JPH07113037A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition, capable of providing moldings excellent in heat resistance, mechanical characteristics and dimensional stability without lowering the fluidity or deteriorating the thermal stability and useful as electri cal and electronic parts, etc., by blending a specific resin component with a specifically treated fibrous reinforcing material. CONSTITUTION:This composition is obtained by blending (A) 100 pts.wt. resin component composed of (i) 55-99.9wt.% polyester resin, (ii) 5-40wt.% aromatic polycarbonate resin and (iii) 0.1-45wt.% epoxy resin, prepared by glycidyl etherifying a linear high-molecular weight cresol novolak, expressed by the formula [R1 is CH3 bound to the o-or p-position; (n) is the number of repetition] and having <=7000 number-average molecular weight with (B) 3-450 pts.wt. fibrous reinforcing material treated with an phenolic novolak type epoxy resin. Furthermore, the component (B) prepared by treating the surface thereof with a silane compound and then carrying out the treatment with the phenolic novolak type epoxy resin as a binder is preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition used as a molding material for various heat appliances, electric / electronic machine parts, automobile parts and the like, more specifically, heat resistance, mechanical properties and dimensional stability. The present invention relates to a polyester resin composition capable of providing a molded article excellent in heat resistance.

[0002]

2. Description of the Related Art Aromatic polyester resins represented by polyethylene terephthalate and polybutylene terephthalate are used as polyester resin compositions for molding materials. Further, for the purpose of improving the heat resistance or mechanical properties of these aromatic polyester resins, as described in JP-A-3-86753, a reinforcing material surface-treated with an epoxy resin is blended, As described in JP-A-2-218738, a polyester resin composition containing an epoxy resin has been proposed. As described above, an epoxy resin used to improve the heat resistance and mechanical properties of an aromatic polyester resin is generally produced from bisphenol A and epichlorohydrin and has about two epoxy groups in one molecule. A so-called bisphenol A type epoxy resin having the following is used.

[0003]

However, such a bisphenol A type epoxy resin has two molecules in one molecule.
Since the aromatic polyester resin has about the number of epoxy groups, the effect of improving the heat resistance or mechanical properties of the aromatic polyester resin is not sufficient. Therefore, it is conceivable to increase the number of epoxy groups in the bisphenol A type epoxy resin.
The type epoxy resin has problems that it is apt to cause gelation and the like, resulting in deterioration of fluidity of the resin composition and instability of thermal stability. An object of the present invention is to provide a polyester resin composition capable of obtaining a molded article excellent in heat resistance, mechanical properties and dimensional stability without deteriorating the fluidity and heat stability of the resin composition. Especially.

[0004]

In view of the above situation, the present inventor has blended a polyester resin with an aromatic polycarbonate resin and a specific linear high molecular weight cresol novolac epoxy resin, and performs a specific treatment. It was found that a molded product excellent in heat resistance, mechanical properties and dimensional stability can be obtained by using the above fibrous reinforcing material together, and the present invention has been achieved. That is,
The polyester resin composition of the present invention comprises 55 to 99.9% by weight of a polyester resin, 5 to 40% by weight of an aromatic polycarbonate resin, and the following general formula (1) obtained by converting a linear high molecular weight cresol novolac into a glycidyl ether. Epoxy resin having a number average molecular weight of 7,000 or less
With respect to 100 parts by weight of the resin component consisting of 45% by weight,
It is characterized in that it comprises 3 to 450 parts by weight of a fiber reinforcing material treated with a phenol novolac type epoxy resin.

[0005]

[Chemical 2]

(In the formula, R ₁ is a CH ₃ group bonded to the ortho or para position, and n is the repeating number.) The polyester resin of the present invention is an aromatic dicarboxylic acid or its ester-forming derivative. And a monomer whose main component is a diol or an ester-forming derivative thereof,
It is a polymer or copolymer obtained by a condensation reaction.

In the present invention, the aromatic dicarboxylic acid used as the acid component is terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,
4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, etc. are mentioned, and these ester-forming derivatives include their dialkyl esters, diaryl esters, etc.

The diol component used in the present invention is ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanediene. Aliphatic diol having 2 to 10 carbon atoms such as methanol, polyethylene glycol, poly-1,
Examples include long-chain glycols having a molecular weight of 400 to 6000 such as 3-propylene glycol and polytetramethylene glycol.

