KR100307994B1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to at least one non-polymeric liquid material which is an additive for thermoplastic resin (A) and thermoplastic resin (A), in which mixing is carried out at a temperature corresponding to a range of 25 to 300 ° C. which can keep material (B) in a liquid state. It relates to a thermoplastic resin composition, characterized in that it is produced by the process consisting of the mixing step of (B), the composition is substantially the same as that produced by the method consisting of dissolving or swelling the resin (A) in the material (B) . Molding of the resin material provides the product with excellent appearance, light resistance and mechanical properties, so that the resin composition can be advantageously used as a molding material in various fields including parts for OA devices, parts for home appliances, and electrical and electronic parts. . Moreover, the resin composition is particularly useful as a masterbatch in which other resins are mixed. The use of the resin composition as a masterbatch enables melt molding of the resin composition comprising the masterbatch and other molding resins and can reduce the thermal deterioration of the resin contained in the masterbatch, thereby providing a molded article having excellent characteristics.

Description

Thermoplastic composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to additives for (A) thermoplastic resins and (B) thermoplastic resins (A), wherein at least one non-polymeric liquid material in a liquid state at a temperature in the range of 25 to 300 ° C., 25 to 300 By mixing together at a temperature in the range of < RTI ID = 0.0 > C < / RTI > (non-polymeric liquid material (B) maintains a liquid state), the thermoplastic resin (A) is dissolved in the non-polymerizable liquid material (B), or And a resin composition substantially the same as that produced by the method comprising the step of swelling. The resin composition of the present invention, unlike the conventional resin composition prepared by melt extrusion method, during the preparation of the resin fired material, the thermoplastic resin (A), which is a component of the resin composition, and each of the nonpolymerizable liquid materials as additives do not experience high temperature conditions. It does not suffer from thermal degradation. Therefore, by molding the resin composition of the present invention, a molded article having excellent appearance, light resistance and mechanical properties can be obtained. The resin composition of this invention can be advantageously used as a molding material for manufacture of various molded objects, such as components for OA machines, components for home appliances, and electrical and electronic components. Moreover, especially when the resin composition of the present invention, in which the masterbatch is added to the same or different resin material as the thermoplastic resin used in the resin composition, is used as a masterbatch for producing molding materials, a great advantage arises. The molding material obtained by adding the resin composition of the present invention as a masterbatch to the resin material not only has improved melt molding ability, but also has a good appearance, excellent appearance, utilizing the fact that the resin in the masterbatch does not experience high temperature conditions. It has the advantage that a molded article having light stability and excellent mechanical properties can be easily produced from the molding material. In addition, in the production of the masterbatch made of the resin composition of the present invention, the excess liquid additive can be easily incorporated into the masterbatch without lowering the productivity of the masterbatch.

Molded bodies produced by molding thermoplastic resins such as polyphenylene ether resins have good heat resistance and good impact resistance. Therefore, thermoplastic resins are widely used as molding materials for the production of various molded articles, such as automobile parts, parts for home appliances, and OA machine parts.

Recently, in order to improve the properties of thermoplastic resins, various additives have been used in thermoplastic resins. For example, in order to improve the processability of the thermoplastic resin, attempts have been made to add liquid paraffin (mineral oil) to the thermoplastic resin. In addition, in order to impart flame retardancy to the thermoplastic resin, it has been attempted to add a liquid organophosphorus compound to the thermoplastic resin. The addition of the liquid additive to the thermoplastic resin is usually carried out using a melt extrusion method. However, when the addition of a liquid additive to a thermoplastic resin having a high melting temperature or a high glass transition temperature is carried out by melt extrusion, not only is a special supply equipment necessary for supplying the liquid additive, but also the handling of the liquid additive is complicated ( Iii) Problems arise. In addition, when melt-mixing a low-viscosity liquid additive and a high-viscosity thermoplastic resin together, the large viscosity difference between them differs from that of the liquid additive in the extrusion amount, so that the extrusion operation is unstable, and the high-viscosity thermoplastic resin during melt extrusion The problem arises that part of the remains unmelted, resulting in a final molded article with poor appearance and degraded mechanical properties.

In order to solve the problem caused by the large viscosity difference between the high viscosity thermoplastic resin and the liquid additive, a method of further melt mixing the resin material obtained by melt mixing of the polystyrene resin and the polyphenylene ether resin with the liquid additive for the polymer. (See Japanese Patent No. 2612396 and Japanese Patent Laid-Open No. 5-295249). The technique has made it possible to reduce the incidence of problems in which some of the high viscosity resin, polyphenylene ether resin, remains unmelted during melt extrusion. However, in the above technique, when the polyphenylene ether resin and the polystyrene resin are melted at a high temperature, there arises a problem that the resin suffers from a noticeable discoloration, a decrease in light stability, and a decrease in mechanical properties due to breakage of the molecular chain.

In order to solve the problem, various proposals have been made. Examples of the above proposals include a method of using a resin composition consisting of a thermoplastic resin and an oil-containing resin obtained by impregnating a liquid oil in a porous, styrene-divinyl benzene copolymer (Japanese Patent Publication No. 7-122024); Prevention of the occurrence of bleeding-out of the additive from the molding material during molding, comprising using as a molding material a resin composition composed of a thermoplastic resin and a resin additive made by impregnating a liquid additive into the oil-absorbing crosslinked polymer. Method (Japanese Laid-Open Patent Publication 5-214114); A method in which a molded article having a matte appearance can be obtained using a resin composition obtained by incorporating a specific polymer into a thermoplastic resin as a molding material (Japanese Patent Laid-Open No. 6-57007); A method in which a molded article having improved impact resistance can be obtained using a resin composition obtained by incorporating a specific polymer into a thermoplastic resin as a molding material (Japanese Patent Laid-Open No. 6-73190); A method of using a powdery flame retardant for polymers obtained by impregnating phosphorus-containing flame retardant with amorphous silica (Japanese Patent Laid-Open No. 7-331244); A method of using an additive for a polymer, wherein the additive contains an inorganic carrier and a phosphorus-containing flame retardant supported thereon (Japanese Patent No. 2588331); A method of using a resin composition obtained by gelling a liquid additive with a gelling agent to obtain a solidified liquid additive and mixing the solidified liquid additive into a synthetic resin (Japanese Patent Office 56-42619); A method of using a resin composition obtained by dissolving a phosphate compound in a solvent to obtain a solution and dispersing the solution in polypropylene by melt kneading (Japanese Patent Laid-Open No. 4-1233); And a method of using a masterbatch composed of an oil absorbent polymer and an additive for a polymer (Japanese Patent Laid-Open No. 9-52956). Each of the above techniques aims at improving the handleability of the liquid additive which absorbs or adsorbs the liquid additive to the oil absorbent resin to reduce the appearance amount of the liquid additive. Therefore, in the resin composition obtained by any of the above techniques, the oil-absorbent resin in which the liquid additive is absorbed or adsorbed is in a powder or non-powder solid state, so that when the resin composition is melt-molded using an extruder, improved appearance and excellent mechanical A molded article having the properties can be obtained.

It is known to use a resin composition obtained by dissolving or impregnating a thermoplastic resin in a polymerizable monomer or crosslinkable compound and then polymerizing the polymerizable monomer or crosslinkable compound. Examples of the above technique are methods of using a resin composition prepared by impregnating polyvinyl chloride with an aromatic vinyl monomer and then polymerizing the aromatic vinyl monomer (JP-A-61-40702 and 62-1972, and JP-A-3). 197521); A method of using a resin composition prepared by dissolving a polyphenylene ether resin and a rubber polymer in an aromatic vinyl monomer and then polymerizing the aromatic vinyl monomer (European Patent No. 226149 and Japanese Patent Laid-Open No. 7-242791); A method of using a polyphenylene ether resin solution containing an aromatic vinyl monomer to form a coating or film (Russian Patent No. 2069674); A method for producing a thermosetting laminate using a polyphenylene ether resin, a liquid epoxy compound, a flame retardant, and a curing catalyst as an electric component in which they are mixed with each other and the resulting mixture is reacted by heating at high temperature (Japanese Patent Laid-Open No. 7-3053); A method of using a polyphenylene oxide composition composed of a polyphenylene ether resin, a crosslinkable flame retardant and an initiator (Japanese Patent Laid-Open No. 62-148564). In each of the above examples, a mixture of an additive and a resin solution is provided and the mixture is polymerized or otherwise reacted. In this method, it is relatively easy to obtain a composition in which the resin and the liquid additive are uniformly mixed with each other. However, the above method has a disadvantage in that the polymerizable monomer is easily grafted to the thermoplastic resin, or the thermoplastic resin is easily crosslinked, and the characteristics inherent in the thermoplastic resin change.

In addition, Japanese Patent Laid-Open No. 50-50 describes a method for producing a molded article using a resin composition prepared by dissolving polyamide and phosphate in formic acid as a solvent. However, in the above method, after the removal of the solvent from the resin composition, the polyamide and the phosphate are not uniformly mixed, so that it is impossible to obtain a resin composition exhibiting excellent appearance and excellent light stability. Other examples of known techniques are methods for producing a porous polymer structure, in which a polymer, such as a polyphenylene ether resin, is dissolved in diphenyl sulfone as a solvent and the resulting solution is contacted with a mixed solvent of acetone and methanol (Japanese Patent Laid-Open No. 8-24582). ); A process for producing a polyphenylene ether-containing molding material, in which a polyphenylene ether resin and another polymer are dissolved in a solvent to obtain a solution, and the solvent is removed from the solution in multiple steps (Japanese Patent Laid-Open No. 58-34829); And a method for producing fibers from a solution obtained by dissolving polyacrylonitrile in a solvent consisting of a solution of rhodanate (Japanese Patent Laid-Open No. 50-20029). However, in the above known technique, no additives for polymers are used to obtain a resin composition in which the resin and liquid additives are uniformly mixed with each other. In addition, a method of lowering the melting temperature of a polyphenylene ether resin, in which a plasticizer is dissolved in a solvent to obtain a solution, and the obtained solution is used for treating the polyphenylene ether resin is known (Japanese Patent Laid-Open No. 52-90596). ). However, in the above method, since the polyphenylene ether resin is not dissolved in the solution, it is impossible to obtain a resin composition usable for producing a molded article having good appearance, good light stability and good mechanical properties.

In addition, it is known to use resin compositions prepared by the process of dissolving resins such as polyphenylene ether resins in additives used for surface modification of polymers. For example, it is known to use an antistatic resin composition prepared from a solution obtained by dissolving a thermoplastic resin such as polyphenylene ether or polypropylene in an amine antistatic agent (Japanese Patent Laid-Open No. 50-105293 and U.S. Pat. 4,210,556, 4,314,040 and 4,147,742). As another example of the above technique, a method is known in which both a lubricating oil and a synthetic resin are dissolved in a solvent to obtain a solution and the solvent is removed from the solution to obtain a resin composition in which the lubricating oil is uniformly distributed in the synthetic resin (Japanese Patent Publication). 51-34536). However, additives (ie, antistatic agents and lubricants) used in the art are aimed at modifying the surface properties of the shaped bodies. Therefore, in the above technique, it is important that the additive is mainly present on the surface portion of the molded body. For this purpose, it is necessary that the additive has a moderately low compatibility with the resin. Therefore, when a resin composition having a high content of additives is intended to be produced by the above technique, it is necessary to melt-knead the resin and the additive at a high temperature, which inevitably degrades the resin and the additive. Therefore, it is impossible to mold the resin composition prepared by the above technique to obtain a molded article having excellent appearance, excellent light stability and excellent mechanical properties.

In this situation, the present inventor has made extensive and intensive studies to develop a resin composition which can be advantageously used for the production of various molded articles having the above problems and excellent appearance, excellent light stability and excellent mechanical properties. As a result, there is no problem that the resin composition produced by a specific method as described later is parallel to the resin composition prepared by the conventional melt extrusion method, such as thermal deterioration of the resin contained in the resin composition, and therefore the appearance of the resin composition of the present invention It has been found that it can advantageously be used for the production of molded articles which are much improved in terms of light stability and mechanical properties. A specific process according to the invention comprises (A) a thermoplastic resin and (B) an additive for the thermoplastic resin (A), wherein at least one non-polymeric liquid material in a liquid state at a temperature in the range of 25 to 300 ° C., 25 to 300 ° C. The thermoplastic resin (A) is dissolved in the non-polymerizable liquid material (B) or swelled into the non-polymerizable liquid material (B) by mixing together at a temperature in the range (at this temperature, the nonpolymerizable liquid material (B) maintains the liquid state). Making a step. When using the resin composition of this invention as a masterbatch for materials of a molding material which adds a masterbatch to resin same or different from resin used in a resin composition, especially a big advantage arises. In other words, the molding material obtained by adding the resin composition of the present invention as a masterbatch to the resin material not only has improved melt molding ability, but also that the resin in the masterbatch does not experience high temperature conditions. It has the advantage that an improved molded body can be produced from the molding material in terms of properties. Further, in the preparation of the masterbatch composed of the resin composition of the present invention, it has been found that an excess of liquid additive can be easily incorporated into the masterbatch without lowering the productivity of the masterbatch. The present invention has been completed based on the novel finding.

Accordingly, a first object of the present invention is to provide a resin composition which can be advantageously used for the production of a molded article having good appearance, excellent light stability and excellent mechanical properties.

It is still another object of the present invention to provide a masterbatch which can easily impart excellent characteristics of the above object to a molded article produced from the molding material obtained by adding the masterbatch to a resin material.

The later and other objects, features and advantages of the present invention will become apparent from the claims associated with the latter specification and the accompanying drawings.

In the accompanying drawing:

1 is a schematic view showing one way of producing a resin composition of the present invention;

2 is a schematic view showing another mode of the method for producing a resin composition of the present invention;

3 (a) and 3 (b) show the ¹ H-NMR spectrum of the polyphenylene ether resin composition prepared by melt extrusion in Comparative Example 3;

4 (a) and 4 (b) show the ¹ H-NMR spectrum of the polyphenylene ether resin composition prepared by the method of the present invention in Example 1 (FIGS. 4 (a) and 4 (b)). The positions represented by A 'through D' correspond to the positions represented by A through D in FIGS. 3 (a) and 3 (b), respectively);

FIG. 5 shows {polyphenylene ether (PPE) / flame retardant TPP} compositions prepared by melt extrusion method (Comparative Examples 10-12) and {polyphenylene ether (PPE) / flame retardant TPP prepared by the method of the present invention} A graph showing the relationship between the preparation temperature and the color tone (yellowness: YI) for each of the compositions (Examples 2 to 6);

FIG. 6 is a graph showing the relationship between the concentration of PPE and dissolution temperature in the composition of each of the {PPE / Non-polymerizable liquid substance} compositions in Examples 18 to 20 and Comparative Examples 29 to 31 (wherein a silver flame retardant ( TPP) is used as the non-polymerizable liquid material, and ○ indicates the use of an antistatic agent (A-Stat) as the non-polymerizable liquid material, and each of the curves is independently a non-polymerizable liquid liquid in which PPE is selected from a flame retardant and an antistatic agent. The lower limit of the temperature at which the material is completely dissolved, and thus the upper part of the curve is the zone of complete dissolution};

FIG. 7 is a graph showing the relationship between the concentration of monomeric aromatic phosphate esters and dissolution temperatures (in mixtures of monomers and oligomeric aromatic phosphate esters) in the preparation of each of the compositions (mixture of PPE / monomer and oligomeric aromatic phosphate esters) The curve shows the lower limit of the temperature at which PPE completely dissolves into the mixture of monomer and oligomeric aromatic phosphate esters, so that the top of the curve is the zone of complete dissolution (the graph corresponds to Table 6);

8 is a graph showing the relationship between the content of the white pigment (TiO ₂ ) and the color tone (yellowness: YI) and the Izod impact strength in the resin composition, wherein ○ and ☆ are resin compositions prepared by the melt extrusion method. The properties of? And? Indicate the properties of the resin composition of the present invention (the graph corresponds to Table 15);

9 (a) and 9 (b) show the measurement methods of the glass transition temperature (Tg) and the melting temperature (Tm) from the chart obtained by differential scanning calorimetry (DSC).

1 and 2, the same parts are denoted by the same reference numerals.

Reference number mention

1: melting bath

2: raw material supply port

3: stirrer

4: liquid raw material outlet

5: extruder type heating mixing tank

6: Supply port for liquid raw materials

7: Supply port for raw materials containing thermoplastic resin

8: resin composition outlet

9: pump

10: filter

11: droplet preparation device

12: belt cooler

13: 1st heat exchanger

14: second heat exchanger

15: pelletizer

16: belt

17: Packaging device

In the present invention, (A) thermoplastic resin, and (B) at least one non-polymeric liquid material in a liquid state at a temperature in the range of 25 to 300 ° C as an additive for the thermoplastic resin (A), in the range of 25 to 300 ° C Mixing together at a temperature (at this temperature the non-polymeric liquid material (B) maintains a liquid state) causes the thermoplastic resin (A) to dissolve in the non-polymerizable liquid material (B) or to swell into the non-polymerizable liquid material (B). It provides a resin composition substantially the same as that produced by the method comprising the step.

In order to facilitate understanding of the present invention, the main features and various embodiments of the present invention are listed below.

1. (A) a thermoplastic resin, and

(B) at least one non-polymeric liquid material, which is an additive for the thermoplastic resin (A), in the liquid state at a temperature in the range from 25 to 300 ° C.

By mixing together at a temperature in the range from 25 to 300 ° C. (at this temperature the non-polymerizable liquid material (B) maintains the liquid state), so that the thermoplastic resin (A) is dissolved in the non-polymerizable liquid material (B) or Substantially the same resin composition as produced by the process comprising the step of swelling with liquid substance (B).

2. The resin composition according to the above 1, wherein the at least one non-polymerizable liquid substance (B) is selected from the group consisting of flame retardants, plasticizers, thermal stabilizers and light stabilizers.

3. The solid material according to the first or second, wherein the thermoplastic resin (A) and the nonpolymerizable liquid material (B) are crystalline solids or amorphous solids at a temperature of 300 ° C. or less as an additive for the thermoplastic resin (A). Resin composition mixed with (C).

4. The resin composition according to any of the above 1 to 3, wherein the mixing is carried out at a temperature in the range of 100 to 300 ° C., and the at least one nonpolymerizable liquid substance (B) maintains a liquid state.

5. The resin composition according to any of the above 1 to 4, wherein the mixing is carried out at a temperature in the range of 150 to 250 ° C., and the at least one nonpolymerizable liquid substance (B) remains in a liquid state.

6. The resin composition according to any of the above 1 to 5, wherein the weight ratio of the thermoplastic resin (A) to the at least one nonpolymerizable liquid substance (B) is 10/90 to 90/10.

7. The resin composition according to item 6, wherein the weight ratio of the thermoplastic resin (A) to the at least one nonpolymerizable liquid substance (B) is 30/70 to 70/30.

8. The thermoplastic resin (A) according to any one of the above 1 to 7, wherein the thermoplastic resin (A) contains 1 to 100% by weight of polyphenylene ether resin and 0 to 99% by weight of polystyrene resin, and polyphenylene ether resin and polystyrene resin The resin composition has a total amount of 100% by weight.

9. The resin according to the eighth aspect, wherein the thermoplastic resin (A) contains 50 to 99% by weight of polyphenylene ether resin and 1 to 50% by weight of polystyrene resin, and the total amount of polyphenylene ether resin and polystyrene resin is 100% by weight. Phosphorus resin composition.

10. The resin composition according to any one of the first to ninth, wherein the non-polymerizable liquid substance (B) is a flame retardant.

11. The resin composition according to the above 10, wherein the flame retardant contains at least one organic phosphorus compound.

12. The resin composition according to item 11, wherein the organic phosphorus compound is at least one aromatic phosphate ester.

13. The resin composition according to the twelfth aspect, wherein the aromatic phosphate ester is a monomeric aromatic phosphate ester represented by the following general formula (1):

[In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is the same as each other and represents an integer of 0 to 3;

14. The resin composition according to the twelfth aspect, wherein the aromatic phosphate ester is an oligomeric aromatic phosphate ester represented by the following formula (2):

[Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more].

15. The resin composition according to item 12, wherein the at least one aromatic phosphate ester is a mixture of a monomeric aromatic phosphate ester represented by the following formula (1) and an oligomeric aromatic phosphate ester represented by the following formula (2):

[Formula 1]

[In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is identical to each other and represents an integer of 0 to 3;

[Formula 2]

[Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more].

16. The resin according to the above 15, wherein the mixture contains 1 to 99% by weight of the monomeric aromatic phosphate ester and 1 to 99% by weight of the oligomeric aromatic phosphate ester, and wherein the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100% by weight. Composition.

17. The resin according to the above 16, wherein the mixture contains 1 to 50% by weight of the monomeric aromatic phosphate ester and 50 to 99% by weight of the oligomeric aromatic phosphate ester, wherein the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100% by weight. Composition.

18. The resin composition according to any one of the above 3 to 17, wherein the amount of the solid substance (C) is from 0.000001 to 100 parts by weight relative to 100 parts by weight of the thermoplastic resin (A).

19. The resin composition according to item 18, wherein the amount of the solid substance (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin (A).

20. The resin composition according to any one of items 3 to 19, wherein the solid material (C) is at least one additive selected from the group consisting of an antitack agent, an oil absorbent, a heat stabilizer and a light stabilizer.

21. The resin according to any one of the above 1 to 20, wherein the thermoplastic resin (A) contains at least one compound selected from the group consisting of aromatic vinyl polymers and optionally aromatic vinyl monomers, aromatic vinyl dimers and aromatic vinyl trimers, The amount of the at least one compound is 1% by weight or less based on the weight of the resin composition.

22. The process according to the above 1, wherein the mixing of the thermoplastic resin (A) and the nonpolymerizable liquid substance (B) is carried out while heating at a temperature of 300 ° C. or lower, and after mixing, the product is cooled and then pelletized, whereby the resin A resin composition for preparing the composition in the form of pellets.

23. The resin composition according to the above 1, wherein mixing is carried out in the presence of a solvent (D) and after the mixing, the solvent (D) is removed.

24. The resin composition according to the above 23, wherein the amount of the solvent (D) is 0.1 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin (A).

25. The resin composition according to the twenty-third or twenty-fourth aspect, wherein the solvent (D) has a boiling point that is above the temperature at which mixing is performed to 300 ° C or less.

26. A method of making a molded article consisting of melt extruding the following (i) and (ii):

(i) the following (A) and (B):

(A) a thermoplastic resin, and

(B) at least one non-polymeric liquid material, which is an additive for the thermoplastic resin (A), in the liquid state at a temperature in the range from 25 to 300 ° C.

By mixing together at a temperature in the range from 25 to 300 ° C. (at this temperature the non-polymerizable liquid material (B) maintains the liquid state), so that the thermoplastic resin (A) is dissolved in the non-polymerizable liquid material (B) or Substantially the same resin composition as prepared by the process comprising the step of swelling with liquid substance (B); And

(ii) A thermoplastic resin the same as or different from the thermoplastic resin (A).

