JP2005248159A - Polyester material whose hydrolytic property is controlled and its molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester material whose hydrolytic property is controlled, and to provide a molded article using the polyester material. <P>SOLUTION: This polyester material whose hydrolytic property is controlled comprises a polyester-based resin and at least one compatibilizing agent selected from the group consisting of ionomer resins, oxazoline-based compatibilizing agents, elastomer-based compatibilizing agents, reactive compatibilizing agents, and copolymer-based compatibilizing agents. It is preferable to contain the compatibilizing agent in an amount of 0.1 to 100 pts. wt. per 100 pts. wt. of the polyester-based resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyester material with controlled hydrolyzability and a molded body thereof.

  Polyester resins are used as materials for monofilaments, multifilaments, films or sheets, and other various molded articles. Since the polyester resin undergoes a certain degree of hydrolysis during its use, a polyester resin with improved hydrolysis resistance is desired depending on the application of the molded product.

  For example, Japanese Patent Application Laid-Open No. 57-161124 discloses a method for producing a polyester filament having improved hydrolysis resistance by adding a monofunctional epoxy compound to a polyester resin and melt spinning it.

  WO 83/1253 discloses that the hydrolysis resistance of a polyester monofilament is improved by the addition of a polyester stabilizer such as carbodiimide.

  JP-A-10-130482 discloses a polyester resin, a first compound selected from the group consisting of polyalkylene glycol, polyalkylene glycol endcapped with alkoxy, and a mixture thereof, glycidyl ether, carbodiimide, ketenimine, Disclosed is a method for producing a polyester product with improved hydrolysis stability, comprising the step of blending with a second compound selected from the group consisting of aziridine and isocyanate.

JP 57-161124 A WO83 / 1253 JP-A-10-130482

  The present inventors have found that the hydrolysis resistance of a polyester resin can be improved by blending a compatibilizer with the polyester resin.

  An object of the present invention is to provide a polyester material with controlled hydrolyzability and a molded body using the polyester material.

The present invention includes the following inventions.
(1) At least one phase selected from the group consisting of a polyester-based resin (a), an ionomer resin, an oxazoline-based compatibilizer, an elastomer-based compatibilizer, a reactive compatibilizer, and a copolymer-based compatibilizer. A polyester material having controlled hydrolyzability, comprising a solubilizer (c).

  (2) The polyester material according to (1), comprising 0.1 to 100 parts by weight of the compatibilizer (c) with respect to 100 parts by weight of the polyester resin (a).

  (3) A plastic molded body composed of the polyester material according to (1) or (2).

  According to the present invention, the hydrolyzability of the polyester resin can be controlled by adding the compatibilizer (c) to the polyester resin (a).

  In the present invention, the polyester-based resin (a) is not particularly limited and includes various known polyester-based resins. Examples thereof include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). ), A copolymer of polyethylene terephthalate, a copolymer of polybutylene terephthalate, a copolymer of polyethylene naphthalate, and an aliphatic polyester-based biodegradable resin. Examples of the aliphatic polyester-based biodegradable resin include poly (α-hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLLA); and poly (β-hydroxy) such as poly-β-hydroxybutyric acid (PHB). Hydroxy (alkanoates); poly (ω-hydroxyalkanoates) such as poly-ε-caprolactone (PCL); polyalkylene alkanoates such as polybutylene succinate (PBS) and polyethylene succinate (PES). The polyester resin can be synthesized by a known method.

  In the present invention, in order to improve the hydrolysis resistance of the polyester resin (a), an ionomer resin (A), an oxazoline-based compatibilizer (B), an elastomer-based compatibilizer (C), a reactive compatibilizer At least one compatibilizer (c) selected from the group consisting of (D) and a copolymer-based compatibilizer (E) is blended in the polyester resin. The compatibilizing agent (c) is other than the polyester resin (a).

  Various types of ionomer resins (A) are included. Typical ionomers are (i) those in which side chain ionic groups are partially present in the main chain of the host polymer (side chain type). Another type of ionomer is (ii) a polymer obtained by neutralizing a metal ion with a host polymer or oligomer having carboxylic acid groups at both ends (telechelic type). Another type of ionomer is (iii) having a cation in the main chain to which an anion is bound (ionene).

