JP2005187809A - Resin composition and its production process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly structure-controlled resin composition which is excellent in the balance of normally incompatible properties such as impact resistance and rigidity and the like, is unlikely to be damaged in its appearance after deformation and can be usefully used as a structural material or a functional material. <P>SOLUTION: This resin composition is obtained by blending (A) a thermoplastic resin and (B) a resin having a reactive functional group. In this resin composition, either structure of following (I) or (II) is formed: (I) either one of (A) or (B) forms a continuous phase, the other forms a dispersed phase, and fine particles of an average particles size of not more than 300 nm is present in the continuous phase and the dispersed phase; (II) both (A) and (B) form continuous phases and fine particles of an average particles size of not more than 300 nm is present in the two continuous phases. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a resin composition that has an excellent balance of conflicting properties such as impact resistance and rigidity, and that hardly deteriorates the appearance after deformation, and can be used effectively as a structural material or a functional material. The present invention relates to a controlled resin composition and a method for producing the same.

  In recent years, demands for performance and functions of polymer materials are increasing day by day, and in particular, a high balance of conflicting properties is required. For example, there is no time for enumeration, such as compatibility between impact resistance and rigidity required for automotive materials, compatibility between weight reduction and strength, and compatibility between impact resistance and heat resistance due to miniaturization of materials for electrical and electronic equipment. . In addition, the required characteristics are also diversified with the development of the industry, and it is almost difficult to cope with a single polymer. Therefore, in recent years, a polymer alloy method using a plurality of polymers has become the mainstream in the development of polymer materials. In particular, there are now active attempts to achieve dramatic improvements in properties through advanced control of morphology.

For example, by forming a dispersed phase composed of a rubber component in a continuous phase composed of a polypropylene resin, and further allowing a modified polypropylene resin and a compound capable of reacting with the modified polypropylene to be present in the dispersed phase, impact resistance is improved. A method for making the flexural modulus compatible is disclosed (see Patent Document 1). In addition, the (meth) acrylic polymer component is a continuous phase and the modified urethane elastomer component is a dispersed phase, and the dispersed phase has a microphase-separated structure including a part of the (meth) acrylic polymer component. By forming a morphology in which at least a part of the (meth) acrylic polymer component and at least a part of the modified urethane elastomer component are chemically bonded, weather resistance, transparency, scratch resistance, and rigidity are improved. A method for improving impact resistance without sacrificing is disclosed (see Patent Document 2). In addition, by dispersing the hydrogenated block copolymer in a continuous phase composed of a polypropylene resin and a dispersed phase composed of a rubber-like polymer, impact resistance, embrittlement temperature, rigidity, surface hardness, tensile elongation at break Has been disclosed (see Patent Document 3).
Among polymer materials, especially engineering plastics are widely used in various industrial fields such as structural materials and functional materials because they have excellent heat resistance, mechanical properties, and impact resistance properties.

  For example, the use of polyamide resins and polybutylene terephthalate resins, which are typical engineering plastics, is limited only by using them individually, so improvement by alloying with other resins, especially in recent years, morphology Many improvements have been made by controlling the above.

  Examples of improving the properties by controlling the morphology include a continuous phase composed of a polyamide resin and a particulate dispersed phase composed of a polyolefin modified with an α, β-unsaturated carboxylic acid dispersed in the continuous phase. Thus, a method of improving impact strength and surface peel strength by controlling the number average particle size of the dispersed phase and its distribution has been disclosed (see Patent Document 4). In addition, the presence of a modified polyolefin and an unmodified polyolefin as a dispersed phase of a core-shell type particle structure in a polyamide resin continuous phase provides a good balance of low water absorption, dimensional stability, rigidity, toughness, and moldability. A method of improving is disclosed (see Patent Document 5).

