JPS6410008B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel resin composition comprising an aliphatic polyester amide and a modified polyolefin having a specific composition. Aliphatic polyesteramides having ester units and amide units in the polymer main chain are attracting attention as molding materials with excellent flexibility, impact resistance, heat resistance, chemical resistance, moldability, etc. However, polyesteramides containing a large amount of amide components have a problem of being water absorbent and being relatively hard.
Furthermore, extremely high melt viscosity and high melt tension are required especially when extruding irregularly shaped extrusions or blow molding hollow products, but extending the polymerization time to obtain high viscosity tends to result in severe discoloration. It has been found that it is relatively difficult to efficiently produce high-viscosity polyesteramide. On the other hand, polyolefin resins generally have low melting points and softening points, and are disadvantageous in that they lack heat resistance. The present inventors solved the various drawbacks mentioned above and discovered a new resin composition suitable for a wide range of uses, from polyesteramide with high viscosity and high melt tension to polyolefin-based flexible materials with good heat resistance. Reached. That is, the present invention provides (A) an aliphatic diol having 2 to 6 carbon atoms and 6 carbon atoms.
Ester units containing ~12 aliphatic dicarboxylic acids as main constituents, aliphatic amino acids having 11 or 12 carbon atoms, lactams, aliphatic diamines having 4 to 12 carbon atoms, and aliphatic dicarboxylic acids having 6 to 12 carbon atoms. Polyester amide consisting of amide units having at least one selected from acids as the main constituent: 2 to 98% by weight, and (B) carboxylic acid groups, carboxylic acid metal bases, carboxylic ester groups, acid anhydride groups, and epoxy groups The present invention provides a resin composition containing 98 to 2% by weight of a modified polyolefin having at least one functional group selected from the following. The aliphatic polyesteramide (A) used in the present invention is a copolymer obtained by copolymerizing an aliphatic polyester-forming component and an aliphatic polyamide-forming component. The ester unit, which is one component of this polyesteramide, mainly has 2 to 2 carbon atoms.
It is composed of an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. Representative examples of the constituent components include ethylene glycol,
1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, ester derivatives thereof, etc. be. The ester constituents can be used individually or in the form of copolymers and, within the scope of small amounts of copolymerization, other polyester-forming constituents, such as diols such as cyclohexanedimethanol, trimesic acid, glycerin, pentafluoride, etc. Polyfunctional compounds such as erythritol, ε-caprolactone, polycaprolactone, etc. may also be used. The amide unit, which is another component of the polyesteramide in the present invention, mainly includes aliphatic amino acids having 11 or 12 carbon atoms, lactams, aliphatic diamines having 4 to 12 carbon atoms, and aliphatic diamines having 6 to 12 carbon atoms. It is composed of at least one kind selected from dicarboxylic acids, and representative examples of the constituent components include 11-aminoundecanoic acid,
12-aminododecanoic acid, ω-laurolactam and tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine and adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc. Examples include molar salts. Each of these amide constituents can be used alone or in the form of a copolymer of two or more. The polyester amide used in the present invention can be produced by the method already proposed by the present inventors (Japanese Patent Application No. 56-90855, etc.). , a polyamide-forming component consisting of a lactam or an aliphatic diamine and an aliphatic dicarboxylic acid are mixed together and melt-polymerized. To give an example of a suitable polymerization method, in the presence of an esterification catalyst, a mixture of dicarboxylic acid, diol and amino acid, lactam, or diamine and dicarboxylic acid in an amount of 1.05 to 2.0 times the mole of the dicarboxylic acid, in the presence of an esterification catalyst, is added. After heating reaction at normal pressure at 150 to 260℃ under an inert gas seal in the absence of water, the reaction is carried out in the presence of a polymerization catalyst at 10 mmHg or less, preferably 1 mmHg.