27. The method according to the above 26, wherein the thermoplastic resin (ii) contains at least one thermoplastic elastomer.

28. The method according to item 26 or 27, wherein the resin composition (i) and the thermoplastic resin (ii) are selected from the group consisting of flame retardants, flame retardant aids, light stabilizers, mold release agents, rheology improvers, heat stabilizers, antistatic agents, colorants and foaming agents. Melt extrusion with at least one additive (E), wherein the at least one additive (E) is the same or different than the nonpolymerizable liquid material (B).

29. A molded article made by the method according to any one of items 26 to 28 above.

30. Polyphenylene ether resin composition containing the following (A ') and (B'):

(A ') Polyphenylenes containing a plurality of polymer chains, each polymer chain comprising a repeating oxyphenylene unit and containing a hydroxyl group in an amount of 0.5 mol or less with respect to 100 mol of the repeating oxyphenylene unit. Ether resins; And

(B ') at least one additive for said polyphenylene ether resin (A').

31. The resin composition according to item 30, wherein the at least one additive (B ') is selected from the group consisting of flame retardants, plasticizers, thermal stabilizers and light stabilizers.

32. The resin composition according to the above 30 or 31, wherein the weight ratio of polyphenylene ether resin (A ') to at least one additive (B') is 10/90 to 90/10.

33. The resin composition according to any one of items 30 to 32, wherein at least one additive (B ') is a flame retardant.

34. The resin composition according to the above 33, wherein the flame retardant contains at least one organophosphorus compound.

35. The resin composition according to the above 34, wherein the organic phosphorus compound is at least one aromatic phosphate ester.

36. The resin composition according to item 35, wherein the aromatic phosphate ester is a monomeric aromatic phosphate ester represented by the following general formula (1):

[Formula 1]

[In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is the same as each other and represents an integer of 0 to 3;

37. The resin composition according to item 35, wherein the aromatic phosphate ester is an oligomeric aromatic phosphate ester represented by the following formula (2):

[Formula 2]

[Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more].

38. The resin composition according to item 35, wherein the at least one aromatic phosphate ester is a mixture of a monomeric aromatic phosphate ester represented by the following formula (1) and an oligomeric aromatic phosphate ester represented by the following formula (2):

[Formula 1]

[In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is identical to each other and represents an integer of 0 to 3;

[Formula 2]

[Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more].

39. The resin according to the above 38, wherein the mixture contains 1 to 99% by weight of the monomeric aromatic phosphate ester and 1 to 99% by weight of the oligomeric aromatic phosphate ester, and wherein the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100% by weight. Composition.

40. The resin according to the above 39, wherein the mixture contains 1 to 50% by weight of the monomeric aromatic phosphate ester and 50 to 99% by weight of the oligomeric aromatic phosphate ester, wherein the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100% by weight. Composition.

41. A molded article made from the resin composition of any one of the first to twenty-five, which is a film, sheet or foamed article.

42. A molded article prepared from the resin composition of any one of the first to twenty-five, which is a component for an OA device, a component for an electrical device, a component for an electronic device, or an automotive part.

43. Use of the resin composition as described in any one of said 1st-25th as an injection molding material.

44. The molded article according to item 29 above, which is a film, sheet or foamed article.

45. The molded article according to item 29 above, which is a component for an OA device, an electrical device, an electronic device, or an automotive part.

46. The molded article according to item 29, which is a pellet used as an injection molding material.

47. A molded article prepared from the resin composition of any one of the thirty to forty years, which is a film, sheet or foamed article.

48. A molded article prepared from the resin composition according to any one of items 30 to 40, which is a component for an OA device, a component for an electrical device, a component for an electronic device, or an automotive part.

49. Use of the resin composition according to any one of items 30 to 40 as a material for injection molding.

The present invention will now be described in detail.

In one aspect of the invention, (A) a thermoplastic resin; (B) at least one nonpolymerizable liquid substance as an additive for the thermoplastic resin (A); And optionally (C) a resin composition consisting of a crystalline or amorphous solid material as an additive for the thermoplastic resin (A).

In the composition of the present invention, the thermoplastic resin (A) acts as a resin component, and each of the nonpolymerizable liquid material (B) and the solid material (C) has a desired property such as flame retardancy and fluidity in the thermoplastic resin (A). Grant.

In the resin composition of the present invention, the thermoplastic resin (A) is dissolved or swelled in at least one nonpolymerizable liquid substance (B). The resin composition of the present invention is prepared, for example, in the form of pellets (for example cylindrical pellets or spherical pellets) having a diameter of 0.01 to 10 mm. The pellet may be extruded to obtain a sheet or injection molded to obtain a molded body of a desired mold. In addition, as detailed below, it is particularly advantageous to use the resin composition of the present invention as a masterbatch for the production of molding materials, wherein the masterbatch is applied to the same or different resin material as the thermoplastic resin (A) used in the resin composition. Add.

The resin composition of the present invention can be produced without the need for the step of molding the thermoplastic resin (A) to keep the resin in a molten state. “Melted state” refers to the state of a thermoplastic resin having a temperature above the softening point of the thermoplastic resin, where the resin is melted and fluid. Usually, melt processing is performed in manufacture of the conventional (resin / additive) composition or conventional molded resin body used as a molding material. Regarding the temperatures conventionally used in melt processing (these temperatures are often referred to as simplifying later as "traditional melt processing temperatures"):

(1) for the preparation of a resin composition containing an amorphous polymer or for the production of a molded resin body using an amorphous polymer, conventional melt processing temperatures are above about 50 to 100 ° C. higher than the glass transition temperature (Tg) of the polymer;

(2) In the case of production of the resin composition containing the crystalline polymer or production of the molded resin body using the crystalline polymer, the conventional melt processing temperature is higher than about 50 to 100 ° C higher than the melting temperature (Tm) of the polymer.

When the polymer is in the molten state, the high temperature of the polymer in the molten state not only causes the cleavage of the polymer chain, but also causes side reactions, such as dislocation reactions, of the polymer chain (which are present in adjacent positions), which worsens the polymer. Therefore, in order to avoid the above disadvantages and to obtain a molded resin body having excellent appearance, light stability and mechanical properties, it is very important to give a thermoplastic resin used as a molding material having satisfactory fluidity at the lowest possible temperature. Therefore, it is preferable to carry out the production of the resin additive composition or the molded resin body used as the molding material at a temperature below the conventional melt processing temperature. Specifically,

In the case of production of a resin composition containing an amorphous polymer or production of a molded resin body using an amorphous polymer, the production method is within a range lower than the conventional melt processing temperature and 50 to 100 ° C. or lower than the glass transition temperature (Tg) of the polymer. Running at a temperature selected, most preferably at temperatures up to 90 ° C. below the Tg of the polymer (ie, preparation temperature ≦ Tg + 90 ° C.); And

In the production of a resin composition containing a crystalline polymer or in the production of a molded resin body using the crystalline polymer, the production method is in a range lower than the conventional melt processing temperature and 50 to 100 ° C. or lower than the melt temperature (Tm) of the polymer. It is preferable to carry out at a temperature selected in the above, most preferably at a temperature higher than 90 ° C. below the Tg of the polymer (ie production temperature ≦ Tm + 90 ° C.).

In the resin composition of the present invention, the preparation of the resin composition can be carried out at a temperature lower than the conventional melt processing temperature using a method consisting of the mixing steps of (A) and (B):

(A) a thermoplastic resin, and

(B) at least one nonpolymerizable liquid substance as an additive to the thermoplastic resin (A),

Wherein the nonpolymerizable liquid substance (B) is in a liquid state at a temperature in the range from 25 to 300 ° C, preferably from 100 to 300 ° C, most preferably from 150 to 250 ° C

Mixing is carried out at a temperature in the range from 25 to 300 ° C., preferably from 100 to 300 ° C., most preferably from 150 to 250 ° C., in which the nonpolymerizable liquid substance (B) remains in a liquid state,

The thermoplastic resin (A) is thereby dissolved or swelled in at least one nonpolymerizable liquid substance (B).

Regarding the thermoplastic resin (A) and the nonpolymerizable liquid material (B), when the nonpolymerizable liquid material (B) is adsorbed or absorbed by the thermoplastic resin (A), the resin composition is a part of the thermoplastic resin (A) is powdered. It exists in the form of a resin composition, and since the molded resin body manufactured from the said resin composition has a rough surface, and the mechanical property of the molded resin body manufactured from the said resin composition becomes low, it is disadvantageous. In the present invention, a mixture of the thermoplastic resin (A) and the nonpolymerizable liquid material (B) (the thermoplastic resin (A) is dissolved or swelled in at least one nonpolymerizable liquid material (B)) is continuously operated at a temperature within the above range. Or batchwise.

A resin composition of the present invention which dissolves or swells the thermoplastic resin (A) in at least one nonpolymerizable liquid material (B) and a resin composition which adsorbs or absorbs the nonpolymerizable liquid material (B) in the thermoplastic resin (A) (the The difference between the resin composition, which is often then simplified as the "adsorption / absorption composition") is described below.

In the case of the resin composition of the present invention, when the resin composition is placed in the container and the container is tilted, the resin composition flows along the inner surface of the container. On the other hand, in the case of the adsorption / absorption resin composition, the resin composition is in powder form or in the form of a solid mass. Therefore, when the resin composition is placed in the container and the container is tilted, the resin composition does not flow.

On the other hand, in the resin composition of the present invention, the non-polymerizable liquid material (B) dissolves the thermoplastic resin (A) in at least one non-polymerizable liquid material (B) at a mixing temperature selected within a range of 25 to 300 ° C. As long as it swells, the non-polymerizable liquid substance (B) may be in a state of being adsorbed or absorbed by the thermoplastic resin (A) at a temperature lower than the temperature at which mixing of the thermoplastic resin (A) and the non-polymerizable liquid substance (B) is performed. For example, the adsorption / absorption composition as a masterbatch using polyphenylene ether resin (PPE) as the thermoplastic resin (A), and a resin (which may be the same as or different from the polyphenylene ether resin used in the resin composition). When molding a molding material consisting of the material, the resulting molded product has a large number of undissolved melts of PPE that have not experienced melting, so that the appearance of the molded product is poor. Additionally, while the resin composition undergoes the molten state during molding, the resulting molten product has an adversely high yellowness (YI) and an amount greater than 0.5 mole, relative to 100 moles of repeating oxymethylene units of polyphenylene ether resin. It has a hydroxyl group. On the other hand, the resin composition of the present invention and the polyphenylene used in the resin composition as a masterbatch {dissolves or swells the polyphenylene ether resin as the thermoplastic resin (A) in the non-polymerizable liquid material (B)}. When molding a molding material made of a resin material (which may be the same as or different from an ether resin), it is possible to obtain a molded article having an excellent appearance without undergoing the above disadvantageous phenomenon. In the present invention, when the temperature at which the mixing of the thermoplastic resin (A) and the nonpolymerizable liquid substance (B) is performed exceeds 300 ° C, each of the thermoplastic resin (A) and the nonpolymerizable liquid substance (B) undergoes thermal degradation. It should be noted that the resulting resin composition has poor mechanical strength, light stability and color tone.

As already mentioned above, in the present invention, the nonpolymerizable liquid substance (B) as an additive to the thermoplastic resin (A) is a substance in a liquid state at a temperature in the range of 25 to 300 ° C. The nonpolymerizable liquid substance (B) acts to impart the desired properties to the thermoplastic resin (A). When the molded resin body is obtained using the resin composition of the present invention, most of the nonpolymerizable liquid substance (B) usually used in the production of the resin composition of the present invention remains in the obtained molded body. The non-polymerizable liquid substance (B) is not included in the non-polymerizable liquid substance (B) as defined in the present invention.

In the present invention, the nonpolymerizable liquid substance (B) preferably has compatibility with the nonpolymerizable liquid substance. In the present invention, compatibility is defined as follows. 50 parts by weight of the particulate thermoplastic resin (A) and 50 parts by weight of the non-polymerizable liquid substance (B) having an average particle diameter of 15 μm to 1 mm are mixed and then stirred at a temperature of 200 ° C. for 1 hour. The resulting mixture is filtered using a glass filter having a pore diameter of 120 μm while maintaining the temperature of the mixture at 200 ° C. The weight of the mixture remaining in the glass filter is then measured. The ratio of the weight of the component (A) / component (B) mixture remaining in the glass filter to the compatibility of the thermoplastic resin with the nonpolymerizable liquid material (B) to the weight of the thermoplastic resin in the resin composition before filtration (% of filtration) It is defined as). In the present invention, the filtration residual ratio is preferably 50% or less, more preferably 30% or less, even more preferably 10% or less.

In the present invention, it is not preferable to use the additive used in the surface modification of the thermoplastic resin (hereinafter often referred to simply as "surface modifier") as the non-polymeric liquid material (B), as the additive is defined above. This is because it is poor in compatibility. Specific reasons for the above are as follows. With respect to surface modifiers, it is very important that the surface modifiers bleed during molding so that the surface modifiers are predominantly located in the surface portion of the resulting molded body so as to exhibit surface modification effects. Therefore, surface modifiers are necessary to have low compatibility with the resin. In the case of obtaining the resin composition using the surface modifier, it is necessary to carry out hot melt processing, thereby deteriorating the resin and the additive. In addition, in order to obtain a resin composition containing a high content of the surface modifier, it is necessary to carry out melt processing, particularly at very high temperatures. Therefore, as defined above, it is not preferable to use surface modifiers as nonpolymerizable liquid substance (B). However, the surface modifiers can be used in conjunction with another nonpolymeric material (B) to avoid the above disadvantages associated with the use of surface modifiers. In this case, the compatibility between the thermoplastic resin (A) and the mixture of the surface modifier and the other nonpolymerizable liquid substance (B) is preferably used in the amount of 50% or less with respect to the filtration residual ratio. Specifically, the amount of surface modifier is preferably 30% by weight, more preferably 20% by weight or less, even more preferably 10% by weight or less, relative to the weight of the other nonpolymerizable liquid material (B).

On the other hand, the conventional additives used for improving the flame retardancy, fluidity and the like of the thermoplastic resin have satisfactorily high compatibility with the thermoplastic resin (A) and can dissolve the thermoplastic resin (A) at a relatively low temperature. Therefore, when the additive is used as the nonpolymerizable liquid substance (B), thermal degradation of the thermoplastic resin can be controlled. As another index for evaluating the compatibility of the nonpolymerizable material (B) with the thermoplastic resin (A), a solubility parameter SP can be mentioned. In the present invention, the difference between the SP value of the thermoplastic resin and the SP value of the non-polymerizable liquid substance (B) is preferably 3 or less, more preferably 2 or less, most preferably 1 or less.

In the present invention, the solid material (C) is a material which is a crystalline solid or an amorphous solid at a temperature of 300 ° C. or less. In the case of the nonpolymerizable liquid substance (B), the solid substance (C) functions to impart desired properties to the thermoplastic resin (A). The solid material (C) is used in an amount such that satisfactory compatibility between the non-polymeric material (B) and the thermoplastic resin (A) does not adversely affect.

In the present invention, the resin composition of the present invention is prepared using a solvent (D) capable of decomposing or swelling the thermoplastic resin (A) in order to improve the compatibility of the nonpolymerizable material (B) with the thermoplastic resin (A). . Specifically, in this case, the above-described mixing of the thermoplastic resin (A) and the non-polymerizable material (B) is carried out in the presence of the solvent (D) in the resin composition of the present invention, and after mixing, the solvent (D) is removed. It can manufacture. Regarding the solvent (D), 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and still more preferably 5 to 20 parts by weight of the solvent (D) are used relative to the thermoplastic resin (A). In order to achieve the desired compatibility of the non-polymeric material (B) and the thermoplastic resin (A), the difference in the SP value between the thermoplastic resin (A) and the solvent (D) and the SP between the non-polymerizable liquid (B) and the solvent (D), respectively The difference in teeth is 3 or less, more preferably 2 or less, even more preferably 1 or less. Furthermore, it is preferable that the solvent (D) has a boiling point that is higher than the temperature at which the mixing of the thermoplastic resin (A) and the nonpolymerizable liquid substance (B) is carried out to 300 ° C or lower.

In the present invention, it is preferable to perform mixing of the thermoplastic resin (A) and the nonpolymerizable liquid substance (B) in the absence of a polymerizable compound, such as a vinyl monomer. When mixing is carried out in the presence of a polymerizable compound, the compound is liable to be grafted onto the thermoplastic resin or to cause a crosslinking reaction, resulting in disadvantages such as changes in the intrinsic properties of the thermoplastic resin (A) or of the thermoplastic resin (A). It leads to a deterioration of the thermoplastic.

The resin composition of the present invention can be advantageously used as a masterbatch for producing a molding material for melt extrusion, wherein the masterbatch is added to a resin material which may be the same as or different from the thermoplastic resin (A) used in the resin composition. The molding materials can be advantageously used for the production of various molded articles, such as injection molded articles (eg casings or internal parts for OA machines, household appliances, etc.), films, sheets and foamed articles.

Hereinafter, the components of the composition of the present invention will be described in detail.

In this invention, it is preferable that a thermoplastic resin (A) shows high compatibility with a nonpolymerizable liquid substance (B). Examples of the thermoplastic resin (A) include polyphenylene ether resin, polystyrene resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyolefin resin, polyamide resin, polymethacrylate resin, polyacetal resin , Polyarylate resins, polysulfone resins, polyether imide resins, polyether sulfone resins, polyether ether ketones and the like. In the present invention, examples of the thermoplastic resin (A) also include thermoplastic elastomers having the same polymer structure as those of the above optional thermoplastic resins.

Regarding the index for selecting a thermoplastic resin preferred as the thermoplastic resin (A), when the amorphous polymer is used as the thermoplastic resin (A), the glass transition temperature (Tg) can be used as the index, and the crystalline polymer is used as the thermoplastic resin (A). When used as), the melting temperature (Tm) can be used as an index. The glass transition temperature (Tg) of the amorphous polymer or the melting temperature (Tm) of the crystalline polymer is preferably at least 85 ° C, more preferably at least 100 ° C. When an amorphous polymer having a glass transition temperature (Tg) of less than 85 ° C or a crystalline polymer having a melting temperature (Tm) of less than 85 ° C is used as the thermoplastic resin (A), the advantages of the present invention in the conventional melt extrusion method The reason for not being large is that the thermoplastic resin having the very low glass transition temperature (Tg) or the very low melting temperature (Tm) can be melt processed or melt molded at a low temperature. On the other hand, when an amorphous polymer having a glass transition temperature (Tg) of 85 ° C. or higher or a crystalline polymer having a melting temperature (Tm) of 85 ° C. or higher is used as the thermoplastic resin (A), the conventional melt extrusion method This is notable because the thermoplastic resin having the very high glass transition temperature (Tg) or the very high melting temperature (Tm) can be melt processed or melt molded at a high temperature. That is, a resin composition containing a thermoplastic resin having a very high glass transition temperature (Tg) or a very high melting temperature (Tm) is subjected to a conventional melt extrusion method, and each thermoplastic resin and its additives inevitably undergo thermal degradation. Suffer. As mentioned above, in the present invention, there is no need for melt processing at a high temperature, and therefore there is no danger of thermal degradation.

Preferred examples of the thermoplastic resin (A) include polyphenylene ether resins, polystyrene resins and polycarbonate resins. Examples of polystyrene resins include rubber modified styrene polymers. A particularly preferred example of the thermoplastic resin (A) is a polymer mixture of a polyphenylene ether resin and a polystyrene resin, because it exhibits excellent solubility in the nonpolymerizable liquid substance (B).

It is preferable that the thermoplastic resin (A) used by this invention is resin which does not experience melt processing. For example, after completion of the preparation of the polyphenylene ether resin, the polyphenylene ether resin is obtained in the form of a solution or slurry containing the polyphenylene ether resin, not in a molten state. If the thermoplastic resin produced in the above non-melt state is used as the thermoplastic resin (A), before use, it does not experience melt processing in which the thermoplastic resin is brought into the molten state as defined above. On the other hand, after completion of the preparation of the polystyrene resin, the polystyrene resin is obtained in a molten state; The production method for producing the thermoplastic resin in the molten state is excluded from the category of melt processing mentioned herein.

Regarding the form of the thermoplastic resin (A) used in the present invention, there is no particular limitation. However, from the viewpoint of improving the solubility of the thermoplastic resin (A), the thermoplastic resin (A) is a powder having a number average particle diameter of 0.01 to 10,000 μm, more preferably 0.1 to 1,000 μm, still more preferably 1 to 100 μm. desirable. When the number average particle diameter of the thermoplastic resin (A) is less than 0.01 µm, aggregation of the thermoplastic resin particles is likely to occur, so that the handleability and the quality of the thermoplastic resin are deteriorated. On the other hand, when the number average particle diameter of the thermoplastic resin (A) is more than 10,000 µm, the dissolution rate of the thermoplastic resin (A) into the nonpolymerizable liquid substance (B) is lowered, so that a part of the thermoplastic resin particles (that is, Cosmetic melt of the resin) tends to remain intact in the resin composition, thereby lowering the appearance and mechanical properties of the final molded article.

In the present invention, polyphenylene ethers which can be used as thermoplastic resins (A), hereinafter often referred to simply as "PPE", are homopolymers and / or copolymers consisting of a plurality of polymer chains, each of which It consists of repeating oxyphenylene units represented by:

[Wherein, each of R ¹ , R ² , R ³ and R ⁴ independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group.].

R ¹ , R ² , R ³ and R ⁴ may be the same or different.

Specific examples of polyphenylene ethers include copolymers of poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethyl phenol and 2,3,6-trimethyl phenol, and the like. Of these, poly (2,6-dimethyl-1,4-phenylene ether) is preferred. The method for producing the PPE is not particularly limited. For example, PPE can be readily prepared by the method described in US Pat. No. 3,306,874 which oxidizes, for example, 2,6-xylenol using a complex of copper (I) salt and amine as catalyst. In addition, the PPE can also be easily produced by other methods described, for example, in US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Office 52-17880, Japanese Patent Application No. 50-51197. . The reduced viscosity ηsp / c (measured at 0.5 g / dl of chloroform solution at 30 ° C.) of PPE used in the present invention is preferably in the range of 0.20 to 0.70 dl / g, more preferably 0.30 to 0.60 dl / g. As a method for achieving the above range of the reduced viscosity of the polyphenylene ether, a method of properly selecting the amount of the catalyst used in the preparation of the polyphenylene ether can be mentioned.

Examples of the polystyrene resin to be used as the thermoplastic resin (A) include a rubber modified styrene polymer.

The rubber modified styrene polymer consists of an aromatic vinyl polymer as the continuous phase and rubber particles dispersed above as the dispersed phase. The rubber-modified styrene polymer can be copolymerized on the rubber polymer, using conventional methods such as bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization, to copolymerize aromatic vinyl monomers and optionally aromatic vinyl monomers. Obtained by graft polymerization of comonomers.