Further, a method for improving impact resistance is disclosed by controlling the distance between average particles of a dispersed phase composed of a modified thermoplastic elastomer using polybutylene terephthalate resin in a continuous phase (see Patent Document 6). .
Japanese Patent Laid-Open No. 08-183887 JP 2000-319475 A JP 2001-106844 A JP 9-31325 A Japanese Patent Laid-Open No. 9-59438 Japanese Patent Laid-Open No. 7-166041

  However, in the methods described in Patent Documents 1 and 2, since the high-level structure control in the continuous phase is not performed, the effect of impact resistance is insufficient. Further, in the method described in Patent Document 3, the dispersion size of the rubber-like polymer is not controlled, and it is difficult to say that the balance of the characteristics is sufficient. In the methods described in Patent Documents 4 and 6, the basic phase structure is a simple sea-island structure, and there is a problem that even if the impact strength is improved, other characteristics such as rigidity and heat resistance are deteriorated. In the method described in Patent Document 5, advanced structural control in the continuous phase is not performed, and it is difficult to say that the improvement effects such as low water absorption, dimensional stability, rigidity, and toughness are necessarily sufficient. In addition, when used for exteriors, these inventions also have problems such as deterioration of the appearance due to whitening after deformation due to external force, and a new technology that can cope with these problems is demanded. .

  The present invention is a resin composition that has an excellent balance of conflicting properties such as impact resistance and rigidity, and that hardly deteriorates the appearance after deformation, and can be used effectively as a structural material or a functional material. It is an object to provide a controlled resin composition.

  As a result of diligent studies to solve the above problems, the present inventors have found that a resin composition having a specific phase structure is blended with a resin having a reactive functional group and has the above characteristics, thereby completing the present invention. I came to let you.

  That is, this invention consists of following (1)-(10).

  (1) A resin composition comprising a thermoplastic resin (A) and a resin (B) having a reactive functional group, wherein the structure shown in either (I) or (II) below is formed A resin composition characterized by comprising:

 (I) One of (A) or (B) forms a continuous phase and the other forms a dispersed phase, and fine particles having an average particle diameter of 300 nm or less exist in these continuous phase and dispersed phase.

 (II) Both (A) and (B) form a continuous phase, and fine particles having an average particle diameter of 300 nm or less exist in both continuous phases.

  (2) The resin composition according to (1) above, wherein the fine particles having an average particle diameter of 300 nm or less are composed of a compound produced by a reaction between the thermoplastic resin (A) and the resin (B) having a reactive functional group.

  (3) The resin composition according to (1) or (2), wherein the average particle size is 1 nm to 300 nm.

  (4) The resin according to any one of (1) to (3), wherein the thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyacetal resin, and styrene resin. Composition.

  (5) The resin composition according to any one of (1) to (4), wherein the resin (B) having a reactive functional group is a rubbery polymer having a reactive functional group.

  (6) The resin composition according to any one of (1) to (5), wherein the reactive functional group is at least one functional group selected from an epoxy group, an acid anhydride group, and an oxazoline group.

  (7) The blending ratio of the thermoplastic resin (A) and the resin (B) having a reactive functional group is 95/5 to 5/95 in a weight ratio, and any one of the above (1) to (6) Resin composition.

  (8) When the screw length of the twin screw extruder is L and the screw diameter is D, a thermoplastic resin (A) and a resin having a reactive functional group using a twin screw extruder with L / D> 45 ( The method for producing a resin composition according to any one of (1) to (7), wherein B) is melt-kneaded.

  (9) A molded article comprising the resin composition according to any one of (1) to (7).

  (10) A film or sheet comprising the resin composition according to any one of (1) to (7) above.

  The present invention provides a resin composition having excellent balance of conflicting properties such as impact resistance and rigidity by highly controlling the structure, and having little damage to the appearance after deformation. It can be usefully used as a structural material or functional material for electronic parts or automobile parts.

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

  The resin composition of the present invention is a resin composition comprising a thermoplastic resin (A) and a resin (B) having a reactive functional group, wherein one of (I) (A) or (B) is A continuous phase, the other forms a dispersed phase, and a structure in which fine particles having an average particle diameter of 300 nm or less exist in these continuous phase and dispersed phase, or (II) (A) and (B) form a continuous phase. A structure in which fine particles having an average particle diameter of 300 nm or less exist in both continuous phases is characterized.

