WO2014051120A1 - ポリアミド樹脂組成物 - Google Patents
ポリアミド樹脂組成物 Download PDFInfo
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- WO2014051120A1 WO2014051120A1 PCT/JP2013/076424 JP2013076424W WO2014051120A1 WO 2014051120 A1 WO2014051120 A1 WO 2014051120A1 JP 2013076424 W JP2013076424 W JP 2013076424W WO 2014051120 A1 WO2014051120 A1 WO 2014051120A1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a polyamide resin composition and a molded article comprising the same.
- polyamides represented by polyamide 6 hereinafter abbreviated as PA6
- polyamide 66 hereinafter abbreviated as PA66
- the polyamide has been pointed out to have problems such as insufficient heat resistance and poor dimensional stability due to water absorption.
- SMT surface mount technology
- the use of conventional polyamides Development of polyamides having excellent heat resistance, low water absorption, mechanical properties, and physicochemical properties has been desired.
- PA6T 1,6-hexanediamine
- PA6T is copolymerized with a dicarboxylic acid component such as adipic acid or isophthalic acid, or an aliphatic polyamide such as PA6.
- a dicarboxylic acid component such as adipic acid or isophthalic acid
- PA6 an aliphatic polyamide
- a semi-aromatic polyamide comprising an aromatic dicarboxylic acid unit containing 60 to 100 mol% of terephthalic acid units and a linear aliphatic alkylenediamine unit having 6 to 18 carbon atoms is added to 100 parts by weight of the polyamide. It is described that a polyamide composition containing 0.5 to 200 parts by weight of a filler has excellent performance in all of heat resistance, mechanical properties, chemical physical properties, and molding properties. Has been.
- Patent Document 2 discloses a polyamide component composed of 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine, and a polyamide component composed of terephthalic acid and 1,6-hexanediamine. Copolyamides obtained by copolymerization in a weight ratio of 25/75 to 85/15 are disclosed, but the melting point is low and the improvement effect in terms of heat resistance is insufficient. Polyamide composed of 1,4-cyclohexanedicarboxylic acid and aliphatic diamine having 6 to 18 carbon atoms described in Patent Document 3 is excellent in heat resistance, light resistance, toughness and low water absorption, but in terms of fluidity. There is room for improvement.
- the object of the present invention is to have excellent heat resistance, low water absorption, high temperature rigidity and fluidity, and crystallization proceeds sufficiently even when molded with a mold at 80 ° C.
- An object of the present invention is to provide a polyamide resin composition with less mold contamination.
- the above object is (1) 95 to 99.95% by mass of polyamide (a-1) having a number average molecular weight of 2000 or more, and 0.05 to 5% by mass of polyamide oligomer (a-2) having a number average molecular weight of 500 to less than 2000 And an alicyclic ring in which 25 mol% or more of all the monomer units constituting the polyamide (a-1) and the polyamide oligomer (a-2) are represented by the following general formula (I) or general formula (II): Polyamide containing a polyamide resin (A) and an inorganic filler (B), which are structural units derived from a formula monomer, wherein the trans isomer structural unit content derived from the alicyclic monomer is 50 to 85 mol% Resin composition (In the formula, X represents a carboxyl group or an amino group, and Z represents an alicyclic structure having 3 or more carbon atoms.) (Wherein X and Z are as defined above, and R 1 and R 2
- a polyamide resin composition is 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 1,8-octanediamine, 1,9
- the above (5) which is at least one selected from the group consisting of nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine
- a polyamide resin composition (7) Containing 25 mol% or more of structural units derived from 1,4-cyclohexanedicarboxylic acid, and as structural units derived from the aliphatic diamine, 1,9-nonanediamine and / or 2-methyl-1,8-
- the polyamide resin composition of the above (6) containing 25 mol% or more of octanediamine; (8)
- the compound (C) acting as the Lewis base is at least one selected from the group consisting of potassium oxide, magnesium oxide, calcium oxide, zinc oxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and zinc hydroxide.
- the polyamide resin composition in (11) above; and (13) A molded article comprising the polyamide resin composition according to any one of (1) to (12) above; Is achieved by providing
- FIG. 4 is a GPC elution curve (vertical axis: signal intensity, horizontal axis: elution time) of the polyamide resin (A) obtained in Reference Example 1. It is a front view of the metal mold
- Polyamide resin (A) The polyamide resin (A) is surrounded by a baseline and an elution curve from the elution curve of each sample obtained under the measurement conditions in Examples described later using a gel permeation chromatograph (hereinafter abbreviated as GPC).
- GPC gel permeation chromatograph
- the polyamide resin (A) contains 0.05 to 5 mass of a polyamide oligomer (a-2) having a number average molecular weight of 500 or more and less than 2000 determined by GPC measurement under the same conditions as the polyamide (a-1). %contains.
- the content (mass%) of the polyamide (a-1) and the polyamide oligomer (a-2) is in the above range, the fluidity of the polyamide resin composition is improved, and the polyamide resin composition is molded with a 80 ° C. mold. However, crystallization proceeds sufficiently. Moreover, mold contamination derived from the polyamide oligomer (a-2) can be prevented.
- the polyamide oligomer (a-2) in the molten state has an advantage in crystallization because of its high molecular chain mobility.
- the polyamide (a-1) is preferably contained in an amount of 97 to 99.95% by mass, more preferably 98 to 99.95% by mass.
- the polyamide oligomer (a-2) is preferably contained in an amount of 0.05 to 3% by mass, more preferably 0.05 to 2% by mass.
- polyamide resin (A) 25 mol% or more of all monomer units constituting the polyamide (a-1) and the polyamide oligomer (a-2) is represented by the following general formula (I) or general formula (II).
- the content of the trans isomer structural unit derived from the alicyclic monomer is 50 to 85 mol%.
- Examples of the alicyclic structure having 3 or more carbon atoms represented by Z include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene group, Examples thereof include monocyclic or polycyclic cycloalkylene groups such as a cyclododecylene group, a dicyclopentylene group, a dicyclohexylene group, a tricyclodecalene group, a norbornylene group, and an adamantylene group.
- Examples of the alkylene group having 1 or more carbon atoms represented by R 1 and R 2 include saturated aliphatic alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Can be mentioned. These may have a substituent. Examples of such a substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group, a hydroxyl group, and a halogen group.
- a cycloaliphatic dicarboxylic acid in which X is a carboxyl group and a cycloaliphatic diamine in which X is an amino group may be used alone or in combination.
- cycloaliphatic dicarboxylic acid examples include cycloaliphatic dicarboxylic acids having 3 to 10 carbon atoms, preferably cycloaliphatic dicarboxylic acids having 5 to 10 carbon atoms, and more specifically 1,4,4. -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid.
- the cycloaliphatic dicarboxylic acid may have a substituent other than a carboxyl group on the alicyclic skeleton.
- substituents include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group.
- 1,4-cyclohexanedicarboxylic acid is more preferable from the viewpoints of heat resistance, fluidity, rigidity at high temperature, and the like.
- cyclic aliphatic dicarboxylic acid may be used individually by 1 type, and may use 2 or more types together.
- Cycloaliphatic dicarboxylic acids have a trans isomer and a cis geometric isomer, and when two carboxyl groups are on different sides of the ring structure, the two carboxyl groups are on the same side of the trans isomer and ring structure. In some cases, it is cis.
- either the trans isomer or the cis isomer may be used, or a mixture of the trans isomer and the cis isomer in any ratio may be used.
- the trans isomer / cis isomer ratio is preferably 50/50 to 0/100 (molar ratio) when used in polymerization, and preferably 40/60 to 10/90. Is more preferably 35/65 to 15/85.
- the trans isomer / cis isomer ratio (molar ratio) of the cycloaliphatic dicarboxylic acid can be determined by 1 H-NMR (see Examples described later).
- cycloaliphatic diamines examples include cycloaliphatic diamines having 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms.
