JP2938299B2 - Aromatic polyester, process for producing the same, and molding resin composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic polyester, a process for producing the same, and a molding resin composition using the same. More specifically, it has excellent heat resistance, flame resistance, mechanical properties and moldability, and is optically isotropic when molten and crystalline in the solid phase (such properties are usually
The present invention relates to an aromatic polyester (called semi-crystalline), an industrially advantageous production method thereof, and a molding resin composition using the same.

[0002]

2. Description of the Related Art U.S. Pat.
A linear superpolyester comprising a p-phenylene isophthalate unit having a p, p'-biphenylene isophthalate unit interposed in a main chain, wherein the linear superpolyester has an intrinsic viscosity of at least 0.5, and the p-phenylene isophthalate "Superpolyesters" are disclosed in which the units are at least 40 mol%, based on the sum of the two units.

Further, US Pat. No. 3,160,602 discloses that when a reaction component substantially consisting of an aromatic dicarboxylic acid halide and a dihydric phenol is mixed and reacted to produce a “superpolyester”, A method for producing a "superpolyester" by dissolving the reaction components in a specific solvent such as benzophenone and m-taphenyl and reacting at a specific temperature is disclosed.

Further, JP-A-58-47019 discloses a mixture comprising a diaryl isophthalate, hydroquinone and 4,4'-dioxybiphenyl,
Alternatively, there is disclosed a method for producing an aromatic copolyester by melt-polymerizing a mixture comprising isophthalic acid, hydroquinone, 4,4'-dioxybiphenyl and diaryl carbonate and, if necessary, further solid-phase polymerizing.

[0005] EP-A-0472366.
The polymer unit A represented by the above formula (1), the polymer unit B represented by the above formula (2), and the following formula (4)

[0006]

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And a polymer unit Z represented by the following formula:
-), And the melting point (T
m),

[0008]

(Equation 3)

(Where X is the molar ratio (%) of the polymerized unit Z based on the total of the polymerized unit B and the polymerized unit Z, and Tm is the melting point (° C.) of the polymer. Is 1
It is a number of 0 to 35 mol%. An aromatic polyester having an intrinsic viscosity of 0.3 or more measured at 35 ° C. in a mixed solvent having a phenol / tetrachloroethane (weight ratio) of 60/40 is disclosed.

On the other hand, Japanese Patent Publication No. 16963/1985 discloses an aromatic dicarboxylic acid A and 5-65 parts by weight of the A component.
Mole% dihydroxybenzene B and 0-80 mole%
Of the aliphatic diol C and the amount of the aromatic monohydroxy compound D in which the sum of the components B and C is 180 mol% or more with respect to the component A in the presence or absence of a medium. The esterification reaction is performed until the conversion of the carboxyl group reaches 80% or more, and then the total amount of the obtained esterification reaction product and the component C used in the esterification reaction step is 0 to 80 mol% based on the component A. Amount of the C component, the sum of the B component and the C component is 95 to
Disclosed is a method for producing a polyester, characterized by adding and reacting an amount of bisphenol of 130 mol%. The polyester obtained by the method of Japanese Patent Publication No. 60-16963 is characterized in that it contains polymer units derived from dihydroxybenzene in a proportion considerably less than 65 mol%, and that polymer units derived from bisphenol are substantially contained. In an appropriate amount and is amorphous (amorphous).

[0011]

SUMMARY OF THE INVENTION It is, therefore, one object of the present invention to provide a novel aromatic polyester. Another object of the present invention is to provide high crystallinity and high melting point (T
An object of the present invention is to provide an aromatic polyester having excellent mouldability, having a low secondary transition point (Tg) and exhibiting a low viscosity in a molten state. Another object of the present invention is an aromatic polyester which is isotropic in the molten state and is crystalline in the solid phase (so-called semi-crystalline),
An object of the present invention is to provide a polyester showing excellent heat resistance, flame resistance, mechanical properties and good moldability. Still another object of the present invention is to provide an inexpensive aromatic polyester which exhibits the above-mentioned excellent performance. Still another object of the present invention is to provide a method for industrially advantageously producing the novel aromatic polyester as described above. Still another object of the present invention is to provide a fiber-reinforced resin composition for molding containing the aromatic polyester described above. Still other objects of the present invention will be apparent from the following description.

[0012]

According to the present invention, the above object is achieved by a novel aromatic polyester having the following features (A) to (D). (A) A polymer unit A represented by the following formula (1), a polymer unit B represented by the following formula (2), and a polymer unit C represented by the following formula (3)

[0013]

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Wherein these polymer units form an ester bond in the polymer chain, and (a) the polymer unit C is 10 to 35 mol based on the total of the polymer unit B and the polymer unit C. (C) crystalline and isotropic, and (d) measured at 35 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 60/40). Intrinsic viscosity of 0.3-1.5 and 280-38
It has a melting point of 0 ° C.

That is, the above aromatic polyester is
It consists essentially of an isophthalic acid component (polymer unit A), a hydroquinone component (polymer unit B) and a neopentylene glycol component (polymer unit C), such that these polymer units form an ester bond (—COO—) with each other. It is a linked random copolymer. These ester bonds are formed by polymer units A and B
And an ester bond between the polymer units A and C. Therefore, it is understood that the polyester of the present invention consists essentially of the following repeating units AB and AC.

[0016]

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In the aromatic polyester of the present invention, the proportion of the polymer unit C is 10 to 35 mol%, preferably 15 to 35 mol%, based on the total of the polymer unit B and the polymer unit C.
３０30 mol%. Therefore, the aromatic polyester of the present invention preferably has a repeating unit AB / repeat unit AC ratio (molar ratio) of 90/10 to 65/35,
More preferably, it is a random copolymer of 85/15 to 70/30.

The melting point of the aromatic polyester of the present invention depends on the copolymerization ratio and is preferably in the range of 380 to 280 ° C.

The aromatic polyester of the present invention is advantageously produced by a heat melting reaction of a starting material comprising isophthalic acid, hydroquinone and neopentylene glycol.

Therefore, according to the present invention, a starting material consisting essentially of isophthalic acid (a), hydroquinone (b) and neopentylene glycol (c) is prepared according to the following formulas (i) and (ii):

[0021]

(Equation 4)

(Where A is the number of moles of isophthalic acid (a), B is the number of moles of hydroquinone (b),
C is the number of moles of neopentylene glycol (c). ) At the same time, and melted by heating in the presence of an esterification catalyst to have an intrinsic viscosity of 0.3 to 1.5.
A method for producing an aromatic polyester, characterized by producing a crystalline and isotropic aromatic polyester having a melting point of 280 to 380 ° C.

In the method of the present invention, as described above, the compounds (a), (b) and (c) are used in a quantitative ratio such that the above two relational expressions (i) and (ii) are simultaneously satisfied. Is done.

