JP2005281514A - Transparent thermoplastic resin composition for extrusion molding and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent thermoplastic resin composition for extrusion molding, excellent in extrusion molding property, mold-transferring property and the balance of physical properties, and an extrusion molded article of the same. <P>SOLUTION: This transparent thermoplastic resin composition for the extrusion molding is provided by containing a rubber-reinforced styrene-based copolymer (I) reinforced by a rubbery polymer, also (A) containing an acetone-soluble resin component in the resin composition, (B) having 0.30-2.00 dl/g reduced viscosity of the acetone soluble resin component in methyl ethyl ketone, (C) containing 0.05-5 pts. wt. fatty acid ester-based wax (II) having 60-90°C melting point and (D) exhibiting ≤15 g/10 min melt flow rate measured at 220°C, at 98 N based on the ISO-1133. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transparent thermoplastic resin composition for extrusion molding and an extrusion molded article, which are excellent in extrusion moldability, mold transferability and physical property balance.

  Rubber polymers such as diene rubbers, aromatic vinyl such as styrene and α-methylstyrene; unsaturated carboxylic acid esters such as methyl methacrylate; vinyl monomers such as vinyl cyanide such as acrylonitrile and methacrylonitrile Rubber-reinforced styrene-based transparent thermoplastic resin using rubber-containing graft copolymer obtained by graft copolymerization is excellent in impact resistance, moldability, appearance, etc. It is widely used for various applications such as sundries.

  In recent years, the movement of dechlorinated vinyl has become active in applications such as building materials and miscellaneous goods for which vinyl chloride resin has been mainly used. For building materials and miscellaneous goods, there are many extrusion moldings including profile extrusion and sheet molding. If sufficient extrudability is imparted while maintaining the excellent transparency and color tone of these rubber-reinforced styrene-based transparent thermoplastic resins, the mold transferability is remarkably inferior, and a molded article having a good appearance cannot be obtained.

For example, Patent Document 1 discloses an extrusion having transparency by setting the weight average molecular weight of acetone-soluble components to 100,000 to 300,000 and the difference in refractive index between the acetone-insoluble portion and the soluble portion to be less than 0.02. A rubber-reinforced styrene-based resin composition for molding is described, and Patent Documents 2 and 3 propose an ABS resin composition excellent in extrusion moldability.
JP 2002-128848 A (Claim 1) JP 2001-329139 A (Claims 1 and 2) JP 2002-60582 A (Claims 1 and 5)

  However, the composition described in Patent Document 1 still has problems in terms of color tone, moldability, and physical property balance. In addition, none of the compositions described in Patent Documents 2 and 3 are highly transparent resin compositions. To make the compositions described in Patent Documents 2 and 3 highly transparent resin compositions, color tone and impact resistance The balance between physical properties and rigidity was still insufficient.

  The object of the present invention is to eliminate the drawbacks of the prior art described above, suitable for extrusion molding, good mold transferability, and excellent transparency, good color balance, impact resistance and rigidity, and a transparent thermoplastic resin composition for extrusion molding. And an extruded product thereof.

  As a result of intensive studies on the achievement of such an object, the rubber-reinforced styrene-based transparent resin containing a specific phosphorus compound and a fatty acid ester wax satisfies a specific fluidity, thereby allowing extrusion moldability, mold transferability, color tone. In addition, the inventors have found that a transparent thermoplastic resin composition for extrusion molding having an excellent physical property balance between impact resistance and rigidity can be obtained, and the present invention has been made.

That is, the present invention is a resin composition containing a rubber-reinforced styrene copolymer (I) reinforced with a rubbery polymer, and
(A) In the resin composition, aromatic vinyl monomer (a1) 5 to 70% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 95% by weight, vinyl cyanide monomer An acetone-soluble resin component produced from a monomer composition consisting of 0 to 50% by weight of the monomer (a3) and another monomer (a4) copolymerizable with these (a4),
(B) The reduced viscosity of the acetone-soluble resin component in methyl ethyl ketone is 0.30 to 2.00 dl / g,
(C) Transparent thermoplasticity for extrusion containing 0.05 to 5 parts by weight of a fatty acid ester wax (II) having a melting point of 60 to 90 ° C. with respect to 100 parts by weight of the rubber-reinforced styrene copolymer (I). A resin composition comprising:
(D) A transparent thermoplastic resin composition for extrusion molding having a melt flow rate of 15 g / 10 min or less measured at 220 ° C. and 98 N in accordance with ISO-1133.

  According to the present invention, a transparent thermoplastic resin composition for extrusion molding excellent in extrusion moldability, mold transferability and physical property balance can be obtained, and a good extrusion molded article can be obtained by using this resin composition. Is obtained.

The present invention will be specifically described below.
The resin composition containing the rubber-reinforced styrene copolymer (I) referred to in the present invention is a resin composition containing a styrene copolymer imparted with impact resistance by a rubbery polymer. , Rubber polymers, aromatic vinyl monomers such as styrene and α-methylstyrene; unsaturated carboxylic acid ester monomers such as methyl methacrylate; and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile It is preferable to use a copolymer of a vinyl monomer mixture containing a monomer.

  Particularly, the vinyl monomer mixture (c) in the presence of 10 to 95 parts by weight of the copolymer (A) obtained by copolymerizing the vinyl monomer mixture (a) and the rubbery polymer (b). Rubber-containing graft copolymer (B) obtained by graft polymerization) is preferably a rubber-reinforced styrene-based transparent resin (I) composed of 90 to 5 parts by weight, wherein vinyl monomer mixture (a) and vinyl The monomer-based monomer mixture (c) is an aromatic vinyl monomer (a1) 5 to 70% by weight, an unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 95% by weight, a vinyl cyanide monomer An unsaturated carboxylic acid monomer having a monomer composition consisting of 0 to 50% by weight of the monomer (a3) and 0 to 50% by weight of another monomer copolymerizable with the monomer (a4) (Excluding unsaturated carboxylic acid alkyl ester monomers (a2)) (a5 It is preferably a substantially monomer mixture containing no In.