Counter ions for the ionic group of the host polymer include alkali metal ions such as Li ⁺ , Na ⁺ and K ⁺ , alkaline earth metal ions such as Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ , Zn Transition metal ions such as ²⁺ , Cu ²⁺ , Mn ²⁺ , Ni ²⁺ , Co ²⁺ , Co ³⁺ , Fe ³⁺ , Cr ³⁺ are used. For the cation host polymer, anions such as Cl ⁻ , Br ⁻ and I ⁻ are used.

  Such an ionomer resin is not particularly limited. For example, ethylene-methacrylic acid copolymer ionomer, ethylene-acrylic acid copolymer ionomer, propylene-methacrylic acid copolymer ionomer, propylene-acrylic acid copolymer ionomer. , Butylene-acrylic acid copolymer ionomer, ethylene-vinylsulfonic acid copolymer ionomer, styrene-methacrylic acid copolymer ionomer, sulfonated polystyrene ionomer, fluorine ionomer, telechelic polybutadiene acrylic acid ionomer, sulfonated ethylene-propylene -Diene copolymer ionomer, hydrogenated polypentamer ionomer, polypentamer ionomer, poly (vinylpyridium salt) ionomer, poly (vinyltrimethyl) Ammonium salt) ionomer, poly (vinylbenzylphosphonium salt) ionomer, styrene-butadiene acrylic acid copolymer ionomer, polyurethane ionomer, sulfonated styrene-2-acrylamido-2-methylpropane sulfate ionomer, acid-amine ionomer, aliphatic System ionene, aromatic ionene and the like.

  Of these ionomer resins, ethylene-methacrylic acid copolymer ionomers and ethylene-acrylic acid copolymer ionomers are preferably used. More specifically, as an ethylene-methacrylic acid copolymer ionomer, High Milan 1554, High Milan 1555, High Milan 1557, High Milan 1601, High Milan 1605, High Milan 1650, High Milan 1652, High Milan 1652 SR, High Milan 1652 SB, High Milan 1702, High Milan 1705 HIMILAN 1706, HIMILAN 1707, HIMILAN 1855, and HIMILAN 1856 (Mitsui DuPont Polychemical Co., Ltd.).

  Only one of these ionomer resins may be used, or two or more may be mixed and used as necessary.

Examples of the oxazoline-based compatibilizer (B) include the following types B1 to B3.
Examples of the B1 type include bisoxazoline / styrene / maleic anhydride copolymer (OXZ; manufactured by Mikuni Pharmaceutical Co., Ltd.).
Examples of the B2 type include bisoxazoline / maleic anhydride-modified polyethylene [OXZ (manufactured by Mikuni Pharmaceutical) / Yumex 2000 (manufactured by Sanyo Chemical)].
Examples of the B3 type include bisoxazoline / maleic anhydride-modified polypropylene [OXZ (manufactured by Mikuni Pharmaceutical) / Yumex 1010 (manufactured by Sanyo Kasei)].

  Only one of these oxazoline-based compatibilizers may be used, or two or more thereof may be mixed and used as necessary.

Examples of the elastomer compatibilizer (C) include the following types of C1 to C4.
Examples of the C1 type include styrene ethylene butadiene copolymer (SEB; manufactured by Asahi Kasei Kogyo Co., Ltd., Tuftec).
Examples of the C2 type include styrene ethylene butadiene styrene copolymer (SEBS; manufactured by Asahi Kasei Kogyo).
Examples of the C3 type include hydrogenated styrene isopropylene styrene copolymer (H-SIS).
Examples of the C4 type include aromatic resins, petroleum resins (Neopolymer manufactured by Nippon Oil Corporation), and the like.

  Only one of these elastomer-based compatibilizers may be used, or two or more may be mixed and used as necessary.

  The reactive compatibilizer (D) is a compound (low molecular compound or polymer) having a double bond, a carboxyl group, an epoxy group, an isocyanate group, etc., and one of the polymers to be compatibilized in the molding process. Or it reacts with both to act as a compatibilizer by acting as a surfactant based on the graft or block structure (Reference: “Polymer Alloy” Fundamentals and Applications, edited by the Society of Polymer Science, published in 1993) ). Examples of the reactive compatibilizing agent (D) include the following types D1 to D6.