  In the case of (I), the resin constituting the continuous phase is either a thermoplastic resin (A) or a resin (B) having a reactive functional group, and is not particularly limited, but the characteristics as the thermoplastic resin (A) If it is mainly required, the continuous phase is preferably composed of the thermoplastic resin (A). In that case, the dispersed phase is composed of a resin (B) having a reactive functional group.

  The fine particles having an average particle diameter of 300 nm or less of the present invention may be present at the interface between the continuous phase and the dispersed phase or at the interface between both continuous phases, in addition to the continuous phase and the dispersed phase or both continuous phases. Further, the substance constituting the fine particles is not particularly limited, but as a preferred example, a resin having a reactive functional group with the thermoplastic resin (A) at the interface between the continuous phase and the dispersed phase or the interface between both continuous layers. The compound produced | generated by reaction with (B) is mentioned. In this case, the compound is affected by an external field such as a shear field and moves from the interface into the continuous phase and the dispersed phase, or into both continuous phases, and a segment having a high affinity with the transferred phase faces outward. It exists as a micelle form.

  Such a dispersed structure can be confirmed by observation with a transmission electron microscope, for example. The magnification that can be confirmed by observation with a transmission electron microscope is the magnification that is observed with ordinary transmission electron microscope observation, and varies depending on the size of the fine particles, but in the present invention, it is used in the range of 5000 to 100,000 times, In particular, when the size of the fine particles is 100 nm or less, it is used in the range of 10,000 times to 100,000 times.

  The average particle size of the dispersion layer is not particularly limited as long as it is a size capable of containing fine particles, but is preferably 100 to 1000 nm, more preferably 100 to 500 nm, and more preferably 100 to 500 nm from the viewpoint of impact resistance and the like. More preferably, it is 200 nm.

  The average particle size of fine particles having an average particle size of 300 nm or less is preferably 1 to 300 nm, but in order not to impair the appearance after deformation, the range of 5 to 100 nm is more preferable, and the range of 10 to 20 nm is preferable. Further preferred.

  The thermoplastic resin (A) used in the present invention is not particularly limited as long as it is a resin that can be molded by heating and melting. For example, polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polysulfone resin, Polyacetal resin, Polytetrafluoroethylene resin, Polyetherimide resin, Polyamideimide resin, Polyimide resin, Polycarbonate resin, Polyethersulfone resin, Polyetherketone resin, Polythioetherketone resin, Polyetheretherketone resin, Polyethylene resin, Polypropylene resin Further, it can be used as at least one resin selected from styrene resins such as polystyrene resin and ABS resin, rubbery polymers, polyalkylene oxide resins and the like.

  Of the thermoplastic resins shown above, polyamide resins, polyester resins, polyphenylene sulfide resins, polyacetal resins, and styrene resins are preferably used. Particularly, polyamide resins and polyester resins have high terminal group reactivity. Most preferably used.

  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 Melendiamine, 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-me Aliphatic, alicyclic, aromatic diamines, and adipic acid, such as til-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 used as moldability, heat resistance, toughness, surface, and the like. Although it is also practically preferable to use it as a mixture depending on required properties such as properties, polyamide 6 is most preferred among these.

  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. The polyester resin refers to a thermoplastic resin composed of a polymer having an ester bond in the main chain, and a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). Examples thereof include a polymer or a copolymer obtained by a condensation reaction having a main component, or a mixture thereof.

  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 and most 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, these polybutylene terephthalate resins are 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). It can be preferably used from the viewpoint of the property and the effect of suppressing anisotropy.

  The resin (B) having a reactive functional group of the present invention is a resin having a reactive functional group in a molecular chain.

  The resin serving as the base of the resin (B) having a reactive functional group of the present invention is not particularly limited. For example, polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polysulfone resin, polyacetal resin, tetrafluoride Polyethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polycarbonate resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyethylene resin, polypropylene resin, polystyrene resin and ABS resin It can be used as at least one kind of resin different from the above-mentioned thermoplastic resin (A) selected from styrene-based resins such as rubber polymer, polyalkylene oxide resin, etc. . Among these, polyethylene resin, polypropylene resin, styrene resin, and rubbery polymer are preferable from the viewpoint of easy introduction of the reactive functional group, and rubber polymer is more preferable from the viewpoint of impact resistance and toughness improvement effect.