Among them, the above formula (i) is obtained by isophthalic acid (a) and a dihydroxy compound [hydroquinone (b)
And neopentylene glycol (c)] should be used in a suitable balance to form the polymer chains. That is, when the above formula (i) is not satisfied, the degree of polymerization of the obtained polymer is difficult to increase, and coloring or the like is liable to occur during the polymerization reaction.

The following relational formula (ia) is preferably satisfied between the compounds (a), (b) and (c).

[0026]

(Equation 5)

The formula (ii) below is intended to define the proportion of the polymer units derived from hydroquinone (b) and neopentylene glycol (c) in the obtained aromatic polyester polymer. That is, when the molar ratio B / C of hydroquinone (b) and neopentylene glycol (c) exceeds 90/10, the melting point of the obtained polymer becomes too high, and melt polymerization and molding become difficult. Not preferred. Also, this value is 65 /
If it is less than 35, the crystallinity of the polymer will decrease,
It is not preferable because heat resistance and the like deteriorate. The following relational expression (iia) is preferably satisfied between hydroquinone (b) and neopentylene glycol (c), and it is particularly preferable that the relational expression (iib) is satisfied.

[0028]

(Equation 6)

In the method of the present invention, in addition to the above compounds (a), (b) and (c), phenols (d) which may be optionally substituted by an alkyl group having 1 to 5 carbon atoms Can be used.

Examples of the phenols (d) include phenol, m-cresol, p-cresol and p-cresol.
Preferred examples include butylphenol and p-amylphenol. Of these, phenol and cresol are more preferred, and phenol is particularly preferred.

These phenols (d) are not used as constituents of the aromatic polyester to be produced, but are used at the beginning of the reaction between the compounds (a), (b) and (c). It acts as a reaction medium.

Therefore, it is not always necessary to use the phenol (d), but the phenol (d) is used because the reaction is faster, the reaction product is less likely to decompose, and the coloring is less. Is more preferred. The preferred amount of the phenol (d) used is a relational formula (iii) with respect to the compound (a): D / A ≦ 10 (where A is the number of moles of the compound (a), and D is the phenol ( d), which is a molar ratio.

More preferably, the relational expression (iiia): 4 ≧
D / A ≧ 0.2 is satisfied, and particularly preferably, the relational expression (ii)
ib): Ratio at which 2 ≧ D / A ≧ 0.3 is satisfied.

In the method of the present invention, the compound (a)
(B), (c) and, if necessary, phenols (d)
Is heated and melted in the presence of an esterification catalyst. As the esterification catalyst, for example, antimony trioxide, stannous acetate, dibutyltin oxide, germanium oxide, titanium tetrabutoxide and the like are suitably used.

During the heating and melting, esterification and transesterification proceed to produce aromatic polyester. It is convenient to separately describe the heat-melting reaction as an initial reaction and a polymerization reaction.

The initial reaction is that at least 50% of the carboxyl groups of the isophthalic acid (a) react with the hydroxy component [ie, hydroquinone (b) and neopentylene glycol (c), and possibly phenols (d)]. This is the stage of esterification. At 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 hydroxy component from distilling out of the reaction system.

The next polymerization reaction is a stage in which the esterification further proceeds, and at the same time, the exchange reaction between the ester formed up to that point and the remaining hydroxy groups proceeds, and the polymerization proceeds. At this stage, the phenol (d) is also distilled out of the reaction system together with the water. Although the initial reaction and the polymerization reaction cannot be clearly distinguished from each other, they are distinguished from each other in that the hydroxy 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 preferably 150 ° C. or higher. It is more preferably at least 180 ° C, particularly preferably at least 230 ° C. The reaction temperature is preferably raised as the reaction proceeds. A preferred upper limit in this case is 330 ° C., and more preferably about 300 ° C.

The initial reaction can be carried out under normal pressure to under pressure. When the reaction temperature is particularly higher than the boiling points of neopentylene glycol and phenols (d), 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 esterification reaction to proceed sufficiently, and this time varies depending on the reaction time, the reaction scale and the like. It is preferably about 30 minutes to 20 hours, more preferably about 1 to 10 hours.

In the initial reaction, it is preferable to remove water generated by the esterification out of the reaction system. The esterification reaction is an equilibrium reaction, and the reaction proceeds as the generated water is removed out of the system, thereby improving the yield and purity of the product. The generated water can be removed out of the reaction system by the difference in boiling point with the phenol (d), but it can also be removed out of the reaction system by azeotropy using an organic solvent that forms an azeotropic mixture with water. it can. 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. In particular,
Aromatic hydrocarbons such as toluene, xylene and ethylbenzene can be preferably used.

The reaction rate 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, a part of the reaction product can be taken out and measured by measuring the unreacted-COOH value. . The esterification rate in the initial reaction is more preferably 60 to 95%, particularly preferably 70 to 95%.
It is.

The reaction temperature in the polymerization reaction is preferably from the initial reaction temperature to 380 ° C. In the method of the present invention, the polymerization reaction needs to be carried out while the polyester is being melted. Since the melting point of the reactant increases as the polymerization proceeds, the reaction is preferably performed while the temperature is gradually increased. For example, when the intrinsic viscosity of the polymer is up to about 0.5, it is preferably about 280 to 340 ° C. Carried out at a temperature of When the intrinsic viscosity becomes higher, the melt polymerization is preferably performed at a temperature of 340 to 380 ° C, more preferably 340 to 360 ° C. At this time, when the phenol (d) is used, the phenol (d) is recovered and reused.

In the polymerization reaction, water produced as a result of the reaction is forcibly removed under reduced pressure or while an inert gas is flowed, and phenols and, if necessary, excess hydroquinone are removed from the reaction system. It is advantageous to do it while doing.

When an aromatic polyester having a high degree of polymerization is to be obtained by the method of the present invention, it is preferable that at least the latter stage of the polymerization reaction is carried out in an extruder type reactor or the like.

Thus, according to the method of the present invention, the intrinsic viscosity is 0.3-1.5 , preferably 0.4-1.5 , only by melt polymerization.
A crystalline and isotropic aromatic polyester of 1.5 is produced. The more preferred intrinsic viscosity of the aromatic polyester according to the present invention is from 0.45 to 1.0, particularly preferably from 0.5 to 1.0.

Further, in a preferred embodiment of the method of the present invention, as described above, the above-mentioned heat melting reaction is carried out under the condition that the hydroxy component is hardly distilled out first out of the system, more than 50% of the carboxyl group of the starting material, preferably, The reaction is carried out while distilling off the water formed until the esterification of 60-95%, particularly preferably 70-95%, is carried out, and then the water formed and optionally the phenols (d) are further removed from the system. It will be understood that the process is carried out while distilling off to obtain a polymer having a desired degree of polymerization.