- 1,4-cyclohexanediamine and 1,3-bis (Aminomethyl) cyclohexane 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl- 4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, methylcyclohexanediamine, isophoronediamine, norbornanediamine, tricyclodecanediamine and the like.
- the cycloaliphatic diamine may have a substituent other than an amino group on the alicyclic skeleton.
- substituents include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
- cyclic aliphatic diamine may be used individually by 1 type, and may use 2 or more types together.
- Cycloaliphatic diamines like cycloaliphatic dicarboxylic acids, have a trans isomer and a cis geometric isomer, and when two amino groups are on different sides of the ring structure, When two amino groups are on the same side, a cis form is obtained.
- either the trans isomer or the cis isomer may be used, or a mixture of the trans isomer and the cis isomer in any ratio may be used.
- the trans isomer / cis isomer ratio is preferably 50/50 to 0/100 (molar ratio) and more preferably 40/60 to 10/90 when used in the polymerization. The ratio is more preferably 35/65 to 15/85.
- the trans isomer / cis isomer ratio (molar ratio) of the cycloaliphatic diamine can be determined by 1 H-NMR.
- the structural unit derived from the alicyclic monomer exists as a trans isomer structural unit and a cis isomer structural unit.
- the trans isomer structural unit content is 50 to 85 mol%, preferably 60 to 85 mol%, and preferably 70 to 85 mol% of the structural unit derived from the alicyclic monomer constituting the polyamide resin (A). Is more preferable, and 80 to 85 mol% is more preferable.
- the polyamide resin (A) is excellent in rigidity and fluidity at high temperatures, and crystallization proceeds sufficiently even when molded with a 80 ° C. mold. . These are particularly remarkable in the case of the polyamide resin (A) using 1,4-cyclohexanedicarboxylic acid as the alicyclic monomer.
- the “trans isomer structural unit” derived from the alicyclic monomer of the polyamide resin (A) means a structural unit in which an amide bond exists on a different side with respect to the alicyclic structure.
- the polyamide resin (A) contains a structural unit derived from an alicyclic monomer represented by the general formula (I) or the general formula (II), as well as a structural unit derived from another monomer capable of forming an amide bond. You may do it.
- examples of such other monomers include dicarboxylic acids such as aliphatic dicarboxylic acids and aromatic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, diamines such as aliphatic diamines and aromatic diamines, trivalent or higher polyvalent amines, A lactam and aminocarboxylic acid are mentioned, These may be used individually by 1 type and may use 2 or more types together.
- aliphatic dicarboxylic acid examples include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, speric acid, 3,3 -Diethylsuccinic acid, azelaic acid, sebacic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, dimer acid, etc. And a straight or branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms.
- aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-phenylenedioxydiacetic acid. 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyl And dicarboxylic acid.
- trivalent or higher polyvalent carboxylic acid examples include trimellitic acid, trimesic acid, and pyromellitic acid.
- Examples of the aliphatic diamine include ethylene diamine, 1,3-propane diamine, 1,4-butane diamine, 1,5-pentane diamine, 1,6-hexane diamine, 1,7-heptane diamine, and 1,8-octane diamine.
- 1,9-nonanediamine 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, Linear saturated aliphatic diamines such as 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosadecanediamine; 2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1- Methyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4- Dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl
- aromatic diamines include metaxylylenediamine and paraxylylenediamine.
- trivalent or higher polyvalent amine include bishexamethylene triamine.
- lactam examples include ⁇ -caprolactam, ⁇ -laurolactam, butyrolactam, pivalolactam, caprilolactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), etc., among which ⁇ -caprolactam, ⁇ -laurolactam Is preferred.
- aminocarboxylic acid examples include ⁇ , ⁇ -aminocarboxylic acid and the like. For example, the number of carbon atoms in which the ⁇ position of 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like is substituted with an amino group.
- Examples thereof include 4 to 14 saturated aliphatic aminocarboxylic acids and paraaminomethylbenzoic acid. When it has a lactam and / or aminocarboxylic acid unit, there exists an effect
- the polyamide resin (A) is an aliphatic diamine having 4 to 12 carbon atoms as a monomer unit constituting the polyamide (a-1) and the polyamide oligomer (a-2) from the viewpoint of heat resistance, low water absorption, and fluidity. It is preferable to contain the structural unit derived from.
- Examples of the structural unit derived from an aliphatic diamine having 4 to 12 carbon atoms include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, Any one or more of 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine Preferably, it contains a structural unit derived from 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine, and is derived from the aliphatic diamine constituting the polyamide resin (A).
- structural units derived from 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine are 2 It is further preferable to contain more than mole%.
- 1,9-nonanediamine and 2-methyl-1,8-octanediamine 99: 1 to 1:99 (molar ratio) ), More preferably 95: 5 to 50:50.
- the structural unit derived from 1,4-cyclohexanedicarboxylic acid is contained in an amount of 25 mol% or more, and the structural unit derived from an aliphatic diamine is 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine.
- the polyamide resin composition containing the polyamide resin (A) containing at least 25 mol% of the structural unit derived from is particularly excellent in heat resistance, low water absorption, chemical resistance and fluidity.
- the melting point of the polyamide resin (A) from which the higher content of the trans isomer structural unit is obtained is required for molding. Therefore, the content of the trans isomer structural unit is preferably 50 to 100 mol%, more preferably 50 to 90 mol%, more preferably 50 to 85 mol%, and more preferably 60 to 85 mol%. More preferred is 70 to 85 mol%, and most preferred is 80 to 85 mol%.
- the structural units derived from the alicyclic monomers constituting the polyamide (a-1) and the polyamide oligomer (a-2) may be the same or different. From the viewpoint of moldability of the product in an 80 ° C. mold, it is preferably the same.
- polyamide resin (A) when 10% or more of the total amount of terminal groups of the molecular chain of the constituent polyamide (a-1) and polyamide oligomer (a-2) is sealed with an end-capping agent, The physical properties such as melt moldability are more excellent.
- the end-capping rate refers to the carboxyl group at the end of the molecular chain, the amino group at the end, and the end-capping of the polyamide (a-1) and polyamide oligomer (a-2), which are the constituent components of the polyamide resin (A).
- the number of end groups sealed with the agent can be measured and calculated by, for example, 1 H-NMR based on the integral value of the characteristic signal corresponding to each end group (see Examples described later).
- the end-capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group, and is monocarboxylic acid, monoamine, acid anhydride, monoisocyanate, monoacid halide, monoester. Examples include esters and monoalcohols. Of these, monocarboxylic acids or monoamines are preferable from the viewpoints of reactivity and stability of the sealing end, and monocarboxylic acids are more preferable from the viewpoint of easy handling.
- Examples of the monocarboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Acid; cycloaliphatic carboxylic acid and other alicyclic monocarboxylic acids; benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids; any of these And the like.
- aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palm
- acetic acid propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, cyclohexane Hexanecarboxylic acid and benzoic acid are preferred.
- the end-capping agent may be added by any of a method of adding a terminal capping agent in advance during polymerization, a method of adding during polymerization, a method of adding in a melt-kneading or molding process, etc. It functions as an end-capping agent.
- the polyamide resin (A) preferably has a sample concentration of 0.2 g / dL in concentrated sulfuric acid and ⁇ inh measured at 30 ° C. within the range of 0.4 to 3.0 dL / g, 0.5 to 2. More preferably, it is within the range of 0 dL / g, and even more preferably within the range of 0.6 to 1.8 dL / g.
- the polyamide resin (A) having ⁇ inh within the above range is used, the resulting polyamide resin composition is more excellent in heat resistance, rigidity at high temperature, and the like.
- polyamide resin (A) As a method for producing the polyamide resin (A), polyamides having different number average molecular weights and molecular weight distributions are produced and then mixed, and the content (mass%) of the polyamide (a-1) and the polyamide oligomer (a-2) is as follows.
