JP2002220461A - Polyamide resin, polyamide resin composition and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin which has such properties for using it suitably to a molding material for electrical and electronic parts, car parts and, etc., which high in crystallinity, low in water absorption and excellent in heat resistance, a polyamide composition and its molded article. SOLUTION: The polyamide resin characterized by having diamine components derived from 1,9-diaminononane, a 6-12C straight chained aliphatic diamine other than 1.9-diaminononane and/or a 6-12C aliphatic diamine having a side chain in an amount of 70-99 mol% of the 1,9-diaminononane component unit, 1-30 mol% of that of the 6-12C straight chained aliphatic diamine other than 1,9-diaminononane and/or 0-15 mol% of that of the 6-12C aliphatic diamine having a side chain, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyamide resin,
Polyamide resin composition and molded articles thereof, in particular, polyamide resin, polyamide excellent in high crystallinity, low water absorption, moldability and heat resistance, particularly suitable for molded articles of electric / electronic parts and automobile parts The present invention relates to a resin composition and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, polyamide 6 nylon and 6
6 nylon and the like are widely known. Since these aliphatic polyamides have excellent moldability, they are widely used for automobile parts, electric / electronic parts, mechanical parts and the like. In general, high heat-resistant polyamide resins have been actively developed, and high heat-resistant resin compositions containing 6-nylon and the like have been put to practical use, but these have not been able to say that their heat-resistant deformation temperatures are sufficient. On the other hand, nylon 46 is used as a high heat resistant polyamide.
However, although its heat-resistant deformation temperature is higher than that of a conventional polyamide, there is a problem that its water absorption is high. Under such circumstances, the applicant of the present application has disclosed Japanese Patent Application Laid-Open No. 3-281532.
In the publication, (a) the dicarboxylic acid component unit is composed of 52 to 58 mol% of a terephthalic acid component unit and 48 to 42 mol% of an aliphatic dicarboxylic acid component unit, and (b) the diamine component unit is composed of an aliphatic alkylenediamine component. And / or an alicyclic alkylenediamine component unit, and
Intrinsic viscosity [η] measured at 25 ° C in concentrated sulfuric acid is 0.5 to 3.0 dl
A polyamide resin composition containing an aromatic polyamide in the range of / g and a fibrous filler has been proposed. Since the polyamide resin composition is relatively excellent in heat resistance, water resistance, mechanical strength, impact resistance and the like, it is widely used for molding materials for automobile parts, electric / electronic parts and the like.

In recent years, from the viewpoint of environmental protection, “lead-free solder” that does not use lead has been used as solder for electric products. The “lead-free solder” tends to have a higher reflow temperature in the surface mounting process than the eutectic solder of lead and tin which has been widely used in the past. For this reason, when using “lead-free solder” to connect electrical and electronic components on a printed wiring board, the resin used for electrical and electronic components must have higher heat resistance than conventional polyamide resins. There is. In such electric / electronic components for surface mounting, if the water absorption of the resin used for the component is high, the surface of the component may swell during the reflow process.

[0004] The polyamide resin composition as described above has relatively high heat resistance, but has a high water absorption. Therefore, when it is used for such surface-mounted electric / electronic parts, the surface of the parts during the reflow process is hardened. There was a problem that swelling often occurred. Under these circumstances, electric and
In order to develop a polyamide resin that can be suitably used for electronic components, studies have been made to suppress water absorption. Incidentally, it is generally known that the water absorption of polyamide is higher in the amorphous part than in the crystalline part. Therefore, development of a resin having high crystallinity has been desired in order to suppress water absorption. However, even if the resin has a high degree of crystallinity, if it is not sufficiently crystallized after molding, deformation may occur during the annealing process or the reflow process as described above.

Accordingly, there has been a demand for a resin which provides a molded article having a high water resistance (low water absorption) and a high crystalline state.

As a polyamide having a low water absorption, a polyamide using 1,9-nonanediamine as a main component of a diamine component is known. Japanese Patent Application Laid-Open No. 7-228689 discloses 1,9-nonanediamine and 2-methyldiamine. A polyamide comprising -1,8-octanediamine and terephthalic acid is disclosed.