The method of the present invention is preferably carried out in the presence of a heat stabilizer. As the heat stabilizer, various phosphorus compounds are preferable. Preferred examples of such phosphorus compounds include phosphorous acid, phosphoric acid, triphenyl phosphite, triphenyl phosphate, triphenyl phosphine, and the like. The preferred use amount of such a stabilizer is about 0.001 to 1 mol% based on isophthalic acid (a),
More preferably, it is about 0.01 to 0.5 mol%. The timing of adding the stabilizer is not particularly limited, but it is preferable to add the stabilizer after the end of the initial reaction and before the start of the polymerization reaction.

The polyester polymer of the present invention can be produced by other methods, for example, a method of reacting a predetermined ratio of diphenyl aromatic dicarboxylic acid with hydroquinone and neopentylene glycol, or a method of reacting a predetermined ratio of aromatic dicarboxylic acid dichloride. Although it can also be produced by a method of reacting hydroquinone and neopentylene glycol, etc., the method of the present invention can be used at low cost because isophthalic acid, hydroquinone and neopentylene glycol can be used as raw materials as they are. This has the advantage that a desired polymer can be produced and a polymer having good moldability can be obtained as compared with other methods.

The crystalline aromatic polyester according to the present invention is optically isotropic in a molten state, has a relatively low secondary transition point, and has a low viscosity. Melt molding is possible. Moreover, the molded product obtained by melt-molding the polyester has mechanical properties,
This aromatic polyester is extremely useful as a material for engineering plastics, fibers, films, and the like, because it has excellent dimensional stability, heat resistance, chemical resistance, and flame retardancy as well as low water absorption.

According to the present invention, there is further provided a reinforced resin composition for molding utilizing the above-mentioned excellent properties of the aromatic polyester of the present invention.

That is, according to the present invention, first, a molding comprising 100 parts by weight of the aromatic polyester (P) of the present invention and 5 to 250 parts by weight of the fibrous reinforcing material (F). A resin composition for use (hereinafter, referred to as a first composition) is provided.

Here, examples of the fibrous reinforcing material (F) include glass fiber, carbon fiber, aramid fiber, silicon carbide fiber, alumina fiber, potassium titanate fiber and the like. These may be in the form of whiskers. These fibrous reinforcing materials preferably 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 fiber used, the average value is defined as the aspect ratio of the fiber. If the spectrum ratio is less than 10, the reinforcing effect on mechanical properties, heat resistance, and the like tends to be insufficient. The fiber length of the fibrous reinforcing material is preferably 0.5 to 10 mm. As the fibrous reinforcing material, among the above fibers, glass fiber is particularly preferable.

The fibrous reinforcing material (F) may be appropriately coated with a surface treatment agent such as a coupling agent or a sizing agent in order to improve the affinity with the aromatic polyester (P) or the handleability of the fiber itself. The one given is preferably used.

The proportions of the aromatic polyester (P) and the fibrous reinforcing material (F) are as follows.
The fibrous reinforcing material (F) is used in an amount of 5 to 200 parts by weight based on 00 parts by weight. The preferred ratio is aromatic polyester (P)
The fibrous reinforcing material (F) is used in an amount of 10 to 150 parts by weight per 100 parts by weight, particularly preferably the aromatic polyester (P).
The fibrous reinforcing material (F) is 15 to 100 parts by weight per 100 parts by weight.

The first composition of the present invention may further contain, if necessary, a filler, a nucleating agent, a lubricant, a release agent, an antioxidant, and an ultraviolet absorber, in addition to the components (P) and (F). , Pigments,
A plasticizer, an antistatic agent, a powdery, granular, or plate-like inorganic filler may be appropriately added.

In particular, the addition of a nucleating agent (N) is recommended. The nucleating agent (N) is preferably used at a ratio of 0.1 to 10 parts by weight per 100 parts by weight of the aromatic polyester (P). Talc is particularly preferably used as the nucleating agent (N).

The mixing of the aromatic polyester (P) with the fibrous reinforcing material (F) or any other additives that may be used can be carried out by a usual compounding method using an extruder.

The first embodiment of the present invention manufactured as described above
Can be formed into housings for electric and electronic parts, printed wiring boards, and other molded products by using a conventional melt molding method, for example, an injection molding method, a compression molding method, or an extrusion molding method. Can be. Further, a connector having a desired shape can be obtained by integrating with a conductor during or after molding.

A preferred example of an electric / electronic component using the first composition of the present invention has a housing made of the above resin composition. Examples of such electric / electronic parts include diodes, transistors, other semiconductor elements, rectifiers, integrated circuits, resistors, variable resistors, capacitors, and the like.

As a method for improving the mounting density of electronic components on the surface of a printed wiring board, an electronic component is temporarily fixed on a substrate on which solder is previously spotted at a place where electronic components are to be fixed on a circuit, and then the substrate is irradiated with infrared rays. A method of fixing an electronic component by heating by means of hot air or the like to melt the solder is known as a reflow method. According to this reflow method, the mounting density of electronic components on the substrate surface can be improved. Conventionally used electronic components do not have sufficient heat resistance of the resin that composes them.In particular, in the reflow method using infrared heating, there was a problem that the temperature of the component surface was locally increased. Since the resin composition of the present invention has excellent heat resistance, the heating temperature can be set high in the soldering step by the reflow method, and the reliability of soldering and the yield of components can be improved.

When an electric / electronic component using the first composition of the present invention is fixed to a printed wiring board by a reflow method, for example, the following is carried out.

That is, first, a solder is placed in a dot shape on a portion of a wiring formed on a printed circuit board to be fixed to an electronic component, and then the electric / electronic component having a housing made of the resin composition of the present invention is bonded to an adhesive. Temporarily fix to the substrate using. At this time, the terminal of the component to be temporarily fixed is brought into contact with the solder placed in a dot shape. The substrate on which the electric and electronic components are temporarily fixed as described above is placed in a reflow furnace such as infrared rays or hot air, and the substrate on which the electric or electronic components are temporarily fixed is heated to melt the solder, and the wiring of the substrate and Solder terminals of electric and electronic parts. The housing formed of the first composition of the present invention is stable even when soldered by such a reflow method.

Further, according to the present invention, secondly, 100 parts by weight of the aromatic polyester (P) of the present invention, crystalline thermoplastic resins (T) 1 to 2 other than the aromatic polyester (P).
It is characterized by comprising fibrous reinforcing material (F) in an amount of 5 to 250 parts by weight based on 200 parts by weight and 100 parts by weight in total of aromatic polyester (P) and crystalline thermoplastic resin (T). A molding resin composition (hereinafter, referred to as a second composition) is also provided. As the crystalline thermoplastic resin (T) other than the aromatic polyester (P), for example, terephthalate polyester, polyphenylene sulfide, liquid crystalline wholly aromatic polyester, polyether ketone and the like are preferably used.