- the method of adjusting suitably is mentioned so that it may become the range which the invention prescribes
- the polyamide can be produced by a known method such as a melt polymerization method using a dicarboxylic acid and a diamine as raw materials, a solid phase polymerization method, or a melt extrusion polymerization method.
- Examples of the mixing method include a method in which polyamides having different number average molecular weights and molecular weight distributions described above are dry-blended and charged simultaneously or separately into a melt-kneading apparatus.
- the content of the polyamide (a-1) and the polyamide oligomer (a-2) is selected by selecting appropriate polymerization conditions when producing the polyamide resin (A) ( The method of superposing
- Appropriate polymerization conditions include, for example, a dicarboxylic acid component, a diamine component constituting the polyamide resin (A), a catalyst and an end-capping agent as necessary, and a nylon salt to produce a nylon salt.
- a solution containing a prepolymer with a water content of preferably 10 to 40% is obtained, and the sample is further sprayed into an atmosphere at 100 to 150 ° C. to obtain a sample in concentrated sulfuric acid.
- a powdery prepolymer having a concentration of 0.2 g / dL and ⁇ inh of 0.1 to 0.6 dL / g at 30 ° C. is obtained. Further, a method of further solid-phase polymerization or polymerization using a melt extruder can be mentioned.
- the catalyst examples include phosphoric acid, phosphorous acid, hypophosphorous acid, salts or esters thereof, and specifically, phosphoric acid, phosphorous acid or hypophosphorous acid and potassium, sodium, magnesium, vanadium. , Calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony and other salts; phosphoric acid, phosphorous acid or hypophosphorous acid ammonium salt; phosphoric acid, phosphorous acid or hypophosphorous acid Examples include acid ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, and phenyl ester.
- the polymerization after obtaining the prepolymer is performed by solid phase polymerization, it is preferably performed in an inert gas atmosphere or in an inert gas flow, and the polymerization temperature is 200 ° C. or higher to 20 ° C. lower than the melting point of polyamide.
- the temperature is within the range and the polymerization time is 1 to 8 hours, the polymerization rate is high, the productivity is excellent, coloring and gelation can be effectively suppressed, and polyamide (a-1) and polyamide are effective. It becomes easy to adjust the content (% by mass) of the oligomer (a-2) within the range defined by the present invention.
- the polymerization temperature is preferably 370 ° C. or less and the polymerization time is preferably 5 to 60 minutes.
- the content (mass%) of the polyamide (a-1) and the polyamide oligomer (a-2) is determined in the present invention. It is easy to adjust to the range specified by.
- the contents of the polyamide (a-1) and the polyamide oligomer (a-2) constituting the polyamide resin (A) are obtained from the elution curve under the measurement conditions in Examples described later using GPC.
- the GPC measurement when the polyamide resin (A) or the polyamide resin composition contains other components that are soluble in a solvent for dissolving the polyamide resin (A), for example, the polyamide resin (A) is insoluble.
- the GPC measurement may be performed after the other components are extracted and removed using a soluble solvent.
- the compound (B) that acts as a Lewis base that is insoluble in the solvent in which the polyamide resin (A) is dissolved, the inorganic filler, etc. are dissolved in the solvent in which the polyamide resin (A) is dissolved in the polyamide resin composition, Subsequently, after filtering and removing an insoluble matter, GPC measurement may be performed.
- the polyamide resin composition of the present invention contains an inorganic filler (B).
- an inorganic filler (B) By including the inorganic filler (B), a polyamide resin composition having excellent low water absorption and rigidity can be obtained without impairing the properties of the polyamide resin (A) having excellent heat resistance, low water absorption, rigidity and fluidity. can get.
- Examples of the inorganic filler (B) include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, silicon nitride, hydrotalcite, calcium carbonate, Zinc carbonate, titanium oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, silicon oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, Furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable fluorine mica, apatite, and the like can be given. These may be used alone or in combination of two or more.
- Fluorine mica and apatite are preferable, and glass fiber and carbon fiber are more preferable.
- the average fiber diameter is 3 to 30 ⁇ m
- the weight average fiber length is 100 to 750 ⁇ m
- the aspect ratio (L / D) between the weight average fiber length and the average fiber diameter is 10 to 100. Is more preferable from the viewpoint of excellent rigidity and the like.
- the average fiber diameter is 3 to 30 ⁇ m
- the weight average fiber length is 10 to 500 ⁇ m
- the aspect ratio (L / D) is 3 to 100.
- the inorganic filler (B) when talc, kaolin, mica and silicon nitride are used as the inorganic filler (B), those having an average particle diameter of 0.1 to 3 ⁇ m are preferable.
- the amount of the inorganic filler (B) is preferably 0.1 to 200 parts by weight, more preferably 1 to 180 parts by weight, and still more preferably 5 to 5 parts by weight with respect to 100 parts by weight of the polyamide resin (A). 150 parts by mass.
- the blending amount of the inorganic filler (B) By setting the blending amount of the inorganic filler (B) to 0.1 parts by mass or more, mechanical properties such as rigidity at high temperatures of the polyamide resin composition are improved, and by blending the blending amount to 200 parts by mass or less. Thus, a polyamide resin composition having excellent moldability can be obtained.
- the polyamide resin composition of the present invention may contain 0.1 to 10 parts by mass of the compound (C) that acts as a Lewis base with respect to 100 parts by mass of the polyamide resin (A). It is more preferable to contain a part.
- the polyamide (a-1) and the polyamide oligomer (a-2) are constituted by the general formula (I) or the general formula (II).
- Polyamide resin composition which can control the content of trans isomer structural unit derived from the alicyclic monomer represented to 50 to 85 mol% as defined in the present invention and is excellent in heat resistance and rigidity at high temperature Is obtained. Furthermore, the crystal structure of the obtained polyamide resin composition becomes stronger and the chemical resistance is improved.
- the compound (C) acting as a Lewis base is selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, zinc oxide and zinc hydroxide. It is preferable to use at least one kind.
- alkali metal oxide and alkaline earth metal oxide examples include potassium oxide, magnesium oxide, and calcium oxide.
- alkali metal hydroxide and alkaline earth metal hydroxide include potassium hydroxide, water, and the like.
- magnesium oxide and calcium hydroxide examples include magnesium oxide and calcium hydroxide. These may be used alone or in combination of two or more.
- the polyamide resin composition may contain other components other than the polyamide resin (A), the inorganic filler (B), and the compound (C) acting as a Lewis base, as long as the effects of the present invention are not impaired. May be included.
- other components include thermoplastic resins other than polyamide (a-1) and polyamide oligomer (a-2), compatibilizers, organic fillers, silane coupling agents, crystal nucleating agents, copper-based heat stabilizers, Antioxidants such as hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, thio antioxidants; dyes, pigments, light stabilizers, antistatic agents, plasticizers, lubricants, flame retardants Flame retardant aids, processing aids, lubricants, fluorescent bleaches, stabilizers, UV absorbers, rubbers and reinforcing agents.
- any method for containing the inorganic filler (B) can be used as long as the polyamide resin (A) and the inorganic filler (B) can be uniformly mixed.
- a melt kneading method using a Banbury mixer or the like is employed.
- the melt-kneading conditions are not particularly limited.
- the polyamide resin composition of the present invention can be obtained by melt-kneading for 1 to 30 minutes in a temperature range 30 to 50 ° C. higher than the melting point.
- the compound (C) that acts as a Lewis base can be previously contained in the polyamide resin (A).
- the polyamide resin (A), the compound (C) acting as a Lewis base and other components are uniformly mixed as necessary.
- a melt kneading method using a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, or the like is employed.
- the melt kneading conditions are not particularly limited, and examples thereof include a method of melt kneading for 1 to 30 minutes in a temperature range 30 to 50 ° C. higher than the melting point.
