JP3321916B2 - Reinforced polyethylene terephthalate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel reinforced polyethylene terephthalate resin composition, a method for producing the reinforced resin composition, and a molded article using the reinforced resin composition.

[0002]

2. Description of the Related Art Reinforced polyethylene terephthalate resin compositions are intended to improve the heat distortion temperature and rigidity by reinforcing glass fibers with polyethylene terephthalate resin. However, since moldability is extremely poor only with glass and excellent heat resistance and dimensional accuracy cannot be obtained, a special plasticizer or a crystal nucleating agent is added.

[0003] Sodium montanate, triallyl phosphate, alkali metal acetylacetone and the like are added as a lubricant, a crystal nucleating agent or a nucleus growth promoting agent added for improving fluidity and mold releasability at the time of thermoforming of a thermoplastic resin. Chelate,
Polyalkylene glycol derivatives, phosphorus compounds, neopentyl glycol, saccharose monobenzoate, monocarboxylates, higher fatty acid soaps, epoxyalkanes, etc. are known, but molding satisfactorily satisfactory are still not available. Not found, and much research continues today. There are still many unclear points about the mechanism of action.

[0004] In principle, a nucleating agent is one whose surface is wetted or adsorbed by a polymer to reduce the interfacial energy, is insoluble in the polymer, melts above the melting point of the polymer, and does not react with the polymer. Is considered necessary.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a novel reinforced polyethylene terephthalate resin composition having excellent physical properties and workability when producing a molded article from the reinforced polyethylene terephthalate resin composition. The task is to provide.

[0006]

The inventor of the present invention has made intensive studies to solve the problems and found that the polyethylene terephthalate tree
As described above, a reinforced polyethylene terephthalate resin composition comprising a fat and a fibrous internal reinforcing agent, and particularly its resin additive, is effective even though many kinds of substances are known. Assuming the presence of the substance,
As a result of intensive studies on resin additives that provide excellent properties of workability of the resin composition in processing and molding, as a result, conventionally, as a resin additive of a reinforced polyethylene terephthalate resin composition, its effect is known to be known. notably polyethylene which was not N- acylamino acid salt, or a titanium-based coupling agent
Workability of processing and molding of reinforced polyethylene terephthalate resin composition consisting of lentephthalate resin and fibrous internal reinforcing agent , that is, improvement of resin crystallization rate, short-term peelability from mold The inventors have found that they provide improvements and completed the present invention.

That is, the present invention provides at least a polyethylene terephthalate - blended with preparative resin composition, the N- acylamino acid salt, or a titanium-based coupling agent - and preparative resin, reinforced polyethylene terephthalate more a fibrous internal reinforcing agents hand
It made it reinforced polyethylene terephthalate, characterized in - DOO resin composition, reinforcing with a composition of polyethylene terephthalate - DOO resin composition reinforced polyethylene terephthalate resin composition obtained by the method and the production method for producing
It is a reinforced polyethylene terephthalate resin molded product obtained by molding a product.

[0008]

The N-acylamino acid or titanium-based coupling agent incorporated in the reinforced polyethylene terephthalate resin composition of the present invention improves the fluidity and crystallization of polyethylene terephthalate resin during molding. It is thought to function as a nucleating agent. Generally speaking, crystallization of macromolecules is promoted by impurities and thermal motion, and occurs in embryos and the like as nuclei. Therefore, when a foreign substance such as a nucleating agent is added, the number of crystal nuclei increases, and as a result, the size of the grown spherulite decreases. The mechanical properties, transparency, etc. of the polymer are affected by the size of the spherulite. The smaller the spherulite, the higher the yield value and the impact strength. Therefore, physical properties can be controlled to some extent by the nucleating agent, which is industrially important.

[0009] The polyethylene terephthalate resin used in the present invention is a polyester resin mainly composed of polyethylene terephthalate, wherein an ester bond between terephthalic acid and ethylene glycol is used as a repeating unit.
This unit is a homopolymer or a copolymer composed of at least 80% by weight based on the total amount of the resin. Phthalic acids such as isophthalic acid, phthalic acid, methyl terephthalic acid, and methyl isophthalic acid; naphthalenedicarboxylic acids such as 2,6-naphthalenedicarboxylic acid and 1,5-naphthalenedicarboxylic acid; 4,4′-diphenyl Dicarboxylic acids such as diphenyldicarboxylic acids such as dicarboxylic acids; and fats such as trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol. And diols such as aromatic or alicyclic glycols and aromatic glycols such as bisphenol. Further, examples of the copolymer include polyethers such as polyethylene glycol, polypropylene glycol and tetramethylene glycol and derivatives thereof, and block copolymers such as aliphatic polyesters and polyamides.

