JP2006306918A - Resin molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent mechanical property, heat resistance and dimension stability, outstandingly excellent in chemical resistance and capable of being suitably used, for example, as molding materials such as automobile part materials, electric/electronic materials, industrial materials, engineering materials and domestic articles. <P>SOLUTION: The resin molded article comprises a resin composition (X) containing 1-99 pts.wt. of polytrimethylene terephthalate (A) and 99-1 pt.wt. of polycarbonate (B). A phase containing the component (A) as a main component and/or a phase containing the component (B) as a main component exist on 50% or more of a depth area from a surface of the resin molded article to depth of 10 &mu;m parallel to the surface of the molded article and in a layer shape. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a resin molded article having a novel phase structure comprising a resin composition containing polytrimethylene terephthalate (hereinafter abbreviated as “PTT”) and polycarbonate (hereinafter abbreviated as “PC”). More specifically, the present invention relates to a resin molded article having excellent mechanical properties and dimensional characteristics and remarkably excellent chemical resistance.

  In general, resin moldings made of a resin composition containing polyester and PC are widely used as automotive parts, electrical / electronic parts, building parts, and industrial parts from the viewpoint of their excellent mechanical properties, dimensional stability, and chemical resistance. Has been. Especially, since the resin molding containing PTT and PC has the characteristic excellent in heat resistance in addition to the said outstanding characteristic, the use under more severe conditions is anticipated. For example, under-hood parts for automobiles require higher levels of heat resistance and chemical resistance.

As a resin composition containing PTT and PC, for example, a resin composition having a specified melt viscosity stability, containing 95 to 5 parts by weight of PTT with respect to 5 to 95 parts by weight of PC is disclosed. (See Patent Document 1).
Furthermore, a resin composition having a prescribed melt viscosity stability, which includes PTT and PC having a bis (3-hydroxypropyl) ether component, is disclosed (see Patent Document 2).
However, the resin molded body obtained by the above method does not satisfy the required chemical resistance.

JP 2002-265771 A JP 2002-275369 A

  The present invention has extremely excellent mechanical properties, heat resistance, dimensional stability, and remarkably excellent chemical resistance. For example, as molding materials for automobile parts materials, electrical and electronic materials, industrial materials, industrial materials, household products, etc. It aims at providing the resin molding which can be used conveniently.

  As a result of intensive studies to solve the above problems, the present inventors have found that (A) a depth region from the surface layer of a resin molded body made of a resin composition containing (P) and (B) PC to a depth of 10 μm. In the case where the phase containing the component (A) as a main component and / or the phase containing the component (B) as a main component is present in layers in parallel with the surface of the molded body, In addition to dimensional stability, the present inventors have found that the chemical resistance is remarkably excellent, and have completed the present invention.

That is, the present invention is as follows.
1. (A) A resin molded body comprising (X) a resin composition comprising 1 to 99 parts by weight of polytrimethylene terephthalate and (B) 99 to 1 part by weight of polycarbonate, and having a depth of 10 μm from the surface of the resin molded body In a depth region of 50% or more, the phase containing the component (A) as a main component and / or the phase containing the component (B) as a main component are present in layers in parallel to the surface of the molded product. Resin molded body.
2. 1. The thickness of the phase containing the component (A) as a main component and / or the phase containing the component (B) as a main component is 1 nm to 500 nm. The resin molding as described in 2.

  The resin molded body comprising the resin composition containing (A) PTT and (B) PC of the present invention is a resin molded body having a novel phase structure, and is a conventional resin containing (A) PTT and (B) PC. Compared to the molded body, it has a remarkable effect of being excellent in chemical resistance while maintaining excellent mechanical properties, heat resistance and dimensional stability. The resin molded body can be suitably used as a molding material for, for example, automobile parts materials, electrical and electronic materials, industrial materials, industrial materials, and household products.

  In the present invention, (A) polytrimethylene terephthalate (hereinafter sometimes abbreviated as PTT) refers to a polyester polymer using terephthalic acid as the acid component and trimethylene glycol as the glycol component. In the present invention, trimethylene glycol is selected from the group consisting of 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, and mixtures thereof. Among these, 1,3-propanediol is particularly preferable from the viewpoint of stability.

In addition, as long as the purpose of the present invention is not impaired, an aromatic dicarboxylic acid other than terephthalic acid, for example, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, Diphenoxyethane dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ketone dicarboxylic acid, diphenyl sulfone dicarboxylic acid and the like; aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; ε-oxy Copolymerization can be carried out using a part of oxydicarboxylic acid such as caproic acid, hydroxybenzoic acid, hydroxyethoxybenzoic acid and the like. Moreover, ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, neopentyl glycol, cyclohexanedimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycol, hydroquinone, etc. are partially used as the glycol component. Can be copolymerized.
The amount of the copolymerization component in the case of copolymerization is not particularly limited as long as it does not impair the object of the present invention, but is usually 0 mol% or more and 20 mol% or less of the acid component, or 0 mol% or more of the glycol component. It is preferable that it is 20 mol% or less.

  In addition, the above-described polyester component may be added to a branched component such as tricarbaric acid, trimesic acid, trimellitic acid, or other trifunctional or tetrafunctional ester-forming acid, or glycerin, trimethylolpropane, pentaerythritol, or the like. An alcohol having a functional or tetrafunctional ester-forming ability may be copolymerized. In that case, they may be 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.3 mol% or less and 0 mol% or more of the total dicarboxylic acid component. Further, PTT may be used in combination of two or more of these copolymer components.