  Here, the rubbery polymer generally includes a polymer having a glass transition temperature lower than room temperature (23 ° C.), and a part of the intermolecular molecule is covalent bond, ionic bond, van der Waals force, entanglement, etc. Refers to polymers that are constrained to each other. For example, polybutadiene, polyisoprene, styrene-butadiene random copolymer and block copolymer, hydrogenated product of the block copolymer, acrylonitrile-butadiene copolymer, diene rubber such as butadiene-isoprene copolymer, Random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and α-olefin, ethylene such as ethylene-methacrylate, ethylene-butyl acrylate -Copolymers with unsaturated carboxylic acid esters, acrylic acid ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, and copolymers of ethylene and fatty acid vinyls such as ethylene-vinyl acetate. Polymer, Eth Ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer, butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer, polyester elastomer, etc. Preferred examples include thermoplastic elastomers. Among these, when a polyamide resin or polybutylene terephthalate is used as the thermoplastic resin (A), a copolymer with an ethylene-unsaturated carboxylic acid ester is preferably used from the viewpoint of compatibility.

  The unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer is an ester of acrylate, preferably acrylic acid and alcohol. Specific examples of the unsaturated carboxylic acid ester include acrylic acid esters such as ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate. The weight ratio of the ethylene component to the acrylate component in the copolymer is not particularly limited, but is preferably in the range of 10: 1 to 1:10, more preferably 5: 1 to 1: 5.

  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 50000 from the viewpoint of fluidity and mechanical properties.

  The reactive functional group in the present invention is not particularly limited as long as it reacts with the functional group present in the thermoplastic resin (A). For example, an amino group, a carboxyl group, a hydroxyl group, an acid anhydride group, Examples thereof include at least one selected from an epoxy group, an isocyanate group, a mercapto group, an oxazoline group, a sulfonic acid group, and the like. Among these, an epoxy group, an acid anhydride group, an isocyanate group, and an oxazoline group are preferably used because of their high reactivity and few side reactions such as decomposition and crosslinking. More preferably used are an epoxy group, an acid anhydride group, and an oxazoline group.

  Examples of the acid anhydride in the 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.

  The method for introducing the acid anhydride group into the rubbery polymer can be performed by a generally known technique, and is not particularly limited. For example, the acid anhydride and the monomer that is a raw material of the rubbery polymer And a method of grafting an acid anhydride onto a rubbery polymer.

  The method for introducing the epoxy group into the rubbery polymer can be carried out by a generally known technique and is not particularly limited. For example, a vinyl monomer having an epoxy group is used as a raw material for the rubbery polymer. A method of copolymerizing with a monomer, a method of polymerizing a rubber polymer using a polymerization initiator or a chain transfer agent having the above functional group, a method of grafting an epoxy compound onto the rubber polymer, and the like. Can do.

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

  The number of functional groups per molecular chain in the resin (B) having a reactive functional group is not particularly limited, but usually 1 to 10 is preferable, and 1 to 5 in order to reduce side reactions such as crosslinking. Preferably. 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 blending ratio of the thermoplastic resin (A) and the resin (B) having a reactive functional group in the present invention is not particularly limited, but for improving mechanical properties, (weight of (A)) / The (weight of (B)) is preferably in the range of 5/95 to 95/5, more preferably in the range of 10/90 to 90/10, and the range of 20/80 to 80/20 is the most effective in improving the mechanical properties. Is high and preferable.

  The method for carrying out the reaction between the thermoplastic resin (A) and the resin (B) having a reactive functional group is not particularly limited, and the reaction in a diluted state in a common solvent, the reaction in a suspension, One is a reaction in a solid state, and a reaction is both in a molten state. The reaction can be properly used depending on the type of the resin / functional group of both, but usually a reaction in a molten state is preferable. The method by melt kneading using a screw extruder is most preferable because it can simultaneously perform reaction and kneading.