The nucleating agent that can be used in the present invention includes a sodium salt type, an inorganic fine powder type and an alkaline earth metal salt type. Specifically, for example, the sodium salt type includes sodium montanate. , Sodium stearate, sodium oleate, inorganic fine powders such as talc, clay and calcium carbonate fine powders, and alkaline earth metal salts such as barium, calcium and aluminum salts of inorganic or organic acids Can be mentioned.

Examples of the lubricant usable in the present invention include alkaline earth metal salts of fatty acids such as calcium stearate, magnesium stearate, aluminum stearate, barium stearate, zinc stearate,
Fatty acid amides, for example, stearic acid amide, stearic acid, various waxes, for example, polyethylene wax and the like can be used.

The internal reinforcing agent which can be used in the present invention is an inorganic or organic polyethylene terephthalate resin-affinity filler, and if necessary, in order to increase the resin affinity, it is necessary to use polyethylene terephthalate in advance. -May be coated with a substance having high compatibility with the resin.

For example, as an inorganic polyethylene terephthalate resin-affinity filler, glass fiber, carbon fiber
And the like .

Also, organic polyethylene terephthalate
As resin-friendly fillers, polyester resin fibers,
Examples include synthetic fibers such as polyamide fibers and acrylic resin fibers, and natural fibers such as hemp, cotton, and pulp.
Furthermore, mixtures of the abovementioned fillers are used.

Examples of the release agent that can be used in the present invention include montan wax, polyethylene wax, and metal salts of montanic acid wax.

The N-acyl amino acid salts used in the present invention include mono- or di-N-acyl amino acid salts of acidic amino acids and N-acyl amino acid salts of neutral amino acids,
Alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, magnesium salt and aluminum salt and various amine salts and basic amino acid salts are used, and sodium salt is particularly suitable. For example, monosodium N-2-ethylhexyl-glutamate, disodium N-2-ethylhexyl-glutamate, monosodium N-caprynoyl-glutamate, disodium N-caprynoyl-glutamate, N
-Lauroyl glutamate monosodium, N-tallow fatty acid-monosodium glutamate, N-tallow fatty acid- disodium glutamate, and the like.

The amount of the N-acyl amino acid salt to be added is preferably in the range of 0.03 to 3 parts based on 100 parts (hereinafter, referred to as part by weight) of the polyethylene terephthalate resin.

Examples of the titanium-based coupling agent used in the present invention include various organic titanium compounds and organic titanium oligomers such as isopropyl tristearoyl titanate and isopropyl tris (dioctyl pyrophosphate) titanate. Tetraisopropylbis (dioctylpyrophosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetraisopropylbis (ditridecylphosphite) titanate
, Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate-titanate, bis (dioctylpyrophosphate) Ethylene titanate, isopropyltrioctanoyl titanate
Isopropyl tridecyl benzene sulfonyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl dimethacryl isostearyl titanate, isopropyl isostearyl diacryl titanate, isopropyl tricumyl phenyl titanate Seed
And dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, and the like.

The amount of the titanium-based coupling agent is 0.03 to 100 parts of the polyethylene terephthalate resin.
~ 3 parts are preferred.

If necessary, other coupling agents such as a chrome coupling agent and a silane coupling agent may be used in combination with the titanium coupling agent.

In order to use the reinforced polyethylene terephthalate resin as an engineering plastic, N-acyl amino acid or a salt thereof or N-acyl amino acid may be added to the reinforced polyethylene terephthalate resin in practicing the present invention in addition to glass fiber as a reinforcing agent. The purpose can be achieved only by adding a titanium-based coupling agent.

The compounding is usually carried out by kneading in a molten state using an extruder. Mixing mica, talc, a flame retardant, a lubricant, a mold release agent, a clarifying agent, an antioxidant, an ultraviolet ray deterioration inhibitor or a pigment as a nucleating agent to form a composite material is no problem.

The N-acylamino acid or its salt or the titanium-based coupling agent used in the present invention is
Alone is effective as a nucleating agent for reinforced polyethylene terephthalate resin, but no effect can be expected in a combined system. However, the combined use of titanium-based coupling agent (0.15 parts) and commercially available sodium montanate (0.15 parts) shortened the molding cycle time and showed a slight synergistic effect.

[0024] In the present invention, reinforced polyethylene terephthalate - DOO resin composition reinforced has been known at the time of manufacture of polyethylene terephthalate - in addition to the preparative resin composition additives, N- acylamino acid salts or titanium-based By adding a coupling agent, a new reinforced polyethylene terephthalate resin composition having improved crystallization properties and improved mold releasability, and thus excellent molding workability, can be obtained.

