JP2672426B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition. More specifically, the present invention relates to a novel thermoplastic resin composition having excellent heat resistance, chemical resistance, mechanical properties, flame retardancy, and the like.

[0002]

2. Description of the Related Art Amorphous engineering plastics, crystalline engineering plastics, and liquid crystal engineering plastics are known as thermoplastic heat-resistant resins, so-called engineering plastics (engineering plastics). I have. Of these, crystalline engineering plastics are generally characterized by being excellent in heat resistance, mechanical properties, and chemical resistance.
Here, the heat resistance, for example, the heat deformation temperature is determined by the melting point (Tm) of the base polymer, and is usually lower by about 5 to 30 ° C. than Tm. For example, this Tm is 225 ° C. for polybutylene terephthalate, 255 ° C. for polyethylene terephthalate, 260 ° C. for nylon 66, and nylon 4.
6 at 290 ° C, terephthalic acid and cyclohexane-1,4
-Polyester composed of dimenol is 290 ℃
With these polymers, it is not possible to obtain a resin having a heat resistance of 300 ° C. or higher, and even if the Tm is 300 ° C. or higher, it is difficult to obtain a polymer having an aliphatic or alicyclic group. In this case, there is a problem that deterioration during melt molding is remarkable. Aromatic polymers include poly (phenylene sulfide), polyether ketone,
Polysulfide ketones and the like are known, but among them, polyphenylene sulfide has a Tm of 285 ° C., and the heat resistance is still insufficient, and polyetherketone, polysulfide ketone, etc. have a high Tm and stability during melting. However, there is a problem that the polymer is extremely expensive.

[0003]

Accordingly, the present inventors conducted research with the aim of providing a new crystalline resin having heat resistance of 300 ° C. or higher and excellent melt moldability and mechanical properties at a low cost. Was.

[0004]

As a result, the object of the present invention is to provide the following formulas (I) (II) and (III)

[0005]

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[0006] The components (II) and (III) have a content equivalent ratio of 60/40 to 90.
It was found to be achieved by a resin composition comprising 95 to 30% by weight of an aromatic polyester of / 10, 5 to 70% by weight of a fibrous reinforcing material having an aspect ratio of 10 or more, and 0.1 to 5% by weight of talc.

The polymer constituting the resin composition of the present invention is a polyester substantially composed of the components of the above formulas (I), (II) and (III). Ingredient (II) and Ingredient (III)
The content equivalent ratio of is 60/40 to 90/10. If the content equivalent ratio is out of this range, Tm is too high and molding becomes difficult, and conversely, Tm becomes low and heat resistance becomes insufficient, which is not preferable.

The method for producing this polymer is not particularly limited. For example, isophthalic acid diphenyl ester, hydroquinone and 4,4'-dihydroxydiphenyl are heated in the presence of a catalyst for polycondensation (A), isophthalic acid. A method (B) in which diacetoxyhydroquinone and 4,4'-diacetoxydiphenyl are heated to cause polycondensation in the presence of a catalyst, isophthalic acid, hydroquinone and 4,4'-dihydroxydiphenyl containing substituents A method (C) in which polycondensation is performed by heating in the presence of a good phenol and a catalyst can be used. In the case of the above method (B), diacetoxyhydroquinone,
Instead of using 4,4'-diacetoxydiphenyl,
An acetoxylation reaction can also be carried out in a polymerization reaction system using hydroquinone, 4,4'-dihydroxydiphenyl and acetic anhydride. As the method for producing the polymer of the present invention, the method (C) can be preferably used.

The above method (C) is a method for obtaining a polyester by esterification and transesterification, and can be roughly divided into two reactions, an initial reaction and a polymerization reaction.

The initial reaction involves at least 50 carboxyl groups.
% Is a stage where it reacts with the hydroxy component and is esterified. In this stage, water is generated by the reaction, and is distilled out of the reaction system. At this stage, it is necessary to prevent the phenol component from distilling out of the reaction system.

The next polymerization reaction is a stage in which the esterification further progresses, and at the same time, the exchange reaction between the ester of the carboxylic acid component and the phenol component and the hydroxy component of another kind progresses so that the polymerization proceeds. At this stage, the phenol component is distilled out of the reaction system together with the water. The initial reaction and the polymerization reaction cannot be clearly distinguished from each other, but are distinguished in that the phenol component is positively suppressed from being distilled out of the reaction system in the initial reaction and is distilled off in the polymerization reaction.

The reaction temperature of the initial reaction varies depending on the catalyst, but is 150 ° C. or higher, preferably 180 ° C. or higher, particularly preferably 230 ° C. or higher, and is preferably raised as the reaction proceeds. In this case, the upper limit is 330 ° C., preferably about 300 ° C. The initial reaction can be performed under normal pressure to pressurization, but when the boiling point of the phenol component at normal pressure is particularly lower than the reaction temperature, the reaction is preferably performed under pressurized conditions. The reaction system is preferably set in an atmosphere of an inert gas such as nitrogen or argon.