  The manufacturing method of PTT used for this invention is not specifically limited. For example, it can be produced by the methods described in JP-A Nos. 51-140992, 5-262862, and 8-311177. As an example, terephthalic acid or an ester-forming derivative thereof (for example, a lower alkyl ester such as dimethyl ester or monomethyl ester) is reacted with trimethylene glycol or an ester-forming derivative thereof at a suitable temperature and time in the presence of a catalyst. And a method of subjecting the resulting terephthalic acid glycol ester to a polycondensation reaction in the presence of a catalyst at a suitable temperature and time to a desired degree of polymerization.

The intrinsic viscosity [η] of the PTT used in the present invention is preferably 0.50 dl / g to 1.50 dl / g from the viewpoint of mechanical properties and chemical resistance of the composition, and [η] is 0.70 dl / g. It is more preferable that it is g-1.40 dl / g, and it is most preferable that [(eta)] is 0.80 dl / g-1.30 dl / g.
With respect to the intrinsic viscosity [η] of PTT, an Ostwald viscometer was used, and a resin composition containing PTT in o-chlorophenol at 35 ° C. was made to have a solute (PTT resin component) /solution=1.00 g / dl. Insoluble matter (inorganic reinforcing material, etc.) is removed with a filter, the specific viscosity ηsp is measured using the solution after the insoluble matter has been removed, and can be determined by the following formula.
[Η] = lim (1 / C) × (ηr−1) [C → 0]
Ηr in the formula is a value obtained by dividing the viscosity at 35 ° C. of a diluted solution of polytrimethylene terephthalate dissolved in o-chlorophenol having a purity of 98% or more by the viscosity of the solvent itself measured at the same temperature. Is defined as C is the solute weight value in grams in 100 ml of the solution.

Further, the PTT of the present invention has various additives as necessary, for example, pH adjusters, antifoaming agents, color adjusters, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystal nucleating agents. In addition, a case where a fluorescent whitening agent, a matting agent, or the like is copolymerized or mixed is also included.
(B) PC of the present invention has a main chain composed of a repeating unit represented by the following formula (1).
-(O-Ar-O-CO)-(1)
(In the formula, Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, pyridylene, and groups represented by the following formula (2).)
—Ar ¹ —Y—Ar ² — (2)
(In the formula, Ar ¹ and Ar ² are each an arylene group, for example, a group such as phenylene, naphthylene, biphenylene, pyridylene, etc. Y is an alkylene group or a substituted alkylene group.)

Moreover, the case where the bivalent aromatic residue shown by following formula (3) is contained as a copolymer component is also included.
—Ar ¹ —Z—Ar ² — (3)
(In the formula, Ar ¹ and Ar ² are the same as those in the formula (2). Z represents a simple bond or two such as —O—, —CO—, —S—, —SO ₂ —, —CO ₂ —, —CONR ¹ —, etc. R ¹ is independently a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms.)

（式中、Ｒ^７及びＲ^８は、それぞれ独立に、水素、ハロゲン、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数５〜１０のシクロアルキル基または炭素数６〜３０のアリール基である。ｍ及びｎは１〜４の整数で、ｍが２〜４の場合には各Ｒ^７はそれぞれ同一でも異なるものであってもよいし、ｎが２〜４の場合は各Ｒ^８はそれぞれ同一でも異なるものであっても良い。） Specific examples of these divalent aromatic residues include those represented by the following formula (4).

(Wherein R ⁷ and R ⁸ are each independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 carbon atoms. M and n are integers of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and n is 2 to 4. In this case, each R ⁸ may be the same or different.)

Among these divalent aromatic residues, a group represented by the following formula (5) is a preferred example.

Particularly preferred is a polycarbonate containing 85 mol% or more (based on all monomer units in the polycarbonate) of a repeating unit having Ar as the group represented by the above formula (5).
Moreover, the polycarbonate which can be used for this invention includes the case where the trivalent or more aromatic residue is contained as a copolymerization component.
Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a phenolic hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. Among these, a phenolic hydroxyl group, a phenyl carbonate group, a pt-butylphenyl carbonate group, p-cumylphenyl carbonate and the like are preferable as a terminal structure. The ratio of the number of phenolic hydroxyl groups to the total number of terminal groups is not particularly limited, but from the viewpoint of obtaining better color tone and mechanical properties, the ratio of phenolic hydroxyl groups is preferably 20% or more of the total number of terminal groups. More preferably, it is in the range of 20 to 80%. When the proportion of phenolic hydroxyl groups exceeds 80% of the total number of terminal groups, the thermal stability during melting of the composition tends to be slightly reduced. The ratio of phenolic hydroxyl terminal is generally measured using NMR (NMR method), measured using titanium (titanium method), or measured using UV or IR (UV method or IR method). ).

The weight average molecular weight (Mw) of the polycarbonate resin used in the present invention is preferably in the range of 5000 or more from the viewpoint of impact resistance, and in the range of 200000 or less from the viewpoint of the melt fluidity of the thermoplastic resin composition. More preferably, it is 10000-60000, More preferably, it is 15000-40000, Most preferably, it is 18000-30000.
The weight average molecular weight (Mw) is measured using gel permeation chromatography (GPC), and the measurement conditions are as follows. That is, it is obtained using a converted molecular weight calibration curve according to the following formula from a standard monodisperse polystyrene composition curve using tetrahydrofuran as a solvent and polystyrene gel.
M _PC = 0.3591 M _PS ^1.0388
(In the formula, _MPC is the weight average molecular weight of polycarbonate, and _MPS is the weight average molecular weight of polystyrene.)

