limit of the proportion of the linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms is preferably 80 mol% or less, more preferably 70 mol% or less, further preferably 60 mol% or less, and further preferably 50 mol% or less. 49 mol% or less.
- the linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms is more preferably an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms.
- Suberic acid, azelaic acid, sebacic acid, 1,9 -Nonanedicarboxylic acid and 1,10-decanedicarboxylic acid are more preferred, and sebacic acid is particularly preferred.
- the linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms may be one type or two or more types. By setting it as such a range, there exists a tendency for the heat aging resistance of a polyamide resin to improve more, and it is preferable.
- the total proportion of isophthalic acid and linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms is preferably 90 mol% or more, and 95 mol% or more. It is preferable that it is 98 mol% or more, and 100 mol% may be sufficient. By setting it as such a ratio, it exists in the tendency for the transparency and heat aging resistance of a polyamide resin to improve more.
- dicarboxylic acids other than isophthalic acid and straight chain aliphatic dicarboxylic acids having 8 to 12 carbon atoms include aliphatic dicarboxylic acids having 7 or less carbon atoms and alicyclic dicarboxylic acids having 6 to 12 carbon atoms. Specific examples thereof include succinic acid, glutaric acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and the like.
- the structural unit derived from dicarboxylic acid in the present invention an embodiment in which 30 to 70 mol% is derived from isophthalic acid and 70 to 30 mol% is derived from a linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms. Is exemplified.
- the structural unit derived from other dicarboxylic acid is preferably 0 to 3 mol%.
- a more preferable range of the present embodiment is the same as the above-described preferable range.
- the polyamide resin of this invention contains the structural unit derived from dicarboxylic acid and the structural unit derived from diamine, structural units other than the structural unit derived from dicarboxylic acid and the structural unit derived from diamine, and other site
- other structural units include structural units derived from lactams such as ⁇ -caprolactam, valerolactam, laurolactam, undecanalactam, and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. It is not limited to these.
- the polyamide resin of the present invention may contain trace components such as additives used in the synthesis.
- the polyamide resin used in the present invention is usually 95% by mass or more, preferably 98% by mass or more of a structural unit derived from dicarboxylic acid or a structural unit derived from diamine.
- the polyamide resin of the present invention is produced by a melt polycondensation (melt polymerization) method with a phosphorus atom-containing compound added.
- melt polycondensation method the raw material diamine is added dropwise to the molten raw material dicarboxylic acid, the temperature is increased under pressure, and polymerization is performed while removing condensed water, or a salt composed of the raw material diamine and the raw material dicarboxylic acid is used.
- a method of raising the temperature under pressure and polymerizing in a molten state while removing added water and condensed water is preferred.
- the phosphorus atom-containing compound added to the polycondensation system of the polyamide resin of the present invention includes dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, hypophosphorous acid.
- hypophosphite metal salts such as sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphite are amidation reaction. It is preferably used because it has a high effect of accelerating the coloration and is excellent in an anti-coloring effect.
- the phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds.
- the polyamide resin of the present invention obtained by melt polycondensation is once taken out, pelletized, and dried before use.
- the polyamide resin of the present invention preferably has a melt viscosity of 200 to 1200 Pa ⁇ s, more preferably 300 to 1000 Pa ⁇ s, more preferably 400 to 1000 Pa ⁇ s at a shear rate of 122 sec ⁇ 1 , 280 ° C. and a holding time of 6 minutes. It can also be set to 900 Pa ⁇ s, in particular 400 to 700 Pa ⁇ s.
- the polyamide resin of the present invention can effectively suppress burrs of a molded product even with such a low melt viscosity.
- the measuring method of melt viscosity follows the method described in the Example mentioned later. In the case where it is difficult to obtain the equipment used in the embodiment due to the out-of-print version or the like, other equipment having equivalent performance can be used. Hereinafter, the same applies to other measurement methods.
- the number average molecular weight of the polyamide resin of the present invention is preferably 8000 to 25000, more preferably 10,000 to 20000, and can also be 12000 to 19000.
- the method for measuring the number average molecular weight follows the method described in the examples described later.