- thermoplastic resin composition of the present invention such as injection molding, extrusion molding, press molding, blow molding, calendar molding, casting molding, etc., depending on the type, application, shape, etc. of the target molded product
- Various molded products can be manufactured by applying a molding method generally used for a product. Moreover, you may employ
- the polyamide resin composition of the present invention can also be made into a composite molded body that is bonded, welded, and bonded to various materials such as various thermoplastic resins, thermosetting resins, paper, metal, wood, and ceramics.
- the polyamide resin composition of the present invention undergoes the molding process as described above, and manufactures electrical and electronic parts, automobile parts, industrial parts, fibers, films, sheets, household goods, and other various shaped products of any shape and application. Can be used effectively.
- Electrical and electronic parts include, for example, SMT connectors such as FPC connectors, BtoB connectors, card connectors, coaxial connectors; SMT switches, SMT relays, SMT bobbins, memory card connectors, CPU sockets, LED reflectors, camera module bases, barrels, holders , Cable sheathing, optical fiber parts, muffler gear for AV / OA equipment, automatic flashing equipment parts, mobile phone parts, heat resistant gears for copiers, end caps, commutators, commercial outlets, command switches, noise filters, magnet switches, Examples include a solar cell substrate, a liquid crystal plate, an LED mounting substrate, a flexible printed wiring board, and a flexible flat cable.
- SMT connectors such as FPC connectors, BtoB connectors, card connectors, coaxial connectors
- Automotive parts include cooling parts such as thermostat housing, radiator tank, radiator hose, water outlet, water pump housing, rear joint; intercooler tank, intercooler case, turbo duct pipe, EGR cooler case, resonator, throttle body, intake manifold Intake and exhaust system parts such as tail pipes; Fuel system parts such as fuel delivery pipes, gasoline tanks, quick connectors, canisters, pump modules, fuel piping, oil strainers, lock nuts, seal materials; mount brackets, torque rods, cylinder head covers Structural parts such as bearing retainers, gear tensioners, headlamp actuator gears, sliding doors Drive system parts such as rails and clutch peripheral parts; Brake system parts such as air brake tubes; Automotive harness parts such as wire harness connectors, motor parts, sensors, ABS bobbins, combination switches, and in-vehicle switches in the engine room; sliding door dampers , Dora mirror stay, door mirror bracket, inner mirror stay, roof rail, engine mount bracket, air cleaner inlate pipe, door checker, plastic chain, emblem, clip, breaker cover, cup holder, air bag
- Industrial parts include, for example, gas pipes, oil field mining pipes, hoses, ant-proof cables (communication cables, pass cables, etc.), powder coating paint parts (inside coating of water pipes), subsea oil field pipes, pressure hoses, hydraulic pressure Tubes, paint tubes, fuel pumps, separators, supercharge ducts, butterfly valves, conveyor roller bearings, railway sleeper spring bearings, outboard engine covers, generator engine covers, irrigation valves, large switches ( Switch), and monofilaments (extruded yarn) such as fishing nets.
- the fiber examples include an airbag base fabric, a heat resistant filter, a reinforcing fiber, a brush bristle, a fishing line, a tire cord, an artificial grass, a carpet, and a seat seat fiber.
- films and sheets include heat-resistant adhesive tapes such as heat-resistant masking tapes and industrial tapes; cassette tapes, magnetic tapes for data storage for digital data storage, magnetic tape materials such as video tapes; retort food pouches, confectionery Food packaging materials such as individual packaging and processed meat products packaging; electronic component packaging materials such as semiconductor packaging packaging.
- the polyamide resin composition of the present invention includes plastic magnets, shoe soles, tennis rackets, skis, bonded magnets, glasses frames, binding bands, tag pins, sash crescents, electric tool motor fans, and motor stator insulating blocks.
- Lawn mower engine cover lawn mower fuel tank, micro slide switch, DIP switch, switch housing, lamp socket, connector shell, IC socket, bobbin cover, relay box, condenser case, small motor case, gear, Cam, Dancing pulley, Spacer, Insulator, Fastener, Caster, Wire clip, Bicycle wheel, Terminal block, Starter insulation, Fuse box, Air cleaner case, Air conditioner fan, Ta Terminal housings, wheel covers, bearing retainer over, water pipe impeller, clutch release bearing hub, can also be suitably used such a heat-resistant vessel, microwave components, cooker parts, printer ribbon guide.
- melting point melting point
- solution viscosity content of polyamide (a-1) and polyamide oligomer (a-2) (% by mass)
- terminal blocking rate trans isomerism derived from alicyclic monomer Body structure unit content
- water absorption tensile strength / tensile fracture strain
- deflection temperature under load melt viscosity, relative crystallinity, and mold contamination were measured or evaluated by the following methods.
- ⁇ Melting point> The melting point of the polyamide (polyamide 9C-1 to 4 to be described later) used in each example etc. was measured in a nitrogen atmosphere using a differential scanning calorimeter (DSC822) manufactured by METTLER TOLEDO. Thus, the peak temperature of the melting peak that appears when the temperature was raised from 30 ° C. to 360 ° C. at a rate of 10 ° C./min was determined as the melting point (° C.). When there are a plurality of melting peaks, the melting point is the peak temperature of the melting peak on the highest temperature side.
- the elution curve (vertical axis: signal intensity obtained from the detector, horizontal axis: elution time), the area of the region with a number average molecular weight of 500 to less than 2000 surrounded by the baseline and elution curve, and the baseline and elution curve It was calculated from the area of the number average molecular weight or less in which the detection of the main peak is completed from the enclosed number average molecular weight of 2000 or more. The measurement was performed under the following conditions.
- ⁇ Detector UV detector (wavelength: 210 nm) -Column: Showa Denko HFIP-806M (inner diameter 8 mm x length 300 mm)
- Solvent hexafluoroisopropanol containing sodium trifluoroacetate at a concentration of 0.01 mol / L Temperature: 40 ° C ⁇ Flow rate: 1 mL / min ⁇ Injection volume: 90 ⁇ L ⁇ Concentration: 0.5 mg / mL Sample preparation: Polyamide resin (A) or polyamide resin composition obtained in each example or the like in hexafluoroisopropanol containing 0.01 mol / L of sodium trifluoroacetate was converted to 0 in terms of polyamide resin (A).
- trans isomerism From the ratio of the peak area of 2.10 ppm derived from ⁇ hydrogen of the cis isomer of the 1,4-cyclohexanedicarboxylic acid structural unit to the peak area of 2.20 ppm derived from ⁇ hydrogen of the trans isomer structural unit, trans isomerism The body structural unit content was determined.
- ⁇ Tensile strength / Tensile fracture strain> Using the polyamide resin composition obtained in each example etc., injection molding (mold temperature 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the melting point of each, and ISO multipurpose test piece A type (length 80 mm) , Width 10 mm, thickness 4 mm). Using the obtained test piece, the tensile strength (MPa) and the tensile fracture strain (%) at 23 ° C. were measured according to ISO 527, and used as an index of rigidity. The higher the tensile strength value and the smaller the tensile fracture strain value, the better the rigidity.
- ⁇ Load deflection temperature> Using the polyamide resin composition obtained in each example etc., injection molding (mold temperature 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the melting point of each, and ISO multipurpose test piece A type (length 80 mm) , Width 10 mm, thickness 4 mm). Using the obtained test piece, the deflection temperature under load (° C.) when a load of 1.8 MPa was applied according to ISO 75-2 / Af was measured (measurement limit: 300 ° C.), and an index of rigidity at high temperature It was.
- the calorie calculated from the crystallization peak is referred to as “crystallization calorie ⁇ Hc”.
- crystal melting calorie ⁇ Hm the calorie calculated from the crystal melting peak.