  In the present invention, the acetone-soluble resin component contained in the transparent thermoplastic resin composition for extrusion molding is an aromatic vinyl monomer (a1) 5 to 70% by weight, an unsaturated carboxylic acid alkyl ester monomer. Monomer comprising 30 to 95% by weight of body (a2), 0 to 50% by weight of vinyl cyanide monomer (a3) and 0 to 50% by weight of other monomer copolymerizable therewith (a4) It is manufactured from the composition.

  The monomer composition of the acetone-soluble resin component is aromatic vinyl monomer (a1) 5 to 70% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 95% by weight, vinyl cyanide The monomer (a3) 0 to 50% by weight and the other monomer (a4) 0 to 50% by weight copolymerizable therewith indicate that the resin composition has transparency, color tone, impact resistance, etc. Is necessary to make the balance excellent.

  The content of the aromatic vinyl monomer (a1) in the monomer composition of the acetone-soluble resin component is 5 to 70% by weight based on the whole monomer composition. If it is less than 5% by weight, the resulting transparent thermoplastic resin composition for extrusion molding is inferior in impact resistance, and if it exceeds 70% by weight, it is inferior in transparency. From the viewpoint of transparency and impact resistance, it is preferably 9 to 50% by weight, particularly preferably 14 to 35% by weight.

  The amount of the unsaturated carboxylic acid alkyl ester monomer (a2) is 30 to 95% by weight based on the whole monomer composition of the acetone-soluble resin component. If it is less than 30% by weight, the resulting transparent thermoplastic resin composition for extrusion molding is inferior in transparency, and if it exceeds 95% by weight, it is inferior in impact resistance. From the viewpoint of impact resistance and transparency, it is preferably 35 to 90% by weight, particularly preferably 40 to 85% by weight.

  The presence of the vinyl cyanide monomer (a3) is not essential, but the amount is 0 to 50% by weight based on the whole monomer composition of the acetone-soluble resin component. If it exceeds 50% by weight, the color tone of the resin composition deteriorates. From the viewpoint of color tone and impact resistance, it is preferably 0.1 to 45% by weight, particularly preferably 1 to 40% by weight.

  In addition to the aromatic vinyl monomer (a1), unsaturated carboxylic acid alkyl ester monomer (a2), and vinyl cyanide monomer (a3), the acetone-soluble resin component of the present invention includes Although not essential, the other monomer (a4) that can be copolymerized with 0 to 50% by weight can be present with respect to the total monomer composition of the acetone-soluble resin component.

The composition of the acetone-soluble resin component of the present invention may be determined quantitatively from the following peak appearing on the FT-IR chart.
Aromatic vinyl monomer (a1): peak at 1605 cm ⁻¹ attributed to vibration of the benzene nucleus,
Unsaturated carboxylic acid alkyl ester monomer (a2): peak at 1730 cm ⁻¹ attributed to C═O stretching vibration of the carbonyl group of the ester,
-Vinyl cyanide monomer (a3): A peak at 2240 cm ^-1 attributable to -C≡N stretching.

  The acetone-soluble resin component is mainly composed of a resin component derived from the copolymer (A) obtained by copolymerizing the vinyl monomer mixture (a), but in the rubber-containing graft copolymer (B). A part of the resin component derived from the copolymer part polymerized from the vinyl monomer mixture (c) is also included. Therefore, in order to control the composition of the acetone-soluble resin component within the above-described predetermined range, it is effective to control the composition of the copolymer (A) constituting the main component within the above-described predetermined range, Furthermore, the composition of the copolymer portion polymerized from the vinyl monomer mixture (c) is also preferably controlled within the above-mentioned predetermined range.

  In the present invention, it is necessary that the reduced viscosity in methyl ethyl ketone soluble in acetone is 0.30 to 2.00 dl / g. If it is less than 0.30 dl / g, it will be drawn down during extrusion molding. If it exceeds 2.00 dl / g, the extruded product will be crushed and the appearance will be poor. Preferably it is 0.32-1.8 dl / g, More preferably, it is 0.33-1.50 dl / g.

  In the monomer composition constituting the acetone-soluble resin component in the resin composition of the present invention, the copolymer (A) and the graft component (b) of the rubber-containing graft copolymer (B) are constituted. An aromatic vinyl monomer (a1), an unsaturated carboxylic acid alkyl ester monomer (a2), a vinyl cyanide monomer (a3), and a copolymer thereof used in a preferred monomer composition Specific examples of the other polymerizable monomer (a4) include the following compounds.

  Examples of the aromatic vinyl monomer (a1) include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o, p-dichlorostyrene. Among them, styrene and α-methylstyrene are particularly preferable. These can use 1 type (s) or 2 or more types.

  Examples of the unsaturated carboxylic acid alkyl ester monomer (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) T-butyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, chloromethyl (meth) acrylate and (meth) acrylic Examples include 2-chloroethyl acid, and methyl methacrylate is particularly preferable. These can use 1 type (s) or 2 or more types.

  Examples of the vinyl cyanide monomer (a3) include acrylonitrile, methacrylonitrile and ethacrylonitrile, with acrylonitrile being particularly preferred. These can use 1 type (s) or 2 or more types.

  Examples of the other monomer (a4) copolymerizable with these include maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, and unsaturated amides such as acrylamide. 1 type (s) or 2 or more types can be used.