  When a twin screw extruder is used, a twin screw extruder having a large L / D value is preferably used. Here, L / D is a value obtained by dividing the screw length L by the screw diameter D. The screw length refers to the length from the position where the screw base material is supplied to the screw tip. The larger the L / D, the longer the residence required for the reaction with the thermoplastic resin (A) and the resin (B) having a reactive functional group, and for the generation of a fine dispersed phase comprising a copolymer formed by the reaction. It is possible to provide both time and shear fields without sacrificing. When sampling from the middle part of the extruder using an extruder having a sampling valve or the like, the length of L is equal to “the length from the position where the raw material at the screw base is supplied to the sampling location”. It can be considered that the screw diameter D is the same as that kneaded by a normal extruder equal to the screw diameter of an extruder having a sampling valve or the like. The sampling location here refers to the position on the screw shaft closest to the hole through which the resin in the cylinder is discharged. The range of L / D size is preferably 46 to 200, more preferably 60 to 200, and even more preferably 80 to 200. Moreover, there is no restriction | limiting in particular as a rotational speed of a screw, Although it can adjust suitably with the raw material to be used, Usually, it is performed in the range of 20-500 times / min, Preferably it is 30-400 times / min, More preferably It is performed in the range of 40 to 300 times / minute.

  In the present invention, a filler may be used as necessary in order 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 is usually 30 to 400 parts by weight based on 100 parts by weight of the resin composition.
Furthermore, in the resin composition of the present invention, other thermoplastic resins, rubbers, and various additives can be blended as required within the range not impairing the characteristics.

Such various additives include crystal nucleating agents, anti-coloring agents, antioxidants such as hindered phenols and hindered amines, mold release agents such as ethylene bisstearylamide and higher fatty acid esters, plasticizers, heat stabilizers, lubricants, Examples thereof include an ultraviolet inhibitor, a colorant, and a flame retardant.
These thermoplastic resins, rubbers, and various additives can be blended at any stage for producing the resin composition of the present invention. For example, they are added simultaneously when blending two-component resins. And a method of adding a two-component resin after melt-kneading in advance, and a method of adding it to one resin first and then melt-kneading and then blending the remaining resin.

  The molding method of the resin composition obtained from the present invention can be any method, and the molding shape can be any shape. Examples of the molding method include extrusion molding, injection molding, hollow molding, calendar molding, compression molding, vacuum molding, foam molding, etc., and pellets, plates, films or sheets, pipes, hollows, boxes It can be formed into a shape such as a shape.

  Applications of the molded body of the resin composition of the present invention include connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various types Terminal board, 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, computer-related parts, etc. Suitable for electronic component applications such as generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, other poles Rod, electrical component cabinet, etc. Electrical equipment parts use, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark) / compact discs, DVD and other audio / video equipment parts, lighting parts , Refrigerator parts, air conditioner parts, typewriter parts, homes such as word processor parts, office electrical product parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motors Machine-related parts represented by parts, lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternator terminals, alternator connectors, IC regulators, potentiometers for light dials Meter base Various valves such as exhaust gas valves, fuel-related / cooling / brake / wiper / exhaust / intake pipes, hoses / tubes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body , Carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve , Brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, distributors, stars Starter relay, 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., 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 parts, register blade, washer lever, window regulator Handle, window regulator knob, passing light lever, sun visor bra , Instrument panel, airbag peripheral parts, door pad, pillar, console box, motor housing, roof rail, fender, garnish, bumper, door panel, roof panel, hood panel, trunk lid, door mirror stay, spoiler, hood louver, It can be applied to automobile / vehicle-related parts such as wheel covers, wheel caps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers and wipers.

  In addition, since the resin composition obtained from the present invention has little discoloration after deformation, it is suitable for film and sheet applications, and is suitably used for soft members for automobile interiors, packaging films, desk mats and the like.

  Hereinafter, an example is given and the effect of the present invention is further explained.

  Unless otherwise specified, the raw materials described below were used.

