JP2003119363A - Reinforced thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reinforced thermoplastic resin composition excellent in mechanical properties, moldability, heat resistance, durability, excellent in appearance, impact resistance, rigidity when heated, low water absorption, chemical resistance, hydrolysis resistance and the like and capable of being suitably used as the molding material for automotive parts materials, electric and electronic materials, industrial materials, engineering materials, household items and the like. SOLUTION: This reinforced thermoplastic resin composition comprises 100 pts.wt. thermoplastic resin composition consisting of 99-1 pts.wt. (A) polytrimethylene terephthalate and 1-99 pts.wt. (B) polycarbonate and 1-250 pts.wt. (C) inorganic filler to be blended.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel reinforced thermoplastic resin composition and a molded article made of the same. The reinforced thermoplastic resin composition provided by the present invention has extremely excellent mechanical properties, moldability, heat resistance, and durability, as well as appearance, impact resistance, thermal rigidity, low water absorption, and chemical resistance. It is excellent in hydrolysis resistance and the like, and can be suitably used as a molding material for automobile part materials, electric / electronic materials, industrial materials, industrial materials, household products, and the like.

[0002]

2. Description of the Related Art Generally, a resin composition composed of polybutylene terephthalate and polycarbonate is widely used in industry. These compositions are used, for example, as automobile parts, particularly automobile exterior parts, and are also widely used as electric / electronic parts, building parts and industrial parts. However, the conventional resin composition composed of polybutylene terephthalate and polycarbonate has low physical properties in a high temperature atmosphere and has a problem that it cannot be used in a high temperature atmosphere such as in an engine room of an automobile. Further, in order to improve the mechanical strength and deflection temperature under load, it has been widely performed to blend an inorganic filler typified by glass fibers into a resin composition consisting of polybutylene terephthalate and polycarbonate, but glass fibers are There is a problem that the surface of the molded piece is raised and the surface gloss is inferior, and the physical properties in a high temperature atmosphere are still not at a satisfactory level.

[0003]

The present invention has extremely excellent mechanical properties, moldability, heat resistance and durability, as well as appearance, impact resistance, heat rigidity, low water absorption, chemical resistance,
Provided is a reinforced thermoplastic resin composition which is excellent in hydrolysis resistance and can be suitably used as a molding material for, for example, automobile part materials, electric / electronic materials, industrial materials, industrial materials, household products and the like. .

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that (A) polytrimethylene terephthalate (99-1% by weight) and (B) polycarbonate (1-99% by weight). Thermoplastic resin composition 100
In addition to mechanical properties, impact resistance, low water absorption and heat resistance, a molded product obtained from a reinforced thermoplastic resin composition obtained by blending 5 to 300 parts by weight of (C) inorganic filler with respect to parts by weight, They have found that they have excellent appearance and rigidity when heated, and have completed the present invention.

That is, the present invention is as follows: To 100 parts by weight of a thermoplastic resin composition consisting of 99 to 1 parts by weight of (A) polytrimethylene terephthalate and 1 to 99 parts by weight of (B) polycarbonate,
(C) A reinforced thermoplastic resin composition containing 5 to 300 parts by weight of an inorganic filler, (A) Polytrimethylene terephthalate has a number average molecular weight of 5,000 to 100,000 and a molecular weight distribution (Mw
/ Mn) is 1.2 to 4.5 and has a molecular weight of 100,00.
The thermoplastic resin composition according to claim 1 or 2, which contains 1 to 20% of 0 or more molecules. 3. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the intrinsic viscosity [η] of (A) polytrimethylene terephthalate in the reinforced thermoplastic resin composition is 0.60 or more. . 4. A molded body obtained by injection molding the reinforced thermoplastic resin composition according to any one of claims 1 to 3. 5. The molded body according to claim 4, which is molded by a hollow injection molding method.

In the present invention, (A) polytrimethylene terephthalate (hereinafter sometimes abbreviated as PTT).
Indicates a polyester polymer using terephthalic acid as an acid component and trimethylene glycol as a glycol component. In the present invention, trimethylene glycol includes 1,3-propanediol, 1,2
-Propanediol, 1,1-propanediol, 2,
It is selected from 2-propanediol or a mixture thereof, and 1,3-propanediol is particularly preferable from the viewpoint of stability.

Besides, aromatic dicarboxylic acids other than terephthalic acid, such as phthalic acid, isophthalic acid, 2,6 naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyl ether, are used as acid components within a range that does not impair the object of the present invention. Dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylketone dicarboxylic acid, diphenylsulfonedicarboxylic acid, etc .; aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid; alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; Using oxydicarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, and hydroxyethoxybenzoic acid, the glycol component is ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene. Recall, octamethylene glycol, neopentyl glycol, cyclohexanedimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycol, may be copolymerized with such a part hydroquinone.