  Although there is no restriction | limiting in particular in the composition of the vinyl-type monomer mixture (a) used as the polymerization raw material of a copolymer (A), Aromatic vinyl-type monomer (a1) 5-70 weight%, unsaturated alkyl carboxylate From 30 to 95% by weight of the ester monomer (a2), 0 to 50% by weight of the vinyl cyanide monomer (a3) and 0 to 50% by weight of other monomers copolymerizable therewith (a4) From the viewpoint of impact resistance, the aromatic vinyl monomer (a1) is preferably 9 to 50% by weight, and the unsaturated carboxylic acid alkyl ester monomer (a2) 35 to 90. A monomer composition comprising 0.1% to 45% by weight of vinyl cyanide monomer (a3) and 0% to 50% by weight of other monomer copolymerizable with these (a4), Preferably, aromatic vinyl monomer (a1) 14 to 35% by weight, unsaturated 40 to 85% by weight of rubonic acid alkyl ester monomer (a2), 1 to 40% by weight of vinyl cyanide monomer (a3) and other monomers copolymerizable with these (a4) 0 to 50 It is a monomer composition consisting of% by weight.

  The vinyl-based monomer mixture (a) substantially contains an acidic monomer such as an unsaturated carboxylic acid-based monomer (excluding the unsaturated carboxylic acid alkyl ester-based monomer (a2)) (a5). It is especially preferable not to contain it in order to make the acid value of the acetone-soluble resin component in the rubber-reinforced styrene-based transparent resin composition a desired level and to improve the color tone. Here, “substantially not containing” means that these acidic monomers are not intentionally added as a monomer mixture. For example, 0.01% or more with respect to the monomer mixture (a). Addition can be considered intentional addition. The unsaturated carboxylic acid derived from impurities in each monomer of the monomer mixture (a), for example, 0.01 contained as an impurity in the unsaturated carboxylic acid alkyl ester monomer (a2). Less than% unsaturated carboxylic acids are not intentionally added. Examples of the unsaturated carboxylic acid monomer (a5) include acrylic acid and methacrylic acid.

  The rubbery polymer (b) constituting the rubbery-containing graft copolymer (B) in the present invention is not particularly limited, but examples thereof include diene rubbers, acrylic rubbers, ethylene rubbers, and the like. Are polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl acrylate), poly (butadiene-methyl methacrylate), poly ( Butadiene-ethyl acrylate), ethylene-propylene rubber, ethylene-propylene-diene rubber, poly (ethylene-isobutylene), poly (ethylene-methyl acrylate), poly (ethylene-ethyl acrylate) and the like. These rubbery polymers are used in one kind or a mixture of two or more kinds. Of these, polybutadiene and styrene-butadiene copolymer rubber are particularly preferably used from the viewpoint of impact resistance improvement effect.

  The weight average particle diameter of the rubber polymer (b) is 0.1 to 1.5 μm from the viewpoint of impact resistance, molding processability, fluidity, and appearance of the rubber-reinforced styrene resin composition (I) to be obtained. It is preferable that it is 0.15-1.2 micrometers.

  There is no particular limitation on the composition of the vinyl monomer mixture (c) used as a polymerization raw material for the graft component of the rubber-containing graft copolymer (B), but the transparency of the resulting transparent thermoplastic resin composition for extrusion molding is not limited. From the viewpoint of balance between physical properties of impact resistance and rigidity, aromatic vinyl monomer (a1) 5 to 70% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 95% by weight, cyanide It is preferable to contain 0 to 50% by weight of vinyl fluoride monomer (a3) and 0 to 50% by weight of another monomer (a4) copolymerizable therewith. The monomer composition constituting the vinyl monomer mixture (c) may be the same as or different from the vinyl monomer mixture (a) constituting the copolymer (A).

  Further, in this vinyl monomer mixture (c), as in the case of the vinyl monomer mixture (a) as a polymerization raw material of the styrene copolymer, an unsaturated carboxylic acid monomer (but unsaturated) is used. The acid value of the acetone-soluble resin component in the rubber-reinforced styrene-based transparent resin composition is desired to be substantially free of acidic monomers such as (a5) except for the carboxylic acid alkyl ester monomer (a2). It is particularly preferable for achieving a level and improving the color tone. Here, “substantially not containing” is the same as in the case of the vinyl monomer mixture (a) as a polymerization raw material of the styrene copolymer.

  The intrinsic viscosity of the rubber-containing graft copolymer (B) is not particularly limited, but is preferably 0.05 to 1.2 dl / g from the viewpoint of the balance between impact resistance and moldability, and more preferably 0.1 to 0. .7 dl / g is more preferable.

  This rubber-containing graft copolymer (B) is obtained by graft polymerization of the vinyl monomer mixture (c) in the presence of the rubber polymer (b). It is not necessary that the total amount of the mixture (c) is grafted. Usually, the mixture (c) obtained as a mixture with an ungrafted copolymer is used. This mixture is originally a composition, but in the present invention, it is collectively referred to as a rubber-containing graft copolymer (B) for convenience. The graft ratio of the rubber-containing graft copolymer (B) is not limited, but is preferably 5 to 150% by weight, more preferably 10 to 100% by weight from the viewpoint of impact resistance.

  The ratio of the rubber-like polymer (b) in the rubber-containing graft copolymer (B) is preferably 5 to 80 parts by weight, more preferably from the viewpoint of mechanical strength and moldability of the resulting resin composition. Is 20 to 70 parts by weight.

  The method of graft polymerization at the time of production of the rubber-containing graft copolymer (B) is not limited, but can be produced by any method such as a known emulsion polymerization method, suspension polymerization method, continuous bulk polymerization method, continuous solution polymerization method and the like. Preferably, it is produced by an emulsion polymerization method or a bulk polymerization method. Among them, in order to suppress deterioration and coloring of the rubber component due to excessive heat history, hydrolysis of the unsaturated carboxylic acid alkyl ester monomer (a2) in the melt-kneading step with the copolymer (A) is also performed. In order to control, it is most preferable to manufacture by an emulsion polymerization method from the viewpoint that it is easy to adjust the emulsifier content and the water content in the rubber-containing graft copolymer (B).