Examples of rubber modified styrene polymers are so-called high impact polystyrenes (hereinafter often referred to as "HIPS"), ABS resins (acrylonitrile / butadiene / styrene copolymers), AAS resins (acrylonitrile / butyl acrylate rubbers / styrene air) Copolymer), AES resin (acrylonitrile / ethylene-propylene rubber / styrene copolymer) and the like.

Regarding the rubber polymer used in the production of the rubber modified styrene polymer, it is preferable that the rubber polymer has a glass transition temperature (Tg) of -30 ° C or lower. If the rubber polymer has a glass transition temperature greater than -30 ° C, the improvement in impact resistance may in some cases be unsatisfactory.

Examples of suitable rubber polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene); Saturated rubber obtained by hydrogenation of the diene rubber; Isoprene rubber; Chloroprene rubber; Acrylic acid rubbers such as polybutyl acrylate; And ethylene / propylene / diene terpolymers (EDPM). Diene rubber is particularly preferred.

Preferred examples of the rubber polymer and graft polymerizable aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-bromostyrene and 2,4,5-tribromostyrene . Styrene is most preferred, but styrene may be used for copolymerization with the other aromatic vinyl monomers.

As above, one or more vinyl comonomers copolymerizable with aromatic vinyl monomers may be introduced into the rubber modified styrene polymer. As one or more vinyl comonomers copolymerizable with aromatic vinyl monomers, unsaturated nitrile monomers such as acrylonitrile or methacrylonitrile can be used to obtain rubber modified styrene copolymers with good oil resistance. Moreover, in order to lower the melt viscosity of an aromatic vinyl monomer, the acrylate comonomer which has a C1-C8 alkyl group can be used. In addition, other comonomers such as α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like may be used to improve the heat resistance of the final resin composition.

When aromatic vinyl monomers are used in the form of monomer mixtures with comonomers, the amount of vinyl monomer copolymerizable with aromatic vinyl monomers in the monomer mixture is usually in the range of 0 to 40% by weight.

In the present invention, the content of the rubber polymer in the rubber modified styrene polymer is preferably in the range of 5 to 80% by weight, more preferably 10 to 50% by weight. The content of comonomers copolymerizable with aromatic vinyl monomers in the rubber modified styrene polymer is preferably in the range of 95 to 20% by weight, more preferably 90 to 50% by weight. When the content of the rubber polymer and the comonomer in the rubber modified styrene polymer is within the above range, a good balance of impact resistance and rigidity can be achieved with respect to the final molded product. The diameter of the rubber particles in the rubber modified styrene polymer is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm. When the rubber particle diameter is in the above range, the impact resistance is particularly improved.

Regarding the rubber modified styrene polymer, the reduced viscosity ηsp / c (measured at 0.5 g / dl of the solution at 30 ° C.) of the solvent soluble material, which is a measure of the molecular weight, is preferably 0.30 to 0.80 dl / g, more preferably 0.40 to 0.60 dl / In the range of g, where toluene is used as the solvent when the styrene polymer is a polystyrene resin, methyl ethyl ketone is used as the solvent when the styrene polymer is an unsaturated nitrile / aromatic vinyl copolymer. In the preparation of rubber modified styrene polymers, the reduced viscosity ηsp / c can be controlled by the choice of the type and amount of initiator, the polymerization temperature and the amount of chain transfer agent.

The aromatic polycarbonate used as the thermoplastic resin (A) in the present invention can be selected from aromatic homopolycarbonates and aromatic copolycarbonates. Examples of the method for producing an aromatic polycarbonate include a phosgene method of blowing phosgene into a bifunctional phenolic compound in the presence of a caustic alkali and a solvent, and, for example, a difunctional phenolic compound and di And transesterification method of transesterifying ethyl carbonate. The preferable range of the viscosity average molecular weight of aromatic polycarbonate is 10,000 to 100,000.

Examples of difunctional phenolic compounds include 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxy Hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxy-3,5 -Diphenyl) butane, 2,2'-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclohexane and 1-phenyl-1, 1'-bis (4-hydroxyphenyl) ethane. Especially preferred is 2,2'-bis (4-hydroxyphenyl) propane (ie bisphenol A). In the present invention, difunctional phenolic compounds may be used alone or in combination.

The nonpolymerizable liquid substance (B) used in the present invention is a component that acts as an additive to the thermoplastic resin (A) for imparting desired properties, such as flame retardancy, to the thermoplastic resin (A). In the present invention, it is necessary for the nonpolymerizable liquid substance (B) to be in a liquid state and flowable at a temperature in the range of 25 to 300 ° C. Regarding the viscosity of the non-polymerizable liquid substance (B), it is preferable that the viscosity measured at a temperature of 100 ° C. is 1,000,000 centistokes or less, more preferably 100,000 centistokes or less, most preferably 10,000 centistokes or less. When a nonpolymerizable liquid substance (B) having a viscosity of 10,000 centistokes or less is used, the thermoplastic resin (A) can be dissolved well in the nonpolymerizable liquid substance. In order to achieve a viscosity of 10,000 centistokes or less, it is preferred that the nonpolymerizable liquid substance (B) is a compound having a molecular weight of 1,000 or less. The nonpolymerizable substance is a polymer or oligomeric compound.

As described above, the non-polymerizable liquid substance (B) used in the present invention is an additive such as a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant, a colorant, a foaming agent, a lubricant, a flavoring agent, a fuming inhibitor, a tackifier, and a preservative. It acts as a warming agent, impact strength improver, repellent, wetting agent, surfactant, emulsifier, destabilizer, coagulant, antifoaming agent, cryoprotectant, creaming agent, thickener, heat reducing agent and foaming agent. In the present invention, as the non-polymerizable liquid substance (B), a plasticizer, a heat stabilizer, a flame retardant or a light stabilizer is used in view of the high compatibility of the thermoplastic resin (A) with the additive.

Regarding the amount of the nonpolymerizable liquid substance (B) used in the resin composition of the present invention, the amount of the nonpolymerizable liquid substance (B) is preferably 1 to 99% by weight, more preferably 10 to 90, based on the weight of the resin composition. % By weight, even more preferably 20 to 80% by weight, most preferably 30 to 70% by weight.

Examples of plasticizers used as nonpolymerizable liquid substance (B) include phthalic acid esters such as dimethyl phthalate, diethyl phthalate and diisobutyl phthalate; Phthalic acid containing esters such as butylbenzyl phthalate; Aliphatic dibasic acid esters such as diisodecyl succinate and dioctyl adipate; Glycol esters such as diethylene glycol dibenzoate; Aliphatic acid esters such as butyl oleate and methyl acetylrisinolate; Epoxy compounds such as epoxidized soybean oil and epoxidized linseed oil; Trioctyl trimellitate; Ethylphthalylethyl glycolate; Butylphthalylbutyl glycolate; Tributyl acetyl citrate; Chlorinated paraffins; Polypropylene adipate; Polyethylene sebacate; Triacetin; Tributyrin; Toluenesulfonamide; Alkylbenzenes; Biphenyls; Partially hydrogenated terphenyls; And camphor.

Examples of the thermal stabilizer to be used as the nonpolymerizable liquid substance (B) include metal soaps, lead stabilizers, organotin stabilizers, composite stabilizers and epoxy compounds.

Examples of light stabilizers used as nonpolymerizable liquid substances (B) include ultraviolet absorbers, hindered amine light stabilizers, antioxidants, active species trapping agents, light blocking agents, metal inerts and quenchers. .

Examples of flame retardants used as nonpolymerizable liquid substances (B) include halogen-containing flame retardants and phosphorus-containing flame retardants. With regard to the phosphorus-containing flame retardant, organophosphorus compounds are particularly preferred.

Examples of organophosphorus compounds include phosphine, phosphine oxide, bisphosphine, phosphonium salts, phosphinates, phosphate esters and phosphite esters. More specific examples of the organophosphorus compound include triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyldiphosphate, and dish Clopentyl hypodiphosphate, dinopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypodiphosphate.

Regarding the organic phosphorus compound used as the nonpolymerizable liquid substance (B), from the viewpoint of compatibility with the thermoplastic resin, it is preferable to use the monomeric aromatic phosphate ester represented by the following formula (1) and the oligomeric aromatic phosphate ester represented by the following formula (2). :

[Formula 1]

[Formula 2]

[Wherein each Ar^One, Ar², Ar³, Ar⁵And Ar⁶Is independently one or more C_One-C₁₀C unsubstituted or substituted with hydrocarbon groups₆-C₂₀Monovalent aromatic groups (such as phenyl groups); Ar⁴C₆-C₂₀A divalent aromatic group; Each n is identical to each other and represents an integer of 0 to 3; m is an integer of 1 or more].

Regarding the monomeric aromatic phosphate ester of the general formula (1), hydroxyl group-containing monomeric aromatic phosphate esters such as those having at least one phenolic hydroxyl group (for example, tricresylphosphate and triphenyl phosphate) and represented by the following general formula (4) Monomer aromatic phosphate esters are preferred:

[Wherein, a, b and c each independently represent an integer of 1 to 3, and each of R ¹ , R ² and R ³ independently represents a hydrogen atom or a C _{1 to} C ₃₀ alkyl group].

When using a plurality of different compounds of formula 4, the sum of the individual carbon numbers of the substituents R ¹ , R ² and R ³ is preferably on average 12 to 30, more preferably 15 to 30, even more preferably 20 to 30, The average here is the sum of the values obtained by multiplying the individual weight percents of the different compounds of formula 4 by the respective total number of carbon atoms of R ¹ , R ² and R ³ in the different compounds of formula 4.

Specific examples of the substituents R ¹ , R ² and R ³ include nonyl, butyl (eg t-butyl), t-amyl, hexyl, cyclohexyl, heptyl, octyl, decyl, Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonnodecyl group and octadodecyl group. With regard to the substitution of the compound of formula 4, one or more substituents may be bonded to the aromatic ring of formula 4 at any one or more positions selected from the group consisting of ortho-position, meta-position and para-position. Among these, the para position is preferable. In the compound of the formula (4), it is preferable that the sum of the individual carbon numbers of the substituent alkyl groups is 12 to 30. Compared to the compound of the formula (4) having only one aromatic ring substituted with only one long chain alkyl group, each substituted with an alkyl group (its carbon number is smaller than that of the long chain alkyl group) is excellent in terms of heat resistance and water resistance. For example, with respect to octadecylphenyldiphenyl phosphate and bis (nonylphenyl) phenyl phosphate, the sum of the number of carbon atoms of the alkyl group or alkyl groups in each of the above is 18, and the latter is preferable in view of high heat resistance.

In the present invention, among the monomeric aromatic phosphate esters represented by the general formula (4), from the viewpoint of high fluidity and low volatility, it is particularly preferable that at least one of R ¹ , R ² and R ³ is a nonyl group, and each of R ¹ , R ² and Most preferably R ³ is a nonyl group [ie, tris (nonylphenyl) phenyl phosphate].

In particular, when the flame retardant used as the non-polymerizable liquid substance (B) contains the formula (4) in an amount of 50% by weight or more based on the weight of the flame retardant, the flame retardant exhibits excellent ability to impart flame retardancy to the thermoplastic resin. In addition, the compounds of formula 4 have high anti-dropping properties and exhibit particularly good self-extinguishing properties in flame retardants at the "V-2" level in the flame retardancy evaluation according to UL-Subject 94.

Further, for a flame retardant composed of a single compound of formula 4 or a flame retardant composed of a plurality of different compounds of formula 4, the flame retardant when the sum or sum of the individual carbon numbers of R ¹ , R ² and R ³ is within the above individual range Indicates low volatility. With regard to flame retardants consisting of a number of different compounds of formula 4, when the content of compounds of formula 4 in which the sum of the individual carbon numbers of R ¹ , R ² and R ³ is less than 12 is less than 1% by weight, the flame retardants exhibit particularly good low volatility Indicates.

In order to achieve satisfactory thermal stability of the flame retardant consisting of at least one compound of the formula (4), in particular in terms of thermochromic resistance, the content of impurities in the compound of the formula (4) is as low as possible. Specifically, the acid value of the flame retardant measured according to JIS-K6751 (the acid value is used as an indicator for the amount of acidic substance remaining in the flame retardant) is preferably 1 mg KOH / g or less, more preferably 0.5 mg KOH / g or less And / or the content of alkylphenols in the flame retardant is preferably 1% by weight, more preferably 0.5% by weight. In addition, the content of aluminum, magnesium, sodium and antimony in the flame retardant is preferably 1,000 ppm or less. In addition, especially the flame retardant contains 1 to 1,000 ppm by weight of hindered phenolic antioxidant, with respect to the weight of the flame retardant, and the flame retardant exhibits very improved thermal stability.

In flame retardants consisting of one or more compounds of formula (4), substituents R ¹ , R ² and R ³ are all alkyl groups. When the aryl group is used as the substituents R ¹ , R ² and R ³ instead of the alkyl group, the light stability of the flame retardant is lowered. With regard to the alkyl groups used in the compounds of the formula (4), the amount of the branched structure is preferably as small as possible. It is particularly preferred that the alkyl group has a straight chain structure or a chain structure with only one branch.

With respect to the compound of formula 4, it is preferred that each aromatic ring has only one substituent bonded thereto. When a large number of substituents are bonded to an aromatic ring, the viscosity of the compound of formula 4 becomes high. The greater the number of substituents bonded to the aromatic ring, the higher the viscosity of the compound of formula (4). If the viscosity of the compound of formula 4 is too high, various disadvantages arise, which makes the compound difficult to handle and also makes it difficult to purify the compound, thereby increasing the content of the impurity in the compound of formula 4, whereby the compound of formula 4 Properties, such as photostability and heat discoloration resistance, are lowered.

Specific examples of flame retardants composed of many different compounds of formula 4 include flame retardants consisting primarily of tris (nonylphenyl) phosphate (TNPP) and small amounts of bis (nonylphenyl) phenyl phosphate (BNPP), wherein the substituents R ¹ , The sum of the individual carbon numbers of R ² and R ³ is on average 20 to 27, preferably 25 to 27, more preferably 26 to 27, most preferably 26.5 to 27. In order to obtain the flame retardant, for example, the content of BNPP in the flame retardant is 78 to 0% by weight, preferably 22 to 0% by weight, more preferably 11 to 0% by weight, most preferably 5 to 0% by weight. It is recommended that the content of, and TNPP is 22 to 100% by weight, preferably 78 to 100% by weight, more preferably 89 to 100% by weight, most preferably 95 to 100% by weight. The use of the flame retardant consisting of TNPP and BNPP in the resin composition of the present invention not only provides excellent fluidity to the resin composition, but also provides excellent balance of various properties such as flame retardancy, thermal stability, impact strength, water resistance, gloss retention and surface hardness. It is advantageous to obtain the final molded resin having. In addition, the use of TNPP not only means that it has low volatility, but it also imparts excellent thermal stability, water resistance and gloss retention (achievement of excellent gloss retention due to the symmetrical structure of TNPP) to the final molded resin body. It is advantageous in that it can. Therefore, TNPP is particularly preferable as the nonpolymerizable liquid substance (B) in the resin composition of the present invention.

Regarding the preparation method of the compound of the formula (4), various known methods, for example, the methods described in Japanese Patent Laid-Open No. 1-95149 and Japanese Patent Laid-Open No. 3-294284 can be mentioned. Specifically, a method of reacting an alkylphenol with phosphorus oxychloride while heating the compound of formula 4 in the presence of, for example, aluminum chloride anhydride as a catalyst, and phosphite triesters are oxidized with oxygen, thereby phosphite tri It can be obtained by converting the ester to the corresponding aromatic phosphite ester.

Regarding the oligomeric aromatic phosphate ester represented by the above formula (2), from the viewpoint of hydrolysis resistance and thermal stability, the compound of formula (2) in which Ar ⁴ is a divalent group derived from a phenyl group or a diarylalkane is preferable. Specific examples of the compound of Formula 2 include bisphenol A bis (diphenylphosphate) and bisphenol A bis (dicresylphosphate).

In addition, preferred examples of the compound of formula (2) include oligomeric aromatic phosphate esters represented by the following formula (5):

[Wherein each a, b, c, d and e independently represent an integer of 0 to 3; Each R ¹ to R ⁵ independently represents a C ₁ to C ₁₀ hydrocarbon group; n represents an integer of 1 to 3].

Regarding the oligomeric aromatic phosphate ester represented by the formula (5), a is 0; Each of b, c, d and e is 2; It is preferable that the substituted position of each disubstituted aromatic ring is 2 and 6 positions. The compound of formula 5 having a disubstituted aromatic ring is in a solid state at room temperature; Since the rate of crystallization of the compound is relatively small, the compound is liquefied by addition of another nonpolymeric liquid material such as TNPP, which is liquid at room temperature. The compound of formula (5) having a disubstituted aromatic ring can be produced by a known method, such as the method described in Japanese Patent Laid-Open No. 5-1079. Specifically, the compound of formula 5 having a di-substituted aromatic ring is reacted with, for example, a monofunctional phenol substituted with a C ₁ -C ₁₀ hydrocarbon group at the 2 and 6 positions of the phenol with a phosphorus oxyhalogenated phosphorus in the presence of a Lewis acid catalyst. After obtaining a phosphoro halide, the obtained diarylphospho halide can be prepared by a reaction with a bifunctional phenol in the presence of a Lewis acid catalyst.

Examples of blowing agents for use as the nonpolymerizable liquid substance (B) include azo blowing agents, N-nitroso blowing agents and sulfonylhydrazines.

Examples of lubricants used as nonpolymerizable liquid substances (B) include hydrocarbon lubricants such as liquid paraffin; Fatty acid lubricants; Fatty amide lubricants; Alcohol lubricants; And metal soaps.

Further, in the present invention, even if the non-polymerizable liquid material (B) is in the form of powder or solid at a temperature in the range of 25 to 300 ° C., as long as it is soluble in the non-polymerizable liquid material (B), it is used as the non-polymerizable liquid material (B). Can be used and so liquefied at temperatures in the above range.

In the present invention, in order to improve compatibility between the thermoplastic resin (A) and the non-polymerizable liquid material (B), another non-polymerizable liquid material or a non-polymerizable liquid material (B) different from the non-polymerizable liquid material (B) Surfactants that interact with soluble or nonpolymerizable liquid substances (B) can be used as compatibilizers. Even solid surfactants that do not meet the requirements for nonpolymerizable liquid materials (B) can be used because of their solubility in the nonpolymerizable liquid materials (B).

In the present invention, the thermoplastic resin (A) (such as polyphenylene ether, etc.) is dissolved in an oligomeric non-polymerizable liquid substance which is at least a dimer (for example, aromatic phosphate ester condensation products, etc.) selected from various nonpolymerizable liquid substances (B). In this case, a resin composition having excellent appearance, light resistance and mechanical properties can be obtained in combination with a non-polymerizable liquid substance (such as TNPP, etc.) in the form of a monomer which also functions as a compatibilizer. The content of the nonpolymerizable liquid substance in monomeric form in the nonpolymerizable liquid substance (B) is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight, even more preferably 1 to 20% by weight, most preferably 2 to 10 Weight percent.

Examples of compatibilizers that can be used to improve the compatibility between the thermoplastic resin (A) and the nonpolymerizable liquid material (B) include aliphatic hydrocarbons, high fatty acids, high fatty amides and high fatty alcohols. The compatibilizer in the nonpolymerizable liquid material (B) is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the nonpolymerizable liquid material (B) and the compatibilizer. It is contained in an amount.

Examples of aliphatic hydrocarbons as compatibilizers include liquid paraffins, natural paraffins, microwaxes, polyolefin waxes and synthetic paraffins; Partial oxidation products thereof; Fluorides thereof; And chlorides thereof.

Examples of high fatty acids include saturated fatty acids; And unsaturated fatty acids such as ricinoleic acid, ricinoleic acid and 9-oxy-12-octadecenoic acid.

Examples of high fatty amides include saturated fatty monoamides such as phenylstearicamide, methylolstearicamide, methylolbehenamide; N, N'-2 substituted monoamides such as coconut oil fatty diethanolamide, lauric diethanolamide, oleic acid diethanolamide; Saturated fatty bisamides such as methylenebis (12-hydroxyphenyl) stearamide, ethylenebis (stearamide), ethylenebis (12-hydroxyphenyl) stearamide, hexamethylenebis (12-hydroxyphenyl) stearamide; And aromatic bisamides such as m-xylenebis (12-hydroxyphenyl) stearamide.

Examples of high fatty alcohols as compatibilizers include monohydric alcohols such as stearyl alcohol and cetyl alcohol; Polyhydric alcohols such as sorbitol and mannitol; Polyoxyethylene dodecylamine; Polyoxyethylene octadecylamine; Allylated ethers with polyalkylene ether units, such as polyoxyethylene allylated ethers; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene dodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Dihydric alcohols with polyoxyethylene units such as polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol ether, polyoxypropylene bisphenol A ether and polyoxyethylene polyoxypropylene glycol ether .

The solid substance (C) used in the present invention, which is a crystalline solid or an amorphous solid at a temperature of 300 ° C., imparts desired properties to the resin composition. The solid substance (C) is dispersed, swelled or dissolved in the thermoplastic resin (A) and the nonpolymerizable liquid substance (B). As for the form of the solid material (C), there is no particular limitation as long as the above requirements are satisfied. Examples of the solid substance (C) include anti-sticking agents, oil absorbing compounds, heat stabilizers and light stabilizers.

The amount of the solid substance (C) is preferably 0.000001 to 100 parts by weight, more preferably 0.01 to 20 parts by weight, most preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).

As the solid substance (C), the anti-sticking agent is a component used to improve the handleability (such as anti-deposition resistance) of the resin composition composed of the thermoplastic resin (A) and the non-polymerizable liquid substance (B). Examples of antifouling agents include organic acid metal salts such as metal soaps; Metal oxides; Inorganic acid salts; Wax; Inorganics such as silica, alumina, talc and diatomaceous earth; Metal, eg iron; Fibers such as cotton and pulp. The solid materials may be used alone or in combination. Among the solid materials, it is preferable to use a powdery material having a number average particle diameter of 0.01 to 300 μm. When using a powdery substance having a number average particle diameter of less than 0.01 μm, aggregation of the powdery substance is advantageously generated. When a powdery substance having a number average particle diameter of more than 300 µm is used, it is easy to reduce the dissolution rate of the thermoplastic material (A) into the nonpolymerizable liquid material (B).

