WO2013129547A1 - 熱可塑性樹脂組成物およびその成形品 - Google Patents
熱可塑性樹脂組成物およびその成形品 Download PDFInfo
- Publication number
- WO2013129547A1 WO2013129547A1 PCT/JP2013/055329 JP2013055329W WO2013129547A1 WO 2013129547 A1 WO2013129547 A1 WO 2013129547A1 JP 2013055329 W JP2013055329 W JP 2013055329W WO 2013129547 A1 WO2013129547 A1 WO 2013129547A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- weight
- styrene
- thermoplastic resin
- resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present invention relates to a thermoplastic resin composition containing a styrene resin and a polyethylene terephthalate resin, and a molded product thereof.
- Styrenic resin represented by ABS resin
- ABS resin has excellent mechanical properties, molding processability and electrical insulation, so it is used in a wide range of fields including home electrical equipment, OA equipment and automobile parts. Has been.
- PET polyethylene terephthalate
- the PET resin Since the PET resin has the characteristics that the impact resistance becomes high when it is stretched and the heat resistance becomes high when it is crystallized, the use ratio in the above application is high, but the injection molding method has impact resistance.
- the present situation is that the use ratio as an injection-molded product is extremely low due to remarkable defects such as low.
- Patent Document 1 discloses a composition and manufacturing conditions for improving impact resistance by blending ABS resin with recycled PET resin.
- the compatibility between the PET resin and the ABS resin is not good, and in the composition obtained by the method described in this patent document, good impact resistance is not necessarily obtained. It was.
- Patent Document 2 discloses an example using an acrylonitrile / styrene copolymer having an epoxy group as a modifier
- Patent Document 3 discloses a vinyl monomer having an epoxy group in addition to acrylonitrile and styrene as a diene rubber.
- graft copolymerization There has been proposed a method for improving the compatibility by graft copolymerization.
- these methods can improve the mechanical strength, a cross-linked product may be generated in the extruder or the molding machine, and the surface gloss may be impaired.
- an acrylic / styrene copolymer containing an epoxy group is composed of a recycled PET resin and a linear low-density polyethylene resin (Patent Document 4), and a composition composed of a polylactic acid resin and an ABS resin (Patent Document).
- Patent Document 4 a composition composed of a polylactic acid resin and an ABS resin
- Patent Document 5 there is no example added to the composition consisting of PET resin and ABS resin to improve compatibility and provide good surface gloss.
- An object of the present invention is to provide a thermoplastic resin composition including a styrene-based resin and a polyethylene terephthalate resin, which is excellent in mechanical properties and surface glossiness, and a molded product thereof, by eliminating the above-described drawbacks of the prior art.
- the present invention relates to a thermoplastic resin composition and a molded product thereof as described in the following (1) to (7).
- (1) 0.01 to 1 part by weight of an acrylic / styrene copolymer (III) containing an epoxy group with respect to 100 parts by weight of a resin composition comprising a styrene resin (I) and a polyethylene terephthalate resin (II)
- a thermoplastic resin composition 0.01 to 1 part by weight of an acrylic / styrene copolymer (III) containing an epoxy group with respect to 100 parts by weight of a resin composition comprising a styrene resin (I) and a polyethylene terephthalate resin (II)
- a thermoplastic resin composition A thermoplastic resin composition.
- (2) The thermoplastic resin composition according to (1), wherein the acrylic / styrene copolymer (III) containing an epoxy group has a weight average molecular weight of 2,000 to 20,000.
- thermoplastic resin according to (1) or (2) wherein the epoxy value of the acrylic / styrene copolymer (III) containing an epoxy group is 0.5 to 4.0 (meq / g) Composition.
- Styrenic resin (I) is added to rubbery polymer (a), aromatic vinyl monomer (b), vinyl cyanide monomer (c) and other vinyl resins that can be copolymerized.
- Graft copolymer (A) obtained by graft copolymerization of at least one monomer selected from monomers (d), aromatic vinyl monomer (b), vinyl cyanide monomer ( A vinyl (co) polymer (B) obtained by polymerizing at least one monomer selected from c) and other copolymerizable vinyl monomers (d) is used at a weight ratio of 10:90.
- (7) A molded product obtained by molding the thermoplastic resin composition according to any one of (1) to (6).
- thermoplastic resin composition containing a styrene resin and a polyethylene terephthalate resin excellent in mechanical properties and surface gloss and a molded product thereof can be obtained.
- the styrene resin (I) in the present invention is selected from aromatic vinyl monomers (b), vinyl cyanide monomers (c), and other copolymerizable vinyl monomers (d).
- the styrene resin (I) is a vinyl (co) polymer (B) added with a rubber polymer (a), the vinyl (co) polymer (B) and the rubber polymer (a ) From the viewpoint of compatibility of the rubbery polymer (a), the aromatic vinyl monomer (b), the vinyl cyanide monomer (c) and other copolymerizable vinyl monomers.
- a graft copolymer (A) obtained by graft copolymerization of at least one monomer selected from the body (d), an aromatic vinyl monomer (b), a vinyl cyanide monomer (c) And a vinyl (co) polymer (B) comprising at least one monomer selected from other vinyl monomers (d) capable of copolymerization.
- the monomer mixture blended in the graft copolymer (A) does not have to be all grafted by bonding to the rubber polymer (a). They may be bonded together and included as an ungrafted polymer.
