JPH0412303B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyester copolymer composition that has excellent compatibility and improved heat aging resistance, hydrolysis resistance, and flexibility. (Prior art and problems) Polyester copolymers containing soft segments have poor tensile strength, tear strength, impact resilience, cold resistance,
As a thermoplastic elastomer with excellent abrasion resistance and bending resistance, it is widely used in various tubes, hoses, automobile parts, etc., but in order to further expand its use in the market, it must have heat aging resistance and hydrolysis resistance. ，
It is necessary to provide high flexibility. In order to improve the above properties, various polymers,
For example, attempts have been made to blend ethylene copolymers (Japanese Unexamined Patent Publication No. 52-958), but the compatibility with polyester copolymers containing soft segments is insufficient, and mechanical strength may deteriorate. Although it is large, it is still difficult to say that the objective has been fully achieved. (Means for Solving the Problem) As a result of extensive studies, the present inventors have found that a composition comprising a polyester copolymer containing a soft segment and an olefin copolymer containing a carboxyl group and/or an epoxy group is We have discovered an extremely practical composition that has excellent compatibility and is endowed with heat aging resistance, hydrolysis resistance, and high flexibility without losing the excellent properties of a polyester copolymer containing soft segments. The present invention has now been completed. That is, the present invention provides a polyester block copolymer (hereinafter abbreviated as polyester copolymer) (A) consisting of a high melting point hard segment and a low melting point soft segment and an olefin copolymer containing a carboxyl group and/or an epoxy group. (B) and (A)／(B)
The present invention provides a polyester copolymer composition which is blended in a weight ratio of =90/10 to 55/45 and contains no other polyester resin. The polyester copolymer used in the present invention consists of a high melting point hard segment mainly composed of alkylene terephthalate units, an aliphatic polyether and/or
Or it is a block copolymer with a low melting point soft segment made of aliphatic polyester. High melting point hard segments mainly composed of alkylene terephthalate units include terephthalic acid or its dimethyl ester, ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyl-trimethylene glycol, hexamethylene glycol, Examples include those mainly composed of units consisting of alkylene glycol such as decamethylene glycol, but in some cases dicarboxylic acids such as isophthalic acid, phthalic anhydride, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid , diphenyl dicarboxylic acid, bis(p-carboxyphenyl) methane, aromatic dicarboxylic acid such as 4,4'-sulfonyl dibenzoic acid, carbon number 2
~12 aliphatic dicarboxylic acids, p as glycols
- Diols such as xylylene glycol and cyclohexanedimethanol, p-oxybenzoic acid, p-(β-hydroxyethoxy)benzoic acid, and the like as oxyacids may be included as components. In addition, examples of the low melting point soft segment made of aliphatic polyether and/or aliphatic polyester include poly(ethylene oxide) glycol, poly(propylene oxide) glycol,
Polyether glycols such as poly(tetramethylene oxide) glycol, mixtures or copolymers of these polyether glycols, polyε-caprolactone, aliphatic dicarboxylic acids having 2 to 12 carbon atoms and aliphatic glycols having 2 to 10 carbon atoms Polyesters produced from polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene dodecanate, polytetramethylene acetate, polyhexamethylene acetate, etc., as well as the above-mentioned aliphatic polyesters and aliphatic Examples include polyester-polyether copolymers in which polyether is combined. In such polyester copolymers, the molecular weight of the low melting point soft segment block is usually 400 to 6000,
It is preferably 400 to 3000, and the proportion of the soft segment in the polyester copolymer is usually 5 to 80% by weight, preferably 20 to 70% by weight. These polyester copolymers can be produced by conventionally known normal polycondensation methods.