Polyamide 6 resin: “CM1017” (manufactured by Toray Industries, Inc.)
Polybutylene terephthalate resin (hereinafter abbreviated as PBT resin)
: "1401X06" (Toray Industries, Inc.)
Glycidyl methacrylate-modified polyethylene copolymer (hereinafter abbreviated as GMA-modified PE copolymer): “Bond First BF-7L” (manufactured by Sumitomo Chemical Co., Ltd.)
Unmodified polyethylene copolymer (hereinafter abbreviated as unmodified PE copolymer)
: "Elvalloy AC" (DuPont)

Examples 1-6, Comparative Examples 1-3
While mixing the polyamide resin, PBT resin, GMA-modified PE copolymer and unmodified PE copolymer shown above in the composition shown in Tables 1-2, removing volatiles by a vacuum pump and performing nitrogen flow , Screw diameter 37mm, L / D100.2, same direction rotating twin screw extruder (Toshiba Machine Co., Ltd., TEM-37BS-25 / 2V): The screw uses two screws with two threads, barrel set temperature Melt extrusion was performed at 260 ° C. The screw rotation speed was 100 times / minute.

  For the observation of morphology, a sample obtained by quenching a molten resin discharged by melt extrusion with cold water was stained with a PE copolymer with ruthenium tetroxide, and then an ultrathin section was cut out. Thereafter, the sample was observed with a transmission electron microscope at a magnification of 35,000 times, and the obtained image was confirmed for the basic structure and the presence or absence of fine particles of 300 nm or less. One of the structures shown in Fig. 1 was obtained. In addition, “Yes” is entered when fine particles are present in each phase, and “None” is indicated otherwise.

(I) One forms a continuous layer and the other forms a dispersed layer.
(II) Both form a continuous layer.

  The average particle size of the dispersed phase and / or fine particles was calculated by image analysis. As an image analysis method, Scion Corporation's image analysis software “Scion Image” is used to calculate the average value of the major axis and minor axis of the dispersed layer or fine particles present in the electron micrograph, and the major axis and minor axis. The average particle size was calculated as the average value of.

Moreover, the discharged strand-shaped molten resin was cooled by passing through a cooling bath, and was cut while being wound by a pelletizer to obtain a pellet-shaped sample. After the sample was dried, test specimens for evaluation were prepared under the following conditions, and various characteristics were evaluated.
(1) Flexural modulus A strip-shaped test piece using an injection molding machine (J55ELII) manufactured by Nippon Steel Works under the conditions of molding temperature: 240 ° C., mold temperature: 40 ° C., injection pressure: lower limit pressure + 10 kgf / cm ^2. Was prepared, and the flexural modulus was measured according to ASTM D-790 for a sample conditioned for 48 hours at 23 ° C. and 50% RH.
(2) Izod impact strength Izod impact test specimens using an injection molding machine (J55ELII) manufactured by Nippon Steel Works under the conditions of molding temperature: 240 ° C., mold temperature: 40 ° C., injection pressure: lower limit pressure + 10 kgf / cm ² The sample was notched with a notch cutter, and the Izod impact strength was measured at 23 ° C. according to ASTM D-256 for a sample conditioned for 48 hours under the conditions of 23 ° C. and 50% RH. (3) Surface appearance after deformation Using an injection molding machine (J55ELII) manufactured by Nippon Steel Co., Ltd., 5 inches under conditions of molding temperature: 240 ° C., mold temperature: 40 ° C., injection pressure: lower limit pressure + 10 kgf / cm ² A strip-shaped test piece of × 1/2 inch × 1/8 inch (127.0 mm × 12.7 mm × 3.2 mm) was prepared, conditioned at 23 ° C. and 50% RH for 48 hours, and then bent 180 °. Then, the deformation part of the test piece returned to the original state was observed visually and judged by the following index.

  ○: No or almost no change in appearance due to whitening, Δ: Appearance change due to whitening is observed, ×: Whitening is remarkable.

  From Examples 1 and 2, it was confirmed that the samples kneaded with the polyamide resin 6 and the GMA-modified PE copolymer had fine particles in the continuous phase and the dispersed phase. It was revealed that these mechanical properties and the appearance after deformation are very excellent.