Examples of organic acid metal salts as anti-sticking agents include lithium salts, copper salts, beryllium salts, magnesium salts, calcium salts, strontium salts, barium salts, zinc salts, cadmium salts, aluminum salts, cerium salts, and titanium salts of the following organic carboxylic acids. Salts, zirconium salts, lead salts, chromium salts, manganese salts, cobalt salts and nickel salts: straight saturated fatty acids such as butyric acid, n-caproic acid, pelagonic acid, n-capric acid, undecanoic acid, lauric acid, myristic acid , Palmitic acid, stearic acid and arachic acid; Straight chain unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid; Branched fatty acids such as isostearic acid; Hydroxyl group-containing fatty acids such as ricinolic acid and 12-hydroxystearic acid; Benzoic acid; Naphthenic acid; Abietic acid; And resinous acids of rosin, such as dextrosemaric acid.

Examples of metal oxides as anti-sticking agents include zinc oxide, alumina (aluminum oxide), aluminum silicate, silica (silicon oxide), calcium oxide, calcium carbonate, titanium oxide, iron oxide, barium oxide, manganese dioxide and magnesium oxide. Particularly preferred are the aluminas and silicas mentioned above as minerals.

Examples of inorganic acid salts as anti-sticking agents include barium titanate, barium sulfate, manganese carbonate, magnesium carbonate and calcium carbonate.

Examples of waxes as anti-sticking agents include organosiloxane waxes, polyolefin waxes and polycaprolactones.

As anti-stick agents, hydrophobic metal oxides such as hydrophobic silica and hydrophobic alumina are particularly preferred. To prepare hydrophobic metal oxides, the surface of the metal oxide may be coated with a silane coupling agent such as an alkylalkoxysilane or an alkyl halogenated silane; Polysiloxanes such as dimethylsiloxane; Synthetic Wax A chemical or physical treatment with natural wax, thereby deactivating the surface of the metal oxide.

The oil absorbent compound as the solid substance (C) is a component used by the thermoplastic resin (A) to improve dissolution into the nonpolymerizable liquid substance (B). It is preferable to use an oil-absorbing compound having a number average particle diameter of 0.001 to 1000 µm from the viewpoint of improving the dissolution properties of the thermoplastic resin (A) into the nonpolymerizable liquid substance (B). Examples of oil absorbing compounds include those made of powdery or porous powdery materials such as thermoplastics, thermosetting resins, metals, metal oxides, flame retardants, reinforcing agents and ceramics.

As one of the oil absorbing compounds as the solid substance (C), a thermoplastic resin of a substituent having an affinity for the nonpolymerizable liquid substance (B) can be mentioned. The thermoplastic resin preferably has a number average particle diameter of 0.001 to 1000 μm. The thermoplastic resins are unsaturated carboxylic esters such as alkyl (meth) acrylates; (Meth) acrylamides having hydrocarbon groups such as dialkyl (meth) acrylamides; α-olefins such as 1-hexene; Alicyclic vinyl compounds such as vinylcyclohexane; Allyl ethers having hydrocarbon groups, such as dodecyl allyl ether; Vinyl esters having hydrocarbon groups such as vinyl caproate; Vinyl ethers having hydrocarbon groups such as butyl vinyl ether; And at least one monomer (containing a polymerizable unsaturated group) selected from the group consisting of aromatic vinyl compounds such as styrene.

As the oil absorbing compound, the thermoplastic resin may include a small amount of a crosslinkable monomer having one or more polymerizable unsaturated groups containing thermoplastic. Examples of such crosslinkable monomers include (meth) acrylates of dihydric alcohols such as ethylene glycol di (meth) acrylate; (Meth) acrylates of polyhydric alcohols such as glycerol or tetramethylolmethane; And divinylbenzene.

Examples of thermosetting resins as oil absorbing compounds include aromatic vinyl monomers (such as styrene-divinylbenzene copolymers) and crosslinkable monomers having a plurality of unsaturated bonds; Copolymers of (meth) acrylate and the crosslinkable monomer; Phenolic resins; Melamine resins; Epoxy resins; Unsaturated polyester resins; Furan resin; Urea resins; Xylene-formaldehyde resins; Silicone resins; Diallyl phthalate resin; And aramids.

In the present invention, in order to improve the compatibility between the thermoplastic resin (A) and the non-polymerizable liquid material (B) during mixing, the mixing between the components (A) and (B) may be carried out by the high compatibility between the components (A) and (B). It is preferable to carry out in the presence of a solvent (D) having and after mixing, the solvent (D) is removed from the mixture in which the component (A) is dissolved or swelled in the component (B).

Examples of the solvent (D) include hydrocarbons, halogenated hydrocarbons, alcohols, phenols, ethers, acetals, ketones, fatty acids, acid anhydrides, esters, nitrogen compounds, sulfur compounds, and inorganic solvents. The amount of the solvent (D) is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, most preferably 5 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin (A).

Among the above solvents, it is preferred that they are selected from ethers, acetals and hydrocarbons and have a boiling point in the range from 200 to 300 ° C. Examples of ethers include diphenyl ether and butyl phenyl ether. Examples of acetals include 1,1-diethoxyethane and 2,2-diethoxypropane. Examples of hydrocarbon solvents include pentane, 2-methyl butane, hexene, 2-methyl pentane, 2,2-dimethyl butane, 2,3-dimethyl butane, heptane, octane, 2,2,3-trimethyl pentane, isooctane, nonane, 2,2,5-trimethyl hexane, decane, dodecane, unsaturated aliphatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, amylbenzene, isopropylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene, p- Cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, biphenyl, cyclopentane, mitelcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-mentane, bicyclohexyl, Cyclohexene, α-pinene, dipentene, decalin, petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, kerosene, solvent naphtha, camphor oil, terpentine oil, pine oil and the like. Among them, those having a boiling point at 200 to 300 ° C, such as amylbenzene, cyclohexylbenzene, dodecylbenzene, fine oil and biphenyl, are preferable.

When the resin composition of the present invention is intended to be produced in the form of pellets, the nonpolymerizable liquid substance (B) is heated, the thermoplastic resin (A) and the nonpolymerizable liquid substance (B) are mixed while heating, and the product is cooled. Preference is given to using a method of post-pelletization. In this method, it is necessary to carry out the heating at a temperature in the range of 25 to 300 ° C.

It is preferable to perform mixing of a thermoplastic resin (A) and a nonpolymerizable liquid substance (B) using a dissolution tank equipped with a stirrer or an extruder while heating. Regarding the mixing method using an extruder, the method is different from the conventional melt extrusion method in that a thermoplastic resin dissolved in or swelled with a liquid additive is supplied to the extruder. Regarding the cooling and pelletizing method of the resin composition comprising the components (A) and (B), the resin composition is passed through a cooling water tank and the cooled resin composition is pelleted using a pelletizing agent equipped with a rotary cutter (see FIG. 1). And a pelletization can be carried out using a conveyor belt cooler (developed by Sandvik Co., Sweden) with a cooling system (see FIG. 2).

Regarding the extruder used for mixing the thermoplastic resin (A) and the nonpolymerizable liquid substance (B), there is no particular limitation, and the components (A) and (B) are mixed under an appropriate shearing force for a suitable existence time so that the optional component (A) And conventional extruders for melt extrusion, as long as component (A) is dissolved or swelled in component (B) without bringing (B) into a molten state (as defined in the present invention).

Another preferred embodiment of the method for producing the resin composition of the present invention is a method in which the heating and melting of the nonpolymerizable liquid substance (B) is carried out simultaneously with the heat mixing of the thermoplastic resin (A) and the nonpolymerizable liquid substance (B). Specifically, in the above preferred embodiment, the non-polymeric material (B) is added to the dissolution tank and heated at a temperature in the range of 25 to 300 ° C. and the thermoplastic resin (A) is added thereto with gradual stirring to add the component (A) to the component. It is dissolved or swelled in (B) and the product is cooled and then pelletized. It is preferable to carry out the mixing of the components (A) and (B) in the presence of an organic solvent (D) and to remove the organic solvent (D) after mixing.

The thermoplastic resin composition of the present invention can be used as it is, for example, as a molding material for use in injection molding. Instead, the resin composition can also be used as a masterbatch for the production of molding materials, wherein the masterbatch is added to the same or different thermoplastic resin material as the thermoplastic resin (A) and the resulting mixture is for example in the range of 100 to 300 ° C. Melt extrusion at temperature. In this case, various liquid and solid additives may also be added together with the masterbatch, wherein the liquid and solid additives may comprise the same as the non-polymeric liquid material (B) and the solid material (C). .

Regarding the selection criteria of the appropriate combination of the thermoplastic resin (A) used in the masterbatch and the thermoplastic resin material melt-extruded with the masterbatch, in the case of the amorphous polymer, it can be selected according to its glass transition temperature (Tg), and the crystalline polymer In the case of, it can be selected according to the melting temperature (Tm). Tg and Tm of the thermoplastic resin (A) used in the masterbatch are preferably at least 100 ° C, more preferably at least 140 ° C, most preferably at least 200 ° C. On the other hand, the Tg or Tm of the thermoplastic resin material melt-extruded with the masterbatch is preferably 85 to 200 ° C, more preferably 85 to 120 ° C. When both the thermoplastic resin (A) used in the masterbatch and the thermoplastic resin material melt-extruded with the masterbatch satisfy the above individual preferred range of Tg or Tm, the effect of the present invention is most remarkable.

There is no particular limitation regarding the thermoplastic resin melt-extruded together with the masterbatch which comprises the resin composition of this invention. Examples of the thermoplastic resin include polystyrene resin, polyphenylene ether resin, polyolefin resin, polyvinyl chloride resin, polyamide resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polymethacrylate resin, polyacetal Resins, polyarylate resins, and polysulfone resins. The said thermoplastic resin can be used individually or in mixture. Of the thermoplastic resins, polystyrene resins and polycarbonate resins are preferable. Examples of polystyrene resins include rubber modified styrene polymers.

In the present invention, various solid materials can be added to the masterbatch constituting the resin composition of the present invention. Examples of solid materials include flame retardants, flame retardant aids, thermoplastic elastomers, antioxidants, heat stabilizers (such as tin compound type heat stabilizers), light resistance improvers, flow improvers, lubricants, fillers, reinforcing agents (such as glass, other than non-polymeric liquid materials (B)). Fibers), colorants (such as dyes or pigments), blowing agents, antistatic agents and release agents. A detailed description of the solid material that can be added to the masterbatch is then provided.

Examples of flame retardants other than the nonpolymerizable liquid substance (B) include halogen-containing flame retardants, phosphorus-containing flame retardants and inorganic flame retardants.

Specific examples of halogen-containing flame retardants include bisphenol halides, aromatic halides, polycarbonate halides, aromatic vinyl polymer halides, cyanurate halide-containing resins and polyphenylene ether halides. Among the above, decabromodiphenyl oxide, tetrabromobisphenol A, oligomer of tetrabromobisphenol A, bisphenol bromide-containing phenoxy resin, bisphenol bromide-containing polycarbonate, polystyrene bromide, crosslinked polystyrene bromide, polyphenylene jade Seed bromides, polydibromophenylene oxides, condensation products of decabromodiphenyl oxide bisphenols, halogen-containing phosphates, fluororesins and the like are preferred.

Examples of phosphorus-containing flame retardants include red phosphorus, inorganic phosphates and the like.

Examples of red phosphorus flame retardants typically include red phosphorus products as well as red phosphorus products coated with a coating of one or more metal hydroxides selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. As another red phosphorus product, mention may be made of a coating with a coating consisting of a mixture of a metal hydroxide and a thermosetting resin (selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide). As another red phosphorus product, mention may be made of the coating with a double coat layer comprising an inner coat of metal hydroxide (selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide) and an outer coat of thermosetting resin.

A representative example of the inorganic phosphate used as the phosphorus-containing flame retardant is ammonium polyphosphate.

Examples of inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, hydrates of inorganic metal compounds (such as tin oxide hydrate), zinc borate, zinc metaborate, metaborate Barium, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate and the like. The compounds may be used alone or in combination. Among them, at least one compound selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite can be used as the inorganic flame retardant which not only has excellent flame retardancy but also is economically advantageous.

Regarding the amount of flame retardants other than the non-polymerizable liquid substance (B), the amount is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, relative to 100 parts by weight of the masterbatch including the resin composition of the present invention. Even more preferably 3 to 20 parts by weight, most preferably 5 to 15 parts by weight.

Furthermore, if desired, one or more flame retardant aids selected from the group consisting of novolak resins, triazine structure-containing compounds, silicone resins, silicone oils, fluororesins, aramid fibers and polyacrylonitrile fibers may comprise the resin composition of the present invention. Can be added to the masterbatch.

Regarding the amount of the flame retardant aid, the amount is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, most preferably 5 to 10 parts by weight based on 100 parts by weight of the masterbatch.

When the novolak resin is used in admixture with the aromatic phosphate ester, the novolak resin also acts to improve the melt flow and heat resistance of the resin composition of the present invention; The compatibility between the thermoplastic resin (A) and the aromatic phosphate ester (B) slightly decreases. Novolak resins are thermoplastic resins which can be obtained by condensation of phenols and aldehydes in the presence of a catalyst such as sulfuric acid or hydrochloric acid. For example, a method for obtaining a novolak resin is described in 437 of "Kobunshi Jikkengaku 5, Jushukugo to Jufuka (Experimental Polymer Chemistry, Series 5, Condensation Polymerization and Polyaddition)" (published by Kyoritsu Shuppan Co., Ltd., Japan). To page 455.

Chemical formula 6 which demonstrates a representative example of preparation of novolak resin is shown below.

Specific examples used in the production of novolak resins include phenol; o-cresol; m-cresol; p-cresol; 2,5-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, pt-butylphenol, pn-octylphenol, p-stearylphenol, p- Phenylphenol, p- (2-phenylethyl) phenol, o-isopropylphenol, p-isopropylphenol, m-isopropylphenol, p-methoxyphenol and p-phenoxyphenol; Pyrocatechol; Resorcinol; Hydroquinone; Salicylate; Salicylic acid; p-hydroxybenzoic acid; Methyl p-hydroxybenzoate; p-cyanophenol and o-cyanophenol; p-hydroxybenzenesulfonic acid; p-hydroxybenzenesulfonamide; Cyclohexyl p-hydroxybenzenesulfonate; (4-hydroxyphenyl) phenylphosphinic acid; Methyl (4-hydroxyphenyl) phenylphosphinate, 4-hydroxyphenylphosphonic acid; Ethyl 4-hydroxyphenylphosphonate; And diphenyl 4-hydroxyphenylphosphonate.

Specific examples of aldehydes used in the production of novolak resins include formaldehyde, acetaldehyde, n-propanal, n-butanal, isobutyl aldehyde, 3-methyl-n-butanal, benzaldehyde, p-tolylaldehyde and 2 -Phenylacetoaldehyde.

The triazine structure-containing compound acts as a flame retardant aid for improving the flame retardancy of the phosphorus flame retardant. Specific examples of the triazine structure-containing compound include melamine, melam represented by the formula (7), melem represented by the formula (8), melon (melon) (obtained by the deammonium reaction of three melem molecules at 600 ° C. or higher to generate three molecules of ammonia). Product), melamine cyanurate represented by the formula (9), melamine phosphate represented by the formula (10), succinoguanamine represented by the formula (11), adifoguanamine, methyl glutaroguanamine, a melamine resin having a structure represented by the formula (12), and BT resin which has a structure represented by General formula (13) is included. Among the above, melamine cyanurate is preferable in view of the volatility.

Wherein each Ar ¹ is Indicates,

Ar ² is ].

The silicone resin used as a flame retardant aid has a three-dimensional network structure obtained by the combination of structural units SiO ₂ , RSiO _3/2 , RSiO and RSiO _1/2 . In the structural units, each R independently represents a vinyl group-containing substituent obtained by introducing an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a vinyl group introduced into the alkyl group or the aromatic group. Specifically, a silicone resin wherein R is the vinyl group-containing substituent obtained by introducing the alkyl group or the aromatic group into a vinyl group is preferred.

The silicone resin may be obtained by hydrolyzing the organic halosilane corresponding to the structural unit and then polymerizing the hydrolyzed product.

Silicone oils used as flame retardant aids are polydiorganosiloxanes comprising structural units represented by the following formula (14):

In Formula 14, each R independently represents a C ₁ -C ₈ alkyl group, a C ₆ -C ₁₃ aryl group, a vinyl group-containing group represented by Formula 15 or a vinyl group represented by Formula 16:

CH ₂ = CH-

A silicone oil used as a flame retardant aid is a silicone oil comprising, as R, a structural unit of formula 14 containing one or more substituents selected from the group consisting of a vinyl group-containing group of formula (15) and a vinyl group of formula (16).

Regarding the viscosity of the vinyl group-containing silicone oil, the viscosity is preferably 600 to 1,000,000 centistokes (measured at 25 ° C.), more preferably 90,000 to 150,000 centistokes (measured at 25 ° C.).

The fluororesins used as flame retardant aids are resins containing fluorine atoms. Specific examples of fluororesins include polymonofluoroethylene, polytetrafluoroethylene and tetrafluoroethylene-hexafluoropropylene copolymers. If desired, the fluorine-containing monomer, which is a monomer selected from the monomers contained in the fluororesin, may optionally be polymerized or copolymerized with monomers copolymerizable with the fluorine-containing monomer.

Regarding the method for preparing the fluororesin, reference may be made to US Pat. Nos. 2,393,697 and 2,534,058. For example, tetrafluoroethylene in an aqueous medium is polymerized with a radical initiator (such as ammonium persulfate or potassium persulfate) at 0-200 ° C. under conditions of 7-70 kg / cm ² , and the resulting reaction mixture ( Powdery polytetrafluoroethylene can be obtained by agglomeration or precipitation in the form of suspensions, dispersions or emulsions).

In order to effectively prevent the melt dropping of the molded product, a special high-order structure as a flame retardant aid obtained by melt-kneading the fluoro resin with a thermoplastic resin (the state and action thereof will be described later) at a temperature above the melting temperature of the fluoro resin. It is preferable to use the fluoro resin which has. For example, polytetrafluoroethylene is preferably melt kneaded with the thermoplastic resin at a temperature of 300 to 350 ° C. While applying the shear force, the fluororesin is melted together with the thermoplastic resin at a temperature below the melting temperature of the fluororesin, and the fluororesin is highly fibrillated in the thermoplastic resin and orientation crystallized. As a result, a fluororesin having a specific higher order structure can be obtained. As a result, the fluororesins obtained are branched fibrils, wherein the branched fibrils are branched fibers branched from oriented liver fibers and liver fibers. In the form of branched fibrils, the fluororesin can be mixed with the thermoplastic resin three-dimensionally to prevent melt dripping of the molded product. A thermoplastic resin melt-kneaded together with a fluororesin, wherein a hard resin (such as polyphenylene ether) having a high melt viscosity is more effective than a rubber modified resin (such as rubber modified polystyrene) in view of ease of applying high shear force to the fluororesin. More preferred.

As the method for producing the fluororesin having a special higher order structure, the following two methods can be mentioned. In the first method (two step process), the fluororesin, the thermoplastic resin, and optionally the dispersant are melt kneaded together at a temperature above the melting temperature of the fluororesin, thereby obtaining a masterbatch. Subsequently, the obtained masterbatch is melt kneaded together with a thermoplastic resin and a flame retardant. In a second method (one step process), an extruder having a second extrusion zone having a first extrusion zone and a side feed port is used. The fluororesin, the thermoplastic resin and optionally the dispersant are melt kneaded at a temperature above the melting temperature of the fluororesin in the first extrusion zone, and then further supplied with a flame retardant through the side feed in the second extrusion zone to the first extrusion zone. Melt kneading is carried out at a temperature below that at.

Regarding the aramid fibers as the flame retardant aid, the fibers preferably have an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. Isophthalamide or polyparaphenylene terephthalamide can be dissolved in a polar solvent containing amide or sulfuric acid, and the resulting solution can be dry spun or wet spun to obtain aramid fibers.

Regarding the polyacrylonitrile as the flame retardant aid, it is preferable that the average diameter is 1 to 500 µm and the average fiber length is 0.1 to 10 mm. Regarding the method for producing polyacrylonitrile fibers, the dry spinning method in which the acrylonitrile polymer is dissolved in a solvent (such as dimethylformamide) and the resulting solution is spun at 400 ° C. under air circulation, and the acrylonitrile polymer is solvent (such as Wet spinning method, which dissolves in nitric acid) and spuns the resulting solution in water.

As examples of the thermoplastic elastomer which may be optionally contained in the resin composition of the present invention, polystyrene elastomer, polyolefin elastomer, polyurethane elastomer, 1,2-polybutadiene elastomer, polyvinyl chloride elastomer and the like can be mentioned. Particular preference is given to thermoplastic polystyrene elastomers. The amount of thermoplastic elastomer is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, most preferably 2 to 10 parts by weight based on 100 parts by weight of the masterbatch.

The thermoplastic polystyrene elastomer is selected from block copolymers consisting of aromatic vinyl compound units and conjugated diene compound units and hydrogenated block copolymers obtained by partially hydrogenating the conjugated diene portion of the block copolymer. Examples of the aromatic vinyl monomer used in the preparation of the block copolymer include styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene, and the like. Include. Styrene is most preferred, but styrene can be copolymerized with the other aromatic vinyl monomers.

As an example of the conjugated diene monomer used for manufacture of the said block copolymer, 1, 3- butadiene, isoprene, etc. can be mentioned.

Regarding the block structure of the block copolymer, the block copolymer is a linear block copolymer having a structure of, for example, SB, S (BS) _n , S (BSB) _m , or a conjugated diene at the binding center (SB) _p Is a star block copolymer having a structure of X, where S represents a polymer block consisting of aromatic vinyl compound units, B represents a polymer block consisting of conjugated diene compound units and / or partial hydrogenated products thereof, and X is a couple Ring agent residues (e.g., silicon tetrachloride, tin tetrachloride, polyepoxy compound), n represents an integer of 1 to 3, m represents an integer of 1 or 2, and p represents an integer of 3 to 6. Of these, linear block copolymers having a two-block structure "SB", a three-block structure "SBS" and a four-block structure "SBSB" are preferable.

The resin composition of the present invention may optionally contain one or more release agents selected from the group consisting of highly saturated aliphatic carboxylic acids and metal salts thereof, carboxylic acid ester waxes, organosiloxane waxes, polyolefin waxes and polycaprolactam waxes.

The amount of the releasing agent is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, most preferably 0.3 to 1 parts by weight based on 100 parts by weight of the masterbatch.

Among the release agents, at least one compound selected from the group consisting of highly saturated aliphatic carboxylic acids and metal salts thereof is preferred.

As a preferred example of the highly saturated aliphatic carboxylic acid, mention may be made of C _{12 to} C ₄₂ straight chain saturated monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid and the like. .

Preferred examples of the metal salt of the highly saturated aliphatic carboxylic acid include lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, aluminum salt, zinc salt and the like. Of these, zinc stearate, magnesium stearate, calcium stearate and aluminum stearate are preferred.

The resin composition of the present invention comprises at least one fluidity improving agent selected from the group consisting of copolymers comprising aromatic vinyl compound units and acrylic acid ester compound units, aliphatic hydrocarbons, high fatty acids, high fatty acid esters, high fatty acid amides, high aliphatic alcohols, and metal soaps. It may optionally contain.

