JPH0395265A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a nylon 46 resin composition improved in water absorbency without detriment to the excellent heat resistance and mechanical properties inherent in the resin by compounding the resin with a polyarylate and a phenoxy resin. CONSTITUTION:A resin composition comprising 100 pt.wt. nylon 46 resin, 5-200 pts.wt. polyarylate, and 1-40 pts.wt. phenoxy resin. A preferable nylon resin is one with a limiting viscosity of 1.10 to 1.50 when measured in m-cresol at 35 deg.C. A preferable polyarylate is one prepared from a bisphenol and terephthalic and/or isophthalic acid. The phenoxy resin is a high molecular-thermoplastic resin which is composed of the structural units of formula 1, has an average molecular weight of 10,000 to 100,000, and is prepared from 2,2-bis(4- hydroxyphenyl)propane and epichlorohydrin.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to resin compositions, and more specifically to polytetramethylene azibamide (nylon 46), which exhibits excellent heat resistance, mechanical properties, GT impact properties, and water absorption properties. ) Regarding resin. [Prior art] Nylon 46 obtained from tetramethylene diamine or its functional derivative and adivic acid or its functional derivative
resin is known. This nylon 46 resin has excellent mechanical properties such as tensile strength and bending strength, as well as excellent maturing properties and sliding properties, so it is considered to be of great value in terms of its use as a useful engineering plastic. ．． However, this nylon 46 resin has a higher proportion of amide groups than normal polyamide resins such as nylon 6 resin and nylon 66 resin, so it has a disadvantage that its water absorption rate is higher than that. Immediately after drying, it has better mechanical properties and durability than ordinary polyamide T1 resins, but during actual use, it has a higher water absorption rate than ordinary polyamide resins. Although the impact characteristics etc. are improved, the mechanical properties,
The decrease in durability will be more significant than these, and in some cases, the superiority of nylon 46 resin will be lost.

Furthermore, like normal polyamide resin, nylon 46 resin also changes the dimensions of certain molded products due to water absorption, resulting in deterioration of other properties. This is a major obstacle in applying II to applications where its excellent properties can be utilized.

[Object of the invention] The present invention was made against the background of the above-mentioned circumstances, and
Its purpose is 46t nylon! The excellent heat resistance of fat,
The aim is to improve water absorption while maintaining mechanical properties. [Structure of the Invention] As a result of intensive research to improve the water absorption properties of nylon 46 resin, the present inventors found that a composition in which specific amounts of polyarylate and phenoxy resin were blended with nylon 46 resin met the above objectives. We have discovered that this is the case and have arrived at the present invention. That is, the resin composition of the present invention is (^) nylon 46
(13) Polyarylate 5-2 per 100 parts by weight of resin
This is a resin composition formed by blending 1 part by weight of 000 and 1 to 40 parts by weight of fc) phenoxy resin.

The present invention will be explained. The nylon 46 resin as component (A) used in the present invention is a polyamide obtained by a condensation reaction using adipic acid or a functional derivative thereof as an acid component and tetramethylene diamine or a functional derivative thereof as an amine component. However, a part of the adivic acid component or tetramethylenediamine component may be replaced with other copolymerized components. The preferred function of nylon 46 resin is disclosed in Japanese Patent Application Laid-open No. 56-i49.
430 and JP-A-58-149431.

The intrinsic viscosity of the nylon 46 resin used in the present invention is m
-0.90~ when measured at 35°C using cresol
1.90, more preferably in the range of 1.10 to 1.50. When a nylon 46 resin with an intrinsic viscosity exceeding 1.90 is used, the fluidity of the composition in the molten state is poor, and not only does the resulting product lose its glossy appearance, but also its r
! A: Not preferable because variations in mechanical properties and thermal properties become large.

On the other hand, if the intrinsic viscosity is lower than 0.90, the mechanical strength of the composite will be reduced. The polyarylate resin as component (B) used in the present invention is obtained from a bisphenol compound represented by the following general formula (I) and an aromatic dicarboxylic acid. Examples of the bisphenol compound of the general formula (I) include 4.4°-dihydroxy-diphenyl ether, bis(4-hydroxy-2
-methylphenyl)ether, bis(4-hydroxy-
3-chlorophenyl)ether, bis(4-hydroJI)
Ccyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl) ) methane, bis(4-hydroxy-3.5-dibromophenyl)methane, 1.1-bis(4-hydroxydiphenyl)ethane, 2.2-bis(4-hydroxydiphenyl)propane, 2.2-bis (4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane,
-hydroxy 3,5-cyclophenyl)propane, 2
．． 2-bis(4-hydroxy-3.5-dibromophenyl)propane, 1,1-bis(4-hydroxydiphenyl)butane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane , bis(4-hydroxyphenyl)-4°-methylphenylmethane, 1,1-bis(4-hydroxydiphenyl)-2.2.2-}lichloroethane, bis(
4-hydroxyphenyl)-<4'-chlorophenyl)
Methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxynatiflu)
Examples include propane, and 2,2-bis(4-hydroxynatiflu)broban is particularly preferred.These bisphenol compounds may be a mixture of two or more types, and may further include other divalent compounds, such as 2,2" -dihydroxydiphenyl, dihydroxynaphthalene, hydroquinone, resorcinol, 2,6-dihydroxychlorobenzene, 2,
A mixture with 6-dihydroxytoluene, 3,6-dihydroxytoluene, etc. may also be used. The aromatic dicarboxylic acid is preferably terephthalic acid, isophthalic acid, or a mixture thereof. Further, these terephthalic acid and isophthalic acid may be substituted with a halogen or an alkyl group having 1 to 8 carbon atoms. Furthermore, in addition to these, a small amount of aromatic or aliphatic dicarboxylic acid or a functional derivative thereof may be copolymerized.