However, since these polyamides contain a large amount of diamine containing a side chain, crystallization is inhibited, and the above-mentioned deformation may be caused. In order to increase the crystallinity, there is a method of extending the cooling time during injection molding, but in this case, there is a problem such as an increase in molding time. In these documents, there is also a description of a resin that rapidly crystallizes, as judged from the peak derived from crystallization in DSC, but there is no specific description of the crystallinity to be reached, and the crystallization after molding is not described. May be low.

Japanese Patent Application Laid-Open No. 7-228690 discloses a polyamide comprising 1,9-nonanediamine and terephthalic acid. Since these polyamides do not contain a diamine containing a side chain, it is thought that crystallization inhibition may be prevented. However, in these polyamides, the melting point of the resin is high, and when a composition using the polyamide is produced, and when the composition is melt-molded, some of the additives forming the composition are decomposed. Problems such as poor appearance of the molded product, mold contamination, and gas burning of the molded product due to blockage of the gas vent of the mold may occur.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has high crystallinity and low crystallinity suitable for molding materials for electric / electronic parts and automobile parts. An object of the present invention is to provide a polyamide resin and a polyamide composition having excellent water absorption and heat resistance, and a molded product thereof.

[0010]

Means for Solving the Problems In order to overcome the above problems, the present inventors have studied the components constituting the polyamide resin in more detail, and as a result, have been able to provide a molded article in a highly crystalline state. A resin having low water absorption and further excellent heat resistance was found. The present invention is as follows.

(1) The polyamide resin of the present invention comprises (i) 1,9
Derived from -diaminononane, a linear aliphatic diamine having 6 to 12 carbon atoms other than 1,9-diaminononane, and / or an aliphatic diamine having 6 to 12 carbon atoms having a side chain; -Diaminononane component unit is 70 to 99 mol%, 1,9-
A diamine component containing 1 to 30 mol% of a linear aliphatic diamine having 6 to 12 carbon atoms other than diaminononane, and / or 0 to 15 mol% of an aliphatic diamine having 6 to 12 carbon atoms having a side chain; (ii) a terephthalic acid component unit of 50 to 100 mol%,
Aromatic dicarboxylic acid component units other than terephthalic acid 0 to 50
And / or a dicarboxylic acid component comprising 0 to 50 mol% of an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms.

(2) The above polyamide resin is 96.5 ° C at 25 ° C.
The intrinsic viscosity measured in sulfuric acid is in the range of 0.5 to 3.0 dl / g, the melting point measured by DSC is 280 ° C or higher and lower than 315 ° C, and the crystallinity measured by X-ray diffraction is 15%. It is characterized by the above.

(3) Further, the polyamide resin composition according to the present invention is characterized in that it contains the polyamide resin and 0.1 to 200 parts by weight of a filler with respect to 100 parts by weight of the polyamide resin.

(4) The molded article of the present invention is characterized by comprising the polyamide resin or the polyamide resin composition.

(5) An electric / electronic part according to the present invention is characterized by comprising the polyamide resin or the polyamide resin composition.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polyamide resin, the polyamide resin composition, and the molded product thereof according to the present invention will be specifically described.

[Diamine Component] The diamine component constituting the polyamide resin of the present invention comprises 1,9-diaminononane,
A linear aliphatic diamine other than 9-diaminononane having 6 to 12 carbon atoms and / or 6 to 12 carbon atoms having a side chain;
It is preferred to be derived from aliphatic diamines.

Specific examples of the linear aliphatic diamine component other than 1,9-diaminononane used in the present invention include:
6-diaminohexane, 1,7-diaminoheptane, 1,8-
Diaminooctane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane can be mentioned. Of these, component units derived from 1,8-diaminooctane, 1,10-diaminodecane, and 1,11-diaminoundecane are particularly preferred.

C6 having a side chain used in the present invention
The aliphatic diamine component to is not particularly limited as long as it is an aliphatic diamine having a side chain alkyl group, but specific examples thereof include 2-methyl-1,5-diaminopentane and 2-methyl-1 , 6-Diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane,
2-methyl-1,9-diaminononane, 2-methyl-1,10-
Examples thereof include diaminodecane and 2-methyl-1,11-diaminoundecane. Among these, 2-methyl-1,
Component units derived from 7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane are particularly preferred.

The above-mentioned diamine component formed together with 1,9-diaminononane can be used by mixing a linear aliphatic diamine component and an aliphatic diamine component having a side chain alkyl group at an arbitrary ratio. Only the aliphatic diamine component may be used.