- the graft ratio is preferably 10 to 100%, more preferably 20 to 50%.
- the amount of the rubbery polymer (a) used in the graft copolymer (A) is not particularly limited, but is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, and still more preferably 35 to 65 parts by weight. Parts by weight.
- the amount of the monomer mixture in the graft copolymer (A) is preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight, and still more preferably 35 to 65 parts by weight.
- the ratio of the monomer mixture to be blended with the graft copolymer (A) is not particularly limited, but the aromatic vinyl monomer (b) is 20 to 99% by weight, the vinyl cyanide monomer.
- the body (c) is preferably used in an amount of 1 to 40% by weight, and the other vinyl monomer (d) copolymerizable therewith is preferably used in an amount of 0 to 79% by weight. Good impact resistance and molding Workability can be obtained.
- the ratio of the monomer mixture to be blended with the vinyl (co) polymer (B) is not particularly specified, but preferably 20 to 99% by weight of the aromatic vinyl monomer (b), vinyl cyanide It is preferable to use the monomer (c) in an amount of 1 to 40% by weight, and other vinyl monomers (d) copolymerizable with these monomers in an amount of 0 to 79% by weight. Good impact resistance and molding Workability can be obtained.
- the mixing ratio of the graft copolymer (A) and the vinyl-based (co) polymer (B) is preferably such that the weight ratio of (A) :( B) is 10:90 to 50:50. More preferably, it is 20:80 to 40:60.
- the proportion of the graft copolymer (A) is less than the above range or the proportion of the vinyl (co) polymer (B) exceeds the above range, the impact strength tends to decrease.
- the ratio of the graft copolymer (A) exceeds the above range, the fluidity tends to decrease.
- the reduced viscosity ( ⁇ sp / c) of the acetone-soluble component of the graft copolymer (A) is not particularly limited, but is preferably 0.1 to 0.6 dl / g. In other cases, the impact resistance is lowered, or the melt viscosity is increased and the moldability tends to be deteriorated. More preferably, it is 0.3 to 0.5 dl / g.
- the reduced viscosity ( ⁇ sp / c) of the vinyl (co) polymer (B) is not particularly limited, but is preferably 0.1 to 0.6 dl / g. In other cases, the impact resistance is lowered, or the melt viscosity is increased and the moldability tends to be deteriorated. More preferably, it is 0.3 to 0.5 dl / g.
- the rubbery polymer (a) is not particularly limited, but diene rubber, acrylic rubber, ethylene rubber and the like can be used. Specific examples include polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl methacrylate), poly (butyl acrylate-methyl methacrylate). ), Poly (butadiene-ethyl acrylate), ethylene-propylene rubber, ethylene-propylene-diene rubber, poly (ethylene-isoprene), poly (ethylene-methyl acrylate), and the like.
- rubbery polymers (a) are used in one kind or a mixture of two or more kinds.
- polybutadiene poly (butadiene-styrene), poly (butadiene-acrylonitrile), and ethylene-propylene rubber are preferably used in terms of impact resistance.
- the weight average particle diameter of the rubber polymer (a) is not particularly limited, but is preferably 0.1 to 0.5 ⁇ m from the viewpoint of the mechanical strength such as impact resistance and the balance of the appearance of the molded product. If the thickness is less than 0.1 ⁇ m, the impact strength of the resulting thermoplastic composition may be reduced, and if it exceeds 0.5 ⁇ m, the appearance of the molded product is often reduced. More preferably, it is 0.15 to 0.4 ⁇ m.
- the aromatic vinyl monomer (b) used for the graft copolymer (A) and the vinyl (co) polymer (B) is not particularly limited, but specific examples include styrene, ⁇ -methylstyrene, orthomethyl. Examples thereof include styrene, paramethyl styrene, para-t-butyl styrene, and halogenated styrene, and one or more can be used. Of these, styrene and ⁇ -methylstyrene are preferable, and styrene is particularly preferable.
- the vinyl cyanide monomer (c) used for the graft copolymer (A) and the vinyl (co) polymer (B) is not particularly limited, and specific examples include acrylonitrile and methacrylonitrile. 1 type (s) or 2 or more types can be used. Of these, acrylonitrile is preferable in terms of impact resistance.
- the other copolymerizable vinyl monomer (d) used in the graft copolymer (A) and the vinyl (co) polymer (B) is not particularly limited, but specific examples include (meth) acrylic acid. Methyl, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic acid Unsaturated carboxylic acid esters such as cyclohexyl, chloromethyl (meth) acrylate and 2-chloroethyl (meth) acrylate, maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, and maleic acid Instead of unsaturated dicarboxylic acid anhydrides such as saturated dicarboxylic acid and maleic anhydride, and unsaturated
- the method for producing the graft copolymer (A) or the vinyl (co) polymer (B) is not particularly limited, and any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like may be used.
- the method for charging the monomer is not particularly limited, and any method of initial batch charging, continuous charging of part or all of the monomer, or partial charging of part or all of the monomer may be used.
- styrene resin (I) used in the present invention include, for example, polystyrene, high impact polystyrene (HIPS), AS resin, AAS resin, AES resin, ABS resin, MAS resin, MABS resin, MBS resin, An alloy of these resins with other resins can be used.
- HIPS high impact polystyrene
- AS resin AS resin
- AAS resin AES resin
- ABS resin ABS resin
- MAS resin MAS resin
- MABS resin MABS resin
- MBS resin MBS resin
- An alloy of these resins with other resins can be used.
