JP2977261B2 - Resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel resin composition comprising poly (1,4-butylene terephthalate) and polycarbonate.

More specifically, the composition is a resin that has greatly improved impact strength, heat deformation temperature, and flexural modulus while maintaining the excellent sliding properties and chemical resistance of poly (1,4-butylene terephthalate). A composition.

[Problems to be solved by conventional technology and invention]

Poly (1,4-butylene terephthalate) is a resin having excellent physical properties and a good balance of physical properties among engineering plastics.

In particular, it has excellent sliding properties and is expected to replace polyacetal, but its use is limited due to its lower heat resistance (thermal deformation temperature) and lower moldability (molding cycle, sink mark, etc.) than polyacetal. Have been.

On the other hand, polycarbonate resin is a useful engineering plastic having excellent impact resistance, heat resistance, and dimensional stability, but has a problem of poor solvent resistance.

In order to improve the moldability of polycarbonate and obtain resins with improved physical and chemical properties, polycarbonate
A composition comprising 50 parts by weight or more and 50 parts by weight or less of poly (1,4-butylene terephthalate) has been proposed (Japanese Patent Publication No. 53-12537).

This composition had insufficient improvement in solvent resistance and a large coefficient of friction.

Add a copolyester, a graft polymer or a metal salt of a phosphorus compound to a composition of polycarbonate and poly (1,4-butylene terephthalate) to increase the transparency of the composition, improve the heat distortion temperature and color tone, Also, a method of preventing the composition from being colored yellow (JP-B-60-10544, JP-B-54-37632, JP-B-52-48630).
However, these methods have not been able to balance heat resistance, solvent resistance, sliding characteristics, and impact strength.

Furthermore, U.S. Pat. No. 3,218,372 proposes a composition comprising a polyalkylene terephthalate and a polycarbonate, in which case the examples are all polyethylene terephthalate.

Until now, a composition having a high heat distortion temperature and a high flexural modulus, excellent solvent resistance, sliding properties and impact resistance has not been obtained.

[Means for solving the problem]

The present inventors have conducted various studies with the aim of providing a resin composition having excellent sliding properties, solvent resistance and impact resistance, high heat distortion temperature, and flexural modulus. Excellent sliding properties, solvent resistance and impact resistance, high heat distortion temperature and flexural modulus are obtained by compounding a polycarbonate mixture in which polycarbonates having different molecular weights are mixed in a specific ratio with respect to 4-butylene terephthalate). They have found that a resin composition can be obtained, and have completed the present invention based on this finding.

That is, the present invention relates to (A) 10 to 90% by weight of poly (1,4-butylene terephthalate), (B) a high molecular weight aromatic polycarbonate having a weight average molecular weight of 40,000 to 300,000, and a low molecular weight having a weight average molecular weight of 7,000 to 16,500. Weight ratio with aromatic polycarbonate: 1:10 to 10: 1
Or a weight ratio of 1 to the mixture, or
A resin composition comprising 90 to 10% by weight of a mixed polycarbonate component blended with a medium-molecular-weight aromatic polycarbonate having a weight-average molecular weight of 17,000 to 35,000 at a ratio of 2: 1 to 1: 3.

 Hereinafter, the present invention will be described in detail.

The poly (1,4-butylene terephthalate) used in the present invention is represented by the following formula (hereinafter abbreviated as component (A)): Which is synthesized by a transesterification method of dimethyl terephthalate and 1,4-butanediol or a direct esterification method of terephthalic acid and 1,4-butanediol.

It has an intrinsic viscosity of 0.3 or more measured at 25 ° C. using orthochlorophenol as a solvent. Further, a dibasic acid or a diol may be copolymerized as long as the characteristics of the composition of the present invention are not changed. Examples of the dibasic acid include isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, sebacic acid, adipic acid, and cyclohexanedicarboxylic acid. Examples of the diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 1,6-hexanediol. ,
Examples thereof include 1,2-cyclohexanediol and 1,4-cyclohexanediol.