The amount of the fluidity improver is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, most preferably 1 to 5 parts by weight based on 100 parts by weight of the masterbatch.

Examples of aromatic vinyl monomer units in the aromatic vinyl-acrylic acid ester copolymer as the fluidity improving agent include styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribro And those derived from mostyrene and the like. Styrene is most preferred, but styrene can be copolymerized with the other aromatic vinyl monomers.

As examples of the acrylic acid ester in the aromatic vinyl-acrylic acid ester copolymer as the fluidity improving agent, mention may be made of acrylates having an alkyl group having 1 to 8 carbon atoms such as methyl acrylate, butyl acrylate and the like.

The acrylic acid ester compound unit content of the aromatic vinyl-acrylic acid ester copolymer as the fluidity improving agent is preferably 3 to 40% by weight, more preferably 5 to 20% by weight. It is preferred that the copolymer has a solution viscosity of 2 to 10 cp (centipoises) as measured at 10% by weight in methyl ethyl ketone at 25 ° C., which is a measure of molecular weight. If the solution viscosity is less than 2 cp, the impact strength of the resin composition is lowered. On the other hand, if the solution viscosity is greater than 10 cps, the improved effect on flowability is reduced.

Aliphatic hydrocarbons as fluidity improvers can be selected from liquid paraffins, natural paraffins, microwaxes, polyolefin waxes, synthetic paraffins, and partial oxidation products thereof, fluorides thereof, chlorides thereof, and the like.

High fatty acids as fluidity improving agents can be selected from saturated fatty acids other than those mentioned above as release agents. Specifically, as the fluidity improving agent, ricinolic acid, ricinoleic acid, 9-oxy-12-octadecenoic acid; Etc. can be used.

Highly fatty acid esters as flow improving agents include monohydric alcohol esters of fatty acids such as methyl phenylstearate and butyl phenylstearate; Monohydric alcohol esters of polybasic acids such as diphenylstearyl phthalate; Sorbitan esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan mono Palmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate; Fatty acid esters of glycerin monomers, such as stearic acid monoglycerides, oleic acid monoglycerides, capric acid monoglycerides, behenic acid monoglycerides; Fatty acid esters of polyglycerine, such as polyglycerol stearic acid ester, polyglycerol oleic acid ester, polyglycerol lauric acid ester; Fatty acid esters of polyalkylene ether units such as polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate; Neopentyl polyol esters of fatty acids such as neopentyl polyol distearate; Etc. can be selected.

As the fluidity improving agent, a high fatty acid amide may be selected from monoamides of saturated fatty acids, such as phenyl stearamide, methylol stearamide, methylol behenylamide; N, N'-2 substituted monoamides such as coconut oil fatty acid diethanolamide; Saturated fatty acid bisamides, such as methylene bis (12-hydroxyphenyl) stearamide, ethylene bis stearamide, ethylene bis (12-hydroxyphenyl) stearamide, hexamethylene bis (12-hydroxyphenyl) stearamide; Aromatic bisamides such as m-xylene bis (12-hydroxyphenyl) stearamide and the like.

As the fluidity improving agent, high aliphatic alcohols may be selected from monohydric alcohols such as stearyl alcohol, cetyl alcohol; Polyhydric alcohols such as sorbitol, mannitol; Polyoxyethylene dodecylamine; Polyoxyethylene octadecylamine; Allyl ethers with polyalkylene ether units, such as polyoxyethylene allyl ether; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether; Dihydric alcohols with polyalkylene ether units such as polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A ether, polyoxyethylene polyoxypropylene glycol ether; Etc. can be selected.

The resin composition of the present invention may optionally contain one or more light resistance improving agents selected from the group consisting of ultraviolet absorbers, hindered amine light stabilizers, antioxidants, active species trapping agents, light shields, metal deactivators and quenchers.

The amount of the light resistance improving agent is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, most preferably 0.1 to 5 parts by weight based on 100 parts by weight of the masterbatch.

As a lightfastness improver, UV absorbers harmlessly heat energy due to their absorption of light energy and their transformation into keto forms through intramolecular proton transfer (in the case of benzophenones and benzotriazoles) or cis-trans isomerization (in the case of cyanoacrylates). It is a component that emits absorbed light energy. Specific examples of UV absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5 , 5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2'-hydroxyphenyl) benzotriazole such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-

(2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl)

Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'

-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, and 2, 2'-methylenebis (4-t-octyl-6-benzotriazolyl) phenol; Benzoates such as phenylsalicylate, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, and hexadecyl -3,5-di-t-butyl-4-hydroxybenzoate; Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanide and 2-ethoxy-4'-dodecyloxanide; And cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

As a light resistance improving agent, a hindered amine light stabilizer is a component which decomposes hydroperoxide generated by light energy into stable N-0 radicals, N-OR or N-OH, thereby providing light stability. Specific examples of hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidinylstearate, 1,2,2,6,6-pentamethyl-4-piperidinylstearate, 2 , 2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-penta-methyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-penta Methyl-4-piperidyl) -di (tridecyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl)- 2-butyl-2- (3 ', 5'-di-t-butyl-4-chlorobenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4- Piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis ( 2,2, 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-t-octylamino-s-triazine polycondensate, 1,6-bis (2,2,6,6- Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate and the like.

Antioxidants as light resistance improvers are components for the stabilization of peroxide radicals, such as hydroperoxide radicals, which occur during heat forming or photoexposure, and for decomposing generated peroxides, such as hydroperoxides. Examples of antioxidants include hindered phenolic antioxidants and peroxide degradants. To prevent autooxidation, hindered phenolic antioxidants act as radical chain inhibitors and break down the peroxide decomposed peroxide into stable alcohols.

Specific examples of the hindered phenol type antioxidant include 2,6-di-t-butyl-4-methylphenol, styrenated phenol, n-octadecyl-3- (3,5-di-t-butyl-4-hydride Hydroxyphenyl) propionate, 2,2'-methylene bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methyl Benzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 4,4 '-Butylidene bis (3-methyl-6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), alkylated bisphenol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) -Propionyloxy} -1,1-dimethyl-ethyl] -2,4,8,10-tetraoxyspiro [5 · 5] undecane.

Specific examples of the peroxide degrading agent as the antioxidant include organic phosphorus type peroxide degrading agents such as trisnonylphenyl phosphite, triphenyl phosphite and tris (2,4-di-t-butylphenyl) phosphite; And organic thiotype peroxide degradants such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodi Propionate, pentaerythryltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate and 2-mercaptobenzimidazole.

Active species trapping agents as light resistance enhancers are components used to capture active species, such as free halogen radicals generated during heating or photoexposure. Specific examples of active species trapping agents include basic metal salts such as calcium stearate and zinc stearate; Hydrotalcite; Zeolites; Magnesium oxide; Organotin compounds; And organic epoxy compounds.

As the active species trapping agent, hydrotalcite can be selected from basic carboxylates of metals such as magnesium, calcium, zinc, aluminum and bismuth, and the basic carboxylate may contain water or may not contain water. . Natural or synthetic products can be used. As natural hydrotalcite, mention may be made of the structure of the formula: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · H ₂ 0. Examples of synthetic hydrotalcites include:

_{Mg 0.7 Al 0.3 (OH) 2} (CO 3) 0.15 · 0.54H 2 0,

_{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 0, Mg 4.2 Al 2 (OH) 12.4 CO 3,

Zn ₆ Al ₂ (OH) ₁₆ CO ₃ 4H ₂ 0, Ca ₆ Al ₂ (OH) ₁₆ CO ₃ 4H ₂ 0, and

_{Mg 14 Bi 2 (OH) 29.6} · 4.2H 2 0.

As the zeolite, a zeolite of the type A represented by the following formula: Na ₂ O.Al ₂ 0 ₃ · 2SiO ₂ · XH ₂ 0, and a zeolite substituted with at least one metal selected from the group of metals belonging to groups II and IV of the periodic table May be mentioned. Examples of substituted metals include Mg, Ca, Zn, Sr, Ba, Zr and Sn. Of these, Ca, Zn and Ba are particularly preferred.

The organic epoxy compound is epoxidized soybean oil, tris (epoxypropyl) isocyanurate, hydroquinone glycidyl ether, diglycidyl terephthalate, 4,4'-sulfobisphenol-polyglycidyl ether as the active species trapping agent. , And N-glycidylphthalimide; And cycloaliphatic epoxy compounds such as hydrogenated bisphenol A glycidyl ether, 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxycyclohexylspiro [5, 5] -3,4-epoxy) -cyclohexane-m-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexenedioxide, 4-vinylepoxycyclohexane, bis (3,4 -Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexane carboxylate, methylenebis (3,4-epoxycyclohexane ), Dicyclopentadiene epoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexane carboxylate), dioctyl epoxyhexahydrophthalate, and di- It can be chosen from 2-ethylhexyl epoxy hexahydrophthalate.

As light resistance improvers, light shields are components used to prevent light from penetrating into the interior of the polymer. Specific examples of the light shielding agent include titanium oxide (Ti0 ₂ ), zinc oxide (ZnO), chromium oxide (Cr ₂ O ₃ ), and cerium oxide (CeO ₂ ) having a rutile structure.

Metal light deactivators as light resistance improvers are components used to deactivate heavy metal ions in the resin through the formation of chelate compounds. Specific examples of metal deactivators include acid amine derivatives, and benzotriazoles and derivatives thereof.

As light resistance improvers, matting agents are components used to deactivate photoexcited functional groups, such as hydroperoxide and carbonyl groups, formed in the polymer. Deactivation occurs due to energy transfer from the functional group. Organic nickel compounds and the like are known as quenchers.

In the present invention, when a polymer mixture of a plurality of different thermoplastic resins is used as the thermoplastic resin (A), the distribution regarding the composition of the component monomers constituting the copolymer to give further improved impact strength to the final molded resin body Preference is given to using a copolymer having non-uniformity as a compatibilizer. Especially when a polymer mixture comprising a styrene polymer is used as the thermoplastic resin (A), the use of the compatibilizer is effective.

For example, when a polymer mixture comprising an aromatic polycarbonate and a styrene polymer is used as the thermoplastic resin (A), it has non-uniformity in the distribution regarding the fraction of the component monomers constituting the copolymer, and therefore different solubility. It is preferable to use a copolymer consisting of copolymer molecules having a parameter (SP) as a compatibilizer. In this case, the intermolecular SP value (ΔSP value) between the copolymer molecule having the maximum SP value and the minimum SP value is 0.3 to 1.0 [(cal / cm ³ ) ^1/2 ], and the average SP value of the individual copolymer molecules is 10.6 to 11.0, more preferably 10.6 to 10.9, even more preferably 10.7 to 10.8. Regarding the ΔSP value, in order to achieve high impact strength of the final molded resin body, the ΔSP value is preferably in the above range of 0.3 to 1.0 [(cal / cm ³ ) ^1/2 ], more preferably 0.3 to 0.8 [( cal / cm ³ ) ^1/2 ], even more preferably 0.4 to 0.6 [(cal / cm ³ ) ^1/2 ].

As mentioned above, the resin composition of this invention can be used as a masterbatch which melt-extrudes with the resin material same or different from thermoplastic resin (A), and optionally with various solid additives. When the resin composition of the present invention is used as a masterbatch as described above, it is possible to melt-extrude a thermoplastic resin having a high viscosity such as polyphenylene ether at a relatively low temperature. Examples of methods for carrying out melt extrusion are methods of simultaneously supplying all materials (including the masterbatch, thermoplastic material other than the thermoplastic resin (A) and optionally solid additives) to the extruder and the masterbatch and thermoplastics ( A resin material comprising a thermoplastic material other than A) and a method of injecting the solid additive into the extruder at its different inlet, wherein the inlet for the solid additive is as defined in the extrusion direction of the extruder. Located at the bottom, a solid additive is added to the molten resin.

As for the extruder used for melt extrusion, a single screw extruder or a twin screw extruder can be used. In the case of using the solid additive, it is preferable to use a twin screw extruder in order to uniformly disperse the solid additive in the resin material. Regarding the twin screw extruder, it is preferable that L / D (the ratio of the length L of each axis to the inner diameter D of the cylinder portion of the extruder) is 20 to 50. In addition, a kneading zone located in the zone of the extruder in which the twin screw extruder extends from at least two inlets comprising a main feed inlet and a subfeed inlet, and an inlet provided at one end portion of the extruder at a position adjacent to the other end of the extruder. Wherein the kneading zone has a length corresponding to 1D to 10D.

In another aspect of the invention, there is provided a polyphenylene ether resin consisting of polyphenylene ether resin (A ') and at least one additive (B') for polyphenylene ether resin (A '), wherein the polyphenylene ether resin The ethylene ether resin (A ') contains hydroxyl groups in an amount of 0.5 moles or less with respect to 100 moles of the repeating oxyphenylene units of the polyphenylene ether resin. Regarding the additive (B '), there is no particular limitation, and any conventional additive for the polymer can be used. However, it is preferable to use the above nonpolymerizable liquid substance (B) as an additive (B ').

In the conventional production method of the composition of the polyphenylene ether resin and the additive (having high heat resistance), it is necessary to perform melt mixing at 300 to 350 ° C. Therefore, in the above conventional melt mixing method, for example, reaction of end groups of polymers other than hydroxyl groups (as shown in Scheme i, wherein the end groups of polymers are aminoalkyl groups) or Scheme ii As can be seen, polyphenylene ether resins having a methylene bridged structure formed by the Fries potential arise, thereby increasing the hydroxyl group content of the polyphenylene ether resin. Therefore, in the polyphenylene ether resin composition prepared by the conventional melt-mixing method, due to the high content of hydroxyl groups, the molded resin body prepared from the polyphenylene ether resin composition discolors and has poor light stability. there is a problem.

Methylene bridge structure

Upper end of polymer

The inventors have found that the photostability and discoloration resistance of polyphenylene ether resins {not only the content of hydroxyl groups formed due to the generation of methylene bridge structures, but also the polyphenylene ethers inherently possessed (i.e. the top of each polyphenylene ether chain The total hydroxyl group content of the polyphenylene ether resin, including the hydroxyl group present at the terminal), to 100 mol of repeating oxyphenylene units, to a level of 0.5 mol or less, to significantly improve It was found that it can be done.

The inventors have also conducted mixing to obtain a resin composition comprising said excellent polyphenylene ether resin (A ') and additives for polyphenylene ether resin (B') having significantly improved light stability and discoloration resistance. The non-polymerizable liquid substance (B) is run at a temperature in the range of 25 to 300 ° C., and the non-polymerizable liquid substance (B) is maintained at a liquid state at a temperature in the range of 25 to 300 ° C. as an additive for (A) thermoplastic resin and (B) thermoplastic resin (A). It has been found to be effective to use a method consisting of mixing one or more nonpolymerizable liquid substances in a liquid state, thereby dissolving or swelling the thermoplastic resin (A) in the nonpolymerizable liquid substance (B). Examples of additives as additives for polyphenylene ether resins (A ') are not limited to those described above as non-polymerizable liquid substances (B). The specific organophosphorus compound is preferably used as a flame retardant which is a preferred additive.

Another preferred embodiment of the present invention is (A) 20 to 80 parts by weight of polyphenylene ether resin having a number average particle diameter of 10 to 100 μm, (B) 20 to 80 parts by weight of aromatic phosphate ester and (C) silica to 0.01 to 1 part by weight is mixed at a temperature in the range from 150 to 250 ° C., whereby the polyphenylene ether resin is dissolved or swelled in an aromatic phosphate ester to prepare a masterbatch, and the obtained masterbatch is a styrene polymer resin and a solid material (such as Melt-extruded with a light resistance improving agent, a releasing agent, etc.), thereby obtaining a molding material, and extruding the molding material to obtain a molded body having a desired shape, wherein the molded body, such as pellets, is further formed as a molding material. Can be used.

The obtained molded article has an excellent balance of various properties such as flame retardancy, impact resistance, heat resistance and the like. It has further been found that even better flame retardance can be achieved when the total content of residual aromatic vinyl monomers, dimers and trimers in the resin composition is 1% by weight or less. When the total content of the residual aromatic vinyl monomers, dimers and trimers is more than 1% by weight, the flame retardancy is poor because the vinyl compound evaporates and acts as a flammable gas when burning the resin composition.

The invention will now be described in more detail with reference to the following examples and comparative examples, but should not be construed as limiting the scope of the invention.

In Examples and Comparative Examples, measurements are made using the following methods and apparatus.

(1) Analysis of Resin Composition Containing Phosphate Ester Flame Retardant:

5 g of the resin composition is dissolved in 100 ml of methyl ethyl ketone and the resulting solution is ultracentrifuged (20,000 rpm, 1 hour) to obtain a supernatant. Then, methanol is added to the supernatant in twice the amount of the supernatant, thereby precipitating the resin composition. The resulting mixture containing the precipitated resin component is ultracentrifuged to separate the resin component from the mixture. The resulting solution was prepared and sold by a differential refractometer (column: G100HXL × 2, Japan, Tosoh Corp .; mobile phase: tetrahydrofuran; flow rate: 0.8 ml / min; pressure: 60 kgf / cm ² ; inlet temperature HLC-8020 (manufactured and marketed by Tosoh) with 35 ° C., oven temperature: 40 ° C., temperature in a differential refractometer: 35 ° C., incoming sample volume: 100 ml; sample concentration: 0.08 g / 20 ml) It is analyzed by gel permeation chromatography (GPC), and the composition and amount of the phosphate ester contained in the solution are measured from each area ratio (measured on the chromatogram) to the components of the solution. On the other hand, the resin component is dissolved in deuterated chloroform to obtain a sample solution. Regarding the sample solution obtained, the ratio of the integrals of the aromatic protons and the aliphatic protons and the chemical shift were determined by Fourier transform nuclear magnetic resonance (proton-FT-NMR) apparatus (DPX-400, Germany, Bruker, USA). Measured using a commercially available and manufactured by Bruker Analytik GMBH), and the composition and content of the resin composition (in the resin component a thermoplastic resin component such as rubber modified styrene resin, polyphenylene ether resin and / or Polycarbonate) is measured.

(2) Analysis of the hydroxyl groups contained in the polyphenylene ether resin:

5 g of the resin composition was dissolved in 100 ml of methyl ethyl ketone and the resulting solution was evaporated after ultracentrifugation (20,000 rpm, 1 hour) to obtain a residue. The obtained residue is dissolved in methylene chloride to give a methylene chloride solution having a solid content of 5% by weight. The methylene chloride solution is left for 24 hours in a refrigerator at -15 ° C to thereby obtain a precipitate. The precipitate is then obtained by filtration under cold conditions. The precipitate is washed with methylene chloride and then dried in vacuo, whereby a polyphenylene ether is obtained. The obtained polyphenylene ether is dissolved in deuterated chloroform to obtain a sample solution, which is then analyzed. The amount of hydroxyl groups present in the methylene bridge structure of the polyethylene ether resin and the hydroxyl present at the upper end of the polymer chain of the polyphenylene ether resin, using a Fourier transform nuclear magnetic resonance (proton-FT-NMR) apparatus Measure the amount of skill. In the NMR spectra shown in FIGS. 3 (a), 3 (b), 4 (a) and 4 (b), hydrogen atoms bonded to aromatic rings, hydrogen atoms of a methylene group, and hydroxyl groups present in a methylene bridge structure The peaks corresponding respectively to the hydrogen atoms of are denoted as A or A ', D or D' and B or B ', respectively, and the peaks corresponding to the hydrogen atoms of the hydroxyl group present at the upper end of the polymer chain are C or C. ' Usually, the peak corresponding to the hydrogen atom present in the hydroxyl group is in the range of 4.2 to 4.4 ppm.

(3) SP value (δ) (solubility parameter) and average SP value:

The SP value is calculated according to the Fedors equation described in Polymer Engineering and Science, 14, (2), 147 (1974), using data of Δe1 and Δv1 of the functional groups of the polymer, which is also described below:

[Wherein, Δe1 represents the cohesive energy per functional group of the unit, Δv1 represents the molecular volume per unit functional group, and the unit of δ is (cal / cm ³ ) ^1/2 ].

Assuming that the additive SP applies the average SP value of a copolymer or mixture of copolymers, the copolymer is proportional to the individual SP values of different constituent monomers or different constituent copolymers according to each weight of the constituent monomer units or constituent copolymer units. It is calculated from the SP values of different constituent monomer units of or the SP values of different constituent copolymers of the copolymer mixture. For example, the SP value of polyacrylonitrile (14.39) is determined by proportional distribution of the individual SP values of polyacrylonitrile and polystyrene according to the individual weight ratios of acrylonitrile and styrene in the polymer. ) And the SP value (10.52) of polystyrene.

(4) Glass transition temperature (Tg) and melting temperature (Tm):

Differential scanning calorimetry (DSC) method described in the glass transition temperature (Tg) and melting temperature (Tm) described in "Polymer Handbook" (J. Brandrup Edit, A Wiley-Interscience Publication, John Wiley & Sons, New York, USS, 1975). Measure with In the differential scanning measurement (DSC) method, the glass transition temperature (Tg) is measured by observing a change in specific heat capacity, and the melting temperature (Tm) is measured as a temperature corresponding to the position of the peak of the melting curve. Specifically, evaluation is performed as follows. The evaluation is carried out using a thermal analysis device (model DT-40, manufactured and marketed by Shimadzu Corporation, Japan) that heats 5 mg of the sample at a rate of 10 ° C./min under a stream of nitrogen gas. As shown in Fig. 9 (a), Tg is defined as the temperature corresponding to the intersection of the baseline and the straight line constructed from the first line of the specific heat capacity. As shown in Fig. 9B, Tm is defined as the temperature corresponding to the intersection of the reference line and the rising line of the endothermic peak.

The determination as to whether the polymer is a crystalline polymer or an amorphous polymer is performed by observing the presence or absence of an endothermic peak. The area of the endothermic peak corresponds to the heat of crystallization (Cal / g) and is used as an index of crystallinity of the polymer.

In the "Polymer Handbook", the glass transition temperatures (Tg) of poly (2,6-dimethyl-1,4-phenylene oxide), polycarbonate of bisphenol A, polystyrene and poly (vinyl chloride) are 209 ° C., respectively. 145 ° C, 100 ° C and 81 ° C.

(5) reduced viscosity ηsp / c of rubber-modified styrene resin and polyphenylene ether resin:

The viscosity ηsp / c of the rubber-modified styrene resin is evaluated as follows. A mixed solvent of 18 ml of methyl ethyl ketone and 2 ml of methanol was added to 1 g of the rubber-modified styrene resin, followed by stirring at 25 ° C. for 2 hours. The resulting mixture is centrifuged at 5 ° C. for 30 minutes at 18,000 rpm to obtain a supernatant. The obtained supernatant is taken out, the resin component is precipitated from the supernatant with methanol, and then dried.