- the polyethylene terephthalate resin (II) in the present invention refers to a high molecular weight thermoplastic polyester resin having an ester bond in the main chain, using terephthalic acid as an acid component and ethylene glycol as a glycol component.
- isophthalic acid, adipic acid, oxalic acid, etc. as glycol components, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, Cyclohexanedimethanol, cyclohexanediol, or the like, or a long chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like can be used at 20 mol% or less. .
- the polyethylene terephthalate resin (II) in the present invention may be a virgin material that has not been subjected to a thermal history such as molding, and is also abbreviated as a recycled material (hereinafter referred to as a recycled material) of a polyethylene terephthalate resin molded product.
- a recycled material hereinafter referred to as a recycled material
- recycled materials include waste materials obtained by collecting molded products molded into PET bottles at least once, and scrap materials generated in the trimming process when molding sheet-shaped products.
- Specific examples of the shape include flakes, powders, or repellets for removing foreign substances.
- the recycled material is preferably one in which a reinforcing material such as glass fiber is not mixed.
- the weight ratio of the styrene resin (I) and the polyethylene terephthalate resin (II) in the resin composition comprising the styrene resin (I) and the polyethylene terephthalate resin (II) in the present invention is not particularly limited, the effects of the present invention are exhibited.
- the styrene-based resin (I) and the polyethylene terephthalate resin (II) are preferably in a weight ratio of 50:50 to 99: 1, more preferably 100 parts by weight.
- the weight ratio is 55:45 to 90:10.
- the production method of the acrylic / styrene copolymer (III) containing an epoxy group in the present invention is not particularly limited.
- (Meth) acrylic acid in the copolymer after copolymerizing a monomer having no group and styrene, or copolymerizing a monomer having no epoxy group such as (meth) acrylic acid and styrene A method of adding an alcohol having an epoxy group to the carboxyl group of the unit by a condensation reaction is exemplified.
- Examples of the (meth) acrylic ester monomer having an epoxy group that can be used when an acrylic / styrene copolymer (III) having an epoxy group is produced by copolymerization include glycidyl methacrylate and glycidyl acrylate. Is preferred.
- the monomer having no epoxy group such as (meth) acrylic acid
- (meth) acrylic acid examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( N-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate and 2-chloroethyl (meth) acrylate, etc.
- (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate are preferably used. These may be used alone or in combination of two or more.
- the weight average molecular weight of the acrylic / styrene copolymer (III) containing an epoxy group is preferably from 2,000 to 20,000, from the viewpoint of fluidity and suppression of bleeding out, and preferably from 5,000 to 15, 000 is more preferable.
- the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
- the epoxy value of the acrylic / styrene copolymer (III) containing an epoxy group is preferably 0.5 to 4.0 (meq / g) from the viewpoint of mechanical strength and surface gloss. 0 to 3.5 (meq / g) is more preferable.
- the epoxy value here is a value measured by the hydrochloric acid-dioxane method.
- the polymerization method of the acrylic / styrene copolymer (III) containing an epoxy group is not particularly limited, and known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used.
- the method of continuous bulk polymerization at a high temperature of 150 ° C. or higher and under a pressurized condition (preferably 1 MPa or higher) in a short time (preferably 5 to 30 minutes) has a high polymerization rate and contains impurities and sulfur. It is more preferable from the viewpoint of not using a causative polymerization initiator, chain transfer agent and solvent.
- the blending amount of the acrylic / styrene copolymer (III) containing an epoxy group used in the present invention is 0.01 with respect to 100 parts by weight of the resin composition comprising the styrene resin (I) and the polyethylene terephthalate resin (II). To 1 part by weight, preferably 0.03 to 0.7 part by weight, more preferably 0.05 to 0.5 part by weight. If the added amount of the acrylic / styrene copolymer (III) containing an epoxy group is less than the above range, the mechanical strength is not sufficient, and conversely, if it exceeds the above range, the surface gloss of the thermoplastic resin composition obtained. This is not preferable because the tendency to deteriorate the property is invited.
- thermoplastic resin composition of the present invention is characterized by having excellent surface gloss by blending (I) to (III).
- the surface gloss referred to here is evaluated by numerical values measured in accordance with the provisions of JIS Z 8741 (1997), as described in Patent Document 4 (Japanese Patent Laid-Open No. 2005-200534).
- the surface property (evaluation of shading) is different in evaluation contents. Since the thermoplastic resin composition of the present invention has a surface gloss of 90 or more, preferably 95 or more, it can be preferably used as an appearance product.
- thermoplastic resin composition of the present invention includes polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6 and nylon 66, polybutylene terephthalate and polycyclohexanedimethyl terephthalate as long as the object of the present invention is not impaired. You may mix
- thermoplastic resin composition of the present invention may further include glass fiber, glass powder, glass bead, glass flake, alumina, alumina fiber, carbon fiber, graphite fiber as long as it does not impair the purpose of the present invention.
