JPS6248702B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9) and a compound of the general formula Bisphenols represented by (however, -X-
is selected from the group consisting of -O-, -S-, _-SO2- , -CO-, an alkylene group and an alkylidene group,
R ₁ , R ₂ , R ₃ , R ₄ , R′ ₁ , R′ ₂ , R′ ₃ and R′ ₄ are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups). The present invention relates to a method for producing a resin composition that is transparent and has good mechanical properties from an arylene ester (hereinafter referred to as PAR) and a polyalkylene phenylene ester (hereinafter referred to as PES). Resin compositions consisting of PAR and PES are known (Japanese Patent Application Laid-open Nos. 49-23844 and 49-61247). The content of PES component in these resin compositions is
If the content exceeds 50% by weight, the content is 50% by weight.
Although it has a lower heat distortion temperature than the following, it has favorable performance such as excellent solvent resistance and low gas permeability. It also has improved transparency compared to PES. In particular, resin compositions that use polyethylene terephthalate as a PES component have superior molding stability during injection molding and blow molding compared to polyethylene terephthalate, so they are widely used in the plastics field that uses injection molding and blow molding. Be expected. However, since PAR is a resin with extremely high melt viscosity, when melt-kneading PAR and PES,
When a large amount of PAR components are mixed, homogeneous kneading is possible relatively easily, but when a large amount of PES components are mixed, for example, when that amount accounts for the majority, melt-kneading becomes extremely difficult. As a result, unmelted PAR substances called fisheye were usually present in the resulting resin composition. Resin compositions containing fisheyes have the drawbacks of being cloudy and having low elongation and low impact strength. Once such fish eyes are formed, they almost disappear, probably because no shear stress is transferred from PES, which forms the sea component, to PAR, which forms the island component, even if kneading is continued for a long time. There's nothing to do. If the kneading temperature is extremely raised in order to eliminate such hard eyes, the resin composition will be decomposed and deteriorated, and the resin composition will not only become colored but also deteriorate its mechanical properties, and the melt viscosity will drop significantly. It becomes difficult to remove from the nozzle.
In this way, when a resin composition in which the PES component accounts for the majority of the mixed amount, especially when a resin composition in which the PES component accounts for 55% by weight or more is produced by the melt mixing method, the resin composition is transparent and has good mechanical properties. There was a problem that it was difficult to obtain a resin composition. In order to solve this problem, a method has been proposed in which a resin composition containing a large amount of PAR components is first prepared by a melt-kneading method, and then a PES component is melt-kneaded into this resin composition (Japanese Patent Application Laid-Open No. 52−
Publication No. 100553). It is true that a resin composition with improved transparency and mechanical properties can be obtained by such a method, but since it requires two or three or more stages of melt-kneading, it is inferior in productivity. It was hoped that an effective method would be developed. As a result of intensive research in order to solve the above problems, the present inventors found that the logarithmic viscosity of the PES component conventionally used in the production of such resin compositions was 0.6.
By using PES with a higher molecular weight than that of PES, it is possible to obtain a resin composition with transparency and mechanical properties equivalent to or better than those obtained by multi-step melt-kneading, even with one-step melt-kneading. Having discovered this fact, we have completed the present invention. That is, the present invention has the following configuration. (A) A mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups and isophthalic acid groups is 9:1 to 1:9)
and general formula Bisphenols represented by (however, -X-
is selected from the group consisting of -O-, -S-, _-SO2- , -CO-, an alkylene group and an alkylidene group,
R ₁ , R ₂ , R ₃ , R ₄ , R′ ₁ , R′ ₂ , R′ ₃ and R′ ₄ are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups). In a method for producing a resin composition by melt-mixing 5 to 45 parts by weight of arylene ester and 95 to 55 parts by weight of polyalkylene phenylene ester (B), the component (A) and
The logarithmic viscosity of component (B) is as follows [],
[] A method for producing a resin composition, characterized by using a resin composition that satisfies the formula. 0.3≦ηA≦ηB+0.3 [] 0.65≦ηB≦1.5 [] [However, ηA represents the logarithmic viscosity of the (A) component, and ηB represents the logarithmic viscosity of the (B) component. Logarithmic viscosity is phenol/
Tetrachloroethane mixed solvent (6/4, weight ratio)
Medium, concentration 1 g/100 c.c., measured at 25°C. ] The PAR used in the present invention is a mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups and isophthalic acid groups is 1:9 to 9:1) and a compound of the general formula Bisphenols represented by (however, -X-
is selected from the group consisting of -O-, -S-, _-SO2- , -CO-, an alkylene group and an alkylidene group.
R ₁ , R ₂ , R ₃ , R ₄ , R′ ₁ , R′ ₂ , R′ ₃ , and R′ ₄ are
(selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups). Specific examples of bisphenols represented by the above general formula include 4,4'-dihydroxy-diphenyl ether, bis(4-hydroxy-2-methylphenyl)-ether, and bis(4-hydroxy-3
-chlorophenyl)-ether, bis(4-hydroxyphenyl)-sulfide, bis(4-hydroxyphenyl)-sulfone, bis(4-hydroxyphenyl)-ketone, bis(4-hydroxyphenyl)-methane, bis(4-hydroxy-
3-methylphenyl)-methane, bis(4-hydroxy-3,5-dichlorophenyl)-methane,
Bis(4-hydroxy-3,5-dibromophenyl)-methane, bis(4-hydroxy-3,5-
difluorophenyl)-methane, 1,1-bis(4-hydroxyphenyl)-ethane, 2,2-bis(4-hydroxy-3-methylphenyl)-propane, 2,2-bis(4-hydroxy-3 -chlorophenyl)-propane, 2,2-bis(4-
Hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 1,1-bis(4-
hydroxyphenyl)-n-butane, bis(4-
hydroxyphenyl)-phenylmethane, bis(4-hydroxyphenyl)-diphenylmethane,