0.1 g of the obtained resin is used as a solvent (toluene is used as a solvent when the rubber-modified styrene resin is a rubber-modified polystyrene; and methyl ethyl ketone is used as a solvent when the rubber-modified styrene resin is a rubber-modified acrylonitrile / styrene copolymer. To a solution having a resin concentration of 0.5 g / dl. 10 ml of the obtained solution is placed in a Cannon-Fenske viscometer, and the drop time T ₁ (second) of the solution is measured at 30 ° C. In addition, the individual fall times T ₀ (sec) of pure toluene and pure methyl ethyl ketone are evaluated using the same viscometer as above. The reduced viscosity of the rubber modified styrene resin is calculated by the following formula:

ηsp / c = (T ₁ / T ₀ -1) / C

[Wherein, C represents the concentration (g / dl) of the rubber-modified styrene resin in the solution].

Regarding the polyphenylene ether resin, its reduced viscosity ηsp / c is evaluated as follows. 0.1 g of polyphenylene ether resin is dissolved in chloroform to thereby obtain a solution of polyphenylene ether resin concentration of 0.5 g / dl, and the measurement of the reduced viscosity is carried out in substantially the same manner as above.

(6) hue (yellowness):

The yellowness of the resin composition is measured using SM color tone computer model SM-5 (manufactured and marketed by Suga Test Industruments Co., Ltd., Japan) according to JIS-Z-8722.

(7) Izod impact strength:

Izod impact strength of V-notched species is measured at 23 ° C. according to ASTM-D256, unless 1/4 inch thick (unless otherwise noted).

(8) Volatility (thermogravimetric analysis; TGA method):

Volatility is measured using a thermogravimetric analyzer DT-40 (manufactured and manufactured by Shimadzu Corporation, Japan) by measuring the heating temperature under a stream of nitrogen gas at a rate of 40 ° C / min. The temperature at which 1% by weight loss occurs is used as a measure of volatility.

(9) Vicat softening temperature:

Vicat softening temperature is measured according to ASTM-D1525 and used as a measure of heat resistance.

(10) Melt flow rate (MFR):

Melt flow rate is measured substantially in accordance with ISO-R1133 and used as a measure of melt flowability. That is, the melt flow rate is measured from the extrusion rate (g / 10 min) of the resin composition measured at a melt temperature of 200 ° C. under a load of 5 kg.

(11) flame retardant:

Flame retardancy of 1/8 or 1/16 inch thick species is measured according to the VB (Vertical Burning) method described in UL-Subject 94. Regarding the method described in the VB (Vertical Burning) method described in UL-Subject 94, reference may be made, for example, to US Pat. No. 4,966,814.

(12) Light resistance of the molded body:

Light resistance is measured using an ATLAS CI35W Weatherometer (manufactured and marketed by ATLAS Elatric Device Co., USA) as a light resistance test apparatus according to JIS K7102. The exposure conditions are as follows: 300 hours of irradiation of the internal temperature of the test apparatus at 55 ° C., 55% humidity, no rain, and xenon light (wavelength: 340 nm, energy: 0.30 W / m ² ). The color difference ΔE between the pre-irradiated and post-irradiated molded bodies was measured using the SM color tone computer model SM-3 (manufactured and marketed by Suga Test Instruments Co., Ltd., Japan) according to the Lab method, and the change in color tone was measured. do. The smaller the hue change, the higher the light resistance.

(13) Evaluation of the compatibility between the thermoplastic resin (A) and the nonpolymerizable liquid material (B):

50 parts by weight of the powdered thermoplastic resin (A) and 50 parts by weight of the nonpolymerizable liquid material (B) having an average particle diameter of 15 μm to 1 mm are mixed with stirring at 200 ° C. for 1 hour, thereby obtaining a thermoplastic resin composition. Subsequently, the obtained resin composition was filtered through a glass filter having an average pore diameter of 10 μm while maintaining the temperature of the resin composition at 200 ° C. under a reduction pressure of about 50 mmHg, and the mixing of the component (A) / component (B) mixture on the filter. Measure the weight.

The weight ratio of the component (A) / component (B) mixture remaining in the filter to the thermoplastic resin (A) used in the resin composition is used as a measure of compatibility between the thermoplastic resin (A) and the nonpolymerizable liquid material (B). The lower the filter residual ratio, the higher the compatibility between the thermoplastic resin (A) and the nonpolymerizable liquid substance (B).

The number average particle diameter of powdery thermoplastic resin (A) is measured using an optical microscope or an electron microscope. The average particle diameter of the powdered thermoplastic resin is obtained as an arithmetic mean value of the diameters of 100 particles, wherein the long and short diameter arithmetic mean values of the particles are each particle irrespective of the shape of the particles (for example, spherical or pelletized). Consider as the diameter of.

(14) Measurement of stability of production (by melt extrusion) of resin composition:

The preparation of the resin composition was carried out using a twin screw extruder (ZSK-40; nominal maximum extrusion amount: 100 kg / hr; L / D = 46) (manufactured and marketed by Werner Pfleiderer GmbH, Germany) Run Specifically, the thermoplastic resin (A) is fed from the main feeder and then melt kneaded at a melting temperature of the thermoplastic resin (A) (for example, about 310 ° C. when using a polyphenylene ether resin (PPE)). Then, after supplying the non-polymerizable liquid material (B) from the subfeeder to the melt kneading PPE, the extrusion amount 30 kg / at a temperature below the melting temperature of the thermoplastic resin (A) (for example, about 230 ° C. when using PPE). Melt extrusion is performed at hr (step II-1).

Evaluation of the stability of the production (by melt extrusion) is made according to the following criteria.

Unmanufacturing: A nonpolymerizable liquid substance (B) is ejected out of a die, and manufacture of a molded object is impossible.

Extrusion instability: production of shaped bodies is possible; The fluctuation of the extrusion amount during production is more than ± 20% relative to the set value, and the moisture on the surface of the molded product produced with the non-polymerizable liquid substance (B) is observed.

Slightly Unstable Extrusion: The fluctuation in the amount of extrusion during manufacture is ± 5% to less than ± 20%, and no moisture on the surface of the molded article produced with the non-polymerizable liquid material (B) is observed.

Good: The variation in extrusion amount during manufacture is less than ± 5%.

The materials used in the examples and comparative examples are as follows:

(a) Thermoplastic (A)

(1) Preparation of Polyphenylene Ether (PPE)

The preparation of the PPE is carried out using a stainless steel reactor with an inlet for oxygen supply, a cooling coil and stirring blades at the bottom. Clean the reactor with nitrogen gas. Obtained by dissolving 8.75 kg of 2,6-xyleneol in a mixed solvent of 54.8 g of cupric copper bromide, 1,110 g of di-n-butylamine, and 20 liters of toluene, 16 liters of n-butanol, and 4 liters of methanol The prepared solution is added to the reactor. The polymerization reaction is stirred while running for 90 minutes and oxygen is then supplied to the reactor at internal temperature adjusted to 30 ° C. After completion of the reaction, the precipitated polymer is collected by filtration. A mixture of methanol and hydrochloric acid is added to the collected polymer to decompose the catalyst remaining in the polymer. In addition, the polymer is washed well with methanol to give a powdery polyphenylene ether (hereinafter often referred to as "PPE-1"). PPE-1 obtained has a reduced viscosity ηsp / c of 0.41 dl / g.

Except for changing the amount of catalyst and polymerization time, polyphenylene ethers of different reducing viscosities (ηsp / c) are prepared in substantially the same manner as above. The results are shown in Table 12. Each of the obtained polyphenylene ethers has a number average particle diameter of 20 µm and an SP value of 11.2.

(2) Rubber Unmodified Polystyrene (General Purpose Polystyrene) (GPPS):

Commercial polystyrene (weight average molecular weight: 200,000, manufactured and marketed by Asahi Chemical Industry Co., Ltd., Japan) is used (hereinafter often referred to as "GPPS"). The SP value of GPPS is 10.5.

(3) rubber modified styrene polymer (HIPS)

Polybutadiene (weight ratio of cis-1,4 bond / trans-1,4 bond / vinyl-1,2 bond = 95/2/3) (trade name: Nipol 122 OSL, Japan, by Nippon Zeon Co., Ltd.) Prepared and commercially available) to form a homogeneous solution having the following composition.

Polybutadiene 10.5 wt%

Styrene 74.2 wt%

Ethylbenzene 15.0 wt%

α-methylstyrene dimer0.27 wt%

t-butylperoxyisopropyl0.03 wt%

Carbonate

The solution obtained is fed continuously to the reactor with four different reaction zones connected in series, each with a stirrer. Polymerization was carried out at 126 ° C. and 190 rpm in a first zone; 133 ° C. and 50 rpm in the second zone; 140 ° C. and 20 rpm in the third zone; In a fourth zone at 155 ° C. and 20 rpm. The resulting polymerization reaction mixture (solid content: 73%) is transferred to a degassing apparatus to remove unreacted monomers and solvents. Thus, a rubber modified styrene polymer (hereinafter referred to as "HIPS-1") is obtained. The rubber modified styrene polymer obtained is analyzed. Eventually, it is found that the rubber content is 12.1% by weight, the weight average particle diameter of the rubber particles is 1.5 μm, the reduced viscosity ηsp / c is 0.53 dl / g, and the SP value is 10.3.

Except for changing the amount of polymerization initiator, polymerization temperature and amount of chain transfer agent, rubber modified styrene polymers having different reducing viscosities (ηsp / c) are prepared in substantially the same manner as above. The results are shown in Table 11.

HIPS used in Examples and Comparative Examples is as follows (see also Table 11).

HIPS-1: rubber component: polybutadiene rubber; Rubber content of HIPS-1: 12.1 wt%; Weight average particle diameter of the polybutadiene rubber: 1.5 μm; And reduced viscosity ηsp / c: 0.53 dl / g.

HIPS-2: Rubber component: polybutadiene rubber; Rubber content of HIPS-2: 12.1 wt%; Weight average particle diameter of the polybutadiene rubber: 1.5 μm; And reduced viscosity ηsp / c: 0.79 dl / g.

HIPS-3: Rubber component: polybutadiene rubber; Rubber content of HIPS-3: 12.1 weight%; Weight average particle diameter of the polybutadiene rubber: 1.5 μm; And reduced viscosity ηsp / c: 0.60 dl / g.

HIPS-4: Rubber component: polybutadiene rubber; Rubber content of HIPS-4: 12.1 wt%; Weight average particle diameter of the polybutadiene rubber: 1.5 μm; And reduced viscosity eta sp / c of HIPS-4: 0.58 dl / g.

HIPS-5: Rubber component: polybutadiene rubber; Rubber content of HIPS-5: 12.1 wt%; Weight average particle diameter of the polybutadiene rubber: 1.5 μm; And reduced viscosity ηsp / c: 0.40 dl / g.

HIPS-6: Rubber component: polybutadiene rubber; Rubber content of HIPS-6: 12.1 wt%; Weight average particle diameter of the polybutadiene rubber: 1.5 μm; And reduced viscosity ηsp / c: 0.35 dl / g.

(4) aromatic polycarbonate (PC)

Commercial bisphenol A polycarbonate [Novarex 7025A, Japan, Mitsubishi Chemical Industries, Ltd.]. And commercially available (hereinafter often referred to as "PC")] are used. The SP value of the PC is 11.3.

(5) ABS resin (ABS)

Commercial ABS resins [acrylonitrile / butadiene / styrene = 26/14/60 (weight ratio)] (hereinafter often referred to as “ABS”) are used.

(6) Compatibilizer: Acrylonitrile-styrene copolymer (AS)

A mixture of 3.4 parts by weight of acrylonitrile, 81.6 parts by weight of styrene, 15 parts by weight of ethylbenzene, and 0.03 parts by weight of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator The feeds were continuously fed to a plug flow reactor with three zones connected each with a stirrer at a rate of 0.7 liters / hr. Polymerization was carried out at 126 ° C. and 100 rpm in a first zone; 135 ° C. and 20 rpm in the second zone; And in the third zone at 147 ° C. and 10 rpm. Subsequently, the resulting polymerization reaction mixture is transferred to a degassing apparatus at a temperature of 230 ° C. to remove unreacted monomers and solvent. Thus, a random copolymer (hereinafter referred to as "AS") is obtained. The obtained copolymer is analyzed. Eventually, it was found that the copolymer contained 6% by weight of acrylonitrile monomer units and 94% by weight of styrene monomer units (measured by an infrared absorption spectrometer) and had an SP value of 10.75. In addition, the proportional distribution of the component monomers of the copolymer is measured by gas chromatography (according to the method described in WO-95-35346). Eventually, it was found that the proportion of acrylonitrile monomer units changed in the range of 0 to 12% by weight in the copolymer, the maximum SP value was 11.0, the minimum SP value was 10.5, and the ΔSP value was 0.5.

(7) Thermoplastic Elastomers:

Commercial styrene-butadiene block copolymers {styrene block / butadiene block = 40/60 (weight ratio), trade name: Tufprene 125, Japan, Asahi Chemical Industry Co., Ltd. And commercially available by the present invention (hereinafter often referred to as "TPE").

(8) polyamide

Commercial polyamide 6 (trade name: UBE Nylon 1013B, manufactured and marketed by Ube Industries, Ltd., Japan) is hereafter used (hereinafter often referred to as "PA6").

(b) non-polymeric liquid substance (B)

(1) Preparation of Tris (nonylphenyl) phosphate (TNPP)

431.0 parts by weight of nonylphenyl (molar ratio: 3.0) and 0.87 parts by weight of aluminum chloride (molar ratio: 0.01) are placed in a flask. Then, 100 parts by weight of phosphorus oxychloride (molar ratio: 1.0) is added dropwise to the flask at 90 ° C for 1 hour. The temperature in the flask is gradually raised to 180 ° C., thereby completing the esterification reaction. The resulting reaction is then cooled and washed with water to remove the catalyst and chlorine to give a mixture of tris (nonylphenyl) phosphate (hereinafter often referred to as "TNPP").

The average value of the sum of the number of individual carbon atoms of the substituent is 27.0.

(2) 1,3-phenylene-bis (diphenylphosphate) (FR-1):

Commercial oligomeric aromatic phosphate esters derived from resorcinol (manufactured and sold under the trade name "CR733S" by Daihachi Chemical Industry Co., Ltd., Japan) are used.

Analysis by GPC finds that FR-1 consists of the TPP dimer (n = 1) and the TPP oligomer (n ≧ 2) represented by the following formula (17) in a ratio of 65/35:

(3) 1,3-phenylene-bis {di (2,6-dimethylphenyl) phosphate} (FR-2)

244 parts by weight of 2,6-xyleneol, 20 parts by weight of xylene, and 1.5 parts by weight of magnesium chloride are placed in a reactor, mixed while heating to carry out the reaction. The temperature of the reaction mixture is gradually raised and after the temperature of the reaction mixture reaches 120 ° C., 153 parts by weight of phosphorus oxychloride is added dropwise to the reaction mixture for 2 hours. Hydrogen chloride gas formed during the reaction is introduced into a water scrubber. After completion of the addition of phosphorus oxychloride, the temperature of the reaction mixture is gradually raised to 180 ° C. for 2 hours to complete the reaction. The yield of the resulting intermediate {di (2,6-xylyl) phosphochloride} is 99.7%. Then, 45 parts by weight of the intermediate, 55 parts by weight of resorcinol and 1.5 parts by weight of aluminum chloride are placed in a reactor and mixed while heating. The temperature of the resulting reaction mixture is raised to 180 ° C. for 2 hours, whereby the dehydrochlorination reaction is carried out. The resulting reaction mixture is then aged at 180 ° C. for 2 hours and further aged at 180 ° C. under a reducing pressure of 200 mm Hg, thereby completing the dehydrochlorination reaction. 500 parts by weight of xylene and 200 parts by weight of a 10% aqueous solution of hydrogen chloride were added to the resulting reaction mixture to remove residual catalyst, and the product was then washed repeatedly with water to thereby obtain a purification reaction mixture. The purification reaction mixture obtained is crystallized by cooling with stirring. Then, the crystals were obtained by filtration and washed with methanol, and then dried under reduced pressure at 100 ° C. to thereby give 1,3-phenylene-bis- (di-2,6-dimethylphenylphosphate) represented by the following formula (18) ( Then often referred to as "FR-2").

(4) bisphenol A-bis (diphenylphosphate) (FR-3)

Commercial oligomeric aromatic phosphate esters (trade name: CR 741, manufactured and marketed by Daihachi Chemical Industry Co., Ltd., Japan) prepared from Bisphenol A are used. According to analysis by GPC, FR-3 found TPP-A-2 monomer, TPP-A-oligomer and trisphenylphosphate (TPP) to a weight ratio of 84.7 / 13.0 / 2.3, where TPP-A- Dimers (n = 1) and TPP-A-oligomers (n ≧ 2) have the structure represented by Formula 19:

(5) triphenyl phosphate (TPP):

Commercially available monomeric aromatic phosphate esters (hereinafter referred to as "TPP") (trade name: TPP, manufactured and marketed by Daihachi Chemical Industry Co., Ltd., Japan) are used.

(6) antistatic agent

Commercially available amine-containing antistatic agent N, N-bis- (2-hydroxyethyl) tallow amine (hereinafter referred to as "A-stat") (trade name: Armostat 310, manufactured and marketed by Armak Company, USA) is used. .

(7) lubricant

Use a commercial lubricant, SAE # 30 engine oil (hereinafter referred to as "Lb").

(8) Bromine-containing flame retardants

A commercial brominated epoxy resin (hereinafter referred to as "Br-EP") (trade name: Pratherm EC-14, manufactured and marketed by Dainippon Ink & Chemicals, Inc., Japan) is used.

(9) stabilizer

A commercial phosphorus stabilizer {tris (nonylphenyl) phosphite (hereinafter referred to as "TNP") (trade name: TNP, Japan, manufactured and sold by Asahi Denka Kogyo K.K.) is used.

(10) mineral oil

Commercial mineral oils (hereinafter referred to as "MO") (trade name: Kaydol, manufactured and marketed by Witch Corp., USA) are used.

(11) Bromine and phosphorus containing flame retardants

Commercial tris (2-chloro-3-bromopropyl) phosphate (hereinafter referred to as "PB") (manufactured and sold by Daihachi Chemical Industry Co., Ltd., Japan) is used.

(c) solid material (C): antifouling agent

(1) silicon compounds

Commercial silica (hereinafter referred to as "SI") (trade name: Nipsil VN3LP, manufactured and marketed by Nippon Silica Industrial Co., Japan) is used.

(2) oil absorption material

A commercially available porous styrene-vinylbenzene copolymer (hereinafter referred to as "SDV") (trade name: Diaion MP-A, manufactured and marketed by Mitsubishi Chemical Corporation, Japan) is used. SDV has a number average particle diameter of 10 μm and a number average pore diameter of 0.01 μm.

(d) solvent (D)

Commercial xylenes, methylene chloride, methanol and formic acid (hereinafter referred to as "XY, MCl, MeOH, FA", respectively) are used.

(e) other solid materials

(1) phenol novolak resin (softening temperature: 120 ℃)

A commercial novolac resin (hereinafter referred to as "NK") (trade name: SP1006N, manufactured and sold by Asahi Organic Chemicals Industry Co., Ltd., Japan) is used.

(2) UV absorbers

Commercial benzotriazole containing ultraviolet absorbers (hereinafter referred to as "UVA") (trade name: Tinuvin P, Switzerland, manufactured and marketed by CIBA-GEIGY) are used.

(3) Hindered piperidine-containing light stabilizer

Commercially available hindered piperidine-containing light stabilizers (hereinafter referred to as "HALS") (trade name: Tinuvin 770, Switzerland, manufactured and marketed by CIBA-GEIGY) are used.

(4) white pigment (shading agent)

Commercial powdery titanium oxide (hereinafter referred to as "TiO ₂ ") having an average particle diameter of 0.2 µm (trade name: TIPAQUE PF-691, manufactured and marketed by Ishihara Sangyo Kaisya, Ltd., Japan) is used.

(5) organic epoxy compound

Commercial epoxidized soybean oil (hereinafter referred to as "EP") (trade name: O-130P, manufactured and sold by Asahi Denka Kogyo K.K., Japan) is used.

(6) fluororesins

Commercial polytetrafluoroethylene (hereinafter referred to as "PTFE") (trade name: Teflon 6J, manufactured and marketed by Du Pont-Mitsui Fluorochemicals Co., Ltd., Japan) is used.

Example 1 and Comparative Examples 1 to 4

Each of the five forms of the resin composition shown in Table 1 is independently produced by a process selected from the following four processes and evaluated for various properties such as color tone (yellowness: YI). The results are shown in Table 1.

Process i

Using a batch type mixing vessel equipped with a stirrer, the thermoplastic resin (A) is dissolved in the nonpolymerizable liquid substance (B) at the temperature shown in Table 1 while stirring. The product is introduced into a belt conveyor type dry cooler (belt cooler), whereby pellets are obtained.

Process II-1

A twin screw extruder having a main feeder and a subfeeder is used. The thermoplastic resin (A) is fed from the main feeder and the non-polymerizable liquid substance (B) is fed from the subfeeder, followed by melt extrusion at the temperatures shown in Table 1, whereby pellets are obtained.

Process II-2

A twin screw extruder having a main feeder and a subfeeder is used. The thermoplastic resin (A) and the nonpolymerizable liquid substance (B) are fed from the main feeder, and then melt-extruded at the temperatures shown in Table 1, whereby pellets are obtained.

Process III

The nonpolymerizable liquid substance (B) is added to the thermoplastic resin (A) in a small amount and adsorbed to the thermoplastic resin (A), thereby obtaining an adsorption mixture of the thermoplastic resin (A) and the nonpolymerizable liquid substance (B). The mixture is introduced into a belt conveyor cooler (belt cooler), whereby pellets are obtained.

From Table 1, PPE-1 was dissolved as a thermoplastic resin (A) at a temperature of less than 300 ° C. to suppress the formation of OH groups in the PPE unit (see FIGS. 3 and 4), which was prepared by Process I (invention). Regarding the resin composition, it can be observed that the resin composition not only has excellent appearance, color tone, and light stability with respect to that of other resin compositions produced by melt extrusion, but can also be stably produced. On the other hand, in each of the processes II-1 and II-2, the extrusion of the resin composition is unstable when the content of the non-polymerizable liquid substance (B) in the resin composition is about 60% by weight. In addition, the resin composition prepared in Step II-1 (executed under the conditions of melting PPE-1) does not melt, and thus does not contain any undissolved melt of resin having a good appearance; It is poor with respect to color tone and light stability (reference comparative example 3). The resin composition prepared in step II-2, in which the thermoplastic resin (A) and the non-polymerizable liquid substance (B) are supplied from the main feeder and then melt-extruded, contains a large number of cosmetic melts of PPE-1 that are not melted and therefore have poor appearance. Have Particularly in the case of the process III, the resin composition prepared in the process III of adsorbing the non-polymerizable liquid substance (B) to the thermoplastic resin (A) contains a large number of undissolved PPE-1 unmelted melts and therefore has a very poor appearance.

