JP4807005B2 - FDM or SLS thermoplastic resin composition and molding - Google Patents

Description

The present invention relates to the shaping thermoplastic resin composition and molded article according to FDM system or SLS method, particularly, granulated form thermoplastic resin composition for heat stability superior when forming shape in Japanese and the thermoplastic resin composition It relates to a shaped object consisting of objects.

  A system for directly modeling a three-dimensional shape input on a CAD (CAD) is called a rapid prototyping (RP) system, a rapid new manufacturing (RM) system or the like (hereinafter collectively referred to as “RP”). System "). In this RP system, in a temperature-controlled room (construction chamber) maintained at a predetermined temperature determined by the thermoplastic resin to be used, a method of melting and extruding a thermoplastic resin strand (FDM method), There is a method (SLS method) in which a thermoplastic resin powder is melt bonded and laminated.

Known thermoplastic resins include acrylonitrile-butadiene-styrene (ABS) resins, compositions composed of ABS resins and aromatic polycarbonate (PC) resins, and the like (for example, Patent Document 1).
JP-T-2004-532753

  However, in the FDM method and SLS method, when the ABS resin as described above is used as a modeling material, the temperature in the building chamber is 50 to 130 ° C, and depending on the model size, it takes a long time to build. There is a problem that the initial color tone of the material changes and the shaped object is colored yellow or brown.

An object of the present invention may be used in FDM method and SLS method, excellent thermal stability, provide a molded object made of colored occur such gastrostomy form thermoplastic resin composition of the shaped article and the thermoplastic resin composition There is to do.

  As a result of intensive studies, the present inventor has obtained the knowledge that the above object can be easily achieved by the thermoplastic resin composition having a specific composition, and has completed the present invention.

That is, the first gist of the present invention is the presence of at least one rubbery polymer (a) selected from the group consisting of ethylene-α / olefin copolymer rubber, acrylic rubber, hydrogenated rubber and silicone rubber. It consists of a copolymer (A) obtained by graft copolymerizing an aromatic vinyl compound (b) and a polymer (B) obtained by polymerizing the aromatic vinyl compound (b). The weight ratio of the polymer (A): the polymer (B) is 5 to 95:95 to 5, and the ratio of the rubbery polymer (a) to the total amount of the copolymer (A) and the polymer (B) is It exists in the thermoplastic resin composition for shaping | molding by the FDM system or SLS system characterized by being 15 to 70 weight%.

The second aspect of the present invention resides in shaped object made of a concrete form of the thermoplastic resin composition.

According to the present invention are used in FDM method and SLS method, molded article comprising a coloring occur such gastrostomy form thermoplastic resin composition of the shaped article and the thermoplastic resin composition is provided.
Is done.

Hereinafter, the present invention will be described in detail. Concrete form thermoplastic resin composition of the present invention, the rubbery polymer exists aromatic vinyl compound under (a) (b) a copolymer obtained by graft copolymerization (A) and the aromatic vinyl compound And a polymer (B) obtained by polymerizing (b).

<Copolymer (A)>
In the present invention, when producing the copolymer (A), the rubbery polymer (a) was selected from the group of ethylene-α / olefin copolymer rubber, acrylic rubber, hydrogenated rubber, and silicone rubber. Use at least one.

  As said ethylene-alpha * olefin type copolymer rubber, the single quantity which consists of a mixing ratio of ethylene / alpha-olefin of 3-20 carbon atoms / non-conjugated diene = 5-95 / 95-5 / 0-30% by weight A copolymer rubber obtained by copolymerizing the body is preferred.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-decene, Although dodecene etc. are mentioned, Preferably, it is propylene, 1-butene, 1-octene, More preferably, it is propylene. Two or more of these can be used in combination.

  The number of carbon atoms of the α-olefin is usually 3-20, preferably 3-12, and more preferably 3-8. When the number of carbon atoms exceeds 20, the copolymerizability is extremely lowered, which is not preferable. The weight ratio of ethylene and α · olefin is usually 5 to 95/95 to 5, preferably 60 to 88/40 to 12, more preferably 70 to 85/30 to 15.

  Examples of the non-conjugated diene include alkenyl norbornenes, cyclic dienes and aliphatic dienes, and 5-ethylidene-2-norbornene or dicyclopentadiene is preferable. Two or more of these can be used in combination. The content of the non-conjugated diene in the ethylene-α / olefin copolymer rubber is usually 0 to 30% by weight, preferably 0 to 15% by weight. In addition, the unsaturated group amount of said copolymer rubber is the range of 0-40 normally converted into an iodine value.