  Moreover, the transparent thermoplastic resin composition for extrusion molding of the present invention needs to contain 0.05 to 5 parts by weight of fatty acid ester wax (II) having a melting point of 60 to 90 ° C. Examples of fatty acid ester waxes include higher fatty acid ester waxes, glycerin fatty acid waxes, pentaerythritol fatty acid waxes, and the like, and there is no limitation on the type thereof, but the melting point must be 60 to 90 ° C. When the melting point is less than 60 ° C., the mold and the polishing roll are contaminated. When the melting point is 90 ° C. and higher, the transferability of the mold and the polishing roll is inferior. Moreover, the content needs 0.05-5 weight part. If it is less than 0.05 part by weight, the transferability of the mold or polishing roll is inferior, and if it exceeds 5 parts by weight, the transparency is remarkably inferior. Preferably it is 0.1-3 weight part, More preferably, it is 0.2-2 weight part.

  Furthermore, in the transparent thermoplastic resin composition for extrusion molding according to the present invention, the difference in refractive index between the acetone-soluble resin component and the acetone-insoluble resin component is preferably less than 0.03. It is excellent in transparency as it is less than 0.03.

The transparent thermoplastic resin composition for extrusion molding of the present invention is required to have an MFR (melt flow rate) of 15 g / 10 min or less at 220 ° C. and 98 N load in accordance with ISO-1133. If it exceeds 10 g / 10 min, the resin draw-down is remarkable during extrusion molding, and a good molded product cannot be obtained.
More preferably, it is less than 0.025, More preferably, it is less than 0.02.

The transparent resin composition for extrusion molding of the present invention preferably has a melt viscosity of 10,000 Pa · s or more when the acetone-soluble resin component has a glass transition temperature of + 100 ° C. and a shear rate of 6.1 s ⁻¹ . If the melt viscosity is less than 10,000 Pa · s when the shear rate is 6.1 s ⁻¹ , draw-down occurs during extrusion molding, and a good extruded product cannot be obtained. On the other hand, when the temperature at which the melt viscosity is 10,000 Pa · s is less than the glass transition temperature of acetone-soluble component + 100 ° C., the transferability of the mold is remarkably inferior, and the surface appearance of the molded product is remarkably inferior.

As a method for setting the transparent resin composition for extrusion molding to 10000 Pa · s or higher when the melt viscosity is glass transition temperature of acetone-soluble component + 100 ° C. and the shear rate is 6.1 s ⁻¹ , the viscosity of the resin is increased. Methods such as rubberization and addition of additives such as ultra high molecular weight resins are used. In particular, it is preferable to use a resin having a high viscosity and a high rubber in terms of transparency.

  In the transparent thermoplastic resin composition for extrusion molding of the present invention, at least one selected from the group consisting of 3 to 29 parts by weight of polyamide elastomer (III) and a carboxyl group, an epoxy group, an amino group and an amide group Antistatic property can also be expressed by adding 0.1 to 15 parts by weight of the modified vinyl copolymer (IV) having the above functional group.

  Examples of the polyamide elastomer (III) in the present invention include a graft or block copolymer obtained by a reaction with a polyamide-forming component (a) having 6 or more carbon atoms and a poly (alkylene oxide) glycol (b). Here, as the amide-forming component (a) having 6 or more carbon atoms, specifically, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid Aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid; Mention may be made of nylon salts such as methylenediamine-isophthalate. Examples of poly (alkylene oxide) glycol (b) include polyethylene oxide glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly ( Hexamethylene oxide) glycol, ethylene oxide and propylene oxide block or random copolymer, ethylene oxide and tetrahydrofuran block or random copolymer, and the like are used. The number average molecular weight of the poly (alkylene oxide) glycol is preferably in the range of 200 to 6000 from the viewpoint of polymerizability and rigidity, and more preferably 300 to 4000. Further, if necessary, both ends of the component (b) may be aminated or carboxylated.

  In the polyamide elastomer (III) of the present invention, the bond between the polyamide-forming component (a) having 6 or more carbon atoms and the poly (alkylene oxide) glycol component (b) is usually an ester bond or an amide bond. It is not limited to. It is also possible to use a third component such as dicarboxylic acid (c) or diamine (d) as a reaction component of both components. In this case, the dicarboxylic acid component (c) is terephthalate having 4 to 20 carbon atoms. Acid, isophthalic acid, phthalic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4 -Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, aliphatics such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanediic acid Dicarboxylic acids, in particular 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dodecanedi But polymerizable, color tone, from the viewpoint of physical properties. On the other hand, as the diamine component (d), aromatic, alicyclic and aliphatic diamines are used, and among them, the aliphatic diamine hexamethylene diamine is preferable from the viewpoints of polymerizability, color tone and physical properties.

  The method for polymerizing the polyamide elastomer (III) is not particularly limited. For example, an aminocarboxylic acid or lactam (a) and a dicarboxylic acid (c) are reacted in an equimolar ratio to form a polyamide prepolymer having both ends at the carboxylic acid group. A method in which poly (alkylene oxide) glycol (b) is reacted under vacuum, and each of the above compounds (a), (b) and (c) is charged into a reaction vessel, and water is present or absent. Under pressure at a high temperature to produce a carboxylic acid-terminated polyamide prepolymer, and then proceeding the polymerization under normal pressure or reduced pressure, or (a), (b) and (c) above. A known method such as a method in which a compound is charged into a reaction vessel at the same time and subjected to melt polymerization, followed by polymerization at a time under high vacuum can be employed.

  The content of the polyamide elastomer (III) is 3 in terms of the balance of antistatic property, rigidity and molding processability with respect to 100 parts by weight of the vinyl copolymer (A) and the graft copolymer (B) in total. -29 weight part is preferable, More preferably, it is 5-20 weight part. When the content of the polyamide elastomer (IV) is less than 3 parts by weight, the resulting thermoplastic resin composition has insufficient antistatic properties, and when it exceeds 29 parts by weight, the rigidity and heat resistance decrease.