D1 type:
Ethylene glycidyl methacrylate copolymer (E-GMA; copolymer weight composition such as E / GMA = 100/6 to 12), ethylene glycidyl methacrylate-vinyl alcohol copolymer (E-GMA-VA; copolymer weight composition such as E / GMA / VA = 100/3 to 12/8 to 5), ethylene glycidyl methacrylate-methacrylate copolymer (E-GMA-MA; copolymer weight composition, for example, E / GMA / MA = 100/3 to 6 / 30). Specific examples include Sumitomo Chemical Co., Ltd., Bond First E, Bond First 2C; Nippon Polyolefin Co., Ltd., Lex Pearl RA, Lex Pearl ET, and Lex Pearl RC.

D2 type:
And ethylene maleic anhydride ethyl acrylate copolymer (E-MAH-EA; manufactured by Sumitomo Chemical Co., Ltd.).

D3 type:
Ethylene glycidyl methacrylate-acrylonitrile styrene (EGMA-AS; copolymer weight composition, eg EGMA / AS = 70/30), ethylene glycidyl methacrylate-polystyrene (EGMA-PS; copolymer weight composition, eg EGMA / PS = 70/30) And ethylene glycidyl methacrylate-polymethyl methacrylate (EGMA-PMMA, for example, EGMA / PMMA = 70/30). Specifically, the product made from Japanese fats and oils and a modiper are mentioned.

D4 type:
Examples include acid-modified polyethylene wax (APEW; manufactured by Mitsui Chemicals, high wax).

D5 type:
COOH-ized polyethylene graft polymer, COOH-ized polypropylene graft polymer and the like can be mentioned.

D6 type:
Polyisocyanate containing 5 to 30% by weight of isocyanate groups. Specific examples include VESTANAT T1890 (Degussa).

  Only one of these reactive compatibilizers may be used, or two or more thereof may be mixed and used as necessary.

  Examples of the copolymer-based compatibilizer (E) include polyethylene-polyamide graft copolymer (PE-PA GP) and polypropylene-polyamide graft copolymer (PP-PA GP). Further, it contains at least one group selected from the group consisting of alkoxy groups, amino groups, mercapto groups, vinyl groups, epoxy groups, acetal groups, maleic acid groups, oxazoline groups and carboxylic acid groups, and has a melt flow rate of 1 or more Specifically, a low-viscosity copolymer polymer such as methyl methacrylate-butadiene-styrene resin, acrylonitrile-butadiene rubber, EVA / PVC / graft copolymer, vinyl acetate-ethylene copolymer resin, ethylene- Examples include α-olefin copolymers, propylene-α-olefin copolymers, hydrogenated styrene-isopropylene-block copolymers, and the like. Specific examples include Elvalloy manufactured by Mitsui DuPont Polychemical.

  Only one of these copolymer-based compatibilizers may be used, or two or more thereof may be mixed and used as necessary.

  In the present invention, the compatibilizer is preferably blended in an amount of 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polyester resin. In the case where a plurality of compatibilizers are used, the total amount thereof should be within the above range. When the compounding amount of the compatibilizer is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the hydrolysis resistance of the polyester resin. On the other hand, when the compatibilizer exceeds 100 parts by weight, the effect of improving hydrolysis resistance is saturated. In consideration of the use of the polyester material, the amount of the compatibilizer used may be appropriately determined.

  The reason why the hydrolysis resistance of the polyester resin is improved by adding a compatibilizer to the polyester resin is not clear, but for example, a cross-linked structure between the compatibilizer and the polyester is formed, and the network has moisture. It is thought that it will prevent the entrance of.

  In the present invention, the polyester material further includes other additives such as organic or inorganic fillers, flame retardants, anti-blocking agents, crystallization accelerators, gas adsorbents, anti-aging agents (esters, amides, etc.), and antioxidants. Agent, ozone degradation inhibitor, ultraviolet absorber, light stabilizer, tackifier, plasticizer (fatty acid such as stearic acid and oleic acid or metal salts thereof), softener (mineral oil, wax, paraffins, etc.) Additives such as stabilizers, lubricants, mold release agents, antistatic agents, modifiers, colorants, coupling agents, preservatives, and antifungal agents may be appropriately blended.