Polyester resins obtained from such aromatic dicarboxylic acid components and diol components include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-. Examples thereof include naphthalate and the like, or copolymers containing these as the main components. Among them, polyethylene terephthalate and polybutylene terephthalate are preferable because they have appropriate mechanical strength.

These polyester resins are phenol /
In a mixed solvent of tetrachloroethane (mixing ratio is 1: 1 by weight), the intrinsic viscosity [η] at a temperature of 23 ° C. is [0].
It is preferably 5 to 1.4. This is because when the intrinsic viscosity is less than 0.5, the strength of the obtained molded product tends to decrease, and when it exceeds 1.4, the fluidity at the time of molding may decrease and the filling property may be insufficient. Is.

The aromatic polycarbonate resin used in the present invention has a viscosity average molecular weight derived from a dihydric phenol of 10,000 to 100,000, preferably 15,000.
40,000 aromatic polycarbonate resins, which are produced from a divalent phenol and a carbonate precursor by a melting method or a solution method. The dihydric phenol is not particularly limited, but bisphenol A (2,2-bis (4-hydroxyphenyl) propane) which is usually used is preferable. Further, examples of the carbonate precursor include carbonyl halides and carbonyl esters, and specific examples include phosgene, diphenyl carbonate and the like, and mixtures thereof. The epoxy resin used in the present invention is an epoxy resin represented by the following general formula (1) obtained by converting a linear high molecular weight cresol novolac into a glycidyl ether.

[0012]

[Chemical 3]

(In the formula, R ₁ is a CH ₃ group bonded to the ortho or para position, and n is the number of repetitions.) The linear high molecular weight cresol novolac used as the raw material for the epoxy resin is cresol and aldehyde. And have 3 to 1 carbon atoms
Produced by polycondensation in the presence of an acidic catalyst in a solvent selected from an aliphatic alcohol having 2 to 3, a glycol ether having 3 to 6 carbon atoms, a benzyl ether and an aliphatic carboxylic acid having 2 to 6 carbon atoms. It is possible. The high molecular weight linear cresol novolak resin thus obtained is reacted with epihalohydrin to form a glycidyl ether, whereby the epoxy resin used in the present invention is obtained.

The linear high molecular weight cresol novolac epoxy resin thus obtained has a number average molecular weight of 70.
00 or less. It has a number average molecular weight of 70.
This is because if it exceeds 00, it becomes difficult to produce an epoxy resin. Preferably, the number average molecular weight is 500 to 7,000.
Is an epoxy resin. The epoxy equivalent of the epoxy resin is preferably in the range of 176 to 280.

The polyester resin composition of the present invention comprises a resin component containing the above polyester resin, an aromatic polycarbonate and a linear high molecular weight cresol novolac epoxy resin, and a fibrous reinforcing material. The resin component includes 55 to 94.9% by weight of polyester resin, 5 to 40% by weight of aromatic polycarbonate resin, and 0.1 to 45% of linear high molecular weight cresol novolac epoxy resin.
It is blended in a blending amount of wt%. This is because when the polyester resin content exceeds 99.9% by weight, the aromatic polycarbonate resin content is less than 5% by weight, or the linear high molecular weight cresol novolac epoxy resin content is less than 0.1% by weight, the obtained molded article is obtained. This is because the effect of improving the mechanical properties and dimensional stability of is not recognized. Also, the polyester resin content is less than 55% by weight, or the aromatic polycarbonate resin content is 40%.
This is because when the content exceeds 50% by weight or the linear high molecular weight cresol novolac epoxy resin exceeds 45% by weight, the shapeability of the material and the mechanical properties of the molded product are deteriorated. Preferably, the polyester resin is 80 to 99.5% by weight, the aromatic polycarbonate resin is 10 to 30% by weight, and the linear high molecular weight cresol novolac epoxy resin is 20 to 0.
The compounding amount is 5% by weight.

The fibrous reinforcing material used in the present invention has been previously treated with a phenol novolac type epoxy resin, and the fibrous reinforcing material subjected to such a specific treatment and the low molecular weight mentioned above. By using the gresol novolac epoxy resin in combination, the mechanical strength and dimensional stability of the obtained molded product can be further improved.

