JPH027969B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a polyetheresteramide resin composition having excellent rubber elasticity, mechanical properties, and moldability. <Prior art> Polyetheresteramides having polyamide repeating units, polyether repeating units, and ester bonds in the polymer main chain are well known, and have excellent impact resistance and rubber elasticity like polyetheresters or polyesteramides. Therefore, it is attracting attention as a new material in the elastomer field. <Problems with conventional technology> Polyether ester amide is lightweight, has excellent low-temperature impact resistance, and is less likely to cause burrs or sink marks during molding, so it is promising for various molding applications, but it is less flexible than rubber. It has the disadvantage of being inferior. Production of polyetheresteramide with a hardness comparable to that of rubber can be achieved by increasing the content of the soft component, but this tends to result in a decrease in melting point, high-temperature properties, and moldability. On the other hand, polystyrene type block copolymers exhibit excellent properties such as rubber elasticity and low-temperature properties, but have the disadvantage of being inferior in mechanical strength and heat resistance. Moreover, in particular, during injection molding, since the adhesiveness during melting is strong, release properties from the mold are poor, molding cycle time becomes long, and productivity is low. The inventors of the present invention have made extensive studies to solve the above-mentioned drawbacks of polyetheresteramide, and as a result, have discovered the present invention. The present inventors have discovered that a blend of polyether ester amide and a polystyrene type block copolymer retains the excellent features of polyether ester amide, while significantly improving flexibility, which is its disadvantage. Ta. <Means for Solving the Problems> In other words, the present invention provides a salt (a) of an aminocarboxylic acid having 6 or more carbon atoms or a lactam or a diamine and a dicarboxylic acid having a number average molecular weight of 6 or more carbon atoms.
1 to 99 parts by weight of a polyether ester amide (A) derived from a poly(alkylene oxide) glycol (b) having a molecular weight of 300 to 6,000 and a dicarboxylic acid having a carbon number of 4 to 20 and having a hardness of Shore D60 or less, This is a resin composition containing a polystyrene type block copolymer (B) in an amount of 99 to 1 part by weight. Examples of the aminocarboxylic acid or lactam having 6 or more carbon atoms or the diamine and dicarboxylic acid salt (a) having 6 or more carbon atoms in the present invention include ω-aminocaproic acid, ω-aminoenanthate, ω-aminocaprylic acid, ω - Aminocarboxylic acids such as aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or lactams such as caprolactam, enantholactam, capryllactam, laurolactam, and hexamethylenediamine-sebacate; There are salts of diamine dicarboxylic acids such as hexamethylene diamine isophthalate, but 11-aminoundecanoic acid and 12-aminododecanoic acid are particularly preferred, and these can also be used in combination depending on the purpose and use. . It is also permissible to use other amide-forming components as copolymerization components in small amounts for the purpose of lowering the melting point of polyether ester amide or increasing adhesiveness. The poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6000 in the present invention includes polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol,
Poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc., among others, have excellent heat resistance and water resistance. Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether esteramide, such as mechanical strength and elastic recovery.
The number average molecular weight of poly(alkylene oxide) glycol can be used in the range of 300 to 6000, but a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low temperature properties and mechanical properties is selected, and this optimum molecular weight range is selected. varies depending on the type of poly(alkylene oxide) glycol. For example, in the case of polyethylene glycol, it is 300~
6000, particularly preferably 1000-4000, 300-5000 in the case of poly(propylene oxide) glycol,
Particularly preferably 500 to 3000, and in the case of poly(tetramethylene oxide) glycol, 500 to 3000;
Particularly preferably, those in the molecular weight range of 500 to 2,500 are preferably used. Dicarboxylic acid (c) having 4 to 20 carbon atoms in the present invention
Examples include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid.
- dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate, 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, Alicyclic dicarboxylic acids such as dicyclohexyl-4,4'-dicarboxylic acid, and succinic acid, oxalic acid,
Mention may be made of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodecanedic acid (decanedicarboxylic acid). In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. The present invention provides a salt (a) of the above-mentioned aminocarboxylic acid or lactam or a diamine having 6 or more carbon atoms and a dicarboxylic acid, a poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6000, and a poly(alkylene oxide) glycol having 4 to 6000 carbon atoms.