- FIGS. 2 and 3 Using the polyamide resin composition obtained in each of the examples, etc., the molds having the shapes shown in FIGS. 2 and 3 (FIG. 2: front view, FIG. 3: sectional view with the k-axis as the cut surface) are subjected to the following conditions. Injection molding was performed. The polyamide resin composition enters from the protruding end m in the figure, and flows from the outer periphery of the circle n in FIG. The contamination (discoloration) of the flow end ⁇ of the mold was visually confirmed after 500 shots of continuous injection. If the mold was not fogged and no deposits or fog was observed, the mold was clouded.
- the polyamide resin (A), inorganic filler (B), and compound (C) acting as a Lewis base used in each example are shown below.
- Polyamide resin (A)> The following polyamides were blended in the proportions shown in Table 1 to obtain a polyamide resin (A).
- Polyamide 9C-3 Polyamide PA9C-1 was extracted in hot water at 80 ° C. for 8 hours. Thereafter, it was dried at 120 ° C. under reduced pressure for 12 hours to obtain polyamide 9C-3 having a solution viscosity ⁇ inh of 0.89 dL / g.
- Examples 1 to 6, Reference Examples 1 to 3 and Comparative Examples 1 to 3 A mixture containing polyamide 9C-1, polyamide 9C-2, polyamide 9C-3 and polyamide 9C-4 in the amounts shown in Table 1 was dried under reduced pressure at 120 ° C. for 24 hours, and then the Lewis bases in the amounts shown in Table 1 were used.
- the inorganic filler (B) was fed from the downstream side feed port and melt-kneaded.
- the melt-kneaded resin or resin composition was extruded into a strand shape, and then cut by a pelletizer to obtain a pellet-shaped polyamide resin (A) or a polyamide resin composition.
- a pellet-shaped polyamide resin (A) or a polyamide resin composition was obtained using the obtained polyamide resin (A) or polyamide resin composition, test pieces having a predetermined shape were prepared according to the method described above, and various physical properties were evaluated. The results are shown in Table 1.
- Example 1 to 6 the content of the polyamide (a-1) and the polyamide oligomer (a-2) and the trans isomer structural unit content are in the ranges specified in the present invention, and the inorganic filler (B) is used. Therefore, compared to polyamide resin (A) alone, heat resistance, low water absorption, rigidity (tensile strength, tensile fracture strain, deflection temperature under load), fluidity, moldability (high relative crystallinity value) Excellent and no mold contamination. On the other hand, since Reference Examples 1 to 3 and Comparative Examples 1 to 3 do not contain the inorganic filler (B), they are inferior in low water absorption and rigidity as compared with Examples 1 to 6 described above. Among them, Comparative Examples 1 to 3 are inferior in fluidity and moldability because there are few polyamide oligomers (a-2).
- the polyamide resin composition of the present invention is excellent in heat resistance, low water absorption, rigidity and fluidity at high temperature, sufficiently crystallizes even when molded with a 80 ° C. mold, There is little mold contamination, and it can be widely used as various parts materials for, for example, electric and electronic parts, automobile parts, industrial material parts, daily necessities and household goods.
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Abstract
Description
(1) 数平均分子量2000以上のポリアミド(a-1)を95~99.95質量%、数平均分子量500以上2000未満のポリアミドオリゴマー(a-2)を0.05~5質量%の範囲で含有し、前記ポリアミド(a-1)および前記ポリアミドオリゴマー(a-2)を構成する全モノマー単位のうち25モル%以上が下記一般式(I)または一般式(II)で表される脂環式モノマーに由来する構造単位であり、前記脂環式モノマーに由来するトランス異性体構造単位の含有率が50~85モル%であるポリアミド樹脂(A)および無機充填材(B)を含有するポリアミド樹脂組成物
(2) 前記ポリアミド樹脂(A)を構成する前記ポリアミド(a-1)および前記ポリアミドオリゴマー(a-2)の分子鎖の末端基の総量の10%以上が末端封止剤によって封止されている、上記(1)のポリアミド樹脂組成物;
(3) 前記脂環式モノマーが、前記一般式(I)または一般式(II)におけるXがカルボキシル基である環状脂肪族ジカルボン酸である、上記(1)または(2)のポリアミド樹脂組成物;
(4) 前記環状脂肪族ジカルボン酸が1,4-シクロヘキサンジカルボン酸である、上記(3)のポリアミド樹脂組成物;
(5) 前記ポリアミド(a-1)および前記ポリアミドオリゴマー(a-2)が、炭素数4~12の脂肪族ジアミンに由来する構造単位を含有する、上記(1)~(4)のいずれかのポリアミド樹脂組成物;