A preferred method is to heat a low melting point soft segment component consisting of terephthalic acid or its dimethyl ester, alkylene glycol, aliphatic polyether and/or aliphatic polyester to about 150-250°C in the presence of a catalyst; A method for obtaining a polyester block copolymer by carrying out an esterification or transesterification reaction and then carrying out polycondensation while removing excess alkylene glycol under vacuum, a pre-prepared high melting point polyester segment-forming prepolymer and a low melting point Aliphatic diisocyanates, such as tetramethylene diisocyanate and hexamethylene diisocyanate, which react with the terminal functional groups of those prepolymers; trilene-
2,4-diisocyanate, tolylene-2,6-
Diisocyanate, diphenylmethane-4,4'-
Aromatic diisocyanates such as diisocyanate, m- and p-phenylene diisocyanate, and naphthalene-1,5-diisocyanate; cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanate; two or more isocyanate groups in one molecule such as crude diphenylmethane diisocyanate compounds, tolylene diisocyanate dimer, diphenylmethane-4,4'-diisocyanate dimer, and other isocyanate compounds, β, γ
-Epoxypropyl ether, 1,4-bis(β,γ-epoxypropoxy)butane, 1,6
-bis(epoxyethyl)-hexane, 2,2-
Bis[p-(β,γ-epoxypropoxy)phenyl]propane, 1-epoxyethyl-3,4-
Epoxycyclohexane, 1-(β,γ-epoxypropoxy)-2-benzyloxyethane, 1
- Modified polyether ester block copolymerization by mixing and reacting diglycidyl ether compounds such as -(β,γ-epoxypropoxy)-2-ethoxyethane, 1,4-bis(β,γ-epoxypropoxy)benzene, etc. There are methods for obtaining coalesced and modified polyester ester block copolymers. On the other hand, in the present invention, the carboxyl group-containing olefin copolymer mixed with the polyester copolymer contains at least 50 mol%, preferably 70 mol% of 1-olefin, such as ethylene, propylene,
Butene-1, Isobutene, Pentene-1, Hexene-1, Decene-1, 4-methylbutene-1,4
-Methylpentene-1,4,4-dimethylpentene-1, vinylcyclohexane, styrene, α-
It should contain methylstyrene, styrene substituted with lower alkyl substituents or the like; it is also possible to use mixtures of the above olefins. Copolymers obtained from ethylene and butene-1 or propylene are preferred, and commercially available products include Tafmer A series [ethylene-butene-1 copolymers, Mitsui Petrochemical Industries Co., Ltd. products] and Tafmer P0280, Tafmer
Examples include the Tafmer P series (ethylene-propylene copolymer, manufactured by Mitsui Petrochemical Industries, Ltd.) such as P0480, Tafmer P0680, and Tafmer P0880. The above carboxyl group-containing olefin copolymer is produced by a known method such as direct copolymerization of an α,β-unsaturated carboxylic acid comonomer and the above olefin or graft copolymerization with a polyolefin and a polyolefin copolymer. . Examples of acid components used here include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, (anhydrous) maleic acid, fumaric acid, cis-4-cyclohexene-
1,2-dicarboxylic acid (anhydride), endo-bicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid (anhydride), methyl-endo-cis-
Bicyclo-[2,2,1]-5-heptene-2,3
Examples include -dicarboxylic acids (anhydrides) and monoesters of the above-mentioned carboxylic acids, and preferred examples include acrylic acid, methacrylic acid, and maleic acid (anhydride). Among these, maleic acid (anhydride) is particularly preferred since a sufficient acid modification effect can be obtained with addition of a small amount compared to other acids. Suitable carboxyl group-containing olefin copolymers include ethylene-butene-1-(anhydrous) maleic acid copolymer, ethylene-propylene-(anhydrous) maleic acid copolymer, and the like. The epoxy group-containing olefin copolymer has α, β
- Manufactured by known methods such as direct copolymerization of glycidyl ester of unsaturated carboxylic acid and the above-mentioned olefin, or graft copolymerization with polyolefin and polyolefin copolymer. The glycidyl ester of α,β-unsaturated carboxylic acid used here has the general formula (In the formula, R is a hydrogen atom or a lower alkyl group.) Examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. Among them, methacrylic acid Glycidyl is preferably used. Such a carboxyl group- and/or epoxy group-containing olefin copolymer is usually contained in an amount of 0.01 to 20% by weight, preferably 0.05 to 5% by weight, as a monomer component having these functional groups. The amount of the olefin copolymer added is 10 to 45 parts by weight based on 90 to 55 parts by weight of the polyester copolymer. As the amount of the olefin copolymer added increases, flexibility, hydrolyzability, etc. improve, but on the other hand, oil resistance, moldability, etc. tend to decrease, so the amount added should be determined appropriately depending on the purpose. This is useful. Furthermore, if the amount added is less than 10 parts by weight, the effect of the present invention will be small and it will be difficult to achieve the present invention. The polyester copolymer composition of the present invention contains small amounts of release agents, coupling agents, colorants, lubricants, weathering stabilizers, foaming agents, rust preventives, retardants, antimony trioxide, and other additives. Known additives such as antioxidants and antioxidants may also be added. In addition, when carrying out the present invention, other thermoplastic resins or elastomers other than the polyester polymer may be used, such as polyvinyl chloride, ethylene-vinyl acetate copolymer,