The amount of the copolymerization in the case of copolymerization is not particularly limited as long as the object of the present invention is not impaired, but is usually 20 mol% or less of the acid component or 2 of the glycol component.
It is preferably 0 mol% or less. Further, a branched component in the above polyester component, for example, tricarballylic acid, trimesic acid, trimellitic acid, etc., an acid having a trifunctional or tetrafunctional ester forming ability or a trifunctional such as glycerin, trimethylolpropane, pentaerythritol, etc. Alternatively, tetrafunctional ester-forming alcohols may be copolymerized, in which case they are 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0 mol% or less of the total dicarboxylic acid components. It is 0.3 mol% or less. Furthermore, PT
T may be a combination of two or more of these copolymerization components.

The method for producing PTT used in the present invention is as follows:
Although not particularly limited, for example, JP-A-51-
140992, JP-A-5-262862,
According to the method described in JP-A-8-311177, terephthalic acid or its ester-forming derivative (for example, lower alkyl ester such as dimethyl ester or monomethyl ester) and trimethylene glycol or its ester-forming derivative, In the presence of a catalyst, the mixture is heated and reacted at a suitable temperature and for a time, and the glycol ester of terephthalic acid obtained is further reacted in the presence of a catalyst at a suitable temperature and
A method of conducting a polycondensation reaction to a desired degree of polymerization in time can be mentioned. The PTT of the present invention has a number average molecular weight of 5,000.
It is preferably 0 to 100,000, and Mw / Mn showing a molecular weight distribution is preferably 1.2 to 4.5. Furthermore, a molecule having a molecular weight of 100,000 or more is 1
˜20% is preferable.

Regarding the method for measuring the number average molecular weight and the molecular weight distribution, for example, the molecular weight can be measured by an osmotic pressure method, a terminal quantitative method or a GPC method (gel permeation chromatography). For example, Tohso Co., Ltd. HLC-8120, Showa Denko KK HFIP804-803 (two 30 cm columns) as a column, hexafluoroisopropanol (hereinafter referred to as HFIP) as a carrier, and Polymer Laboratory PMMA as a standard sample. Using a temperature of 40
It can be carried out at 0 ° C. and a flow rate of 0.6 ml / min.

In the reinforced thermoplastic resin composition of the present invention, the intrinsic viscosity [η] of (A) polytrimethylene terephthalate in the composition is preferably 0.60 or more from the viewpoint of mechanical properties, particularly toughness. [η] is more preferably 0.68 or more, and from the viewpoint of moldability, especially burr characteristics, [η]
Is most preferably 0.75 or more. When [η] is less than 0.60, the required mechanical properties and toughness may not be sufficiently exhibited. Regarding the intrinsic viscosity [η], an Ostwald viscometer was used to dissolve the composition in solute (PTT resin component) /solution=1.00 g / dl at 35 ° C. in o-chlorophenol, and the insoluble matter was dissolved. The specific viscosity ηsp can be obtained by removing the (inorganic reinforcing material and the like) with a filter and then measuring the specific viscosity ηsp using the solution from which the insoluble matter has been removed. [Η] = 0.713 × ηsp / C + 0.1086 C = 1.00 g / dl

The polytrimethylene terephthalate of the present invention may optionally contain various additives such as a heat stabilizer,
Antifoaming agent, toning agent, flame retardant, antioxidant, ultraviolet absorber,
Infrared absorbers, crystal nucleating agents, optical brighteners, matting agents and the like may be copolymerized or mixed.

The (B) polycarbonate resin of the present invention is
It 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, for example, phenylene, naphthylene, biphenylene, pyridylene, or
Examples thereof include 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, and examples thereof include phenylene, naphthylene, biphenylene, and
Represents a group such as pyridylene. Y is an alkylene group or a substituted alkylene group. ) Further, a divalent aromatic residue represented by the following formula (3) may be contained as a copolymer component. —Ar ¹ —Z—Ar ² — (3) (wherein Ar ¹ and Ar ² are the same as those in formula (2). Z is a bond or —O—, —CO—, —S—, —SO ₂ —, -C
It is a divalent group such as O ₂ − and —CONR ¹ −. ) Examples of these divalent aromatic residues include those represented by the following formula.

[0014]

[Chemical 1]

(In the formula, R ⁷ and R ⁸ are each independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or It is an aryl group having 6 to 30 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
When R is 2 to 4, each R ⁸ may be the same or different. Among these, a group represented by the following formula (4) is a preferred example.

[0016]

[Chemical 2]

In particular, the group represented by the above formula (4) is Ar
A polycarbonate containing 85 mol% or more of the repeating units (based on all the monomer units in the polycarbonate) is particularly preferable. The polycarbonate that can be used in the present invention may contain a trivalent or higher aromatic residue as a copolymerization component.