(6) 前記脂肪族ジアミンが1,4-ブタンジアミン、1,5-ペンタンジアミン、1,6-ヘキサンジアミン、2-メチル-1,5-ペンタンジアミン、1,8-オクタンジアミン、1,9-ノナンジアミン、2-メチル-1,8-オクタンジアミン、1,10-デカンジアミン、1,11-ウンデカンジアミンおよび1,12-ドデカンジアミンからなる群より選ばれる少なくとも1種である、上記(5)のポリアミド樹脂組成物;
(7) 1,4-シクロヘキサンジカルボン酸に由来する構造単位を25モル%以上含有し、かつ前記脂肪族ジアミンに由来する構造単位として1,9-ノナンジアミンおよび/または2-メチル-1,8-オクタンジアミンを25モル%以上含有する、上記(6)のポリアミド樹脂組成物;
(8) さらに、ラクタムおよび/またはアミノカルボン酸に由来する構造単位を含有する、上記(1)~(7)のいずれかのポリアミド樹脂組成物;
(9) 前記ポリアミド樹脂(A)100質量部に対して前記無機充填材(B)を0.1~200質量部含有する、上記(1)~(8)のいずれかのポリアミド樹脂組成物;
(10) 前記ポリアミド樹脂(A)100質量部に対してルイス塩基として作用する化合物(C)を0.1~10質量部含有する、上記(1)~(9)のいずれかのポリアミド樹脂組成物;
(11) 前記ルイス塩基として作用する化合物(C)がアルカリ金属酸化物、アルカリ金属水酸化物、アルカリ土類金属酸化物、アルカリ土類金属水酸化物、酸化亜鉛および水酸化亜鉛からなる群より選ばれる少なくとも1種である、上記(10)のポリアミド樹脂組成物;
(12) 前記ルイス塩基として作用する化合物(C)が酸化カリウム、酸化マグネシウム、酸化カルシウム、酸化亜鉛、水酸化カリウム、水酸化マグネシウム、水酸化カルシウムおよび水酸化亜鉛からなる群より選ばれる少なくとも1種である、上記(11)にポリアミド樹脂組成物;および、
(13) 上記(1)~(12)のいずれかのポリアミド樹脂組成物からなる成形品;
を提供することにより達成される。
ポリアミド樹脂(A)は、ゲルパーミエーションクロマトグラフ(以下、GPCと略称する)を用いて、後述する実施例での測定条件において得られる各試料の溶出曲線から、ベースラインと溶出曲線によって囲まれる数平均分子量2000以上から主ピークの検出が終了する分子量以下の領域の面積より算出できる、標準ポリメチルメタクリレート(標準PMMA)換算で求められる数平均分子量が2000以上のポリアミド(a-1)を95~99.95質量%含有する。また、ポリアミド樹脂(A)は、前記ポリアミド(a-1)と同様の条件でのGPC測定によって求められる数平均分子量が500以上2000未満のポリアミドオリゴマー(a-2)を0.05~5質量%含有する。
本発明のポリアミド樹脂組成物は無機充填材(B)を含有する。無機充填材(B)を含有することにより、耐熱性、低吸水性、剛性および流動性に優れるポリアミド樹脂(A)の性質を損なうことなく、さらに低吸水性および剛性により優れるポリアミド樹脂組成物が得られる。
本発明のポリアミド樹脂組成物は、ポリアミド樹脂(A)100質量部に対してルイス塩基として作用する化合物(C)を0.1~10質量部含有していてもよく、0.1~5質量部含有していることがより好ましい。ルイス塩基として作用する化合物(C)の量を前記範囲内にすることで、ポリアミド(a-1)およびポリアミドオリゴマー(a-2)を構成する、一般式(I)または一般式(II)で表される脂環式モノマー由来のトランス異性体構造単位の含有率を本発明の規定である50~85モル%に制御することができ、耐熱性や高温下での剛性に優れるポリアミド樹脂組成物が得られる。さらに、得られるポリアミド樹脂組成物の結晶構造がより強固なものとなり、耐薬品性も向上する。
ポリアミド樹脂組成物には、必要に応じて本発明の効果を損なわない範囲で、上記ポリアミド樹脂(A)、無機充填材(B)およびルイス塩基として作用する化合物(C)以外の他の成分を含んでいてもよい。他の成分としては、例えばポリアミド(a-1)およびポリアミドオリゴマー(a-2)以外の熱可塑性樹脂、相溶化剤、有機充填材、シランカップリング剤、結晶核剤、銅系熱安定剤、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、リン系酸化防止剤、チオ系酸化防止剤などの酸化防止剤;染料、顔料、光安定剤、帯電防止剤、可塑剤、滑剤、難燃剤、難燃助剤、加工助剤、潤滑剤、蛍光漂白剤、安定剤、紫外線吸収剤、ゴムおよび強化剤などが挙げられる。
本発明のポリアミド樹脂組成物の製造方法としては、ポリアミド樹脂(A)に無機充填材(B)を含有させる方法などが挙げられる。
本発明のポリアミド樹脂組成物を、目的とする成形品の種類、用途、形状などに応じて、射出成形、押出成形、プレス成形、ブロー成形、カレンダー成形、流延成形など、熱可塑性重合体組成物に対して一般に用いられる成形方法を適用することにより、各種の成形品を製造できる。また上記の成形方法を組み合わせた成形方法を採用しても良い。さらに、本発明のポリアミド樹脂組成物を、各種熱可塑性樹脂、熱硬化性樹脂、紙、金属、木材、セラミックスなどの各種材料と接着、溶着、接合した複合成形体とすることもできる。
各実施例等で用いたポリアミド(後述するポリアミド9C-1~4。以下同様。)の融点は、メトラー・トレド(株)製の示差走査熱量分析装置(DSC822)を使用して、窒素雰囲気下で、30℃から360℃へ10℃/minの速度で昇温した時に現れる融解ピークのピーク温度を融点(℃)とすることで求めた。なお、融解ピークが複数ある場合は最も高温側の融解ピークのピーク温度を融点とした。
各実施例等で用いたポリアミドの溶液粘度ηinhは、ポリアミド50mgをメスフラスコ中で98%濃硫酸25mLに溶解させ、ウベローデ型粘度計にて、得られた溶液の30℃での落下時間(t)を計り、濃硫酸の落下時間(t0)から下記数式(1)より算出した。
ηinh(dL/g)={ln(t/t0)}/0.2 (1)
各実施例等で得られたポリアミド樹脂(A)またはポリアミド樹脂組成物におけるポリアミド(a-1)とポリアミドオリゴマー(a-2)の含有量(質量%)は、GPCを用いて得られる各試料の溶出曲線(縦軸:検出器から得られるシグナル強度、横軸:溶出時間)から、ベースラインと溶出曲線によって囲まれる数平均分子量500以上2000未満の領域の面積、およびベースラインと溶出曲線によって囲まれる数平均分子量2000以上から主ピークの検出が終了する数平均分子量以下の領域の面積より算出した。測定は下記の条件で行った。
・検出器:UV検出器(波長:210nm)
・ カラム:昭和電工株式会社製 HFIP-806M(内径8mm×長さ300mm)
・ 溶媒:トリフルオロ酢酸ナトリウムを0.01モル/Lの濃度で含有するヘキサフルオロイソプロパノール
・ 温度:40℃
・ 流速:1mL/min
・ 注入量:90μL
・ 濃度:0.5mg/mL
・ 試料調製:トリフルオロ酢酸ナトリウムを0.01モル/L含有するヘキサフルオロイソプロパノールに、各実施例等で得られたポリアミド樹脂(A)またはポリアミド樹脂組成物を、ポリアミド樹脂(A)換算で0.5mg/mLになるように秤量して室温で1時間攪拌して溶解させ、得られた溶液をメンブレンフィルター(孔径0.45μm)でろ過して試料を調製した。
・ PMMA標準試料:昭和電工株式会社製 STANDARD M-75(数平均分子量範囲:1,800~950,000)を用いて標準溶出曲線(校正曲線)を作成した。
後述する参考例1で得られたポリアミド樹脂組成物(実際にはポリアミド樹脂(A)単独に相当する)を上記の条件で測定した際の溶出曲線を、ポリアミド(a-1)およびポリアミドオリゴマー(a-2)の領域とともに図1に示す。
各実施例等で得られたポリアミド樹脂組成物を用いて、各々の融点よりも約20℃高いシリンダー温度で射出成形(金型温度:80℃)を行い、長さ100mm、幅40mm、厚み1mmの試験片を作製し、得られた試験片から20~30mgを削りとって、トリフルオロ酢酸-d(CF3COOD)1mLに溶解し、日本電子株式会社製核磁気共鳴装置JNM-ECX400(400MHz)を用いて、室温、積算回数256回の条件で1H-NMRを測定した。そして、カルボキシル基末端(a)、アミノ基末端(b)および末端封止剤によって封止された末端(c)を各末端基の特性シグナルの積分値よりそれぞれ求め、数式(2)から末端封止率(%)を求めた。
末端封止率(%)=c/(a+b+c)×100 (2)
各実施例等で得られたポリアミド樹脂組成物を用いて、各々の融点よりも約20℃高いシリンダー温度で射出成形(金型温度:80℃)を行い、長さ100mm、幅40mm、厚み1mmの試験片を作製し、得られた試験片から20~30mgを削りとって、トリフルオロ酢酸-d(CF3COOD)1mLに溶解させ、グラスフィルターでろ過して不溶物を除去して測定資料を調製し、日本電子株式会社製核磁気共鳴装置JNM-ECX400(400MHz)を用いて、室温、積算回数256回の条件で1H-NMRを測定した。1,4-シクロヘキサンジカルボン酸構造単位のシス異性体のβ水素に由来する2.10ppmのピーク面積と、トランス異性体構造単位のβ水素に由来する2.20ppmのピーク面積の比率から、トランス異性体構造単位含有率を求めた。