  In the production of the above ethylene-α / olefin copolymer rubber, either a heterogeneous or homogeneous catalyst may be used. Examples of the heterogeneous catalyst include a vanadium catalyst in which a vanadium compound and an organoaluminum compound are combined. In addition, examples of the homogeneous catalyst include a metallocene catalyst. In particular, a metallocene catalyst is effective when an α-olefin having 6 to 20 carbon atoms is used.

  The Mooney viscosity (ML1 + 4, 100 ° C.) of the ethylene-α / olefin copolymer rubber is usually 40 or less, preferably 25 to 35. The Mooney viscosity can be adjusted by changing the monomer concentration and reaction temperature in addition to the type and amount of the molecular weight regulator. In the ethylene-α / olefin copolymer rubber, the content of the component having a weight average molecular weight of 1,000,000 or more in terms of polystyrene is usually 10% by weight or less, preferably 8% by weight or less. Such a copolymer rubber can be produced by changing the type / amount of the molecular weight regulator and the type / amount of the catalyst. Furthermore, the glass transition temperature (Tg) of the ethylene-α / olefin copolymer rubber is usually −110 to −40 ° C., preferably −70 to −50 ° C., and the melting point (Tm) is usually 30 to 110 ° C., preferably Is 40-70 ° C.

  The acrylic rubber is a polymer of an alkyl acrylate having 2 to 8 carbon atoms in the alkyl group, and specific examples of the alkyl acrylate include ethyl acrylate, propyl acrylate, n-acrylate. Examples include butyl, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. Two or more of these can be used in combination. Preferred alkyl acrylates are (n-, i) -butyl acrylate or 2-ethylhexyl acrylate. A part of the alkyl acrylate ester can be substituted with another copolymerizable monomer up to 20% by weight. Examples of the other monomer include vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ester, alkyl methacrylate ester, methacrylic acid, acrylic acid, and styrene.

  In the acrylic rubber, it is preferable to select the kind of monomer and the amount of copolymerization so that the glass transition temperature of the rubbery polymer is −10 ° C. or lower. The acrylic rubber is preferably copolymerized with a crosslinkable monomer, and the amount of the crosslinkable monomer used is usually 0 to 10% by weight, preferably 0, as a proportion in the acrylic rubber. 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.

  Specific examples of the crosslinkable monomer include mono- or polyethylene glycol diacrylate such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Mono- or polyethylene glycol dimethacrylate such as ethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, diallyl maleate, diallyl succinate, triallyl triazine and other di- or triallyl compounds, allyl methacrylate, allyl acrylate, etc. Examples include allyl compounds and conjugated diene compounds such as 1,3-butadiene. It is. The acrylic rubber is produced by a known polymerization method, and a preferred polymerization method is an emulsion polymerization method.

  The hydrogenated rubber is a hydride of a conjugated diene rubbery polymer. Hydrogenated products of conjugated diene polymers such as hydrogenated products of conjugated diene polymers, hydrogenated products of random copolymers of conjugated dienes and aromatic vinyl compounds, etc. Preferably, it is a hydrogenated product of a butadiene-based polymer, a hydrogenated product of a block copolymer of a conjugated diene polymer block and an aromatic vinyl compound polymer block, or a block copolymer obtained by combining these. is there. Among these, the hydrogenated butadiene polymer includes a hydrogenated block copolymer comprising an aromatic vinyl compound polymer block and an aromatic vinyl compound-conjugated diene random copolymer block, and 1 in polybutadiene. , A hydrogenated block copolymer comprising a block having a 2-vinyl bond content of 20% by weight or less and a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight.

  The block copolymer comprising the conjugated diene polymer block and the aromatic vinyl compound polymer block includes AB type, ABA type, (AB) n type, (AB) nA type, taper type, radial teleblock. Includes types.

  As the aromatic vinyl compound used here, all of the aromatic vinyl compounds described later can be used, but styrene is preferred. Conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4 , 5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like, preferably 1,3-butadiene, isoprene or 1,3-pentadiene, more preferably 1, 3-Butadiene or isoprene.