In the present invention, when the total amount of the diamine component units constituting the diamine component is 100 mol%, 1,9-
The structural unit derived from the diaminononane component unit is 70
~ 99 mol%, preferably 85-99 mol%,
Constituent units derived from linear C6-C12 aliphatic diamine component units other than 1,9-diaminononane are contained in an amount of 1 to 30 mol%, preferably 1 to 15 mol%, and / or Alternatively, it is preferable that a constituent unit derived from an aliphatic diamine component unit having 6 to 12 carbon atoms having a side chain is contained in an amount of 0 to 15 mol%, preferably 0 to 10 mol%.

[Dicarboxylic Component] The dicarboxylic acid component constituting the polyamide resin of the present invention comprises 50 to 100 mol% of a terephthalic acid component unit and 0 to 50 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid. The aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms preferably comprises 0 to 50 mol%.

Among these, examples of the aromatic dicarboxylic acid component unit other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and combinations thereof.

The number of carbon atoms in the aliphatic dicarboxylic acid component unit is not particularly limited.
~ 20, more preferably from 6-12 aliphatic dicarboxylic acids. Examples of aliphatic dicarboxylic acids used to derive such aliphatic dicarboxylic acid component units include, for example, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid And the like. Among these, adipic acid is particularly preferred. In the present invention, when the total amount of the dicarboxylic acid component units constituting the dicarboxylic acid component (b) is 100 mol%, the constitutional unit derived from the terephthalic acid component unit is 50 to 100 mol%, preferably 80 to 100 mol%. Constituent units derived from aromatic dicarboxylic acid component units other than terephthalic acid are contained in an amount of 0 to 50 mol%, preferably 0 to 20 mol%, and / or carbon atoms It is preferable that the structural unit derived from the aliphatic dicarboxylic acid component unit of the number 4 to 20, preferably 4 to 12, is contained in an amount of 0 to 50 mol%, preferably 0 to 20 mol%.

In the present invention, a small amount of the dicarboxylic acid component (b) may be used together with the above-mentioned terephthalic acid component unit, an aromatic dicarboxylic acid component unit other than terephthalic acid, and / or an aliphatic dicarboxylic acid component unit. For example, a polycarboxylic acid component unit in an amount of about 10 mol% or less may be contained. Specific examples of such a polycarboxylic acid component unit include tribasic acids and polybasic acids such as trimellitic acid and pyromellitic acid.

[Production of Polyamide Resin] In order to produce the polyamide resin (A) of the present invention, the above-mentioned diamine component (a) and dicarboxylic acid component (b) are added, and the mixture is added in the presence of a catalyst. It can be produced by heating. In this reaction, it is preferable that the total number of moles of the diamine component (a) is more than the total number of moles of the dicarboxylic acid component (b). The total diamine component is 100-120 mol%. This reaction is usually performed in an inert gas atmosphere, and the inside of the reaction vessel is generally replaced with an inert gas such as nitrogen gas. In order to control the polycondensation reaction of the polyamide, it is preferable that water is sealed in advance, and an organic solvent soluble in water, for example, alcohols such as methanol and ethanol may be contained.

The catalyst used for producing the polyamide resin used in the present invention includes phosphoric acid, its salts and phosphate ester compounds; phosphorous acid, its salts and ester compounds; Its salts and ester compounds can be used. Among them, sodium phosphate, sodium phosphite, potassium hypophosphite, sodium hypophosphite and the like are preferable.

These phosphate compounds can be used alone or in combination. Such a phosphorus compound is usually used for the above-mentioned dicarboxylic acid.
It is used in a proportion of 0.001 to 5 mol%, preferably 0.002 to 2 mol%.

In order to produce the polyamide resin of the present invention, it is preferable to use a terminal blocking agent. As the terminal blocking agent, benzoic acid, an alkali metal salt of benzoic acid, acetic acid and the like can be used. Such an end capping agent is usually used in an amount of 0.001 to 5 per mole of dicarboxylic acid.
Mol, preferably in an amount in the range from 0.01 to 2 mol. The limiting viscosity [η] of the resulting polycondensate can be controlled by adjusting the amount of the terminal blocking agent used.