[0025]

【Example】

(Example 1) A reinforced polyethylene terephthalate composition having the following composition was kneaded at a maximum temperature of 255 ° C and pelletized. The device used is KCK80X2-35VEX (5). Next, after drying at 140 ° C. for 5 hours, the injection molding machine N
Molding was performed under the following molding conditions using 40-B-II “Products of Japan Steel Works, Ltd.”. The molding cycle was gradually shortened, and those having a good time until the molded articles dropped naturally and a good surface gloss state were evaluated as satisfactory for crystallization.

Composition: polyethylene terephthalate resin ... 70 parts: Teijin TR4550BH
Photo late glass fiber 30 parts: Asahi Fiera-Class
03JA429A Silane treatment talc ・ ・ ・ ・ ・ ・ 2 parts: Takehara Chemical Hitron A, 3μm or less low molecular weight polyethylene ・ ・ ・ 0.5 parts: Mitsui Petrochemical Hiwawax (Offplate II) crystal nucleus 0.1 to 5 parts: N-acylamino acid or titanium-based coupling agent
.. 0.3 parts:

Molding conditions Molding machine: Nippon Steel Works N40B-II injection molding machine Pre-drying: 140 ° C. × 5 hours or more Molding temperature (° C.): nozzle = 255, metering = 26
0, compression = 255, feed = 250 Mold temperature (° C.): 130 ± 5 (standard condition), sometimes set to 130 ° C. or less Injection pressure: 40 kg / cm ² Injection speed: 4.0 m / sec Screw rotation speed: 100 rpm Back pressure: 1-2 kg / cm ² Setting time: Injection 7 seconds (standard conditions) Cooling time: 10 seconds (depends on sample. Release time from mold, shorter when performance is good.)

Table 1 shows the mold release time from the mold when various N-acylamino acid salts or titanium coupling agents are added and molded.

[0029]

[Table 1]

(Example 2) Measurement of relative crystallization rate: The following reinforced polyethylene terephthalate resin composition was kneaded with a kneader (KCK80X2-35V).
It was pelletized at a maximum temperature of 250 ° C. using EX (5). Next, after drying at 140 ° C. for 5 hours, a test piece [127 × 12.7 × 1.6 mm] was prepared at a mold temperature of 40 to 130 ° C. using an injection molding machine (Clockner-F85), and subjected to a test, and subjected to a heat distortion temperature (HDT). The test method ASTM0648
It measured according to. Test stress 18.6 kgf / cm ² ,
The test was performed at a heating rate of 130 ° C./hour using a tester HD tester “Toyo Seiki Co., Ltd. product”.

Formulation: (Values are parts by weight) Formulation A Formulation B Comparative Example Polyethylene terephthalate resin (Teijin, TR4550BH): 70 70 70 70 Glass fiber: 30 30 30 30 Talc: 222 2 KR-38S (Ajinomoto, Ti-based coupling agent): 0.2---N-Ducanoyl-L-quartamic acid monosodium salt (CAP):-0.2--Polyethylene wax: 0.5 0.5 0.5-Sodium montanate:---0.2

Table 2 shows the test results. From this result, KR
Both -38S and CAP have a relative crystallinity of 100% at a mold temperature of 130 ° C, and can be said to be typical high-temperature mold grades.

[0033]

[Table 2]

Comparative Example Table 1 also shows the results of a comparative example using sodium montanate as a control substance for various N-acyl amino acid salts or titanium-based coupling agents.

[0035]

As described above, by carrying out the present invention, the fluidity of the resin composition is good, the physical properties of the resin composition are not reduced in the molding machine, and the appearance of the molded article is not reduced. "Sledding" on molded products, with better mold release properties than molds
, Which can reduce the occupation time in the mold during the molding operation, does not cause coloring of the molded product during the stagnation of the molding, and can keep the temperature in the mold during the molding operation as low as possible. There is an effect that a novel reinforced polyethylene terephthalate resin composition having various advantages such as a molded article having excellent heat resistance and capable of maintaining toughness against impact external stress can be obtained.

Claims (3)

(57) [Claims] 1. A least Polyethylene terephthalate - DOO resin and, reinforced polyethylene terephthalate more a fibrous internal reinforcing agent - in DOO resin composition, and N- acylamino acid salt
Reinforced polyethylene terephthalate, characterized in that by blending a titanium-based coupling agent - DOO resin composition. Wherein at least a polyethylene terephthalate - DOO resin and, reinforced polyethylene terephthalate more a fibrous internal reinforcing agent - in DOO resin composition, and N- acylamino acid salt
A method for producing a reinforced polyethylene terephthalate resin, which comprises mixing a titanium-based coupling agent. Wherein at least a polyethylene terephthalate - DOO resin and, reinforced polyethylene terephthalate more a fibrous internal reinforcing agent - in DOO resin composition, and N- acylamino acid salt
Is a reinforced polyethylene terephthalate molded product obtained by molding a reinforced polyethylene terephthalate resin composition containing a titanium-based coupling agent.