- the polyamide resin of the present invention preferably has a glass transition temperature of 100 to 190 ° C, more preferably 120 to 170 ° C.
- a glass transition temperature of 100 to 190 ° C, more preferably 120 to 170 ° C.
- the method for measuring the glass transition temperature follows the method described in the examples described later.
- the polyamide resin of the present invention can be an amorphous polyamide resin.
- the amorphous polyamide resin is a resin having no clear melting point, and specifically means that the crystal melting enthalpy ⁇ Hm is less than 5 J / g.
- the haze of a molded product having a thickness of 2 mm is preferably 4.5% or less, more preferably 4.0% or less, and further preferably 3.5% or less. , 3.0% or less, and further 2.5% or less.
- the lower limit of haze is preferably 0%, but even if it is 0.001% or more, there is no practical problem.
- the haze in this invention is taken as the value measured by the method as described in the Example mentioned later.
- the polyamide resin of the present invention is a polyamide resin excellent in mechanical strength.
- the polyamide resin of the present invention has a flexural modulus according to ISO 178 of preferably 2.0 GPa or more, more preferably 2.2 GPa or more, and particularly preferably 2.5 GPa or more.
- the upper limit is not particularly defined, but can be set to 5.0 GPa or less, for example.
- the polyamide resin of the present invention preferably has a bending strength according to ISO178 of 80 MPa or more, more preferably 100 MPa or more, and particularly preferably 120 MPa or more.
- the upper limit value is not particularly determined, but can be set to 300 MPa or less, for example.
- the polyamide resin of the present invention can be used as a molded product formed by molding a composition containing a polyamide resin.
- the composition may consist of only one or two or more polyamide resins of the present invention, and may contain other components.
- Other components include polyamide resins other than the polyamide resin of the present invention, thermoplastic resins other than polyamide resins, fillers, matting agents, heat stabilizers, weathering stabilizers, ultraviolet absorbers, plasticizers, flame retardants
- Additives such as antistatic agents, anti-coloring agents, and anti-gelling agents can be added as necessary. Each of these additives may be one kind or two or more kinds.
- polyamide resins include polyamide 6, polyamide 66, polyamide 46, polyamide 6/66 (a copolymer comprising a polyamide 6 component and a polyamide 66 component), polyamide 610, polyamide 612, polyamide 11, and polyamide. 12 is exemplified.
- Each of these other polyamide resins may be one kind or two or more kinds.
- the thermoplastic resin other than the polyamide resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.
- One type of thermoplastic resin other than these polyamide resins may be used, or two or more types may be used.
- a molded product formed by molding a composition containing a polyamide resin it can be used for various molded products including films, sheets, thin molded products, hollow molded products and the like.
- the fields of use of such molded products include automobile parts such as automobiles, general machine parts, precision machine parts, electronic / electric equipment parts, OA equipment parts, building materials / residential equipment parts, medical equipment, leisure sports equipment, playground equipment, Medical products, daily necessities such as food packaging films, defense and aerospace products.
- Example 1 Synthesis of 1,3-BAC10I-1> We stir into a pressure-resistant reaction vessel with an internal volume of 50 L equipped with a stirrer, a partial condenser, a full condenser, a pressure regulator, a thermometer, a dripping tank and a pump, an aspirator, a nitrogen introduction pipe, a bottom exhaust valve, and a strand die.
- 1,3-bis (aminomethyl) cyclohexane (1,3-BAC, isomer molar ratio: cis / trans 75/25) stored in a dropping tank into the raw material in the reaction vessel (Mitsubishi Gas (Chemical) 9847 g (69.22 mol) was started to be dropped, and the inside of the reaction vessel was heated to 295 ° C. while removing condensed water produced outside the system while maintaining the inside of the container at 0.4 MPa. After the dropwise addition of 1,3-BAC, the inside of the reaction vessel was gradually returned to normal pressure, and then the inside of the reaction vessel was reduced to 80 kPa using an aspirator to remove condensed water.
- the melt viscosity of the polyamide resin is a condition using a capillograph, a die having a diameter of 1 mm ⁇ 10 mm, an apparent shear rate of 122 sec ⁇ 1 , a measurement temperature of 280 ° C., a holding time of 6 minutes, and a sample moisture of 1000 mass ppm or less. Measured with In this example, Capillograph D-1 manufactured by Toyo Seiki Co., Ltd. was used as the capillograph.
