JP3409400B2 - Resin composition and method for producing the same - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alloy of a polyamide resin, and more particularly to a resin composition suitable for automobile parts, electric and electronic parts, and a method for producing the same. It is about. 2. Description of the Related Art Polyamide resins are used in the automotive field,
Widely used in electric and electronic fields. Among them, resin compositions alloyed with other resins are widely used because they can impart various properties. Conventionally, as alloys of polyamide, for example, alloys with polyphenylene oxide, polyolefin, rubbery polymer and the like have been known, and they meet the requirements of impact resistance, chemical resistance, water resistance, electrostatic resistance and the like. Various alloys have been studied. However, when the alloy is formed, there is a problem of a decrease in color tone and elongation due to a heat history, and the original performance of the alloy has not been sufficiently exhibited. Therefore, the addition of various resins and additives other than polyamides has been studied (Japanese Patent Application Laid-Open Nos. 58-38751 and 5-171037), and the performance has been improved. [0005] However, since it receives two thermal histories of polymerization and alloying, it does not solve the problems of color tone and elongation, etc., but sufficiently enhances the original performance of the alloy. It was hoped that it would be demonstrated. Accordingly, the present invention can sufficiently exhibit the alloy original performance by reducing heat history and provides a manufacturing method of made of Polyamide with simplified production of alloy by performing simultaneously a part alloyed polymerization The task is to Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies on a method for solving the above-mentioned problems, and as a result, the primary condensate of polyamide is alloyed and simultaneously increased in polymerization degree. As a result, the inventors have found that not only can the alloy production method be simplified, but also that the original performance of the alloy can be obtained, and the present invention has been achieved. That is, the present invention relates to a primary condensate of a polyamide having a relative viscosity of 1.04 to 2.5 at 25 ° C. in a 1% sulfuric acid solution , a rubbery polymer,
Lenether, at least one selected from ABS resin
And one single Tsugichijimigo other than product resin, relative <br/> viscosity of the primary condensation product is Do promote high polymerization degree as up 0.3 et
Resin composition characterized by alloying in a melt extruder
It is a method of manufacturing a product . Hereinafter, the present invention will be described in detail. The polyamide of the present invention may be any polymer having an amide bond (—CONH—) as a repeating unit in the molecule, and known polyamides and copolymerized polyamides can be used. For example, nylon 66, nylon 6, nylon 12, nylon 11, nylon 612, nylon 610, nylon 4
6, nylon MXD6 and the like are preferable, and as the copolymerized polyamide, nylon 6/66, nylon 6T / 66,
Nylon 6T / 6I, nylon 6T / 6I / 66, nylon 6T / 6, nylon 6/66 / PACM6, nylon 6/66/610, etc. (where MXD is m-xylylenediamine, T is terephthalic acid, Represents isophthalic acid and PACM represents bis (paraaminocyclohexyl) methane. Preferably, the component composed of a dicarboxylic acid and a diamine is at least 50 mol%. Particularly preferred are (co) polyamides formed from hexamethylene adipamide units and / or diamines having 4 to 16 carbon atoms and units comprising phthalic acid. As the diamine having 4 to 16 carbon atoms, hexamethylenediamine, pentamethylenediamine, tetramethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine,
2,4,4-trimethylhexamethylenediamine, 5-
Methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, m-xylylenediamine, p-xylylenediamine, bis (paraaminocyclohexyl) methane, 1,3-bis (paraaminocyclohexyl) propane, isophoronediamine, 1,3 -Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like. Examples of phthalic acid include terephthalic acid and isophthalic acid. The primary condensate of the polyamide of the present invention generally needs to have a relative viscosity of 1% sulfuric acid solution at 25 ° C. (hereinafter abbreviated as ηr) of 1.04 to 2.5. Preferably, it is 1.1 to 2.0. If the ηr of the primary condensate is less than 1.04, the mechanical properties (eg, elongation) of the alloy are insufficient, and the primary condensate having an ηr of more than 2.5 is already sufficiently heated in the primary condensation step. Therefore, it is not preferable because the heat history is not reduced. As a method for synthesizing the primary condensate of the polyamide of the present invention, a known method is used. It is common to synthesize a primary condensate by polymerization from raw materials, for example, a method in which monomers are melt-polymerized in a pressure polymerization tank or a continuous reaction tank, or a kneader, a biaxial paddle type, a tower type, a rotary type. It can be obtained by a method of solid-phase polymerization using a drum-type or double-cone-type solid-phase polymerization device or the like.