  What was manufactured by the well-known method can be used for the polycarbonate resin used by this invention. For example, it can be produced by a known method in which an aromatic dihydroxy compound and a carbonate precursor are reacted. Specifically, an interfacial polymerization method (for example, phosgene method) in which an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent, an aromatic dihydroxy compound and a carbonic acid diester (for example, A method of solid-phase polymerization of a crystallized carbonate prepolymer obtained by a transesterification method (melting method), a phosgene method or a melting method in which diphenyl carbonate) is reacted [Japanese Patent Laid-Open No. 1-158033 (US Pat. No. 4,948) , 871), JP-A-1-271426, JP-A-3-68627 (corresponding to US Pat. No. 5,204,377)] and the like are used. It is done.

A preferable polycarbonate resin is a polycarbonate resin containing substantially no chlorine atom and produced by a transesterification method from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester. In the present invention, two or more different polycarbonates having different structures and molecular weights can be used in combination.
Furthermore, it is desirable that (A) polytrimethylene terephthalate and (B) polycarbonate have close melt viscosities at the kneading temperature. Moreover, when each melt viscosity (unit; poise) at a shear rate of 100 sec ⁻¹ is expressed by μ (A) and μ (B), it is preferable that the following condition is satisfied.
| Μ (A) −μ (B) | ≦ 18,000 (poise)
This melt viscosity difference is a desirable range in order to promote the compatibilization of (A) polytrimethylene terephthalate with (B) polycarbonate and to exhibit the moldability and physical properties of the resin composition.

The blending amount of (A) PTT and (B) PC of the present invention is 99 to 1 part by weight of (B) component with respect to 1 to 99 parts by weight of (A) component, from the viewpoint of mechanical properties and dimensional stability. (A) It is preferable that it is 95-30 weight part of (B) component with respect to 5-70 weight part of component, It is 90-50 weight part of (B) component with respect to (A) component 10-50 weight part. Most preferred.
In the resin composition (X) of the present invention, it is preferable to add a pH adjuster (C) as the third component from the viewpoint of heat resistance, residence stability, and color tone. (C) The pH adjuster is a compound having a function of adjusting the pH of the entire system to a specific range, and the blending amount of the component (C) is the total weight of the components (A) and (B) ( When the weight ratio of the component (C) is 100 / X, the 20 ° C. pH of the system in which (C) the pH adjuster Xg is dissolved in 100 g of distilled water at pH = 6 is 2.5 to 5.5. It is preferable that the amount is small. Furthermore, it is more preferable to mix | blend the quantity which the said pH shows 3-5 from a heat resistant and retention stability viewpoint of a composition. As the component (C), it is preferable from the viewpoint of the dispersion rate to the resin that the Xg is completely dissolved in 100 g of distilled water having a pH = 6.

The types of (C) pH adjusting agents that satisfy the above items are metal phosphates, metal pyrophosphates, metal metaphosphates, ammonium phosphates, oxo acids, phosphate esters, phosphite compounds, Examples thereof include metal phosphites. Among these, from the viewpoint of the dispersion rate in the resin, a metal phosphate, a metal pyrophosphate, a metal metaphosphate, an ammonium phosphate, and an oxo acid are preferably used.
Specific examples of metal phosphates, metal pyrophosphates, metal metaphosphates, ammonium phosphates and oxo acids include sodium dihydrogen phosphate, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, dihydrogen phosphate Potassium, monoaluminum phosphate, zinc dihydrogen phosphate, ammonium dihydrogen phosphate, disodium dihydrogen pyrophosphate, calcium dihydrogen pyrophosphate, dipotassium pyrohydrogen phosphate, zinc dihydrogen pyrophosphate, dihydrogen pyrophosphate Examples thereof include magnesium, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphate, aluminum metaphosphate, zinc metaphosphate, citric acid, phosphoric acid and phosphonic acid. Among the metal salts, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen pyrophosphate, ammonium dihydrogen phosphate and citric acid are most preferably used.
(C) The pH adjuster should just exist at the time of reaction of polycarbonate resin and polytrimethylene terephthalate resin in the front stage of an extruder. Therefore, the method for adding the (C) pH adjuster is not particularly limited. For example, when the raw material resin is supplied from the supply port, either (C) a pH adjuster is mixed and added to any raw resin, or (C) the pH adjuster is mixed after mixing both raw resin The method to do can be adopted.

Further, the (X) resin composition of the present invention includes blending (D) an inorganic filler for the purpose of improving rigidity and heat resistance within a range not impairing the object of the present invention. (D) As an inorganic filler, a fibrous, granular, or plate-like inorganic filler is used depending on the purpose.
Examples of fibrous inorganic fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, wollastonite, and stainless steel. Inorganic fibrous materials such as metallic fibrous materials such as aluminum, titanium, copper, and brass. Particularly typical fibrous inorganic fillers are glass fibers and carbon fibers. High melting point organic fibrous materials such as polyamide, fluororesin, and acrylic resin can also be used.