  The blending method is not particularly limited and can be carried out by an ordinary melt kneading method. For example, the polyester resin, the compatibilizing agent, and other optional components may be kneaded with a kneader such as a roll kneader, a Banbury mixer, an intermix, a single screw extruder, or a twin screw extruder. Kneading may be performed using one kind of kneader selected from the kneaders, or may be performed using two or more kinds of kneaders.

  A polyester material containing a polyester resin and the compatibilizer is molded by a conventional method to obtain various molded products. Moreover, it is also possible to add an additive to the polyester material as necessary to form a coating material, a coating material or an adhesive material.

  Various molded products from the polyester material can be produced by a conventional molding method. For example, extrusion molded products, injection molded products, blow molded products, sheets or films extruded from T dies, blown films, melt-spun multifilaments, monofilaments, flat yarns, staple fibers, spunbond nonwoven fabrics, flash spun nonwoven fabrics Etc., and various foamed molded articles can be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
100 parts by weight of polybutylene succinate PBS (Bionore 1001, manufactured by Showa Polymer) and 2 parts by weight of ethylene glycidyl methacrylate copolymer E-GMA (reactive compatibilizer, Bond First E, manufactured by Sumitomo Chemical) Using an extruder (manufactured by Technobel Co., Ltd., KZW15-30MG), it is melt kneaded at 130 ° C. in a conventional manner, extruded and solidified in water with a diameter of about 3 mm, then cut into 3 mm lengths, Obtained. The extrusion conditions at this time were as follows.

<Extrusion conditions>
Temperature setting: Feed 100 ° C, Kneading part 130 ° C, Head 130 ° C
Rotation speed: 60rpm

The obtained chip was press-molded (press-molding machine: manufactured by Kondo Metal Industry Co., Ltd.) to prepare No. 2 test piece based on JIS K-7113.
<Press molding conditions>
After pressing at 10 MPa for 1 minute at a press temperature of 160 ° C., pressing was performed at 20 MPa for 2 minutes. Then, it cooled for 3 minutes with the cooling press.

[Comparative Example 1]
Using only polybutylene succinate PBS (Bionore 1001, manufactured by Showa Polymer Co., Ltd.), press molding was performed under the same conditions as in Example 1 to prepare test pieces.

[Example 2]
100 parts by weight of poly-ε-caprolactone PCL (Cell Green PH-7, manufactured by Daicel Chemical Industries) and 2 parts by weight of ethylene glycidyl methacrylate copolymer E-GMA (reactive compatibilizer, Bond First E, manufactured by Sumitomo Chemical) Was melt-kneaded in a conventional manner at 110 ° C. using a twin-screw extruder (manufactured by Technobel Co., Ltd., KZW15-30MG), extruded and solidified in water with a diameter of about 3 mm, and then cut into 3 mm lengths. A resin chip was obtained. The extrusion conditions at this time were as follows.

<Extrusion conditions>
Temperature setting: Feed 60 ° C, Kneading part 110 ° C, Head 110 ° C
Rotation speed: 60rpm

The obtained chip was press-molded (press-molding machine: manufactured by Kondo Metal Industry Co., Ltd.) to prepare No. 2 test piece based on JIS K-7113.
<Press molding conditions>
After pressing at 10 MPa for 1 minute at a press temperature of 160 ° C., pressing was performed at 20 MPa for 2 minutes. Then, it cooled for 3 minutes with the cooling press.

[Comparative Example 2]
Using only poly-ε-caprolactone PCL (Cell Green PH-7, manufactured by Daicel Chemical Industries), press molding was performed under the same conditions as in Example 2 to prepare test pieces.

[Example 3]
100 parts by weight of poly-L-lactic acid PLLA (manufactured by BM Co., Ltd., homo PLLA, weight average molecular weight 201,000), and ethylene glycidyl methacrylate copolymer E-GMA (reactive compatibilizer, Bond First E, Sumitomo) 2 parts by weight) were melt-kneaded in a conventional manner at 220 ° C. using a twin-screw extruder (manufactured by Technobel Co., Ltd., KZW15-30MG), extruded and solidified in water at a diameter of about 3 mm, Subsequently, it cut | disconnected to 3 mm length, and obtained the resin chip. The extrusion conditions at this time were as follows.

<Extrusion conditions>
Temperature setting: Feed 180 ° C, Kneading part 220 ° C, Head 180 ° C
Rotation speed: 60rpm

The obtained chip was press-molded (press-molding machine: manufactured by Kondo Metal Industry Co., Ltd.) to prepare No. 2 test piece based on JIS K-7113.
<Press molding conditions>
After pressing at 10 MPa for 1 minute at a press temperature of 180 ° C., pressing was performed at 20 MPa for 2 minutes. Then, it cooled for 3 minutes with the cooling press.

[Comparative Example 3]
Using only poly-L-lactic acid PLLA (manufactured by BM Co., Ltd., homo PLLA, weight average molecular weight 201,000), press molding was performed under the same conditions as in Example 3 to prepare test pieces.

[Example 4]
100 parts by weight of amorphous copolyester resin PET-G (Easter AN004, manufactured by Eastman Plastics) and ethylene glycidyl methacrylate copolymer E-GMA (reactive compatibilizer, Bond First E, Sumitomo) 2 parts by weight) were melt-kneaded in a conventional manner at 260 ° C. using a twin-screw extruder (manufactured by Technobel Co., Ltd., KZW15-30MG), extruded and solidified in water at a diameter of about 3 mm, Subsequently, it cut | disconnected to 3 mm length, and obtained the resin chip. The extrusion conditions at this time were as follows.

<Extrusion conditions>
Temperature setting: Feed 190 ° C, Kneading part 260 ° C, Head 180 ° C
Rotation speed: 60rpm

The obtained chip was press-molded (press-molding machine: manufactured by Kondo Metal Industry Co., Ltd.) to prepare No. 2 test piece based on JIS K-7113.
<Press molding conditions>
After pressing at 10 MPa for 1 minute at a press temperature of 200 ° C., pressing was performed at 20 MPa for 2 minutes. Then, it cooled for 3 minutes with the cooling press.

[Comparative Example 4]
Using only amorphous copolyester resin PET-G (Easter AN004, manufactured by Eastman Plastics), press molding was performed under the same conditions as in Example 4 to prepare test pieces.

[Evaluation of polyester materials]
(Measurement of tensile properties)
About each obtained test piece, the tensile strength (MPa) was measured according to JISK-7113. Distance between chucks: 115 mm, tensile speed: 50 mm / min, measurement atmosphere: temperature 23 ° C., relative humidity 50%.

(Measurement of hydrolysis resistance)
Each obtained test piece was immersed in a 1 wt% aqueous sodium hydroxide solution maintained at 95 ° C for 30 minutes. The weight loss rate (%) was determined from the weight of the test piece before immersion (w ₁ ) and the weight of the test piece after immersion (w ₂ ). The test specimen weight after immersion (w ₂₎ is washed with water test piece after immersion was measured after drying.
Weight loss rate (%) = [(w ₂ −w ₁ ) / w ₁ ] × 100

The above measurement results are shown in Table 1.
From Table 1, it can be seen that the test piece of each example has improved hydrolysis resistance as compared with the corresponding test piece of each comparative example. In particular, the test piece of Example 1 was significantly improved in hydrolysis resistance as compared with the test piece of Comparative Example 1, and was not hydrolyzed in this hydrolysis test. Moreover, about the test piece of Examples 1, 2, and 4, compared with the test piece of each corresponding comparative example, hydrolysis resistance improved and tensile strength also improved.

Claims (3)

At least one compatibilizer selected from the group consisting of a polyester resin (a), an ionomer resin, an oxazoline compatibilizer, an elastomer compatibilizer, a reactive compatibilizer, and a copolymer compatibilizer ( and a hydrolyzable polyester material comprising c). The polyester material according to claim 1, comprising 0.1 to 100 parts by weight of the compatibilizer (c) with respect to 100 parts by weight of the polyester resin (a). The plastic molded object comprised from the polyester material of Claim 1 or 2.