- Tg glass transition temperature
- DSC differential scanning calorimeter
- the obtained polyamide resin pellets were dried, and the dried pellets were extruded at a set temperature of Tg + 150 ° C. with a single screw extruder to produce a plate having a thickness of 2 mm.
- the haze value was measured by a transmission method using a haze value measuring apparatus.
- a model: COH-300A manufactured by Nippon Denshoku Industries Co., Ltd. was used as a haze value measuring apparatus.
- Example 2 ⁇ Synthesis of 1,3-BAC10I-2>
- the molar ratio of sebacic acid and isophthalic acid was set to 36:64, and the others were carried out in the same manner to obtain a polyamide resin.
- the obtained polyamide resin is referred to as “1,3-BAC10I-2”.
- the polyamide resin was changed to 1,3-BAC10I-2, and the others were performed in the same manner.
- Example 1 Comparative Example 1 ⁇ Synthesis of 1,3-BAC6I>
- an equimolar number of adipic acid was used instead of sebacic acid, and the others were carried out in the same manner to obtain a polyamide resin.
- the obtained polyamide resin is referred to as “1,3-BAC6I”.
- the polyamide resin was changed to 1,3-BAC6I, and the others were performed in the same manner.
- Example 2 Comparative Example 2 ⁇ Synthesis of 1,3-BAC10T>
- an equimolar number of terephthalic acid was used in place of isophthalic acid, and the others were carried out in the same manner to obtain a polyamide resin.
- the obtained polyamide resin is referred to as “1,3-BAC10T”.
- the polyamide resin was changed to 1,3-BAC10T, and the others were performed in the same manner.
- 1,3-BAC represents 1,3-bis (aminomethyl) cyclohexane
- SA represents sebacic acid
- AdA represents adipic acid
- PIA represents isophthalic acid
- PTA represents terephthalic acid.
- the polyamide resin of the present invention was found to have high transparency (low Haze) and excellent heat aging resistance.
- the polyamide resin derived from the dicarboxylic acid-derived structural unit derived from linear aliphatic dicarboxylic acid having 7 or less carbon atoms and isophthalic acid (Comparative Example 1) has low transparency and poor heat aging resistance. It was.
- the polyamide resin (Comparative Example 2) in which the structural unit derived from dicarboxylic acid is derived from a linear aliphatic dicarboxylic acid having 8 to 12 carbon atoms and terephthalic acid had low transparency and was inferior in heat aging resistance.
- the crystal melting enthalpy ⁇ Hm was 0 J / g. That is, it was confirmed that these resins are amorphous resins. Furthermore, when the polyamide resin described in Example 1 of JP 2010-285553 A was reproduced and evaluated in the same manner as described above, it was found that the haze was high and the transparency was low. Moreover, when the polyamide resin described in Production Example 1 of JP-A No. 2001-115017 was reproduced and evaluated in the same manner as described above, it was found that the heat aging resistance was poor.