The reaction conditions for preparing such a polycondensate include, specifically, a reaction temperature of usually 200 to 290 ° C., preferably 220 to 280 ° C., and a reaction time of usually 0.5 to 5 hours, preferably 1-3 hours. Further, this reaction can be carried out under any conditions from normal pressure to pressurization, but it is preferable to carry out the reaction under pressurized conditions, and the reaction pressure is usually 20 to 60 kg / cm ² , preferably 25 to 50 kg / cm ² . It is set within the range of cm ² . Then, by performing the polycondensation reaction in this manner, 25 ° C.
The intrinsic viscosity [η] measured in 96.5% sulfuric acid is usually 0.0
A low-order condensate in the range of 5 to 0.6 dl / g, preferably 0.08 to 0.3 dl / g can be obtained. The polyamide low-order condensate thus formed in the aqueous medium is separated from the reaction solution. For separation of the polyamide low-order condensate and the reaction solution, for example, a method such as filtration and centrifugation can be adopted.However, the reaction solution containing the generated semi-aromatic polyamide low-order condensate is passed through a nozzle. The method of performing solid-liquid separation by flashing into the atmosphere through the air is efficient.

In the present invention, post-polymerization is performed using the polyamide low-order condensate obtained as described above. This post-polymerization is preferably carried out by drying the polyamide low-order condensate and then heating it to a molten state while applying a shear stress to the melt. In this reaction, the polyamide is heated to a temperature at which the dry polyamide low-order condensate is at least melted. Generally, it is heated to a temperature higher than or equal to the melting point of the low-order condensate of the dried polyamide, preferably 10 to 60 ° C. higher than this melting point. The shear stress is, for example, a twin-screw extruder with a vent,
It can be applied to the melt by using a kneader or the like. It is considered that by applying shear stress to the melt in this way, the low-order condensate of the dried polyamide in the molten state is polycondensed with each other, and the polycondensation reaction of the condensate also proceeds.

As another method for producing the polyamide resin of the present invention, the above polyamide low-order condensate is subjected to solid-phase polymerization by a generally known method so that the intrinsic viscosity [η] is 0.5 to 2.0.
Polyamides in the range of dl / g can be prepared.

For the production of the polyamide resin of the present invention,
As still another method, the polyamide low-order condensate is subjected to solid-state polymerization by a generally known method, so that the intrinsic viscosity [η] is 0.5.
~ 1.5 dl / g of a polyamide precursor was prepared, and the precursor was melt-polymerized to have an intrinsic viscosity [η] of 0.8.
It can be in the range of ~ 3.0 dl / g. [Polyamide resin] The polyamide resin (A) having the above composition range can have excellent moldability, low water absorption and heat resistance.

The polyamide resin used in the present invention comprises 25
The intrinsic viscosity measured in 96.5% sulfuric acid at a temperature of 0.5 to 3.0 dl /
g, preferably 0.5 to 2.5 dl / g, particularly preferably 0.6 to 2.0 dl / g. When it is in such a range, the moldability and the strength characteristics of the molded product are excellent.

The polyamide resin of the present invention has a melting point measured by DSC of 280 ° C. or more and less than 315 ° C., particularly 290 ° C. to 315 ° C.
Is preferably within the range. A polyamide resin having such a range has particularly excellent heat resistance. Melting point measurement was performed by using a DSC to hold once at 330 ° C. for 5 minutes, and then
After the temperature was lowered to 23 ° C. at a rate of 0 ° C./min, the temperature was raised at 10 ° C./min. The endothermic peak based on the melting at this time was defined as the melting point (Tm).

The polyamide resin of the present invention preferably has a crystallinity of at least 15%, more preferably at least 20%, as measured by X-ray diffraction. A polyamide resin having a crystallinity within such a range is excellent in shape stability of a molded product. The crystallinity was measured by the X-ray diffraction method, and the peak integrated values of the X-ray scattering curves of the amorphous resin and the molded product were A ₁ and A ₂ , respectively, and were calculated by the following formula. The amorphous resin was prepared by rapidly cooling the molten resin with liquid nitrogen. Crystallinity (%) = (A ₂ −A ₁ ) / A ₂ × 100 A ₁ : Peak integrated value of X-ray scattering curve of amorphous resin A ₂ : Peak integrated value of X-ray scattering curve of crystalline resin