  The modified vinyl copolymer (IV) in the present invention has a structure obtained by copolymerizing two or more kinds of vinyl monomers, and has a carboxyl group, an epoxy group, an amino group, an amide in the molecular chain. It has at least one functional group. Although there is no limitation in particular as content of these functional groups, 0.1 to 20 weight% is preferable, More preferably, it is 0.1 to 15 weight%. If it is less than 0.1% by weight, the effect of improving impact resistance is not sufficient, and if it exceeds 20% by weight, it may be difficult to produce a modified vinyl polymer or gelation may occur due to self-reaction. The method for introducing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, and an amide group into the modified vinyl copolymer (V) is not particularly limited, but usually the above Examples thereof include a method of copolymerizing a vinyl monomer having a functional group, and a method of copolymerizing a predetermined vinyl monomer using the above-described polymerization initiator having a functional group or a chain transfer agent.

  Specific examples of the vinyl monomer having the functional group, the polymerization initiator, and the chain transfer agent are as follows. Examples of vinyl monomers include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or itaconic acid, epoxy groups such as glycidyl acrylate, glycidyl methacrylate or glycidyl itaconate. Monomers having amino acids, aminoalkyl ester derivatives of (meth) acrylic acid such as aminoethyl acrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, vinylamine derivatives such as N-acetylvinylamine, methallylamine, etc. Monomers having an amino group such as allylamine derivatives or aminostyrene, and monomers having an amide group such as acrylamide and N-methylmethacrylamide.

  Examples of the polymerization initiator include initiators having a carboxyl group such as γ, γ′-azobis (γ-cyanovaleric acid) or peroxysuccinic acid, and α, α′-azobis (γ-amino-α, γ- And initiators having an amino group such as divaleronitrile) or p-aminobenzoyl peroxide.

  Examples of chain transfer agents include chain transfer agents having a carboxyl group such as mercaptopropion, 4-mercaptobenzoic acid or thioglycolic acid, mercaptomethylamine, N- (β-mercaptoethyl) -N-methylamine, bis- Examples include chain transfer agents having an amino group such as (4-aminophenyl) disulfide or mercaptoaniline.

  The polymerization method for copolymerizing the modified vinyl copolymer (IV) is not particularly limited, but suspension polymerization, bulk polymerization, emulsion polymerization, solution polymerization and the like are preferable.

  The reduced viscosity of the modified vinyl copolymer (IV) is preferably in the range of 0.2 dl / g to 1.5 dl / g from the viewpoint of molding processability and impact resistance. More preferably, it is the range of 0.4 dl / g-1.0 dl / g. If the reduced viscosity of the modified vinyl copolymer (IV) is less than 0.2 dl / g, the resulting thermoplastic resin composition may not have sufficient impact resistance improving effect, and exceeds 1.5 dl / g. And moldability may be reduced.

  The content of the modified vinyl copolymer (IV) is preferably in the range of 0.1 to 15 parts by weight, more preferably 1.0 to 10 parts by weight, from the viewpoint of the balance between mechanical strength and moldability. Range. When the content of the modified vinyl copolymer (V) is less than 0.1 parts by weight, the impact resistance improvement effect of the obtained thermoplastic resin composition is not sufficiently exhibited, and when it exceeds 15 parts by weight, Molding processability tends to decrease.

  Moreover, it is preferable that the transparent thermoplastic resin composition for extrusion molding of this invention contains 0.01-3 weight part of phosphorus compounds (V) shown by the following formula I.

(In the formula, R 1 and R 2 represent an alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted phenyl group.)

  Examples of the phosphorus compound (II) represented by the above formula 1 include bis-n-octylpentaerythritol diphosphite, bis-n-nonylpentaerythritol diphosphite, bis-n-decylpentaerythritol diphosphite, bis- n-undecylpentaerythritol diphosphite, bis-n-dodecylpentaerythritol diphosphite, bis-n-octadecylpentaerythritol diphosphite, etc. having an alkyl group, diphenylpentaerythritol diphosphite, bis (methylphenyl) Pentaerythritol diphosphite, bis (ethylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (t-butylphenyl) pen Those having a phenyl group such as erythritol diphosphite, bis (2,4-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-t-butyl-4-methylphenyl) pentaerythritol diphosphite Can be mentioned. In particular, in terms of color tone, bis (2,4-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-n-octadecylpenta Erythritol diphosphite is preferred. Moreover, about the addition amount, 0.01-3 weight part is preferable. If it is less than 0.01 part by weight, the color tone of the transparent thermoplastic resin composition for extrusion molding obtained is remarkably inferior, and if it exceeds 3 parts by weight, the transparency is remarkably inferior. Preferably it is 0.05-2 weight part, More preferably, it is 0.1-1 weight part.

  Further, the transparent thermoplastic resin composition for extrusion molding of the present invention is selected from a phenol stabilizer (VI), a phosphorus stabilizer (VII) other than the phosphorus compound (V), and a sulfur stabilizer (VIII). Preferably it contains at least one stabilizer. By containing these stabilizers, color tone and thermal stability are further improved. As these stabilizers, commercially available ones can be used. Although there is no restriction | limiting in particular as addition amount, 0.01-2 weight part is preferable. If it is less than 0.01 part by weight, the effect is small, and if it exceeds 2 parts by weight, the transparency is remarkably lowered.

  The transparent thermoplastic resin composition for extrusion molding of the present invention includes a polyolefin such as vinyl chloride, polyethylene and polypropylene, a polyamide such as nylon 6 and nylon 66, a polyethylene terephthalate and a polybutylene within a range not impairing the object of the present invention. The performance as a molding resin can be improved by adding polyesters such as terephthalate and polycyclohexanedimethyl terephthalate, polycarbonate, and various elastomers. If necessary, antioxidants such as sulfur-containing organic compounds, heat stabilizers such as phenols and acrylates, UV absorbers such as benzotriazoles, benzophenones, and salicylates, organic nickels, and hindered amines Various stabilizers such as light stabilizers, etc., metal salts of higher fatty acids, lubricants such as higher fatty acid amides, plasticizers such as phthalates and phosphates, polybromodiphenyl ether, tetrabromobisphenol-A, bromine Flame retardants and flame retardants such as halogenated compounds such as fluorinated epoxy oligomers and brominated polycarbonate oligomers, phosphorus compounds, antimony trioxide, antistatic agents, titanium oxide, other pigments and dyes may be added. it can. Furthermore, reinforcing agents and fillers such as glass fibers, glass flakes, glass beads, carbon fibers, and metal fibers can be added.