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Abstract
Description
例えば、特許文献1には、ビス(アミノメチル)シクロヘキサンを40モル%以上含むジアミン成分とイソフタル酸および/またはテレフタル酸を50モル%以上含むジカルボン酸成分からなる耐熱性ポリアミド樹脂が開示されている。特許文献1の実施例では、1,3-ビス(アミノメチル)シクロヘキサンと、イソフタル酸と、テレフタル酸の重縮合物であるポリアミド樹脂が記載されている。
また、特許文献2には、ジアミン成分中にシス-1,3-ビス(アミノメチル)シクロヘキサン60~100モル%とトランス-1,3-ビス(アミノメチル)シクロヘキサン40~0モル%の混合物(モル%の合計は100モル%である)を70モル%以上含むジアミンと、ジカルボン酸成分中に炭素数4~20のα,ω-直鎖脂肪族ジカルボン酸を70モル%以上含むジカルボン酸とを重縮合して得られるポリアミド樹脂(A)70~100質量%と、ポリアミド樹脂(A)以外の他の熱可塑性樹脂(B)30~0質量%(質量%の合計は100質量%である)からなる混合樹脂(C)100質量部に対し、無機充填物を10~150質量部配合してなるポリアミド樹脂組成物が記載されている。ここで、特許文献2の実施例では、1,3-ビス(アミノメチル)シクロヘキサンとアジピン酸の重縮合物であるポリアミド樹脂が記載されている。
本発明は、かかる課題を解決することを目的とするものであって、高い透明性および優れた耐熱老化性を有するポリアミド樹脂を提供することを目的とする。
<1>ジアミン由来の構成単位とジカルボン酸由来の構成単位を含み、前記ジアミン由来の構成単位の70モル%以上が、1,3-ビス(アミノメチル)シクロヘキサンに由来し、
前記ジカルボン酸由来の構成単位の、10~90モル%がイソフタル酸に由来し、90~10モル%が炭素数8~12の直鎖脂肪族ジカルボン酸に由来し、かつ、テレフタル酸に由来する構成単位を実質的に含まないポリアミド樹脂。
<2>前記ジカルボン酸由来の構成単位の、30~70モル%がイソフタル酸に由来し、70~30モル%が炭素数8~12の直鎖脂肪族ジカルボン酸に由来する、<1>に記載のポリアミド樹脂。
<3>炭素数8~12の直鎖脂肪族ジカルボン酸が、セバシン酸である、<1>または<2>に記載のポリアミド樹脂。
<4>前記ポリアミド樹脂のせん断速度122sec-1、280℃、保持時間6分における溶融粘度が、200~1200Pa・sである、<1>~<3>のいずれかに記載のポリアミド樹脂。
<5>前記ポリアミド樹脂の数平均分子量が8000~25000である、<1>~<4>のいずれかに記載のポリアミド樹脂。
<6>前記ポリアミド樹脂のガラス転移温度が100~190℃である、<1>~<5>のいずれかに記載のポリアミド樹脂。
<7>前記ジアミン由来の構成単位を構成する1,3-ビス(アミノメチル)シクロヘキサンは、シス体とトランス体のモル比率(シス/トランス)が、100/0~50/50である、<1>~<6>のいずれかに記載のポリアミド樹脂。
<8>非晶性である、<1>~<7>のいずれかに記載のポリアミド樹脂。
<9><1>~<8>のいずれかに記載のポリアミド樹脂を含む組成物を成形してなる成形品。
1,3-ビス(アミノメチル)シクロヘキサン以外のジアミンとしては、1,4-ビス(アミノメチル)シクロヘキサン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン等の脂肪族ジアミン、パラフェニレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン等の芳香族ジアミン等が例示される。これらの他のジアミンは、1種類のみでも2種類以上であってもよい。
ポリアミド樹脂の原料ジアミンである1,3-ビス(アミノメチル)シクロヘキサンは、シス体とトランス体があるが、本発明において、異性体モル比(シス/トランス)は、好ましくは100/0~50/50であり、より好ましくは90/10~60/40であり、さらに好ましくは80/20~70/30である。
ここでテレフタル酸に由来する構成単位を実質的に含まないとは、例えば、ジカルボン酸由来の構成単位を構成する全ジカルボン酸のうち、テレフタル酸が10モル%以下であることをいい、5モル%以下が好ましく、3モル%以下がより好ましく、1モル%以下がさらに好ましい。下限値としては、0モル%であってもよい。