The fibrous reinforcing material of the present invention may be surface-treated with a phenol novolac type epoxy resin, but a phenol novolac type epoxy resin is preferably used as a sizing agent for the fibrous reinforcing material. Is used. When the fibrous reinforcing material is treated with a phenol novolac type epoxy resin, the surface of the fibrous reinforcing material is previously treated with a silane compound such as an aminosilane compound or an epoxysilane compound, and then the phenol novolac type epoxy resin is used. Is preferable because it improves the adhesion between the phenol novolac type epoxy resin and the fibrous reinforcing material. The phenol novolac type epoxy resin may be used alone, but if necessary, an additive such as a urethane compound or an oxidation stabilizer may be used in combination.

Examples of the fibrous reinforcing material include glass fibers, alumina fibers, carbon fibers, silicon carbide fibers, ceramic fibers, inorganic fibers such as asbestos fibers, metal fibers, heat resistant organic fibers and the like. Specifically, the fiber diameter 1 to
20 μm, chopped strands of glass fibers or carbon fibers having a fiber length of 10 mm or less, glass fiber milled fibers, pitch-based carbon fibers, aromatic polyamide fibers, aromatic polyimide fibers, aromatic polyamideimide fibers, and the like, and these may be used alone or It can be used in combination. Of these, chopped strands of glass fiber are preferred.

These fibrous reinforcing materials are blended in the range of 3 to 450 parts by weight with respect to 100 parts by weight of the resin component consisting of polyester resin and linear high molecular weight cresol novolac epoxy resin. This is because if the compounding amount of the fibrous reinforcement is less than 3 parts by weight, the compounding effect of the fibrous reinforcement treated with the linear high molecular weight cresol novolac epoxy resin and the phenol novolac type epoxy resin cannot be obtained. On the contrary, if it exceeds 450 parts by weight, the flow processability at the time of molding is deteriorated.

In the present invention, the dimensional stability of the obtained molded product can be further improved by using a plate-like filler together with the above fibrous reinforcing material. Examples of the plate-shaped filler include muscovite, phlogopite, mica such as serisanite, plate-shaped glass such as glass flake, talc and metal foil, and plate-shaped glass is particularly preferable. These plate-like fillers preferably have a particle size of 20 μm or more and a thickness of about 0.1 to 10 μm, more preferably a particle size of 25 to 500 μm and a thickness of 1 to 5.
It is about μm.

The amount of the plate-like filler compounded is preferably in the range of 5.5 to 70 parts by weight, more preferably 10 to 45 parts by weight, based on 100 parts by weight of the resin component. This is because if the plate-like filler is less than 5.5 parts by weight,
This is because the dimensional stability of the molded product tends to be poor, and in particular, the molded product tends to be easily deformed.
This is because if the amount is more than parts by weight, the fluidity of the resin composition tends to decrease and the mechanical strength of the molded article tends to decrease.

The plate-like filler may be blended as it is, but it is preferable to use a plate-like filler which has been surface-treated with an appropriate surface-treating agent to improve the affinity and adhesiveness with the resin component. This is preferable because For example, when the plate-like filler is treated with a phenol novolac type epoxy resin, the surface of the fibrous reinforcing material is previously treated with a silane compound such as an aminosilane compound or an epoxysilane compound, and then the phenol novolac type epoxy resin is used. Treatment with an epoxy resin is preferable because it improves the adhesion between the phenol novolac type epoxy resin and the fibrous reinforcing material. The phenol novolac type epoxy resin may be used alone, but if necessary, an additive such as a urethane compound or an oxidation stabilizer may be used in combination.