The aromatic polycarbonate (hereinafter abbreviated as component (B)) used in the composition of the present invention includes, for example, a general formula Wherein Ar ¹ and Ar ² are each a phenylene group, a naphthylene group, a biphenylene group, an arylene group such as a pyridylene group, and Y is Alkylene group or substituted alkylene copolymer of (R ¹ to R ⁶ are each a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and these are substituted with a halogen atom or an alkoxy group. And k is an integer of 3 to 11)], or a dihydroxydiarylalkane-based polycarbonate having a repeating unit represented by the following general formula (I) or a repeating unit represented by the above general formula (I) Wherein Ar ³ and Ar ⁴ are each an arylene group such as a phenylene group, a naphthylene group, a biphenylene group, a pyridylene group, and Z is a mere bond, -O-, -CO-, -S-, -SO
_2- , -CO ₂ -or (R ⁷ and R ⁸ are a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, respectively, which may be substituted with a halogen atom or an alkoxy group.) Can be used. Ar ¹ to Ar ⁴ in the general formulas (I) and (II) are each a substituent in which one or more hydrogen atoms do not adversely affect the polymerization reaction, for example, a halogen atom, a lower alkyl group, a lower alkoxy group,
It may be substituted by a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group, or the like.

Among the aromatic polycarbonates described above, 2,2-bis (4-hydroxyphenyl) propane, that is, polycarbonate using bisphenol A or substituted bisphenol A as a raw material is particularly preferable. Further, the polycarbonate may have a branched structure introduced using a polyfunctional monomer.

The composition of the present invention is obtained by blending (B) a high-molecular-weight aromatic polycarbonate and a low-molecular-weight aromatic polycarbonate in combination with the poly (1,4-butylene terephthalate) as the component (A) as an aromatic polycarbonate component. Or a mixed polycarbonate component further added with a medium-molecular-weight aromatic polycarbonate.

In the composition of the present invention, the content of the component (A) is 10
It is necessary to select in the range of ~ 90% by weight, preferably
20-80% by weight. If the content is less than 10% by weight, the fluidity and sliding characteristics are poor, and if it exceeds 90% by weight, the impact resistance and the heat deformation temperature are reduced. The high molecular weight aromatic polycarbonate of the component (B) has a weight average molecular weight of 40,0.
It must be in the range of 00 to 300,000, preferably in the range of 45,000 to 120,000. This molecular weight is 40,000
If it is less than 30, the effect of improving impact resistance and heat distortion temperature is not sufficiently exhibited, and if it exceeds 300,000, it becomes difficult to uniformly disperse during melt mixing.

The low molecular weight aromatic polycarbonate has a weight average molecular weight in the range of 7,000 to 16,500, and this molecular weight is 7.0,
If it is less than 00, impact resistance and heat distortion temperature are insufficient, and 1
If it exceeds 6,500, the melt fluidity and the elastic modulus decrease. The high molecular weight aromatic polycarbonate and the low molecular weight aromatic polycarbonate must be a mixture in a weight ratio of 10: 1 to 1:10, and are preferably used as a mixture in a ratio of 1: 5 to 5: 1. If the proportion of the low molecular weight aromatic polycarbonate is smaller than this, the effect of improving the elastic modulus is not sufficiently exhibited, and if the proportion is larger than this, impact resistance and heat deformation temperature are lowered.

A feature of the composition of the present invention is that the elastic modulus is particularly high.As a composition capable of sufficiently exhibiting such a feature, the weight ratio of the high-molecular-weight aromatic polycarbonate to the low-molecular-weight aromatic polycarbonate is 1: 1. To 1: 5 mixed polycarbonate in a ratio of 20 to 80% by weight.

In the present invention, as the mixed polycarbonate component of the component (B), in addition to a mixture of a high molecular weight aromatic polycarbonate and a low molecular weight aromatic polycarbonate, a mixture of a medium molecular weight aromatic polycarbonate having a weight average molecular weight of 17,000 to 35,000 is further added. Can be used. The mixing ratio of this medium-molecular-weight aromatic polycarbonate is 12: 1 to 1: 3, preferably 10: 1 to 1: 2, by weight relative to the total amount of the high-molecular-weight aromatic polycarbonate and the low-molecular-weight aromatic polycarbonate. Is chosen. The flowability is improved by adding the medium-molecular-weight aromatic polycarbonate, but when the amount is out of the above range, the effect produced by blending the mixture of the high-molecular-weight aromatic polycarbonate and the low-molecular-weight aromatic polycarbonate is sufficiently exhibited. Will not be.

