JPS6024135B2 - Manufacturing method of resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a resin composition comprising a polyarylene ester, a polyalkylene phenylene ester and/or a polyalkylene phenylene ester ether.

A resin composition comprising a polyarylene ester and a polyalkylene phenylene ester or a polyalkylene phenylene ester ether is known (Tokutei Sho 48).
-54159 publication, JP-A-49-23844 publication,
Azusa Kaisho No. 50-15443). In these resin compositions, not only the dimensional stability, impact strength, transparency, heat resistance, etc. of polyalkylene phenylene ester or polyalkylene phenylene ester ether are significantly improved, but also polyarylene Stell's moldability and chemical resistance have also been greatly improved, and its excellent performance cannot be predicted simply from the properties of the component resins. These resin compositions are suitable for vacuum molding, injection molding, and printing due to their excellent performance. Various useful products can be made using commonly known plastic molding methods such as monomolding. A common method for producing these resin compositions is a melt mixing method using an extruder. That is, the two components, which have been adjusted in advance to a desired composition ratio, are heated and melted using an extruder and mixed to obtain a resin composition. However, when producing a resin composition consisting of polyarylene ester, polyalkylene phenylene ester and/or polyalkylene phenylene ester ether by a melt mixing method, the content of polyarylene ester is 7%. If it exceeds the weight percentage (based on the total weight of polyarylene ester and polyalkylene phenylene ester and/or polyalkylene phenylene ester ether), even a normal melting method using an extruded cherry will be relatively Although products of excellent quality can be obtained, in compositions with a polyarylene ester content of 70% by weight or less, resin compositions obtained simply by heating and melting and mixing using extruded cherry. Only molded products with low impact strength can be obtained from molded products, and extremely high extrusion temperatures are required to obtain transparent resin compositions, which not only significantly lowers the melt viscosity and reduces operability. This causes deterioration of the resin composition and significantly reduces its physical properties. That is, when such a resin composition is manufactured in one step as in the past, the polyarylene ester is easily dispersed in the form of minute islands in an unmolten state, and both components are uniformly melted and mixed. An extremely high extrusion temperature is required to achieve this, and if the temperature is low, the polyarylene ester will not be dispersed uniformly and will remain unmolten in the resin composition, resulting in poor impact strength, breaking strength, and breaking elongation. Not only does this significantly reduce physical properties such as strength, but also the uniform transparency is impaired and the appearance of the molded product is also impaired. Conversely, when extruding at high temperatures to obtain transparent products,
Not only does the melt viscosity drop markedly, reducing workability and making it virtually impossible to form a good pellet, but the resin composition also decomposes or deteriorates due to the high temperature, resulting in a drop in physical properties. Both impact strength and transparency are extremely important properties for plastics, and improving these properties will have the effect of significantly expanding the uses of the plastic.

For these reasons, it has been widely desired to develop a method for producing the above-mentioned resin compositions without causing these drawbacks. The present inventors conducted extensive research to solve the above problems, and as a result, they arrived at the present invention. That is, the present invention melt-mixes a polyarylene ester and a polyalkylene phenylene ester and/or a polyalkylene phenylene ester ether so that the content of the polyarylene ester is chromium weight % or less. In the method for producing a resin composition, exceeding a target composition ratio in advance,
And, a resin composition containing 5% by weight or more of polyarylene ester is produced by a melt mixing method, and then a polyalkylene phenylene ester and/or a polyalkylene phenylene ester ether is added thereto, This is a method for producing a resin composition characterized by further melt-mixing.

In order to produce a resin composition by the method of the present invention, first, a polyarylene ester and a polyalkylene phenylene ester and/or a polyalkylene phenylene ester ether are mixed until the content of the polyarylene ester increases. , exceeding the target composition ratio and 5% by weight
Melt and mix to achieve the above results. Next, a polyalkylene phenylene ester and/or a polyalkylene phenylene ester is added to a resin composition containing the polyarylene ester obtained as described above in an amount exceeding the desired composition ratio and at least 5% by weight. All you have to do is add ether and melt and mix. For example, the entire amount of polyarylene ester to be mixed and a portion of polyalkylene 0 phenylene ester and/or polyalkylene phenylene ester ether to be mixed are melt-mixed, and the remaining polyalkylene ester is added to the product. A phenylene ester and/or polyalkylene phenylene ester ether can be added and further melt-mixed to obtain a resin composition having the desired composition. Further, the polyalkylene phenylene ester and/or polyalkylene phenylene ester ether to be mixed can be divided, added in multiple stages, and melt-mixed.

