JP5286630B2 - Method for producing thermoplastic resin composition - Google Patents

Description

  The present invention relates to a method for producing a thermoplastic resin composition, and more particularly to a method for producing a thermoplastic resin composition containing a reactive functional group, which is excellent in heat resistance and impact resistance.

  The reactive processing method is a method in which a processing machine that melts and kneads a polymer is used in a reaction field. Among them, so-called “reactive extrusion processing” using an extruder in particular has a high industrial added value and is actively used worldwide.

  For example, Patent Document 1 relates to an alloy of polyamide and maleic anhydride-modified ethylene / propylene / terpolymer, and a graft polymer produced based on a reaction between an amino terminal group of polyamide and maleic anhydride by melt-kneading in a twin-screw extruder. Is disclosed.

Patent Documents 2 and 3 disclose a method of using a twin-screw extruder as a method for producing a polymer alloy of polyamide and carboxylic anhydride-modified polyphenylene ether. However, the ratio L / D ₀ of the screw length L to the screw diameter D ₀ of the twin screw extruder used is short, and it is not possible to secure a sufficient reaction time (residence time) in the extruder, and impact resistance and heat resistance. These characteristics could not be fully expressed.

In the case of reactive extrusion processing, the extruder to be used is required to control the temperature, secure the reaction time (residence time), uniformly disperse the catalyst, and remove by-products. Among these, securing the residence time is one of important factors in controlling the reaction in the extruder. One way of ensuring the residence time in the extruder, a method of L / D ₀ uses a long extruder are known.

For example, Patent Document 4 discloses a method of using a co-directional twin-screw extruder having an L / D ₀ of 30 to 100 when modifying a polyolefin resin with an unsaturated carboxylic acid derivative or an acid anhydride thereof. . Patent Document 5 discloses a method of securing a residence time by using a twin screw extruder having an L / D ₀ of 50 or more and 110 or less when producing a glutaric anhydride copolymer.

Indeed by increasing the L / D ₀ of the twin-screw extruder, it is possible to lengthen the residence time. However, simply increasing L / D ₀ often fails to achieve a sufficient balance between impact resistance and heat resistance of a resin composition containing a reactive functional group as a raw material.

On the other hand, in Patent Document 6, when a thermoplastic resin composition is melt-kneaded using an extruder, carbon dioxide is added so that a good fine dispersion structure can be obtained without using a compatibilizer or a plasticizer. It is disclosed that it has. This is because the introduction of carbon dioxide reduces the melt viscosity of the thermoplastic resin and improves the uniform dispersibility. However, the point that carbon dioxide introduction kneading part cannot be sufficiently secured, the inefficiency due to the multistage extrusion method connecting three extruders sharing the carbon dioxide introduction part, kneading part, and devolatilization part, In addition, when applied to a resin composition containing a reactive functional group as a raw material, there is a problem that the balance between impact resistance and heat resistance cannot be sufficiently achieved.
JP 51-70254 A JP 59-66452 A JP 61-204262 A JP 2004-114610 A JP 2004-315798 A JP 2002-322288 A

  The objective of this invention is providing the manufacturing method of the thermoplastic resin composition excellent in heat resistance and impact resistance in manufacture of the thermoplastic resin composition which has a reactive functional group.

The method for producing the thermoplastic resin composition of the present invention that achieves the above object comprises a thermoplastic resin composition (I) comprising a thermoplastic resin (A) and a rubbery polymer (B) having a reactive functional group. A process for producing a thermoplastic resin composition (II) comprising a plastic resin (A), a thermoplastic resin (C) different from the thermoplastic resin (A), and a compound (D) having a reactive functional group, comprising: This is a method for producing a thermoplastic resin composition in which a raw resin is melt-kneaded in the presence of a supercritical fluid using a twin screw extruder having a length L and a screw diameter D ₀ ratio L / D ₀ of 60 or more. Here, the thermoplastic resins (A) and (C) are at least one selected from polyamide resins, polyester resins, polyphenylene sulfide resins, polyphenylene oxide resins, and polycarbonate resins. Further, the reactive functional group of the rubber polymer (B) and the compound (D) is at least one selected from an amino group, a carboxyl group, a carboxyl metal salt, an epoxy group, an acid anhydride group, and an oxazoline group.

In the method for producing a thermoplastic resin composition of the present invention, a resin composition containing a reactive functional group as a raw material is used in a presence of a supercritical fluid by using a twin-screw extruder having a specific L / D ₀ screw. It is possible to produce a thermoplastic resin composition having excellent heat resistance and impact resistance by melt kneading with the above.

Hereinafter, the present invention will be described in more detail.

The thermoplastic resin composition produced according to the present invention includes a thermoplastic resin composition (I) comprising a thermoplastic resin (A) and a rubbery polymer (B) having a reactive functional group, or a thermoplastic resin (A). A thermoplastic resin composition (II) comprising a thermoplastic resin (C) different from the thermoplastic resin (A) and a compound (D) having a reactive functional group.

Thermoplastic resin (A) used in the present invention is a moldable resin by heating and melting, polyamides resin, polyester resin, polyphenylene sulfide resin, Po polyphenylene oxide resins, at least one selected polycarbonate resins or al There is .

And Riwake polyamide resins, polyester resins, polyphenylene oxide resins have high reactivity of the end groups, most preferably used.

  In the present invention, the polyamide resin is a resin composed of a polymer having an amide bond, and is mainly composed of amino acid, lactam or diamine and dicarboxylic acid. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, hexa Methylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylyl Range amine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) Methane, bis (3- Aliphatic, alicyclic, aromatic diamines and adipic acid such as methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, Superic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexa Examples thereof include aliphatic, alicyclic and aromatic dicarboxylic acids such as hydroisophthalic acid. In the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture. .

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a crystal melting temperature of 200 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (polyamide 6), polyhexamethylene azide. Pamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene adipamide / polyhexamethylene terephthalate Amide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide Copolymer (polyamide 66 / 6T / 6I), polyxylylene adipamide (polyamide XD6), and mixtures thereof or copolymers, and the like.

  Particularly preferable examples include polyamide 6, polyamide 66, polyamide 610, polyamide 6/66 copolymer, polyamide 6/12 copolymer and the like. Further, these polyamide resins can be molded, heat-resistant, tough, surface properties, etc. Although it is also practically suitable to use as a mixture according to the required properties, polyamide 6 and polyamide 66 are most preferred.

  The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 5.0, particularly in the range of 2.0 to 4.0. Are preferred.