Bis(4-hydroxyphenyl)-4'-methylphenylmethane, 1,1-bis(4-hydroxyphenyl)-2,2,2-trichloroethane, bis(4-hydroxyphenyl)-4'- Examples include chlorophenylmethane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, bis(4-hydroxyphenyl)-cyclohexylmethane, 2,2-bis(4-hydroxynaphthyl)-propane, etc. The most commonly produced and representative one is 2,2-bis(4-hydroxyphenyl)-
It is called propane or bisphenol A. If necessary, mixtures of the bisphenols or bisphenols and small amounts of other divalent compounds, such as dihydroxynaphthalenes such as 2,2-dihydroxynaphthalene, hydroquinone, resorcinol, 2,6-dihydroxytoluene, - A mixture with 6-dihydroxychlorobenzene, 3,6-dirodroxytoluene, etc. can be used. The functional derivatives of terephthalic acid or isophthalic acid include, for example, halides of these acids such as dichloride, or diesters of alkyl and aryl. Further, the phenylene group of terephthalic acid or isophthalic acid or a functional derivative thereof used in the present invention may be substituted with a halogen atom or an alkyl group. PAR used in the present invention is synthesized by any method such as an interfacial polymerization method, a solution polymerization method, or a melt polymerization method. The PES used in the present invention has the general formula refers to something expressed as Here, R ₅ , R ₆ , R ₇ and R ₆ are selected from hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkyl ester groups, cyano groups, sulfone groups, nitro groups, phenoxy groups, etc. m is an integer from 1 to 10. Specific examples of such PES include polyethylene terephthalate, polyethylene isophthalate, polytrimethylene terephthalate, polytrimethylene isophthalate, polytetramethylene terephthalate, and polytetramethylene isophthalate; If so, you can use something else. Preferred PES used in the present invention include polyethylene terephthalate, polytetramethylene terephthalate, and the like, and among them, polyethylene terephthalate is most preferred, including from the viewpoint of economical efficiency. In the production method of the present invention, (A) PAR and (B) PES
The mixing ratio is 5 to 55 parts by weight of component (A) to component (B).
It is in the range of 95 to 55 parts by weight, preferably in the range of 90 to 70 parts by weight of component (B) to 10 to 30 parts by weight of component (A). The effects of the present invention are well exhibited when the mixing ratio of both components is within the above range. When the proportion of component (A) in the resulting resin composition exceeds 55% by weight, the kneading state during melt-mixing is less affected by the logarithmic viscosity of component (B). On the other hand, if the proportion of component (A) is less than 5% by weight, the ability to maintain the transparency of the resin composition will be relatively low. In other words, when molding a resin composition into various molded products by injection molding, extrusion molding, blow molding, vacuum forming, etc., it becomes difficult to maintain a transparent state over a wide range of molding conditions, and the resulting molded product is exposed to heat, etc. devitrification occurs more easily than PES when affected by Logarithmic viscosity η of PAR used in the present invention
A, and the logarithmic viscosity ηB of PES are as follows [],
It is particularly preferably within the range of the following formulas [] and []. 0.3≦ηA≦ηB+0.3 [] 0.65≦ηB≦1.5 [[]] 0.4≦ηA≦ηB+0.1 [] 0.75≦ηB≦1.2 [[] PAR and PES with logarithmic viscosity within the above range
When using this method, a transparent resin composition with excellent mechanical properties can be obtained without raising the temperature excessively and by one-step melt mixing. ηA is
When it is less than 0.3, the mechanical properties of the resin composition are relatively insufficient and the ability to maintain transparency is also low. On the other hand, when ηA exceeds ηB+0.3, uniform kneading is difficult and fisheyes tend to form. Further, when ηB is less than 0.65, uniform kneading is difficult, while when ηB exceeds 1.5, the resin composition tends to decompose during kneading. In the present invention, the method for melt-mixing components (A) and (B) is not particularly limited, and various known methods can be employed. As a device for melt-mixing both components, for example, a known extruder, kneader, etc. can be used, but devices with particularly high kneading ability are preferred. When melt-mixing, it is preferable to give a thermal history of about 5 seconds to 10 minutes at a temperature of 270 to 340°C. During production of the resin composition, a phosphorus compound or an antioxidant can be used to prevent the resin composition from discoloring. Furthermore, organic acid metal compounds such as alkali metal salts of organic carboxylic acids and alkaline earth metal salts of organic carboxylic acids can be used to improve the transparency and mechanical properties of the resin composition. The amount of these additives added is preferably in the range of 0.01 to 1% by weight. The resin composition produced by the method of the present invention has excellent chemical resistance, moldability, transparency, and has excellent mechanical properties such as impact strength, so it is used in a wide range of fields. be. In particular, the resin composition produced by the method of the present invention has excellent transparency and solvent resistance.
Due to its hygienic properties, gas barrier properties, and good processability, it is suitable for uses such as food containers and medical containers. Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples 1 to 4, Comparative Examples 1-1 to 1-3 Interfacial polymerization using a methylene chloride solution of mixed acid dichloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 and an alkaline aqueous solution of bisphenol A. Thus, PAR was manufactured.
This phenol/tetrachloroethane (6:
4. Weight ratio), the logarithmic viscosity at 1g/100c.c. and 25°C was 0.71. Logarithmic viscosity measured by the same method as above is 0.59 (PET1), 0.81 (PET2) and 0.98
Three types of polyethylene terephthalate (PET3) and the above PAR were taken in the proportions shown in Table 1,
Mix in a V-type blender and then heat at 100℃ for 16 minutes.
After vacuum drying for an hour, it was extruded using an extruder with a diameter of 40 mm and L/D=24 under the conditions shown in Table 2, and the appearance of the threads, the formation of fish eyes, and the retractability of the threads were observed. The results were as shown in Table 2. In Table 2, "Fishui" refers to the unmelted material in the resin composition, which is quickly stretched before cooling the extruded material, and is 0.1 to 0.2
It was observed at a diameter of about mmφ.