Further, melt polymerization, solid phase polymerization, polymerization using an extruder, or the like may be used in combination. The resins other than the primary condensate of the present invention include:
Rubber-like polymers (SBS, SEBS, etc. diene polymer), Po polyphenylene ether, from the A BS resins
It is necessary to use at least one selected. Further , these resins may be used in combination. Further, the above-mentioned thermoplastic resin treated with a modifier may be used. The modifier, for example, maleic acid anhydride, epoxy, acrylic, known ones may be used, such as silane, Ru can also be added during alloying. In the present invention, the amount of the resin other than the primary condensate is preferably 0.1 to 90% by weight, more preferably 1 to 60% by weight. The timing of the addition is not particularly limited, and even if a resin other than the primary condensate is added to the melted primary condensate, the primary condensate is added to the melted resin other than the primary condensate. Alternatively, both may be mixed in a molten state, or both may be mixed before melting. In alloying, the change in ηr by increasing the degree of polymerization of the primary condensate must be increased by 0.3 or more.
It is preferably 0.5 or more and 3 or less, particularly preferably 0.5 or more and the polyamide after alloying has an ηr of 1.8 to 4.5.
It is. The method of alloying while increasing the ηr of the primary condensate by 0.3 or more is not particularly limited, but is performed by controlling the conditions of heat melting and dehydration in an alloying method using a known apparatus such as a melting machine. Is preferred. The melting temperature is preferably in the range of the melting point of the primary condensate plus 5 ° C to 370 ° C, and particularly preferably in the range of the melting point of the primary condensate plus 5 ° C to 340 ° C. It is preferable to set the melting point of the primary condensate plus 5 ° C. or more in terms of the melt viscosity required for kneading, and it is preferable to set the upper limit temperature to 370 ° C. or less in order to prevent thermal decomposition and thermal degradation of the polymer. Further, it is preferable to quickly remove water generated by the condensation polymerization, and it is particularly preferable to degas under reduced pressure. For alloying while increasing the degree of polymerization, a melter is generally used, and a melt extruder or a melt kneader can be used. Among them, a melt extruder is preferable, and a twin screw extruder is particularly preferable. Is preferred. The residence time in the melter is not particularly limited, but is preferably 20 seconds or more, particularly preferably 30 seconds or more. If the residence time is short, it is not preferable because the degree of polymerization does not effectively increase. In order to extend the residence time, it is effective to connect two or more melters in series. The phosphorus-based catalyst is effective for increasing the degree of polymerization, and may be added as needed. The resin composition having a high degree of polymerization can be further solid-phase polymerized as needed to further increase the degree of polymerization. In ordinary polymerization of polyamide, the raw materials are generally charged so that the total amount of carboxyl groups and the total amount of amino groups contained in the monomer and the salt of diamine / dicarboxylic acid are equal to each other. As the primary condensate, a primary condensate having a large amount of terminal carboxyl groups or terminal amino groups can also be used. However, when the difference in the amount of terminal groups exceeds 10 mol%, it is difficult to increase the degree of polymerization, which is not preferable. Also, a mixture of primary condensates can be used. In addition, in the polymerization reaction of the primary condensate, the addition of a polymerization degree regulator is effective in order to easily control the degree of polymerization and the degree of polymerization at a high degree of polymerization. As the polymerization degree regulator, a monoamine compound and a monocarboxylic acid compound are usually used, but acetic acid, benzoic acid and stearic acid are preferable, and acetic acid and benzoic acid are particularly preferable. The polymerization degree modifier is used in an amount of from 0 to 0.1 times, preferably from 0.0001 to 0.05 times, the number of moles of the constituent monomer and the total number of moles of the dicarboxylic acid unit and the diamine component unit of the salt.
It is used twice as much. The polyamide resin composition obtained in the present invention may further contain a filler. What is a filler?
Glass fiber or bead, talc, kaolin, wollastonite, mica, silica, alumina, diatomaceous earth, clay, gypsum, bengalara, graphite, titanium dioxide, zinc oxide, copper, stainless steel, etc. Inorganic compounds, other polymer fibers (carbon fibers) and the like, preferably glass fibers. Particularly preferred as glass fibers are glass rovings, glass chopped strands, glass threads and the like made from strands of continuous long fibers having a diameter of about 3 to 20 μm. The compounding ratio of such a filler is generally in the range of 0 to 200 parts by weight, preferably in the range of more than 0 to 150 parts by weight, particularly preferably 10 to 100 parts by weight, per 100 parts by weight of the polyamide.