Further, in the present invention, silicates such as kaolin, clay, wollastonite, bentonite, asbestos and alumina silicate, alumina, silicon oxide, magnesium oxide, and oxidation are used within a range that does not impair the effects of the present invention. Zirconium, titanium oxide and other metal oxides, calcium carbonate, magnesium carbonate, dolomite and other carbonates calcium sulfate, barium sulfate and other sulfates, glass beads, boron nitride, silicon carbide and other particulate fillers, silica and stearin Lubricants and release agents such as acid salts, UV absorbers, colorants containing pigments such as carbon black, flame retardants such as halogen compounds and phosphorus compounds, flame retardant aids, antioxidants, antistatic agents, coupling agents Known additives such as a foaming agent, a cross-linking agent, and a heat stabilizer may be optionally added. Further, other thermoplastic resins such as ABS resin, polycarbonate resin, polyphenylene ether resin, polyacetal resin and ASA resin may be blended within a range that does not impair the effects of the present invention.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. Examples 1 to 8 polybutylene terephthalate having an intrinsic viscosity [η] of 1.0,
Aromatic polycarbonate resin having a viscosity average molecular weight of 22,000, a number average molecular weight of about 1200, and an epoxy equivalent of 218.
The linear high molecular weight cresol novolac epoxy resin, the glass silane having a fiber diameter of 13 μm and a fiber length of 3 mm, which has been surface-treated with an aminosilane compound and then treated with a phenol novolac type epoxy resin as a sizing agent, are shown in Table 1. And blended in a V-type blender for 5 minutes to homogenize. The obtained mixture was charged into a vent type melt extruder having a diameter of 60 mm, and the cylinder temperature was 250 to 290.
Extrusion was carried out at 0 ° C. to obtain pellets of the polyester resin composition.

The polyester resin composition thus obtained was heated at a cylinder temperature of 250 to 270 ° C. and a mold temperature of 80 to 80 by using a screw type injection molding machine having a diameter of 32 mm and a diameter of 32 mm.
A test piece was molded at 130 ° C and a molding cycle of 40 seconds. Using this test piece, tensile strength according to ASTM D638, bending strength according to ASTM D790, ASTM
The deflection temperature under load was measured according to D648, and the results are shown in Table 1. Further, the molded article shown in FIG. 1 was molded under the above-mentioned molding conditions, the roundness thereof was measured, and the results are shown in Table 1.

Examples 9 to 11 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.8,
Aromatic polycarbonate resin having a viscosity average molecular weight of 22,000, a number average molecular weight of about 1200, and an epoxy equivalent of 218.
The linear high molecular weight cresol novolac epoxy resin, the glass silane having a fiber diameter of 13 μm and a fiber length of 3 mm, which has been surface-treated with an aminosilane compound and then treated with a phenol novolac type epoxy resin as a sizing agent, are shown in Table 1. And the pellets of the polyester resin composition were obtained in the same manner as in Examples 1 to 8. Tensile strength, bending strength, deflection temperature under load, and dimensional stability of the obtained polyester resin composition were measured by the same methods as in Examples 1 to 8, and the results are shown in Table 1.

Examples 12 to 13 Polybutylene terephthalate having an intrinsic viscosity [η] of 1.0,
Aromatic polycarbonate resin having a viscosity average molecular weight of 22,000, a number average molecular weight of about 1200, and an epoxy equivalent of 218.
Of linear high molecular weight cresol novolac epoxy resin, aminosilane compound, and then treated with phenol novolac type epoxy resin as a sizing agent. Glass fiber having a fiber diameter of 13 μm, fiber length of 3 mm, and an aminosilane compound. After that, the glass flakes having an average particle diameter of 140 μm and an average thickness of 4 μm were treated with a phenol novolac type epoxy resin as a sizing agent.
Were blended in the proportions shown in Table 1, and pellets of the polyester resin composition were obtained in the same manner as in Examples 1-8.

Tensile strength, bending strength, deflection temperature under load and dimensional stability of the obtained polyester resin composition were measured in the same manner as in Examples 1 to 8 and the results are shown in Table 1.

[0029]

[Table 1]

Comparative Examples 1 to 8 Polybutylene terephthalate having an intrinsic viscosity [η] of 1.0,
Aromatic polycarbonate resin having a viscosity average molecular weight of 22,000, a number average molecular weight of about 1200, and an epoxy equivalent of 218.
The linear high molecular weight cresol novolac epoxy resin of No. 3, a surface treatment with an aminosilane compound, and a glass fiber having a fiber diameter of 13 μm and a fiber length of 3 mm, which was treated with a bisphenol A type epoxy resin as a sizing agent, are shown in Table 2. And the pellets of the polyester resin composition were obtained in the same manner as in Examples 1 to 8. Tensile strength, flexural strength, deflection temperature under load and dimensional stability of the obtained polyester resin composition were measured by the same methods as in Examples 1 to 8, and the results are shown in Table 2.