By heating to 240 to 300°C under the following reduced pressure conditions, a polyesteramide with a high degree of polymerization that is uniform and transparent when melted can be obtained. In addition, a polyester prepolymer with an average degree of polymerization of 2 to 80 is first prepared from both diols and dicarboxylic acid derivatives under normal pressure and 150 to 260°C esterification conditions, and this prepolymer is combined with amino acids, lactams, nylon salts, etc. A uniform polyesteramide with a high degree of polymerization can be similarly obtained by supplying it to a polymerization reactor and carrying out heating polycondensation at 200 to 270° C. under reduced pressure. Conversely, a polyester amide can also be obtained by preparing a polyamide prepolymer having an average degree of polymerization of 2 to 100 consisting of an amide component in advance and carrying out polycondensation of the ester component in the presence of this prepolymer. Furthermore, polycondensation of polyester and polyamide prepolymers is also possible. Polymers polymerized using this prepolymer have more polyester units than those obtained by mixing all the monomers at once and reacting them.
The average segment length of polyamide units increases,
As a result, the melting point of the polymer increases by several to 20°C. Therefore, the optimum method for producing the polymer should be selected depending on the intended use. Titanium-based catalysts give good results in the production of polyesteramides. Particularly preferred are tetraalkyl titanates such as tetrabutyl titanate, tetrapropyl titanate, tetraethyl titanate, and tetramethyl titanate, and metal salts of titanium oxalate such as potassium titanium oxalate. Other catalysts include dibutyltin oxide,
Examples include tin compounds such as dibutyltin laurate, lead compounds such as lead acetate, zirconium compounds such as tetraalkoxyzircon, and hafnium compounds. The copolymerization composition ratio of the polyesteramide of the present invention is such that the composition ratio of ester units to amide units is 5 to 80% by weight to 95 to 20% by weight, more preferably 10 to 70% by weight.
A range of 90 to 30% by weight is appropriate. The aliphatic polyesteramide having this copolymerization composition has good compatibility with the modified polyolefin, and provides a resin composition exhibiting excellent mechanical strength, toughness, high melt tension, and heat resistance. The degree of polymerization of the polyesteramide is not particularly limited, but generally speaking, it can be arbitrarily set as long as it has a relative viscosity within the range of 1.3 to 3.0, and those having a relative viscosity within the range of 1.35 to 2.5 can be particularly preferably used. Typical examples of the modified polyolefin (B) used in the present invention having at least one functional group selected from carboxylic acid groups, carboxylic acid metal bases, carboxylic ester groups, acid anhydride groups, and epoxy groups include ethylene /acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/fumaric acid copolymer, ethylene/methacrylic acid/zinc methacrylate copolymer, ethylene/acrylic acid/
Sodium methacrylate copolymer, ethylene/
Isobutyl acrylate/methacrylic acid/zinc methacrylate copolymer, ethylene/methyl methacrylate/methacrylic acid/magnesium methacrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/vinyl acetate copolymer copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene-g-maleic anhydride copolymer (“g” represents graft, the same applies hereinafter), ethylene/ propylene-g-maleic anhydride copolymer,
Ethylene/propylene-g-acrylic acid copolymer, ethylene/1-butene-g-fumaric acid copolymer, ethylene/1-hexene-g-itaconic acid copolymer, ethylene/propylene-g-endobicyclo[2 ,2,1]-5-heptene-2,3-dicarboxylic anhydride copolymer, ethylene/propylene-g-glycidyl methacrylate copolymer, ethylene/propylene/1,4-hexadiene-g-
Maleic anhydride copolymer, ethylene/propylene/dicyclopentadiene-g-fumaric acid copolymer, ethylene/propylene/norbornadiene-
Examples include g-maleic acid copolymer and ethylene/vinyl acetate-g-acrylic acid copolymer, and it is also possible to use two or more of these modified polyolefins in combination. The above-mentioned modified polyolefin can be produced by a known method.
For example, Special Publication No. 39-6810, Special Publication No. 46-
Publication No. 27527, Special Publication No. 1972-2630, Special Publication No. 1972
-43677 Publication, Special Publication No. 53-5716, Special Publication Sho
It can be produced according to the method disclosed in Japanese Patent Publication No. 53-19037, Japanese Patent Publication No. 53-41173, Japanese Patent Publication No. 56-9925, etc. As for the ethylene ionomer, various grades commercially available under the trade names of "Surlyn,""Himilan," and "Copolene" can be used. The degree of polymerization of the modified polyolefin used in the present invention is not particularly limited, but usually has a melt index of 0.01 to
You can arbitrarily select anything within the range of 50g/10min. Furthermore, in the present invention, it is also possible to mix a small amount of other polyolefins with the above-mentioned modified polyolefin, and the polyolefins include polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/propylene/ Dicyclopentadiene copolymer, ethylene/propylene/5-ethylidene norbornene copolymer and ethylene/propylene/