The molecular structure of the polymer terminal is not particularly limited, but may be a phenolic hydroxyl group, an aryl carbonate group,
One or more end groups selected from alkyl carbonate groups can be attached. Among these, phenolic hydroxyl group, phenyl carbonate group, pt-butylphenyl carbonate group, p-cumylphenyl carbonate and the like are preferable as the terminal structure. In the present application, the ratio of the phenolic hydroxyl group terminal to the other terminal is not particularly limited, but from the viewpoint of obtaining better color tone and mechanical properties, the ratio of the phenolic hydroxyl group terminal is 20 of the total number of terminal groups.
% Or more, more preferably 20 to 80%.

If the ratio of phenolic terminal groups exceeds 80% of the total number of terminal groups, the thermal stability during melting tends to be slightly lowered. The phenolic hydroxyl group terminal amount is generally measured using NMR (NMR method), titanium (titanium method), or UV or IR (UV method or IR method).

The weight average molecular weight (Mw) of the aromatic polycarbonate resin used in the present invention is generally 5,000 to
It is preferably in the range of 200,000, more preferably 10,000 to 60,000, further preferably 15,000 to 40,000, and particularly preferably 180.
It is 00 to 30000. When it is less than 5,000, the resulting reinforced thermoplastic resin composition tends to have insufficient impact resistance, and when it exceeds 200,000, the reinforced thermoplastic resin composition tends to have insufficient melt fluidity. .

The weight average molecular weight (Mw) is measured by gel.
Permeation chromatography (GPC) was used and the measurement conditions are as follows. That is, using tetrahydrofuran as a solvent and polystyrene gel, the conversion molecular weight calibration curve according to the following equation is used to determine from the constitutional curve of standard monodisperse polystyrene. M _PC = 0.3591M _PS ^1.0388 _{(wherein, M PC} is the weight average molecular weight of the polycarbonate,
( _MPS is the weight average molecular weight of polystyrene)

The aromatic polycarbonate resin used in the present invention may be one produced by a known method. Specifically, for example, a known method of reacting an aromatic dihydroxy compound and a carbonate precursor, for example, reacting an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. The crystallized carbonate prepolymer obtained by the interfacial polymerization method (eg, phosgene method), the transesterification method (melting method) in which an aromatic dihydroxy compound is reacted with a carbonic acid diester (eg, diphenyl carbonate), or the phosgene method or the melting method is solidified. Phase polymerization method [JP-A-1-158033 (corresponding to US Pat. No. 4,948,871), JP-A-1-27)
1426, JP-A-3-68627 (corresponding to US Pat. No. 5,204,377)] and the like are used.

The preferred polycarbonate resin is
A polycarbonate resin containing substantially no chlorine atom, which is produced from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester by a transesterification method can be used. In the present invention, it is also possible to use two or more different polycarbonates having different structures and molecular weights in combination.

The compounding amounts of (A) polytrimethylene terephthalate and (B) polycarbonate in the present invention are as follows:
(A) 99 to 1 part by weight, (B) 1 to 99 parts by weight, preferably (A) 90 to 10 parts by weight, (B) 10 to 90 parts by weight, and more preferably (B). 20 to 80 parts by weight of (B) to 80 to 20 parts by weight of (A). (A) Polytrimethylene terephthalate is
From the viewpoint of appearance and chemical resistance, it is 1% by weight or more, and from the viewpoint of impact resistance, it is 99% or less.

Furthermore, it is desirable that (A) polytrimethylene terephthalate and (B) polycarbonate have similar melt viscosities at the kneading temperatures, and a shear rate of 10
When the respective melt viscosities at ⁰ sec ⁻¹ are represented by μ (A) and μ (B), it is desirable that the following conditions be satisfied. | Μ (A) -μ (B) | ≦ 18,000 poise (A) From the viewpoint of compatibilization of the polytrimethylene terephthalate resin and (B) polycarbonate, or from the viewpoint of moldability and physical properties, the difference in melt viscosity is 18 000 pois
It is preferably e or less.

As the inorganic filler (C) used in the present invention, a fibrous, powdery or plate-like inorganic filler is used according to the purpose. As the fibrous inorganic filler, glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whiskers, wollastonite, and stainless steel. , Aluminum, titanium,
Inorganic fibrous substances such as metallic fibrous substances such as copper and brass can be used. Particularly representative fibrous inorganic fillers are glass fibers and carbon fibers. High melting point organic fibrous substances such as polyamide, fluororesin and acrylic resin can also be used.

On the other hand, as the powdery or granular inorganic filler, silicates such as carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth and iron oxide. , Titanium oxide,
Zinc oxide, metal oxides such as alumina, calcium carbonate, metal carbonates such as magnesium carbonate, calcium sulfate, metal sulfates such as barium sulfate, and others, silicon carbide, silicon nitride, boron nitride, various metal powders Can be mentioned. Examples of the plate-like inorganic filler include talc, mica, glass flakes, various metal foils and the like.