- Antioxidants such as sulfur-containing compounds or phosphorus-containing organic compounds, heat stabilizers such as phenols and acrylates, UV absorbers such as benzotriazoles, benzophenones, and salicylates, hindered amine light stabilizers, higher fatty acids And acid esters and acid amides
- Lubricants and plasticizers such as higher alcohols, montanic acid and salts thereof, esters thereof, half esters thereof, release agents such as stearyl alcohol, stearamide and ethylene wax, various flame retardants
- the method for producing the thermoplastic resin composition of the present invention is not particularly limited, and (I) to (III) and other components described above may be mixed with a mixer such as a V-type blender, a super mixer, a super floater, and a Henschel mixer. However, in many cases, it is usually a mixture obtained by uniformly melting and mixing the premix. Such a mixture can be obtained by using a kneading means for the preliminary mixture, for example, melt-kneading at a temperature of preferably about 230 to 300 ° C., more preferably about 250 to 285 ° C., and pelletizing.
- melt-kneading and pelletizing means include a method in which a resin composition is melted and extruded using various melt mixers, for example, a kneader, a single-screw or twin-screw extruder, and pelletized by a pelletizer. It is done.
- thermoplastic resin composition of the present invention obtained by the above is molded by known methods used for molding thermoplastic resins such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding and gas assist molding.
- the molding method itself is not particularly limited.
- Weight average rubber particle diameter It was determined by the sodium alginate method described in “Rubber Age Vol. 88 p. 484-490 (1960) by E. Schmidt, PH Biddison”. That is, utilizing the fact that the diameter of the polybutadiene particles to be creamed differs depending on the concentration of sodium alginate, the particle size of 50% cumulative weight fraction was determined from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration.
- Charpy impact strength was measured under the conditions of V notch (remaining width 8.0 mm), 23 ° C., and 50% RH, in accordance with ISO 179 (2000).
- the graft ratio of this styrene-based graft copolymer (A) was 35%, and the reduced viscosity ⁇ sp / c of the acetone-soluble component was 0.35 dl / g.
- a monomer mixture comprising 70.0 parts by weight of styrene, 30.0 parts by weight of acrylonitrile, 0.15 parts by weight of n-octyl mercaptan and 0.01 parts by weight of 1,1-di (t-butylperoxy) cyclohexane was continuously fed to the polymerization tank at 150 kg / hour, and continuous bulk polymerization was performed while maintaining the polymerization temperature at 130 ° C. and the internal pressure of 0.08 MPa. The polymerization rate of the polymerization reaction mixture at the exit from the polymerization vessel was controlled between 74 and 76%.
- Unreacted monomer was recovered by distillation under reduced pressure from the vent port using a twin-screw extruder type demonomer machine, and the resulting polymerization reaction product was discharged into a strand with an apparent polymerization rate of 99% or more and pelleted by a cutter.
- the vinyl (co) polymer (B) was obtained.
- the vinyl (co) polymer (B) had a reduced viscosity ⁇ sp / c of 0.53 dl / g.
- Polyethylene terephthalate resin (II) Polyethylene terephthalate resin (II) -1 Recycled pellets of polyethylene terephthalate resin (manufactured by Kyoei Sangyo Co., Ltd.) were prepared.
- Polyethylene terephthalate resin (II) -2 Virgin pellets of polyethylene terephthalate resin were prepared TSB900 (Toray Industries, Inc.) having an intrinsic viscosity of 0.90 measured at 25 ° C. using an o-chlorophenol solvent.
- Acrylic / styrene copolymer containing glycidyl methacrylate, (meth) acrylic acid and styrene as monomer units and having an epoxy group having a weight average molecular weight of 7,000 and an epoxy value of 3.5 meq / g (trade name: Jonkrill ADR-4368, manufactured by Johnson Polymer Co., Ltd.) was prepared.
- Table 1 shows the graft copolymer (A), vinyl (co) polymer (B), polyethylene terephthalate resin (II), and acrylic / styrene copolymer (III) containing an epoxy group shown in Reference Examples.
- a multi-purpose test piece A type (total length 150 mm, test portion width 10 mm, thickness 4 mm) was molded, and tensile strength, tensile elongation, and Charpy impact strength were measured.
- a square plate molded product (thickness 3 mm) was also molded and used for measuring the surface gloss.
- Table 2 shows the graft copolymer (A), vinyl (co) polymer (B), polyethylene terephthalate resin (II), and acrylic / styrene copolymer (III) containing an epoxy group shown in Reference Examples.
- the mixture was mixed at the indicated blending ratio, and a pellet-shaped thermoplastic resin composition was produced in the same manner as in the example.
- an acrylonitrile / styrene copolymer (IV) containing an epoxy group was used in a blending ratio shown in Table 2 instead of the acrylic / styrene copolymer (III) containing an epoxy group. used.
- each physical property was measured according to Examples 1 to 6.
- thermoplastic resin compositions (Examples 1 to 6) of the present invention were all excellent in balance of mechanical strength and surface gloss.
- Comparative Example 1 the acrylic / styrene copolymer (III) containing an epoxy group was not added, and the mechanical strength was inferior to Examples 2, 4 and 5, respectively.
- Comparative Examples 3 and 4 the addition amount of the acrylic / styrene copolymer (III) containing an epoxy group was large, and the surface glossiness was inferior compared with Examples 2 and 6, respectively.
- Comparative Example 2 the blending ratio of polyethylene terephthalate resin (II) was large, and the mechanical strength was inferior to Examples 1 to 3, respectively.
- Comparative Example 5 acrylonitrile / styrene copolymer (IV) containing an epoxy group was used in place of the acrylic / styrene copolymer (III) containing an epoxy group. Compared to 5, the surface gloss was inferior.