A 1,4-hexadiene copolymer or the like can be used. The blending ratio of (A) polyester amide and (B) modified polyolefin is polyester amide: 2 to 98% by weight;
Preferably 5-95% by weight and modified polyolefin:
98:2% by weight, preferably in the range of 95-5% by weight. The blending ratio should be selected appropriately depending on the purpose, use, etc., but usually when the purpose is to reduce the cost of polyesteramide, improve impact resistance, increase viscosity, etc., the amount of polyesteramide is larger than that of modified polyolefin. Should. Furthermore, if it is desired to impart mechanical strength, heat resistance, etc. to polyolefin, modified polyolefin should be used as the main ingredient. In any case, the blending ratio of polyester amide and modified polyolefin is not preferable because the objective cannot be achieved if it is outside the above-mentioned range. The method for mixing polyesteramide and modified polyolefin is not particularly limited, and a commonly known method can be employed. Specifically, pellets, powder, pieces, etc. of polyesteramide and modified polyolefin are uniformly mixed using a high-speed stirrer, and then melt-kneaded using a single-screw or multi-screw extruder with sufficient kneading capacity. Any method can be used, such as dry blending polyester amide and modified polyolefin during molding without molding and molding by injection or extrusion, or melt kneading using a Banbury mixer or rubber roll machine. The resin composition of the present invention may contain other ingredients, such as pigments, as long as they do not impair its moldability and physical properties.
Dyes, reinforcing materials, fillers, heat resistant agents, antioxidants, weathering agents, lubricants, crystal nucleating agents, antiblocking agents, plasticizers, antistatic agents, flame retardants, mold release agents, hydrolysis resistance improvers, etc. Polymers and the like can be added and introduced. The composition of the present invention can be used for general injection molded products, hoses,
It is useful for various applications such as tubes, films, monofilaments, wire coatings, hollow molded products, laminates, and heat-sensitive element materials for electric blankets and electric carpets. The present invention will be explained in more detail with reference to Examples below. The physical properties of the test pieces described in Examples and Comparative Examples were measured and evaluated according to the following method. (1) Relative viscosity: 0.5 g of polymer was dissolved in 100 ml of orthochlorophenol and measured at 25°C. (2) Melting point: Endothermic peak temperature measured using a Perkin-Elmer DSC-1B differential calorimeter at a heating rate of 20°C/min. (3) Melt index: ASTM D1238 (4) Melt tension: Measured using a Toyo Seiki Melt Tension Tester. (5) Tensile properties: ASTM D638 (6) Bending properties: ASTM D790 (7) Izot impact strength: ASTM D256 (8) Heat distortion temperature: ASTM D648 Example 1 81.9 parts by weight of 12-aminododecanoic acid, sebacic acid
19.7 parts by weight and 15.8 parts by weight of 1,4-butanediol were placed in a reaction vessel together with 0.04 parts by weight of tetrabutyl titanate, the air was purged with nitrogen, and the mixture was reacted by heating at 220°C for 3 hours with stirring. -A mixture of butanediol was distilled out of the system. Next, the reaction mixture was transferred to a polymerization reaction vessel, and after adding 0.06 parts by weight of tetrabutyl titanate and 0.10 parts by weight of the antioxidant "Irganox" 1010 (Ciba Geigy), it was heated to 250°C and 0.1 mmHg or less for 1 hour. The polymerization reaction was continued at 270° C. for 2 hours. The obtained polymer was discharged from the polymerization container into water in a gut shape and pelletized through a cutter. The polyester amide (A-1) thus obtained had a weight ratio of polyamide (N-12) portion to polyester (PBS) portion of 75:25, a relative viscosity of 1.51, and a melting point of 147°C. Polyesteramide (A-1) and "Himilan" 1855 (Mitsui Polychemical Co., Ltd., ethylene ionomer resin) were supplied to an extruder at the ratios shown in Table 1, and melt-kneaded at 20°C to pelletize. .
After vacuum drying the pellets, the melting properties were adjusted to 2200
When evaluated using a melt indexer set at 210°C and a melt tension measuring device set at 210°C, it was found that the melt index was small as shown in Table 1, and the melt tension and extensibility were good. In addition, the pellets after vacuum drying are molded using an injection molding machine at a cylinder temperature of 200℃ and a mold temperature of 50℃.
Test pieces for various physical property evaluations were molded under the following conditions. The measurement results of the bone dry physical properties of the test piece obtained here are the first
As shown in the table, it was found that this material has excellent impact strength, mechanical strength, heat resistance, etc., and has extremely high practical value.