The high molecular weight aromatic polycarbonate used as one of the components (B) in the composition of the present invention is prepared by polymerizing a crystallized prepolymer in a solid phase (JP-A-1-158803, JP-A-1-271426). Can be manufactured.
In this method, as a crystallized prepolymer, the proportion of aryl carbonate group terminals in all terminal groups of the prepolymer is in the range of 40 to 80 mol%, the weight average molecular weight is 6,000 to 20,000, and the crystallinity is But 10 to 40% is used. Such a solid-phase polymerization method is advantageous because polycarbonate can be obtained as a solid such as a powder, a pellet, and a flake. The high-molecular-weight aromatic polycarbonate having a weight-average molecular weight of 40,000 to 300,000 obtained by this solid-phase polymerization method has a shape such as powder, beads, pellets, and granules depending on the shape of the crystallized prepolymer used. I have.

Further, the low molecular weight aromatic polycarbonate and the medium molecular weight aromatic polycarbonate can be produced by a method such as a solid phase polymerization method, a melting method, and a phosgene method. These polycarbonates are preferably used in the form of a powder having a high bulk density which is easily mixed with the powder of the high molecular weight aromatic polycarbonate.

According to the solid-state polymerization method and the melting method, a hydroxyl terminal derived from dihydroxydiarylalkane exists at the polycarbonate terminal, and a hydroxyl terminal and a chloroformate terminal exist in the case of the phosgene method. This terminal is not preferable because, during melt extrusion, a transesterification reaction occurs with the high-molecular-weight aromatic polycarbonate to reduce the molecular weight of the high-molecular-weight polycarbonate, and the molecular weight of the low-molecular-weight polycarbonate increases, thereby making the molecular weight uniform. .

Therefore, it is desirable to keep the amount of hydroxyl terminals below 0.5% by weight, preferably below 0.2% by weight.

The method for preparing the composition of the present invention is not particularly limited. For example, it is preferable to mix the respective components at a predetermined ratio and melt-knead all at once using a kneader such as a roll, a Banbury mixer, or an extruder. Further, a method of kneading the polycarbonate component in advance and then kneading it with the component (A) can also be used. Further, a method in which each component is dissolved in a solvent and then dried, or a solution in which each component is mixed and dried, and then the mixture is melt-kneaded can also be used.

If necessary, known antioxidants, antistatic agents, flame retardants, ultraviolet absorbers, release agents, coloring agents, inorganic fillers, and the like can be added to the composition of the present invention.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

-Molecular weight of polycarbonate The value of the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) was used.

-Intrinsic viscosity of polybutylene terephthalate Measured at 25 ° C with an Ubbelohde viscometer using orthochlorophenol as a solvent.

Heat distortion temperature Measured at a load of 18.6 kg according to ASTM D648.

-Izod impact value Measured with a notched 3 mm thick piece according to ASTM D256.

Flexural strength (after immersion in CCl ₄ ) Measured on a 3 mm thick molded piece according to ASTM D790.

-Coefficient of friction Measured using a Suzuki-type thrust friction and wear tester.

Example 1 (1) Production of high molecular weight aromatic polycarbonate (B ¹ ) 2,2-bis (4-hydroxyphenyl) propane 13.0k
g and 12.9 kg of diphenyl carbonate, 3.5
After flowing nitrogen gas at 100 Nl / hr for 1.5 hours, the degree of vacuum was reduced to 3 mmHg over 1.5 hours, and the mixture was stirred at that pressure for 1 hour to obtain a prepolymer. This prepolymer had an Mw of 8,100 and the ratio of hydroxyl terminals to all terminals was 48 mol%.

Next, the prepolymer was directly immersed in acetone 22 to be crystallized. This was filtered and dried to obtain a powdery prepolymer.

Next, put this in a turn bull dryer and rotate it while flowing nitrogen gas at 10 Nl / hr to reduce the pressure to 2-3 mmHg,
The temperature was gradually raised, and solid phase polymerization was performed at 220 ° C. for 27 hours to obtain a powder of a high molecular weight aromatic polycarbonate (B ¹ ) having a weight average molecular weight of 97,000. The bulk density of this powder is 0.58 g / cm ³
Met.

(2) Production of low molecular weight aromatic polycarbonate (B ² ) In the above (1), 13.2 kg of diphenyl carbonate
And (3) except that the time of solid-phase polymerization is 3 hours.
In the same manner as in the above, a low molecular weight aromatic polycarbonate (B ² ) having Mw of 16,000 was obtained.

(3) Preparation of composition To a polycarbonate component of 1.5 kg of the high molecular weight aromatic polycarbonate (B ¹ ) obtained in the above (1) and 2.5 kg of the low molecular weight aromatic polycarbonate (B ² ), 15 ppm of bisnonylphenyl phosphite was added. And 200 ppm of tris (2,4-di-tert-butylphenyl) phosphite, and mixed with a Henschel mixer.