  As an example, a photograph of the morphology of the resin composition of Example 2 is shown in FIG. In the drawing, portions A and B are shown as schematic views in FIGS. From these figures, it can be seen that the resin composition of the present invention contains dispersed particles having an average particle diameter of 300 nm or less in the continuous layer and the dispersed layer. Moreover, about the composition of Examples 3-4, the continuous layer was formed together and presence of microparticles | fine-particles was confirmed in both continuous layers. It became clear that these mechanical properties and the appearance after deformation were also excellent.

  On the other hand, from Comparative Examples 1 and 2, it was found that when an unmodified PE copolymer was used, no fine particles were present in either the continuous phase or the dispersed phase. It was found that the mechanical properties and the appearance after deformation of this composition were greatly inferior as compared with Examples 1-2.

  From Examples 5 to 6, it was confirmed that the samples kneaded with the PBT resin and the GMA-modified PE copolymer had fine particles in the continuous phase and the dispersed phase. It was revealed that these mechanical properties and the appearance after deformation are very excellent.

  On the other hand, from Comparative Example 3, it was found that when an unmodified PE copolymer was used, no fine particles were present in the continuous phase or the dispersed phase. It was found that the mechanical properties and the appearance after deformation of this composition were greatly inferior as compared with Examples 5-6.

Examples 7-11, Comparative Examples 4-5
The polyamide resin used in Examples 1 to 4 and the GMA-modified PE copolymer were mixed in the composition shown in Table 3, and the screw diameter was 37 mm and L / D100 while performing the removal of volatiles by a vacuum pump and nitrogen flow. .2 Co-rotating twin screw extruder (Toshiba Machine Co., Ltd., TEM-37BS-25 / 2V): Two screws with two threads were used and melt extrusion was performed at a barrel set temperature of 260 ° C. The screw rotation speed was 100 times / minute.

  Also, a strand-shaped molten resin is taken out from the position of L / D shown in Table 3 through a sampling valve, cooled by passing through a cooling bath, and cut while being wound by a pelletizer to obtain a pellet-shaped sample. It was. Morphology and other various evaluations were performed in the same manner as in Examples 1-6.

  From Examples 7 to 11, when the value of L / D was larger than 45, the presence of fine particles was confirmed in the continuous phase and the dispersed phase. It was revealed that these mechanical properties and the appearance after deformation are very excellent.

  On the other hand, from Comparative Examples 4 to 5, it was found that when the L / D value was less than 45, no fine particles were present in the continuous phase or the dispersed phase. It was found that the mechanical properties and the appearance after deformation of this composition were greatly inferior as compared with Examples 7-11.

Examples 12-16, Comparative Examples 6-7
Polyamide 6 resin: 48.477% of Novamid 1010J manufactured by Mitsubishi Chemical Corporation and 20.7% of Novamid 1020J, 0.5% of antioxidant and 0.5% of dispersant were dry blended.

  Maleic anhydride-modified ethylene-1-butene copolymer (hereinafter abbreviated as MAH-modified ethylene-1-butene copolymer) mixture: 22.2% polypropylene "Mitsubishi Chemical Co., Ltd. Novatec 4100B" and ethylene-butene copolymer Polymer "Tafmer A-4085 made by Mitsui Chemicals Co., Ltd." 7.5% Organic peroxide "Nippon Yushi Co., Ltd. Perbutyl P" 0.015% liquid hydrocarbon at room temperature "Nippon Yushi Co., Ltd. ) NAS-4 "0.028% dissolved or diluted was added and blended with a tumbler for 10 minutes, then maleic anhydride 0.18% was added and blended again with a tumbler for 10 minutes.

  The raw material prepared by the above method is mixed with the composition shown in Table 4, and the same-direction rotating twin-screw extruder with a screw diameter of 37 mm and L / D of 100.2 is performed while removing the volatile matter by a vacuum pump and performing nitrogen flow. (Toshiba Machine Co., Ltd., TEM-37BS-25 / 2V): Two screws, two-threaded screws, were used and melt extruded at a barrel set temperature of 260 ° C. The screw rotation speed was 150 times / minute.