The reaction time may be a time sufficient for the above-mentioned ester reaction to proceed sufficiently. The time varies depending on the reaction time, the reaction scale and the like, but it is 30 minutes to 20 hours, preferably about 1 to 10 hours. It is.

In the above reaction, it is preferable to remove the water generated by the esterification out of the reaction system. The esterification reaction is an equilibrium reaction, and as the generated water is removed out of the system, the reaction proceeds, and the yield and purity of the product are improved. The generated water can be removed out of the reaction system by the difference in boiling point from the phenol component, but can also be removed out of the reaction system by azeotropy using an organic solvent which forms an azeotropic mixture with water. . The organic solvent may be any organic solvent which does not decompose itself under the reaction conditions, is substantially stable in the reaction system, and azeotropes with water. Specifically, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene can be preferably used.

The conversion of the esterification reaction in the initial reaction is preferably 50% or more. This esterification reaction rate can be known from the amount of water generated by the reaction, but for more accurate determination, it is also possible to take out a part of the reaction product and measure it by measuring the unreacted-COOH value. it can.

The esterification ratio in the initial reaction is more preferably 60% or more, particularly preferably 70% or more. The reaction temperature in the polymerization reaction is from the initial reaction temperature to 38.
It is preferably carried out at 0 ° C. Since the melting point of the reaction product rises as the polymerization progresses, it is preferable to perform it while gradually raising the temperature.
To a degree preferably carried out at a temperature of not more than 330 ° C.,
In the case of a higher temperature, the melt polymerization is carried out at a temperature of 380 ° C, preferably 360 ° C or less.

Since the aromatic polyester obtained by the method of the present invention has a relatively high melt viscosity, when the degree of polymerization is increased by melt polymerization, it is preferably carried out in a ruder type reactor or the like.

The polymerization reaction is carried out under reduced pressure or by flowing an inert gas to forcibly remove water and phenol components produced as a result of the reaction and dihydroxy aromatic compounds such as hydroquinone used in excess if necessary out of the reaction system. While doing.

The intrinsic viscosity of the polyester obtained by the method of the present invention is preferably from 0.3 to 1.5, more preferably from 0.4 to 1.2.

The resin composition of the present invention comprises the above-mentioned aromatic polyester, fibrous reinforcing material and talc.

Here, the fibrous reinforcing material is glass fiber,
Examples thereof include carbon fiber, aramid fiber, silicon carbide fiber, alumina fiber and potassium titanate fiber. The fibrous reinforcing material needs to have an aspect ratio of 10 or more. Here, the aspect ratio is the ratio between the length of the fiber and its diameter. When there is a distribution in the aspect ratio of the reinforcing fiber, the average value is defined as the aspect ratio of the fiber. If the aspect ratio is less than 10, the reinforcing effect on mechanical properties, heat resistance and the like becomes insufficient, which is not preferable. As the fibrous reinforcing material, glass fiber is preferable among the above fibers.

As these fibrous reinforcing materials, those to which a surface treating agent such as a coupling agent or a sizing agent is appropriately added are preferably used in order to improve the affinity with the aromatic polyester or the handleability of the fibers themselves.

The talc constituting the resin composition of the present invention is not particularly limited, and those used in the art can be used as they are. Talc acts as a crystal nucleating agent for the aromatic polyester, promotes crystallization of the molded product obtained from the resin composition of the present invention, and consequently improves the heat resistance of the molded product. Further, the temperature of the mold at the time of molding can be lowered as compared with the case where a molded product having the same heat resistance is made by using another resin.

The proportions of the aromatic polyester, the fibrous reinforcing material and the talc used are 5 to 70% by weight of the reinforcing fiber and 0.1 to 5% of the talc with respect to 95 to 30% by weight of the aromatic polyester.
% By weight. The mixing ratio is preferably 90 to 40% by weight of aromatic polyester, 10 to 60% by weight of reinforcing fiber, 0.2 to 4% by weight of talc, particularly preferably 85 to 50% by weight of aromatic polyester and 15 to 50% by weight of reinforcing fiber. %, Talc 0.3 to 3% by weight.

The aromatic polyester, the fibrous reinforcing material and the talc can be mixed by a conventionally known compounding method. In some cases, talc may be added during the production of the aromatic polyester.

In addition to the above-mentioned components, the resin composition of the present invention may optionally contain various stabilizers such as oxidation stabilizers and ultraviolet absorbers, colorants, pigments, lubricants, plasticizers, release agents and the like. You may mix an additive.

[0027]

The aromatic polyester of the present invention can be produced industrially and advantageously at a very low cost because it can be produced by a melt polymerization method using inexpensive raw materials.
The obtained polymer is a crystalline polymer having a melting point of 300 ° C. or higher, and the resin composition of the present invention comprising this, a fibrous reinforcing material and talc has heat resistance, mechanical properties, chemical resistance and flame retardancy. It is excellent and extremely useful as a new heat-resistant resin, and its industrial significance is great.

[0028]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. `` Parts '' in the examples
Means "parts by weight", and the intrinsic viscosity of the polymer is p-chlorophenol / tetrachloroethane mixed solvent (weight ratio 6
0/40) at 35 ° C. The melting point (Tm) and glass transition point (Tg) of the polymer are DS
It was measured using C at a temperature rising rate of 10 ° C./min.