As the terephthalate polyester, polyethylene terephthalate is preferably used. As such polyethylene terephthalate, those in which ethylene terephthalate repeating units account for 90 mol% or more of all repeating units are preferred. The intrinsic viscosity (measured in o-chlorophenol at 35 ° C.) of such polyethylene terephthalate is preferably from 0.3 to 1.3, more preferably from 0.5 to 1.0.

Polyphenylene sulfide is, for example, p-
What consists of a repeating unit of a phenylene sulfide skeleton is preferred. Such polyphenylene sulfides may be partially crosslinked. Such polyphenylene sulfide is available as commercial products "Ryton" (manufactured by Philips Sekiyu) and "Fortron" (manufactured by Polyplastics).

Liquid crystalline wholly aromatic polyester (LCPII)
For example, a copolymer in which a p-hydroxybenzoic acid component and a 2-hydroxy-6-naphthoic acid component are randomly bonded by an ester bond is preferably used. Such a copolymer is known as a type II liquid crystal polymer among engineering plastics, and is marketed, for example, as “VECTRA” (manufactured by Hoechst Celanese).

As the polyether ketone, a polymer in which an aromatic ring, preferably a benzene ring is bonded at the p-position by ether and ketone is used. Such a polyether ketone is, for example, “VICTREX PEE”.
K "(manufactured by ICI).

As the fibrous reinforcing material (F), the same one as described for the first composition of the present invention can be used.

The mixing ratio of the aromatic polyester (P) and the crystalline thermoplastic resin (T) in the second composition of the present invention is such that the crystalline thermoplastic resin (100 parts by weight) per 100 parts by weight of the aromatic polyester (P). T) is 1 to 200 parts by weight, preferably 2 to 150 parts by weight, more preferably 3 to 100 parts by weight.

The amount of the fibrous reinforcing material (F) is from 5 to 250 parts by weight, preferably from 10 to 100 parts by weight of the total weight of the aromatic polyester (P) and the crystalline thermoplastic resin (T). ~ 200 parts by weight, more preferably 15 ~ 15
0 parts by weight. The fibrous reinforcing material (F) used here is preferably glass fiber.

In addition to the components (A), (B) and (C), the second composition of the present invention may further comprise a flame retardant, a flame retardant auxiliary, a filler, a nucleating agent, a lubricant, if necessary. , A release agent, an antioxidant, an ultraviolet absorber, a pigment, a plasticizer, an antistatic agent, a powdery, granular, or plate-like inorganic filler may be appropriately added.

In particular, the addition of a nucleating agent (N) is recommended. The nucleating agent is preferably used in a ratio of 0.1 to 10 parts by weight per 100 parts by weight of the aromatic polyester (P). Talc is particularly preferably used as the nucleating agent (N).

The mixing with the aromatic polyester (P), the crystalline thermoplastic resin (T) and the fibrous reinforcing material (F), or other additives that may be used, may be carried out by a usual compounding method using an extruder. Can be implemented.

The second embodiment of the present invention manufactured as described above
Can be molded into various molded articles by utilizing a usual melt molding method, for example, an injection molding method, a compression molding method, or an extrusion molding method.

The second composition of the present invention is excellent in economy, heat resistance, mechanical properties, flame retardancy, chemical resistance and moldability, and is particularly suitable for molding at a low mold temperature when producing molded articles. It has the advantage that conditions can be selected.

According to the present invention, thirdly, 100 parts by weight of the aromatic polyester (P) of the present invention, 1 to 50 parts by weight of the brominated polymer flame retardant (R) and 5 to 5 parts of the fibrous reinforcing material (F)
A flame-retardant resin composition containing 250 parts by weight (hereinafter, referred to as a third composition) is provided.

As the brominated polymer flame retardant (R), brominated polystyrene and brominated polyphenylene oxide are preferably used.

The brominated polystyrene is represented by the following formula (5)

[0080]

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(Where p is an integer of 1 to 5 and m is an integer of 2 or more). The brominated polystyrene is produced by polymerizing the corresponding brominated styrene or by brominating the polystyrene. The brominated polystyrene may be partially copolymerized with another vinyl compound. In this case, styrene, α
-Methylstyrene and the like.

The degree of polymerization of the brominated polystyrene is not particularly limited, but the weight average molecular weight is 5,000 to 1,000,
Approximately 000 are preferably used.

The brominated polyphenylene oxide has the following formula (b)

[0084]

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(Where t represents an integer of 1 or more) is preferably used.

The brominated polyphenylene oxide is
It can be produced by reacting 2,6-dibromophenol by a conventionally known oxidative coupling polymerization method. The degree of polymerization of the brominated polyphenylene oxide is not particularly limited, but the weight average molecular weight is 2,000 to 1,000.
Those having a molecular weight of about 0000 are preferably used.

Each of the above-mentioned flame retardants may be used alone or in combination depending on the case.

The above-mentioned flame retardant has a large flame-retarding effect on the crystalline aromatic polyester (P) of the present invention and has good affinity.

As the fibrous reinforcing material (F), the same one as described above with respect to the first composition of the present invention is used, and glass fiber is particularly preferable.

The mixing ratio of the aromatic polyester (P) and the brominated polymer flame retardant (R) is such that the brominated polymer flame retardant (R) is 1 to 50 parts by weight per 100 parts by weight of the aromatic polyester (P). . When the compounding amount of the brominated polymer flame retardant (R) as the flame retardant is the aromatic polyester (P) 1
If the amount is less than 1 part by weight with respect to 00 parts by weight, the flame retardancy of the obtained resin composition will be insufficiently improved, while if it is more than 50 parts by weight, mechanical properties, heat resistance, etc. will be adversely affected. .

The preferred compounding ratio of the brominated polymer flame retardant (R) is 2 to 30 parts by weight based on the same standard.

The mixing ratio of the fibrous reinforcing material (F) is as follows:
5-250 per 100 parts by weight of the aromatic polyester (P)
Parts by weight.

If the amount of the fibrous reinforcing material (F) is less than 5 parts by weight, the effect of reinforcing the mechanical properties and heat resistance is insufficient. If the amount is more than 250 parts by weight, the moldability is deteriorated. .

The fibrous reinforcing material (F) is based on the same standard.
It is preferably from 10 to 200 parts by weight, more preferably from 15 to 150 parts by weight.

The third composition of the present invention may contain, in addition to the above-mentioned components, a small proportion of various kinds of other polymers, nucleating agents, oxidation stabilizers, various stabilizers such as ultraviolet absorbers, coloring agents, if necessary. Pigments,
Various additives such as a lubricant, a plasticizer, and a release agent may be compounded. Mixing of the aromatic polyester (P) with the flame retardant (R) and the fibrous reinforcing material (F) can be carried out by a usual compounding method using an extruder.