  In the present invention, the polyester resin is a thermoplastic resin composed of a polymer having an ester bond in the main chain, and mainly comprises a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). A polymer or copolymer obtained by a condensation reaction as a component, or a mixture thereof is preferably mentioned.

  Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid. Acid, aromatic dicarboxylic acid such as 5-sodiumsulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, aliphatic dicarboxylic acid such as dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. And alicyclic dicarboxylic acids and ester-forming derivatives thereof. The diol component is an aliphatic glycol having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol. , Cyclohexanedimethanol, cyclohexanediol and the like, or long-chain glycols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like, and ester-forming derivatives thereof.

  Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), Polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / 5-sodium sulfoisophthalate), polybutylene (terephthalate / 5-sodium sulfoisophthalate), polyethylene Naphthalate, polycyclohexanedimethylene terephthalate, etc. Polybutylene terephthalate, polybutylene (terephthalate / adipate), polybutylene (terephthalate / decane dicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / adipate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, etc. Particularly preferred is polybutylene terephthalate (polybutylene terephthalate resin).

  The polybutylene terephthalate resin preferably has an intrinsic viscosity of 0.36 to 1.60, particularly 0.52 to 1.25, measured at 25 ° C. using an o-chlorophenol solvent. Moreover, you may use together polybutylene terephthalate resin from which intrinsic viscosity differs, and it is preferable that intrinsic viscosity exists in the range of 0.36-1.60.

  Further, the polybutylene terephthalate resin is durable if the COOH end group amount determined by potentiometric titration of the m-cresol solution with an alkaline solution is in the range of 1 to 50 eq / t (end group amount per ton of polymer). From the point of anisotropy suppressing effect, it can be preferably used.

  In the present invention, specific examples of the polyphenylene oxide resin include poly (2,6-dimethyl-1,4-phenylene oxide), poly (2-methyl-6-ethyl-1,4-phenylene oxide), and poly (2 , 6-diphenyl-1,4-phenylene oxide), poly (2-methyl-6-phenyl-1,4-phenylene oxide), poly (2,6-dichloro-1,4-phenylene oxide) and the like are preferable. Further, a copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol) is also preferable. Among them, poly (2,6-dimethyl-1,4-phenylene oxide), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is more preferable, and poly (2,6-dimethyl- 1,4-phenylene oxide) is particularly preferred.

  The polyphenylene oxide resin preferably has a reduced viscosity (0.5 g / dl chloroform solution) measured at 30 ° C. in the range of 0.15 to 0.70.

  The method for producing such a polyphenylene oxide resin is not particularly limited, and those obtained by a known method can be used. For example, it can be easily produced by oxidative polymerization using as a catalyst a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874.

Rubbery polymer having a reactive functional group (B) used in the present invention, that having a reactive functional group in the molecular chain.

  In the present invention, the rubbery polymer contains a polymer having a glass transition temperature lower than room temperature, and a part of the intermolecular molecules is constrained by covalent bonds, ionic bonds, van der Waals forces, entanglements, etc. It is a coalescence. Examples of rubber polymers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like. Diene rubber, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, ethylene and α-olefin copolymer, ethylene-acrylic acid, ethylene -Ethylene-unsaturated carboxylic acid copolymer such as methacrylic acid, ethylene-acrylic acid ester, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-methacrylic acid ester, part of unsaturated carboxylic acid is a metal salt A certain ethylene-acrylic acid-acrylic acid metal salt Acrylic elasticity such as ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer such as ethylene-methacrylic acid-methacrylic acid metal salt, acrylic ester-butadiene copolymer such as butyl acrylate-butadiene copolymer Polymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer Preferred examples include thermoplastic elastomers such as butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer, and polyester elastomer.

  When a polyamide resin is used as the thermoplastic resin (A), among these, from the viewpoint of compatibility, an ethylene-unsaturated carboxylic acid ester copolymer or an ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer is used. A rubbery polymer of a polymer is preferably used.

  The unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer is a (meth) acrylic acid ester, preferably an ester of (meth) acrylic acid and an alcohol. Specific examples of unsaturated carboxylic acid esters include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, stearyl (meth) acrylate Examples include esters.

  The weight ratio of the ethylene component to the unsaturated carboxylic acid ester component in the copolymer is not particularly limited, but is preferably in the range of 90/10 to 10/90, more preferably 85/15 to 15/85.

  The number average molecular weight of the ethylene-unsaturated carboxylic acid ester copolymer is not particularly limited, but is preferably in the range of 1000 to 70000 from the viewpoint of fluidity and mechanical properties.

  Specific examples of the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer include (meth) acrylic acid. Examples of unsaturated carboxylic acid metal salts include (meth) acrylic acid metal salts. Although the metal of unsaturated carboxylic acid metal salt is not specifically limited, Preferably, alkali metals, such as sodium, alkaline-earth metals, such as magnesium, zinc etc. are mentioned.

  The weight ratio of the unsaturated carboxylic acid component to the unsaturated carboxylic acid metal salt component in the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer is not particularly limited, but preferably 95/5 to 5/95, More preferably, it is the range of 90/10-10/90.

  The number average molecular weight of the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer is not particularly limited, but is preferably in the range of 1000 to 70000 from the viewpoint of fluidity and mechanical properties.

Reactive functional groups rubbery polymer having a reactive functional group (B) contains the state, and are not to react with each other with the functional groups present in the thermoplastic resin (A), the amino group, a carboxyl group, It is at least one selected from a carboxyl metal salt, an epoxy group, an acid anhydride group, and an oxazoline group . These reactive functional groups is highly reactive, yet degradation, side reactions have less of such crosslinking.

  When the acid anhydride group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, maleic anhydride, itaconic anhydride, endic acid anhydride, A method of copolymerizing acid anhydrides such as citraconic anhydride and 1-butene-3,4-dicarboxylic acid anhydride and a monomer that is a raw material of the rubber polymer, grafting the acid anhydride onto the rubber polymer Or the like can be used.

  In addition, when the epoxy group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, itacon A method of copolymerizing a vinyl monomer having an epoxy group, such as a glycidyl ester compound of an α, β-unsaturated acid such as glycidyl acid, with a monomer which is a raw material of a rubbery polymer, having the above functional group A method of polymerizing a rubbery polymer using a polymerization initiator or a chain transfer agent, a method of grafting an epoxy compound onto a rubbery polymer, or the like can be used.

  Further, when the oxazoline group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 A method of copolymerizing a vinyl monomer having an oxazoline group such as -acryloyl-oxazoline or 2-styryl-oxazoline with a monomer which is a raw material of a rubbery polymer can be used.