[0029]

[Reference Example 1] 166 parts of isophthalic acid, hydroquinone 9
9 parts, 28 parts of 4,4'-dihydroxydiphenyl, 94 parts of phenol and 0.09 part of antimony trioxide were charged into a reactor equipped with a stirrer and a distillation system, and under a nitrogen pressure of 280.
Heated to ° C. The reaction was carried out for 5 hours while gradually reducing the pressure from 5 kg / cm ² to 2 kg / cm ² and distilling water generated by the reaction out of the system. During this time 29 parts of water were produced. Then, the reaction system was returned to normal pressure, and the reaction was carried out for 60 minutes while distilling volatile components out of the system in a nitrogen stream. During this time, the reaction temperature was raised from 280 ° C to 340 ° C.

Then, the system was gradually evacuated for 60 minutes, and then reacted under high vacuum of about 0.5 mmHg for 50 minutes to obtain a polymer having an intrinsic viscosity of 0.52.

Next, using a L / D42 30 mmφ co-rotating twin-screw extruder having two vent ports capable of vacuuming, the polymer temperature was 350 to 360 ° C., the screw rotation speed was 100 rpm, and the average residence time in the vacuum zone was about 10
The polymer was subjected to a melt reaction under the conditions of minutes. On this occasion,
By installing a screw part in the opposite direction to the normal conveying screw in each vent port and sealing the vacuum zone, each of the two vent ports was kept at a vacuum of about 1 mmHg. The polymer obtained by the melting reaction has an intrinsic viscosity of 0.72, a Tm of 348 ° C., and a Tg of
It was 164 ° C.

[0032]

Examples 1 to 6 and Comparative Example 1 Aromatic polyester obtained in Reference Example 1 and glass fiber chopped strands having a length of 3 mm (Nippon Electric Glass, 717 / P, aspect ratio 230)
And a predetermined amount of talc are dry blended, and the polymer temperature is 3 mm using a 30 mmφ, bi-directional extruder with different rotation.
Melt blending was performed under the conditions of 60 ° C. and average residence time of 2.5 minutes.

The obtained compound was subjected to a polymer temperature of 360 ° C. by using an injection molding machine (N40A type, Japan Steel Works).
Injection molding was performed under the conditions of a molding cycle of 40 to 60 seconds.

The physical properties of the obtained molded product are shown in Table 1. The heat distortion temperature of the molded product shown in Comparative Example 1 is 260 ° C., whereas the heat distortion temperature of the resin composition of the present invention is Also 3
It can be seen that the temperature is 00 ° C. or higher, the heat resistance is extremely excellent, and the mechanical properties are good.

[0035]

[Table 1]

[0036]

[Reference Example 2] 166 parts of isophthalic acid, hydroquinone 9
9 parts, 28 parts of 4,4'-dihydroxydiphenyl, 94 parts of phenol and 0.09 part of antimony trioxide were charged into a reactor equipped with a stirrer and a distillation system, and under a nitrogen pressure of 280.
Heated to ° C. The reaction was carried out for 5 hours while gradually reducing the pressure from 5 kg / cm ² to 2 kg / cm ² and distilling water generated by the reaction out of the system. During this time 29 parts of water were produced. Next, the reaction system was returned to normal pressure, and the reaction was carried out for 30 minutes while distilling volatile components out of the system in a nitrogen stream.

Next, 5 parts of talc was uniformly dispersed in 15 parts of meta-cresol, and this was added. The reaction temperature is 28
The temperature was raised from 0 ° C. to 340 ° C., and then the system was gradually evacuated to vacuum for 60 minutes and then reacted under high vacuum of about 0.5 mmHg for 45 minutes to obtain a polymer having an intrinsic viscosity of 0.50.

This was polymerized under the same conditions using the same reaction type extruder as in Reference Example 1. The obtained polymer had an intrinsic viscosity of 0.70, a Tm of 351 ° C and a Tg of 164 ° C.

[0039]

Example 7 Aromatic Polyester 7 Produced in Reference Example 2
0 part, 3 mm long glass fiber chained strand (Asahi Fiber Glass 03JA PX-1, aspect ratio 2
30) 30 parts were dry-blended, melt-blended in the same manner as in Example 1, and the obtained compound was heated to a barrel temperature of 36.
Injection molding was performed at 0 ° C and a mold temperature of 120 ° C. The obtained molded product has a tensile strength of 960 kg / cm ² and a bending strength of 1410 kg / cm.
² , flexural modulus 96000 kg / cm ² , impact strength 7.8 kg
・ Cm / cm (with Izod and notch), heat distortion temperature 300
It was above ℃.

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Claims (1)

(57) [Claims] (1) The following formulas (I), (II) and (III): 95 to 30% by weight of aromatic polyester having an equivalent equivalent ratio of component (II) to component (III) of 60/40 to 90/10 and an aspect ratio of 1
0-or more fibrous reinforcement 5 to 70% by weight and talc 0.1
A resin composition comprising 5% by weight.