That is, in the second step or a subsequent step, polyalkylene phenylene ester and polyalkylene phenylene ester and Alternatively, a polyalkylene phenylene ester enal may be added and melt-mixed to obtain a resin composition having the desired composition. The content of polyarylene ester in the target resin composition is x% by weight ( However, if x≦50), the content of Polya IJ Renester during melt mixing in the first stage is (50
It is particularly preferable that the amount is about 10x/2)% by weight.

In order to melt-mix both components, a conventionally known melt-mixing method can be employed.

Heat stabilizers, UV absorbers, antioxidants, plasticizers, lubricants, fillers, and other additives can be added in the first, second, or even trillion stages. .

According to the method of the present invention, all the drawbacks of these conventional manufacturing methods are eliminated, and the effects are surprising.

According to the multi-stage method of the present invention, uniform mixing and dispersion of the resin composition is possible in the first stage, the second stage, or any of the two stages at a lower temperature than in the secondary one-stage method, A transparent resin composition can be obtained.

The resin composition produced by the multi-step method of the present invention exhibits a much higher elongation at break and significantly increased impact strength than that produced by the conventional one-step method.

Furthermore, it has excellent transparency and a good appearance. In the multi-step method of the present invention, the thermal history is performed twice or more, but since the melt-mixing temperature is low, the deterioration of the resin composition is rather less than in the conventional one-step method. Furthermore, according to the multi-step method of the present invention, even additives with relatively poor thermal stability can be added in the second step or a step without precipitation, and can be added as in the subordinate one-step method. There are no significant restrictions on the types and amounts of additives that can be used. The polyarylene ester used in the present invention is produced from an aromatic dibasic acid or its functional derivative and a dihydric phenol or its functional conductor. "Lennester 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 bisphenols represented by the general formula (however, 1× - is selected from the group consisting of 10-, 1S-, 1S02-, 1CO-, an alkylene group, and an alkylene group; R,,R2,
R3, R4, R', , R'2, R'3 and R4 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,
bis(4-hydroxy-3-chlorophenyl)-ether, bis(4-hydroxyphenyl)-sulfide,
Bis(4-hydroxyphenyl)-sulfone, bis(4-hydroxyphenyl)-sulfone, bis(4-hydroxyphenyl)-sulfone,
-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'-chlorophenylmethane) The most commonly produced A typical example is 2,2-(4-hydroxyphenyl)-propane, which is called bisphenyl A.

If necessary, mixtures of said bisphenols or bisphenols and small amounts of other divalent compounds, such as dihydroxynaphthalenes such as 2,2'-dihydroxynaphthalene, hydroquinone, resorcinol, 2
, 6-ditahydroxytoluene, 2,6-dihydroxychlorobenzene, 3,6-dihydroxytoluene, 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.

The polyarylene ester 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 polyalkylene phenylene ester or polyalkylene phenylene ester used in the present invention is represented by the general formula.

Here, R5, R6, R7 and R8 are selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyl ester group, a cyano group, a sulfone group, a nitro group, a phenoxy group, etc. is either an ester group or an ether group, and m is an integer of 1 or more and 10 or less. Specific examples of such polyalkylene phenylene esters or polyalkylene phenylene ester ethers include polyethylene terephthalate, polyethylene isophthalate, polytrimethylene terephthalate, polytrimethylene isophthalate, polytetramethylene terephthalate, polytetra Methylene isophthalate, polyethylene-p-phenylene ester ether, polyethylene-m-phenylene ester ether, polytrimethylene-p-phenylene ester, polytrimethylene-m-phenylene Ester ether, polytetramethylene-p-phenylene ester ether,
Examples include polytetramethylene-m-phenylene ester ether, but other materials may be used as long as they are shown in the general formula. Preferred polyalkylene phenylene esters or polyarylene phenylene ester ethers used in the present invention include polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-p-phenylene ester ether, and the like.
The resin composition produced by the present invention has excellent chemical resistance, moldability, transparency, and has excellent mechanical properties such as impact strength, so it can be used in a wide range of fields. .

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1, Comparative Examples 1, 2 Mixed acid chloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1, and bisphenol A
Polyarylene ester 6 obtained by interfacial polymerization method from
and parts by weight of polyethylene terephthalate 4 were mixed for 5 minutes at room temperature using a super mixer.

This was melt-mixed using an extruder to obtain a beret. The extrusion temperature was 270°C and the residence time in the extruder was about 3 minutes. Next, parts by weight of the above pellet 5 and the weight of polyethylene terephthalate 5 were mixed at room temperature 5 using a super mixer.
After mixing for a minute, the mixture was extruded using an extruder at 24,500 mm, and a pellet of a resin composition containing no unmelted material and having uniform transparency was obtained. Residence time in the extruder was approximately 3 minutes. The composition of the obtained resin composition was 3% by weight of polyarylene ester and 7% by weight of polyethylene terephthalate. For comparison, a resin composition having the same composition as the above resin composition was blended in the same manner as in the example, and then 1
It was extruded using a stepwise method.