【table】

[Table] Comparative Example 1 The melting properties of N-12/PBS:75/25 (wt%) used in Example 1 were as follows, and the melt tension and extensibility were unsatisfactory. Melt index: 25g/10min Melt tension: 3g Extensibility: >1500rpm Comparative example 2 The heat distortion temperature of a test piece obtained by molding the ionomer resin “Himilan” 1855 used in Example 1 was 80
℃, indicating poor heat resistance. Example 2 81.2 parts by weight of hexamethylenediamine adipate, 24.3 parts by weight of 1,4-butanediol and 21.9 parts by weight of adipic acid were mixed and polymerized in the same manner as in Example 1 to produce polyamide (N-66). The weight ratio of the part and the polyester (PBA) part is 70:
30, a relative viscosity of 1.70, and a melting point of 225° C. polyesteramide (A-2) was obtained. 0.03 parts by weight of α,α'-bis-t-butylperoxy-p-diisopropylbenzene dissolved in a small amount of acetone and 100 parts by weight of an ethylene/propylene copolymer consisting of 70 mol% ethylene and 30 mol% propylene After adding 0.5 parts by weight of maleic anhydride, using an extruder with a diameter of 40 mm
The mixture was kneaded at 230°C to form pellets. After pulverizing the pellets, unreacted maleic anhydride was extracted with acetone, and then the graft-reacted maleic anhydride was quantified by infrared absorption spectrum of the press film, and it was found that it contained 0.35% by weight of maleic anhydride. Understand that ethylene/propylene
A g-maleic anhydride copolymer (melt index: 1.5) (B-2) was obtained. After mixing polyesteramide (A-2) and modified polyolefin (B-2) in the ratio shown in Table 2, the mixture was fed into an extruder and melt-kneaded at 250°C to form pellets. After vacuum drying this pellet,
Various physical properties were measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

【table】

[Table] Examples 3 to 8 The physical properties of test pieces obtained by changing the types and blending ratios of polyesteramide and modified polyolefin and performing the same operations as in Examples 1 and 2 were shown in Table 3. We obtained the results shown below. It has been found that in all cases shown in Table 3, materials with excellent impact strength, heat resistance, and mechanical strength can be obtained.

【table】

[Table] Comparative Example 3 Polyesteramide was polymerized in the same manner as in Example 1 except that ε-aminocaproic acid and terephthalic acid were used in place of 12-aminododecanoic acid and sebacic acid in Example 1, respectively. /
A polyesteramide called PBT was obtained, but the volatilization of caprolactam during polymerization was significant and the polymer was heavily colored. Using this polymer, the ionomer resin (“Himilan”) used in Example 1 was used.
1855) were blended and kneaded in the same manner as in Example 1 to obtain a composition of polyesteramide:ionomer=80:20, but the flexural modulus and Izot impact strength at 0°C of this composition were each 7800 Kg/cm ² ,13
Kg・cm/cm・notch, and the flexibility and impact resistance were insufficient.

Claims (1)

[Claims] 1 (A) An ester unit whose main components are an aliphatic diol having 2 to 6 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and an aliphatic diol having 11 or 12 carbon atoms.
Polyester amide consisting of amide units whose main constituents are at least one selected from 12 aliphatic amino acids, lactams, aliphatic diamines having 4 to 12 carbon atoms, and aliphatic dicarboxylic acids having 6 to 12 carbon atoms: 2 ~98% by weight and (B) 98 to 2% by weight of a modified polyolefin having at least one functional group selected from a carboxylic acid group, a carboxylic acid metal base, a carboxylic ester group, an acid anhydride group, and an epoxy group. A resin composition made of