  Regarding the method for producing the transparent thermoplastic resin composition for extrusion molding of the present invention, various methods such as melt kneading with a Banbury mixer, a roll and a single-screw or multi-screw extruder can be employed.

  The transparent thermoplastic resin composition for extrusion molding of the present invention is used for extrusion molding such as profile extrusion molding and sheeting molding, and an extrusion molded product such as a sheet, a display shelf board, and a rail can be obtained.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but these examples do not limit the present invention. Unless otherwise specified, “%” means% by weight and “parts” means parts by weight. The measurement methods of characteristics and physical properties used in the examples are shown below.

(1) Weight average rubber particle diameter of rubber polymer Polymerized by the sodium alginate method described in “Rubber Age Vol.88 p.484-490 (1960), by E. Schmidt, PHBiddison”, that is, by the concentration of sodium alginate. The particle diameter of 50% cumulative weight fraction was determined from the weight ratio of cream and the cumulative weight fraction of sodium alginate concentration by utilizing the difference in the polybutadiene particle diameter.

(2) Graft ratio of rubber-containing graft copolymer (B) 100 ml of acetone was added to a predetermined amount (m; about 1 g) of the rubber-containing graft copolymer (B) that had been vacuum-dried at 80 ° C. for 4 hours. The solution was refluxed in a hot water bath at 70 ° C. for 3 hours, and the solution was centrifuged at 8800 rpm (10000 G) for 40 minutes. The insoluble matter was filtered, and the insoluble matter was vacuum-dried at 80 ° C. for 4 hours. (N) was measured. The graft ratio was calculated from the following formula. Here, L is the rubber content of the graft copolymer.
Graft rate (%) = {[(n) − (m) × L] / [(m) × L]} × 100.

(3) Reduced viscosity ηsp / c of acetone-soluble resin component
The measurement sample was dissolved in methyl ethyl ketone, and the reduced viscosity ηsp / c was measured at 30 ° C. using a Ubbelohde viscometer as a 0.4 g / 100 ml methyl ethyl ketone solution.

(4) Monomer composition of acetone-soluble resin component 100 ml of acetone was added to 1 g of a resin composition sample and refluxed in a 70 ° C. water bath for 3 hours, and this solution was centrifuged at 8800 rpm (10000 G) for 40 minutes. Then, insoluble matter was filtered. The filtrate was concentrated with a rotary evaporator, and a film with a thickness of 30 ± 5 μm was prepared by using a heated press set at 220 ° C. using a precipitate dried in vacuo at 80 ° C. for 4 hours (acetone-soluble resin component). The monomer composition was determined from the area of each peak appearing on the chart obtained by analyzing this film as a sample by FT-IR. The correspondence between each monomer and peak is as follows.
Methyl methacrylate monomer unit: peak at 3460 cm ⁻¹ which is a harmonic overtone peak at 1730 cm ⁻¹ attributed to C═O stretching vibration of the carbonyl group of the ester,
Methacrylic acid monomer unit: peak at 1690 cm ⁻¹ attributed to C═O stretching vibration of carbonyl group of carboxylic acid,
Styrene monomer unit: peak of 1605 cm ⁻¹ attributed to vibration of benzene nucleus,
Acrylonitrile monomer unit: peak at 2240 cm ⁻¹ attributed to —C≡N stretching.

(5) Refractive index To 1 g of the thermoplastic resin composition, 200 ml of acetone was added and refluxed in a 70 ° C. hot water bath for 3 hours. p. m. After centrifuging at (10000 G) for 40 minutes, the insoluble matter was filtered. The filtrate was concentrated with a rotary evaporator to obtain a precipitate (acetone soluble matter). Each sample was dried under reduced pressure at 60 ° C. for 5 hours to form a film sample. A small amount of 1-bromonaphthalene was dropped into this measurement sample, and the refractive index was measured using an Abbe refractometer under the following conditions.
Light source: Sodium lamp D-ray measurement temperature: 20 ° C.

(6) Izod Impact Strength of Resin Composition Measured by ASTM D256 (23 ° C., with V notch).

(7) Tensile strength of resin composition Measured according to ASTM 638.

(8) Temperature at which the melt viscosity is 10,000 Pa · s or higher Using a capillary rheometer manufactured by Toyo Seiki Co., Ltd., the temperature was changed by 10 ° C. to obtain a temperature exceeding 10,000 Pa · s. As the capillary, L / D = 20 was used.

(9) Glass transition temperature It was measured using a differential calorimeter manufactured by PerkinElmer.

(10) Extrudability (a) Formability Using a 40φ mm profile extruder manufactured by Tanabe Seisakusho Co., Ltd., drawdown properties were confirmed when sheeting with a width of 500 mm was performed under the following conditions. Judgment was marked with x for those with a significant drawdown, △ for those with a slight drawdown, and ◯ with no drawdown.
-Seating conditions-
Screw rotation speed 900rpm
Polishing roll rotation speed 0.3m / min
Take-up roll speed 0.3 m / min
Polishing roll temperature Upper 95 ° C Medium 80 ° C Lower 95 ° C
(B) Mold transferability The surface of the sheet obtained in (a) was visually observed, ○: good transferability, Δ: slightly uneven, x: scratched, etc. evaluated.
(C) Mold contamination (a) Visual observation of the contamination state of the polishing roll at the time of sheet forming (2 hours): ○: No contamination, Δ: Slightly contaminated, ×: Contaminated And evaluated.