The polyarylate used in the present invention can be produced by a normal manufacturing method.
For example, it can be produced by methods such as interfacial polymerization, solution polymerization, and melt polymerization. The preferred molecular weight of this polyarylate is 11
! The average molecular weight is 5,000 to 100,000. When polyarylate is blended with nylon 46 resin, the water absorption rate of the composite is reduced because the water absorption of polyarylate is extremely small compared to nylon 46 resin. However, due to the poor compatibility between nylon 46t1 resin and polyanate, a composite obtained by kneading the two has extremely poor mechanical properties and is not suitable for practical use.

When this composition is blended with phenoxy resin, nylon 46
The compatibility between the resin and polyarylate is significantly improved, resulting in improved mechanical properties.

TC) A certain amount of phenoxy resin used in the present invention is:
Consisting of a structural unit represented by the following general formula <I[) (n), with an average molecular weight of i0.00
It is a high molecular weight thermoplastic resin with a molecular weight of 0 to 100,000.
This polymer compound can be synthesized from 2,2-bis(4-hydroxyphenyl)propane and shrimp chlorohydrin, for example, by the method described in US Pat. No. 3,356,646.

The amounts of polyarylate (B) and phenoxy resin (C) used in the present invention are 5 to 200 parts by weight and 1 to 40 parts by weight, respectively, per 100 parts by weight of nylon 46 resin (A). be. If the amount of polyarylate blended is less than 5 parts by weight, the effect of improving the water absorption of nylon 46 resin is insufficient (and if it is more than 200 parts by weight, even if phenoxy resin is blended, the compatibility with nylon 46 resin will not be improved. Furthermore, when the amount of phenoxy resin blended is less than 1 part by weight, the effect of improving the compatibility between nylon 46 resin and polyarylate is insufficient, and when it is more than 40 parts by weight, the excellent aging resistance of nylon 46 resin is not achieved. If necessary, a pigment compounding agent may be added to the resin composition of the present invention, which is not preferable because it impairs its properties.Such compounding agents include fillers, such as fillers, etc. Glass fiber cod, aramid fiber, carbon fiber, steel fiber, ceramic fiber, potassium titanate whiskers, boron whisker, kaolin, clay wollastonite, talc, myriki, calcium carbonate, barium sulfate, glass beads Examples include powdered, granular, or plate-like inorganic fillers such as glass flakes.These fillers are usually used as reinforcement materials, surface modification materials, or for the purpose of modifying electrical or thermal properties. However, it should be blended in the minimum amount to achieve the effect of blending, and within the range where excessive blending will not cause loss of the original excellent properties or formative advantages of the composition.Flame retardants, such as brominated polystyrene, Brominated polyphenylene ether, brominated epoxy, brominated bisphenol-A-sidalicidyl ether and its oligomer, polycarbonate oligomer produced using brominated bisphenol A as a raw material, brominated biphenyl ether,
Halogen-containing compounds such as brominated diphthalimide monomer and chlorinated hexabentadiene dimer; phosphorus compounds such as red phosphorus and triphenyl phosphate; nitrogen compounds such as phosphonic acid amide; melamine, melam, melem, melon , cyanuric acid, triazine compounds such as melamine cyanurate; flame retardant aids used in combination with metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dawsonite, gypsum dihydrate, and the above halogen-containing compounds or alone. For example, it is possible to mix antimony compounds such as monohyantimony trioxide, boron oxide, acids (metallic acids such as arsenic), etc. Furthermore, for the purpose of improving heat resistance, copper compounds such as copper iodide,
Antioxidants or heat stabilizers such as hindered phenol compounds, aromatic amine compounds, organic phosphorus compounds, and sulfur compounds may also be added. Furthermore, various epoxy compounds, oxazoline compounds, etc. may be added for the purpose of improving melt viscosity stability and hydrolysis resistance. Examples of epoxy compounds include bisphenol-A type epoxy compounds obtained by reacting bisphenol-A and shrimp chlorohydrin, aliphatic glycidyl ethers obtained by reacting various glycols or glycerol with shrimp chlorohydrin, and novolac type epoxy compounds. , aromatic or aliphatic carboxylic acid type epoxy compounds, alicyclic compound type epoxy compounds, etc. are preferable, and as the oxazoline compound, aromatic or aliphatic bisoxazolines, especially 2,2゛-
Bis(2-oxazoline) and 2,2°-m-phenylenebis(2-oxazoline) are preferred.