In this case, extrusion required a high temperature of 32,000 ℃. (Comparative Example 1) Lower temperature, for example 27000
In Comparative Example 2, a resin composition containing no unmelted materials and having uniform transparency could not be obtained. In this case, the residence time in the extruder was about 3 minutes for Comparative Example and Comparative Example 2 as well. In addition, the unmelted material in the resin composition was observed by immediately grinding it by about 0.1 to 0.2 degrees before cooling the string extruded from the nozzle of the extruder. Next, various test pieces were molded by injection molding using the pellets obtained as described above, and the impact strength, tensile strength, breaking strength, and logarithmic viscosity of the test pieces were measured. The results were as shown in Table 1. Table 1 * Measured using a mixed solvent of phenol/tetrachloroethane (6/4) (weight ratio).

As shown in Table 1, the resin composition produced according to the method of the present invention had significantly superior physical properties compared to the conventional method.

Example 2, Comparative Example 3 A mixed acid chloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 7:3, and parts by weight of polyarylene ester 6 produced by an interfacial polymerization method from tetrabromobisphenol A, 4 parts by weight of polyethylene-p-phenylene ester ether were mixed for 5 minutes at room temperature using a super mixer, and extruded using an extruder.

The extrusion temperature was 280 do, and the residence time in the extruder was about 3 minutes. Then the pellet 3 obtained in the first stage
and parts by weight of polyethylene-P-phenylene ester ether 7 were mixed for 5 minutes at room temperature using a super mixer, and extruded at 23,000 in an extruder. Residence time in the extruder was approximately 3 minutes. A transparent and good pellet was obtained. The composition of the resulting resin composition was 1% by weight of polyarylene ester and 82% by weight of polyethylene-P-phenylene ester ether. For comparison, polyarylene ester and polyethylene-P-phenylene ester ether, which had been adjusted to have the same composition as the above resin composition, were mixed for 5 minutes at room temperature using a super mixer.
Extruded using an extruder. (Comparative Example 3) The extrusion temperature at that time was 330:00, and the residence time in the extruder was about 3 minutes. At temperatures lower than this, a transparent molded article free of unmelted material could not be obtained. Various test specimens were molded by injection molding using the pellets obtained as described above, and various performances of the specimens were measured.The results are shown in Table 2.

As shown in Table 2, the resin composition produced by the method of the present invention had significantly superior performance compared to that produced by the conventional method.

Example 3, Comparative Examples 4, 5 Parts by weight of polyarylene ester 8 obtained by interfacial polymerization from mixed acid chloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 and bisphenol A. and 2 parts by weight of polyethylene terephthalate were mixed for 5 minutes at room temperature using a super mixer.

This was melt-mixed using an extruder to obtain a pellet. The extrusion temperature was 290 oo and the residence time in the extruder was about 3 minutes. Next, parts by weight of the pellet 8 and the weight of polyethylene terephthalate 2 were mixed for 5 minutes at room temperature using a super mixer, and then extruded using an extruder at 27,000 rpm, resulting in a uniform transparency containing no unmelted material. A pellet of a resin composition having the following properties was obtained. The residence time in the extruder is approximately 3
It was a minute. The composition of the obtained resin composition was 3% by weight of polyarylene ester and 3% by weight of polyethylene terephthalate. For comparison, a resin composition having the same composition as the above resin composition was blended in the same manner as in Example 4, and then extruded using a one-step method.

In this case, a high temperature of 34,000 ℃ was required for extrusion (Comparative Example 4). lower temperature, e.g. 290
In case of 0○ (Comparative Example 5), a resin composition containing no unmelted material and having uniform transparency could not be obtained. In this case, the residence time in the extruder was about 3 minutes in both Comparative Examples 4 and 5.
Next, various test pieces were molded by injection molding using the pellets obtained as described above, and the test pieces were measured. The results were as shown in Table 3. Table 3*
Phenol/tetrachloroethane (6/4) (weight ratio)
Measured using a mixed solvent.

As shown in Table 3, the resin compositions produced according to the method of the present invention had significantly superior physical properties as compared to the conventional method.

Claims (1)

[Claims] 1. Polyarylene ester and polyalkylene phenylene ester and/or polyalkylene phenylene ester ether are melt-mixed so that the content of polyarylene ester is 70% by weight or less (polyarylene ester and polyalkylene phenylene ester). ester and/or polyalkylene phenylene ester ether)), a resin containing a polyarylene ester exceeding the desired composition ratio and 50% by weight or more A method for producing a resin composition, which comprises producing a composition by a melt-mixing method, and then adding and melt-mixing a polyalkylene phenylene ester and/or polyalkylene phenylene ester ether.