On the other hand, powdered inorganic fillers include carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, calcined kaolin, clay, oxalate such as diatomaceous earth, iron oxide, Metal oxides such as titanium oxide, zinc oxide, and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, others, silicon carbide, silicon nitride, boron nitride, various Metal powder is mentioned.
Examples of the plate-like inorganic filler include talc, mica, glass flakes, various metal foils and the like.

Among these, the inorganic filler of the present invention is preferably at least one inorganic filler selected from the group consisting of glass fiber, wollastonite, talc, mica, calcined kaolin, barium sulfate, and potassium titanate whiskers. In particular, glass fiber is most preferably used from the viewpoint of a reinforcing effect on mechanical properties.
These inorganic fillers can be used alone or in combination of two or more. The combined use of fibrous inorganic fillers, particularly glass fibers and granular and / or plate-like inorganic fillers, is a preferable combination in order to combine mechanical strength, dimensional accuracy, electrical properties, and the like.

  The average fiber length (hereinafter also referred to as L), average fiber diameter (hereinafter also referred to as d), and aspect ratio (hereinafter also referred to as L / d) of the fibrous inorganic filler used in the present invention are particularly limited. Not. In the case of glass fiber, the average fiber length (L) is 50 to 10,000 μm, the average fiber diameter (d) is 5 to 30 μm, and the aspect ratio (L / d) is 10 to 1000. Most preferable from the viewpoint. Carbon fibers having an average fiber length (L) of 100 to 750 μm, an average fiber diameter (d) of 3 to 30 μm, and an aspect ratio (L / d) of 10 to 100 are preferably used. Further, wollastonite having an average fiber diameter of 3 to 30 μm, an average fiber length of 10 to 500 μm, and an aspect ratio (L / d) of 3 to 100 is preferably used. Other talc, mica, calcined kaolin, barium sulfate and potassium titanate whiskers having an average particle size of 0.1 to 100 μm are most preferably used.

(D) The amount of the inorganic filler added to the resin composition is preferably 0 to 150 parts by weight with respect to 100 parts by weight of the component (A) + the component (B) from the viewpoint of rigidity and appearance of the molded product. -100 parts by weight is more preferable, and 0-50 parts by weight is most preferable.
As these inorganic fillers, those subjected to surface treatment are particularly preferably used. As the surface treatment, a known coupling agent or film forming agent is used. Examples of the coupling agent preferably used include a silane coupling agent and a titanium coupling agent. These compounds may be used after being subjected to surface treatment or convergence treatment in advance, or may be added at the same time as material preparation.

Examples of silane coupling agents include triethoxysilane, vinyltris (β-methoxy-ethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1-epoxycyclohexyl). ) Ethyltrimethoxysilane, N-α- (aminoethyl) -α-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-α-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane , Γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N-methyl-α-aminopropyltrimethoxysilane, N-vinylbenzyl-α -Aminopropyl Triethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-4,5 dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N, N- And bis (trimethylsilyl) urea.
Among these, γ-aminopropyltrimethoxysilane, N-α- (aminoethyl) -α-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1-epoxycyclohexyl) ethyltri Aminosilane such as methoxysilane and epoxysilane are preferably used.

  Titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate Tetra (1,1-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, Isopropyl dimethacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isoprene Pirutori (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl, aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Film forming agents include urethane polymers, acrylic polymers, maleic anhydride and ethylene, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene Examples thereof include a copolymer with an unsaturated monomer such as an epoxy polymer, a polyester polymer, a vinyl acetate polymer, and a polyether polymer. Among these, epoxy polymers, urethane polymers, acrylic acid polymers, butadiene maleic anhydride copolymers, ethylene maleic anhydride copolymers, styrene maleic anhydride copolymers, and mixtures thereof are preferably used.

Furthermore, the (X) resin composition and the resin molded product of the present invention include (E) addition of an impact modifier for the purpose of improving impact characteristics.
(E) Examples of the impact modifier include a core-shell polymer configured by grafting one or more shells on a rubber-like core. The core rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicon composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, styrene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicon Examples thereof include rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to the unsaturated bond portion thereof. Examples of the shell component include vinyl aromatic compounds, vinyl cyanide, acrylic acid esters, (meth) acrylic acid, and copolymerizable vinyl compounds thereof. Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl methacrylate, and the like. Furthermore, the core and / or shell preferably contains a polyfunctional compound that can function as a crosslinking agent and / or a grafting agent.

  Copolymers containing olefins such as olefin acrylates, olefin-diene terpolymers can also be used as impact modifiers. Examples of the olefin acrylate copolymer include DPD-6169 (Union Carbide), which is an ethylene-ethyl acrylate copolymer, Lotadar GMA (ATOFINA), which is an ethylene-methyl acrylate glycidyl methacrylate copolymer, and Lotryr (which is an ethylene acrylate copolymer). ATOFINA). Moreover, as an olefin-diene terpolymer, EPYSN704 (Copolymer Rubber Company) which is an ethylene-propylene-diene terpolymer is mentioned.

Various rubbery polymers and copolymers can also be used as impact modifiers. Examples include polybutadiene, polyisoprene, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicon composite rubber.
Furthermore, styrene-containing polymers are also preferably used as impact modifiers. Examples include acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (AS), acrylonitrile-butadiene, α-methylstyrene, styrene-butadiene, styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene, Examples include methacrylate-butadiene-styrene (MBS) and other impact-resistant styrene-containing polymers.
Other impact modifiers include various elastomeric substances such as organic silicone rubber, elastomeric fluorohydrocarbon, polyester elastomer, polyurethane elastomer, polyetheramide elastomer, random block polysiloxane-polycarbonate, random block polysiloxane-polycarbonate copolymer, etc. Is mentioned.

