JPS63175059A - polyester resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyester resin composition that provides molded products with excellent surface appearance, mechanical strength, etc., and improved sheet resistance.

[Conventional technology]

Glass fiber reinforced thermoplastic polyester resin has excellent mechanical properties such as heat resistance and chemical resistance, so it can be used in various heating appliances (microwave ovens, induction cookers, irons, etc.) and electrical parts (connectors).

Coil bobbins, etc.], automobile parts (reflectors), etc.

However, when a crystalline polymer such as polyethylene terephthalate or polybutylene terephthalate resin is filled with a reinforcing material such as glass fiber, cracks occur in the molded product.
It becomes a problem.

Therefore, the current situation is that reinforced polyester resins have traditionally been filled with inorganic fillers to prevent cracking.

[Problem that the invention seeks to solve]

However, when a large amount of inorganic filler is added to reinforced polyester resin, powdering occurs on the surface of the molded product.
The surface appearance becomes poor.

Therefore, at present, grades containing large amounts of such inorganic fillers cannot be used in housings of heating appliances and the like.

The present invention was developed as a result of intensive studies to solve the above-mentioned drawbacks.
By adding an inorganic filler that has been surface-treated with a specific compound to thermoplastic polyester resin, we can eliminate the surface appearance that has traditionally been a problem, such as dusting, and improve mechanical strength and resistance to scratching. The present invention was completed based on this discovery.

[Means for solving problems]

That is, the polyester resin composition of the present invention contains (N thermoplastic polyester resin 25-97%)
(Cn nuclear agent α03
~30% by weight (D) (I) Inorganic filler surface-treated with a silane coupling agent represented by formula 3-70
Weight% Y-Rx-s 1-Xs
C1) where X: 01. OR, or O
CORsY: OH! =OH, on, =c OIL
,Coo.

Na,,NH,O,H4NH or N'H,0ONHR1
〜R3: Hydrogen or 0nH2n+1 (n=an integer of 1 or more)), and 〜〜(A polyester resin composition characterized in that the total amount of each component is 100 parts by weight.

The polyester resin used in the present invention (- means a polyalkylene terephthalate homopolymer containing terephthalic acid or its alkyl derivative as the main acid component and an aliphatic diol having 2 to 10 carbon atoms as the main diol component, It refers to a copolymer mainly composed of polyalkylene terephthalate copolymerized with other dicarboxylic acid components and diol components, or a mixture of these polymers.

As the copolymerized acid component, dicarboxylic acids such as inphthalic acid, adipinoic acid, sebacic acid, P-B-oxyethoxybenzoic acid, diphenyl ether/4,4'-dicarboxylic acid, and diphenoxyethane-4,4'-dicarboxylic acid are used. In addition to the above-mentioned diol components, cyclohexane dimetatool, cyclopentanedimetatool, etc. are used as the copolymerized diol component. Specific examples of such polyester resins include polyethylene terephthalate, polytetramethylene terephthalate, polytetramethylene terephthalate/inphthalate copolymers, and mixtures of polytetramethylene terephthalate and polyethylene terephthalate.

(The blending amount of ~components is 25% of the total polyester resin composition.
It is in the range of ~96.97xf1%. If it is less than 25% by weight, fluidity decreases, which is not preferable.

In addition, if it exceeds 96.97% by weight, it will not be the object of the present invention)
This is not desirable because it does not prevent this.

The fibrous reinforcement (B) used in the present invention includes glass fiber, carbon fiber, aramid fiber, glass flake, aluminum silicate, asbestos, mica, or a combination thereof.

Among these, any type of material such as glass fiber, roving type, or chopped strand type can be preferably used, but chopped strand is particularly preferred from the viewpoint of production.

In addition, the fibrous reinforcement is contained in the entire polyester resin composition.''
~60] [Blend in proportions. If the blend i exceeds 60% by weight, it is not preferable because the flowability deteriorates.

The nucleating agent (C) used in the present invention has an effect as a nucleating agent for polyester, such as sodium stearate, calcium stearate, sodium benzoate, calcilam benzoate, and sodium terephthalate.
, metal salts of Group 1 a or Group Ⅰ a of organic carboxylic acids such as lithium terephthalate; Oxides and sulfates of metals of Group II of the periodic table, such as valent or divalent metal salts, neutral clays such as Merck, zinc oxide, magnesium oxide, calcium silicate, magnesium silicate, calcium sulfate, and barium sulfate; (by reaction between silicate, organic carboxylic acid and alcohol having one or two hydroxyl groups in one molecule, or alcohol fatty conductor)
The resulting ester compound, specifically a reaction product of a long-chain aliphatic carb/acid and a long-chain aliphatic alcohol, such as all esters such as nonyl stearate, stearyl stearate, stearyl behenate, behenyl behenate, etc. Reaction products of aromatic or aliphatic carboxylic acids having 7 or more carbon atoms and polyalkylene glycol, such as polyethylene glycol distearate, polyethylene glycol dipenzoate, polyethylene glycol dipenzoate, polyethylene glycol polypropylene glycol block copolymer Combined dibenzoates, etc., 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, stearyl glycidyl ether, polyethylene glycol monophenyl monocricidyl ether, polyglopylene glycol monophenyl monoglycidyl ether, polyethylene f I
Examples include J-col monolauryl monoglycidyl ether, polyethylene glycol monostearyl monoglycidyl ether, and epoxy compounds such as glycidyl ether of alcohol having a long-chain alkyl group or monoglycidyl ether containing a polyoxyalkylene chain.