(11) Color tone Using an injection molded product having a thickness of 2.5 mm, X, Y, and Z values were measured using a color computer manufactured by Dainichi Seika Co., Ltd., and the YI value was calculated from the following equation.
YI value = 100 × (1.28X−1.06Z) / Y.

(12) Transparency evaluation method (haze value)
Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., the haze value [%] of a 2.5 mm thick square plate was measured. The lower the haze value, the better the resin.

(Reference Example 1) Production of a copolymer (A) obtained by copolymerizing a vinyl monomer mixture (a) (1) Production of a vinyl copolymer (A-1) The capacity is 20 liters and the baffle And a solution obtained by dissolving 0.05 part of a methyl acrylate / acrylamide copolymer produced by the method of Example 1 of Japanese Patent Publication No. 45-24151 in a stainless steel autoclave equipped with a Foudra type stirring blade in 165 parts of ion-exchanged water. And stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate polymerization.
Methyl methacrylate 70 parts Styrene 25 parts Acrylonitrile 5 parts t-Dodecyl mercaptan 0.05 parts 2,2'-azobisisobutyronitrile 0.4 parts Deionized water 150 parts.

  That is, after raising the reaction temperature to 65 ° C. over 15 minutes, the temperature was raised to 100 ° C. over 50 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to the usual method to obtain a vinyl copolymer (A-1). The reduced viscosity ηsp / c of this vinyl copolymer (A-1) was 0.66 dl / g.

(2) Production of vinyl copolymer (A-2) A vinyl copolymer was produced in the same manner as vinyl copolymer (A-1) except that the amount of t-dodecyl mercaptan added was changed to 0.2 parts. A polymer (A-2) was obtained. The reduced viscosity ηsp / c of this vinyl copolymer (A-1) was 0.33 dl / g.

(3) Production of vinyl copolymer (A-3) A vinyl copolymer (A-3) was prepared in the same manner as A-2 except that the monomer compositions of methyl methacrylate, styrene, and acrylonitrile were changed as follows. ) The reduced viscosity ηsp / c of this vinyl copolymer (A-3) was 0.68 dl / g.
Methyl methacrylate 20 parts Styrene 75 parts Acrylonitrile 5 parts.
The vinyl copolymers (A-1) to (A-3) are shown together in Table 1.

(Reference Example 2) Production of Rubber-Containing Graft Copolymer (B) (1) Production of Graft Copolymer (B-1) 50 parts of polybutadiene latex (rubber particle diameter 0.3 μm, gel content 85%) (In terms of solid content), 180 parts of pure water, 0.4 part of sodium formaldehyde sulfoxylate, 0.1 part of sodium ethylenediaminetetraacetate, 0.01 part of ferrous sulfate and 0.1 part of sodium phosphate are charged into a reaction vessel. After nitrogen substitution, the temperature was adjusted to 65 ° C., and a mixture of 11.5 parts of styrene, 4.0 parts of acrylonitrile, 34.5 parts of methyl methacrylate and 0.3 part of n-dodecyl mercaptan was continuously added over 4 hours with stirring. It was dripped. At the same time, 0.25 parts of cumene hydroperoxide, 2.5 parts of sodium oleate as an emulsifier and 25 parts of pure water were continuously added dropwise over 5 hours, and after completion of the addition, the mixture was further maintained for 1 hour for polymerization. Ended.

  The latex product obtained after completion of polymerization was coagulated by pouring into 2000 parts of 95 ° C. water to which 1.0 part of sulfuric acid was added, and then neutralized with 0.8 part of sodium hydroxide. Thus, a coagulated slurry was obtained. This was centrifuged, washed in 2000 parts of water at 40 ° C. for 5 minutes, centrifuged, and dried in a hot air dryer at 60 ° C. for 12 hours to obtain a powdery graft copolymer (B-1). Prepared. The graft ratio of the obtained graft copolymer (B-1) was as shown in Table 2.

(2) Production of graft copolymer (B-2) The same method as graft copolymer (B-1) except that the vinyl-based monomer mixture and polybutadiene latex were changed to the compositions shown in Table 1 and used. The graft copolymer (B-2) shown in Table 1 was prepared by polymerization, coagulation, neutralization, washing, drying and separation. The graft ratio of the obtained graft copolymer (B-2) was as shown in Table 2.

Reference Example 3 Production of Polyamide Elastomer (III) 40.0 parts caprolactam, 53.1 parts polyethylene glycol having a number average molecular weight of 1000, and 9.2 parts terephthalic acid were added to “Irganox 1098” (antioxidant) 0.2. And 0.1 part of antimony trioxide catalyst and a reaction vessel equipped with a helical ribbon stirring blade, purged with nitrogen and heated and stirred at 260 ° C. for 1 hour to obtain a transparent homogeneous solution, followed by 260 ° C. and 0.5 mmHg. Polymerization was performed for 4 hours under the following conditions to obtain a viscous and transparent polymer. The obtained polymer was discharged in the form of strands and cut to obtain polyether ester amine (III-1) on the pellets.

(Reference Example 4) Production of modified vinyl copolymer (IV) 70 parts of styrene, 25 parts of acrylonitrile and 5 parts of methacrylic acid were subjected to suspension polymerization to obtain a modified vinyl copolymer (IV-1) in the form of beads. Obtained. The reduced viscosity of the modified vinyl copolymer was 0.55 dl / g.

(Examples 1-16, Comparative Examples 1-8)
Rubber reinforced thermoplastic resin (I), polyamide elastomer (III), modified vinyl copolymer (IV) prepared in Reference Examples 1 to 4, the following fatty acid ester wax (II), phosphorus compound (V), Phenol stabilizer (VI), other phosphorus stabilizer (VII) and sulfur stabilizer (VIII) were mixed in the mixing ratio shown in Table 3 and a vented 30 mmφ twin screw extruder (Ikegai Iron Works, “PCM” −30 ″) was used, and melt-kneading and extrusion were performed to produce pellet-shaped resin composition molded bodies.