The third composition of the present invention has excellent heat resistance, good mechanical properties and good dimensional stability, and particularly excellent flame retardancy, as compared with conventional polyester resins. In addition, it has good fluidity and moldability, and can be formed into a molded article having an arbitrary shape and dimensions by various melt molding methods, and a thin molded article can be easily molded.

Therefore, the third composition of the present invention can be preferably used as a material for various molded articles, particularly for electric and electronic parts requiring flame retardancy and solder heat resistance.

Further, according to the present invention, 100 parts by weight of the aromatic polyester (P) of the present invention, fibrous reinforcing material (F)
There is provided a molding resin composition (hereinafter, referred to as a fourth composition) containing 5 to 250 parts by weight and 0.1 to 5 parts by weight of a release agent (M).

The release agent (M) is represented by the following formula (7)

[0100]

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(Wherein a plurality of Rs are the same or different and each is a C ₁₆ -C ₃₀ monovalent aliphatic residue, and u is 0, 1 or 2). It is preferably used.

In the above formula, examples of the C ₁₆ -C ₃₀ monovalent aliphatic residue of R include groups such as hexadecyl, heptadecyl, octadecyl, nanodecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octakosyl, and triacontyl. be able to.

The compound of the above formula (7) is, for example, n = 0
In the case of pentaerythritol tetraester, n = 1
In the case of dipentaerythritol hexaester, n = 2
In the case of, it is a tripentaerythritol octaester.

These compounds can be used alone or in combination of two or more as release agents.

As the fibrous reinforcing material (F), the same one as described above for the first composition can be used, and among them, glass fiber is preferable.

The mixing ratio of the above components is such that the fibrous reinforcing material (F) 5 is added to 100 parts by weight of the aromatic polyester (P).
To 250 parts by weight and 0.1 to 5 parts by weight of the release agent (M).

When the amount of the fibrous reinforcing material (F) is less than 5 parts by weight, the effect of reinforcing the mechanical properties and heat resistance is insufficient, and when it is more than 250 parts by weight, the moldability is deteriorated. Absent.

When the amount of the release agent (M) is less than 0.1 part by weight per 100 parts by weight of the aromatic polyester (P), the resulting resin composition has insufficient release properties and is smooth. Molding becomes difficult, and if the amount is more than 5 parts by weight, the mechanical properties, heat resistance, and the like may be adversely affected, which is not preferable.

The mixing ratio of the fibrous reinforcing material (F) is preferably from 10 to 200 parts by weight, more preferably from 15 to 150 parts by weight, based on the same standard.

The mixing ratio of the release agent (M) is preferably 0.2 to 3 parts by weight based on the same standard.

In the fourth composition of the present invention, in addition to the above-mentioned components, a small proportion of various kinds of other polymers, nucleating agents, oxidation stabilizers, various stabilizers such as ultraviolet absorbers, flame retardants, Various additives such as a coloring agent, a pigment, a lubricant, and a plasticizer may be blended.

In particular, it is recommended to further contain 1 to 50 parts by weight of a flame retardant, preferably a brominated polymer flame retardant, per 100 parts by weight of the aromatic polyester (P).
Suitable such brominated polymer flame retardants are the same brominated polystyrenes or brominated polyphenylene oxides as described for the third composition. Mixing of the above components can be carried out by a conventionally known compounding method using an extruder.

The fourth composition of the present invention has excellent heat resistance and particularly good mechanical properties and dimensional stability as compared with conventional polyester resins. In addition, it has good fluidity and releasability, and can be easily formed into a molded article of any shape and size by various melt molding methods.

[0114]

As described above, the aromatic polyester of the present invention can be produced only by a melt polymerization method using inexpensive raw materials, and if necessary, a phenol used as the component (d). Since can be recovered and reused, it can be produced industrially at a very low cost.

The obtained aromatic polyester is a crystalline polymer having a melting point of 280 to 380 ° C. and a good heat resistance, but has a low melt viscosity and a secondary transition point (Tg).
Low and excellent in moldability.

The first resin composition of the present invention comprising this and the fibrous reinforcing material is particularly useful in heat resistance, mechanical properties,
It has excellent chemical resistance and flame retardancy, is extremely useful as a new heat-resistant resin, and has great industrial significance. The reinforced resin composition of the present invention is subjected to melt molding by a method known per se, such as injection molding, to give a molded article of any form with good moldability.

The third flame-retardant resin composition of the present invention has excellent heat resistance, good mechanical properties and good dimensional stability as compared with conventional polyester resins, and particularly has a flame retardancy of V- 0 is markedly excellent. In addition, it has good fluidity and moldability, and can be formed into a molded article having an arbitrary shape and dimensions by various melt molding methods, and a thin molded article can be easily molded. Therefore, the flame-retardant resin composition of the present invention can be preferably used as a material for various molded articles, particularly electric / electronic parts that require solder heat resistance.

The second resin containing another crystalline thermoplastic resin may be used.
The composition and the fourth composition containing the release agent are particularly excellent in moldability.

[0119]

The present invention will be described below in detail with reference to examples. In the examples, “parts” simply means “parts by weight”, and the intrinsic viscosity (Inherent Viscosity) of the polymer is phenol /
Using 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40), concentration 0.3 g / dl, temperature 35 ° C.
It is the value measured in. The melting point (Tm) and the secondary transition point (Tg) of the polymer were determined by using a DSC at a heating rate of 10 ° C.
/ Min. The melt viscosity was measured at 360 ° C. using a flow tester, and indicated by a value at a shear rate of 100 / sec. The mechanical and thermal properties of the molded article were measured according to the following criteria.

Tensile strength: ASTM D638 Breaking elongation: ASTM D638 Flexural strength: ASTM D790 Flexural modulus: ASTM D790 Impact strength: ASTM D256 (with notch) Thermal deformation temperature: ASTM D648 (18.6 kg / cm ² )

[0121]

Example 1 and Comparative Example 1 166 parts of isophthalic acid, 88 parts of hydroquinone, neopentylene glycol 26
, 47 parts of phenol, 0.09 part of antimony trioxide and 0.33 part of triphenyl phosphate were charged into a reactor equipped with a stirrer and a distilling system (isophthalic acid / hydroquinone / neopenthylene glycol / phenol). The molar ratio was 100/80/25/50), and the mixture was heated to 280 ° C. while pressurizing with nitrogen. Pressure from 5 kg / cm ² to 2 kg /
While gradually lowering to ² cm2, water generated by the reaction was distilled out of the system, and the reaction was carried out for 5 hours. During this period, 30 parts of water was produced (esterification reaction rate: 83%).