[Table] η; Logarithmic viscosity

[Table] As can be seen from Table 2, in the case of the method of the present invention, the appearance of the resin composition was transparent, there were almost no stickiness, and the retractability of the wire was also good, but in the comparative example, the extrusion temperature was changed. However, it was not possible to find suitable conditions. Next, the samples shown in Table 2 were injection molded at 270°C, and the performance of the resulting molded products was measured. The results were as shown in Table 3.

[Table] Example 1 according to the method of the present invention as shown in Table 3
Comparing to Comparative Examples, molded products of No. 4 to No. 4 had a more transparent appearance and significantly better mechanical properties. Reference Examples 1 to 4 A methylene chloride solution of a mixed acid dichloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 4:6 and an alkaline aqueous solution of various bisphenols shown in Table 4 were used to produce various types by an interfacial polymerization method. of PAR was produced. Phenol/tetrachloroethane (6:4, weight ratio) of these PARs
Logarithmic viscosity at medium, 1g/100c.c., 25℃ is shown in Table 4.
It was as shown in .

[Table] Examples 5 to 9, Comparative Examples 2 to 5 Logarithmic viscosity 1.33 (hereinafter referred to as PET4), Logarithmic viscosity
Polyethylene terephthalate with a logarithmic viscosity of 1.65 (hereinafter referred to as PET5), two types of polybutylene terephthalate with a logarithmic viscosity of 0.60 (hereinafter referred to as PBT1) and 0.95 (hereinafter referred to as PBT2), and Reference Examples 1 to 4.
PAR was taken in the ratio shown in Table 5, mixed in a V-type blender, then vacuum dried at 100°C for 16 hours, extruded using an extruder with a diameter of 40 mm and L/D = 24 under the conditions shown in Table 6, and made into Tegus. The appearance, formation of fisheyes, and retractability of the fisheyes were observed. The results were as shown in Table 6.

【table】

【table】

[Table] The samples shown in Table 6 were injection molded at 270°C, and the performance of the resulting molded products was measured. The results were as shown in Table 7.

【table】

Claims (1)

[Scope of Claims] 1 (A) A mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9) and the general formula Bisphenols represented by (however, -X
- is selected from the group consisting of -O-, -S-, _-SO2- , -CO-, an alkylene group and an alkylidene group, and _R1 , _R2 , _R3 , _R4 , _R'1 , _R'2 , R′ ₃ and
R′ ₄ is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group), and (B) 95 to 55 parts by weight of a polyalkylenephenylene ester. A method for producing a resin composition by melt-mixing, characterized by using components (A) and (B) whose logarithmic viscosities are in a range that satisfies the following formulas [] and []. Method for producing resin composition. 0.3≦ηA≦ηB+0.3 [] 0.65≦ηB≦1.5 [] [However, ηA represents the logarithmic viscosity of the (A) component, and ηB represents the logarithmic viscosity of the (B) component. The logarithmic viscosity was measured in a mixed solvent of phenol/tetrachloroethane (6/4, weight ratio) at a concentration of 1 g/100 c.c. at 25°C. ]