[Filler] In the present invention, the following fillers are used in an amount of 0.1 to 200 parts by weight, preferably 100 parts by weight, based on the polyamide resin (A), depending on the use, within a range not to impair the effects of the present invention.
It can be added in a proportion of 20 to 180 parts by weight. Examples of the filler used in the present invention include fibrous fillers (especially glass fibers, aramid fibers, carbon fibers, and the like), powdery, granular, plate-like, and needle-like fillers (particularly, silica, alumina, and carbon dioxide). Calcium, titanium dioxide, talc, wollastonite, diatomaceous earth, clay, kaolin, spherical glass, mica, magnesium oxide, zinc oxide, potassium titanate, whisker, etc., flame retardant (brominated polystyrene,
Polybrominated styrene, brominated polycarbonate, condensates of brominated phenol, red phosphorus, antimony oxide, sodium antimonate, zinc oxide, iron borates such as iron oxide, magnesium oxide, zinc borate, etc.), antioxidants And heat-resistant stabilizers (magnesium oxide, zinc oxide, hydrotalcites, phosphorus compounds, hindered phenols, hydroquinones, copper halides, iodine compounds, etc.), and other polymers (olefins, modified polyolefins, ethylene Propylene copolymer, ethylene / 1-butene copolymer, propylene / ethylene copolymer, olefin copolymer such as propylene / 1-butene copolymer, polystyrene,
Polyamide, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesin, silicone resin, aliphatic polyamide, etc.), plasticizer, thickener,
Examples include an antistatic agent, a release agent, a pigment, a dye, a nucleating agent, and various known compounding agents.

[Polyamide Resin Composition] The polyamide composition according to the present invention can be obtained by mixing the above-mentioned components with various known methods, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, and the like.
Or after mixing, single-screw extruder, multi-screw extruder, kneader,
It can be adjusted by using a method of granulating or pulverizing after melt-kneading with a Banbury mixer or the like.

Specifically, while heating and maintaining the polyamide resin (A) in a molten state, for example, at 280 to 360 ° C., the above fibrous filler, powdery filler, and various additives are blended as necessary. It can be prepared by a method such as kneading. At this time, an ordinary kneading device such as an extruder or a kneader can be used. The polyamide resin and the composition thereof of the present invention can be heated to a temperature not lower than the melting point of the polyamide and lower than the decomposition temperature, and can be molded into a desired shape using a usual molding apparatus. In particular, electric / electronic parts and automobile parts can be efficiently molded by injection molding.

For example, the polyamide resin composition of the present invention prepared as described above may be formed into a powder, pellet, or other form, and then subjected to compression molding, injection molding, extrusion molding, etc. -It can be made into various molded products such as electronic parts and automobile parts.

The polyamide resin composition according to the present invention has a high degree of crystallinity, is excellent in low water absorption, heat resistance, moldability, and various mechanical strength characteristics, and provides a molded article in a highly crystalline state. In particular, it is suitably used as a molding material for electric / electronic parts and automobile parts. Further, a molded article obtained from such a polyamide resin composition has a low water absorption, and is excellent in heat resistance without swelling even at a considerably high temperature in a reflow step.