  Also, a strand-shaped molten resin is taken out from the L / D position shown in Table 4 through a sampling valve, cooled by passing through a cooling bath, and cut while being wound by a pelletizer to obtain a pellet-like sample. It was. Morphology and other various evaluations were performed in the same manner as in Examples 1-6.

  From Examples 12 to 16, when the value of L / D was larger than 45, the presence of fine particles was confirmed in the continuous phase and the dispersed phase. It was revealed that these mechanical properties and the appearance after deformation are very excellent.

  On the other hand, from Comparative Examples 6 to 7, it was found that when the value of L / D was less than 45, no fine particles were present in either the continuous phase or the dispersed phase. It was found that the mechanical properties and the appearance after deformation of this composition were greatly inferior as compared with Examples 12-16.

Examples 17-21, comparative examples 8-9
PBT resin: “1401X06” (manufactured by Toray Industries, Inc.)
MAH-modified ethylene-1-butene copolymer: “Tuffmer MA-8510” (manufactured by Mitsui Chemicals) The above raw materials are mixed in the composition shown in Table 5, while volatile components are removed by a vacuum pump and nitrogen flow is performed. , Screw diameter 37mm, L / D100.2, same direction rotating twin screw extruder (Toshiba Machine Co., Ltd., TEM-37BS-25 / 2V): The screw uses two screws with two threads, barrel set temperature Melt extrusion was performed at 260 ° C. The screw rotation speed was 100 times / minute.

  Also, a strand-like molten resin is taken out from the position of L / D shown in Table 5 through a sampling valve, cooled by passing through a cooling bath, and cut while being wound by a pelletizer to obtain a pellet-like sample. It was. Morphology and other various evaluations were performed in the same manner as in Examples 1-6.

  From Examples 17 to 21, when the value of L / D was larger than 45, the presence of fine particles was confirmed in the continuous phase and the dispersed phase. It was revealed that these mechanical properties and the appearance after deformation are very excellent.

  On the other hand, from Comparative Examples 8 to 9, it was found that when the value of L / D was less than 45, no fine particles were present in either the continuous phase or the dispersed phase. It was found that the mechanical properties and the appearance after deformation of this composition were greatly inferior as compared with Examples 17-21.

  From these results, it can be seen that a resin composition having a specific phase structure blended with a thermoplastic resin and a resin having a reactive functional group is excellent in mechanical properties and appearance after deformation.

It is a transmission electron micrograph of Example 2 of this invention (35,000 times). It is a schematic diagram of the A part in FIG. It is a schematic diagram of the B part in FIG.

Claims (10)

A resin composition comprising a thermoplastic resin (A) and a resin (B) having a reactive functional group, wherein the structure shown in either (I) or (II) below is formed. A resin composition characterized.
(I) One of (A) or (B) forms a continuous phase and the other forms a dispersed phase, and fine particles having an average particle diameter of 300 nm or less exist in these continuous phase and dispersed phase.
(II) (A) and (B) form a continuous phase, and fine particles having an average particle diameter of 300 nm or less exist in both continuous phases.   The resin composition according to claim 1, wherein the fine particles having an average particle size of 300 nm or less are composed of a compound produced by a reaction between the thermoplastic resin (A) and the resin (B) having a reactive functional group.   The resin composition according to claim 1 or 2, wherein the average particle size is 1 nm to 300 nm.   The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyacetal resin, and styrene resin.   The resin composition according to any one of claims 1 to 4, wherein the resin (B) having a reactive functional group is a rubbery polymer having a reactive functional group.   The resin composition according to claim 1, wherein the reactive functional group is at least one functional group selected from an epoxy group, an acid anhydride group, and an oxazoline group.   The resin composition according to any one of claims 1 to 6, wherein a blending ratio of the thermoplastic resin (A) and the resin (B) having a reactive functional group is 95/5 to 5/95 by weight.   When the screw length of the twin screw extruder is L and the screw diameter is D, a thermoplastic resin (A) and a resin (B) having a reactive functional group are obtained using a twin screw extruder of L / D> 45. The manufacturing method of the resin composition in any one of Claims 1-7 which melt-knead.   A molded article comprising the resin composition according to any one of claims 1 to 7. A film or sheet comprising the resin composition according to claim 1.

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