  In the above hydrogenated rubber, the hydrogenation rate of the conjugated diene rubbery polymer is usually 90% or more. The number average molecular weight of the hydrogenated rubber is usually 30,000 to 1,000,000.

  As the silicone rubber, all those obtained by a known polymerization method can be used, but polyorganosiloxane rubbery polymer latex obtained in the form of latex by emulsion polymerization is preferable from the viewpoint of ease of graft polymerization.

  The latex of the above polyorganosiloxane rubbery polymer is obtained by a known method, for example, a method described in US Pat. Nos. 2,891,920 and 3,294,725. I can do it. For example, using a homomixer or an ultrasonic mixer, a method of shearing and mixing the organosiloxane and water in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid can be mentioned. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and also as a polymerization initiator. In this case, it is preferable to use an alkylbenzene sulfonic acid metal salt, an alkyl sulfonic acid metal salt, or the like in combination because it has an effect of maintaining a stable polymer during graft polymerization. If necessary, a graft crossing agent or a crosslinking agent may be co-condensed within a range not impairing the target performance of the present invention.

The organosiloxane used is, for example, the general formula R _m SiO _{(4-m) / 2} (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and m represents an integer of 0 to 3). ) And has a linear, branched or cyclic structure, preferably an organosiloxane having a cyclic structure. Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. I can do it.

  Specific examples of the organosiloxane include, in addition to cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane, linear or A branched organosiloxane can be mentioned. Two or more of these can be used in combination.

  The organosiloxane may be a polyorganosiloxane condensed in advance, for example, having a polystyrene-equivalent weight average molecular weight of about 500 to 10,000. Further, when the organosiloxane is a polyorganosiloxane, the molecular chain terminal may be blocked with, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, or a methyldiphenylsilyl group. Good.

  The graft crossing agent is, for example, a compound having both an unsaturated group and an alkoxysilyl group and represented by the following general formula.

In the above general formula, R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and n is preferably 0.

  Specific examples of the above compounds include p-vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinyl. Phenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, 1- ( p-vinylphenyl) -1,1-diphenyl-3-ethyl-3,3-diethoxydisiloxane, m-vinylphenyl- [3- (triethoxysilyl) propyl] diphenylsilane, [3- (p-iso Propenylbenzoylamino) propyl] phenyldipropoxysilane, 2- (m-vinylpheny E) ethylmethyldimethoxysilane, 2- (o-vinylphenyl) ethylmethyldimethoxysilane, 1- (p-vinylphenyl) ethylmethyldimethoxysilane, 1- (m-vinylphenyl) ethylmethyldimethoxysilane, 1- (o -Vinylphenyl) ethylmethyldimethoxysilane and the like, and mixtures thereof. Among these, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane are preferable, and p-vinylphenylmethyldimethoxysilane is preferred. Is more preferable.

  The proportion of the grafting agent used is generally 0 to 10 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 0.5 to 100 parts by weight based on 100 parts by weight of the total amount of the organosiloxane, the grafting agent and the crosslinking agent. 5 parts by weight. When the amount of the grafting agent used is large, the molecular weight of the grafted vinyl polymer is lowered, and as a result, sufficient impact resistance cannot be obtained. Further, oxidative deterioration is more likely to proceed than the double bond of the polyorganosiloxane rubber polymer after grafting, and a graft copolymer having good weather resistance cannot be obtained.

  The average particle size of the polyorganosiloxane rubbery polymer latex particles is usually 0.5 μm or less, preferably 0.4 μm or less, and more preferably 0.1 to 0.4 μm. This average particle diameter can be easily controlled by the amount of the above-mentioned emulsifier and water, the degree of dispersion when mixed using a homomixer or an ultrasonic mixer, or the organosiloxane charging method. When the average particle diameter of the latex particles exceeds 0.5 μm, the gloss is inferior.

  Moreover, the polystyrene conversion weight average molecular weight of the polyorganosiloxane rubber polymer obtained as described above is usually 30,000 to 1,000,000, preferably 50,000 to 300,000. If it is less than 30,000, the impact resistance of the obtained graft copolymer and the resin composition using this will be inferior. On the other hand, when it exceeds 1,000,000, the polymer chains are strongly entangled, so that the rubber elasticity of the rubber particles is lowered and the impact resistance is lowered.