[0042]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, intrinsic viscosity in Examples and Comparative Examples
[η], melting point, crystallinity, water absorption, and temperature at which swelling occurs during reflow were measured according to the following methods. Intrinsic viscosity [η] : 5 g of polyamide resin in 96.5% sulfuric acid solution 5
Dissolve in 0 ml and use an Ubbelohde viscometer, 25.0 ± 0.0
The number of seconds for the sample solution to flow under the condition of 5 ° C. was measured and calculated based on the following equation. [η] = η _SP /{C(1+0.205η _SP )} η _SP = (tt ₀ ) / t ₀ [η]: intrinsic viscosity (dl / g) η _SP : specific viscosity C: sample concentration (g / dl) t: Second of flowing sample solution (second) t ₀ : Second of flowing blank sulfuric acid (second) Melting point (Tm) : Once using Perkin ELMER DSC7
The temperature was kept at 30 ° C. for 5 minutes, then the temperature was lowered to 23 ° C. at a rate of 10 ° C./min, and then the temperature was raised at 10 ° C./min. The endothermic peak based on the melting at this time was defined as the melting point. Crystallinity : Polyamide resin, injection pressure 1000 kg / c
m ² , set the cylinder temperature to 10 ° C higher than the melting point of the resin, and mold length 120 mm, length 64 mm, width 6 mm, thickness 0.
8 mm test pieces were injection molded. About this test piece,
Crystallinity was measured by X-ray diffraction. R manufactured by Scientific Instruments Co., Ltd.
Using u300, measurement was performed by a Cu target, 50 kv, 300 mA, point focus, and sample rotation transmission method. The peak integrated values of the X-ray scattering curves of the amorphous resin and
_1, and A _2, was calculated by the following equation. The amorphous resin was prepared by rapidly cooling the molten resin with liquid nitrogen. Crystallinity _{(%) = (A 2 -A} 1) / A 2 × 100 A 1: peak integral value of X-ray scattering curve of the amorphous resin A _2: Peak integration value the water absorption of the X-ray scattering curve of the crystalline resin : Injection pressure 1000 kg / cm ² and cylinder temperature of polyamide resin are set to 10 ° C higher than the melting point of resin.
Injection molding was performed at a mold temperature of 120 ° C. to obtain a test piece having a length of 64 mm, a width of 6 mm and a thickness of 0.8 mm. This test piece was stored in a constant temperature and humidity room at 40 ° C. and a relative humidity of 95% to absorb water. After absorbing water for 96 hours, the test piece weight was measured with a precision balance. Water absorption
(% By weight) was determined by the following equation. M = (M ₂ −M ₁ ) / M ₁ × 100 M: Water absorption (% by weight) M ₁ : Absolute dry weight of test piece (g) M ₂ : Weight of test piece after water absorption (g) Evaluation of mold contamination : Using a molding die with a thin gas vent,
The polyamide resin composition was subjected to 2,000 shot continuous injection molding at an injection pressure of 1000 kg / cm ² , a cylinder temperature of 10 ° C. higher than the melting point of the resin, and a mold temperature of 120 ° C. The resin around the gas vent was visually inspected for discoloration which is considered to be caused by gas burning. If there was no discoloration, the mold was stained ○, and if discoloration was observed, the mold was stained ×. Temperature at which swelling occurs during reflow : The set temperature is maintained for 20 seconds using a reflow soldering apparatus (SOLSYS-2001R, manufactured by Nippon Antom Industry Co., Ltd.) for the test piece used for the above-described water absorption measurement. In the temperature profile, the heat resistance during reflow was evaluated in the reflow step in which the peak temperature was set at 10 ° C. higher than the set temperature. If the temperature at which swelling occurs is 250 ° C or higher, ◎, less than 250 ° C, 240 ° C or higher, ○, less than 240 ° C, 230 ° C or higher, 230 ° C
In the case of less than, it was evaluated as ×.

[0043]

EXAMPLE 1 44.2 kg (280 mol) of 1,9-diaminononane, 2.2 kg (15.6 mol) of 1,8-diaminooctane,
2.7 kg (15.6 mol) of 10-diaminodecane, 51 kg (308 mol) of terephthalic acid, 0.5 kg (3.9 mol) of benzoic acid, 0.07 kg (0.6 mol) of sodium hypophosphite monohydrate and 30 parts of distilled water kg was placed in an autoclave, and the inside of the reaction vessel was sufficiently purged with nitrogen. While stirring, the internal temperature was raised to 250 ° C. over 4 hours. The reaction was continued for 1 hour to obtain a polyamide low-order condensate. This polyamide low-order condensate was subjected to solid-state polymerization at 190 ° C. for 12 hours under vacuum. Then, with a screw diameter of 37 mm, L / D = 36 twin screw extruder,
Melt polymerization was performed at a barrel set temperature of 30 ° C. higher than the melting point of the polyamide at a screw rotation speed of 300 rpm and a resin supply speed of 10 kg / h to obtain a polyamide resin. Table 1 below shows [η], melting point (Tm), crystallinity, and water absorption of this polyamide resin.
Shown in Glass fiber (Asahi Fiberglass; CS03JAFT2A) 30 parts by weight, flame retardant (polydibromopolystyrene; Great Lakes Chemical; PDBS-80) 30 parts by weight, flame retardant auxiliary (antimonic acid) (Soda; manufactured by Nissan Chemical Co., Ltd .; Sun Epoch NA-1070L)
4 parts by weight and 1 part by weight of a nucleating agent (talc; Matsumura Sangyo Co., Ltd .; High Filler) are added, and the mixture is melt-kneaded at a temperature 10 to 30 ° C. higher than the melting point of the polyamide resin in a twin-screw extruder to obtain a polyamide resin. A composition was obtained. The polyamide resin composition was injection-molded, the mold stain was evaluated, and the temperature at which swelling occurred during reflow was measured. Table 1 shows the results.