前記ジカルボン酸由来の構成単位を構成する全ジカルボン酸のうち、イソフタル酸の割合の下限値は、20モル%以上が好ましく、30モル%以上がより好ましく、40モル%以上がさらに好ましく、50モル%以上が一層好ましく、51モル%以上とすることもできる。前記イソフタル酸の割合の上限値は、80モル%以下が好ましく、75モル%以下がより好ましく、70モル%以下がさらに好ましく、68モル%以下が一層好ましく、65モル%以下がより一層好ましい。このような範囲とすることにより、ポリアミド樹脂の透明性がより向上する傾向にあり好ましい。
炭素数8~12の直鎖脂肪族ジカルボン酸としては、炭素数8~12のα,ω-直鎖脂肪族ジカルボン酸であることがより好ましく、スベリン酸、アゼライン酸、セバシン酸、1,9-ノナンジカルボン酸、1,10-デカンジカルボン酸がさらに好ましく、セバシン酸が特に好ましい。炭素数8~12の直鎖脂肪族ジカルボン酸は、1種類であってもよいし、2種類以上であってもよい。このような範囲とすることにより、ポリアミド樹脂の耐熱老化性がより向上する傾向にあり好ましい。
溶融粘度の測定方法は、後述する実施例で記載する方法に従う。実施例で採用する機器が、廃版等により入手困難な場合は、他の同等の性能を有する機器を用いることができる。以下、他の測定方法についても、同様である。
本発明のポリアミド樹脂は、ISO178に従った曲げ弾性率が2.0GPa以上であることが好ましく、2.2GPa以上であることがより好ましく、2.5GPa以上であることが特に好ましい。上限値は特に定めるものではないが、例えば、5.0GPa以下とすることができる。
本発明のポリアミド樹脂は、ISO178に従った曲げ強度が80MPa以上であることが好ましく、100MPa以上であることがより好ましく、120MPa以上であることが特に好ましい。上限値は特に定めるものではないが、例えば、300MPa以下とすることができる。
他の成分としては、本発明のポリアミド樹脂以外の他のポリアミド樹脂、ポリアミド樹脂以外の熱可塑性樹脂、充填剤、艶消剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、可塑剤、難燃剤、帯電防止剤、着色防止剤、ゲル化防止剤等の添加剤を必要に応じて添加することができる。これらの添加剤は、それぞれ、1種類であってもよいし、2種類以上であってもよい。
他のポリアミド樹脂としては、具体的には、ポリアミド6、ポリアミド66、ポリアミド46、ポリアミド6/66(ポリアミド6成分およびポリアミド66成分からなる共重合体)、ポリアミド610、ポリアミド612、ポリアミド11、ポリアミド12が例示される。これらの他のポリアミド樹脂は、それぞれ、1種類であってもよいし、2種類以上であってもよい。
ポリアミド樹脂以外の熱可塑性樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等のポリエステル樹脂を例示できる。これらのポリアミド樹脂以外の熱可塑性樹脂は、それぞれ、1種類であってもよいし、2種類以上であってもよい。
<1,3-BAC10I-1の合成>
撹拌機、分縮器、全縮器、圧力調整器、温度計、滴下槽およびポンプ、アスピレーター、窒素導入管、底排弁、ストランドダイを備えた内容積50Lの耐圧反応容器に、精怦したセバシン酸(伊藤精油製)7000g(34.61mol)、イソフタル酸(エイ・ジイ・インタナショナル・ケミカル製)5750g(34.61mol)、次亜リン酸カルシウム(関東化学製)3.3g(0.019mol)、酢酸ナトリウム(関東化学製)1.4g(0.018mol)を入れ、十分に窒素置換した後、反応容器内を密閉し、容器内を0.4MPaに保ちながら撹拌下200℃まで昇温した。200℃に到達後、反応容器内の原料へ滴下槽に貯めた1,3-ビス(アミノメチル)シクロヘキサン(1,3-BAC、異性体モル比:シス/トランス=75/25)(三菱ガス化学製)9847g(69.22mol)の滴下を開始し、容器内を0.4MPaに保ちながら生成する縮合水を系外へ除きながら反応槽内を295℃まで昇温した。1,3-BACの滴下終了後、反応容器内を徐々に常圧に戻し、次いでアスピレーターを用いて反応槽内を80kPaに減圧して縮合水を除いた。減圧中に撹拌機の撹拌トルクを観察し、所定のトルクに達した時点で撹拌を止め、反応槽内を窒素で加圧し、底排弁を開け、ストランドダイからポリマーを抜き出してストランド化したのち、冷却してペレタイザーによりペレット化することにより、ポリアミド樹脂を得た。得られたポリアミド樹脂を、「1,3-BAC10I-1」という。得られたポリアミド樹脂について、以下の評価を行った。結果を表1に示す。