Parts by weight. If the mixing ratio of the filler is more than 200 parts by weight, the fluidity at the time of melting becomes poor, and not only is it difficult to injection-mold a thin molded product, but also the appearance of the molded product is unfavorably deteriorated. The method of blending the filler with the resin composition of the present invention is not particularly limited, and any known method can be used. Specific examples of the compounding method include a method in which a filler is dry-blended into pellets of the resin composition after alloying, and the resulting mixture is melt-kneaded with a single-screw or twin-screw extruder. In addition, a method in which a filler is added while the ηr of the primary condensate is increased by 0.3 or more in a melter and a filler is added in the middle of the melter at the same time is preferable because of high production efficiency. In the present invention, in the synthesis of the primary condensate, alloying while increasing the degree of polymerization, the compounding or molding process, etc., a catalyst, a heat stabilizer, a weather resistance stabilizer, a plasticizer, a mold release agent may be used if necessary. , Lubricants, nucleating agents, pigments,
Dyes, other polymers and the like can be added. These additives include heat-resistant stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substituted products thereof, copper iodide, potassium iodide, etc.), and weather-resistant stabilizers (resorcinol-based, salicylate-based). Benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (montanic acid and its salts, esters, half esters thereof, stearyl alcohol, stearamide, various bisamides, bisureas and polyethylene waxes) And pigments (such as cadmium sulfide, phthalocyanine and carbon black), and dyes (such as nigrosine). From the viewpoint of productivity, the compounding of the additive is more preferably performed simultaneously or continuously with alloying while increasing the degree of polymerization in a melter. The addition of an antioxidant is effective for improving the color tone of the resin composition, and particularly, the addition of a sodium hypophosphite and a hindered phenol type antioxidant is preferred. Sodium hypophosphite is also effective in accelerating the degree of polymerization from the primary condensate. The resin composition of the present invention includes switches, micro slide switches, DIP switches, switch housings, lamp sockets, binding bands, connectors, connector housings, connector shells, IC sockets, coil bobbins, bobbin covers. , Relay, relay box, condenser case, motor internal parts, small motor case, gear cam, dancing pulley, spacer, insulator, fastener, buckle,
Wire clips, bicycle wheels, casters, helmets, terminal blocks, power tool housings, insulating parts of starters, spoilers, canisters, radiator tanks, chamber tanks, reservoir tanks, fuse boxes, air cleaner cases, air conditioner fans,
Terminal housing, wheel cover, intake / exhaust pipe, bearing retainer, cylinder head cover, intake manifold, water pipe impeller, engine roll damper, clutch release, speaker diaphragm, heat-resistant container, microwave oven parts, rice cooker parts, printer ribbon guide, etc. Electrical and electronic related parts, automobile and vehicle related parts, home and office electrical product parts,
It is effective for computer related parts, facsimile / copier related parts, machine related parts, and other various uses. The present invention will be described in more detail with reference to the following examples. Various properties in the examples and comparative examples were measured by the following methods. 1) Melting point (Tm) Using a DSC (PERKIN-ELMER7 type), samples 8 to 10
The temperature which shows the maximum value of the melting curve obtained by measuring mg at a heating rate of 20 ° C./min is defined as (T). Sample 8 ~
10 mg is heated at a heating rate of 20 ° C./min and T + 20 ° C.
For 5 minutes, and then at a cooling rate of 20 ° C./min for 3 minutes.
After cooling to 0 ° C and holding at 30 ° C for 5 minutes,
Heat to T + 20 ° C. at a rate of ° C./min. The maximum value of the melting curve at this time was defined as the melting point (Tm). 2) Relative Viscosity (ηr) According to JIS K6810, 1 g of a sample was dissolved in 100 ml of 98% concentrated sulfuric acid, and the relative viscosity at 25 ° C. was measured. 3) Color tone Suga Test Machine Co., Ltd.
The I value was measured. 4) Tensile strength and tensile elongation Measured according to ASTM D638. Example 1 Hexamethylene ammonium adipate (66 salt) 1
4.00 kg, 6.00 kg of ε-caprolactam, 130 g of benzoic acid and 6.66 kg of ion-exchanged water were added in 0.1 parts.