[0044]

Examples 2 to 7 In Example 1, a diamine component and a dicarboxylic acid component shown in Table 1 below were used.
Polymerization was carried out in the same manner as in Example 1 except that the molar ratio described in was used to obtain a polyamide resin. Then
Using the obtained polyamide resin, a polyamide resin composition was produced in the same manner as in Example 1. These were evaluated in the same manner as in Example 1. Table 1 shows the results.

[0045]

Comparative Examples 1 and 2 In Example 1, the diamine component and dicarboxylic acid component shown in Table 1 below were used, and
Polymerization was carried out in the same manner as in Example 1 except that the molar ratio described in was used to obtain a polyamide resin. Then
Using the obtained polyamide resin, a polyamide resin composition was produced in the same manner as in Example 1. When these were evaluated in the same manner as in Example 1, in Comparative Example 1, mold stains were observed,
Comparative Example 2 was inferior in heat resistance. Table 1 shows the results.

[0046]

Comparative Example 3 In Example 1, the type of diamine was 1,9
Example 1 was repeated except that 1,6-diaminohexane was used in place of -diaminononane, and the mixing ratio (molar ratio) of the diamine component and the dicarboxylic acid component was changed to the molar ratio shown in Table 1.
A polyamide resin and a polyamide resin composition were produced in the same manner as described above. When these were evaluated in the same manner as in Example 1, the water absorption was high and the heat resistance was poor. Table 1 shows the results.

[Table 1]

[0047]

The polyamide resin composition according to the present invention comprises:
Since it contains a specific polyamide resin containing the above component units at the above specific ratio, particularly high crystallinity, low water absorption, heat resistance, moldability, and excellent strength properties, Further, since a molded product in a highly crystalline state can be provided, it is suitable as a molding material for electric / electronic parts, automobile parts, and the like. Further, the molded article according to the present invention formed using the above polyamide resin composition has a low water absorption and is excellent in heat resistance during the reflow step.

Continued on the front page F-term (reference) 4F071 AA55 AA84 AA88 AA89 AE17 AF10 AF45 AH07 BA01 BB03 BB05 BB06 4J001 DA01 DB02 EB08 EB09 EB36 EB37 EB46 EC04 EC08 EC09 EC13 EE74D EE75D EE76D FB03 GB05 FC06 GB05 GB06 JB02 JB06 JB08 JB17 JB18 4J002 CL031 CL062 DA016 DE076 DE106 DE136 DE146 DE186 DE236 DJ006 DJ016 DJ036 DJ046 DL006 FA042 FA046 FA086 FD012 FD012 FD016 FD030 FD070 FD130 GN00

Claims (5)

[Claims] (1) 1,9-diaminononane, a linear aliphatic diamine other than 1,9-diaminononane having 6 to 12 carbon atoms, and / or 6 to 12 carbon atoms having a side chain. Derived from an aliphatic diamine, 70 to 99 mol% of a 1,9-diaminononane component unit, 1 to 30 mol% of a linear aliphatic diamine having 6 to 12 carbon atoms other than 1,9-diaminononane, and And / or 0 to 15 aliphatic diamine having 6 to 12 carbon atoms having a side chain.
Mole% diamine component and (ii) terephthalic acid component unit
A dicarboxylic acid comprising 50 to 100 mol%, 0 to 50 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid, and / or 0 to 50 mol% of an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms. A polyamide resin comprising a component. 2. An intrinsic viscosity measured in 96.5% sulfuric acid at 25 ° C. in the range of 0.5 to 3.0 dl / g, a melting point measured by DSC of 280 ° C. or more and less than 315 ° C., and X-ray diffraction 2. The polyamide resin according to claim 1, wherein the crystallinity measured by the method is 15% or more. 3. A polyamide resin composition comprising the polyamide resin according to claim 1 and 0.1 to 200 parts by weight of a filler with respect to 100 parts by weight of the polyamide resin. . 4. A molded article comprising the polyamide resin or the polyamide resin composition according to claim 1. 5. An electric / electronic part and / or an automobile part comprising the polyamide resin or the polyamide resin composition according to claim 1.