This is a resin composition prepared by blending a polyether ester amide (A) obtained by polymerizing No. 20 dicarboxylic acid (c) with a polystyrene type block copolymer (B) described below. The relative viscosity of the polyether ester amide (A) used in the present invention is preferably in the range of 1.2 to 3.5, particularly preferably in the range of 1.5 to 2.0. The polystyrene type block copolymer used in the present invention is a block copolymer consisting of a high melting point polystyrene block and a rubber phase block. The high melting point polystyrene block is a polymer of styrene or a derivative thereof having a glass transition temperature of 25° C. or higher, preferably 50° C. or higher, such as polystyrene, polyα-methylstyrene, polychlorostyrene, and the like. Further, the rubber phase block is a polymer having a glass transition temperature of 0°C or lower, preferably -25°C or lower, such as polybutadiene, polyisoprene, polymethylisoprene, and the like. There are many combinations of high melting point polystyrene blocks and rubber phase blocks, and any of them may be used; however, a type of block copolymer in which a rubber phase block is bonded in the middle is preferred. The proportion of the high melting point polystyrene block in the polystyrene type block copolymer is preferably 10 to 50% by weight, and the proportion of the rubber phase block is preferably 90 to 50% by weight. The polystyrene type block copolymer can be produced using a known living anionic polymerization method, but is not particularly limited thereto, and can also be produced by cationic polymerization or radical polymerization. The method for polymerizing polyether ester amide (A) is not particularly limited, and any known method can be used. For example, a polyamide prepolymer with carboxylic acid groups at both ends is produced by reacting an aminocarboxylic acid or a lactam or a diamine with a dicarboxylic acid salt (a) and a dicarboxylic acid (c), and this is then injected with poly(alkylene oxide) glycol (b). Carboxylic acid-terminated polyamide can be produced by reacting under vacuum, or by charging the compounds (a), (b), and (c) above into a reaction tank and heating them to react at high temperature in the presence or absence of water. A method is known in which a prepolymer is produced and then polymerization is proceeded under normal pressure or reduced pressure. There is also a method in which the compounds (a), (b), and (c) above are charged into a reaction tank at the same time, melt-polymerized, and then polymerized all at once under high vacuum; this method actually causes less coloring of the polymer. preferable. In the present invention, polyether ester amide (A)
The blending ratio of polystyrene type block copolymer (B) is 1 to 99 parts by weight of polyether ester amide (A) to 99 parts by weight of polystyrene type block copolymer (B).
It is necessary to make the proportion of polystyrene type block copolymer (B) 50 to 95 parts by weight to 50 to 95 parts by weight of polyether ester amide (A).
~5 parts by weight. If the blending ratio of the polystyrene type block copolymer (B) is less than 1 part by weight, the blending effect will not be clearly apparent. Furthermore, if the blending ratio of the polystyrene type block copolymer (B) is greater than 99 parts by weight, the features of the polyether ester amide (A) will be completely lost. Of course, the physical properties of the resin composition of the present invention are also influenced by the composition of the polyether ester amide (A), but the copolymerized amount of poly(alkylene oxide) glycol in the polyether ester amide (A) is 5 to 90% by weight is desirable. The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the resin composition can be prepared by melt-kneading using a Banharry mixer, a rubber roll machine, a single-screw or twin-screw extruder, etc., usually at a temperature of 100 to 250°C. The resin composition of the present invention also includes known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, and reinforcing agents. Agents, fillers, lubricants, nucleating agents, mold release agents, plasticizers, adhesion aids, adhesives, etc. can be optionally contained. The present invention will be explained below with reference to Examples. In the examples, unless otherwise specified, parts mean parts by weight. <Example> Polymerization of reference example polyether ester amide (A-1) ω-aminododecanoic acid 81.9 parts, terephthalic acid
5.3 parts of poly(tetramethylene oxide) glycol and 20.8 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 650 were charged together with 0.5 parts of "Irganox" 1098 (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated at 260°C. After heating and stirring for 1 hour to form a homogeneous transparent solution, 0.015 parts of antimony trioxide catalyst, 0.015 parts of monobutyl monohydroxytin oxide catalyst,
0.005 parts of phosphoric acid (anti-coloring agent) was added and the polymerization conditions were brought to below 1 mmHg in 1 hour according to a vacuum program. When reacted under these conditions for 2.5 hours, a viscous colorless and transparent molten polymer was obtained.
