JPH032903B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a flexible material or a softened polyvinyl chloride resin composition that is flame retardant and has excellent low- and high-temperature properties and mechanical strength by blending polyetheresteramide and polyvinyl chloride. be. Methods of softening polyvinyl chloride include adding plasticizers and blending flexible polymers, but methods that use plasticizers cause the plasticizer to bleed out during or after molding. Not only is there a safety problem, but the plasticizing effect at low temperatures is also poor. Additionally, methods of blending elastomers such as polyurethane are known, but polyurethane has poor thermal stability and cold resistance, as well as low hydrolysis resistance and mechanical strength, which severely limits its practical use. be. On the other hand, Japanese Patent Publication No. 51-48167 describes a blend composition of polyvinyl chloride and polyether ester, which is said to be effective in softening polyvinyl chloride or making polyether ester flame retardant. . It is true that polyether ester is a polymer with excellent flexibility, chemical resistance, and heat resistance, and when blended with polyvinyl chloride, flame retardancy is imparted, and in areas with a high proportion of polyvinyl chloride, it is not softened. However, the compatibility of polyether ester with polyvinyl chloride is not sufficient, and there is a problem that phase separation progresses and physical properties change due to heat treatment after molding. It has not reached the point where it can be used for a purpose. On the other hand, like polyether ester, polyether ester amide, which contains polyether repeating units in the molecule and also has polyamide repeating units and ester bonds in the main chain, is also known, and has excellent durability like polyether ester or polyester amide. It has recently attracted attention as a new material in the elastomer field because of its impact resistance and rubber elasticity. In particular, polyether ester amide has excellent lightness, transparency, and low-temperature impact resistance, and is less likely to cause burrs, sink marks, etc. during molding, so it is promising for injection molding applications. Therefore, the present inventors came up with the idea that by blending polyvinyl chloride and polyether ester amide, it is possible to impart flexibility to polyvinyl chloride and flame retardancy to polyether ester amide, and conducted experiments. As a result of layering, we discovered that it was possible to obtain a resin composition that could withstand industrial production.
The present invention has been achieved as follows. That is, the present invention uses an aminocarboxylic acid having 6 or more carbon atoms or lactam a, a number average molecular weight of 300
~6000 poly(alkylene oxide) glycol b and dicarboxylic acid c having 4 to 20 carbon atoms, 5 to 95% by weight of polyether ester amide A with a melting point of 100 to 200°C, and polyvinyl chloride B95 to 5 % by weight. Examples of the aminocarboxylic acid or lactam a having 6 or more carbon atoms in the present invention include ω-aminocaproic acid, ω-aminoenanthanoic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, and 11-aminoundecane. acids, aminocarboxylic acids such as 12-aminododecanoic acid, or caprolactam, enantlactam, capryllactam,
There are lactams such as laurolactam, especially 11−
Aminoundecanoic acid and 12-aminododecanoic acid are preferred, and these may 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. 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, elastic recovery, etc.
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 optimal molecular weight range is Varies depending on the type of poly(alkylene oxide) glycol. For example, in the case of polyethylene glycol, it is 300 to 6000, particularly preferably 500 to 6000.
When 4000 is poly(propylene oxide) glycol, it is preferably 300 to 2000, particularly preferably 500 to 1200, and in the case of poly(tetramethylene oxide) glycol, it is preferably 500 to 2500, particularly preferably 500 to 1500. It will be done. Dicarboxylic acid c having 4 to 20 carbon atoms in the present invention
Examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid aliphatic dicarboxylic acids such as acids, and succinic acid,
Mention may be made of aliphatic dicarboxylic acids such as oxalic acid, 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. Polyetheresteramide A of the present invention is composed of the above-mentioned a, b and c, and this polymer has a melting point of 70 to 200°C. Note that the melting point here is measured using a thermomechanical analyzer (TMA: Thermo
Mechanical Aralysis) and pin size
Measurements were made at the temperature at which the needle penetrated 250 μm into the sample under measurement conditions of 0.5 mmφ, 5 g load, and 10° C./min heating rate. On the other hand, polyvinyl chloride B that can be used in the present invention is a known vinyl chloride homopolymer or a copolymer of vinyl compounds such as vinyl acetate, vinylidene chloride, acrylonitrile, methyl acrylate, and methyl methacrylate in a proportion of 30 mol% or less. It is something. Further, although it is not necessary to add a plasticizer to the polyvinyl chloride of the present invention, a known plasticizer may be added depending on the purpose. The method for polymerizing polyether ester amide A is not particularly limited, and any known method can be used. For example, a method in which aminocarboxylic acid or lactam a and dicarboxylic acid c are reacted in an equal molar ratio to produce a polyamide prepolymer having carboxylic acid groups at both ends, and then poly(alkylene oxide) glycol is reacted with this under vacuum; A carboxylic acid-terminated polyamide prepolymer is produced by charging the compounds a, b, and c into a reaction tank and reacting them under pressure at high temperature in the presence or absence of water, and then reacting them under normal pressure or reduced pressure. A method of proceeding with polymerization is known. In addition, the above a, b, c
There is also a method in which the following compounds are simultaneously charged into a reaction tank, melted and mixed, and then polymerized all at once under high vacuum.
Rather, this method is preferable since it causes less coloring of the polymer. In the present invention, polyether ester amide A
The blending ratio of polyvinyl chloride and polyvinyl chloride B must be such that A is 95 to 5% by weight and B is 5 to 95% by weight. This blending ratio should be selected appropriately depending on the purpose and use, but the following blending ratio can usually be used as a guideline for the use. (1) (A):(B)=95-60:5-40 Compositions in this range are polyetheresteramides with flame retardant properties, and are suitable for use as flame-retardant polyetheresteramide molded products. Highly useful. (2) (A):(B)=70~35:30~65 Compositions in this range are flame retardant, provide flexible materials with excellent low- and high-temperature properties, and mechanical properties, and also have excellent transparency. , available as a transparent flexible tube. (3) (A):(B)=40~5:60~95 The composition in this range is a polyvinyl chloride composition that has been given flexibility and has excellent low and high temperature properties and chemical resistance. Therefore, it can be used as a high-temperature oil-resistant tube or a low-temperature tube. Of course, the physical properties of the compositions of the invention depend on the composition of the polyether ester amide A and, in particular, on the copolymerized amount of poly(alkylene oxide) glycol C therein. The preferred copolymerization amount of component C is 5 to 95% by weight. As a method for blending polymers A and B, an ordinary melt-kneading method can be applied. The resin composition of the present invention includes known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers,
Colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing 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 1 54.57 parts of ω-aminododecanoic acid, dodecanedioic acid,
13.42 parts and 38.68 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 663 determined by the end group determination method were mixed with 0.2 parts of "Irganox" 1098 (antioxidant) and 0.05 parts of tetrabutyl titanate catalyst using a helical ribbon stirring blade. The mixture was charged into a reaction vessel equipped with the same equipment, purged with _N2 , heated and stirred at 220°C for 30 minutes to obtain a homogeneous clear solution, and then brought to polymerization conditions of 250°C < 1 mmHg in 30 minutes according to a temperature increase and pressure reduction program. When reacted under these conditions for 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 was dissolved in orthochlorophenol at 25°C and 0.5
The relative viscosity (ηr) measured in % concentration is 1.80,
The melting point was 156°C. Polyetheresteramide A pellets and polyvinyl chloride powder (“Zeon” manufactured by Nippon Zeon Co., Ltd.)
103Ep-8 (average degree of polymerization 800) was dry blended in the quantitative ratio shown in Table 1, then introduced into a 300 mmφ extruder heated to 180°C, melt-kneaded, and pelletized. The pellets of the resin composition thus obtained were injection molded into UL combustion test pieces under conditions of a cylinder temperature of 180°C and a mold temperature of 60°C. Mechanical properties of molded products and
Table 1 shows the UL flammability. For comparison, the physical property values of polyvinyl chloride and polyether ester amide A alone are also shown.