The thermoplastic resin (C) of the present invention is a resin different from the thermoplastic resin (A) described above, and is a resin that can be molded by heat melting (excluding vulcanizable rubber) . The thermoplastic resin (C) can be selected and used from the same group of resins as the thermoplastic resin (A) as long as a combination different from the thermoplastic resin (A) is selected. The thermoplastic resin (C) can be used as at least one resin different from the thermoplastic resin (A) selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, and polycarbonate resin.

  In the present invention, the compound (D) having a reactive functional group is a compound having a reactive functional group in the molecular chain. Such a compound (D) may be a low molecular weight body or a high molecular weight body.

The reactive functional groups in the compound having a reactive functional group of the present invention (D), all SANYO that react with one another with the functional groups present in the thermoplastic resin (A) or thermoplastic resin (C), A It is at least one selected from a mino group, a carboxyl group, a carboxyl metal salt, an epoxy group, an acid anhydride group, and an oxazoline group . These reactive functional groups is highly reactive, yet degradation, side reactions have less of such crosslinking.

  Examples of the compound (D) having an acid anhydride group include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic acid anhydride, 1-butene-3,4-dicarboxylic acid anhydride, and the like. Two or more of these may be used simultaneously. Of these, maleic anhydride and itaconic anhydride are preferably used.

  Preferred examples of the compound (D) having an epoxy group include glycidyl ester compounds of α, β-unsaturated acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate.

  The compound (D) having an oxazoline group can preferably include vinyl monomers such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline.

The reactive functional groups in the rubbery polymer (B) having a reactive functional group and the compound (D) having a reactive functional group of the present invention can be selected from the same functional group group.

In the rubbery polymer (B) having a reactive functional group and the compound (D) having a reactive functional group, the number of functional groups per molecular chain is not particularly limited, but usually 1 to 10 is preferable. In order to reduce side reactions such as crosslinking, 1 to 5 is preferable. Moreover, although the molecule | numerator which does not have a functional group at all may be contained, it is so preferable that the ratio is small.

The compounding ratio of the thermoplastic resin (A) and the rubbery polymer (B) having a reactive functional group in the production method of the present invention is not particularly limited, but the weight Aw and reactivity of the thermoplastic resin (A) are not particularly limited. The ratio Aw / Bw to the weight Bw of the rubbery polymer (B) having a functional group is preferably in the range of 5/95 to 95/5, more preferably in the range of 10/90 to 90/10, and 15/85. The range of ~ 85/15 is most preferred. When Aw / Bw is lower than 5/95, the reaction between the rubbery polymers (B) having a reactive functional group becomes prominent, and there is a tendency that molding processing becomes difficult due to an increase in viscosity. If it exceeds 95/5, the amount of the functional group that reacts with the thermoplastic resin (A) decreases, and the effect of improving the heat resistance and impact resistance of the thermoplastic resin composition tends to be small, such being undesirable.

  Although there is no restriction | limiting in particular about the compounding ratio with the thermoplastic resin (A) and the thermoplastic resin (C) in the manufacturing method of this invention, The weight Aw of a thermoplastic resin (A) and the weight Cw of a thermoplastic resin (C) The ratio Aw / Cw is preferably in the range of 5/95 to 95/5, more preferably in the range of 10/90 to 90/10, and most preferably in the range of 15/85 to 85/15. When Aw / Cw is lower than 5/95, the property improvement effect due to the thermoplastic resin (A) tends to be small, and when it exceeds 95/5, the property improvement effect due to the thermoplastic resin (C) tends to be small. Is not preferable.

  In the production method of the present invention, the addition amount of the compound (D) having a reactive functional group is not particularly limited, but is preferably based on 100 parts by weight of the total of the thermoplastic resin (A) and the thermoplastic resin (C). Is 0.1 to 50 parts by weight, more preferably 0.2 to 40 parts by weight, still more preferably 0.3 to 30 parts by weight. When the addition amount of the compound (D) having a reactive functional group is less than the above range, the reaction amount with the thermoplastic resin (A) or the thermoplastic resin (C) becomes small, and the heat resistance of the thermoplastic resin composition. And the impact resistance improving effect tends to be small. When the above range is exceeded, the reaction between the compounds (D) having a reactive functional group becomes remarkable, and unreacted compounds remain to increase low molecular weight components. As a result, the properties of the resin composition may be deteriorated, which is not preferable.

  The method for producing the thermoplastic resin composition of the present invention is a method for producing a thermoplastic resin composition containing a reactive functional group by melt kneading using a twin screw extruder. When a single screw extruder is used, the kneadability and reactivity are not sufficient, and improvement of the properties (heat resistance, impact resistance, etc.) of the thermoplastic resin composition is not achieved.

The twin screw extruder used in the present invention has an L / D ₀ value of 60 or more, preferably 60 to 200, more preferably 80 to 200. The L / D ₀ is a value obtained by dividing the screw length L by the screw diameter D ₀ . The screw length is the length from the upstream end of the screw segment at the position (feed port) to which the screw base material is supplied to the screw tip. Here, the screw of the twin screw extruder is configured by combining screw segments having different lengths and shape characteristics such as full flight and kneading disc. In the extruder, the side to which raw materials are supplied may be referred to as upstream, and the side from which molten resin is discharged may be referred to as downstream.

If L / D _{0 of the} screw to be used is 60 or more, the reaction with the thermoplastic resin (A) and the rubbery polymer (B) having a reactive functional group, the thermoplastic resin (A), and the thermoplastic resin The reaction region where the reaction with (C) and the compound (D) having a reactive functional group proceeds, and the thermoplastic resin composition containing the copolymer produced by the reaction is passed through a shearing field into a fine dispersed phase. And a supercritical fluid processing region that is melt-kneaded and finely dispersed in the presence of a supercritical fluid to be described later can be provided without sacrificing. When L / D ₀ is less than 60, it is insufficient to secure the respective fields in the reaction region, the shear region, and the supercritical fluid treatment region, and the improvement of the properties of the thermoplastic resin composition is not realized.

In addition, when using an extruder having a sampling valve or the like and sampling from a sampling valve in the middle of the extruder, the screw length L is “the screw segment at the position (feed port) where the raw material of the screw is supplied” The screw diameter D ₀ is equal to the length from the upstream end to the sampling location ”and the screw diameter D ₀ is equal to the screw diameter of the extruder having a sampling valve or the like. Can do. The sampling location here refers to a position on the screw shaft on the upstream side closest to the port through which the resin in the cylinder is discharged.