Fatty acid ester wax (II-1): Glycerin fatty acid ester ("Rikemar B-100" manufactured by Riken Vitamin Co., Ltd.)
Fatty acid ester wax (II-2): Higher fatty acid ester ("Kawa Wax L" manufactured by Kawaken Fine Chemical Co., Ltd.)
Phosphorus compounds (V)
Phosphorus compound (V-1): bis (2,4-t-butylphenyl) pentaerythritol diphosphite ("PEP24G" manufactured by Asahi Denka Kogyo Co., Ltd.)
Phosphorus compound (V-2): bis (2,6-t-butyl-4-methylphenyl) pentaerythritol diphosphite ("PEP36" manufactured by Asahi Denka Kogyo Co., Ltd.)
Phenolic stabilizer (VI)
Phenol stabilizer (VI-1): “AO50F” manufactured by Asahi Denka Kogyo Co., Ltd.
Phenol stabilizer (VI-2): “Yoshinox” 425 manufactured by Yoshitomi Pharmaceutical Co., Ltd.

Other phosphorus stabilizer (VII): Tris (2,4-t-butylphenyl) phosphite (2112 manufactured by Asahi Denka Kogyo Co., Ltd.).
Sulfur stabilizer (VIII): “DMTP” manufactured by Yoshitomi Pharmaceutical.

  Next, each test piece was molded by an injection molding machine (Sumitomo Heavy Industries Co., Ltd., “Promat 40/25”) with an injection pressure of lower limit pressure + 1 MPa, and physical properties were measured. The results are shown in Table 5.

  For comparison, Table 6 shows the results of measuring each characteristic of the resin composition obtained by changing the composition components of Examples as shown in Table 4.

  The rubber-reinforced styrene-based transparent resin compositions of Examples 1 to 16 of the present invention had excellent physical property balance in extrusion moldability, mold transferability, transparency, color tone, impact resistance and rigidity, and were excellent. . However, the resin compositions obtained in Comparative Examples 1 and 5 are inferior in mold transferability. Comparative Examples 2 and 6 are greatly inferior in mold contamination. Moreover, since Comparative Example 3 and 7 was outside the range which MFR specified by this invention, a moldability is inferior and Comparative Examples 4 and 8 are inferior in transparency.

Claims (9)

A resin composition containing a rubber-reinforced styrene-based copolymer (I) reinforced with a rubbery polymer, and
(A) In the resin composition, aromatic vinyl monomer (a1) 5 to 70% by weight, unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 95% by weight, vinyl cyanide monomer An acetone-soluble resin component produced from a monomer composition consisting of 0 to 50% by weight of the monomer (a3) and another monomer (a4) copolymerizable with these (a4),
(B) The reduced viscosity of the acetone-soluble resin component in methyl ethyl ketone is 0.30 to 2.00 dl / g,
(C) Transparent thermoplasticity for extrusion containing 0.05 to 5 parts by weight of fatty acid ester wax (II) having a melting point of 60 to 90 ° C. with respect to 100 parts by weight of the rubber-reinforced styrene copolymer (I). A resin composition comprising:
(D) A transparent thermoplastic resin composition for extrusion molding having a melt flow rate measured at 220 ° C. and 98 N of 15 g / 10 min or less in accordance with ISO-1133. 2. The transparent heat for extrusion molding according to claim 1, wherein the melt viscosity measured under a measurement temperature condition (glass transition temperature of acetone-soluble resin component + 100 ° C.) and a shear rate condition of 6.1 s ⁻¹ is 10000 Pa · s or more. Plastic resin composition.   Further, a modified vinyl copolymer (IV) having 3 to 29 parts by weight of polyamide elastomer (III) and at least one functional group selected from the group consisting of carboxyl group, epoxy group, amino group and amide group The transparent thermoplastic resin composition for extrusion molding according to claim 1 or 2, comprising 0.1 to 15 parts by weight. Furthermore, the transparent thermoplastic resin composition for extrusion molding in any one of Claims 1-3 containing 0.01-3 weight part of phosphorus compound (V) of following formula 1.

(In the formula, R 1 and R 2 represent an alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted phenyl group.)   Furthermore, it contains at least one kind of stabilizer selected from a phenol-based stabilizer (VI), a phosphorus-based stabilizer (VII) other than the phosphorus-based compound (V), and a sulfur-based stabilizer (VIII). 4. The transparent thermoplastic resin composition for extrusion molding according to any one of 4 above.   In the presence of 10 to 95 parts by weight of a copolymer (A) obtained by copolymerizing a rubber-reinforced styrene copolymer (I) with a vinyl monomer mixture (a), and a rubbery polymer (b) The transparent thermoplastic resin for extrusion molding according to any one of claims 1 to 5, comprising 90 to 5 parts by weight of a rubber-containing graft copolymer (B) obtained by graft polymerization of a vinyl monomer mixture (c). Resin composition.   The vinyl-based monomer mixture (a) and the vinyl-based monomer mixture (c), which are raw materials for the rubber-reinforced styrene-based copolymer (I), are 5 to 70% by weight of the aromatic vinyl-based monomer (a1). Unsaturated carboxylic acid alkyl ester monomer (a2) 30 to 95% by weight, vinyl cyanide monomer (a3) 0 to 50% by weight and other monomers copolymerizable therewith (a4) A monomer composition consisting of 0 to 50% by weight, and an unsaturated carboxylic acid monomer (excluding the unsaturated carboxylic acid alkyl ester monomer (a2)) (a5) The transparent thermoplastic resin composition for extrusion molding according to claim 7, which is a monomer mixture not containing.   The transparent thermoplastic resin composition for extrusion molding according to any one of claims 1 to 7, wherein the refractive index difference between the acetone-soluble resin component and the acetone-insoluble resin component is less than 0.03.   The extrusion molded article manufactured from the transparent thermoplastic resin composition for extrusion molding in any one of Claims 1-8.