  The weight average molecular weight can be easily adjusted by changing the condensation polymerization temperature and time when preparing the polyorganosiloxane rubber polymer. That is, the lower the condensation polymerization temperature and the longer the cooling time, the higher the molecular weight. Moreover, high molecular weight can also be achieved by adding a small amount of a crosslinking agent.

  The molecular chain terminal of the polyorganosiloxane rubber polymer may be blocked with, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, or a methyldiphenylsilyl group.

  The amount of the emulsifier used is usually 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the total amount of the organosiloxane, the grafting agent and the crosslinking agent. In addition, the usage-amount of the water in this case is 100-500 weight part normally with respect to 100 weight part of total amounts of organosiloxane, a graft crossing agent, and a crosslinking agent, Preferably it is 200-400 weight part. The condensation temperature is usually 5 to 100 ° C.

  In the production of the polyorganosiloxane rubber polymer, a crosslinking agent can be added as a third component in order to improve the impact resistance of the resulting graft copolymer. Examples of this crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. Two or more of these can be used in combination. Moreover, you may use the crosslinked prepolymer prepolymerized by condensation as these crosslinking agents. The addition amount of the crosslinking agent is usually 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of the organosiloxane, the grafting agent and the crosslinking agent. is there. If it exceeds 10 parts by weight, the flexibility of the polyorganosiloxane rubber-like polymer is impaired, so that the slidability and impact resistance are lowered.

  In the present invention, examples of the aromatic vinyl compound (b) include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p. -Aminoethyl styrene, N, N-diethyl-p-aminomethyl styrene, vinyl pyridine, vinyl xylene, monochloro styrene, dichloro styrene, monobromo styrene, dibromo styrene, tribromo styrene, fluoro styrene, vinyl naphthalene, etc. Styrene or α-methylstyrene is preferable. Two or more of these can be used in combination.

  In the present invention, other vinyl monomers (c) copolymerizable with the aromatic vinyl compound (b) can be used.

  Examples of the vinyl monomer (c) include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate Acrylates such as cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, Dodecyl methacrylate, Methacrylic acid esters such as tadecyl methacrylate, phenyl methacrylate, benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methyl Imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; epoxy groups such as glycidyl methacrylate and allyl glycidyl ether Contains unsaturated compounds; unsaturated carboxylic amides such as acrylamide and methacrylamide; amino groups such as acrylic amine, aminomethyl methacrylate, amino ether methacrylate, aminopropyl methacrylate, and aminostyrene Unsaturated compound; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1 -Hydroxyl-containing unsaturated compounds such as propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and hydroxystyrene; and oxazoline group-containing unsaturated compounds such as vinyl oxazoline. Two or more of these can be used in combination.

  The copolymer (A) can be obtained by a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these. The content of the rubbery polymer in the copolymer (A) is usually 3 to 80% by weight, preferably 5 to 65% by weight, and more preferably 5 to 50% by weight. The graft ratio of the copolymer (A) is usually 5 to 150% by weight. When the graft ratio is less than 5% by weight, the mechanical strength and appearance of the resin composition may be inferior. When the graft ratio exceeds 150% by weight, the mechanical strength of the resin composition may be inferior. Moreover, the intrinsic viscosity measured at 30 degreeC in the dimethylformamide of the acetone soluble part of a copolymer (A) is 0.1-0.8 dl / g normally. When the intrinsic viscosity is less than 0.1 dl / g, the mechanical strength of the resin composition may be inferior, and when the intrinsic viscosity exceeds 0.8 dl / g, the processability of the resin composition may be inferior. The average particle size of the rubber particles dispersed in the copolymer (A) is usually 0.05 to 10 μm. When the average particle size is less than 0.05 μm, the mechanical strength of the resin composition may be inferior, and when the average particle size exceeds 10 μm, the mechanical strength and appearance of the resin composition may be inferior.

<Polymer (B)>
In the present invention, the aromatic vinyl compound (b) used for the production of the polymer (B) includes the same aromatic vinyl compound (b) as described for the copolymer (A). In the production of the polymer (B), the same vinyl monomer (c) as described for the copolymer (A) can be used as a copolymerization component.

  In the present invention, it is preferable to use a vinyl cyanide compound together with an aromatic vinyl compound. In this case, the ratio of the aromatic vinyl compound / vinyl cyanide compound is usually 95 to 50/5 to 50% by weight, preferably 75 to 65/25 to 35% by weight, more preferably 73 to 69/27 to 31% by weight. %. And the ratio of the copolymerizable other vinyl-type monomer (monomer other than a vinyl cyanide compound) in a polymer (B) is 0-30 weight% normally, Preferably it is 0-20 weight%. is there.