[Table] Example 2 40,926 parts of ω-aminododecanoic acid, 41,189 parts of ω-aminoundecanoic acid, 15,370 parts of terephthalic acid, and 62,963 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 680. Block polyether ester amide B having ηr of 1.85 and Tm of 139° C. was prepared in the same manner as in Example 1 using the above as a starting material. This Polymer B is polyvinyl chloride “Zeon”
103Ep-8 in the ratio shown in Table 2 in the same manner as in Example 1, and the mechanical properties of the blended polymer and its temperature change were measured. For comparison, the properties of plasticized PVC containing 33% of dioctyl phthalate, a common plasticizer for vinyl chloride, were measured. As is clear from the results in Table 2, polyvinyl chloride resins containing 20% and 40% polyetheresteramide maintain flexibility and impact resistance not only at room temperature but also at low temperatures, and maintain rigidity even at high temperatures. It has a wide usable temperature range.

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Claims (1)

[Claims] 1 Consists of aminocarboxylic acid or lactam a having 6 or more carbon atoms, poly(alkylene oxide) glycol b having a number average molecular weight of 300 to 6000, and dicarboxylic acid c having 4 to 20 carbon atoms, with a melting point of
Polyether ester amide A5 which is 70~200℃
A resin composition comprising ~95% by weight of polyvinyl chloride B and 95~5% by weight of polyvinyl chloride B.