Comparative Examples 9 to 11 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.8,
Aromatic polycarbonate resin having a viscosity average molecular weight of 22,000, a number average molecular weight of about 1200, and an epoxy equivalent of 218.
The linear high molecular weight cresol novolac epoxy resin of No. 3, a surface treatment with an aminosilane compound, and a glass fiber having a fiber diameter of 13 μm and a fiber length of 3 mm, which was treated with a bisphenol A type epoxy resin as a sizing agent, are shown in Table 2. And the pellets of the polyester resin composition were obtained in the same manner as in Examples 1 to 8. Tensile strength, flexural strength, deflection temperature under load and dimensional stability of the obtained polyester resin composition were measured by the same methods as in Examples 1 to 8, and the results are shown in Table 2.

[0032]

[Table 2]

Comparative Examples 12 to 22 Polybutylene terephthalate having an intrinsic viscosity [η] of 0.8,
Aromatic polycarbonate resin having a viscosity average molecular weight of 22000, a number average molecular weight of about 1600 and an epoxy equivalent of 218.
Linear high molecular weight cresol novolac epoxy resin, bisphenol A type epoxy resin having an epoxy equivalent of 875 to 975, and a fiber diameter of 13 μm treated with a phenol novolac type epoxy resin as a sizing agent after surface treatment with an aminosilane compound, Glass fibers having a fiber length of 3 mm were mixed in the proportion shown in Table 3 and pellets of the polyester resin composition were obtained in the same manner as in Examples 1 to 8. Tensile strength, bending strength, deflection temperature under load, and dimensional stability of the obtained polyester resin composition were measured by the same methods as in Examples 1 to 8, and the results are shown in Table 3.

Comparative Examples 23 to 25 Polyethylene terephthalate having an intrinsic viscosity [η] 0.8,
Aromatic polycarbonate resin having a viscosity average molecular weight of 22,000, a number average molecular weight of about 1600, and an epoxy equivalent of 875.
Glass fibers having a fiber diameter of 13 μm and a fiber length of 3 mm, which have been surface-treated with a bisphenol A type epoxy resin or an aminosilane compound and then treated with a phenol novolac type epoxy resin as a sizing agent, in the proportions shown in Table 3. Blending was carried out in the same manner as in Examples 1 to 8 to obtain pellets of the polyester resin composition. Tensile strength, bending strength, deflection temperature under load, and dimensional stability of the obtained polyester resin composition were measured by the same methods as in Examples 1 to 8, and the results are shown in Table 3.

[0035]

[Table 3]

[0036]

EFFECT OF THE INVENTION The polyester resin composition of the present invention contains a specific linear high molecular weight cresol novolac epoxy resin and a fibrous reinforcing material to impair the fluidity and heat stability of the resin composition. Without heat resistance,
It is possible to obtain a molded product having excellent mechanical properties and dimensional stability, and to provide a polyester resin composition for a molding material that can be used in a wide variety of fields such as various heat appliances, electric / electronic parts, and automobile parts. Is.

[Brief description of drawings]

FIG. 1 is a perspective view of a molded body used for measuring roundness.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location C08L 63:04) (72) Inventor Tomohiko Yoshida 2/3 of Ushikawa Dori, Toyohashi City, Aichi Prefecture Ryo Rayon Co., Ltd. Toyohashi Office

Claims (3)

[Claims] 1. Polyester resin 55 to 99.9% by weight
And 5 to 40% by weight of an aromatic polycarbonate resin and a number average molecular weight represented by the following general formula (1) obtained by converting a linear high molecular weight cresol novolac into a glycidyl ether of 70.
100 parts by weight of a resin component consisting of 0.1 to 45% by weight of an epoxy resin of 00 or less and 3 to 450 of a fiber reinforced material treated with a phenol novolac type epoxy resin.
A polyester resin composition blended by weight. [Chemical 1] (In the formula, R ₁ is CH bonded to the ortho or para position.
_{It is 3} groups, and n is the number of repetitions. ) 2. The polyester resin composition according to claim 1, wherein the fibrous reinforcing material is surface-treated with a silane compound and then treated with a phenol novolac type epoxy resin as a sizing agent. object. 3. The polyester resin composition according to claim 1, wherein 5.5 to 70 parts by weight of the plate-like filler is mixed with 100 parts by weight of the resin component.