ポリアミド樹脂の溶融粘度は、キャピログラフを用い、ダイとして直径1mm×10mm長さのものを用い、見かけのせん断速度122sec-1、測定温度280℃、保持時間6分、サンプル水分1000質量ppm以下の条件で測定した。本実施例では、キャピログラフとして、(株)東洋精機製のキャピログラフD-1を用いた。
ガラス転移温度は、示差走査熱量計(DSC)を用いて、窒素気流中、室温から250℃まで昇温速度10℃/分で加熱したのち、ただちに室温以下まで冷却し、再び室温から250℃まで昇温速度10℃/分で加熱した際のガラス転移温度を測定した。本実施例では、示差走査熱量計として、(株)島津製作所製DSC-60を用いた。
また、JIS K7121に準じて、昇温過程におけるポリアミド樹脂の結晶融解エンタルピーΔHm(X)を測定した。
ポリアミド樹脂0.3gを、フェノール/エタノール= 4/1容量溶液に20~30℃ で撹拌溶解させ、完全に溶解した後、撹拌しつつ、メタノール5mlで容器内壁を洗い流し、0.01m ol/L塩酸水溶液で中和滴定して末端アミノ基濃度〔NH2〕を求めた。また、ポリアミド樹脂0.3gを、ベンジルアルコールに窒素気流下160~180℃で撹拌溶解させ、完全に溶解した後、窒素気流下80℃以下まで冷却し、撹拌しつつメタノール10mlで容器内壁を洗い流し、0.01mol/L水酸化ナトリウム水溶液で中和滴定して末端カルボキシル基濃度〔COOH〕を求めた。測定した末端アミノ基濃度〔NH2〕および末端カルボキシル基濃度〔COOH〕から、次式によって数平均分子量を求めた。
数平均分子量=2/(〔NH2〕+〔COOH〕)
〔NH2〕: 末端アミノ基濃度(当量/g)
〔COOH〕: 末端カルボキシル基濃度(当量/g)
得られたポリアミド樹脂ペレットを乾燥させ、乾燥したペレットを単軸押出機にて設定温度をTg+150℃として押出し、厚さ2mm厚のプレートを作製した。曇価測定装置を使用して透過法によりヘイズ値を測定した。本実施例では、曇価測定装置として、日本電色工業(株)製、型式:COH-300Aを用いた。
得られたポリアミド樹脂ペレットを、120℃(露点-40℃)で24時間真空乾燥したのち、射出成形機(住友重機械工業(株)SE130DU-HP)にて、金型温度100℃、シリンダー温度を280℃の条件で、4mm×10mm×80mmの試験片を作製した。この試験片を熱風乾燥機(ヤマト科学(株)製、DF611)にて、内部温度120℃の条件で、試験片を加熱した。30日経過後に取出し、ISO178に準じて、オートグラフ(東洋精機(株)製、ベントグラフ)にて、23℃/50%RH環境下で曲げ強度(MPa)を測定し、初期値からの保持率(%)を求めた。
得られたポリアミド樹脂ペレットを、120℃(露点-40℃)で24時間真空乾燥したのち、射出成形機(住友重機械工業(株)SE130DU-HP)にて、金型温度100℃、シリンダー温度を280℃の条件で、4mm×10mm×80mmの試験片を作製した。
ISO178に準じて、オートグラフ(東洋精機(株)製、ベントグラフ)にて、23℃/50%RH環境下で曲げ弾性率(GPa)および曲げ強度(MPa)を測定した。
<1,3-BAC10I-2の合成>
実施例1において、セバシン酸とイソフタル酸のモル比率を、36:64とし、他は同様に行って、ポリアミド樹脂を得た。得られたポリアミド樹脂を、「1,3-BAC10I-2」という。
<各種性能評価>
実施例1において、ポリアミド樹脂を1,3-BAC10I-2に変更し、他は同様に行った。
<1,3-BAC6Iの合成>
実施例1において、セバシン酸の代わりに等モル数のアジピン酸を使用し、他は同様に行って、ポリアミド樹脂を得た。
得られたポリアミド樹脂を、「1,3-BAC6I」という。
<各種性能評価>
実施例1において、ポリアミド樹脂を1,3-BAC6Iに変更し、他は同様に行った。
<1,3-BAC10Tの合成>
実施例1において、イソフタル酸の代わりに等モル数のテレフタル酸を使用し、他は同様に行って、ポリアミド樹脂を得た。
得られたポリアミド樹脂を、「1,3-BAC10T」という。
<各種性能評価>
実施例1において、ポリアミド樹脂を1,3-BAC10Tに変更し、他は同様に行った。