When the (F) moldability improving agent is further added to the (X) resin composition of the present invention, a resin composition or a resin molded body more suitable for the purpose of the present invention can be obtained. (F) Moldability improvers include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amide compounds, polyalkylene glycols or terminal modified products thereof, low molecular weight polyethylene or oxidized low molecular weight polyethylenes, Examples thereof include substituted benzylidene sorbitols, polysiloxanes, and caprolactones. Particularly preferred are (x) higher fatty acids, (y) higher fatty acid metal salts, and (z) higher fatty acid esters. Hereinafter, these (F) moldability improving agents will be described in detail.
(X) Higher fatty acids As the higher fatty acids, higher saturated fatty acids, higher unsaturated fatty acids or mixtures thereof are preferably used.

(X-1) Higher saturated fatty acids Higher fatty saturated fatty acids are, for example, capric acid, uradecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, Examples thereof include behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melissic acid, and laccelic acid, and mixtures thereof.
(X-2) Higher unsaturated fatty acids As the higher unsaturated fatty acids, unsaturated fatty acids having 6 to 22 carbon atoms are preferably used. Among them, more preferable examples include undecylenic acid, oleic acid, and elaidic acid. , Cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, 2-hexadecenoic acid, 7-hexadecenoic acid, 9-hexadecenoic acid, gadoleic acid, gadoelasinic acid, 11-eicosene An acid etc. or a mixture thereof can be mentioned.

(Y) Higher fatty acid metal salts As the higher fatty acid metal salts, higher saturated fatty acid metal salts, higher unsaturated fatty acid metal salts, or mixtures thereof are preferably used.
(Y-1) Higher saturated fatty acid metal salts The higher fat saturated fatty acids are represented by the following general formula.
_{CH 3 (CH 2) n COO} (M)
Here, n = 8 to 30, and the metal element (M) is preferably 1A, 2A, 3A group element, zinc, aluminum or the like of the periodic table.
Among these, more preferred are, for example, capric acid, uradecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid , Heptacosanoic acid, montanic acid, mellicic acid, lithium salt of lactic acid, sodium salt, magnesium salt, calcium salt, zinc salt, aluminum salt, etc., or a mixture thereof.

(Y-2) Higher unsaturated fatty acid metal salts As higher unsaturated fatty acid metal salts, unsaturated fatty acids having 6 to 22 carbon atoms, elements 1A, 2A and 3A of the periodic table, zinc, aluminum and the like Of these, the metal salts of these are preferably used, and among them, undecylenic acid, oleic acid, elaidic acid, cetreic acid, erucic acid, brassic acid, sorbyl acid, linoleic acid, linolenic acid, arachidonic acid, stearic acid, 2-hexadecenoic acid, 7-hexadecenoic acid, 9-hexadecenoic acid, gadoleic acid, gadoelaidic acid, lithium salt of 11-eicosenoic acid, sodium salt, magnesium salt, calcium salt, zinc salt, aluminum salt, etc., or a mixture thereof Can be mentioned.

(Z) Higher fatty acid esters As the higher fatty acid esters in the present invention, an ester of a higher alcohol and a higher fatty acid, an ester of a polyhydric alcohol and a higher fatty acid, or a mixture thereof is preferably used.
(Z-1) Esters of higher alcohols and higher fatty acids As esters of higher alcohols and higher fatty acids, preferred are esters of aliphatic alcohols having 8 or more carbon atoms and higher fatty acids having 8 or more carbon atoms. is there. Preferred higher fatty acid esters include, for example, lauryl laurate, lauryl myristate, lauryl palmitate, lauryl stearate, lauryl behenate, lauryl lignocerate, lauryl meristate, myristyl laurate, myristyl myristate, myristyl stearate. , Myristyl behenate, myristyl lignocerate, myristyl melysate, palmityl laurate, palmityl myristate, palmityl stearate, palmityl behenate, palmityl lignocerate, palmityl meristate, stearyl laurate , Stearyl myristate, stearyl palmitate, stearyl stearate, stearyl behenate, stearyl arachinate, stearyl lignocerate, stearyl melicate, eye Syl laurate, eicosyl palmitate, eicosyl stearate, eicosyl behenate, eicosyl lignocerate, eicosyl meristate, behenyl laurate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl behenate, behenyl Arachinate, behenyl merisate, tetracosanyl laurate, tetracosapalmitate, tetracosanyl stearate, tetracosanyl behenate, tetracosanyl lignocerate, tetracosanyl serotete, serotinyl stearate, Mention may be made of serotinyl behenate, serotinyl serotinate, merisyl laurate, merisyl stearate, merisyl behenate, merisyl meristate, etc., or mixtures thereof.

(Z-2) Esters of polyhydric alcohol and higher fatty acid Partial esters of polyhydric alcohol and higher fatty acid are, for example, glycerin, 1,2,3-butanetriol, 1,2,3- Pentanetriol, erythritol, pentaerythritol, trimethylolpropane, mannitol, sorbitol and the like are preferably used.
Examples of higher fatty acids include capric acid, uradecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosane Acid, montanic acid, melissic acid, laccelic acid and the like are preferably used.