  The intrinsic viscosity [η] of the polymer (B) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.9 dl / g, more preferably 0.3 to 0.8 dl / g. is there. When the intrinsic viscosity is less than 1.1 dl / g, the mechanical strength of the resin composition may be insufficient, and when it exceeds 1.0 dl / g, the processability of the resin composition may be inferior. . Here, the intrinsic viscosity [η] is a value obtained by dissolving 0.1 g of the polymer (B) in 100 ml of dimethylformamide and measuring with a Ubbelohde viscometer under a temperature condition of 30 ° C.

  The above intrinsic viscosity, weight average molecular weight, and number average molecular weight of the polymer (B) can be controlled by changing the type and amount of the polymerization initiator, chain transfer agent, emulsifier, solvent and the like. Further, it can be controlled by changing the monomer component addition method, addition time, polymerization time, polymerization temperature and the like. Here, as a polymerization method, a known polymerization method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, or a polymerization method combining these can be used.

  Usually, the above-mentioned polymer (B) is obtained by emulsion polymerization, and known radical polymerization initiators, emulsifiers, chain transfer agents and the like are used for emulsion polymerization.

  Examples of the radical polymerization initiator include an oxidizing agent composed of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, t-butyl peroxylaurate, and sugar-containing pyrophosphate. Redox initiators in combination with reducing agents such as iron prescription, sulfoxylate prescription, sugar-containing iron pyrophosphate prescription / sulfoxylate prescription; persulfates such as potassium persulfate and ammonium persulfate; Azobis Examples include azo compounds such as isobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide. . A preferred radical polymerization initiator is a water-soluble initiator such as potassium persulfate. The amount of these radical polymerization initiators used is usually 0.05 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, based on 100 parts by weight of the monomer component used.

  As an emulsifier, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenyl ether disulfonate, sodium succinate dialkali ester sulfonate, sodium salt or potassium salt of aliphatic carboxylic acid having 10 to 20 carbon atoms, sodium salt of rosin acid Or nonionic emulsifiers, such as anionic emulsifiers, such as potassium salt, polyoxyethylene alkyl ester, polyoxyethylene alkyl allyl ether, etc. are mentioned, These can use 2 or more types together. The usage-amount of an emulsifier is 0.5-5 weight part normally with respect to 100 weight part of said monomer components.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan; tetraethylthiuram sulfide, Hydrocarbon salts such as carbon tetrachloride, ethylene bromide, pentanephenylethane; terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, α-methylstyrene dimer, and the like. Two or more of these can be used in combination. The usage-amount of a chain transfer agent is 0-1 weight normally with respect to 100 weight part of monomer components.

  The emulsion polymerization for producing the polymer (B) is usually performed using 100 to 500 parts by weight of water with respect to 100 parts by weight of the monomer component, and the polymerization temperature is usually 40 to 100 ° C., preferably Is 50 to 90 ° C., and the polymerization time is usually 1 to 10 hours. The latex obtained by emulsion polymerization is coagulated by a conventional method, and the resulting powder is washed with water and then dried.

  Examples of the coagulant include sodium chloride, calcium chloride, aluminum chloride, magnesium sulfate, ferrous sulfate, ferric sulfate, ferric chloride, aluminum sulfate, activated silica, calcium phosphate, sulfuric acid, and acetic acid. It is done.

<Optional component>
Concrete form thermoplastic resin composition of the present invention contains an antioxidant in its preferred embodiments. Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and the like.

  Examples of the phenolic antioxidant include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityltetrakis [3- (3,5-di-t-butyl). -4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis [2- {3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (4-tert-butyl-3-hydroxy-2,6-di) Methylbenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, tris (3,5 -Di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,2'-ethylidenebis (2,4-di-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, 2 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-ethylenebis (4-methyl-6-t-butylphenol) and the like.

  Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite. Phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) diphosphite, 2,2 '-Ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4 6- tri -t- butylphenyl) pentaerythritol diphosphite, and the like.

  Examples of the sulfur-based antioxidant include pentaerythrityl tetrakis (3-lauryl thiopropionate), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3, 3'-thiodipropionate etc. are mentioned.