- Table 3 shows the graft copolymer (A), vinyl (co) polymer (B), polyethylene terephthalate resin (II), and acrylic / styrene copolymer (III) containing an epoxy group shown in Reference Examples.
- the mixture was mixed at the indicated blending ratio, and a pellet-shaped thermoplastic resin composition was produced in the same manner as in the above-described example.
- an acrylonitrile / styrene copolymer (IV) containing an epoxy group was used in a blending ratio shown in Table 3 instead of the acrylic / styrene copolymer (III) containing an epoxy group. used.
- each physical property was measured according to the said Example.
- thermoplastic resin compositions of the present invention were both excellent in mechanical strength and surface gloss.
- Comparative Example 6 the acrylic / styrene copolymer (III) containing an epoxy group was not added, and the mechanical strength was inferior to Examples 7 and 8, respectively.
- Comparative Example 7 an acrylonitrile / styrene copolymer (IV) containing an epoxy group was used instead of the acrylic / styrene copolymer (III) containing an epoxy group. The surface gloss was inferior compared.
- thermoplastic resin composition of the present invention is excellent in mechanical properties and surface glossiness, it is used for various applications such as electrical and electronic parts, automobile parts, mechanical mechanism parts, OA equipment, housings for home appliances, and parts thereof. be able to.
- Audio equipment parts such as Kutto disk, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copying machines
- Various parts such as related parts, cleaning jigs, oilless bearings, stern bearings
- Optical equipment, precision machinery-related parts alternator terminals, alternator connectors, IC regulators, various valves such as exhaust gas valves, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant Joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve Brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor parts, dust distributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils , Fuse connector, horn terminal, electrical component insulation plate, step motor rotor , Lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and the like, which are extremely useful for these various applications.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
(1)スチレン系樹脂(I)およびポリエチレンテレフタレート樹脂(II)からなる樹脂組成物100重量部に対し、エポキシ基を含有するアクリル・スチレン系共重合体(III)を0.01~1重量部含む、熱可塑性樹脂組成物。
(2)エポキシ基を含有するアクリル・スチレン系共重合体(III)の重量平均分子量が2,000~20,000である、(1)に記載の熱可塑性樹脂組成物。
(3)エポキシ基を含有するアクリル・スチレン系共重合体(III)のエポキシ価が0.5~4.0(meq/g)である、(1)または(2)に記載の熱可塑性樹脂組成物。
(4)スチレン系樹脂(I)およびポリエチレンテレフタレート樹脂(II)の重量比が50:50~99:1である、(1)~(3)のいずれかに記載の熱可塑性樹脂組成物。
(5)スチレン系樹脂(I)が、ゴム質重合体(a)に、芳香族ビニル系単量体(b)、シアン化ビニル系単量体(c)および共重合可能なその他のビニル系単量体(d)から選ばれた1種以上の単量体をグラフト共重合せしめたグラフト共重合体(A)ならびに芳香族ビニル系単量体(b)、シアン化ビニル系単量体(c)および共重合可能なその他のビニル系単量体(d)から選ばれた1種以上の単量体を重合してなるビニル系(共)重合体(B)を、重量比10:90~50:50の割合で含む組成物である、(1)~(4)のいずれかに記載の熱可塑性樹脂組成物。
(6)ポリエチレンテレフタレート樹脂(II)としてポリエチレンテレフタレート樹脂成形品のリサイクル材を全部または一部使用する、(1)~(5)のいずれかに記載の熱可塑性樹脂組成物。
(7)(1)~(6)のいずれかに記載の熱可塑性樹脂組成物を成形してなる、成形品。
「Rubber Age Vol.88 p.484~490(1960)by E.Schmidt, P.H.Biddison」記載のアルギン酸ナトリウム法によって求めた。すなわち、アルギン酸ナトリウムの濃度によりクリーム化するポリブタジエン粒子径が異なることを利用して、クリーム化した重量割合とアルギン酸ナトリウム濃度の累積重量分率より累積重量分率50%の粒子径を求めた。