The inorganic filler of the present invention is, among others, glass fiber, wollastonite, talc, mica, kaolin,
At least one inorganic filler selected from the group of calcium carbonate, carbon fiber (CF), and potassium titanate whiskers is preferred. Of these, glass fibers are most preferably used from the viewpoint of reinforcing the mechanical properties. These inorganic fillers can be used alone or in combination of two or more. Fibrous inorganic filler, especially glass fiber and granular and / or
Alternatively, the combined use of the plate-like inorganic filler is a preferable combination particularly in terms of having both mechanical strength, dimensional accuracy, electrical properties and the like.

The average fiber length (hereinafter also referred to as L), the average fiber diameter (hereinafter also referred to as D), and the aspect ratio (hereinafter also referred to as L / D) of the fibrous inorganic filler used in the present invention. Is not particularly limited, but the average fiber length (L)
Is 50 μm or more, the average fiber diameter (D) is 5 μm or more, and the aspect ratio (L / D) is 10 or more is most preferable from the viewpoint of exhibiting high characteristics. The carbon fibers have an average fiber length (L) of 100 to 750 μm, a number average fiber diameter (D) of 3 to 30 μm, and an aspect ratio (L / D).
Is preferably 10 to 100. Further, wollastonite has an average fiber diameter of 3 to 30 μm.
m, the average fiber length is 10 to 500 μm, and the aspect ratio (L / D) is 3 to 100 are preferably used.
Other talc, mica, kaolin, calcium carbonate,
Most preferably, potassium titanate having an average particle size of 0.1 to 100 μm is used.

The addition amount is required to be 5 to 300 parts by weight with respect to 100 parts by weight of (A) + (B).
00 parts by weight is preferable, and 5 to 100 parts by weight is more preferable. The inorganic filler (C) is 5 parts by weight or more from the viewpoint of the effect of improving the mechanical strength, and 3 from the viewpoint of the gloss of the surface of the molded product.
It is not more than 00 parts by weight. As these inorganic fillers, those subjected to surface treatment are preferably used. The surface treatment is performed using a known coupling agent or film forming agent. Examples of coupling agents that are preferably used include silane coupling agents and titanium coupling agents. These compounds may be subjected to a surface treatment or a converging treatment in advance, or may be added at the same time when the material is prepared.

As the silane coupling agent, 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-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-4,5 dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane,
Examples thereof include N, O- (bistrimethylsilyl) amide and N, N-bis (trimethylsilyl) urea.

Among these, γ-aminopropyltrimethoxysilane, N-α- (aminoethyl) -α-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1-epoxycyclohexyl) ) Aminosilanes such as ethyltrimethoxysilane and epoxysilanes are preferably used.

Titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl 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 (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, Isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate Isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl, aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

As the film forming agent, urethane type polymer, acrylic acid type polymer, maleic anhydride and ethylene, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene,
Examples thereof include copolymers with unsaturated monomers such as 1,3-pentadiene and cyclooctadiene, and polymers such as epoxy polymers, polyester polymers, vinyl acetate polymers and polyether polymers. Among these, epoxy-based polymers, urethane-based polymers, acrylic acid-based polymers, butadiene maleic anhydride copolymers, ethylene-maleic anhydride copolymers, styrene-maleic anhydride copolymers, and mixtures thereof are preferably used.

When the composition of the present invention is further blended with a crystal nucleating agent, a composition more suitable for the purpose of the present invention can be obtained. As the crystal nucleating agent, both organic substances and inorganic substances can be used. As the inorganic substance, Zn powder, Al
Powder, graphite, carbon black etc.,
ZnO, MgO, Al ₂ O ₃ , TiO ₂ , MnO ₂ , S
Metal oxides such as iO ₂ and Fe ₃ O ₄ , aluminum nitride, silicon nitride, titanium nitride, nitrides such as boron nitride, Na ₂ C
O ₃ , CaCO ₃ , MgCO ₃ , CaSO 4, CaSi
Inorganic salts such as O ₃ , BaSO ₃ , Ca ₃ (PO ₄ ) ₂ ,
Clays such as talc, kaolin, clay and clay can be used alone or in admixture of two or more. Also, as organic substances, calcium oxalate, sodium oxalate,
Calcium benzoate, calcium phthalate, calcium tartrate, magnesium stearate, organic salts such as polyacrylates, polymers such as polyester, polyethylene, polypropylene, etc., and cross-linked polymers etc. alone or 2
A mixture of two or more species can be used. Particularly preferred are boron nitride, clays such as talc, kaolin, clay and clay, and organic salts.

Regarding the amount of addition of these crystal nucleating agents, PT
It is 0.001 to 5 parts by weight with respect to 100 parts by weight of T, but an addition amount of 0.01 to 3 parts by weight is particularly preferable in terms of mechanical properties.