  In the present invention, so-called bifunctional processing stabilizers can be used in order to achieve thermal stability during high-temperature processing. Examples of the above-mentioned bifunctional processing stabilizer include acrylate compounds described in JP-A-7-26107: 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl). ) -4-methylphenyl acrylate, 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2,4-di- t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5 -Methylbenzyl) -4-methylphenyl methacrylate, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl methacrylate, and the like. It is done.

  In the present invention, it is preferable to use a phenol-based antioxidant in combination with a phosphorus-based antioxidant and / or a sulfur-based antioxidant. Furthermore, it is preferable to use a combination of an antioxidant and a functional processing stabilizer.

  Further, in the present invention, an inert and / or active filler material can be used to improve RF shielding characteristics, conductive characteristics, high frequency impermeability characteristics, and the like. Typical fillers include glass fibers, carbon fibers, carbon black, glass microspheres, calcium carbonate, mica, talc, silica, alumina, silicon carbide, wollastonite, graphite, metals and salts. It is also possible to color using dyes or pigments.

<Concrete form thermoplastic resin composition>
In concrete form for the thermoplastic resin composition of the present invention, the copolymer (A): the weight ratio of the polymer (B), 5 to 100: 95 to 0, preferably from 10 to 90: A 90 to 10, The ratio of the rubber-like polymer (a) to the total amount of the copolymer (A) and the polymer (B) is 3 to 50% by weight, preferably 5 to 40% by weight.

  When the weight ratio of the copolymer (A) is smaller than the above range, the mechanical strength of the resin composition is inferior. Moreover, when the ratio of rubber-like polymer (a) is smaller than said range, the mechanical strength of a resin composition is inferior, and when larger than said range, the workability of a resin composition is inferior.

In concrete form for the thermoplastic resin composition of the present invention, the proportion of the antioxidant and the so-called bifunctional processing stabilizer, respectively, of the thermoplastic resin composition 100 parts by weight, usually 0.01 to 1 part by weight The amount is preferably 0.05 to 0.5 parts by weight. Also, the upper limit of the amount of filler material is about 20% by weight.

Conforming to ISO 1133 of concrete form for the thermoplastic resin composition of the present invention, the temperature 220 ° C., a melt flow rate measured under conditions of a load 10 kg (MFR) is usually 5 to 100 g / 10min, preferably 10~80g / 10 min. If the MFR is less than 5 min, when building a model by the FDM method, the filament described later may not be formed, or the model may not be built without obtaining a continuous load (molten strand). Appearance may deteriorate. These problems may be solved by raising the melting temperature of the resin composition or the temperature in the building chamber, but the problem is that the initial color of the modeling material changes and the model is colored yellow or brown. Is triggered. If the MFR exceeds 100 min, the model may not be constructed because the filament described later cannot be formed, the formed filament breaks, or a continuous load (melted strand) cannot be obtained.

<RP system>
Concrete form thermoplastic resin composition of the present invention may be used in FDM method and SLS method, RP system itself directly to the stereoscopic model the three-dimensional shape input on CAD is a known method It can be adopted. Incidentally, concrete shapes for thermoplastic resin composition of the present invention, in FDM scheme is used to filamentation are used in granulated in SLS method. Usually, the diameter of the filament is 1 to 3 mm, and the diameter of the particle is 0.01 to 0.5 mm.

<Support material>
For example, in the case of forming a complicated shape by FDM method, substances called granulated form for the thermoplastic resin composition of the present invention together with (modeling material) and "support material" is used. The modeling material and the support material should have the same thermal deformation characteristics so that both materials (filaments) can be successfully extruded into the same build chamber. Of course, the support material needs to have characteristics (for example, incompatibility) that can be easily removed from the modeling material after shaping. As an example of a support material that may be used with granulated form for the thermoplastic resin composition of the present invention (the modeling material), high impact polystyrene composition comprising a polyphenylene ether 40-80 wt% polystyrene 20 to 60% by weight Can be mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “parts” and “%” are parts by weight and% by weight unless otherwise specified.

<Evaluation method>
The evaluation methods used are as follows.

(1) Intrinsic viscosity:
The intrinsic viscosity [η] was determined from the results obtained by completely dissolving the copolymer in dimethylformamide, making 5 points with different concentrations, and measuring the reduced viscosity at each concentration of 30 ° C. using an Ubbelohde viscosity tube.