グラフト共重合体所定量(m)にアセトンを加え、3時間還流し、この溶液を8800r/min(10000G)で40分間遠心分離後、不溶分を濾取し、この不溶分を60℃で5時間減圧乾燥し、重量(n)を測定した。グラフト率は、下記式より算出した。
グラフト率(%)={[(n)-(m)×L]/[(m)×L]}×100
ここで、Lはグラフト共重合体のゴム含有率である。
サンプル1gにアセトン200mlを加え、3時間還流し、この溶液を8800r/min(10000G)で40分間遠心分離した後、不溶分を濾過する。濾液をロータリーエバポレーターで濃縮し、析出物(アセトン可溶分)を60℃で5時間減圧乾燥後、0.4g/100ml(メチルエチルケトン、30℃)に調整し、ウベローデ粘度計を用い[ηsp/c]を測定した。
サンプル1gをジクロロメタン100cm3に均一溶解させ、ウベローデ粘度計を用い比粘度[ηsp]を測定した。更に濃度を変えて同様に比粘度を測定し、濃度[c]と[ηsp/c]とをプロットしたグラフを濃度ゼロ側へ外挿した値を極限粘度[η]とした。即ち、η=limηsp/c(c→0)より算出した。
ISO 527(1993年)の規定に準拠し、速度50mm/min、23℃、50%RHの条件で測定した。
ISO 179(2000年)の規定に準拠し、Vノッチ入り(残り幅8.0mm)、23℃、50%RHの条件で測定した。
JIS Z 8741(1997年)の規定に準拠し、入射角および反射角が60°の条件で測定した。
窒素置換した反応器に、純水120重量部、ブドウ糖0.5重量部、ピロリン酸ナトリウム0.5重量部、硫酸第一鉄0.005重量部およびポリブタジエンラテックス(重量平均ゴム粒子径0.3μm、ゲル含有率85%)60重量部(固形分換算)を仕込み、撹拌しながら反応器内の温度を65℃に昇温した。内温が65℃に達した時点を重合開始としてモノマー(スチレン30重量部およびアクリロニトリル10重量部)およびt-ドデシルメルカプタン0.3重量部からなる混合物を5時間かけて連続滴下した。同時に並行してクメンハイドロパーオキサイド0.25重量部、オレイン酸カリウム2.5重量部および純水25重量部からなる水溶液を7時間かけて連続滴下し、反応を完結させた。得られたスチレン系共重合体ラテックスを硫酸で凝固し、苛性ソーダで中和した後、洗浄、濾過、乾燥してグラフト共重合体(A)を得た。このスチレン系グラフト共重合体(A)のグラフト率は35%、アセトン可溶分の還元粘度ηsp/cは0.35dl/gであった。
単量体蒸気の蒸発還流用コンデンサーおよびヘリカルリボン翼を有する2m3の完全混合型重合槽と、単軸押出機型予熱機と、2軸押出機型脱モノマー機および脱モノマー機の先端から1/3長のバレル部にタンデムに接続した加熱装置を有する2軸押出機型フィーダーとからなる連続式塊状重合装置を用いて、次のように、共重合と樹脂成分の混合を実施した。
ポリエチレンテレフタレート樹脂(II)-1
ポリエチレンテレフタレート樹脂のリサイクルペレット(協栄産業株式会社製)を準備した。
ポリエチレンテレフタレート樹脂のバージンペレットは、o-クロロフェノール溶媒を用いて25℃で測定した固有粘度が0.90であるTSB900(東レ株式会社製)を準備した。
エポキシ基を含有したアクリル・スチレン系共重合体(III)-1
モノマー単位としてグリシジルメタクリレート、(メタ)アクリル酸およびスチレンを含有する、重量平均分子量が11,000、エポキシ価が1.8meq/gのエポキシ基を含有したアクリル・スチレン系共重合体(商品名:ARUFON UG-4035、東亞合成株式会社製)を準備した。
モノマー単位としてグリシジルメタクリレート、(メタ)アクリル酸およびスチレンを含有する、重量平均分子量が7,000、エポキシ価が3.5meq/gのエポキシ基を含有したアクリル・スチレン系共重合体(商品名:ジョンクリル ADR-4368、ジョンソンポリマー社製)を準備した。
スチレン73重量部、アクリロニトリル26重量部、グリシジルメタクリレート1重量部を懸濁重合して、ビーズ状のエポキシ基を含有したアクリロニトリル・スチレン共重合体を得た。
参考例で示したグラフト共重合体(A)、ビニル系(共)重合体(B)、ポリエチレンテレフタレート樹脂(II)、エポキシ基を含有するアクリル・スチレン系共重合体(III)を表1に示した配合比で混合し、ベント付30mm二軸押出機を用いシリンダー設定温度260℃で溶融混練、押出しを行うことによって、ペレット状の熱可塑性樹脂組成物を製造し、得られた熱可塑性樹脂組成物を105℃熱風乾燥機中で5時間予備乾燥し、住友重機械工業社製電動射出成形機SE50を用いシリンダー温度260℃、金型温度60℃でISO 3167 (2002年)で規定された多目的試験片A形(全長150mm、試験部の幅10mm、厚さ4mm)について成形し、引張強度、引張伸度、シャルピー衝撃強度を測定した。また、角板成形品(厚さ3mm)についても成形し、表面光沢性の測定に用いた。
参考例で示したグラフト共重合体(A)、ビニル系(共)重合体(B)、ポリエチレンテレフタレート樹脂(II)、エポキシ基を含有するアクリル・スチレン系共重合体(III)を表2に示した配合比で混合し、実施例と同様の方法でペレット状の熱可塑性樹脂組成物を製造した。また、比較例5においては、エポキシ基を含有するアクリル・スチレン系共重合体(III)の代わりに、エポキシ基を含有するアクリロニトリル・スチレン共重合体(IV)を表2に記載の配合比で使用した。得られた熱可塑性樹脂組成物については実施例1~6に準じて各物性を測定した。
参考例で示したグラフト共重合体(A)、ビニル系(共)重合体(B)、ポリエチレンテレフタレート樹脂(II)、エポキシ基を含有するアクリル・スチレン系共重合体(III)を表3に示した配合比で混合し、前記実施例と同様の方法でペレット状の熱可塑性樹脂組成物を製造した。また、比較例7においては、エポキシ基を含有するアクリル・スチレン系共重合体(III)の代わりに、エポキシ基を含有するアクリロニトリル・スチレン共重合体(IV)を表3に記載の配合比で使用した。得られた熱可塑性樹脂組成物については前記実施例に準じて各物性を測定した。
Claims (7)
- スチレン系樹脂(I)およびポリエチレンテレフタレート樹脂(II)からなる樹脂組成物100重量部に対し、エポキシ基を含有するアクリル・スチレン系共重合体(III)を0.01~1重量部含む、熱可塑性樹脂組成物。
- エポキシ基を含有するアクリル・スチレン系共重合体(III)の重量平均分子量が2,000~20,000である、請求項1に記載の熱可塑性樹脂組成物。
- エポキシ基を含有するアクリル・スチレン系共重合体(III)のエポキシ価が0.5~4.0(meq/g)である、請求項1または2に記載の熱可塑性樹脂組成物。
- スチレン系樹脂(I)およびポリエチレンテレフタレート樹脂(II)の重量比が50:50~99:1である、請求項1~3のいずれかに記載の熱可塑性樹脂組成物。
- スチレン系樹脂(I)が、ゴム質重合体(a)に、芳香族ビニル系単量体(b)、シアン化ビニル系単量体(c)および共重合可能なその他のビニル系単量体(d)から選ばれた1種以上の単量体をグラフト共重合せしめたグラフト共重合体(A)ならびに芳香族ビニル系単量体(b)、シアン化ビニル系単量体(c)および共重合可能なその他のビニル系単量体(d)から選ばれた1種以上の単量体を重合してなるビニル系(共)重合体(B)を、重量比10:90~50:50の割合で含む組成物である、請求項1~4のいずれかに記載の熱可塑性樹脂組成物。