In the production method of the present invention, melt kneading is performed in the presence of a supercritical fluid when melt kneading using a twin screw extruder having an L / D ₀ of 60 or more. Such a supercritical fluid is in a state that exceeds the limit point (critical point) at which gas and liquid can coexist, and has both a property as a gas (diffusibility) and a property as a liquid (solubility). . Examples of such supercritical fluid include supercritical carbon dioxide, supercritical nitrogen, supercritical water, etc., but the supercritical fluid used in the present invention is preferably supercritical carbon dioxide and supercritical nitrogen, most Supercritical carbon dioxide is preferable.

The method for producing a thermoplastic resin composition of the present invention uses a twin screw extruder having a screw having an L / D ₀ of 60 or more as a resin composition containing a reactive functional group as a raw material, and the presence of a supercritical fluid. By melting and kneading below, the molten resin can be finely dispersed, and the heat resistance, impact resistance and tensile properties of the resulting thermoplastic resin can be improved. In particular, since the dispersed phase of the thermoplastic resin is finely and uniformly distributed and dispersed, in addition to the impact resistance, the tensile elongation at break can be improved and the properties excellent in ductility can be expressed.

  In the present invention, the position where the supercritical fluid is introduced in the twin-screw extruder is a ratio with respect to the screw length L as a region from the root of the extruder in order to sufficiently secure the introduction kneading part of the supercritical fluid in the extruder. When expressed, it is preferably 0.2 L to 0.9 L, more preferably 0.25 L to 0.85 L, and still more preferably 0.3 L to 0.8 L. In addition, the root of an extruder shall be the edge part of the upstream of the screw segment in the position (feed port) where the raw material of a screw root is supplied similarly to the above. Further, the position where the supercritical fluid is introduced in the twin-screw extruder is not limited to one, but may be two or more.

  In the present invention, it is preferable to have a devolatilization mechanism such as a vacuum vent on the downstream side of the position where the supercritical fluid is introduced in the twin-screw extruder. This is because the supercritical fluid kneaded in the extruder is devolatilized and removed by reducing the pressure and the vacuum state by a vacuum vent or the like.

  In the production method of the present invention, in order to maintain the supercritical state of the supercritical fluid in the twin-screw extruder, the upstream of the supercritical fluid introduction position and the upstream of the devolatilization mechanism are pressure-held by a molten resin seal. It is preferable. The molten resin seal refers to a state in which the molten resin can fill and seal the clearance between the screw and the cylinder barrel (the inner wall surface of the cylinder that houses the screw) to maintain pressure without leaking gas. .

  For example, FIG. 1 is an explanatory view of a seal plate (so-called seal ring) that is a screw segment that is preferably used in the manufacturing method of the present invention. As shown in FIG. 1, the pair of left and right sealing plates 2 and 2 are mounted on the intermediate portions of biaxial screws 1 and 1 extending to the cylinder barrel 3 with the flanges 2f and 2f overlapping each other. . Unlike the full flight type screw segment, the seal plate installed in this way has almost no effect of transporting the molten resin, so when incorporated in the screw configuration, the molten resin accumulates around and upstream of the seal plate and melts. As the resin seal is formed and the resin pressure is increased, the gas phase pressure is also increased, and the supercritical state can be maintained.

  In addition to arranging a sealing plate, such a molten resin seal has a screw segment in which the molten resin feed direction is reversed (screw segment in which the spiral winding direction is reversed) incorporated into a predetermined position of the screw configuration. A pressurizing region by a molten resin seal can be formed.

In the present invention, when the length of the melt-kneaded region in the presence of the supercritical fluid is Ls, Ls / D ₀ is preferably 20 or more, more preferably 21 or more, and even more preferably 22 or more. The upper limit is not particularly limited, and may extend to the tip of the screw. When Ls / D ₀ is less than 20, there may be a case where a sufficient area for melting and kneading in the presence of the supercritical fluid cannot be secured, and the effect of miniaturizing the dispersed phase by the supercritical fluid tends not to be sufficiently exhibited. It is not preferable. The screw length melted and kneaded in the presence of the supercritical fluid in such a twin-screw extruder is a region where the pressure of the supercritical fluid is applied, and the molten resin seal disposed upstream of the position where the supercritical fluid is introduced. This is the length from the downstream end to the upstream end of the molten resin seal disposed upstream of the devolatilization mechanism.

  In the production method of the present invention, the amount of supercritical fluid introduced is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 150 parts by weight, and more preferably 100 parts by weight of the thermoplastic resin composition. Preferably it is 1-100 weight part. If the introduction amount of the supercritical fluid is less than the above range, fine dispersion of the molten resin by the supercritical fluid may be insufficient, and the improvement of the properties of the obtained thermoplastic resin composition may not be achieved. If it exceeds, there is a tendency that the decrease in the melt resin viscosity due to the supercritical fluid becomes large, sufficient shear cannot be imparted to the melt resin, and the improvement of the properties of the obtained thermoplastic resin composition may not be achieved, It is not preferable.

  In the present invention, the temperature and pressure of the supercritical fluid introduced into the twin-screw extruder are not particularly limited as long as they are above the critical point of the fluid, but when supercritical carbon dioxide is used as the supercritical fluid, the temperature Must be 31.3 ° C. or higher, and the pressure must be 7.4 MPa or higher.

  In addition, the molten resin pressure in the extruder from the position where the supercritical fluid is introduced into the extruder to the position where the supercritical fluid is removed from the extruder by devolatilization or the like is to maintain the supercritical state. There is no particular limitation as long as it is above the critical pressure of the fluid, but when supercritical carbon dioxide is used as the supercritical fluid, it is preferably 7.4 MPa or more, more preferably 8 to 50 MPa, and even more preferably 10 to 30 MPa. .

  In the production method of the present invention, the extrusion rate of the thermoplastic resin composition is preferably 0.01 kg / h or more, more preferably 0.05 to 1 kg / h, still more preferably 0.08 to 0 per 1 rpm of the screw rotation. 0.5 kg / h, particularly preferably 0.1 to 0.3 kg / h. The extrusion amount is an extrusion speed at which the thermoplastic resin composition is discharged from the extruder, and is a weight (kg) extruded per hour.