By further adding a moldability improver to the composition of the present invention, a resin composition more suitable for the purpose of the present invention can be obtained. Moldability improvers include phosphoric acid esters, phosphite esters, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amide compounds, polyalkylene glycol or terminal modified products thereof, low molecular weight Examples thereof include polyethylene or low-molecular weight oxidized polyethylenes, 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. It is a kind. These moldability improvers will be described in detail below.

(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 saturated fatty acids include, for example, capric acid, uradecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, Examples thereof include behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laxeric acid, and the like, or a mixture 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, and among them, more preferable ones are, for example, 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, gadoelaidic acid, 11-eicosene Acids and the like, or mixtures 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 salt The higher saturated fatty acid fatty acid is represented by the following general formula. _{CH 3 (CH 2) n COO} (M) where a n = 8 to 30, the metal element (M) is, 1A of the Periodic Table of the Elements, 2A, 3A group elements, zinc, and aluminum are preferably used . Among them, more preferred are, for example, capric acid, uradecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid,
Palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laccelic acid lithium salt, sodium salt, magnesium salt, calcium salt, zinc salt , Aluminum salts, etc., or a mixture thereof.

(Y-2) Higher unsaturated fatty acid metal salt The higher unsaturated fatty acid metal salt has 6 to 22 carbon atoms.
Unsaturated fatty acids and metal salts of 1A, 2A and 3A elements of the periodic table of elements, zinc, aluminum and the like are preferably used, and among them, undecylenic acid, oleic acid, elaidic acid, cetrain are more preferable. 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, gadoelaidic acid, 11-eicosenoic acid Examples thereof include lithium salt, sodium salt, magnesium salt, calcium salt, zinc salt, aluminum salt, and the like, or a mixture thereof.

(Z) Higher Fatty Acid Esters As the higher fatty acid esters in the present invention, esters of higher alcohols and higher fatty acids, esters of polyhydric alcohols and higher fatty acids, or mixtures thereof are preferably used.

(Z-1) Esters of higher alcohols and higher fatty acids As esters of higher alcohols and higher fatty acids, preferred are aliphatic alcohols having 8 or more carbon atoms and higher fatty acids having 8 or more carbon atoms. Esters. Preferred higher fatty acid esters include, for example, lauryl laurate, lauryl myristate, lauryl palmitate, lauryl stearate, lauryl behenate, lauryl lignocerate, lauryl melicate, myristyl laurate, myristyl myristate, myristyl stearate. , Myristyl behenate, myristyl lignocerate, myristyl melissate, palmityl laurate, palmityl myristate, palmityl stearate, palmityl behenate, palmityl lignocerate, palmityl melicate, stearyl laurate , Stearyl myristate, stearyl palmitate, stearyl stearate, stearyl behenate, stearyl arachinate, stearyl lignocerate, stearyl melissate, eye Shiruraureto, Aiko sill palmitate,
Aicosyl stearate, aicosyl behenate, aicosyl lignocerate, aicosyl melissate, behenyl laurate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl behenate,
Behenyl arachinate, behenyl melissate, tetracosanyl laurate, tetracosa palmitate, tetracosanyl stearate, tetracosanyl behenate, tetracosanyl lignocerate, tetracosanyl serrate, cerotinyl stearate. , Cerotinyl behenate,
Mention may be made of cerotinyl serotinate, melisyl laurate, melisyl stearate, melisyl behenate, melisyl merisate and the like, or mixtures thereof.

(Z-2) Esters of Polyhydric Alcohol and Higher Fatty Acids Partial esters of polyhydric alcohols and higher fatty acids include polyhydric alcohols such as glycerin, 1,2,3-butanetriol and 1,2. , 3-pentanetriol, erythritol, pentaerythritol, trimethylolpropane, mannitol, sorbitol and the like are preferably used, and higher fatty acids include, for example, capric acid, uradecyl acid, lauric acid, tridecyl acid, myristic acid,
Pentadecylic acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laxeric acid and the like are preferably used.

The esters of these polyhydric alcohols and higher fatty acids may be monoesters, diesters or triesters. More preferred are higher fatty acid monoglycerides such as glycerin monolaurate, glycerin monomyristate, glycerin monostearate, glycerin monobehenate, glycerin monolignocellate, glycerin monomerisate, 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 di-behenate, pentaerythritol-mono or di- Mono- or di-higher fatty acid esters of pentaerythritol, such as lignocerate, pentaerythritol-mono or di-merisate, trimethylolpropane-mono- or di-laurate, trimethylolpropane-mono-
Or di-myristate, trimethylolpropane-mono- or di-palmitate, trimethylolpropane-mono- or di-stearate.