- ポリエチレンテレフタレート樹脂(II)としてポリエチレンテレフタレート樹脂成形品のリサイクル材を全部または一部使用する、請求項1~5のいずれかに記載の熱可塑性樹脂組成物。
- 請求項1~6のいずれかに記載の熱可塑性樹脂組成物を成形してなる、成形品。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147018361A KR101949555B1 (ko) | 2012-02-29 | 2013-02-28 | 열가소성 수지 조성물 및 그 성형품 |
JP2013511430A JP5565523B2 (ja) | 2012-02-29 | 2013-02-28 | 熱可塑性樹脂組成物およびその成形品 |
CN201380009742.4A CN104114635B (zh) | 2012-02-29 | 2013-02-28 | 热塑性树脂组合物及其成型品 |
PH12014501843A PH12014501843A1 (en) | 2012-02-29 | 2014-08-15 | Thermoplastic resin composition and molded article of same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012043706 | 2012-02-29 | ||
JP2012-043706 | 2012-02-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013129547A1 true WO2013129547A1 (ja) | 2013-09-06 |
Family
ID=49082739
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/055329 WO2013129547A1 (ja) | 2012-02-29 | 2013-02-28 | 熱可塑性樹脂組成物およびその成形品 |
Country Status (7)
Country | Link |
---|---|
JP (1) | JP5565523B2 (ja) |
KR (1) | KR101949555B1 (ja) |
CN (1) | CN104114635B (ja) |
MY (1) | MY167375A (ja) |
PH (1) | PH12014501843A1 (ja) |
TW (1) | TW201343763A (ja) |
WO (1) | WO2013129547A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024010749A1 (en) * | 2022-07-06 | 2024-01-11 | Kaneka Americas Holding, Inc. | Modifiers for polyesters that improve viscosity in melt |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016132718A (ja) * | 2015-01-19 | 2016-07-25 | 富士ゼロックス株式会社 | 樹脂組成物及び樹脂成形体 |
CA3035496A1 (en) * | 2016-09-01 | 2018-03-08 | Techno-Umg Co., Ltd. | Epoxy-modified vinyl copolymer, thermoplastic resin composition including said copolymer, and shaped article of said composition |
EP3369797B1 (en) * | 2017-03-02 | 2021-01-06 | EKWB d.o.o. | Cooling liquid composition for a liquid cooling system for cooling a heat generating element arranged on a printed circuit board |
KR20190055573A (ko) * | 2017-11-15 | 2019-05-23 | 에스케이케미칼 주식회사 | 폴리아미드 수지 조성물 및 이를 포함하는 수지 성형품 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62285947A (ja) * | 1986-06-04 | 1987-12-11 | Toray Ind Inc | ポリエステル樹脂組成物 |
JPH05320487A (ja) * | 1992-05-22 | 1993-12-03 | Sumitomo Bakelite Co Ltd | 熱可塑性樹脂組成物 |
JPH07292183A (ja) * | 1994-04-28 | 1995-11-07 | Daicel Chem Ind Ltd | 易引裂き性フィルムおよびその製造方法 |
JP2001139782A (ja) * | 1999-11-11 | 2001-05-22 | Aron Kasei Co Ltd | ポリエステル樹脂組成物 |
JP2003286382A (ja) * | 2002-03-28 | 2003-10-10 | Toray Ind Inc | シート状樹脂およびそれからなる成形品 |
JP2005200534A (ja) * | 2004-01-15 | 2005-07-28 | Fukuvi Chem Ind Co Ltd | 成形材料用樹脂組成物 |
JP2012017451A (ja) * | 2010-07-08 | 2012-01-26 | Chi Mei Corp | 相溶化剤を含むブレンドポリマー組成物 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH075814B2 (ja) | 1988-07-05 | 1995-01-25 | 東レ株式会社 | 繊維強化熱可塑性樹脂組成物 |
JP2004067728A (ja) | 2002-08-01 | 2004-03-04 | Umg Abs Ltd | ポリエチレンテレフタレート樹脂リサイクル材を活用した熱可塑性樹脂組成物 |
CN101238177B (zh) * | 2005-08-04 | 2012-12-26 | 东丽株式会社 | 树脂组合物和由该树脂组合物形成的成型品 |
JP2008106091A (ja) | 2006-10-23 | 2008-05-08 | Sumitomo Bakelite Co Ltd | ポリ乳酸含有樹脂組成物 |
-
2013
- 2013-02-27 TW TW102106813A patent/TW201343763A/zh unknown
- 2013-02-28 JP JP2013511430A patent/JP5565523B2/ja active Active
- 2013-02-28 KR KR1020147018361A patent/KR101949555B1/ko active IP Right Grant
- 2013-02-28 MY MYPI2014002377A patent/MY167375A/en unknown