Next, the pressure of the reaction system was returned to normal pressure, and the reaction was carried out for 60 minutes in a nitrogen stream while distilling volatile components out of the system. During this time, the reaction temperature rose from 280 ° C. to 330 ° C. Next, the pressure inside the system was gradually reduced, and after about 60 minutes, the pressure was reduced to about 0.2.
The reaction was carried out for 60 minutes under a high vacuum of 5 mmHg to obtain a polymer (aromatic polyester). The resulting polymer is
The polymer had an intrinsic viscosity of 0.71, a Tm of 321 ° C., and a Tg of 121 ° C., and had good crystallinity. The polymer was optically isotropic in the molten state, and the melt viscosity of the polymer was 4700 poise at 360 ° C.

As Comparative Example 1, a polymer having an intrinsic viscosity of 0.72 was obtained in the same manner as in Example 1 except that 4,4'-dihydroxydiphenyl was used in the same moles instead of neopentylene glycol. The polymer had a Tm of 329 ° C., a Tg of 163 ° C., and a melt viscosity of 14,000 poise.

When comparing the two, the polymer of the present invention has an equivalent melting point and a lower T than the comparative polymer.
g, low melt viscosity.

[0125]

EXAMPLE 2 In the same reactor as in Example 1, 166 parts of isophthalic acid, 99 parts of hydroquinone, 15.6 parts of neopentylene glycol, 94 parts of phenol, and 0.1 part of stannous acetate were added.
1 part, 0.34 part of triphenylphosphite and 100 parts of ethylbenzene were charged (the molar ratio of isophthalic acid / hydroquinone / neopentyl glycol / phenol is equivalent to 100/90/15/100), and the internal temperature was 230 ° C. From 280 ° C. to 280 ° C. while controlling the pressure so that water generated during the reaction is distilled out of the reaction system by azeotropic distillation with ethylbenzene. About 7
By the reaction over time, 31 parts of water were distilled off (esterification reaction rate: 86%).

Next, the polymer was obtained by performing a melt polymerization reaction in the same manner as in Example 1 except that the reaction system was returned to normal pressure, the final reaction temperature was set to 340 ° C., and the high vacuum time was set to 40 minutes. Was. The intrinsic viscosity of the obtained polymer is 0.5
It was 2.

Next, using a 30 mmφ co-rotating twin-screw extruder (L / D = 42) having two vent holes capable of vacuuming at two positions, the polymer temperature is 350 to 360 ° C., the screw rotation speed is 50 rpm, and the average residence time in the vacuum zone is The polymer was allowed to undergo a melt reaction under the conditions of about 10 minutes. At this time, a screw section in the opposite direction to the usual screw for conveyance was provided at the front of each vent port to seal the vacuum zone, so that each of the two vent ports was maintained at a vacuum of about 1 mmHg.

The polymer (aromatic polyester) thus obtained was optically isotropic and crystalline, had an intrinsic viscosity of 0.87, a Tm of 351 ° C. and a Tg of 134 ° C.

[0129]

Comparative Examples 2 to 3 In Example 1, the same reaction was carried out using the same moles of ethylene glycol (Comparative Example 2) or hexamethylene glycol (Comparative Example 3) in place of neopentylene glycol. When a polymer was used, the polymer was colored during the reaction under high vacuum and became a polymer containing a branched insoluble gel. On the other hand, when hexamethylene glycol was used, the reaction product solidified during the high vacuum reaction, and the intrinsic viscosity increased only to 0.21. The solidified product had a Tm of 350 ° C. higher than that of Example 1, and it is considered that hexamethylene glycol was decomposed and reduced.

[0130]

Examples 3 and 4 A predetermined amount of the aromatic polyester obtained in Example 2 was dry-blended with a predetermined amount of 3 mm long glass fiber chopped strand (03JA PX-1 manufactured by Asahi Fiberglass), Using a uniaxial extruder having an inner diameter of 30 mmφ, melt blending was performed under the conditions of a polymer temperature of 360 ° C. and an average residence time of about 5 minutes. Using an injection molding machine (manufactured by Nippon Steel Works, Model N40A), the obtained compound was polymerized at a temperature of 360 ° C. and molded and recycled 40 to
A test piece for evaluation was injection molded under the condition of 60 seconds.

The physical properties of the obtained molded product are shown in Table 1 below.
Table 1 shows that the resin composition of the present invention has excellent heat resistance and mechanical properties.

[0132]

[Table 1]

[0133]

Example 5 (1) Production of polymer: 166 parts of isophthalic acid, 94 parts of hydroquinone, 21 parts of neopentylene glycol, 94 parts of phenol and 0.09 part of antimony trioxide
The reactor was equipped with a stirrer and a distilling system, and heated to 280 ° C. under nitrogen pressure. Pressure from 5 kg / cm ² to 2 kg / cm ²
The reaction was carried out for 5 hours while gradually lowering the temperature and distilling water generated by the reaction out of the system. During this time 29 parts of water were produced. Next, the pressure of the reaction system was returned to normal pressure, 0.33 part of triphenyl phosphate was added, and the reaction was carried out for 60 minutes while distilling off volatile components from the system in a nitrogen stream. During this time, the reaction temperature was raised from 280 ° C to 340 ° C.

Subsequently, the inside of the system was gradually evacuated to 60
After minutes, the mixture was reacted under a high vacuum of about 0.5 mmHg for 50 minutes to obtain a polymer having an intrinsic viscosity of 0.46.

Next, the polymer was supplied to a 30 mmφ co-rotating twin-screw extruder (L / D = 42) having two vent holes capable of vacuuming at two places, and the polymer temperature was changed to 350.
The polymer was melt-reacted under the conditions of -360 ° C, screw rotation speed of 100 rpm, and average residence time in a vacuum zone of about 8 minutes. At this time, a screw section in the opposite direction to the usual screw for conveyance was provided at the front of each vent port to seal the vacuum zone, so that each of the two vent ports was maintained at a vacuum of about 1 mmHg. The polymer obtained by the melt reaction in the extruder has an intrinsic viscosity of 0.6.
5, Tm 341 ° C, Tg 132 ° C.

(2) Production of resin composition: Aromatic polyester produced as described above, glass fiber chopped strand having a length of 3 mm (03JA manufactured by Asahi Fiberglass Co., Ltd.)
A predetermined amount of PX-1, aspect ratio 230) and talc (manufactured by Hayashi Kasei Co., Ltd., PKNN) (see Table 2 below) was blended, and a polymer temperature of 360 ° C. was obtained using a 30 mmφ different direction rotating biaxial extruder. Melt blending was performed under the conditions of an average residence time of about 2 minutes.

Each of the obtained compounds (4 types) was injection-molded using an injection molding machine (N40A type, manufactured by Nippon Steel Works) under the conditions of a cylinder temperature of 360 ° C. and a mold temperature of 150 ° C. A strip test piece of 0.8 × 10 × 25 mm was prepared.