The extrusion rate of the thermoplastic resin composition per 1 rpm of the screw rotation is an index of kneadability and reactivity, and if it is less than 0.01 kg / h, the extrusion rate with respect to the rotational speed tends to be insufficient. In addition, the residence time in the extruder may become long and the thermoplastic resin composition may be thermally deteriorated, and the resin filling rate in the extruder may become small and sufficient shearing may not be imparted. Moreover, when the extrusion amount of the thermoplastic resin composition per 1 rpm of the screw rotation exceeds 0.3 kg / h, the residence time in the extruder becomes too short, and the reaction of the reactive functional group is not sufficiently progressed. In addition, such a tendency that the distribution / dispersion action is insufficient and the contact with the supercritical fluid is insufficient is not preferable.

  Moreover, there is no restriction | limiting in particular as a rotational speed of a screw, However, Preferably it is 10 rpm or more, More preferably, it is 15 rpm or more, More preferably, it is 20 rpm or more. The extrusion rate is not particularly limited as long as it is within the above range, but is preferably 0.1 kg / h or more, more preferably 0.15 kg / h or more, and further preferably 0.2 kg / h or more.

  In the production method of the present invention, the numerical limitation related to the extrusion amount in the twin-screw extruder is based on the extrusion amount of the twin-screw extruder having a screw diameter of 37 mm. When the screw diameters are significantly different, for example when using a twin screw extruder with a diameter of less than 30 mm or more than 50 mm, the extrusion rate is preferably 2. It can be read as an increase / decrease according to the fifth power law or the third power law, more preferably according to the 2.5 power law.

  For example, when a twin screw extruder having a screw diameter of 20 mm is used, assuming that the extrusion amount conforms to the 2.5th power rule of the screw diameter ratio before and after the scale down, the extrusion amount of the thermoplastic resin composition is 1 rpm. It is 0.002 kg / h or more, preferably 0.01 to 0.2 kg / h, more preferably 0.017 to 0.11 kg / h, still more preferably 0.02 to 0.06 kg / h.

  Further, when a twin screw extruder having a screw diameter of 100 mm is used, if the extrusion amount conforms to the 2.5th power rule of the screw diameter ratio before and after the scale-up, the extrusion amount of the thermoplastic resin composition is 1 rpm. It is 0.12 kg / h or more, preferably 0.6 to 12 kg / h, more preferably 0.96 to 6 kg / h, still more preferably 1.2 to 3.6 kg / h.

  In the production method of the present invention, the residence time of the thermoplastic resin composition in the twin-screw extruder is preferably 1 to 30 minutes, more preferably 1.5 to 28 minutes, and further preferably 2 to 25 minutes. The residence time is an average of the residence time from when the raw material is supplied to the twin screw extruder until it is discharged, and is a steady melt kneading in which the uncolored thermoplastic resin composition is adjusted to a predetermined extrusion amount. In the state, from the position of the screw base to which the raw material is supplied, about 1 g of the colorant is usually added together with the raw material, and the thermoplastic resin composition is extruded from the discharge port of the extruder when the colorant is added. The time until the time when the degree of coloring by the colorant on the extrudate is maximized is taken.

  When the residence time is less than 1 minute, the reaction time in the extruder is short, the reaction does not proceed sufficiently, and there is a tendency that the reaction does not sufficiently contact with the supercritical fluid. The effect of improving (heat resistance, impact resistance, tensile properties, etc.) may be low, which is not preferable. If the residence time is longer than 30 minutes, thermal degradation of the resin due to the long residence time may occur, which is not preferable.

  The screw of the twin-screw extruder used in the production method of the present invention is not particularly limited, and a complete mesh type, an incomplete mesh type, a non-mesh type screw, or the like can be used, but from the viewpoint of kneadability and reactivity, Preferably, it is a complete mesh type. Further, the rotation direction of the screw may be either the same direction or a different direction, but from the viewpoint of kneading property and reactivity, the rotation direction is preferably the same direction. The screw of the twin-screw extruder used in the production method of the present invention is most preferably a co-rotating fully meshing type.

  As the screw configuration of the twin-screw extruder used in the production method of the present invention, a full flight and / or a kneading disk are used in combination, but a shear field is effectively applied to the molten thermoplastic resin composition. A screw configuration is preferred. Therefore, it is preferable that the screw of the twin screw extruder has a plurality of kneading zones made of kneading disks in the longitudinal direction, and the total length of these kneading zones is preferably 5 to 5 times the total length of the screw. The range is 50%, more preferably 10 to 40%, and still more preferably 15 to 30%. If the total length of the kneading zone is less than the above range, the shearing region is shortened, the reaction does not proceed sufficiently, the kneading effect in the presence of the supercritical fluid is reduced, and the thermoplastic resin composition The effect of improving the heat resistance, impact resistance, and tensile properties of the resin composition may not be sufficiently obtained. There is a possibility of deterioration, which is not preferable.

In the production method of the present invention, when the length of each kneading zone in the screw of the twin screw extruder is Lk, all kneading zones have a length of Lk / D ₀ = 0.2-10. It is preferable from the viewpoint of kneadability and reactivity. The length Lk / _{D 0} of each kneading zone is more preferably 0.3 to 9, more preferably from 0.5 to 8. The length Lk of the kneading zone is determined by the perpendicular line from the upstream end of the most upstream kneading disk constituting the kneading zone to the screw shaft center line and the screw from the downstream end of the most downstream kneading disk. The distance between the vertical line to the axis center line.

  Further, in the present invention, the kneading zone of the twin screw extruder is preferably arranged over the entire region without being unevenly distributed at a specific position in the screw.

  In the present invention, the thermoplastic resin composition may contain other components in addition to the above (A) to (D) as necessary. Examples of other components include fillers, thermoplastic resins, rubbers, and various additives.

  For example, the filler may be used as necessary to improve strength and dimensional stability. The filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used.

  Examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, It is preferable in terms of obtaining superior mechanical strength.

  In order to improve strength, dimensional stability and the like, when such a filler is used, the amount of the filler is not particularly limited, but it is preferably 30 to 400 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

  Further, in the thermoplastic resin composition produced according to the present invention, other rubbers and various additives can be blended as necessary within the range not impairing the characteristics.

  Such rubbers include, for example, polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like. Diene rubbers, ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, ethylene and α-olefin copolymers, ethylene-acrylate esters, Ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-methacrylic acid ester, acrylic acid ester-butadiene copolymer, acrylic elastic polymer such as butyl acrylate-butadiene copolymer, ethylene such as ethylene-vinyl acetate And fatty acid vinyl Copolymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene non-conjugated diene terpolymer such as ethylene-propylene-hexadiene copolymer, butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer Preferred examples include thermoplastic elastomers such as polyester elastomers and modified products thereof. Two or more kinds of such rubbers can be used in combination. When such rubbers are used, the blending amount thereof is not particularly limited, but is preferably blended by 1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  The various additives that can be added to the production method of the present invention are preferably crystal nucleating agents, anti-coloring agents, antioxidants such as hindered phenols and hindered amines, ethylene bisstearyl amide and higher fatty acid esters. Examples include release agents, plasticizers, heat stabilizers, lubricants, ultraviolet light inhibitors, colorants, and flame retardants.