Examples 2 to 17 and Comparative Examples 5 to 28

The resin composition is prepared using the materials and methods (step I or II) as described in Tables 2 to 4, using PPE-1, PC, GPPS and HIPS-1 independently as the thermoplastic resin (A). The obtained resin composition is evaluated for various properties such as color tone (yellowness: YI). The results are shown in Tables 2 to 4 and FIG. 5.

From Tables 2 to 4 and Fig. 5, the resin composition obtained by the method of the present invention, which is carried out by the process I (dissolution) at a temperature of 300 DEG C or lower, is compared with a resin composition obtained by the conventional melt extrusion method. It is clear that the appearance and color are excellent.

Examples 18-34 and Comparative Examples 29-32, and 52-55

The resin composition is prepared using materials and methods (steps I or II) as described in Tables 5 to 7, wherein PPE-1 and GPPS are independently used as the thermoplastic resin (A). The obtained resin composition is evaluated for various properties such as color tone (yellowness: YI). The results are shown in Tables 5 to 7 and FIGS. 6 and 7.

From Tables 5-7 and Figures 6 and 7, the following is observed:

When the production of the resin body is carried out by the process I (dissolution) using a surface modifier such as an anti-sticking agent or a lubricant instead of the non-polymerizable liquid substance (B), since the surface modifier has poor compatibility with the thermoplastic resin (A), Dissolving the thermoplastic resin (A) with the surface modifier at a high temperature, which in turn promotes deterioration of the thermoplastic resin (A) and the surface modifier (Comparative Examples 29 to 32);

The compatibility of oligomeric aromatic phosphate esters with PPE-1 (often, a flame retardant having excellent compatibility with thermoplastic resins, in which the oligomeric aromatic phosphate esters have somewhat inferior compatibility with thermoplastic resins such as PPE-1) is compatible with oligomeric aromatic phosphate esters. Can be significantly improved by the compatibility of monomeric aromatic phosphate esters or GPPS in mixing; And

With respect to step II-1 (melt extrusion), extrusion can be stably performed when the amount of the nonpolymerizable liquid substance (B) is 20% by weight or less relative to the total weight of (A) and (B); Extrusion is unstable when the amount of the nonpolymerizable liquid substance (B) exceeds 20% by weight.

Examples 35-50 and Comparative Examples 33-34

The resin composition is prepared using the materials and methods (step I) as described in Tables 8 and 9. The obtained resin composition is evaluated for various properties such as color tone (yellowness: YI). The results are shown in Tables 8 and 9.

From Tables 8 and 9, the following is observed:

When the PPE-1 / nonpolymerizable liquid material (B) (flame retardant) weight ratio is in the range of 30/70 to 70/30, it is possible to obtain a molded resin body excellent in terms of ease of operation;

When a solid material (C), such as an oil absorbent material and an antifouling agent, is added to the component (A) / component (B) mixture having a weight ratio within the above range in an amount in which the mixture is present in the liquid state, the resulting resin mixture does not adhere Not; And

When the component (A) / component (B) mixture (in the liquid state) to which the solid substance (C) is added is uneven or has poor fluidity, the appearance of the produced resin composition is very poor (Comparative Example 34).

Examples 51 to 53 and 108, and Comparative Examples 35 to 38, 50 and 51

A resin composition used as a masterbatch was prepared using the materials and methods shown in Table 10, wherein the dissolution of PPE-1 into a non-polymerizable liquid substance (B) improved the compatibility of component (B) with PPE-1. It carries out in presence of the solvent (D) which acts, and introduce | transduces the resulting resin composition into a belt conveyor type cooling drier (belt cooler). Using a twin screw extruder (ZSK-40 mmØ, manufactured and marketed by Werner Pfleiderer GmbH, Germany), the obtained masterbatch and HIPS-1 were removed with solvents under vacuum of 0.1 mmHg, Melt extrusion is carried out depending on the composition and the preparation conditions, thereby obtaining a final product in pellet form. Using an injection molding machine (Model JSW J100EP manufactured and marketed by Japan Steel Works, Ltd., Japan), the obtained pellets were injection molded at a cylinder temperature of 230 ° C. and a molding temperature of 60 ° C. to obtain test specimens. Is evaluated for various properties such as color tone (yellowness: YI). The results are shown in Table 10.

From Table 10 the following is observed:

Compatibility of the oligomeric aromatic phosphate ester with PPE-1 A small amount of solvent (D) (the oligomer aromatic phosphate ester has relatively poor compatibility with PPE-1 among various flame retardants which usually have excellent compatibility with PPE-1). That can be significantly improved by the addition of;

However, when the amount of the solvent (D) exceeds 100 parts by weight of the thermoplastic resin (A), it becomes difficult to maintain the vacuum condition, so that the solvent (D) remains in the resin composition. Lowering the vicat softening temperature of the resin composition thus prepared (the role of the solvent (D) is secondary, the compatibility between the thermoplastic resin (A) and the nonpolymerizable liquid material (B) is relatively low, and the solvent (D) A small addition of is indicative of a satisfactory improvement in compatibility);

When lubricating oil, which is not compatible with the thermoplastic resin (A), is used as the nonpolymerizable liquid substance (B), the amount of the solvent (D) is adjusted in order to achieve satisfactory compatibility between the component (A) and the component (B). Unnecessarily high use is necessary and therefore it is difficult to achieve the vacuum condition, thereby generating the above disadvantages (Comparative Examples 35 and 36);

When manufacturing a resin composition by the method of disperse | distributing a nonpolymerizable liquid substance (B) to a thermoplastic resin (A), since the thermoplastic resin (A) does not melt | dissolve in a nonpolymerizable liquid substance (B), the external appearance of the manufactured resin composition Is very poor (Comparative Examples 37 and 38);

When polyamide (PA) is used as the thermoplastic resin (A) and phosphate ester (PB) as the nonpolymerizable liquid substance (B), which is very poor in compatibility between components (A) and (B), solvents (FA) A large amount of) dissolves the PA unevenly in the PB; When the resulting mixture is used as the masterbatch in the second stage, phase separation occurs during removal of the solvent (Comparative Examples 50 and 51).

Examples 54-69 and Comparative Examples 39-42

The resin compositions having the compositions shown in Tables 11 and 12 were prepared by the following three preparation methods, wherein HIPS and PPE having different reducing viscosities ηsp / c as shown in Tables 11 and 12 were independently used as thermoplastic resins (A). use. Each of the obtained resin compositions was injection molded according to the same composition and conditions as shown in Table 10 to thereby obtain a test piece. Test specimens are evaluated for flame retardancy, MFR, Izod impact strength, vicat softening temperature and color tone (yellowness: YI). The results are shown in Tables 11 and 12.

From Tables 11 and 12, the following is observed:

In the case of using the production method (a) (using the resin composition of the present invention as a masterbatch), the resulting final resin composition exhibits excellent properties compared to that of the resin composition prepared in the production methods (b) and (c). Will;

When HIPS having a reducing viscosity ηsp / c in the range of 0.4 to 0.6 is used as the thermoplastic resin composition (A), the obtained resin composition exhibits an excellent balance of fluidity, Izod impact strength and flame retardancy;

In particular, when using PPE having a reduced viscosity ηsp / c in the range of 0.3 to 0.6, the produced resin composition exhibits excellent balance of fluidity, heat resistance, Izod impact strength and flame retardancy.

(Production method)

(a): The thermoplastic resin (A) is dissolved in a nonpolymerizable liquid substance (B) at 200 degreeC, stirring, using the batch type mixing container with a stirrer. The product is introduced into a belt conveyor type cold drier (belt cooler) to thereby obtain a resin composition to be used as a masterbatch. The masterbatch and HIPS are then melt extruded at 230 ° C. using a twin screw extruder ZSK-40 mmØ (manufactured and sold by Werner Pfleiderer GmbH, Germany).

(b) A twin screw extruder with main and sub feeders is used. The thermoplastic resin (A) is fed from the main feeder and melted at 350 ° C. The non-polymerizable liquid substance (B) is then fed from a subfeeder and kneaded at 230 ° C. to thereby obtain a resin composition to be used as a masterbatch, followed by melt extrusion in the same manner as in the production method (a).

(c): A small amount of a nonpolymerizable liquid substance (B) is added to a thermoplastic resin (A), and a component (B) is made to adsorb | suck to a thermoplastic resin (A). The resulting adsorption mixture of components (A) and (B) is mixed with HIPS to thereby obtain a mixture, which is then melt-extruded at 230 ° C. in the same manner as in production process (a).

The production methods (a), (b) and (c) are used in the following Examples and Comparative Examples.

Comparative Examples 70 to 107 and Comparative Examples 43 to 49

The resin composition which has a composition shown in Tables 13-17 is manufactured using the material and method (manufacturing method (a) or (b)) of Tables 13-17. The obtained resin composition is evaluated for flame retardancy, MFR, Izod impact strength, vicat softening temperature, temperature at 1 wt% loss of light stability, and color tone (yellowness: YI). The results are shown in Tables 13 to 17.

Table 13 shows the relationship between the form of the aromatic phosphate ester and the properties of the resin composition.

Table 14 shows the effect of the amount of styrene monomer and styrene oligomer remaining in the resin composition on the flame retardancy of the resin composition and the addition effect of the novolak resin and the fluororesin.

Table 15 shows the effect of the white pigment and the light resistance improving agent. From Table 15, in particular, when the purpose is to obtain a light colored molded resin body, since the resin composition of the present invention can be colorized by the use of a small amount of white pigment, the molded product obtained by using the resin composition of the present invention The mechanical properties (such as Izod impact strength), which are a problem in parallel with the molded article obtained by using the conventional resin composition obtained by the conventional melt extrusion method, are not reduced (Comparative Example).

Tables 16 and 17 describe the effects of the addition of aromatic phosphate esters, compatibilizers (AS), thermoplastic elastomers, TPE and PPE-1, and the properties of the resin compositions on the properties of the PC / HIPS type (such as Izod impact strength). The influence of the ratio is shown.

Examples and Comparative Examples Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Composition (weight ratio) Thermoplastic Resin (A) (PPE-1) 40 40 Nonpolymerizable Liquid Substance (B) (TNPP) 60 60 Compatibility between (A) and (B) (filtration residual ratio,%) 7) 0 Manufacture state of resin composition Temperature (℃) 2) 250 350 Process 1) I II-1 III II-1 II-2 Manufacturing stability Good Extrusion instability Good Extrusion instability Evaluation of Resin Composition Exterior Good PPE-1 Multiple Cosmetic Melt5) PPE-1 Excess Cosmetic Melt6) Good PPE-1 Multiple Cosmetic Melt5) Yellow Degree (YI) 41 4) 4) 69 4) Izod impact strength (J / m) 88 29 10 69 29 Light stability 3) (△ E measurement after 300 hours irradiation) 12.1 4) 26.8 4)

Examples and Comparative Examples Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Evaluation of Resin Composition Amount of OH groups in PPE (moles / 100 moles of PPE unit) 0.3 4) 0.8 4) Note: 1) Process-I (melt), Process-II-1 (melt extrusion), Process-II-2 (melt extrusion) and Process-III (melt extrusion) are as described above. 2) Temperature: (A) 3) The smaller the value of ΔE, the better the light stability. 4) The surface state is coarse and uneven, and yellowness (YI) cannot be measured. 5) Multiple undissolved melts of PPE-1 not observed 6) Excess undissolved melts of PPE-1 are observed 7) Weight of component (A) / component (B) mixture remaining in the filter To ratio of weight of thermoplastic resin (A) in the resin composition before filtration.

Examples and Comparative Examples Composition (% by weight) Compatibility between (A) and (B) (filtration residual ratio,%) 5) Manufacture state of resin composition Manufacturing stability Thermoplastic Resin (A) (PPE-1) Nonpolymerizable Liquid Substance (B) (TPP) Temperature (℃) 2) Process 1) Example 2 ^* 30 70 0 150 I (melting) Good Example 3 ^* 200 Example 4 250 Example 5 300 Comparative Example 5 310 Comparative Example 6 350 Comparative Example 7 150 II-1 (melt extrusion) Melt instability Comparative Example 8 200 Comparative Example 9 250 Comparative Example 10 300 Comparative Example 11 310 Comparative Example 12 350

Examples and Comparative Examples Evaluation of Resin Composition Exterior Yellow Degree (YI) Amount of OH groups in PPE (moles / 100 moles of PPE unit) Example 2 ^* Good 28 0.2 Example 3 ^* 32 0.2 Example 4 37 0.2 Example 5 46 0.3 Comparative Example 5 56 0.6 Comparative Example 6 64 0.7 Comparative Example 7 PPE-1 Multiple Beauty Melt 4) 3) 3) Comparative Example 8 Comparative Example 9 Comparative Example 10 Good 65 0.8 Comparative Example 11 71 0.9 Comparative Example 12 78 1.0 Note: ^* : more preferred embodiments. 1) Process-I (dissolution) and Process-II-1 (melt extrusion) are as described above. 2) Temperature: (A) is dissolved in (B) or (B) 3) The surface condition is coarse and uneven, and yellowness (YI) cannot be measured. 4) Many unmelted PPE-1 unmelted melts are observed. 5) Component (A) remaining in the filter. Ratio of the weight of the / component (B) mixture to the weight of the thermoplastic resin (A) in the resin composition before filtration.

Examples and Comparative Examples Composition (% by weight) Compatibility between (A) and (B) (filtration residual ratio,%) 6) Manufacture state of resin composition Manufacturing stability Thermoplastic Resin (A) (PPE-1) Nonpolymerizable Liquid Substance (B) (TPP) Temperature (℃) 2) Process 1) Example 6 ^* 30 70 0 150 I (melting) Good Example 7 ^* 200 Example 8 ^* 230 Example 9 240 Example 10 250 Example 11 300 Comparative Example 13 310 Comparative Example 14 350 Comparative Example 15 150 II (melt extrusion) Extrusion instability Comparative Example 16 200 Comparative Example 17 250 Comparative Example 18 300 Comparative Example 19 310 Comparative Example 20 350

Examples and Comparative Examples Evaluation of Resin Composition Note ^* : more preferred embodiments. 1) Process-I (dissolution) and Process-II-1 (melt extrusion) are as described above. 2) Temperature: (A) is dissolved in (B) or (B) 3) Melt mixing temperature. 3) Surface condition is coarse and uneven, and yellowness (YI) cannot be measured. 4) Many unmelted PPE-1 unmelted melts are observed. A melt is observed. 6) The ratio of the weight of the component (A) / component (B) mixture remaining in the filter to the weight of the thermoplastic resin (A) in the resin composition before filtration. Exterior Yellow Degree (YI) Example 6 ^* Good 9 Example 7 ^* 10 Example 8 ^* 11 Example 9 17 Example 10 18 Example 11 22 Comparative Example 13 37 Comparative Example 14 45 Comparative Example 15 PPE-1 Multiple Beauty Melt 4) 3) Comparative Example 16 Comparative Example 17 PPE-1 hydrophobic beauty melt 5) Comparative Example 18 Good 44 Comparative Example 19 50 Comparative Example 20 56

Examples and Comparative Examples Composition (% by weight) Compatibility between (A) and (B) (filtration residual ratio,%) 3) Manufacture state of resin composition Manufacturing stability Thermoplastic Resin (A) Nonpolymerizable Liquid Substance (B) Temperature (℃) 2) Process 1) Example 12 ^* GPPS (30) TPP (70) 0 150 I (melting) Good Example 13 ^* 180 Example 14 200 Example 15 250 Example 16 300 Comparative Example 21 310 Comparative Example 22 350 Comparative Example 23 150 II (melt extrusion) Extrusion instability Comparative Example 24 200 Comparative Example 25 250 Comparative Example 26 300 Comparative Example 27 310 Comparative Example 28 350 Example 17 HIPS-1 (30) TPP (70) 4 200 I (melting) Good

Examples and Comparative Examples Evaluation of Resin Composition Note ^* : more preferred embodiments. 1) Process-I (dissolution) and Process-II-1 (melt extrusion) are as described above. 2) Temperature: (A) is dissolved in (B) or (B) 3) the ratio of the weight of the component (A) / component (B) mixture remaining in the filter to the weight of the thermoplastic resin (A) in the resin composition before filtration. Exterior Yellow Degree (YI) Example 12 ^* Good 8 Example 13 ^* 9 Example 14 15 Example 15 16 Example 16 18 Comparative Example 21 30 Comparative Example 22 41 Comparative Example 23 Good 13 Comparative Example 24 17 Comparative Example 25 22 Comparative Example 26 24 Comparative Example 27 36 Comparative Example 28 50 Example 17 Good 8

Examples and Comparative Examples Composition (weight ratio) Compatibility between (A) and (B) (filtration residual ratio,%) 5) Manufacture state of resin composition Thermoplastic Resin (A) Nonpolymeric Liquid Substance (B) (or Comparative Liquid Substance) Lower temperature limit for melting (℃) 2) Process 1) Example 18 PPE-1 (20) TPP (80) 0 109 I (melting) Example 19 PPE-1 (50) TPP (50) 131 Example 20 PPE-1 (80) TPP (20) 172 Comparative Example 29 PPE-1 (20) A-Stat (80) 61 302 I (melting) Comparative Example 30 PPE-1 (50) A-Stat (50) 329 Comparative Example 31 PPE-1 (80) A-Stat (20) 370 Comparative Example 32 PPE-1 (20) Lb (80) 75 Insoluble at temperatures above 300 ° C I (melting) Comparative Example 52 PPE-1 (20) TPP (80) 0 310 (melting temperature) (° C) II-1 (melt extrusion) Comparative Example 53 PPE-1 (50) TPP (50) Comparative Example 54 PPE-1 (70) TPP (30) Comparative Example 55 PPE-1 (80) TPP (20)

Comparative Example and Example Manufacturing stability Evaluation of Resin Composition Exterior Yellow Degree (YI) Amount of OH groups in PPE (moles / 100 moles of PPE unit) Example 18 Good Good 15 0.2 Example 19 46 0.3 Example 20 70 0.4 Comparative Example 29 Good 31 0.6 Comparative Example 30 61 0.7 Comparative Example 31 91 0.9 Comparative Example 32 PPE-1, aesthetic melt 4) and instability PPE-1, many cosmetic melts 3) Comparative Example 52 TPP is taken out from the die and cannot be manufactured stably. Comparative Example 53 Extrusion instability Good 73 1.1 Comparative Example 54 Extrusion slightly unstable 88 1.2 Comparative Example 55 Good 99 1.3 Note 1) Process-I (dissolution) and Process-II-1 (melt extrusion) are as described above. 2) The resin composition is introduced at the lower limit of the temperature at which (A) is completely dissolved in (B). The condition is coarse and nonuniform, making yellowness (YI) not measurable. 4) Multiple cosmetic melts of unmelted PPE-1 are observed. 5) Weight of component (A) / component (B) mixture remaining in the filter versus The percentage by weight of the thermoplastic resin (A) in the resin composition before filtration.

Examples and Comparative Examples Composition (weight ratio) Compatibility between (A) and (B) (filtration retention ratio,%) 3) Thermoplastic Resin (A) (PPE-1) Non-polymerizable Liquid Substance (B) Stabilizer (TNP) Aromatic phosphate esters Monomer (TNPP) Oligomer (FR-1) Example 21 50 0 0 50 9 Example 22 ^* 5 45 0 Example 23 ^* 10 40 0 Example 24 30 20 0 Example 25 50 0 0 Example 26 ^* 50 0.5 0 50 9

Examples and Comparative Examples Manufacture state of resin composition Evaluation of Resin Composition Melting limit temperature (℃) 2) Process 1) Exterior Yellow Degree (YI) Amount of OH groups in PPE (moles / 100 moles of PPE unit) Example 21 200 I (melting) Good 56 0.5 Example 22 ^* 171 51 0.4 Example 23 ^* 163 50 0.3 Example 24 151 48 0.3 Example 25 139 47 0.3 Example 26 ^* 200 50 0.4 Note ^* More preferred embodiment 1) Process-I (dissolution) is as described above. 2) A resin composition is prepared at the lower limit of the temperature at which (A) is completely dissolved in (B). 3) Components remaining in the filter ( The ratio (%) of the weight of the A) / component (B) mixture to the weight of the thermoplastic resin (A) in the resin composition before filtration.

Examples and Comparative Examples Composition (weight ratio) Compatibility between (A) and (B) (filtration retention ratio,%) 3) Thermoplastic Resin (A) Non-polymeric liquid substance (B) (SP level) PPE-1SP value: 11.2 GPPSSP value: 10.5 Example 27 50 0 FR-1 (50) (11.0) 9 Example 28 49 One Example 29 45 5 Example 30 40 10 Example 31 45 5 FR-2 (50) (10.6) 6 Example 32 FR-3 (50) (10.9) 4 Example 33 TPP (50) (10.7) 0 Example 34 TNPP (50) (9.4) 0

Examples and Comparative Examples Manufacture state of resin composition Evaluation of Resin Composition Melting limit temperature (℃) 2) Process 1) Exterior Yellow Degree (YI) Amount of OH groups in PPE (moles / 100 moles of PPE unit) Example 27 200 I (melting) Good 56 0.5 Example 28 181 50 0.4 Example 29 177 49 0.4 Example 30 161 47 0.3 Example 31 158 I (melting) Good 46 0.3 Example 32 140 45 0.3 Example 33 119 43 0.3 Example 34 121 44 0.3 Note 1) Process-I (dissolution) is as described above. 2) A resin composition is prepared at the lower limit of the temperature at which (A) is completely dissolved in (B). 3) Component (A) / component (remaining in the filter) B) The ratio of the weight of the mixture to the weight of the thermoplastic resin (A) in the resin composition before filtration.

Examples and Comparative Examples Composition (weight ratio) Compatibility between (A) and (B) (filtration retention ratio,%) 3) Manufacture state of resin composition Thermoplastic Resin (A) (PPE-1) Nonpolymerizable Liquid Substance (B) (TPP) Solid substance (C) Temperature (℃) 2) Process 1) Example 35 10 90 0 0 220 I (melting) Example 36 20 80 Example 37 ^* 30 70 Example 38 ^* 40 60 Example 39 ^* 50 50 Example 40 ^* 60 40 Example 41 ^* 70 30 Example 42 80 20 Example 43 90 10 Example 44 10 90 0.5 (SI) 220 I (melting) Example 45 20 80 0.5 (SI) Example 46 30 70 0.5 (SI) Example 47 20 80 0.5 (SDV)

Examples and Comparative Examples Evaluation of Resin Composition Exterior Yellow Degree (YI) Amount of OH groups in PPE (moles / 100 moles of PPE unit) Example 35 Good but slightly bleeding 5 0.2 Example 36 20 0.2 Example 37 ^* Good 34 0.2 Example 38 ^* 43 0.2 Example 39 ^* 55 0.3 Example 40 ^* 63 0.3 Example 41 ^* 71 0.3 Example 42 79 0.5 Example 43 86 0.5 Example 44 Good (in particular, the resin composition has no adhesion) 6 0.2 Example 45 18 0.2 Example 46 32 0.2 Example 47 17 0.2 Note ^* More preferred embodiment 1) Process-I (dissolution) is as described above. 2) A resin composition is prepared at the lower limit of the temperature at which (A) is completely dissolved in (B). 3) Components remaining in the filter ( The ratio (%) of the weight of the A) / component (B) mixture to the weight of the thermoplastic resin (A) in the resin composition before filtration.