Also, trimethylolpropane-mono- or di-behenate, trimethylolpropane-mono-
Or mono- or di-higher fatty acid esters of trimethylolpropane, such as di-lignocerate, trimethylolpropane-mono- or di-merisate, sorbitan-mono, di- or tri-laurate, sorbitan-
Mono, di or tri-myristate, sorbitan-mono, di or tri-stearate, sorbitan-mono,
Sorbitan-mono, di- or tri-higher fatty acid esters such as di- or tri-behenate, sorbitan-mono, di- or tri-lignocerate, sorbitan-mono, di- or tri-merisate, 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,
Mention-mono, di- or tri-lignocerate, mannitan-mono, di- or tri-meriselate and other mannitane-mono, di- or tri-higher fatty acid esters, etc., or mixtures thereof may be mentioned.

The amount of these (x) higher fatty acids, (y) higher fatty acid metal salts, and (z) higher fatty acid esters blended is such that molding processability is based on 100 parts by weight of PTT in the PTT resin composition of the present invention. From the viewpoint of 0.001 part by weight or more, preferably 5 parts by weight or less, more preferably 0.01 to 3 parts by weight, from the viewpoint of silver appearance on the surface of the molded product or the mechanical properties of the molded product. Is. In the present invention,
If necessary, other resins or additives such as antioxidants, flame retardants, plasticizers, flame retarding aids, weather resistance (light) improving agents, impact resistance, etc., within a range that does not impair the characteristics and effects of the present invention. You may add a improver, a filler, a slip agent, various coloring agents, etc.

Since the thermoplastic resin composition of the present invention is excellent in various molding processability, known molding methods such as press molding, injection molding, gas assist injection molding, fusion molding, extrusion molding, blow molding, film molding, Hollow molding, multi-layer molding,
Good molding can be performed using foam molding. In particular, hollow injection molding is preferably used for the purpose of improving sink marks, warpage and appearance of the molded product. The hollow injection molding method is to pressurize a pressurized gas into the mold during or after the injection of the molten resin to form a hollow part in the molten resin in the mold cavity by the pressurized gas. A molding method in which cooling of a molded body is carried out while appropriately maintaining the pressure of the pressurized gas in the hollow portion. To further explain the hollow injection molding method, the injection amount of the molten resin in the hollow injection molding is full shot for injecting a sufficient amount to fill the mold cavity,
Any of short shots in which an amount insufficient to fill the mold cavity is injected may be used.

The pressurized gas may be any gas as long as it is inert to the polytrimethylene terephthalate resin, and examples thereof include inert gases such as nitrogen, helium, neon and argon. Further, in order to prevent decomposition and burning of the polytrimethylene terephthalate resin during molding, it is preferable to use a gas having a small amount of impure components. The pressurization of the pressurized gas can lead the pressurized gas stored in the accumulator to the mold, or can be continuously supplied to the mold by a pump.

Usually, after the required cooling is completed, the molded body is taken out of the mold after discharging the pressurized gas in the hollow portion and opening the inside of the hollow portion to atmospheric pressure. Therefore, the hollow part of the molded product according to the present invention is usually at atmospheric pressure. However, it may be a molded body in which a pressurized gas is sealed in the hollow portion. Since the molded product according to the present invention is molded by the hollow injection molding method as described above, it has a hollow portion. The hollow rate is preferably 3 to 50%, more preferably 5 to 40%.

The hollow portion in the present invention means a hollow portion formed by pressurizing a pressurized gas in hollow injection molding,
It is essentially different from voids or voids created by foaming. The molded product obtained from the thermoplastic resin composition of the present invention has extremely excellent mechanical properties, moldability, heat resistance and durability, as well as appearance and impact resistance, as compared with conventional reinforced thermoplastic resin compositions. Since it is excellent in low water absorption, chemical resistance, hydrolysis resistance, etc., it can be suitably used as a molding material for automobile part materials, electric / electronic materials, industrial materials, industrial materials, household products, etc.

[0051]

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. The thermoplastic resin and its compounding agent used are as follows. (1) PTT: polytrimethylene terephthalate resin. Intrinsic viscosity [η] = 0.89 × dl / g polytrimethylene terephthalate The intrinsic viscosity [η] was calculated based on the following definition formula. [Η] = lim (1 / C) × (ηr−1) [C → 0] ηr in the defining formula is 35 ° C. of a dilute solution of polytrimethylene terephthalate dissolved in o-chlorophenol having a purity of 98% or more. Relative viscosity is defined as the value obtained by dividing the viscosity of the above-mentioned by the viscosity of the solvent itself measured at the same temperature. Further, C is a solute weight value in gram unit in 100 ml of the above solution. Number average molecular weight 9800, Mw / M
n = 2.1, the ratio occupied by 100,000 or more molecules is 5.8%
Met.

The molecular weight and molecular weight distribution of the polytrimethylene terephthalate resin were measured by GPC (gel permeation chromatography). The measurement conditions are HLC-8120 manufactured by Tosoh Corporation and HFIP804-803 Showa Denko KK as a column.
(2 columns of 30 cm), HFIP was used as a carrier, the temperature was 40 ° C., and the flow rate was 0.6 ml / min. A calibration curve was created and measured using PMMA manufactured by Polymer Laboratory as a standard sample. The molecular weight of standard PMMA is 6
20, 1680, 3805, 7611, 13934, 2
Those of 4280, 62591, 186000 were used.