When this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (A-1) had a relative viscosity ηr of 1.81 when measured in orthochlorophenol at 25°C at a concentration of 0.5%.
The crystal melting point according to DSC was 167°C. Polymerization of polyether ester amide (A-2) 49.1 parts of ω-aminododecanoic acid, terephthalic acid
7.9 parts, 48.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1020, 0.5 parts of "Irganox" 1098, 0.015 parts of antimony trioxide,
0.015 parts of monobutyl monohydroxytin oxide,
and 0.005 part of phosphoric acid under the same conditions as Polymer (A-1) to obtain polyetheresteramide (A-2) having a relative viscosity of 1.93 and a melting point of 154°C. Polymerization of polyether ester amide (A-3) 27.3 parts of ω-aminododecanoic acid, 5.7 parts of terephthalic acid, 70.5 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 2060, 0.5 parts of “Irganox” 1098, Antimony oxide 0.015 part,
0.015 parts of monobutyl monohydroxytin oxide,
and 0.005 part of phosphoric acid under the same conditions as Polymer (A-1) to obtain polyetheresteramide (A-3) having a relative viscosity of 1.92 and a melting point of 145°C. Polymerization of polyether ester amide (A-4) Undecamethylenediamine-adipate 44.9
12.8 parts of terephthalic acid, 50.0 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 650.
1 part, "Irganox" 1098 0.5 part, antimony trioxide 0.015 part, monobutyl monohydroxytin oxide 0.015 part, and phosphoric acid 0.005 part under the same conditions as Polymer (A-1), and the relative viscosity was 1.80.
Polyether ester amide (A-
4) was obtained. Examples 1 to 9 A styrene-butadiene block copolymer (hereinafter referred to as SBS) or a styrene-isoprene block copolymer (hereinafter referred to as SIS) was blended with polyether ester amide polymerized according to the above reference examples. Commercial products can be used as polystyrene type block copolymers, and in this example, Aron Kasei AR-480 was used as the SBS and Aron Kasei AR-800 was used as the SIS. First, SBS or SIS was blended in the ratio shown in Table 1 to polyether ester amide A polymerized according to the above reference example, and in the case of SBS, 200%
In the case of SIS, it was melt-kneaded and pelletized at 220°C. Next, using an injection molding machine with a 5oz injection capacity, the obtained pellets are heated to 200℃ for SBS, 220℃ for SIS, and a JIS No. 2 tensile test piece at a mold temperature of 80℃. was molded. Tensile properties and hardness are ASTM D-638 and ASTM, respectively.
Measured according to D-2240. <Effects of the present invention> As is clear from the hardness values shown in Table 1, SBS or
By blending SIS, the hardness was significantly reduced and the flexibility of polyetheresteramide was significantly improved.

【table】

[Table] Mixing ratio means number of parts.

Claims (1)

[Claims] 1 Aminocarboxylic acid or lactam having 6 or more carbon atoms or salt of diamine and dicarboxylic acid having 6 or more carbon atoms (a), poly(alkylene oxide) glycol having a number average molecular weight of 300 to 6000 (b) and 4 carbon atoms
Derived from dicarboxylic acids with ~20% hardness
Polyether ester amide (A) 1 with D60 or less
~99 parts by weight of polystyrene block copolymer
A resin composition containing (B) in a proportion of 99 to 1 part by weight.