    These rubbers and various additives can be blended at any stage of producing the thermoplastic resin composition of the present invention. For example, when blending the resin composition (I) or (II) Or a method of adding the resin composition (I) or (II) by means of a side feed or the like during melt kneading, or after the resin composition (I) or (II) has been melt kneaded in advance. And a method of first adding the resin composition (I) or (II) to one resin constituting the resin composition (I) and melt-kneading, and then blending the remaining resin.

  The molding method using the thermoplastic resin composition produced according to the present invention can be any method, and the molding shape can be any shape. The molding method is preferably extrusion molding, injection molding, hollow molding, calendar molding, compression molding, vacuum molding, foam molding, etc., pellet shape, plate shape, film or sheet shape, pipe shape, hollow shape It can be formed into a box-like shape.

  The molded product of the thermoplastic resin composition produced according to the present invention is used for connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups. , Oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna In addition to being suitable for electronic parts such as computer-related parts, generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, Knife switch, other pole rod, electric Applications of electrical equipment parts such as cabinets, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark) / compact discs, audio / video equipment such as DVDs Parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office electrical product parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts, washing Machine-related parts represented by jigs, motor parts, lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternator terminals, alternator connectors, IC regulators, light diodes For Various valves, such as a nichiometer base, exhaust gas valve, fuel-related / cooling system / brake system / wiper system / exhaust system / intake system pipe / hose / tube, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant Joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioning thermostat base, heating Hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dus Tributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, wire harness connector, SMJ connector, PCB connector, door grommet connector, fuse connector, etc. Connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, torque control lever, safety belt component, register blade, washer lever , Window regulator handle, knob of window regulator handle, passing light levelー, Sun visor bracket, instrument panel, airbag peripheral parts, door pad, pillar, console box, various motor housings, roof rail, fender, garnish, bumper, door panel, roof panel, hood panel, trunk lid, door mirror stay, spoiler, Applicable to automobile / vehicle related parts such as hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers, wipers, etc.

  The thermoplastic resin composition produced according to the present invention is suitable for film and sheet applications, and is suitably used for soft members for automobile interiors, packaging films, desk mats, and the like.

  The thermoplastic resin composition produced according to the present invention is suitable as an automotive part, and is particularly suitably used for an impact absorbing member such as an automotive interior / exterior component and an automotive exterior plate.

  Hereinafter, the effects of the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example.

The following twin screw extruder was used for melt kneading of the thermoplastic resin composition.
Twin screw extruder: Co-rotating fully meshed twin screw extruder (TEM-37BS-26 / 2V manufactured by Toshiba Machine Co., Ltd., screw diameter 37 mm, L / D ₀ = 100, screw cross section is double thread) Provides six kneading zones starting from the positions L / D ₀ = 22, 28, 43, 55, 69, 77, 93, and the length Lk / D ₀ of each kneading zone is Lk / D ₀ = 1.8, 1.8, 2.3, 2.3, 2.3, 2.3, and 3.0.

In the same direction rotation complete meshing type twin screw extruder, sampling valves are installed at positions of L / D ₀ = 40 and 72, and the resin composition can be discharged also from these sampling valves. .

Furthermore, when the ratio (%) of the total length of the kneading zone to the total length of the screw is calculated by (total length of kneading zone) / (total length of screw) × 100, the discharge port (L / D ₀ = 100) When discharged from the kneading zone, the ratio of the total length of the kneading zone was 16%. Further, when discharged from a sampling valve with L / D ₀ = 40, it becomes 9%, and when discharged from a sampling valve with L / D ₀ = 72, it becomes 15%.

The thermoplastic resin composition was evaluated by molding the following test pieces and measuring physical properties.
(1) Injection molding of test piece Using Nissei Plastic Industries injection molding machine (NP7-1F), molding temperature: 260 ° C. or 290 ° C., mold temperature: 80 ° C., injection pressure: lower limit pressure + 5 kgf / cm ² A strip type test piece (width 10 mm × length 80 mm × thickness 4 mm) and a dumbbell type test piece (2 mm thickness) were prepared according to the above conditions.
(2) Measurement of impact strength The strip-shaped test piece obtained by injection molding was subjected to a Charpy impact tester 611 manufactured by Toyo Seiki Co., Ltd., and a Charpy impact test at a temperature of 23 ° C. and a humidity of 50% RH was performed according to ISO179.
(3) Measurement of load deflection temperature A strip-shaped test piece obtained by injection molding was conditioned for 48 hours under conditions of a temperature of 23 ° C. and a humidity of 50% RH. Using the test piece that had been subjected to state adjustment, the load deflection temperature at a load of 0.45 MPa or 1.80 MPa was measured in accordance with ISO 75-1,2.
(4) Measurement of tensile properties The dumbbell-shaped test piece obtained by injection molding was conditioned for 48 hours under the conditions of a temperature of 23 ° C. and a humidity of 50% RH. The tensile strength and tensile breaking elongation at a tensile speed of 5 mm / min were measured in accordance with ISO527-1, using the test piece that had been conditioned.

Unless otherwise indicated, the following were used for the raw material which comprises a thermoplastic resin composition.
PA6 resin: Polyamide 6 resin (“CM1017” manufactured by Toray Industries, Inc.)
PPO resin: Polyphenylene oxide resin ("PX-100F" manufactured by Mitsubishi Engineering Plastics)
GMA-modified PE copolymer: Glycidyl methacrylate-modified polyethylene copolymer ("Bond First BF-7L" manufactured by Sumitomo Chemical Co., Ltd.)
EMAA-Zn copolymer: ethylene-methacrylic acid-zinc methacrylate copolymer (Mitsui / DuPont Polychemical "High Milan 1706")
SMA copolymer: styrene-maleic anhydride copolymer ("Dylark 332" manufactured by Nova Chemical)
SEBS: Hydrogenated styrene-butadiene-styrene copolymer (“Clayton G1650” manufactured by Kraton Polymer Japan)

Example 1
While using PA6 resin as the thermoplastic resin (A) and GMA-modified PE copolymer as the rubbery polymer (B) having a reactive functional group, mixing in the composition shown in Table 1 and performing nitrogen flow Then, melt kneading was performed using the above-mentioned same-direction rotating fully meshed twin screw extruder, a cylinder temperature of 260 ° C., a screw rotation speed of 100 rpm, and an extrusion rate of 10 kg / h. At that time, the coloring agent was added together with the raw materials, and the residence time was measured as the time during which the coloration on the extrudate was maximized, and the residence time was 5 minutes.