  Esters of these polyhydric alcohols and higher fatty acids may be monoesters, diesters or triesters. More preferred examples include higher fatty acid monoglycerides such as glycerin monolaurate, glycerin monomyristate, glycerin monostearate, glycerin monobehenate, glycerin monolignocerate, glycerin monomellate, pentaerythritol mono- or di- Laurate, pentaerythritol mono- or di-laurate, pentaerythritol mono- or di-myristate, pentaerythritol mono- or di-palmitate, pentaerythritol mono- or di-stearate, pentaerythritol mono- or Mono- or di-higher fats of pentaerythritol, such as di-behenate, pentaerythritol mono- or di-lignocerate, pentaerythritol mono- or di-melissate Esters, trimethylolpropane-mono- or di-laurate, trimethylolpropane-mono- or dimyristate, trimethylolpropane-mono- or dipalmitate, trimethylolpropane-mono- or di-stearate, trimethylol Mention may be made of mono- or di-higher fatty acid esters of trimethylolpropane, such as propane-mono- or di-behenate, trimethylolpropane-mono- or di-lignocerate, trimethylolpropane-mono- or di-melisate.

  Also, sorbitan-mono, di- or tri-laurate, sorbitan-mono, di- or tri-myristate, sorbitan-mono, di- or tri-stearate, sorbitan-mono, di- or tri-behenate, sorbitan-mono, di- or Sorbitan-mono, di- or tri-higher fatty acid esters such as tri-lignocerate, sorbitan-mono, di- or tri-melisate, mannitan-mono, di- or tri-laurate, mannitan-mono, di- or tri-myristate, mannitan- Mono-, di- or tri-palmitate, mannitan-mono, di- or tri-stearate, mannitan-mono, di- or tri-behenate, mannitan-mono, di- or tri-lignoselate, mannitan-mono, di- or tri-meliselate, etc. Mannita - it can be mentioned higher fatty acid esters, or mixtures thereof - mono-, di- or tri.

  The blending amount of these (x) higher fatty acids, (y) higher fatty acid metal salts, and (z) higher fatty acid esters is 0.001-5 with respect to 100 parts by weight of PTT in the thermoplastic resin composition of the present invention. It is preferable that it is a weight part, More preferably, it is 0.01-3 weight part. When the compounding amount of the moldability improving agent is less than 0.001 part by weight, the moldability is not improved until the object of the present invention is achieved. On the other hand, when the amount exceeds 5 parts by weight, it is not preferable because it tends to cause silver blurring on the surface of the molded product or to lower the mechanical properties of the molded product.

When (G) a crystallization accelerator is further added to the (X) resin composition of the present invention, a resin composition or a resin molded body more suitable for the purpose of the present invention can be obtained.
(G) Examples of the crystallization accelerator include inorganic fillers such as glass fiber, talc, mica, and wollastonite, organic carboxylic acid metal salts, inorganic carboxylic acid metal salts, ionomer resins, and thermoplastic polyester resins. A thermoplastic polyester resin is preferably used because of its large crystallization promoting effect.
In the present invention, (G) the thermoplastic polyester resin preferably used as the crystallization accelerator is not particularly limited as long as it is a thermoplastic polyester resin other than polytrimethylene terephthalate. For example, aromatic dicarboxylic acid components such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, and ethylene Aromatic polyesters obtained from aliphatic diol components such as glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, adipic acid, azelaic acid, sebacic acid , Dodecanedicarboxylic acid, hexadecanedicarboxylic acid,
It is obtained from an aliphatic dicarboxylic acid component such as eicosane dicarboxylic acid and an aliphatic diol component such as ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, or 1,9-nonanediol. Aliphatic polyesters may be mentioned.

  The said polyester resin can also be used independently and 2 or more types of mixtures can be used. Among them, in particular, polyethylene terephthalate resin and polybutylene terephthalate resin are more preferably used because they have the effect of remarkably increasing the crystallization speed of the resin composition containing (A) polytrimethylene terephthalate and (B) polycarbonate of the present invention. The addition amount of the crystallization accelerator is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the (A) polytrimethylene terephthalate resin, from the viewpoint of heat resistance and thermal rigidity of the composition. The amount is more preferably 0.1 to 50 parts by weight, and most preferably 0.5 to 30 parts by weight.