- 2013-02-28 WO PCT/JP2013/055329 patent/WO2013129547A1/ja active Application Filing
- 2013-02-28 CN CN201380009742.4A patent/CN104114635B/zh active Active
-
2014
- 2014-08-15 PH PH12014501843A patent/PH12014501843A1/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62285947A (ja) * | 1986-06-04 | 1987-12-11 | Toray Ind Inc | ポリエステル樹脂組成物 |
JPH05320487A (ja) * | 1992-05-22 | 1993-12-03 | Sumitomo Bakelite Co Ltd | 熱可塑性樹脂組成物 |
JPH07292183A (ja) * | 1994-04-28 | 1995-11-07 | Daicel Chem Ind Ltd | 易引裂き性フィルムおよびその製造方法 |
JP2001139782A (ja) * | 1999-11-11 | 2001-05-22 | Aron Kasei Co Ltd | ポリエステル樹脂組成物 |
JP2003286382A (ja) * | 2002-03-28 | 2003-10-10 | Toray Ind Inc | シート状樹脂およびそれからなる成形品 |
JP2005200534A (ja) * | 2004-01-15 | 2005-07-28 | Fukuvi Chem Ind Co Ltd | 成形材料用樹脂組成物 |
JP2012017451A (ja) * | 2010-07-08 | 2012-01-26 | Chi Mei Corp | 相溶化剤を含むブレンドポリマー組成物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024010749A1 (en) * | 2022-07-06 | 2024-01-11 | Kaneka Americas Holding, Inc. | Modifiers for polyesters that improve viscosity in melt |
Also Published As
Publication number | Publication date |
---|---|
JP5565523B2 (ja) | 2014-08-06 |
KR20140133498A (ko) | 2014-11-19 |
PH12014501843B1 (en) | 2014-11-17 |
TW201343763A (zh) | 2013-11-01 |
CN104114635B (zh) | 2015-09-09 |
CN104114635A (zh) | 2014-10-22 |
KR101949555B1 (ko) | 2019-02-18 |
JPWO2013129547A1 (ja) | 2015-07-30 |
PH12014501843A1 (en) | 2014-11-17 |
MY167375A (en) | 2018-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4788824B2 (ja) | 熱可塑性樹脂組成物の製造方法 | |
EP2231777B1 (en) | Chemical and impact resistant thermoplastic resin composition having improved extrudability. | |
JP5565523B2 (ja) | 熱可塑性樹脂組成物およびその成形品 | |
JP4600016B2 (ja) | 熱可塑性樹脂組成物およびその製造方法 | |
JP2012201857A (ja) | ポリブチレンテレフタレート樹脂組成物及びこれを用いた樹脂成形品 | |
CN104169361A (zh) | 热塑性树脂组合物及其模制形式 | |
WO2013125495A1 (ja) | 熱可塑性樹脂組成物および成形品 | |
KR101924672B1 (ko) | 스티렌 공중합체를 포함하는 내후성 폴리에스테르 성형 화합물 | |
US8889769B2 (en) | Weathering-resistant polyester molding compositions with styrene copolymers | |
JP6464746B2 (ja) | 熱可塑性樹脂組成物およびその製造方法 | |
JP2001139742A (ja) | 難燃性樹脂組成物、その製造方法および成形品 | |
JP6354162B2 (ja) | 難燃性熱可塑性樹脂組成物 | |
JP2015042703A (ja) | 難燃性熱可塑性樹脂組成物およびその成形品 | |
JP2001200134A (ja) | 透明性樹脂組成物およびそれからなる成形品 | |
JP2011132523A (ja) | スチレン系樹脂組成物およびそれからなる成形品 | |
JP2002284816A (ja) | 耐熱性共重合体およびその製造方法 | |
JP2002128984A (ja) | 熱可塑性樹脂組成物 | |
JP2001059046A (ja) | 難燃性樹脂組成物、その製造方法および成形品 | |
JP4075355B2 (ja) | 耐熱性共重合体、耐熱性熱可塑性樹脂組成物、それからなる樹脂成形品および耐熱性共重合体の製造方法 | |
JP4296640B2 (ja) | 熱可塑性樹脂組成物および成形品 | |
JP2000351881A (ja) | 難燃性樹脂組成物及びその成形品 | |
JP2009068005A (ja) | 熱可塑性樹脂組成物およびそれからなる成形品 | |
JP2003313237A (ja) | 透明耐熱性共重合体、透明耐熱性樹脂組成物、および成形品 | |
JP2000336227A (ja) | 難燃性樹脂組成物、その製造方法および成形品 | |
JP2000336226A (ja) | 難燃性樹脂組成物、その製造方法および成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013511430 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13755393 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147018361 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12014501843 Country of ref document: PH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: IDP00201405498 Country of ref document: ID |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13755393 Country of ref document: EP Kind code of ref document: A1 |