These nucleating agents (C) may be used alone or in combination, and the blending amount is in the range of α03 to 50% by weight based on the total polyester resin composition.

That is, even when using a metal salt of an organic carboxylic acid that has a relatively high nucleating effect, if it is less than 1103% by weight, the excellent heat resistance and appearance improvement effect will be insufficient, and on the contrary, there will be relatively little decrease in strength. Even when Kei rR1 is used, it is sufficient to use less than 30 weights and 1 inches, except when the effect of addition as an inorganic filler is required.

The q component used in the present invention is an inorganic filler surface-treated with a silano coupling agent represented by the general formula (13).

Preferred silane coupling agents include epoxysilane, aminosilane, and the like.

The above-mentioned silane coupling agents are used alone or in combination, and the inorganic filler is usually surface-treated at an α2 to 1 weight ratio relative to the inorganic filler.

Examples of inorganic fillers include oxidation of metals from group Ⅰ of the periodic table such as Merck, wollastonite, glass peas, mica, zinc oxide, magnesium oxide, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, and calcium carbonate. Examples include salts, sulfates, carbonates, silicates, and the like.

Further, examples of methods for surface treating these inorganic fillers with a silane coupling agent include the following methods.

1) Add a predetermined amount of silane coupling agent to 2 to 5 times as much water or alcohol water bath solution (water/alcohol ratio 1/9).
) and mix until completely dispersed.

2) Put a predetermined amount of inorganic filler into a mixer.

3) Add the above silane coupling agent solution over several minutes while stirring the inorganic filler uniformly.

4) After adding the entire amount of the silane coupling agent solution, stir and mix for an additional 5 to 10 minutes.

5) After mixing is completed, take out the wet inorganic filler and spread it evenly in a shallow tray.

d) Dry at 100-150°C for 1 hour.

7) After drying, loosen it well before use.

The inorganic fillers surface-treated as described above may be used alone or in combination.

The blending amount is 6 to 7 ON in the entire polyester resin composition.

If it is less than 3% by weight, no improvement in physical properties such as (fk) is observed, and if it exceeds 70% by weight, mechanical properties deteriorate, which is not preferable.

Additionally, additives such as light or heat stabilizers, dyes, or pigments may be added to the polyester resin composition of the present invention, if necessary.

When manufacturing a molded article from the resin composition of the present invention,
As in the past, a predetermined amount of the composition components is put into a kneading machine such as an extruder, melt-kneaded to form pellets, and then injection molding or pressure molding is performed to obtain a molded product.

The present invention will be explained below using examples.

[Examples 1 to 5] Chopped strand glass fiber with a length of 3 Waa (abbreviated as GF in the table) was added to (polyethylene 7 terephthalate homobolymer-CPET with an inherent viscosity of L72).
Components (0) and (D) were blended and homogenized in the types and proportions shown in the table. The obtained mixture was put into a vent type melt extruder with a diameter of 40 m, and the temperature of the cylinder 7 was 260 to 280.
"C" to obtain a pellet of the resin composition of the present invention.

8 ounces of the resin composition obtained here was molded into a cylinder at a temperature of 280°C using a complete screw injection molding machine with a diameter of 45 mm.
, a tensile strength specimen of ABTMD-638 from the pellet at a mold temperature of 140°C and a molding cycle of 30 seconds, ASTM
Izot impact specimens of D-256 and flat specimens measuring 100 x 100 x 1 m were molded to examine the surface appearance.

The table shows the results obtained.

[Examples 6 to 8] A molded article was obtained in the same manner as in Example 1 except that polybutylene terephthalate homopolymer (PBT) with [l] = L1 was used for Q instead of polyethylene terephthalate,
An evaluation was conducted.

The results obtained are shown in the table.

[Comparative Examples 1 and 2] Resin compositions were produced in the same manner as in Example 1, except that component (D) shown in the table was used as an additive, and molded articles were evaluated. The results obtained are shown in the table.

Emulgen 950: 09 HI3-min0-(CH2CH,O)so-H (polyethylene glycol nonylphenyl ether) KRM
7003 A flat plate of 1100 x 100 x 1n was pressed at one place and the height of the floating point was measured.

〔Effect of the invention〕

As detailed above, the polyester resin composition of the present invention has an excellent surface by blending the nucleating agent (3) and the silane-coupled inorganic filler (D) component into the reinforced polyester resin. It is possible to obtain a molded product that has a good appearance, improved mechanical strength, and reduced warpage, and the effect is extremely high.

Claims (1)

[Scope of Claims] A) 25 to 96.97% by weight of thermoplastic polyester resin B) 1 to 60% by weight of fibrous reinforcement C) 0.03 to 30% by weight of nucleating agent D) Silane represented by [I] 3-70% by weight inorganic filler surface treated with coupling agent Y-R_1-S
i-X_3 [I] where X: Cl, OR_2 or OCOR_3Y: CH_
2=CH_2, CH_2=CCH_3COO, ▲ Formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, HS, Cl, NH_2, NH_2C_2H_4NH or NH_2CO
NHR_1 to R_3: Hydrogen or C_nH_2_n_+_
1 (n = an integer of 1 or more), and (A) to (D)
A polyester resin composition characterized in that the total amount of each component is 100% by weight.