In the resin composition (X) of the present invention, other resins or additives, for example, antioxidants, flame retardants, plasticizers, flame retardant aids, as necessary, as long as the characteristics and effects of the present invention are not impaired. A weather resistance (light) improver, slip agent, various colorants and the like may be added.
Unlike the conventional resin molding containing the component (A) and the component (B), the resin molding comprising the (X) resin composition of the present invention is 50% of the depth region from the surface to a depth of 10 μm. In the above, the phase having the component (A) as the main component and / or the phase having the component (B) as the main component has a structure in which the phase is present in parallel with the surface of the molded body. From the viewpoint of chemical resistance, the molded body has a phase mainly composed of component (A) and / or component (B) as a main component in 50% or more of a depth region from the surface to a depth of 50 μm. It is preferable that the phase to be present in a layered structure parallel to the surface of the molded body, and in 50% or more of the depth region from the surface to a depth of 100 μm, the phase containing the component (A) as a main component, It is most preferable that the phase containing the component (B) as a main component has a structure in which the phase exists in parallel with the surface of the molded body. Specifically, the phase structure of (A) PTT and (B) PC of the resin molded product is a direction perpendicular to the resin flow direction (hereinafter abbreviated as “MD” direction) and the resin flow direction (hereinafter “ The cross section of the molded product can be observed using an electron microscope (TEM) (referred to as FIG. 1). It is said MD direction that the phase which has (A) component as a main component or the phase which has (B) component as a main component is 50% or more of the depth area | region from the resin molding surface to the said depth. In both cross-sectional views (TEM photograph) in the TD direction, the phase structure of each phase is a ratio of 50% or more of the total area in the aforementioned depth region of each phase, and L (length) / D (thickness) is It indicates that the structure is 5 or more. From the viewpoint of chemical resistance, it is preferable that a linear structure having an L / D of 10 or more is 50% or more of the total area of each phase, and a linear structure having an L / D of 100 or more is More preferably, the linear area having an L / D of 1000 or more is most preferably 50% or more based on the total area of each phase. The thickness of (A) component phase and / or (B) component phase is preferably 1 to 500 nm, more preferably 1 to 200 nm, and more preferably 1 to 100 nm, from the viewpoint of chemical resistance. Most preferred. The thicknesses of the (A) component phase and (B) component phase layers can be determined from images in the MD direction or TD direction using an electron microscope (TEM).
In the resin molded body of the present invention, in the depth region from the surface layer to a depth of 10 μm, it is important to control the (A) component layer and / or the (B) component layer parallel to the surface layer. The molded body is achieved by applying an optimal molding method, molding conditions, and mold shape. Specifically, as the molding method, a molding method having a high injection speed such as injection molding, injection compression molding, or gas assist injection molding is preferably used. Furthermore, the most important point for achieving the resin molded body structure of the present invention is a mold shape, particularly a gate shape, and a film gate is optimal.

The resin molded body of the present invention is a molded body molded by the known molding method described above, and the shape thereof is not particularly limited, but it is easy to form a layered structure with respect to (A) PTT and (B) PC. From this viewpoint, the gate shape is preferably a film type.
The resin molded body comprising the (X) resin composition of the present invention has extremely excellent mechanical properties, heat resistance, and dimensional characteristics as compared with conventional resin molded bodies containing the component (A) and the component (B). Excellent chemical resistance. Therefore, for example, it can be suitably used as a molding material for automobile part materials, electrical and electronic materials, industrial materials, industrial materials, household goods, and the like.

The effects of the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. In addition, the used thermoplastic resin and its compounding agent are as follows.
-PTT1: Polytrimethylene terephthalate resin.
Intrinsic viscosity [η] = 0.72 × dl / g of polytrimethylene terephthalate The intrinsic viscosity [η] was determined based on the following defining formula.
[Η] = lim (1 / C) × (ηr−1) [C → 0]
Ηr in the formula is a value obtained by dividing the viscosity at 35 ° C. of a diluted solution of polytrimethylene terephthalate dissolved in o-chlorophenol having a purity of 98% or more by the viscosity of the solvent itself measured at the same temperature. Is defined as C is the solute weight value in grams in 100 ml of the solution.
PTT2: Polytrimethylene terephthalate resin Intrinsic viscosity [η] = 0.89 × dl / g polytrimethylene terephthalate PTT3: Polytrimethylene terephthalate resin Intrinsic viscosity [η] = 1.00 × dl / g polytrimethylene Methylene terephthalate

・ PC1: Polycarbonate resin; Iupilon S-2000, manufactured by Mitsubishi Engineering Plastics ・ MF1: Talc; M-SP, manufactured by Nippon Talc ・ S1: IRGANOX 1098, manufactured by Ciba Specialty Chemicals ・ S2: Na dihydrogen phosphate , Manufactured by Taihei Chemical Industrial Co., Ltd. S3: Phosphite compound; PEP8, manufactured by Asahi Denka Co.

In addition, the physical property evaluation of the resin molded product described in the following examples and comparative examples was performed as follows.
1. Production of resin molded product and various characteristics The resin molded product shown in FIGS. 2 and 3 was produced using an injection molding machine. The apparatus was set to Nissei Resin Co., Ltd. FN3000, cylinder temperature 260 ° C., mold temperature 80 ° C., and a resin molded product was obtained under injection molding conditions of injection 20 seconds and cooling 20 seconds. The injection speed was 99%, the injection pressure was constant for both the primary pressure and the secondary pressure, and the molding was performed under the conditions of the minimum injection pressure for full filling of the mold + 20 kgf / cm ² .
The molded product shown in FIG. 2 is a 150 mm × 150 mm × 2 mm thick flat plate, and the gate is a 150 mm × 1 mm thick film gate.
The molded product shown in FIG. 3 is a 150 mm × 150 mm × 2 mm thick flat plate, and the gate is a 2.5 mmφ pin gate.

(1-1) Surface Morphology A JISK7113-1 type (1B type) test piece cut out from the flat plate shown in FIG. 2 and FIG. 3 was taken from the MD direction and the TD direction as shown in FIG. ) Was observed from the surface layer to a depth of 10 μm. As a transmission electron microscope (TEM), H-600A manufactured by HITACHI was used. For TEM observation, a sample in which the test piece was sliced at 80 nm with a microtome and the section was stained with ruthenic acid was used. Whether observed from the MD direction or from the TD direction, the molded product having a structure in which the linear structure having an aspect ratio (L / D) ≧ 5 is 50% or more of the phase area is a layered structure. Whether observed from the MD direction or the TD direction, the structure in which the island-like structure having an aspect ratio (L / D) <5 is 50% or more of the total area is a sea-island structure.