It is also possible to use polyurethane, styrene elastomer, polybutadiene, vinyl chloride elastomer, acrylic polymer, polyamide, polyimide, polyamideimide, polyphenylene sulfide, etc. in combination. The thermoplastic resin composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are uniformly mixed in advance in a mixer such as a tumbler or a Henschel mixer, and then fed into a single-screw or twin-screw extruder for melt-kneading and then prepared as pellets. The thermoplastic resin composition of the present invention can be used for various purposes due to its excellent properties, such as tubes, hoses, pipes, rods, films, sheets, electric wire coatings, wire coatings, optical fiber coatings, and various other applications. Brushes, fishing nets, nets, hot melt adhesives, conveyor belts, V-belts, sports shoe soles for golf, baseball, soccer, track and field, etc., ski boots, gears, cams, bearings, bearings, packing, gaskets, O-rings, Fasteners, valves, joints, grips, casters, rollers, switch cases, clips, watch bands, emblems, badminton shuttlecocks, tennis racket parts, gasoline tanks, bellows, floats, ball games, fishing buoys,
It can be used as a coating for the inner surface of tanks, as well as various other automobile parts, electronic/electrical equipment parts, precision machinery parts, etc. It can also be used as powder coatings, solution-type adhesives, paints, etc. (Effects of the Invention) The polyester copolymer composition of the present invention thus obtained contains a carboxyl group- and/or epoxy group-containing olefin copolymer that has excellent compatibility with the polyester copolymer. A composition that has heat aging resistance, hydrolysis resistance, and high flexibility without losing the properties of polyester copolymers, such as excellent tensile strength, tear strength, cold resistance, abrasion resistance, and bending resistance. This is a highly practical composition. (Examples) The present invention will be specifically explained below with reference to Examples, but the present invention is not limited only to these Examples. In addition, parts in the examples mean parts by weight. Reference Example 1 (Production of carboxyl group-containing olefin copolymer) Ethylene-butene-1 copolymer (Tafmer
A4090), 0.5 part of 1,3-bis(tert-butylperoxypropyl)benzene, and 1 part of maleic anhydride were uniformly mixed. The mixture was then kneaded in an extruder set at a cylinder temperature of 220°C and pelletized to obtain a carboxyl group-containing olefin copolymer. When the amount of maleic anhydride grafted was measured using an infrared spectrum, it was confirmed that this olefin copolymer had 0.75 parts of maleic anhydride grafted to 100 parts of the ethylene-butene-1 copolymer. Ta. This is called a copolymer (). Reference Example 2 (Production of epoxy group-containing olefin copolymer) Ethylene-butene-1 copolymer (Tafmer
A4090), 0.5 part of dicumyl peroxide, and 2 parts of glycidyl methacrylate were uniformly mixed. The mixture was then kneaded in a twin-screw extruder set at a cylinder temperature of 200°C and pelletized to obtain an epoxy group-containing olefin copolymer. Hydrochloric acid-
When the amount of methacrylic acid glycidyl ether grafted was measured using a methyl ethyl ketone solution, it was found that this olefin copolymer had 1.25 parts by weight of methacrylic acid glycidyl ether grafted to 100 parts of ethylene-butene-1 copolymer. did. This is called a copolymer (). Examples 1 to 6 and Comparative Examples 1 to 10 Polyester copolymers [Polyether ester copolymers Perprene P-40H and P-150B manufactured by Toyobo Co., Ltd.], copolymers obtained in Reference Example 1 ( ), copolymer () obtained in Reference Example 2 and ethylene-butene-1 copolymer (Tafmer
A4090) in the proportions shown in Table 1 were kneaded at 220°C using a 40m/m extruder and pelletized. The pellets were molded into test pieces using an injection molding machine, and compatibility tests, hot water resistance tests, heat aging resistance tests, and measurements of tensile properties and hardness were conducted. The results are summarized in Table 1. The test method and measurement method are as follows. (1) Tensile properties and hardness: According to JIS K-6301. (2) Compatibility test: A test piece with a thickness of 3 mm is repeatedly folded 24 times, and the state of the folds is observed and evaluated. ○: No layer peeling ×: Layer peeling (3) Hot water resistance test: After immersing in hot water at 100°C for 20 days, the tensile strength retention rate of the test piece is measured after drying at 100°C for 2 hours. (4) Heat aging resistance test: Measure the tensile strength retention of a test piece left at 150°C for 7 days. (5) Izot impact strength: According to ASTM D256. 【table】

Claims (1)

[Claims] 1 Polyester block copolymer consisting of a high melting point hard segment and a low melting point soft segment
(A) and the carboxyl group- and/or epoxy group-containing olefin copolymer (B), (A)/(B)=90/10~
A polyester copolymer composition characterized in that it is blended in a weight ratio of 55/45 and does not contain other polyester resins.