This mixture was then combined with the method of Whintield et al. (Chem. Ab
str 1949 43 4896 g) and 6 kg of poly (1,4-butylene terephthalate) (intrinsic viscosity 0.82)
Extrusion granulation was performed at 300 ° C. using a 0 mmφ twin screw extruder. Table 1 shows the physical properties of this product.

Example 2 (1) Production of high molecular weight aromatic polycarbonate (B ³ ) Mw was 65,000 in the same manner as in Example 1 (1), except that the solid phase polymerization time was changed to 20 hours. A high molecular weight aromatic polycarbonate (B ³ ) was obtained.

(2) Production of low molecular weight aromatic polycarbonate (B ⁴ ) In Example 1 (2), diphenyl carbonate 1
A low molecular weight aromatic polycarbonate (B ⁴ ) having a Mw of 14,000 was obtained in the same manner as in Example 1 (2) except that 3.1 kg was used and the solid phase polymerization time was changed to 2.5 hours.

(3) Preparation of composition 1.0 kg of the high molecular weight aromatic polycarbonate (B ³ ) obtained in the above (1) and 1.0 kg of the molecular weight aromatic polycarbonate (B ⁴ ) obtained in the above (2) were prepared. ) Was granulated in the same manner as in Example 1 (3) except that 8.0 kg of poly (1,4-butylene terephthalate) (intrinsic viscosity 0.87) obtained by the same method as in Example 1) was mixed. Table 1 shows the physical properties of this product.

Example 3 (1) Production of High Molecular Weight Aromatic Polycarbonate (B ⁵ ) Mw was 51,000 in the same manner as in Example 1 (1) except that the solid phase polymerization time was changed to 16 hours. A high molecular weight aromatic polycarbonate (B ⁵ ) was obtained.

(2) Production of low molecular weight aromatic polycarbonate (B ⁶ ) 13.0 kg of bisphenol A and diphenyl carbonate 14.
Using 3 kg, flow nitrogen gas at 100 Nl / hr at 250 ° C for 3.5 hours, reduce the degree of vacuum to 3 mmHg over 1.5 hours, and stir at that pressure for 50 minutes to obtain a low molecular weight aromatic polycarbonate (B ⁶ ) Was. This polymer had a Mw of 9.100 and a hydroxyl terminal proportion of 0.04% by weight.

(3) Production of Medium Molecular Weight Aromatic Polycarbonate (B ⁷ ) In Example 1 (1), diphenyl carbonate 1
A medium molecular weight aromatic polycarbonate (B ⁷ ) having a Mw of 26,100 was obtained in the same manner as in Example 1 (1) except that 3.5 kg was used and the solid phase polymerization time was changed to 10 hours.

(4) Preparation of composition: 2.0 kg of the high molecular weight aromatic polycarbonate (B ⁵ ) obtained in the above (1) and 2.0 kg of the low molecular weight aromatic polycarbonate (B ⁶ ) obtained in the above (2) and (3) To a polycarbonate component of 2.0 kg of the obtained medium molecular weight aromatic polycarbonate (B ⁷ ), 10 ppm of bisnonylphenyl phosphite,
150 ppm of stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Geigy) was added and mixed with a Henschel mixer.

Next, this mixture and poly (1,4-butylene terephthalate) obtained in the same manner as in Example 1 (3) (intrinsic viscosity 0.9
0) Granulation was carried out in the same manner as in Example 1 (3) except that 4.0 kg was used. Table 1 shows the physical properties of this product.

Example 4 (1) Production of High Molecular Weight Aromatic Polycarbonate (B ⁸ ) It was produced in the same manner as in Example 3 (1).

(2) Production of low molecular weight aromatic polycarbonate (B ⁹ ) 13.0 kg of bisphenol A and diphenyl carbonate 14.
Using 3 kg, flow nitrogen gas at 100 Nl / hr at 250 ° C for 3.5 hours, reduce the degree of vacuum to 3 mmHg over 1.5 hours, and stir at that pressure for 1 hour to obtain a low molecular weight aromatic polycarbonate (B ⁹ ). Was. This polymer had a Mw of 10,300 and a hydroxyl terminal proportion of 0.04% by weight.