(1-2) PTT layer average thickness Using the TEM image (depth of 50 μm from the surface layer) observed in (1-1) above, the thickness of the PTT layer was measured, and the average value was obtained.
(1-3) PC Layer Average Thickness Using the TEM image (depth of 50 μm from the surface layer) observed in (1-1) above, the thickness of the PC layer was measured and the average value was obtained.
(1-4) Tensile strength (MPa)
It measured according to ISO 527-1.

(1-5) Deflection temperature under load (° C)
It measured according to ISO 75-1. The load at that time was 0.46 MPa.
(1-6) Mold shrinkage (%)
The molding shrinkage rate (%) in the MD direction and TD direction of the molded product shown in FIGS. 2 and 3 was determined by actually measuring the molded product size and the mold size. The dimensions of the molded product were measured after being molded and left in a constant temperature and humidity chamber (23 ° C., 50% RH) for 24 hours. The dimensions of the molded product of the flat plate and the dimensions of the mold were measured at the positions shown in FIGS.

(1-7) Chemical resistance A gauze is wound around the parallel part of a JISK7113-1 type (1B type) test piece cut out from the flat plate shown in FIGS. 2 and 3, and an aluminum foil is wound around the sample. The test stress was applied in the state set in the tensile creep tester. After 30 seconds, 2 ml of reviewer gasoline (manufactured by Nippon Oil Corporation) was dropped onto gauze wound around the parallel part, and the breaking time was measured. In order to prevent evaporation of regular gasoline, regular gasoline was dropped every 5 minutes. The test temperature was 23 ° C. With respect to the test stress, the tensile yield stress was measured for each material, and an experiment was conducted by applying a stress of 30%.

[Examples 1-6 and Comparative Examples 1-3]
PTT1 to PTT3, PC1, and S1 to S3 were dry blended at a blending ratio shown in Table 1 below. The blend was melt-kneaded using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM58), and MF1 was added from the side feeder at a blending ratio shown in Table 1. Extrusion was performed at a screw speed of 300 rpm, a cylinder temperature of 250 ° C. (the polymer temperature near the tip nozzle was 280 ° C.), an extrusion rate of 150 kg / hr (residence time of 1 minute), and a reduced pressure of 0.05 MPa. The polymer was discharged in a strand form from the tip nozzle, and water-cooled and cut into pellets. After the pellets were dried at 120 ° C. for 5 hours with a dehumidifying dryer, test pieces were prepared by the injection molding method described above, and the test pieces were analyzed and measured for various properties according to the measurement methods described above. The results are shown in Table 1.
The phase structure in the TD direction of the surface layer of the molded product shown in Example 2 and Comparative Example 1 is shown in FIGS. In Example 2, it was found that (A) PTT and (B) PC had a layered structure and were extremely excellent in chemical resistance as compared with Comparative Example 1.

  According to the present invention, it is possible to provide a thermoplastic resin composition which is remarkably excellent in chemical resistance in addition to excellent mechanical properties, heat resistance and dimensional stability. Therefore, the high performance required for various applications such as automotive exterior / skin parts, automotive interior parts, automotive underhood parts, motorcycle parts, furniture parts, OA equipment field products, electronic parts, industrial parts, etc.・ It is expected to contribute greatly to the solution of the demand for higher functionality.

It is a figure explaining the imaging | photography direction at the time of imaging | photographing the resin flow direction ("MD" direction) cross section of a resin molded product, and a cross section perpendicular to a resin flow direction ("TD direction") with an electron microscope (TEM). It is a figure explaining the molded article (flat plate) injection-molded with the film gate, and the JISK7113-1 type | mold (1B type) test piece cut out from this flat plate. It is a figure explaining the molded article (flat plate) injection-molded with the pin film gate and the JISK7113-1 type (1B type) test piece cut out from the flat plate. It is a figure explaining the measurement position of a molded product dimension and a metal mold | die dimension for calculating the mold shrinkage rate (%) of MD direction and TD direction of the molded product (flat plate) injection-molded with the film gate. It is a figure explaining the measurement position of a molded product dimension and a metal mold | die dimension for calculating the molding shrinkage | contraction rate (%) of MD direction and TD direction of the molded product (flat plate) injection-molded with the pin film gate. 4 is a TEM photograph obtained by photographing a phase structure in a TD direction of a surface layer of a molded product of Example 2. FIG. 4 is a TEM photograph taken of the phase structure in the TD direction of Comparative Example 1.

Claims (2)

  (A) A resin molded body comprising (X) a resin composition comprising 1 to 99 parts by weight of polytrimethylene terephthalate and (B) 99 to 1 part by weight of polycarbonate, and having a depth of 10 μm from the surface of the resin molded body In a depth region of 50% or more, the phase containing the component (A) as a main component and / or the phase containing the component (B) as a main component are present in layers in parallel to the surface of the molded product. Resin molded body.   The resin molded product according to claim 1, wherein the thickness of the phase mainly comprising the component (A) and / or the phase mainly comprising the component (B) is 1 nm to 500 nm.

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