各実施例等で得られたポリアミド樹脂組成物を用いて、各々の融点よりも約20℃高いシリンダー温度で射出成形(金型温度80℃)を行い、ISO 62に準じて長さ60mm、幅60mm、厚み2mmの試験片を作製した。得られた試験片を、23℃の水中に1日間浸漬したときの質量増加分を測定し、浸漬前質量に対する増加割合(%)を算出し、低吸水性の指標とした。値が小さいほど低吸水性である。
各実施例等で得られたポリアミド樹脂組成物を用いて、各々の融点よりも約20℃高いシリンダー温度で射出成形(金型温度80℃)を行い、ISO多目的試験片A型(長さ80mm、幅10mm、厚み4mm)を作製した。得られた試験片を用いて、ISO 527に従って23℃における引張強さ(MPa)および引張破壊ひずみ(%)を測定し、剛性の指標とした。引張強さの値が大きく、かつ引張破壊ひずみの値が小さいほど剛性に優れる。
各実施例等で得られたポリアミド樹脂組成物を用いて、各々の融点よりも約20℃高いシリンダー温度で射出成形(金型温度80℃)を行い、ISO多目的試験片A型(長さ80mm、幅10mm、厚み4mm)を作製した。得られた試験片を用いて、ISO 75-2/Afに従って1.8MPaの負荷を与えたときの荷重たわみ温度(℃)を測定し(測定限界:300℃)、高温下での剛性の指標とした。
各実施例等で得られたポリアミド樹脂組成物について、キャピログラフ(株式会社東洋精機製作所製)を用いて、バレル温度340℃、せん断速度121.6sec-1(キャピラリー:内径1.0mm×長さ10mm、押出速度10mm/min)の条件下で溶融粘度(Pa・s)を測定し、流動性の指標とした。
各実施例等で得られたポリアミド樹脂組成物を用い、下記条件にて射出成形を行い、長さ100mm、幅40mm、厚み1mmの試験片を作製した。得られた試験片から約10mgを削りとり、DSC822を用いて窒素雰囲気下で、30℃から360℃へ10℃/minの速度で昇温した。ポリアミド樹脂組成物を構成するポリアミド樹脂(A)に非晶領域が存在すれば、この昇温過程のうち80~150℃の温度領域において該非晶領域の結晶化が進むことに起因する結晶化ピークが観測される。本明細書では、かかる結晶化ピークから算出される熱量を「結晶化熱量ΔHc」と称する。上述の、30℃から360℃へ10℃/minの速度での昇温過程において、前記した結晶化ピークが検出される後か結晶化ピークが検出されずに、結晶融解ピークが観測される。本明細書では、かかる結晶融解ピークから算出される熱量を「結晶融解熱量ΔHm」と称する。かかるΔHcとΔHmを用いて、相対結晶化度(%)を下記数式(3)にて算出し、80℃の金型での成形性の指標とした。
・射出成形時のポリアミド樹脂(A)またはポリアミド樹脂組成物温度:340℃
・金型温度:80℃
・ 射出速度:60mm/sec
・ 射出時間:2sec
・ 冷却時間:5sec
相対結晶化度(%)=(ΔHm-ΔHc)/ΔHm×100 (3)
各実施例等で得られたポリアミド樹脂組成物を用いて、図2および3に示す形状の金型(図2:正面図、図3:k軸を切断面とする断面図)で下記条件にて射出成形を行った。ポリアミド樹脂組成物は、図中の突出末端mから浸入し、図2の円nの外周部から流動末端Оに向かって流れる。金型の流動末端部Оの汚れ(変色度)を500ショット連続射出後に目視で確認し、金型に曇りが付着物や曇りが認められなかった場合を○、金型に曇りが認められた場合を△、金型に付着物の認められた場合を×で評価することで、金型汚染性の指標とした。
・ 射出成形時のポリアミド樹脂組成物温度:340℃
・金型温度:80℃
・ 射出速度:60mm/sec
・ 射出時間:2sec
・ 冷却時間:5sec
以下のポリアミドを表1に示す割合で配合してポリアミド樹脂(A)とした。
トランス体/シス体比=30/70(モル比)の1,4-シクロヘキサンジカルボン酸5111.2g(29.7モル)、1,9-ノナンジアミン4117.6g(26.0モル)、2-メチル-1,8-オクタンジアミン726.6g(4.59モル)、末端封止剤としての酢酸110.4g(1.84モル)、触媒として次亜リン酸ナトリウムー水和物10g、および蒸留水2.5Lを、内容積40Lのオートクレーブに入れ、窒素置換した。2時間かけて内部温度を200℃に昇温した。この時、オートクレーブは2MPaまで昇圧した。その後2時間、水蒸気を徐々に抜いて圧力を2MPaに保ちながら反応させた。次いで、30分かけて圧力を1.2MPaまで下げ、プレポリマーを得た。このプレポリマーを粉砕し、120℃、減圧下で12時間乾燥した。これを230℃、13.3Paの条件で10時間固相重合し、溶液粘度ηinhが0.87dL/gであるポリアミド9C-1を得た。
トランス体/シス体比=30/70(モル比)の1,4-シクロヘキサンジカルボン酸5111.2g(29.7モル)、1,9-ノナンジアミン4117.6g(26.0モル)、2-メチル-1,8-オクタンジアミン726.6g(4.59モル)、末端封止剤としての酢酸110.4g(1.84モル)、触媒として次亜リン酸ナトリウムー水和物10g、および蒸留水2.5Lを、内容積40Lのオートクレーブに入れ、窒素置換した。2時間かけて内部温度を200℃に昇温した。この時、オートクレーブは2MPaまで昇圧した。その後2時間、水蒸気を徐々に抜いて圧力を2MPaに保ちながら反応させた。次いで、30分かけて圧力を1.2MPaまで下げ、プレポリマーを得た。このプレポリマーを粉砕し、120℃、減圧下で12時間乾燥し、溶液粘度ηinhが0.23dL/gであるポリアミド9C-2を得た。
ポリアミドPA9C-1を80℃の熱水中で8時間、抽出処理を行った。その後、120℃、減圧下で12時間乾燥し、溶液粘度ηinh0.89dL/gであるポリアミド9C-3を得た。
トランス体/シス体比=30/70(モル比)の1,4-シクロヘキサンジカルボン酸5111.2g(29.7モル)、1,9-ノナンジアミン4117.6g(26.0モル)、2-メチル-1,8-オクタンジアミン726.6g(4.59モル)、末端封止剤としての酢酸110.4g(1.84モル)、触媒として次亜リン酸ナトリウムー水和物10g、および蒸留水2.5Lを、内容積40Lのオートクレーブに入れ、窒素置換した。2時間かけて内部温度を200℃に昇温した。この時、オートクレーブは2MPaまで昇圧した。その後2時間、水蒸気を徐々に抜いて圧力を2MPaに保ちながら反応させた。次いで、30分かけて圧力を1.2MPaまで下げ、プレポリマーを得た。このプレポリマーを粉砕し、120℃、減圧下で12時間乾燥した。これを温度350℃、減圧下、押出重合装置にて滞留時間が30分になるように重合することで、溶液粘度ηinhが0.78dL/gであるポリアミド9C-4を得た。
日本電気硝子株式会社製、「ECS03T275H」(ガラス繊維:平均繊維径10μmφ、カット長3mm)
(1)酸化マグネシウム:
協和化学工業株式会社製、「MF-150」(平均粒径:0.71μm)
(2)酸化カルシウム:
関東化学株式会社製、「酸化カルシウム」(平均粒径:15μm)
(3)酸化亜鉛:
和光純薬工業株式会社製、「酸化亜鉛」(平均粒径:5.0μm以下)
ポリアミド9C-1、ポリアミド9C-2、ポリアミド9C-3、ポリアミド9C-4を表1で示す量で配合した混合物を減圧下、120℃で24時間乾燥した後、表1に示す量のルイス塩基として作用する化合物(C)をドライブレンドし、得られた混合物を二軸押出機(スクリュー径:30mm、L/D=28、シリンダー温度350℃、回転数150rpm)のホッパーからフィードし、押出機下流側のサイドフィード口から無機充填材(B)をフィードして溶融混練した。溶融混練した樹脂または樹脂組成物をストランド状に押出した後、ペレタイザにより切断してペレット状のポリアミド樹脂(A)またはポリアミド樹脂組成物を得た。得られたポリアミド樹脂(A)またはポリアミド樹脂組成物を使用し、前記した方法に従って所定形状の試験片を作製し、各種物性を評価した。結果を表1に示す。
Claims (13)
- 数平均分子量2000以上のポリアミド(a-1)を95~99.95質量%、数平均分子量500以上2000未満のポリアミドオリゴマー(a-2)を0.05~5質量%の範囲で含有し、前記ポリアミド(a-1)および前記ポリアミドオリゴマー(a-2)を構成する全モノマー単位のうち25モル%以上が下記一般式(I)または一般式(II)で表される脂環式モノマーに由来する構造単位であり、前記脂環式モノマーに由来するトランス異性体構造単位の含有率が50~85モル%であるポリアミド樹脂(A)および無機充填材(B)を含有するポリアミド樹脂組成物。
(式中、Xはカルボキシル基またはアミノ基を表し、Zは炭素数3以上の脂環構造を表す。)
- 前記ポリアミド樹脂(A)を構成する前記ポリアミド(a-1)および前記ポリアミドオリゴマー(a-2)の分子鎖の末端基の総量の10%以上が末端封止剤によって封止されている、請求項1に記載のポリアミド樹脂組成物。
- 前記脂環式モノマーが、前記一般式(I)または一般式(II)におけるXがカルボキシル基である環状脂肪族ジカルボン酸である、請求項1または2に記載のポリアミド樹脂組成物。
- 前記環状脂肪族ジカルボン酸が1,4-シクロヘキサンジカルボン酸である、請求項3に記載のポリアミド樹脂組成物。