PTT2: Polytrimethylene terephthalate resin Intrinsic viscosity [η] = 0.80 × dl / g Polytrimethylene terephthalate number average molecular weight 8500, Mw / Mn = 2.1, ratio occupied by 100,000 or more molecules Was 4.7%. -PTT3: Polytrimethylene terephthalate resin Intrinsic viscosity [η] = 0.70 x dl / g polytrimethylene terephthalate number average molecular weight 7200, Mw / Mn = 2.1, 100,000 or more molecules occupy the ratio. It was 5%. -PTT4: Polytrimethylene terephthalate resin Intrinsic viscosity [η] = 0.60 x dl / g polytrimethylene terephthalate number average molecular weight 6100, Mw / Mn = 2.1, 100,000 or more molecules occupy the ratio. It was 4%.

PBT: Polybutylene terephthalate resin Polyplastics Co., Ltd. Duranex 2002 PC: Polycarbonate resin Mitsubishi Engineering Plastics Co., Ltd. Iupilon H-3000 (2) Glass fiber: Nippon Electric Glass Co., Ltd. 03T -1
87 / PL (3) Inorganic filler (MF-1) Wollastonite: manufactured by Tomoe Kogyo Co., Ltd. N
YGLOS5

The physical properties described in the following examples and comparative examples were evaluated as follows. 1. Preparation of molded products and physical properties Molded products were prepared using an injection molding machine. The apparatus was PS40E manufactured by Nissei Plastic Co., Ltd., the mold temperature was set to 95 ° C., and a molded product was obtained under the injection molding conditions of injection for 20 seconds and cooling for 15 seconds.
The cylinder temperature was set to 260 ° C. (1-1) Bending elastic modulus and bending strength (MPa) The test piece was left at 23 ° C. and 80 ° C. for 1 hour or more, and then measured. It carried out according to ASTM D790. (1-2) Bending elastic modulus retention rate and bending strength retaining rate (%) Bending elastic modulus (80 ° C.) / Bending elastic modulus (23 ° C.) × 100
= Flexural modulus retention rate Flexural strength (80 ° C) / Flexural strength (23 ° C) x 100 = Flexural strength retention rate (1-3) Tensile strength (Mpa) and Tensile elongation (%) It was measured according to ASTM D638. (1-4) Notched Izod Impact Strength (J / m) It was measured according to ASTM D256.

(1-5) Deflection temperature under load (° C.) It was measured according to ASTM D648. The load is 1.82Mp
It went in a. (1-6) Deflection (mm) A flat plate having a thickness of 3 mm and a side of 130 mm was injection-molded, the three corners of the flat plate were attached to a horizontal plane, and the maximum gap distance (mm) between the remaining one corner and the horizontal plane was measured. (1-7) Appearance of molded product (1) A flat plate having a thickness of 3 mm and a side of 130 mm is injection-molded, and a handy gloss meter IG320 manufactured by Horiba is used to perform JIS-K7.
Gs60 ° C. was measured according to 150. When the numerical value was 80 or more, it was marked with ⊚, when it was 70 or more, it was marked with ◯, and when it was less than 70, it was marked with x.

(1-8) Hollow ratio As will be described later, the inside dimension of the cavity is 10 mm in length and 1 in width.
Apparent volume (V) of a hollow-injection-molded product by a die processed into a prismatic shape having a length of 0 mm and a length of 150 mm.
And the density (ρ) of the resin material used and the mass (M) of the obtained molded product were calculated by the following formula. Hollow rate (%) = {(V × ρ-M) / (V × ρ)} × 10
0 Further, the evaluation was carried out with an arithmetic average value of 100 shots.

(1-9) Difference between mold size and molded product size As will be described later, the inside dimension of the cavity is 10 mm in length and 1 in width.
The central axis length (L1; mm) of a molded body molded by a die processed into a prismatic shape having a length of 0 mm and a length of 150 mm was measured, and L1 was subtracted from the dimension of the die of 150 mm. The evaluation was carried out with an arithmetic average value of 100 shots. In addition, among 100 shots, those in which gas penetration was observed in molding were indicated by "x".