(3) Test using an infrared reflow device:
Each test piece prepared as described above was subjected to an infrared reflow test using an infrared reflow apparatus (manufactured by Asahi Engineering, TPF-15). Heating is 100-150
After preheating for about 80 seconds at
The temperature was raised to 0 ° C., 280 ° C., and 300 ° C., and the surface of each test piece was observed. Table 2 shows the composition of the resin composition and the test results. As a result of the test, the case where there was no damage such as melting, swelling or deformation on the surface was evaluated as “○”, and the case where damage was clearly observed was evaluated as “×”.

[0139]

Comparative Example 4 A commercially available polyphenylene sulphite resin (PPS: manufactured by Philips, trade name "Ryton") was molded using an injection molding machine (manufactured by Nippon Steel Works, N40A type) at a cylinder temperature of 320 ° C and a mold temperature of 140 ° C. A test piece similar to that of Example 5 was prepared by injection molding under the conditions, and an infrared reflow test was performed as in Example 5. The results are also shown in Table 2.

[0140]

Comparative Example 5 A commercially available poly-1,4-cyclohexane dimethylene terephthalate resin (PCT: manufactured by Toray, trade name “Ector”) was mixed with a similar injection molding machine (manufactured by Nippon Steel Works, Ltd.).
Using an N40A type), injection molding was performed at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. to produce a test piece similar to that in Example 5, and an infrared reflow test was performed in the same manner as in Example 5. The results are shown in Table 2 together with the results of Example 5 and Comparative Example 4.

[0141]

[Table 2]

As shown in Table 2, it is clear that the aromatic polyester resin composition according to the present invention has extremely excellent heat resistance, and does not cause damage to the molded product surface even when reflowed at a high temperature.

[0143]

Example 6 Aromatic polyester produced in the same manner as in Example 5 and glass fiber chopped strand having a length of 3 mm (Asahi Fiberglass Corp., 03JA PX-1, aspect ratio 230) were blended at a weight ratio of 60/40. , 30mm
Melt blending was performed using a φ different direction rotating biaxial extruder under the conditions of a polymer temperature of 360 ° C. and an average residence time of about 2 minutes.

In order to evaluate the solder heat resistance as a printed circuit board, each of the obtained compounds was subjected to a cylinder temperature of 36 using an injection molding machine (N40A, manufactured by Nippon Steel Works).
Injection molding was performed at 0 ° C. and a mold temperature of 160 ° C. to prepare a test piece (0.8 × 10 × 25 mm) for evaluating solder heat resistance.

Using a test piece for evaluating solder heat resistance, a solder heat resistance test was performed by infrared reflow (infrared reflow apparatus: TPF-1 manufactured by Asahi Engineering).
5). The temperature was raised at 100 to 150 ° C. for about 80 seconds, and then the temperature was raised to 280 ° C. and 300 ° C. at the peak temperature, and the surface was observed. The results are shown in Table 3 below.
The results were determined based on the same criteria as in Example 5.

[0146]

[Table 3]

Table 3 shows, as a comparison, PPS resin (manufactured by Philips, "Ryton" R-4) at a cylinder temperature of 3
The results of the heat resistance test for test pieces of the same size molded under the conditions of 20 ° C. and a mold temperature of 140 ° C. are also shown. This indicates that the printed circuit board made of the resin composition of the present invention has extremely high heat resistance as compared with that made of PPS resin.

[0148]

Example 7 An aromatic polyester produced in the same manner as in Example 5 and a chopped strand of glass fiber having a length of 3 mm (made by Asahi Fiberglass, 03JA PX-1, aspect ratio 230) were blended at a weight ratio of 60/40. 30
Melt blending was performed using a mmφ bi-directional rotating twin-screw extruder under the conditions of a polymer temperature of 360 ° C. and an average residence time of about 2 minutes.

Each of the obtained compounds was subjected to a cylinder temperature of 3 using an injection molding machine (N40A, manufactured by Nippon Steel Works).
Injection molding is performed under the conditions of 60 ° C. and mold temperature of 160 ° C. for 20 minutes.
× 5 × 5 mm, 12 × 2 rows of 24-pin connectors (insulating portions) were prepared.

The obtained connector (insulating portion) was completely filled up to the thin portion, and no sink marks, blisters or burrs were observed.

Next, a heat resistance test by infrared reflow was performed using the connector (infrared reflow apparatus: TPF-15, manufactured by Asahi Engineering). After raising the temperature at 100 to 150 ° C for about 80 seconds,
The temperature was raised to 280 ° C. and 300 ° C. at the peak temperature, and the surface was observed. Table 4 shows the results. The results were determined based on the same criteria as in Example 5.

[0152]

[Table 4]

Table 4 shows, as a comparison, PPS resin (“Ryton” R-4 manufactured by Philips) with a cylinder temperature of 3
The results of the heat resistance test for the connector (insulating portion) molded under the conditions of 20 ° C. and the mold temperature of 140 ° C. are also shown. From this, it is found that the connector of the present invention has extremely high heat resistance as compared with the one made of PPS resin. I understand.

[0154]

Examples 8 to 10 For 40 parts of the aromatic polyester produced as in Example 5, 20 parts of PPS resin and 3 mm long glass fiber chopped strand (Asahi Fiberglass, 03JA PX-1, aspect ratio 230) Then, a predetermined amount of talc (manufactured by Hayashi Kasei, PKNN) as a nucleating agent (see Table 5 below) was blended, and a polymer temperature of 350 ° C. and an average residence time of about 2 minutes were used using a 30 mmφ different direction rotating biaxial extruder. Under the following conditions.

Similarly, instead of PPS, PET20
Melt blending was performed using 20 parts or 20 parts LCPII.

Each of the obtained compounds was subjected to a bar flow test of 0.7 mm thickness at a cylinder temperature of 350 ° C. using an injection molding machine (N40A type, manufactured by Nippon Steel Works). The molding was performed under the conditions of injection pressure, and the moldability was compared based on the flow length.

Here, as the PPS resin, “Ryton” is used.
(Manufactured by Philips) and "Vectra" (manufactured by Hoechst Celanese) as LCPII. Also PET
Used had an intrinsic viscosity of 0.71.

Further, each of the compositions was subjected to a molding cycle 40
The test piece for evaluation was injection molded in ６０60 seconds, and its physical property values were obtained. In addition, "GP" in Table 5
Is an abbreviation for glass fiber.

[0159]

[Table 5]

[0160]

Examples 11 to 14 (1) Production of polymer: 166 parts of isophthalic acid, 94 parts of hydroquinone, 18 parts of neopentylene glycol, 94 parts of phenol and 0.09 part of antimony trioxide were equipped with a stirrer and a distilling system. Into a reactor, and pressurize under nitrogen
Heated to 80 ° 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 30 parts of water were produced. Next, the reaction system was returned to normal pressure, 0.33 parts of triphenyl phosphate was added, and the reaction was carried out for 60 minutes while distilling off volatile components from the system in a nitrogen stream. During this time, the reaction temperature was raised from 280 ° C to 340 ° C.