Pond stabilizers, colorants, lubricants, ultraviolet absorbers, and antistatic agents can be added.

Furthermore, in small proportions other thermoplastic resins, such as other polyamide resins, polyester resins, polyphenylene sulfide resins, polyphenylene ester resins, polycarbonate resins, polyethylene and its copolymers, polypropylene and its copolymers, polystyrene and copolymers thereof, acrylic resins and acrylic copolymers, polyamide elastomers, polyester elastomers, etc.; thermosetting resins, such as phenolic resins, melamine
! ! The resin composition of the present invention may be obtained by any blending method.

Generally, it is preferable to disperse these ingredients more uniformly, and it is preferable to homogenize them by mixing all or some of them simultaneously or separately using a mixer such as a blender, kneader, roll, or extruder. A method can be used in which some of the components are mixed simultaneously or separately using, for example, a blender, roll, extruder, etc., and then the remaining components are mixed and homogenized using these mixers or extruders. Furthermore, there is a method in which a pre-dry blended composition is melt-kneaded in a heated extruder to homogenize it, extruded into a wire shape, and then cut into desired lengths and granulated. The kimono kimono assembled in this way is usually kept in a sufficiently dry state before being placed into the hopper of the molding machine and used for kimono production. Furthermore, it is also possible to dry blend the constituent raw materials of the composition, directly charge them into the hopper of a molding machine, and melt and knead them in the molding machine.

[Examples] The present invention will be explained in detail with reference to Examples below. In addition, various characteristics during the implementation were measured by the following methods.

(1) Mechanical strength: Bending test: Based on ASTH 0790.

Impact test: ASTH D256 (Izod, notched, thickness 3.2 mm) (2 Mature deformation temperature: Based on ASTH 0648. (Load 1 8.6 kg)
/ cA ) (3l Water absorption characteristics: After being left in an atmosphere of 90°C and 60% relative humidity for 200 hours, the weight increase and strength change of the sample were measured.

(4)? Intrinsic viscosity: Measured at 35°C with an Ostold viscosity tube using m-cresol as a solvent.

Examples 1 to 5 Comparative Examples 11 to 4 46vA resin ('ST
ANYLJ (manufactured by DSM, Netherlands) and polyarylate <ru polymer Ll-1 dried with hot air at 130°C for 5 hours.
00J Unitika system) and phenoxy resin (rBA
KELI T E P K 1 (manufactured by Union Carbide, USA) was mixed uniformly in advance in a tumbler in the proportions shown in Table 1, and then vacuumed using a vented twin-screw extruder with screw diameters of 44 mm each. While pulling, the cylinder temperature was 320°C, the screw rotation speed was 15Orpm,
The mixture was melted and kneaded at a discharge rate of 40 bg/h, and the thread discharged from the die was cooled and cut to obtain pellets for use as a precept. Next, using this pellet, various properties were evaluated using an injection molding machine with an injection capacity of 5 ounces under the conditions of a cylinder temperature of 300°C, a mold temperature of 120°C, an injection pressure of 800 kg/aa, a cooling time of 15 seconds, and a total molding cycle of 40 seconds. A molded article for measurement was molded. Each characteristic was measured using these molded products. Molded products are stored at 23℃ and relative humidity 50% according to JIS κ7100 before measurement.
% atmosphere for 88 hours. The measurement results are shown in Table 1. Nylon 46 resin itself has a high heat distortion temperature! Although it has I-impact strength and bending strength, the strength decreases significantly after absorbing moisture due to its high moisture absorption rate (Comparative Example 1). When polyarylate is blended with this nylon 46 resin, the hygroscopicity of the polyarylate is extremely lower than that of nylon 46 resin, so the moisture absorption rate of the composition is reduced and the decrease in bending strength is also suppressed (Comparative Example 2). Although the composition has a uniquely high heat distortion temperature compared to nylon 6 and nylon 66 resins, its impact strength is reduced and its mechanical properties are not at a satisfactory level (
Comparative example). However, this is the case with a composition containing nylon 461!1 fat, polyarylate, and phenoxy resin! No decrease in I impact strength was observed, resulting in a composition exhibiting excellent properties in all aspects of mechanical strength, heat distortion temperature, and water absorption properties (Execution ρ11 to 4). When the amount of phenoxy resin blended is small, the effect of suppressing the decrease in impact strength does not appear (Comparative Example 3), and when the amount of phenoxy resin blended is large, the reduction in heat distortion temperature becomes large and the excellent heat resistance of nylon 46 resin is no longer maintained. It will not be possible (Compare Fuchi 4)

Claims (1)

[Scope of Claims] 1. A resin composition comprising (A) 5 to 200 parts by weight of (B) polyarylate and 1 to 40 parts by weight of phenoxy resin per 100 parts by weight of (A) nylon 46 resin. 2. The resin composition according to claim 1, wherein the polyarylate component (B) is obtained from a bisphenol compound and terephthalic acid and/or isophthalic acid.