また、実施例1および2の樹脂について、結晶融解エンタルピーΔHmは、0J/gであった。すなわち、これらの樹脂が非晶性樹脂であることが確認された。
さらに、特開2010-285553号公報の実施例1に記載のポリアミド樹脂を再現し、上記と同様に評価したところ、ヘイズが高く透明性が低いことが分かった。
また、特開2001-115017号公報の製造例1に記載のポリアミド樹脂を再現し、上記と同様に評価したところ、耐熱老化性に劣ることが分かった。
Claims (9)
- ジアミン由来の構成単位とジカルボン酸由来の構成単位を含み、
前記ジアミン由来の構成単位の70モル%以上が、1,3-ビス(アミノメチル)シクロヘキサンに由来し、
前記ジカルボン酸由来の構成単位の、10~90モル%がイソフタル酸に由来し、90~10モル%が炭素数8~12の直鎖脂肪族ジカルボン酸に由来し、かつ、テレフタル酸に由来する構成単位を実質的に含まないポリアミド樹脂。 - 前記ジカルボン酸由来の構成単位の、30~70モル%がイソフタル酸に由来し、70~30モル%が炭素数8~12の直鎖脂肪族ジカルボン酸に由来する、請求項1に記載のポリアミド樹脂。
- 炭素数8~12の直鎖脂肪族ジカルボン酸が、セバシン酸である、請求項1または2に記載のポリアミド樹脂。
- 前記ポリアミド樹脂のせん断速度122sec-1、280℃、保持時間6分における溶融粘度が、200~1200Pa・sである、請求項1~3のいずれか1項に記載のポリアミド樹脂。
- 前記ポリアミド樹脂の数平均分子量が8000~25000である、請求項1~4のいずれか1項に記載のポリアミド樹脂。
- 前記ポリアミド樹脂のガラス転移温度が100~190℃である、請求項1~5のいずれか1項に記載のポリアミド樹脂。
- 前記ジアミン由来の構成単位を構成する1,3-ビス(アミノメチル)シクロヘキサンは、シス体とトランス体のモル比率(シス/トランス)が、100/0~50/50である、請求項1~6のいずれか1項に記載のポリアミド樹脂。
- 非晶性である、請求項1~7のいずれか1項に記載のポリアミド樹脂。
- 請求項1~8のいずれか1項に記載のポリアミド樹脂を含む組成物を成形してなる成形品。
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WO2020040009A1 (ja) | 2018-08-21 | 2020-02-27 | 三菱瓦斯化学株式会社 | 非晶性ポリアミド樹脂の製造方法 |
WO2020137350A1 (ja) | 2018-12-27 | 2020-07-02 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品、成形品の製造方法および酸化防止剤 |
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WO2020040010A1 (ja) | 2018-08-21 | 2020-02-27 | 三菱瓦斯化学株式会社 | 非晶性ポリアミド樹脂の製造方法 |
WO2020040009A1 (ja) | 2018-08-21 | 2020-02-27 | 三菱瓦斯化学株式会社 | 非晶性ポリアミド樹脂の製造方法 |
WO2020137350A1 (ja) | 2018-12-27 | 2020-07-02 | 三菱瓦斯化学株式会社 | 樹脂組成物、成形品、成形品の製造方法および酸化防止剤 |
WO2021070629A1 (ja) | 2019-10-08 | 2021-04-15 | 三菱瓦斯化学株式会社 | 多層容器の製造方法 |
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JPWO2016208272A1 (ja) | 2018-04-12 |
US20180171075A1 (en) | 2018-06-21 |
EP3312215A4 (en) | 2019-02-13 |
JP6825562B2 (ja) | 2021-02-03 |
EP3312215A1 (en) | 2018-04-25 |
TW201706362A (zh) | 2017-02-16 |
CN107709406A (zh) | 2018-02-16 |
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