- 前記ポリアミド(a-1)および前記ポリアミドオリゴマー(a-2)が、炭素数4~12の脂肪族ジアミンに由来する構造単位を含有する、請求項1~4のいずれかに記載のポリアミド樹脂組成物。
- 前記脂肪族ジアミンが1,4-ブタンジアミン、1,5-ペンタンジアミン、1,6-ヘキサンジアミン、2-メチル-1,5-ペンタンジアミン、1,8-オクタンジアミン、1,9-ノナンジアミン、2-メチル-1,8-オクタンジアミン、1,10-デカンジアミン、1,11-ウンデカンジアミンおよび1,12-ドデカンジアミンからなる群より選ばれる少なくとも1種である、請求項5に記載のポリアミド樹脂組成物。
- 1,4-シクロヘキサンジカルボン酸に由来する構造単位を25モル%以上含有し、かつ前記脂肪族ジアミンに由来する構造単位として1,9-ノナンジアミンおよび/または2-メチル-1,8-オクタンジアミンを25モル%以上含有する、請求項6に記載のポリアミド樹脂組成物。
- さらに、ラクタムおよび/またはアミノカルボン酸に由来する構造単位を含有する、請求項1~7のいずれかに記載のポリアミド樹脂組成物。
- 前記ポリアミド樹脂(A)100質量部に対して前記無機充填材(B)を0.1~200質量部含有する、請求項1~8のいずれかに記載のポリアミド樹脂組成物。
- 前記ポリアミド樹脂(A)100質量部に対してルイス塩基として作用する化合物(C)を0.1~10質量部含有する、請求項1~9のいずれかに記載のポリアミド樹脂組成物。
- 前記ルイス塩基として作用する化合物(C)がアルカリ金属酸化物、アルカリ金属水酸化物、アルカリ土類金属酸化物、アルカリ土類金属水酸化物、酸化亜鉛および水酸化亜鉛からなる群より選ばれる少なくとも1種である、請求項10に記載のポリアミド樹脂組成物。
- 前記ルイス塩基として作用する化合物(C)が酸化カリウム、酸化マグネシウム、酸化カルシウム、酸化亜鉛、水酸化カリウム、水酸化マグネシウム、水酸化カルシウムおよび水酸化亜鉛からなる群より選ばれる少なくとも1種である、請求項11に記載のポリアミド樹脂組成物。
- 請求項1~12のいずれかに記載のポリアミド樹脂組成物からなる成形品。
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Families Citing this family (10)
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CN103403237A (zh) * | 2010-10-13 | 2013-11-20 | 索维特殊聚合物有限责任公司 | 抗染色的纤维、纺织品及地毯 |
CN105255171A (zh) * | 2015-09-16 | 2016-01-20 | 安徽省和翰光电科技有限公司 | 一种led用纳米氧化铝-石墨短纤维填充改性的pa6/abs复合导热塑料及其制备方法 |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6411073B2 (ja) | 1982-09-20 | 1989-02-23 | Mitsui Petrochemical Ind | |
JPH05194841A (ja) * | 1992-01-21 | 1993-08-03 | Toray Ind Inc | ポリアミド樹脂組成物 |
JPH0742397B2 (ja) | 1987-11-11 | 1995-05-10 | 住友ベークライト株式会社 | 積層板用熱硬化性樹脂組成物 |
JPH0912868A (ja) | 1995-06-26 | 1997-01-14 | Kuraray Co Ltd | ポリアミド組成物 |
JP2004107576A (ja) * | 2002-09-20 | 2004-04-08 | Kuraray Co Ltd | ポリアミド組成物 |
JP2006510780A (ja) * | 2002-12-19 | 2006-03-30 | デーエスエム アイピー アセッツ ベー. ヴェー. | 難燃性ポリアミド配合物 |
JP2011080046A (ja) * | 2009-09-09 | 2011-04-21 | Asahi Kasei Chemicals Corp | ポリアミド組成物、並びにポリアミド組成物を含む成形品及び電気部品 |
JP2011080056A (ja) * | 2009-09-11 | 2011-04-21 | Asahi Kasei Chemicals Corp | ポリアミド及びポリアミド組成物 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4742397Y1 (ja) | 1968-10-29 | 1972-12-21 | ||
JPS6411073A (en) | 1987-07-06 | 1989-01-13 | Nissan Motor | Wear resistance treating method for al alloy |
DE102005023420A1 (de) * | 2005-05-20 | 2006-11-23 | Ems-Chemie Ag | Polyamidformmassen mit verbesserter Fliessfähigkeit, deren Herstellung sowie deren Verwendung |
KR101744001B1 (ko) | 2009-09-07 | 2017-06-07 | 주식회사 쿠라레 | Led용 반사판 및 그것을 구비하는 발광 장치 |
EP2896657B1 (en) * | 2012-09-14 | 2021-02-24 | Kuraray Co., Ltd. | Polyamide resin |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6411073B2 (ja) | 1982-09-20 | 1989-02-23 | Mitsui Petrochemical Ind | |
JPH0742397B2 (ja) | 1987-11-11 | 1995-05-10 | 住友ベークライト株式会社 | 積層板用熱硬化性樹脂組成物 |
JPH05194841A (ja) * | 1992-01-21 | 1993-08-03 | Toray Ind Inc | ポリアミド樹脂組成物 |
JPH0912868A (ja) | 1995-06-26 | 1997-01-14 | Kuraray Co Ltd | ポリアミド組成物 |
JP2004107576A (ja) * | 2002-09-20 | 2004-04-08 | Kuraray Co Ltd | ポリアミド組成物 |
JP2006510780A (ja) * | 2002-12-19 | 2006-03-30 | デーエスエム アイピー アセッツ ベー. ヴェー. | 難燃性ポリアミド配合物 |
JP2011080046A (ja) * | 2009-09-09 | 2011-04-21 | Asahi Kasei Chemicals Corp | ポリアミド組成物、並びにポリアミド組成物を含む成形品及び電気部品 |
JP2011080056A (ja) * | 2009-09-11 | 2011-04-21 | Asahi Kasei Chemicals Corp | ポリアミド及びポリアミド組成物 |
Non-Patent Citations (2)
Title |
---|
K. P. C. VOLLHARDT; N. E. SCHORE: "Modern Organic Chemistry", vol. 1, 1 April 2004, KAGAKU-DOJIN PUBLISHING, pages: 174 |
See also references of EP2902445A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10294366B2 (en) * | 2014-05-16 | 2019-05-21 | Toyobo Co., Ltd. | Crystalline polyamide resin composition |
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US20150240079A1 (en) | 2015-08-27 |
KR102066765B1 (ko) | 2020-01-15 |
CN104662095A (zh) | 2015-05-27 |
KR20150063045A (ko) | 2015-06-08 |
JP6152383B2 (ja) | 2017-06-21 |
US9714343B2 (en) | 2017-07-25 |
EP2902445A4 (en) | 2016-05-25 |
EP2902445B1 (en) | 2021-02-24 |
CN104662095B (zh) | 2017-10-24 |
JPWO2014051120A1 (ja) | 2016-08-25 |
EP2902445A1 (en) | 2015-08-05 |
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