(3) Preparation of composition The polycarbonate component of 4.0 kg of the high molecular weight aromatic polycarbonate (B ⁸ ) obtained in the above (1) and 4.0 kg of the low molecular weight aromatic polycarbonate (B ⁹ ) obtained in the above (2) , 10 ppm of bisnonylphenyl phosphite and 150 ppm of stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Geigy) were added and mixed with a Henschel mixer.

Next, this mixture was mixed with poly (1,4-butylene terephthalate) (intrinsic viscosity) obtained in the same manner as in Example 1 (3).
0.86) and 2.0 kg, and granulated in the same manner as in Example 1 (3). Table 1 shows the physical properties of this product.

Example 5 (1) Production of High Molecular Weight Aromatic Polycarbonate (B ¹⁰ ) It was produced in the same manner as in Example 2 (1).

(2) Production of low molecular weight aromatic polycarbonate (B ¹¹ ) The production was carried out in the same manner as in Example 3 (2).

(3) Production of Medium Molecular Weight Aromatic Polycarbonate (B ¹² ) This was carried out in the same manner as in Example 3 (3).

(4) Preparation of composition 3.0 kg of the high molecular weight aromatic polycarbonate (B ¹⁰ ) and 2.0 kg of the low molecular weight aromatic polycarbonate (B ¹¹ ) obtained in (1), (2) and (3) above, and medium molecular weight aromatic To a polycarbonate component of 2.0 kg of aromatic polycarbonate (B ¹² ), 10 ppm of diphenyl phosphite and 200 ppm of trisnonylphenyl phosphite were added and mixed with a Henschel mixer.

Next, this mixture was mixed with poly (1,4-butylene terephthalate) (intrinsic viscosity) obtained in the same manner as in Example 1 (3).
0.78) and mixed with 3.0 kg, and granulated in the same manner as in Example 1 (3). Table 1 shows the physical properties of this product.

Comparative Example 1 (1) Production of Medium-Molecular-Weight Aromatic Polycarbonate In Example 3 (3), except that the solid-phase polymerization time was changed to 11 hours, the medium molecular weight of Mw was 30,000 in the same manner as in Example 3 (3) An aromatic polycarbonate was obtained.

 Table 1 shows the physical properties of the granulated product.

Comparative Example 2 In the same manner as in Example 1 (3), poly (1,
4-butylene terephthalate) was obtained. Table 1 shows the physical properties of the granulated product.

Comparative Example 3 Same medium molecular weight aromatic polycarbonate 7.0 k as Comparative Example 1
g and 3.0 kg of the same poly (1,4-butylene terephthalate) as in Comparative Example 2 were granulated in the same manner as in Example 1 (3).
Table 1 shows the physical properties of this product.

Comparative Example 4 In the same manner as in Example 1, the weight average molecular weight was 28,500 and 1
0,300 polycarbonates were produced. The procedure was performed in the same manner as in Example 1 except that the polycarbonate and the PBT used in Example 4 were mixed at the compounding ratio shown in Table 1. First evaluation result
It is shown in the table. As a medium molecular weight component, the weight average molecular weight is 28,5
When 00 (less than 40,000) is used, the effect of the present invention is not exhibited at all.

[Effect of the Invention] The composition of the present invention is a novel resin composition having high heat distortion temperature, flexural modulus, excellent solvent resistance, sliding properties, and impact resistance.

Continuation of front page (56) References JP-A-62-89762 (JP, A) JP-A-57-195145 (JP, A) JP-A-62-32143 (JP, A) JP-A-61-238823 (JP) , A) JP-A-58-138733 (JP, A) JP-A-4-136064 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 67/00-69/00

Claims (2)

(57) [Claims] (A) 10-90% by weight of poly (1,4-butylene terephthalate); (B) a high molecular weight aromatic polycarbonate having a weight average molecular weight of 40,000-300,000 and a weight average molecular weight of 7,000-16,500.
Weight ratio with low molecular weight aromatic polycarbonate 1: 10-1
A resin composition comprising 90 to 10% by weight of a mixed polycarbonate in a ratio of 0: 1. 2. (A) 10 to 90% by weight of poly (1,4-butylene terephthalate), (B) a high molecular weight aromatic polycarbonate having a weight average molecular weight of 40,000 to 300,000, and a weight average molecular weight of 7,000 to 16,500.
Weight ratio of low molecular weight aromatic polycarbonate of 1:10 to 10: 1
Of the mixture having a weight average molecular weight of 17,000-35,000 at a weight ratio of 12: 1 to 1: 3.
Resin composition consisting of about 10% by weight.