(2) Weight average molecular weight (Mw) and number average molecular weight (Mn):
Measured under the conditions of "GPC-244" manufactured by Waters as a GPC device, "TSK-gel-GMH" manufactured by Tosoh Corporation as a column, and dimethylformamide as a solvent at a flow rate of 0.8 ml / min and a temperature of 23 ° C. Calibrated with polystyrene standards.

(3) Average particle size:
Measurement was performed using a laser particle size analysis system “LPA-3100” manufactured by Otsuka Electronics Co., Ltd.

(4) Graft rate:
A certain amount (x) of a sample was put into acetone, shaken with a shaker for 2 hours to dissolve the free copolymer, and then centrifuged at 23,000 rpm for 30 minutes to obtain an insoluble matter. Then, it vacuum-dried at 120 degreeC for 1 hour, the insoluble matter (y) and the free polymer were obtained, and the graft ratio was computed from the following formula.

(6) MFR:
According to ISO 1133, measurement was performed at a temperature of 220 ° C. and a load of 10 kg.

(7) Molten state:
1 g of sample pellets were weighed on an aluminum dish having a diameter of 5 cm and allowed to stand at 230 ° C. for 1 hour, and the surface shape and color tone in the molten state were evaluated according to the criteria shown in Tables 1 and 2 below.

<Preparation of copolymer (A)>
The rubbery polymer used for the preparation of the copolymer (A) is as shown in the following (1) to (7).

(1) Rubber polymer 1 (ethylene-α / olefin copolymer rubber):
The composition of ethylene / propylene / dicyclopentadiene = 47/38/5%, Mooney viscosity (ML1 + 4, 100 ° C.) 34, weight average molecular weight (Mw) 270,000, molecular weight distribution (Mw / Mn) 3.4 A rubbery polymer was used.

(2) Rubber polymer 2 (ethylene-α / olefin copolymer rubber):
“ENGAGE 8450” (ethylene-octene copolymer) manufactured by DuPont was used.

(3) Rubber polymer 3 (hydrogenated rubber):
“KRATON G1650” (hydrogenated block copolymer (SEBS)) manufactured by Shell Chemical Company was used.

(4) Rubber polymer 4 (hydrogenated rubber):
(I) After charging 2500 g of degassed and dehydrated cyclohexane and 350 g of 1,3-butadiene in an autoclave having an internal volume of 5 liters, 0.50 g of n-butyllithium was added, and isothermal polymerization at a polymerization temperature of 50 ° C. Went. After the polymerization conversion rate reached 31%, 12.5 g of tetrahydrofuran was added, and the temperature rising polymerization was performed at 50 to 80 ° C. After the polymerization conversion rate was almost 100%, 150 g of styrene was added and polymerization was carried out for 15 minutes. The molecular characteristics of the obtained ABC triblock copolymer (unhydrogenated polymer) are shown in Table 3 below.

(Ii) Next, 1.95 g of titanocene dichloride was dispersed in 30 ml of cyclohexane in a separate container and reacted with 2.68 g of triethylaluminum at room temperature. The resulting dark blue apparently uniform solution was added to the polymer solution obtained in (i), and a hydrogenation reaction was carried out at 50 ° C. under a hydrogen pressure of 5.0 kgf / cm ² for 2 hours. Then, after adding methanol and hydrochloric acid, 2,6-di-t-butylcatechol was added and dried under reduced pressure to obtain a hydrogenated ABC triblock copolymer.

(5) Rubber polymer 5 (acrylic rubber):
After sufficiently replacing the inside of the polymerization reactor with nitrogen, distilled water and potassium rosinate and potassium fatty acid were added as emulsifiers. As a monomer, 100 parts of n-butyl acrylate and 5 parts of allyl methacrylate as a crosslinking agent were charged and heated. Cumene hydroperoxide and sulfoxylate-based redox initiation assistant (ferrous sulfate / sodium formaldehyde sulfoxylate / ED) were added at an internal temperature of 40 ° C. to conduct a polymerization reaction, and the mixture was cooled at a polymerization conversion rate of 99%. After cooling to 40 ° C., an electrolyte was added to enlarge the particle size to obtain an acrylic rubber latex having an average particle size of 0.3 μm.