The mixture was charged into a 0 m ³ batch-type pressure polymerization kettle, and after sufficiently purging with nitrogen, heating was continued. 230 ° C with stirring for 5 hours
And the polymerization pressure was adjusted to 17 kg / cm ² -G, and then the reaction was completed at 230 ° C. to 235 ° C. for 30 minutes. Discharge is 2 l / h of ion-exchanged water by a fixed amount pump.
And the water vapor pressure was maintained at 10 kg / cm ² -G for 1 hour. The melting point of the primary condensate of the obtained polyamide was 217 ° C, and ηr was 1.5. After adding and mixing 0.05% by weight of sodium hypophosphite to 100% by weight of the primary condensate, 20% by weight of Kraton G1652 (manufactured by Shell Chemical Co., Ltd.), which is a SEBS resin, is charged from a side feeder. Alloying and melt polymerization were simultaneously performed at a residence time of 85 seconds, a vent vacuum of -700 mmHg, and a maximum resin temperature of 300 ° C. using a 30 mmφ vent-type twin-screw extruder. When the polyamide was fractionated and measured by gel permeation chromatography, the polymer viscosity ηr was 2.7 and the polymer melting point was 223 ° C. Table 1 shows the physical properties. [0030] In Example 2 resin, denatured polyphenylene oxide, using the ABS resin was subjected to alloying while synthesis and high polymerization degree of the primary condensation product of the polyamide according to the method of Example 1. Table 1 shows the results. In the methods of Examples 1 to 3 , the color tone,
A resin composition having excellent elongation was obtained. Comparative Example 1 Nylon 66 (CM3001N, manufactured by Toray, ηr =
2.8) 100% by weight of a 30 mmφ vent type twin screw extruder with a residence time of 65 seconds and a degree of vacuum of the vent of −700 mmH
g, at the highest resin temperature of 310 ° C., alloying and melting high polymerization were simultaneously performed. When the polyamide was fractionated and measured by gel permeation chromatography, the polymer viscosity ηr was 2.8 and the polymer melting point was 265 ° C. Table 1 shows the physical properties. Comparative Example 2 Hexamethylene ammonium adipate (66 salt) 1
4.00 kg, 6.00 kg of ε-caprolactam, 130 g of benzoic acid and 6.66 kg of ion-exchanged water were added in 0.1 parts.
The mixture was charged into a 0 m ³ batch-type pressure polymerization kettle, and after sufficiently purging with nitrogen, heating was continued. 200 ° C with stirring for 1 hour
And the polymerization pressure was adjusted to 10 kg / cm ² -G, and then the reaction was completed at 200 ° C. to 205 ° C. for 30 minutes. Discharge is 2 l / h of ion-exchanged water by a fixed amount pump.
And the water vapor pressure was maintained at 10 kg / cm ² -G for 0.5 hour. The melting point of the obtained primary condensate was 165 ° C., and ηr was a primary condensate of 1.03. After adding and mixing 0.05% by weight of sodium hypophosphite to 100% by weight of the primary condensate, Kraton G16 was added.
52, 20% by weight was charged from a side feeder with a 30 mmφ vent type twin screw extruder, residence time 65 seconds, degree of vacuum of vent -300 mmHg, maximum resin temperature 300 ° C.
, Alloying and melting high polymerization degree were simultaneously performed. Alloying was not stable and foamed during kneading and discharging. When the polyamide was fractionated by gel permeation chromatography and measured, the polymer viscosity ηr was 1.3 and the polymer melting point was 2
05 ° C. Table 1 shows the physical properties. The primary condensate having ηr of more than 2.5 (Comparative Example 1) is insufficient in color tone and elongation, and the primary condensate having ηr of less than 1.04 (Comparative Example 2) is alloy. During foaming, the polymer foamed. [Table 1] The resin composition obtained according to the present invention sufficiently exhibits the performance of a polyamide alloy,
Because of its excellent elongation, it is particularly suitable as a material for electric / electronic parts and automobile parts.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-97513 (JP, A) JP-A-7-196916 (JP, A) JP-A-3-275762 (JP, A) JP-A-3-975 290431 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 C08G 69/00-69/48 C08L 101/00

Claims (1)

(57) [Claim 1] A primary condensate of a 1% sulfuric acid solution having a relative viscosity of 1.04 to 2.5 at 25 ° C. and a rubber
Polymer, polyphenylene ether, ABS resin
At least one of a resin other than one condensate, the relative viscosity of the primary condensation product is alloyed in a melt extruder while advancing high polymerization degree in so that the upper 0.3 or more selected from A method for producing a resin composition, comprising: