JP4581420B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition comprising a poly-3-hydroxybutyrate polymer and / or polylactic acid and a halogenated elastomer, which is excellent in impact resistance and exhibits a high crystallization rate.

  Since poly-3-hydroxybutyrate-based polymers and polylactic acid are obtained from plants as raw materials, they have recently attracted attention as materials with little environmental impact. However, poly-3-hydroxybutyrate-based polymers and polylactic acid have problems that the crystallization speed is slow and the molding processability is inferior and the impact resistance is also inferior. The cycle had to be lengthened, and when forming by extrusion, it was necessary to reduce the discharge amount or introduce a large apparatus with a long production line.

  As a method for solving these problems, a method of mixing polycaprolactone or polybutylene succinate resin has been proposed (for example, see Patent Documents 1 and 2).

  In addition, as a method for improving the crystallization speed of poly-3-hydroxybutyrate polymer or polylactic acid and improving the molding processability thereof, a method of adding a plasticizer or a crystal nucleating agent to the pellet has been proposed. 1) A method of adding a plasticizer such as fatty acid, aliphatic ester, aliphatic amide, or fatty acid metal salt (see, for example, Patent Document 3). 2) Adding silicon nitride as a crystal nucleating agent to increase the crystal growth rate. Method (for example, refer to Patent Document 4), 3) A method for increasing the crystal growth rate by adding ammonium chloride as a crystal nucleating agent (for example, refer to Patent Document 5).

JP-A-9-194281

JP-A-11-323141 Japanese Patent Laid-Open No. 7-188573 European Published Patent No. 0291024 International Patent Publication No. 91/197559

  However, in the method of mixing the different polymers proposed in Patent Documents 1 and 2, the impact resistance effect is not sufficient. Further, in the method of adding a plasticizer proposed in Patent Document 3, the plasticizer bleeds to the product surface or the plasticizer migrates to other products, particularly to products made of polyvinyl chloride or polystyrene resins. There were problems such as rapid migration of plasticizers and contamination of production lines such as cooling rolls. Furthermore, in the method of adding the crystal nucleating agent proposed in Patent Documents 4 and 5, the crystal nucleating agent is expensive, and there are problems such as impairing the cost performance of the resin composition.

  Therefore, the present invention is excellent in impact resistance and has a high crystallization speed, so that the poly-3-hydroxybutyrate polymer and / or polylactic acid and halogenated elastomer are excellent in molding processability and molded product productivity. The resin composition which consists of this is provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition comprising a poly-3-hydroxybutyrate polymer and / or polylactic acid and a halogenated elastomer has excellent moldability and impact resistance. As a result, the present invention has been completed.

That is, the present invention provides a poly 3-hydroxybutyrate polymer and / or polylactic acid in an amount of 1 to 99% by weight, and a mixture of chlorosulfonated polyethylene, alkylated chlorosulfonated polyethylene, chlorosulfonated polyethylene and chlorinated polyethylene. A resin composition comprising 99 to 1% by weight of a halogenated elastomer selected from the group consisting of a mixture of alkylated chlorosulfonated polyethylene and chlorinated polyethylene, and further 0.001 to 10% by weight of an epoxy compound It is about.

  The present invention is described in detail below.

  Examples of the poly-3-hydroxybutyrate polymer (hereinafter referred to as a PHB polymer) used in the present invention include other than poly-3-hydroxybutyrate homopolymer and 3-hydroxybutyrate / 3-hydroxybutyrate. Examples of the hydroxyalkanoate other than 3-hydroxybutyrate in the case of the copolymer include 3-hydroxypropionate, 3-hydroxyvalerate, 3-hydroxy Examples include hexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate, 4-hydroxybutyrate, and hydroxylaurylate. The copolymer is particularly excellent in molding processability Since the resin composition is obtained, hydroxyalkanoate other than the 3-hydroxybutyrate is preferably one that is copolymerized than 25 mol%. In particular, poly-3-hydroxybutyrate homopolymer, 3-hydroxybutyrate / 3-hydroxyvalerate copolymer, and 3-hydroxybutyrate / 4-hydroxybutyrate copolymer are preferable because they are easily available. Moreover, since it becomes a resin composition excellent in molding processability, it is preferable that the PHB polymer is produced in a microorganism. Such a PHB polymer can be obtained as a commercial product. Moreover, as the manufacturing method, it can also obtain by the method currently disclosed by the US Patent 4477654 gazette, the international publication 94/115519 gazette, the US Patent 5502273 gazette, etc., for example. Moreover, as polylactic acid (hereinafter referred to as PLA), a commercially available product can be used without any particular limitation. For example, (trade name) Lacia (manufactured by Mitsui Chemicals, Inc.) is sold as a commercially available product. .

  In the resin composition of the present invention, it is also possible to use a mixture of a PHB polymer and PLA, and the PHB polymer / PLA weight ratio may be used in the range of 100/0 to 0/100. Among them, it is preferable to use only a PHB polymer without mixing PLA because a resin composition with little change in physical properties after molding can be obtained.

  The halogenated elastomer used in the present invention is a substance obtained by halogenating various elastomers and resins with a halogen such as chlorine or bromine, specifically, chlorinated polyethylene, chlorinated vinyl acetate, chlorinated butyl rubber, brominated butyl rubber, Examples thereof include chlorosulfonated polyethylene, alkylated chlorosulfonated polyethylene, and chloroprene rubber. Among these, one kind is used alone, or two or more kinds are used in combination. Of these, chlorinated polyethylene, chlorosulfonated polyethylene, and alkylated chlorosulfonated polyethylene are particularly preferably used.

  The mixing ratio of the PHB polymer and / or PLA and the halogenated elastomer in the resin composition of the present invention is 99/1 to 1/99 in terms of the weight ratio of (PHB polymer and / or PLA) / halogenated elastomer. Yes, preferably 95/5 to 30/70, more preferably 90/10 to 50/50. When the weight ratio of the halogenated elastomer is less than 1%, the resulting resin composition is inferior in impact resistance. On the other hand, when it exceeds 99%, the resin composition obtained is inferior in moldability.

  Since the resin composition of the present invention is a resin composition that is particularly excellent in heat resistance and molding processability, the temperature is increased from room temperature to 10 ° C./min with a differential scanning calorimeter (hereinafter referred to as DSC). The crystal melting point observed when heated at a rate is preferably 130 ° C. or higher and 185 ° C. or lower, particularly 140 ° C. or higher and 185 ° C. or lower, more preferably 150 ° C. or higher and 185 ° C. or lower. The crystal melting point in the present invention refers to DSC (trade name DSC-7, manufactured by Perkin Elmer Co., Ltd.), an aluminum pan loaded with 5 mg of sample, and the temperature of the pan is increased from room temperature to 10 ° C./min. It represents the highest temperature among the peak temperatures of the heat flux based on the crystal melting observed when heated at.

  Furthermore, since the resin composition of the present invention becomes a resin composition having a high crystallization rate and excellent molded product production efficiency, the DSC is heated from room temperature to 180 ° C. at a temperature rising rate of 80 ° C./min. After maintaining at 180 ° C. for 1 minute, the crystallization temperature cooled at a rate of temperature decrease of 10 ° C./min is preferably 100 ° C. or higher and 170 ° C. or lower, more preferably 110 ° C. or higher and 165 ° C. or lower, and further 120 It is preferable that it is at least 160 ° C. The crystallization temperature refers to DSC (manufactured by Perkin Elmer, trade name DSC-7), an aluminum pan loaded with 5 mg of sample, and the pan is heated from room temperature to 180 ° C./min at 180 ° C./min. The sample is heated up to 180 ° C., held at 180 ° C. for 1 minute, then cooled at a rate of temperature drop of 10 ° C./min, and is the highest of the heat flux peak temperatures observed based on the crystallization of the PHB polymer and / or PLA. Represents a high temperature.

  Since the resin composition of the present invention is a resin composition that is particularly excellent in moldability and excellent in mechanical strength when formed into a molded product, the chloroform-dissolved component of the resin composition is gel permeation chromatography (hereinafter referred to as GPC). The weight average molecular weight (hereinafter referred to as Mw) in terms of polystyrene when measured by (2) is preferably 20000 or more and 3000000 or less, particularly preferably 50000 or more and 1000000 or less. In addition, Mw of the chloroform melt | dissolution component of a resin composition can also be measured by the molecular weight of the melt | dissolution part obtained by melt | dissolving a molding in 60 degreeC chloroform for 2 hours. In addition, the measurement of Mw in the present invention uses a GPC apparatus (manufactured by Tosoh Corporation, trade name HLC8020GPC) equipped with two columns (trade name TSKgel GMHHR-H, manufactured by Tosoh Corporation) and measuring solvent: chloroform. Using a standard polystyrene (manufactured by Tosoh Corporation), the column elution volume was measured at a measurement temperature of 40 ° C., a sample dissolution condition: 60 ° C., and a sample prepared at a measurement concentration of 50 mg / 50 mL in 2 hours with an injection volume of 100 μL. This was calibrated.

The resin composition of the present invention is preferably formed by blending 0.1 to 10% by weight of an acid-containing thermoplastic polyolefin because the resin composition is further excellent in impact resistance. The acid-containing thermoplastic polyolefin contains one or more functional groups selected from the group consisting of a carboxylic acid group, a carboxylic acid group, and a carboxylic acid anhydride group in its main chain or side chain. Examples thereof include a modified polyolefin obtained by grafting an unsaturated carboxylic acid or a derivative thereof or other functional vinyl monomer onto a polyolefin. In this case, the polyolefin includes olefins such as high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, a copolymer of ethylene and α-olefin; an ethylene-propylene elastomer; Polyolefin heat comprising ethylene-propylene-diene terpolymer elastomer, butyl elastomer, low crystalline ethylene-propylene copolymer or low crystalline ethylene-butene copolymer, or low crystalline propylene-butene copolymer Plastic elastomers; polyolefin elastomers based on blends of polypropylene and ethylene-propylene elastomers; and ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, etc. Blends of various polyolefins each other are also included. On the other hand, unsaturated carboxylic acids or derivatives thereof, and other functional vinyl monomers include, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, sorbic acid, and acid anhydrides thereof. Amides such as acrylic amide and methacrylic acid amide, epoxies such as glycidyl acrylate and glycidyl methacrylate; hydroxy compounds such as acrylic acid 2-hydroxy ester, methacrylic acid 2-hydroxy ester, and polyethylene glycol monoacrylate; acrylic Metal salts such as sodium acid, sodium methacrylate, zinc acrylate and the like can be mentioned, and they can be mixed and used. Of these, acrylic acid, maleic acid, and maleic anhydride are preferable. In addition, when using said monomer, it can also be used simultaneously with various monomers, such as styrene, vinyl acetate, an acrylic ester, and a methacrylic ester, and can also be graft-copolymerized.

  Further, the amount of the unsaturated carboxylic acid or its derivative or other functional vinyl monomer contained in the graft-modified polyolefin used as the acid-containing thermoplastic polyolefin is preferably 0.05 to 20% by weight, more preferably 0. .5 wt% to 20 wt% is desirable.

  The resin composition of the present invention can be blended with 0.001 to 10% by weight of an epoxy compound for the purpose of making the resin composition further improved in impact resistance. The epoxy compound preferably has an oxirane oxygen amount derived from an epoxy group of 1% by weight or more. Examples of the method for measuring the amount of oxirane oxygen include those described in Koichi Murai, “Plasticizers: Theory and Application” (published by Koshobo Publishing, published March 1, 1973, page 664).

  Such epoxy compounds include, for example, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; epoxidized elastomers such as epoxidized polybutadiene and epoxidized polyisoprene; homopolymers of glycidyl esters such as glycidyl methacrylate; glycidyl methacrylate and the like Copolymer of glycidyl ester and monomer having unsaturated double bond such as styrene, acrylic acid, acrylic ester; phthalic acid diglycidyl ester, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A-epichlorohydride A phosphorus type epoxy resin etc. can be mentioned, These 1 type (s) or 2 or more types are used.

  A commercially available epoxy compound can be used. For example, as epoxidized soybean oil (trade name) Adeka Sizer O-130P (manufactured by Asahi Denka Kogyo), (trade name) New Sizer 510R (manufactured by NOF Corporation), ( (Product name) Capox S-6 (made by Kao) and other epoxidized linseed oils (Product name) Adeka Sizer O-180A (made by Asahi Denka Kogyo), (Product name) New Sizer 512 (made by Nippon Oil & Fats), etc. Examples of the polybutadiene include (trade name) Epolide PB3600 (manufactured by Daicel Chemical Industries), (trade name) BF-1000 (manufactured by Asahi Denka Kogyo Co., Ltd.), and others (trade name) Blemmer CP, Falpack series (manufactured by NOF Corporation), and the like. .

  Examples of the shape of the resin composition of the present invention include a pellet shape, a powder shape, a lump shape, and the like. Among them, the pellets are excellent in production efficiency at the time of manufacture and excellent in handleability at the time of molding. The shape is preferred. As a method for forming a pellet shape, for example, a strand cutting method in which a strand-shaped molten granule is cut with a strand cutter, an underwater cutting method in which a molten resin is cut in water, or the molten resin is cooled or cut by mist or the like. Examples include the hot-cut method and the sheet pelletizing method in which a sheet-shaped molten granule is cut with a sheet pelletizer. Among them, strand cutting is particularly possible because pellets with good resin bite can be obtained during injection molding and extrusion molding. Method, underwater cut method and hot cut method are preferably used.

  As a method for producing the resin composition of the present invention, since a resin composition having particularly good production efficiency and excellent moldability is obtained, the temperature of the molten resin discharged from the die of the extruder is 160 ° C. or higher and 185 ° C. or lower. It is preferable to produce using a kneader whose temperature is set to be. Examples of the kneader include a bi-directional extruder such as a same-direction twin-screw extruder and a conical twin-screw extruder, a batch mixer such as a Banbury mixer and a pressure kneader; and a roll kneader.

  When the resin composition of the present invention is produced, it is desirable to dry the PHB polymer and / or PLA in advance, and the drying conditions are arbitrary, for example, at a temperature of 40 to 90 ° C. for 30 minutes. It is preferable to dry for about 3 days. Further, when molding the resin composition of the present invention, it is desirable to dry the resin composition in advance, and the drying conditions are arbitrary, for example, at a temperature of 40 to 90 ° C. for 30 minutes to It is preferable to dry for about 3 days.

  The molding method of the resin composition of the present invention is arbitrary, and examples thereof include profile extrusion, film, sheet, blow, injection, foaming, extrusion coating, rotational molding, etc. Among them, the injection molding property is excellent. In the case of performing injection molding, if the temperature of the molten resin is 230 ° C. or lower, preferably 210 ° C. or lower, the time required for crystallization in the mold is small, and the molding cycle can be shortened.

  Examples of the resin composition of the present invention include calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline cinnite, attapulgite, wollastonite, ferrite, Inorganic fillers such as calcium silicate, magnesium carbonate, dolomite, antimony trioxide, titanium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, glass fiber, quartz, quartz glass, montmorillonite Various kinds of plant fibers such as starch, cellulose fiber and kenaf; natural fillers such as wood flour, okara, fir shell, bran and organic fillers such as modified products thereof may be mixed. In particular, calcium carbonate and talc also have a function of increasing the crystallization speed, so it is desirable to add them. When a filler is added, the resin composition has an excellent balance between rigidity and impact resistance. Therefore, the filler is preferably used in an amount of 150 parts by weight or less with respect to 100 parts by weight of the resin composition of the present invention.

  Furthermore, it is also possible to add plasticizers such as fatty acids, aliphatic esters, aliphatic amides, and fatty acid metal salts to the resin composition of the present invention.

  In addition, the resin composition of the present invention may contain a crystal nucleating agent as necessary, which further increases the crystal growth rate. Examples of the crystal nucleating agent include nitrided nectar, mica, talc, alumina, calcium hydroxyapatite, and aluminum chloride. Among these, talc and silicon nitride are preferable. Further, it may contain a plasticizer such as fatty acid, aliphatic ester, aliphatic amide, fatty acid metal salt, etc., thereby further increasing the crystal growth rate.

  Furthermore, the resin composition of the present invention includes an antihydrolysis agent represented by carbodiimide, an antiblocking agent, a release agent, an antistatic agent, a slip agent, an antifogging agent, a lubricant, a heat resistance stabilizer, an ultraviolet ray, if necessary. Stabilizers, light stabilizers, weathering stabilizers, antifungal agents, rust inhibitors, ion trap agents, foaming agents, flame retardants, flame retardant aids, and the like may be included. Furthermore, other thermoplastic resins and rubbers, particularly thermoplastic resins called biodegradable resins may be blended.

  The resin composition of the present invention is used for the housing and structure of electrical products; automotive exterior parts such as bumpers, rocker moldings, side moldings, and over fenders; automotive interior parts such as carpets, head liners, door trims, sun visors, etc. For example, it is suitably used.

  Since the resin composition of the present invention has a high crystallization rate, it is excellent in moldability, productivity of a molded product, and excellent in impact resistance.

  Hereinafter, the present invention will be described with reference to examples, but these are illustrative and the present invention is not limited to these examples.

  Various measurements in Examples and Comparative Examples are shown below.

~ Measurement of crystallization temperature ~
The crystal growth rate was measured using a differential scanning calorimeter (manufactured by Perkin Elmer, trade name DSC-7). A 5 mg sample is cut from the pellet and loaded into an aluminum pan. The pan is heated from room temperature to 180 ° C. at a heating rate of 80 ° C./min and held at 180 ° C. for 1 minute. Then, it cooled at the speed | rate of 10 degree-C / min, and measured the highest temperature among the peak temperature of the heat flux based on crystallization as crystallization temperature.

~ Measurement of crystal melting point ~
The crystal melting point was measured using a differential scanning calorimeter (trade name DSC-7, manufactured by Perkin Elmer). A 5 mg sample is cut from the pellet and loaded into an aluminum pan. The highest temperature among the peak temperatures of the heat flux based on crystal melting observed when the pan was heated from room temperature at a heating rate of 10 ° C./min was measured as the crystal melting point.

~ Measurement of weight average molecular weight ~
The molecular weight was measured by gel permeation chromatography using only the dissolved components obtained by dissolving the pellets obtained by granulation in chloroform at 60 ° C. for 2 hours. Calibration was performed using standard polystyrene (manufactured by Tosoh Corporation), and the weight average molecular weight (Mw) was determined in terms of polystyrene. The measurement conditions are shown below.
Model: Product name HLC8020GPC (manufactured by Tosoh Corporation)
Solvent: Chloroform sample dissolution conditions: 60 ° C, 2 hours temperature: 40 ° C
Measurement concentration: 50 mg / 50 mL
Injection volume: 100 μL
Column: Two trade names TSKgel GMHHR-H (manufactured by Tosoh Corporation) -Measurement of solidification time in injection molding-
Injection molding was performed using an injection molding machine (trade name IS100E, manufactured by Toshiba Machine Co., Ltd.), and the solidification time was measured. The set temperature is NH: 180 ° C., H1: 175 ° C., H2: 160 ° C., H3: 140 ° C., mold temperature: 60 ° C., injection pressure: 6.8 MPa, a total of 10 seconds of injection time and compensation time Injection molding was performed under the conditions, and after completion of the pressure-compensating step, the cooling time was increased every other second and an attempt was made to take out the molded product with an ejector pin. The minimum cooling time during which the product can be taken out by ejection with an ejector pin was measured as the minimum solidification time. In addition, the temperature of the molten resin when molding is performed under these conditions is 183 ° C.

~ Measurement of Izod impact strength ~
The Izod impact strength at 23 ° C. was measured using a notched Izod test piece obtained by injection molding.

Example 1
100 parts by weight of a poly-3-hydroxybutyrate polymer (manufactured by PHB Industrial S / A, trade name Biocycle 1000) preliminarily dried in an oven at 80 ° C. for 4 hours, chlorosulfonated polyethylene (trade name, TOSO, trade name TOSO) -CSM TS430; chlorine content 35 wt%) 40 parts by weight, maleic anhydride modified polyethylene (manufactured by Sigma Aldrich Co., Ltd., maleic anhydride modified amount 3 wt%), epoxidized soybean oil (Asahi Denka Kogyo Co., Ltd.) 1 part by weight, trade name Adeka Sizer O-130P), 100 parts by weight of talc (trade name LSM # 300, manufactured by Fuji Talc Co., Ltd.), hindered phenol heat stabilizer (trade name IRGANOX 1010, manufactured by Ciba Geigy) 0.5 Part by weight, phosphorus stabilizer (Ciba Geigy, trade name IRGAF S168) 0.5 parts by weight are melt-extruded and mixed in a different-direction twin-screw extruder (product name: Labo Blast Mill; manufactured by Toyo Seiki Seisakusho; resin temperature 181 ° C., rotation speed 60 rpm), and the extruded strand is brought to 60 ° C. The resin composition was obtained by solidifying with a set hot tub and pelletizing with a strand cutter.

  Table 1 shows the crystallization temperature, crystal melting point, chloroform-dissolved weight average molecular weight of the obtained resin composition, solidification time in injection molding, and Izod impact strength.

Example 2
Instead of 100 parts by weight of the poly-3-hydroxybutyrate polymer, 80 parts by weight of the poly-3-hydroxybutyrate polymer and 20 parts by weight of polylactic acid (trade name Lacia H280, manufactured by Mitsui Chemicals) are used. Instead of 40 parts by weight of sulfonated polyethylene, 20 parts by weight of alkylated chlorosulfonated polyethylene (trade name: EXTOS ET8510, chlorine content: 30% by weight, manufactured by Tosoh Corporation) and chlorinated polyethylene (product name: DAISO, trade name: Daiisolac H-135, chlorine content) 35 wt%) A resin composition was obtained in the same manner as in Example 1 except that the amount was 20 parts by weight.

  Table 1 shows the crystallization temperature, crystal melting point, chloroform-dissolved weight average molecular weight of the obtained resin composition, solidification time in injection molding, and Izod impact strength.

Comparative Example 1
Pellets were obtained in the same manner as in Example 1 except that chlorosulfonated polyethylene was not mixed.

  Table 1 shows the crystallization temperature, the crystal melting point, the weight-average molecular weight of the dissolved chloroform, the solidification time in the injection molding, and the Izod impact strength.

  The obtained resin was inferior in Izod impact strength.

Comparative Example 2
Pellets were obtained in the same manner as in Example 2 except that the alkylated chlorosulfonated polyethylene and chlorinated polyethylene were not mixed.

  Table 1 shows the crystallization temperature, the crystal melting point, the weight-average molecular weight of the dissolved chloroform, the solidification time in the injection molding, and the Izod impact strength.

  The obtained resin was inferior in Izod impact strength.

Claims (3)

1-99% by weight of poly-3-hydroxybutyrate polymer and / or polylactic acid, chlorosulfonated polyethylene, alkylated chlorosulfonated polyethylene, mixture of chlorosulfonated polyethylene and chlorinated polyethylene, alkylated chlorosulfonated A resin composition comprising 99 to 1% by weight of a halogenated elastomer selected from the group consisting of a mixture of polyethylene and chlorinated polyethylene, and further 0.001 to 10% by weight of an epoxy compound. The resin composition according to claim 1, wherein the resin composition satisfies the following characteristics (a) and (b).
(A) The crystal melting point observed when heated from room temperature at a heating rate of 10 ° C./min with a differential scanning calorimeter is 130 ° C. or higher and 185 ° C. or lower.
(B) The polystyrene equivalent weight average molecular weight (Mw) when the chloroform-dissolved component is measured by gel permeation chromatography is 20,000 or more and 3000000 or less. The resin composition according to claim 1, further comprising 0.1 to 10% by weight of an acid-containing thermoplastic polyolefin.