(6) Rubber polymer 6 (silicone rubber):
1.3 parts of p-vinylphenylmethyldimethoxysilane and 98.7 parts of octamethylcyclotetrasiloxane are mixed, and this is put into 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid is dissolved, and 3 parts by a homogenizer. The mixture was stirred and dispersed for emulsification. This mixed solution was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, and heated at 90 ° C. for 6 hours and kept at 5 ° C. for 24 hours while stirring and mixing, thereby completing the condensation. The resulting polyorganosiloxane rubbery polymer had a condensation rate of 93%. The latex was neutralized to pH 7 with an aqueous sodium carbonate solution. The resulting polyorganosiloxane rubbery polymer latex had an average particle size of 0.3 μm.

(7) Rubber polymer 7 (butadiene rubber):
First, a mixture of 100 parts of butadiene, 150 parts of distilled water, 2.0 parts of potassium oleate, 0.1 part of potassium hydroxide, 0.2 part of t-dodecylbenzene, and 0.25 part of potassium persulfate was prepared. Next, the above mixture was charged into a pressure-resistant reactor and polymerization was started at 55 ° C., and the reaction temperature was raised according to the polymerization conversion rate. Finally, the conversion rate reached 90% at 75 ° C. for 50 hours. . After completion of the polymerization, unreacted butadiene was removed by steam distillation to obtain a polybutadiene latex. The gel content was 74% and the average particle size was 0.3 μm.

  Various vinyl monomers are polymerized in the presence or absence of each of the rubber polymers (1) to (7), and copolymers having the composition and intrinsic viscosity [η] shown in Table 4 below. A-1 to 9 and B-1 to 4 were obtained. In addition, toluene was used for the solvent in the solution polymerization in the table.

Examples 1-11 and Comparative Examples 1-2:
The copolymer and the auxiliary agent shown in Table 5 below were mixed according to the formulation shown in Tables 6 and 7 to be described later, melt-kneaded with a twin screw extruder, and extruded into a pellet shape. The obtained pellets were sufficiently dried, and MFR was measured and the molten state was evaluated. The results are shown in Tables 6 and 7.

  The following can be understood from the results shown in Tables 6 and 7. That is, Examples 1 to 7 using the rubbery polymer specified in the present invention for preparing the resin composition were excellent in the surface shape and color tone of the molten state of the sample pellets, and further increased the MFR of the above resin composition. Examples 8 and 9 have a more excellent surface shape, and Examples 10 and 11 in which a specific antioxidant and a bifunctional processing stabilizer are added to the above resin composition have a more excellent color tone. On the other hand, in Comparative Examples 1 and 2 in which the rubbery polymer specified in the present invention is not used for preparing the resin composition, the color tone is changed to black or brown.

Claims (8)

In the presence of at least one rubbery polymer (a) selected from the group consisting of ethylene-α / olefin copolymer rubber, acrylic rubber, hydrogenated rubber and silicone rubber, an aromatic vinyl compound (b) is added. It consists of a copolymer (A) obtained by graft copolymerization and a polymer (B) obtained by polymerizing the aromatic vinyl compound (b), and the copolymer (A): polymer (B) The weight ratio is 5 to 100: 95 to 0, and the ratio of the rubber polymer (a) to the total amount of the copolymer (A) and the polymer (B) is 3 to 50% by weight. A thermoplastic resin composition for modeling by the FDM method or SLS method . Copolymer (A) forming a form thermoplastic resin composition according to claim 1 graft rate is from 5 to 150% by weight of. Copolymer (A) acetone-soluble fraction of granulated form thermoplastic resin having an intrinsic viscosity measured at 30 ° C. in dimethylformamide stated Motomeko 1 or 2 is 0.1~0.8dl / g of Composition. Conforms to ISO 1133, temperature 220 ° C., granulated form thermoplastic resin composition according to any one of claims 1 to 3 melt flow rate measured under a load of 10kg is 5 to 100 g / 10min. Concrete form thermoplastic resin composition according to claim 1 comprising a phenolic antioxidant. Phenolic antioxidant and a phosphorus-based antioxidant and / or a sulfur-based comprising the antioxidant granulated form thermoplastic resin composition according to any one of claims 1 to 5. Bifunctional processing stabilizers comprising granulated form thermoplastic resin composition according to any one of claims 1 to 6. Shaped article comprising a granulated form thermoplastic resin composition according to any one of claims 1 to 7.