(1-10) Appearance of molded product (2) Visual judgment was carried out based on the following criteria. ◯: No sink mark was generated in all 100 shots. X: There is a molded product with a sink mark. (1-11) Appearance of molded product (3) As a sample surface, the appearance of matt textured grain provided on the outer side (10 mm x 150 mm) of the gate facing the four peripheral surfaces of the molded product described later is visually observed. It was judged by. ◯: Good wrinkle development ×: Poor wrinkle development

[0060]

Examples 1-8 and Comparative Examples 1-3 PTT, PBT
And PC were dry blended at the compounding ratio shown in Table 1,
Table 1 shows the glass fibers (average fiber diameter 13 μm × average fiber length 3 mm) and inorganic filler (MF-1) melt-kneaded using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM58), and from a side feeder. The compounding ratio was added. Screw rotation speed 300 rpm, cylinder temperature 250 ℃ (polymer temperature near the tip nozzle was 280 ℃),
The extrusion rate was 150 Kg / hr (retention time 1 minute), and the degree of reduced pressure was 0.04 MPa. The polymer was discharged in a strand form from the tip nozzle, cooled with water and cut into pellets. After drying the pellets at 120 ° C. for 5 hours in a dehumidifying dryer, a test piece was prepared by the injection molding method described above, and the test piece was analyzed and various properties were measured according to the above measuring method.

[0061]

[Embodiment 9] Using a resin pellet obtained by melt-kneading PTT, PC and glass fiber at a compounding ratio shown in Table 2, a mold processed into a prismatic shape having a cavity internal dimension of 10 mm in length, 10 mm in width and 150 mm in length. Hollow injection molding was performed. The gate was set at one point and was provided at the center of gravity of one of the four peripheral surfaces of the molded body. In addition, the outside of the gate (10 mm
× 150 mm) was provided with a satin texture. Mold temperature is 95
℃, the cylinder set temperature was 240 ℃. Nitrogen gas was used as the pressurized gas, a shut-off valve was provided to prevent the gas from flowing back into the injection cylinder, and the gas was injected from the gas nozzle incorporated in the injection nozzle. The pressurization of the pressurized gas was performed by pressurizing the nitrogen gas to 150 kg / cm ² and storing it in the accumulator, and after injecting the molten resin, sending it through the pipe into the mold from the gas nozzle. The pressurization condition for the pressurized gas is 0.5 seconds for the gas injection delay time (the time from the completion of the injection of the molten resin until the start of the injection of the pressurized gas), and the gas injection time (the time for performing the injection of the pressurized gas).
For 5 seconds, and the pressure holding time (the time of stopping the pressurization of the pressurized gas and maintaining the gas in a closed state plus the gas pressurization time) was set to 60 seconds. The mold opening was performed 5 seconds after the pressure holding time was completed, after the pressurized gas in the hollow portion was discharged.
Table 2 shows the measurement results of this molded body.

[0062]

[Comparative Example 4] Hollow injection molding was carried out in the same manner as in Example 9 using the pellets obtained by melt-kneading PBT, PC and glass fiber at the compounding ratio shown in Table 2. Table 2 shows the measurement results of this molded body.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

INDUSTRIAL APPLICABILITY The present invention has extremely excellent mechanical properties, moldability, heat resistance and durability, as well as appearance, impact resistance, thermal rigidity, low water absorption, chemical resistance and hydrolysis resistance. It is a reinforced thermoplastic resin composition having excellent properties. Therefore, high performance required for various applications such as automobile exterior / outer panel parts, automobile interior parts, automobile underhood parts, motorcycle parts, furniture parts, office automation equipment parts, electronic appliances parts, industrial parts, etc. -It is expected that it will be able to contribute significantly to the solution of the demand for higher functionality.

Continued front page    F-term (reference) 4F071 AA45 AA50 AA80 AA81 AB01                       AB26 AB28 AD01 AE17 AH07                       AH12 BA01 BB05                 4J002 BD123 BG003 CF05W CG00X                       CL003 DA016 DA076 DA096                       DA116 DC006 DE096 DE146                       DE186 DE236 DG046 DG056                       DJ006 DJ016 DJ026 DJ036                       DJ046 DJ056 DK006 DL006                       FA016 FA046 FD016 GC00                       GN00 GQ00

Claims (5)

[Claims] 1. (A) Polytrimethylene terephthalate 99-1 parts by weight, and (B) Polycarbonates 1-9.
With respect to 100 parts by weight of the resin composition consisting of 9 parts by weight,
(C) A reinforced thermoplastic resin composition containing 5 to 300 parts by weight of an inorganic filler. 2. The number average molecular weight of (A) polytrimethylene terephthalate is 5,000 to 100,000, the molecular weight distribution (Mw / Mn) is 1.2 to 4.5, and the molecular weight is 1.
The reinforced thermoplastic resin composition according to claim 1 or 2, which contains 1 to 20% of molecules of 0,000 or more. 3. The intrinsic viscosity [η] of (A) polytrimethylene terephthalate in the reinforced thermoplastic resin composition is 0.
It is 60 or more, The thermoplastic resin composition in any one of Claims 1-3. 4. A molded product obtained by injection molding the reinforced thermoplastic resin composition according to claim 1. 5. The molded product according to claim 5, which is molded by a hollow injection molding method.