During melt kneading, in the region of L / D ₀ = 40 to 95, supercritical carbon dioxide is introduced into the twin screw extruder at a flow rate of 0.5 kg / h to perform melt kneading, and the position of L / D ₀ = 96 The supercritical carbon dioxide was removed from the vacuum vent under reduced pressure and discharged from the discharge port (L / D ₀ = 100). The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa.

  Moreover, the discharged strand-shaped molten resin was cooled by passing through a cooling bath, and was cut while being taken out by a pelletizer, thereby obtaining a pellet-shaped sample of the thermoplastic resin composition. After the sample was dried, strip-type test pieces and dumbbell-type test pieces were prepared under the above conditions at a molding temperature of 260 ° C., and various characteristics were evaluated. The load at the load deflection temperature was 0.45 MPa. The results are shown in Table 1.

Example 2
Except for the following points, melt kneading was performed in the same manner as in Example 1, and the obtained thermoplastic resin composition was evaluated.

At the time of melt kneading, in the region of L / D ₀ = 40 to 67, supercritical carbon dioxide was introduced into the twin screw extruder at a flow rate of 0.5 kg / h to perform melt kneading, and the position of L / D ₀ = 68 The supercritical carbon dioxide was removed from the vacuum vent under reduced pressure and discharged from a sampling valve with L / D ₀ = 72. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa. The residence time was 3.5 minutes. The evaluation results of the obtained thermoplastic resin composition are shown in Table 1.

Example 3
An EMAA-Zn copolymer was used as the rubbery polymer (B) having a reactive functional group, and melt kneading was carried out in the same manner as in Example 1 except that it was mixed in the composition shown in Table 1. The obtained thermoplastic resin composition was evaluated. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa, and the residence time was 5 minutes. The evaluation results of the obtained thermoplastic resin composition are shown in Table 1.

Example 4
An EMAA-Zn copolymer was used as the rubbery polymer (B) having a reactive functional group, and melt kneading was carried out in the same manner as in Example 2 except that it was mixed in the composition shown in Table 1. The obtained thermoplastic resin composition was evaluated. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa, and the residence time was 3.5 minutes. The evaluation results of the obtained thermoplastic resin composition are shown in Table 1.

Comparative Example 1
Except for the following points, melt kneading was performed in the same manner as in Example 1, and the obtained thermoplastic resin composition was evaluated.

At the time of melt kneading, the extrusion rate is 20 kg / h, L / D ₀ = 20 to 35, supercritical carbon dioxide is introduced into the twin screw extruder at a flow rate of 0.5 kg / h, and melt kneading is performed. Supercritical carbon dioxide was removed from the vacuum vent at a position of L / D ₀ = 36 in a reduced pressure state, and discharged from a sampling valve of L / D ₀ = 40. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 21) was 10 MPa. The residence time was 0.5 minutes. Table 1 shows the evaluation results of the obtained thermoplastic resin composition.

Comparative Example 2
Except that supercritical carbon dioxide was not introduced into the twin screw extruder, melt kneading was carried out in the same manner as in Example 1, and the obtained thermoplastic resin composition was evaluated. The residence time was 5 minutes. The evaluation results of the obtained thermoplastic resin composition are shown in Table 1.

Comparative Example 3
An EMAA-Zn copolymer was used as the rubbery polymer (B) having a reactive functional group, and melt kneading was carried out in the same manner as in Comparative Example 1 except that it was mixed in the composition shown in Table 1. The obtained thermoplastic resin composition was evaluated. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 21) was 10 MPa, and the residence time was 0.5 minutes. The evaluation results of the obtained thermoplastic resin composition are shown in Table 1.

Comparative Example 4
Except that supercritical carbon dioxide was not introduced into the twin screw extruder, melt kneading was carried out in the same manner as in Example 3, and the obtained thermoplastic resin composition was evaluated. The residence time was 5 minutes. The evaluation results of the obtained thermoplastic resin composition are shown in Table 1.

From Examples 1 to 4, a thermoplastic resin composition produced by introducing supercritical carbon dioxide at the time of melt-kneading using a twin-screw extruder having an L / D ₀ of 60 or more has impact resistance, Excellent heat resistance and tensile elongation were observed.

On the other hand, when Comparative Example 1 was produced by using a twin screw extruder having an L / D ₀ of less than 60 and introducing supercritical carbon dioxide, the thermoplastic resin composition was the same as in Examples 1 and 2. In comparison with Examples 1 to 4, it was revealed that the impact resistance, heat resistance and tensile elongation were inferior. In addition, the same relationship is recognized between Comparative Example 3 and Examples 3 and 4.

In Comparative Example 2, even when a twin screw extruder having an L / D ₀ of 60 or more is used, when supercritical carbon dioxide is not introduced at the time of melt kneading, compared with Example 1, impact resistance and heat resistance It became clear that it was inferior in property and tensile elongation. The same can be seen from the comparison between Comparative Example 4 and Example 1.

Examples 5 and 6
PA6 resin is used as the thermoplastic resin (A), PPO resin is used as the thermoplastic resin (C), and SMA copolymer is used as the compound (D) having a reactive functional group. While performing the nitrogen flow, the above-mentioned co-rotating fully meshing type twin screw extruder was used, melt kneading was performed at a cylinder temperature of 290 ° C., a screw rotation speed of 25 rpm, and an extrusion rate of 5 kg / h. At the time of melt kneading, in the region of L / D ₀ = 40 to 95, supercritical carbon dioxide was introduced into the twin screw extruder at a flow rate of 0.25 kg / h to perform melt kneading, and the position of L / D ₀ = 96 The supercritical carbon dioxide was removed from the vacuum vent under reduced pressure and discharged from the discharge port (L / D ₀ = 100). The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa. At that time, the residence time was 20 minutes.

  Moreover, the discharged strand-shaped molten resin was cooled by passing through a cooling bath, and was cut while being taken out by a pelletizer, thereby obtaining a pellet-shaped sample of the thermoplastic resin composition. After the sample was dried, strip-type test pieces and dumbbell-type test pieces were prepared under the above conditions at a molding temperature of 290 ° C., and various characteristics were evaluated. The load deflection temperature load was 1.80 MPa. The results are shown in Table 2.