Subsequently, the inside of the system was gradually evacuated to 60
After a minute, the mixture was reacted under a high vacuum of about 0.5 mmHg for 65 minutes to obtain a polymer having an intrinsic viscosity of 0.47.

Next, using a 30 mmφ co-rotating twin-screw extruder (L / D = 42) having two vacuum vent holes at two locations, the above polymer was heated at a polymer temperature of 360.
The melt reaction was carried out under the conditions of ° C, a screw rotation speed of 100 rpm, and an average residence time of about 8 minutes in a vacuum zone. On this occasion,
At the front of each vent port, a screw section opposite to the usual transport screw was provided to seal the vacuum zone, so that the two vent ports were each maintained at a vacuum of about 1 mmHg. The polymer obtained by the melt reaction in this extruder has an intrinsic viscosity of 0.64, a Tm of 345 ° C., and a Tg of 1
36 ° C.

(2) Production and molding of resin composition: 100 parts of the polymer (crystalline aromatic copolyester) produced in (1) above, 65 parts of 3 mm long glass fiber chopped strand, 0.8 parts of talc Part and Example 11
In Nos. 13 to 13, 3 to 5 parts of the flame retardants shown in Table 6 were dry-blended and melt-blended using a 30 mm φ bidirectionally rotating biaxial extruder under the conditions of a polymer temperature of 360 ° C. and an average residence time of about 2 minutes.

Each of the obtained compounds was injection-molded using an injection molding machine (N40A, manufactured by Nippon Steel Works) under the conditions of a cylinder temperature of 360 ° C. and a mold temperature of 140 ° C.
A test piece for evaluating physical properties was obtained. Table 6 shows the physical properties of each molded article (test piece) thus obtained.

[0165]

[Table 6]

As shown in Table 6 above, the flame-retardant resin composition of the present invention containing the flame retardant (Examples 11 to 13) was excellent in mechanical properties and heat resistance and evaluated according to UL-94 standard. The obtained flame retardancy was equivalent to V-0 in a 1/32 inch sample, and the flame retardancy was particularly good.

[0167]

Examples 15 to 18 Based on 100 parts of the polymer (aromatic copolyester) produced in Examples 11 to 13 (1),
65 parts of 3 mm glass fiber chopped strand (made by Asahi Fiberglass, 03JAPX-1), 0.8 part of talc (manufactured by Hayashi Kasei, PKNN) and 0.8 parts of the release agent shown in Table 7 are dry-blended, Using a 30 mmφ different direction rotating twin-screw extruder, melt blending was performed under the conditions of a polymer temperature of 350 ° C. and an average residence time of about 2.5 minutes.

The obtained resin composition was injected into an injection molding machine (FAN).
UC, AUTOSHOT MATE) at a polymer temperature of 360 ° C. and a mold temperature of 150 ° C. under a condition of 20 × 5.
× 5mm, 12 × 2 rows of 24-pin connectors are molded,
The releasability was evaluated by measuring the load applied to the extrusion pin when the molded article was released from the mold.

The results are shown in Table 7. Table 7 shows that these compositions are excellent in heat resistance, mechanical properties, and releasability.

[0170]

[Table 7]

[0171]

Embodiments 19 and 20 In Embodiment 3, the length is 3 mm.
3mm length instead of glass fiber chopped strand
Chopped Carbon Fiber (Toray T-30
0) or 1 mm long chopped aramid fiber (manufactured by Teijin, trade name "Technola") was used in the ratio shown in Table 8, and the other properties were measured in the same manner as in Example 3 to measure the physical properties of the obtained injection molded product. did. Table 8 shows the results.

[0172]

[Table 8]

Continued on the front page (31) Priority claim number Japanese Patent Application No. 4-247841 (32) Priority date Hei 4 (1992) September 17 (33) Priority claim country Japan (JP) Preliminary examination (72) Inventor Toshio Hatayama 3-37-19 Koyama, Sagamihara-shi, Kanagawa Prefecture, Sagamihara Research Center, Teijin Limited (56) References JP-A-3-26751 (JP, A) JP-A-52-6797 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 63/181, 63/191

Claims (7)

(57) [Claims] 1. A polymer unit A represented by the following formula (1), a polymer unit B represented by the following formula (2),
And a polymer unit C represented by the following formula (3): Wherein each of the polymer units forms an ester bond in the polymer chain, and (a) the polymer unit C accounts for 10 to 35 mol% based on the total of the polymer unit B and the polymer unit C. (C) shows crystalline and isotropic properties, and (d) intrinsic viscosity measured at 35 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 60/40) 0.3 to 1.5 and 280 to 38
An aromatic polyester having a melting point of 0 ° C. 2. A repeating unit AB represented by the following formula (1-2) and a repeating unit AC represented by the following formula (1-3): The aromatic polyester according to claim 1, wherein the aromatic polyester substantially consists of the repeating unit AB / the repeating unit AC (molar ratio) in the range of 90/10 to 65/35. 3. A starting material consisting essentially of isophthalic acid (a), hydroquinone (b) and neopentylene glycol (c) is prepared according to the following formulas (i) and (ii): (Where A is the number of moles of isophthalic acid (a) and B is
Is the number of moles of hydroquinone (b) and C is the number of moles of neopentylene glycol (c). ) At the same time, and melted by heating in the presence of an esterification catalyst, and the intrinsic viscosity measured at 35 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 60/40). Is 0.3 to 1.5, and the melting point is 280.
A method for producing an aromatic polyester, which comprises producing a crystalline and isotropic aromatic polyester at a temperature of from 380 ° C to 380 ° C. 4. A phenol (d) which may be substituted by an alkyl group having 1 to 5 carbon atoms upon heating and melting is converted into a compound represented by the following formula (iii): 4. The process according to claim 3 , wherein the process is carried out under conditions in which the definition of A is the same as above and D is the number of moles of the phenol (d). 5. The above-mentioned heat melting is carried out under conditions where phenols (d) are hardly distilled out of the system until at least 50% of the carboxyl groups of the starting material are esterified.
4. The method according to claim 3 , wherein the reaction is carried out while distilling off the generated water out of the system, and then the distillation is carried out while distilling off the phenols (d) and the generated water out of the system, thus achieving the desired esterification.
Process for the preparation of the other four described. 6. 100 parts by weight of the aromatic polyester (P) according to claim 1, and 5 to 25 fibrous reinforcing materials (F).
A molding resin composition comprising 0 parts by weight. 7. 100 parts by weight of the aromatic polyester (P) according to claim 1, 1 to 200 parts by weight of a crystalline thermoplastic resin (T) other than the aromatic polyester (P), and a fibrous reinforcing material (F). A molding resin composition comprising 5-250 parts by weight (based on 100 parts by weight of the total weight of the aromatic polyester (P) and the thermoplastic resin (T)).