Example 7
Except for the following points, melt kneading was carried out in the same manner as in Example 6, and the obtained thermoplastic resin composition was evaluated.

At the time of melt kneading, in the region of L / D ₀ = 40 to 67, supercritical carbon dioxide is introduced into the twin screw extruder at a flow rate of 0.25 kg / h to perform melt kneading, and the position of L / D ₀ = 68 The supercritical carbon dioxide was removed from the vacuum vent under reduced pressure and discharged from a sampling valve with L / D ₀ = 72. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa. The residence time was 12 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Example 8
Melt kneading was carried out in the same manner as in Example 5 except that maleic anhydride was used as the compound (D) having a reactive functional group and the composition shown in Table 2 was adopted. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa, and the residence time was 20 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Example 9
Melt kneading was carried out in the same manner as in Example 5 except that SEBS was blended as the other components to obtain the blending composition shown in Table 2. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 41) was 10 MPa, and the residence time was 21 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Comparative Example 5
Except for the following points, melt kneading was carried out in the same manner as in Example 5, and the obtained thermoplastic resin composition was evaluated.

During _{melt-kneading,} in the region of L / D 0 = 20~35, performed introducing the kneaded biaxial extruder supercritical carbon dioxide at a flow rate of 0.5 kg / h, the position of _{L /} D 0 = 36 Supercritical carbon dioxide was removed from the vacuum vent in a reduced pressure state, and discharged from a sampling valve with L / D ₀ = 40. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 21) was 10 MPa. At that time, the residence time was 5 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Comparative Example 6
Except that supercritical carbon dioxide was not introduced into the twin screw extruder, melt kneading was carried out in the same manner as in Example 5, and the obtained thermoplastic resin composition was evaluated. The residence time was 20 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Comparative Example 7
Except for the following points, melt kneading was carried out in the same manner as in Example 6, and the obtained thermoplastic resin composition was evaluated.

During _{melt-kneading,} in the region of L / D 0 = 20~35, performed introducing the kneaded biaxial extruder supercritical carbon dioxide at a flow rate of 0.5 kg / h, the position of _{L /} D 0 = 36 Supercritical carbon dioxide was removed from the vacuum vent in a reduced pressure state, and discharged from a sampling valve with L / D ₀ = 40. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 21) was 10 MPa. At that time, the residence time was 5 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Comparative Example 8
Except that supercritical carbon dioxide was not introduced into the twin screw extruder, melt kneading was carried out in the same manner as in Example 6, and the obtained thermoplastic resin composition was evaluated. The residence time was 20 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Comparative Example 9
Melt kneading was carried out in the same manner as in Comparative Example 5 except that maleic anhydride was used as the compound (D) having a reactive functional group and the blending composition shown in Table 2 was adopted. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 21) was 10 MPa, and the residence time was 5 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

Comparative Example 10
Melt kneading was carried out in the same manner as in Comparative Example 5 except that SEBS was blended as the other components to obtain the blending composition shown in Table 2. The molten resin pressure in the extruder at the supercritical carbon dioxide introduction position (L / D ₀ = 21) was 10 MPa, and the residence time was 5 minutes. Table 2 shows the evaluation results of the obtained thermoplastic resin composition.

From Examples 5 to 9, a thermoplastic resin composition produced by introducing supercritical carbon dioxide at the time of melt-kneading using a twin-screw extruder having an L / D ₀ of 60 or more has impact resistance, Excellent heat resistance and tensile elongation were observed.

On the other hand, when Comparative Examples 5, 7, 9, and ₁₀ were produced by introducing supercritical carbon dioxide using a twin screw extruder having an L / D ₀ of less than 60, the resulting thermoplastic resin composition was Even when the resin composition was the same, it was revealed that the resin composition was inferior in impact resistance, heat resistance and tensile elongation as compared with the corresponding Examples 5 to 9.

Further, from Comparative Examples 6 and 8, even when a twin screw extruder having an L / D ₀ of 60 or more is used, when no supercritical carbon dioxide is introduced during melt kneading, the resulting thermoplastic resin composition has a resin composition Even if is the same, it became clear that it was inferior in impact resistance, heat resistance and tensile elongation as compared with the corresponding Examples 5 and 6.

It is explanatory drawing of the screw segment used suitably for the manufacturing method of this invention.

Explanation of symbols

1 Screw 2 Seal plate 2f (Seal plate) Flange 3 Cylinder barrel

Claims (7)

A method for producing a thermoplastic resin composition of the following (I) or (II), wherein a raw resin is used by using a twin screw extruder having a screw length L and a screw diameter D ₀ ratio L / D ₀ of 60 or more. A method for producing a thermoplastic resin composition in which melt kneading is carried out in the presence of a supercritical fluid.
(I) At least one thermoplastic resin (A) selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, and amino group, carboxyl group, carboxyl metal salt, epoxy group, acid anhydride group A thermoplastic resin composition (II) comprising a rubbery polymer (B) having at least one reactive functional group selected from oxazoline groups (from polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin) At least one selected from the group consisting of at least one thermoplastic resin (A), polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, and polycarbonate resin. Kinetsu (excluding vulcanizable rubber) different thermoplastic resin as the thermoplastic resin (A) (C) and an amino group, a carboxyl group, a carboxyl metal salt, epoxy group, acid anhydride group, at least one selected from an oxazoline group A thermoplastic resin composition comprising a compound (D) having a kind of reactive functional group.   The residence time from the supply of the raw material resin to the twin-screw extruder until the extrusion is 1 minute to 30 minutes, and the amount of extrusion is melt-kneaded under conditions of 0.01 kg / h or more per 1 rpm of the screw rotation. A method for producing a thermoplastic resin composition.   The method for producing a thermoplastic resin composition according to claim 1 or 2, wherein the screw of the twin-screw extruder is a co-rotating fully meshing type. Method for producing a supercritical the length of the melt-kneading area in the presence of fluid and Ls, the thermoplastic resin composition according to any one of claims 1 to 3 Ls / D ₀ is 20 or more.   The method for producing a thermoplastic resin composition according to any one of claims 1 to 4, wherein the supercritical fluid is supercritical carbon dioxide or supercritical nitrogen.   The screw of the twin-screw extruder has a plurality of kneading zones in the longitudinal direction, and the total length of these kneading zones is 5 to 50% of the screw length. A process for producing the thermoplastic resin composition according to claim 1. Production method of the respective lengths Lk of the kneading zone, a thermoplastic resin composition according to any one of claims 1 to 6 satisfy Lk / D ₀ = 0.2~10.

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