Examples and Comparative Examples Composition (weight ratio) Compatibility between (A) and (B) (filtration retention ratio,%) 7) Manufacture state of resin composition Thermoplastic Resin (A) Non-polymerizable Liquid Substance (B) Solid substance (C) Temperature (℃) 2) Process 1) Example 48 GPPS (30) Br-EP (70) 0 0 200 I (melting) Example 49 HIPS-1 (30) Br-EP (70) 0 4 200 Example 50 ABS (30) Br-EP (70) 0 5 200 Comparative Example 33 PPE-1 (30) TPP (70) 0 0 20 Comparative Example 34 PPE-1 (30) TPP (70) SDV (50) 0 200

Examples and Comparative Examples Dissolution state Evaluation of Resin Composition Exterior Yellow Degree (YI) Example 48 3) Good 9 Example 49 4) 10 Example 50 12 Comparative Example 33 Paste PPE-1, many cosmetic melts 6) 5) Comparative Example 34 Paste Note 1) Process-1 (dissolution) is as described above. 2) Temperature: The temperature at which (A) is dissolved in (B) or melt mixed into (B). 3) Non-uniform dissolution. 4) (mostly) dissolution and (Partial) Swelling. 5) Surface condition is coarse and uneven, and yellowness (YI) cannot be measured. 6) Many unmelted PPE-1 unmelted melts are observed. 7) Component (A) / remaining in filter Ratio of weight of component (B) mixture to weight of thermoplastic resin (A) in the resin composition before filtration.

Examples and Comparative Examples Step 1: Preparation of the Masterbatch (MB) Compatibility between (A) and (B) (filtration retention ratio,%) 1) Composition of MB (weight ratio) State of the resin composition Mixed state of (A) and (B) Thermoplastic resin (A) (PPE-1) Non-polymeric liquid substance (B) (or comparative liquid substance) Solvent (D) Melt temperature (℃) fair Example 108 50 50 (FR-1) 0 100 I (melting) 3) 9 Example 51 50 50 (FR-1) 0 150 4) 9 Example 52 50 50 (FR-1) 10 (XY) 150 5) 9 Example 53 50 50 (FR-1) 60 (XY) 100 5) 9 Comparative Example 35 50 50 (Lb) 0 300 6) 75 Comparative Example 36 50 50 (Lb) 100 (MCl) 40 5) 75 Comparative Example 37 98 2 (TPP) 98 (MeOH) 20 Dispersion 7) 0 Comparative Example 38 83 17 (MO) 0 20 7) 52 Comparative Example 50 50 (PA6) 50 (PB) 0 150 I (melting) 6) 86 Comparative Example 51 50 (PA6) 50 (PB) 250 (FA) 150 5) 86

Examples and Comparative Examples Second Step: Melting Step Using MB Evaluation of Resin Composition Composition of the final composition (weight ratio) 2) Manufacture state of resin composition MB Thermoplastic Resin (HIPS-1) Melt Extrusion Temperature (℃) Vacuum devolatilization Yellow Degree (YI) Izod impact strength (J / m) Vicat Softening Temperature (℃) Amount of OH groups in PPE (moles / 100 moles of PPE unit) Example 108 20 80 230 radish 7 80 94 0.2 Example 51 20 80 radish 7 88 94 0.2 Example 52 22 80 U 5 88 93 0.2 Example 53 32 80 U 6 78 85 0.2 Comparative Example 35 20 80 radish The surface condition is coarse and uneven so that the above properties cannot be measured. Comparative Example 36 40 80 U Phase separation is impossible due to the above measurement Comparative Example 37 20.2 80 U Observing many cosmetic melts of PPE-1, the surface condition is coarse and uneven, so the above properties cannot be measured Comparative Example 38 20 80 radish Comparative Example 50 20 80 radish The surface condition is coarse and uneven so that the above properties cannot be measured. Comparative Example 51 70 80 U Phase separation is impossible due to the above measurement Note 1) The ratio of the weight of the component (A) / component (B) mixture remaining in the filter to the weight of the thermoplastic resin (A) in the resin composition before filtration. (2) of the PPE-1 / nonpolymerizable liquid material. Prepare the final product so that the weight ratio is 10/10. 3) Swelling. 4) (mostly) dissolution and (partly) swelling. 5) heterogeneous dissolution. 6) phase separation. 7) dispersion.

Item Example 54 Example 55 ^* Example 56 ^* Example 57 ^* Example 58 ^* Example 59 Comparative Example 39 Comparative Example 40 Process 1) (a) (b) (c) Composition (weight ratio) First step (A) PPE-1 20 (B) FR-1 14 2nd step ηsp / c HIPS-2 0.79 80 -3 0.60 80 -4 0.58 80 -1 0.53 80 80 80 -5 0.40 80 -6 0.35 80 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 14.6 13.1 12.5 11.2 10.5 9.8 15.1 28.2 Digestion particle drop U U U U U U U U Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-2 V-2 V-2 V-2 V-2 V-2 V-2 HB 2) MFR (g / 10 min) 3.8 4.0 5.0 5.2 7.0 8.0 4.9 12.5 Izod impact strength (J / m) 70 67 64 62 59 40 56 13 Vicat Softening Temperature (℃) 95 95 95 95 95 95 96 85 Surface of molded body Good Good 3) Yellow Degree (YI) 19 23 18 21 20 21 53 4) Note ^* More Preferred Embodiments 1) Processes (a), (b) and (c) are as described above (Examples 54-69 and Comparative Examples 39-42). 2) HB is the standard V-0 of UL-94. , Flame retardancy of the sample that does not match any of V-1 and V-2. 3) Many unmelted PPE-1 undissolved melts are observed. 4) Surface condition is coarse and uneven, resulting in yellowness ) It is impossible to measure.

Item Example 60 Example 61 ^* Example 62 ^* Example 63 ^* Example 64 Example 65 Example 66 ^* Example 67 ^* Process 1) (a) Composition (weight ratio) First step (A) Polyphenylene ether (part by weight) Reduction Viscosity ηsp / c 50.14 100.41 200.41 250.41 300.41 200.25 200.30 200.60 (B) FR-1 15 2nd step HIPS-1 95 90 80 75 70 80 80 80 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 15.1 12.3 9.5 8.1 5.1 8.1 8.9 10.3 Digestion particle drop U U U U radish U U U Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-2 V-2 V-2 V-2 V-1 V-2 V-2 V-2 MFR (g / 10 min) 12.3 8.1 5.5 5.4 3.9 7.9 6.1 5.0 Izod impact strength (J / m) 69 67 65 64 59 40 55 70 Vicat Softening Temperature (℃) 82 90 94 99 104 94 95 95 Surface of molded body Good Yellow Degree (YI) 2 5 19 23 29 20 18 21

Item Example 68 Comparative Example 41 Comparative Example 42 Example 69 Note ^* More Preferred Embodiments 1) Processes (a), (b) and (c) are as described above (Examples 54-69 and Comparative Examples 39-42). 2) HB is the standard V-0 of UL-94. , Flame retardancy of the sample that does not match any of V-1 and V-2. 3) Excess cosmetic melt of unmelted PPE-1 is observed. 4) Surface condition is coarse and uneven and yellowness (YI) ) It is impossible to measure. Process 1) (a) (b) (c) (a) Composition (weight ratio) First step (A) Polyphenylene ether (part by weight) Reduction Viscosity ηsp / c 200.65 200.41 100.41 350.41 (B) FR-1 15 15 15 15 2nd step HIPS-1 80 80 90 65 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 12.1 16.1 27.6 3.0 Digestion particle drop U U U radish Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-2 V-2 HB 2) V-0 MFR (g / 10 min) 3.8 5.0 15.1 2.0 Izod impact strength (J / m) 76 57 13 69 Vicat Softening Temperature (℃) 95 94 79 110 Surface of molded body Good Good 3) Good Yellow Degree (YI) 19 55 4) 32

Item Example 70 Example 71 Example 72 Example 73 Example 74 Example 75 Comparative Example 43 Process 1) (a) (b) Composition (weight ratio) First step (A) PPE-1 15 15 (B) FR-1FR-2TNPPFR-3TPP 14 14 77 14 14 14 14 2nd step HIPS-2 85 85 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 15.3 14.2 18.1 21.3 20.0 12.1 17.3 Digestion particle drop U U U U U U U Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-2 V-2 V-2 V-2 V-2 V-2 V-2 MFR (g / 10 min) 9.8 7.3 9.3 9.5 7.2 13.2 9.9 Izod impact strength (J / m) 65 68 72 68 52 77 57 Vicat Softening Temperature (℃) 92 97 97 95 95 86 92 Temperature at 1 wt% loss (℃) 299 300 299 298 320 194 297 Yellow Degree (YI) 12 13 13 14 13 12 48 Note: 1) Manufacturing steps (a), (b) and (c) were as described above (Examples 54 to 69 and Comparative Examples 39 to 42).

Item Example 76 ^* Example 77 ^* Example 78 Example 79 Example 80 Example 81 Process 1) (a) Composition (weight ratio) First step (A) PPE-1GPPS 1515 (B) FR-1 15 2nd step HIPS-1 70 NK 0 3 3 PTEK 0 0 0.1 The content of styrene monomer and styrene oligomer in the resin composition (% by weight) 0.1 1.0 1.2 2.0 0.3 0.3 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 9 12 20 25 10 15 Digestion particle drop U U U U U radish Evaluation according to UL-94 (test piece thickness: 1/16 inch) V-2 V-2 V-2 V-2 V-2 V-1 MFR (g / 10 min) 11.0 11.2 11.4 11.5 11.9 11.5 Izod impact strength (J / m) 61 60 58 57 60 63 Vicat Softening Temperature (℃) 93 92 91 90 99 100 Surface of molded body Good Yellow Degree (YI) 12 13 14 16 13 11

Item Comparative Example 44 Example 82 Example 83 Example 84 Example 85 Process 1) (b) (a) Composition (weight ratio) First step (A) PPE-1GPPS 1515 300 300 500 700 (B) FR-1 15 20 20 20 30 2nd step HIPS-1 70 70 70 50 30 NK 0 0 0 0 0 PTEK 0 0 0.1 0 0 Content of styrene monomer and styrene oligomer in the resin composition (% by weight) 0.4 0.5 0.4 0.4 0.7 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 13 3 5 4 2 Digestion particle drop U U radish radish radish Evaluation according to UL-94 (test piece thickness: 1/16 inch) V-2 V-2 V-0 V-0 V-0 MFR (g / 10 min) 11.0 7.1 7.0 4.9 2.3 Izod impact strength (J / m) 60 79 81 96 113 Vicat Softening Temperature (℃) 93 105 106 121 138 Surface of molded body Good Yellow Degree (YI) 46 27 28 40 51 Note: ^* more preferred embodiment.

Item Example 86 Example 87 Example 88 Comparative Example 45 Comparative Example 46 Comparative Example 47 Process 1) (a) (b) Composition (weight ratio) First step (A) PPE-1 20 20 (B) FR-1 13 13 2nd step HIPS-1 80 80 White Pigment (TiO ₂ ) 0 2 4 0 2 4 UVA 0 0 HALS 0 0 EP 0 0 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 10 11 13 11 12 14 Digestion particle drop U U U U U U Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-2 V-2 V-2 V-2 V-2 V-2 MFR (g / 10 min) 7 7 8 7 7 8 Izod impact strength (J / m) 118 108 98 69 49 29 Vicat Softening Temperature (℃) 102 102 101 102 101 101 Surface of molded body Good Good Yellow Degree (YI) 19 14 7 54 43 36 Light stability (△ E measurement after 300 hours of irradiation) 9 8 6 16 14 13

Item Example 89 Example 90 Example 91 Example 92 Process 1) (a) Composition (weight ratio) First step (A) PPE-1 20 (B) FR-1 13 2nd step HIPS-1 80 White Pigment (TiO ₂ ) 2 UVA 0.3 0.3 0.3 0.3 HALS 0 0.2 0 0.2 EP 0 0 0.1 0.1 Evaluation of Resin Composition Flame retardant Digestion time (seconds) 11 12 13 12 Digestion particle drop U U U U Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-2 V-2 V-2 V-2 MFR (g / 10 min) 7 8 9 8 Izod impact strength (J / m) 108 108 108 108 Vicat Softening Temperature (℃) 102 101 100 101 Surface of molded body Good Yellow Degree (YI) 14 14 15 14 Light stability (△ E measurement after 300 hours of irradiation) 6 4 2 4 Note: 1) Manufacturing steps (a), (b) and (c) were as described above (Examples 54 to 69 and Comparative Examples 39 to 42).

Item Example 93 Example 94 Example 95 Example 96 Example 97 Example 98 Process 1) (a) Composition (weight ratio) First step (A) PC 62 PPE-1 0 (B) 14 (FR-2) 14 (TNPP) 7/7 (FR-2 / TNPP) 14 (FR-3) 14 (FR-1) 14 (TPP) 2nd step HIPS-1 38 AS 0 Evaluation of Resin Composition Flame retardant Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-0 V-2 V-0 V-0 V-0 V-0 Evaluation according to UL-94 (test piece thickness: 1/16 inch) V-1 V-2 V-1 V-1 V-1 V-1 MFR (g / 10 min) 3 4 5 5 6 9 Izod impact strength (J / m) 147 108 137 88 108 108 Vicat Softening Temperature (℃) 116 114 115 111 109 99 Temperature at 1% by weight loss 300 298 299 320 280 194 Yellow Degree (YI) 16 15 12 14 13 13

Item Example 99 Example 100 Comparative Example 48 Process 1) (a) (b) Composition (weight ratio) First step (A) PC 57 57 PPE-1 0 5 5 (B) 14 (FR-1) 14 (FR-1) 2nd step HIPS-1 38 38 AS 5 0 0 Evaluation of Resin Composition Flame retardant Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-0 V-0 V-0 Evaluation according to UL-94 (test piece thickness: 1/16 inch) V-1 V-0 V-0 MFR (g / 10 min) 6 5 4 Izod impact strength (J / m) 294 98 78 Vicat Softening Temperature (℃) 109 115 116 Temperature at 1% by weight loss 281 282 281 Yellow Degree (YI) 16 21 43 Note: 1) Manufacturing steps (a), (b) and (c) were as described above (Examples 54 to 69 and Comparative Examples 39 to 42).

Item Example 101 Example 102 Example 103 Example 104 Example 105 Example 106 Example 107 Comparative Example 47 Process 1) (a) (b) Composition (weight ratio) First step (A) PC 5 20 30 60 70 95 30 30 (B) FR-1 20 20 20 2nd step HIPS-1 95 80 70 40 30 5 65 70 TPE 0 5 0 Evaluation of Resin Composition Flame retardant Evaluation according to UL-94 (test piece thickness: 1/8 inch) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Evaluation according to UL-94 (test piece thickness: 1/16 inch) V-1 V-1 V-1 V-1 V-0 V-0 V-0 V-1 MFR (g / 10 min) 12 10 8 6 3 2 8 8 Izod impact strength (J / m) 176 167 157 137 108 98 304 108 Vicat Softening Temperature (℃) 99 101 111 114 116 118 110 111 Yellow Degree (YI) 7 11 13 15 17 21 14 23 Note: 1) Manufacturing steps (a), (b) and (c) were as described above (Examples 54 to 69 and Comparative Examples 39 to 42).

The resin composition of the present invention can be advantageously used to obtain a molded article which is clearly demonstrated in terms of appearance, such as color tone, light stability and mechanical properties, since there is no problem in parallel with the resin composition prepared by the melt extrusion method, such as thermal degradation. In addition, especially when the resin composition of this invention is used as a masterbatch for manufacture of a molding material which adds a masterbatch to the resin material same or different from the thermoplastic resin used for a resin composition, a big advantage arises. The molding material obtained by adding the resin composition of the present invention as a masterbatch is not only not only that the molding material has improved melt moldability, but also due to the fact that the resin in the masterbatch does not experience a high temperature situation. There is an advantage in that the improved molded body can be easily produced from the molding material. Therefore, the resin composition of the present invention is a molding material for producing various molded articles, for example, home appliances such as VTRs (video tape recorders), distribution panels, TVs, audio players, capacitors, household plug sockets, cassette tape recorders. , Videocassettes, video disc players, air conditioners, humidifiers and electrical appliances to provide warm air; Parts for OA devices, eg CD-ROM main body (machine part), printer, facsimile, plain paper copier (PPC), cathode-ray tube (CRT), word processor, copier, electronic cash register, office computer system, floppy Disk drives, keyboards, typewriters, electronic cash registers, electronic calculators, toner cartridges, and telephones; Electronic and electrical components such as connectors, coil reels, switches, relays, relay sockets, light-emmiting diodes (LEDs), various capacitors, alternating current (AC) adapters, FBT high voltage reels, FBT cases, FIT coil reels, jacks, volumes Shaft and motor parts; And automotive parts such as instrument panels, radiator grilles, clusters, speaker grills, louvers, console boxes, defrosters, ornaments, fuse boxes, relay cases and connector shift tapes.

Claims (45)

(A) and (B) below: (A) polyphenylene ether resin, polystyrene resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyolefin resin, polyamide resin, polymethacrylate resin, polyacetal resin, polyarylate resin , Polysulfone resins, polyether imide resins, polyether sulfone resins, polyether ether ketone resins, or thermoplastic elastomers having the same backbone as the polymer backbone of the resin, wherein the number average particles are 0.01 to 10,000 μm. Thermoplastic resin which is a powder having a diameter; And (B) an additive for the thermoplastic resin (A), which is in a liquid state at a temperature in the range of 25 to 300 ° C .; Phthalic acid ester, phthalic acid containing ester, aliphatic dibasic acid ester, glycol ester, aliphatic acid ester, epoxy compound, trioctyl trimellitate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate, tributyl acetyl citrate, chlorination Plasticizers selected from paraffin, polypropylene adipate, polyethylene sebacate, triacetin, tributyrin, toluenesulfonamide, alkylbenzene, biphenyl, partially hydrogenated terphenyl or camphor; Thermal stabilizers selected from metal soaps, lead stabilizers, organotin stabilizers, composite stabilizers or epoxy compounds; Light stabilizers selected from ultraviolet absorbers, hindered amine light stabilizers, antioxidants, active species trapping agents, light shielding agents, metal inerts or quenchers; Flame retardants selected from halogen-containing flame retardants or phosphorus-containing flame retardants; coloring agent; blowing agent; slush; Spices; Fuming inhibitors; Tackifiers; antiseptic; Warming agent; Impact strength improver; Repellents; Wetting agents; Surfactants; Emulsifiers; Destabilizing agents; coagulant; Antifoam; Cryoprotectants; Creaming agents; Thickeners; At least one non-polymeric liquid substance selected from the group consisting of heat-sensitive agents and foaming agents Thermoplastic resin (A) by mixing together at a weight ratio of 10/90 to 90/10, at a temperature in the range from 25 to 300 ° C., wherein the at least one non-polymeric liquid material (B) remains liquid at this temperature). ) Is substantially the same as the resin composition prepared by the process comprising dissolving in) at least one nonpolymerizable liquid material (B) or swelling with at least one nonpolymerizable liquid material (B). The solid material (C) according to claim 1, wherein the thermoplastic resin (A) and the nonpolymerizable liquid material (B) are mixed together with the solid material (C) as an additive for the thermoplastic resin (A), wherein the solid material ( C) is at least one additive selected from the group consisting of an anti-sticking agent, an oil absorbent, a heat stabilizer and a light stabilizer, which is a crystalline solid or an amorphous solid at a temperature of 300 ° C. or less, and the amount of the solid material (C) is the thermoplastic resin. (A) The resin composition, characterized in that from 0.000001 to 100 parts by weight based on 100 parts by weight. The resin composition according to claim 1, wherein the mixing is carried out at a temperature in the range of 100 to 300 ° C. in which the at least one nonpolymerizable liquid substance (B) maintains a liquid state. The resin composition according to claim 1, wherein the mixing is carried out at a temperature in the range of 150 to 250 ° C. in which at least one non-polymerizable liquid substance (B) remains in a liquid state. The resin composition according to claim 1, wherein the weight ratio of said thermoplastic resin (A) to said at least one nonpolymerizable liquid substance (B) is 30/70 to 70/30. The thermoplastic resin (A) according to claim 1, wherein the thermoplastic resin (A) contains 1 to 100% by weight of polyphenylene ether resin and 0 to 99% by weight of polystyrene resin, and the total amount of the polyphenylene ether resin and the polystyrene resin is 100% by weight. Phosphorus resin composition. 7. The thermoplastic resin (A) according to claim 6, wherein the thermoplastic resin (A) contains 50 to 99% by weight of polyphenylene ether resin and 1 to 50% by weight of polystyrene resin, and the total amount of the polyphenylene ether resin and the polystyrene resin is 100% by weight. Phosphorus resin composition. The resin composition according to claim 1, wherein the nonpolymerizable liquid substance (B) is a flame retardant. 9. The resin composition of claim 8, wherein said flame retardant contains at least one organophosphorus compound. 10. The resin composition of claim 9, wherein said organic phosphorus compound is at least one aromatic phosphate ester. The resin composition according to claim 10, wherein the aromatic phosphate ester is a monomeric aromatic phosphate ester represented by Formula 1 below: [Formula 1] [In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is the same as each other and represents an integer of 0 to 3; The resin composition according to claim 10, wherein the aromatic phosphate ester is an oligomeric aromatic phosphate ester represented by Formula 2 below: [Formula 2] [Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more]. The resin composition of claim 10, wherein the at least one aromatic phosphate ester is a mixture of a monomeric aromatic phosphate ester represented by the following formula (1) and an oligomeric aromatic phosphate ester represented by the following formula (2): [Formula 1] [In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is identical to each other and represents an integer of 0 to 3; [Formula 2] [Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more]. The method of claim 13, wherein the mixture contains 1 to 99% by weight of the monomeric aromatic phosphate ester and 1 to 99% by weight of the oligomeric aromatic phosphate ester, and the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100% by weight. Resin composition which is%. 15. The method of claim 14, wherein the mixture contains 1 to 50% by weight of the monomeric aromatic phosphate ester and 50 to 99% by weight of the oligomeric aromatic phosphate ester, wherein the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100% by weight. Resin composition which is%. The resin composition according to claim 2, wherein the amount of the solid material (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin (A). The method of claim 1, wherein the thermoplastic resin (A) contains at least one compound selected from the group consisting of aromatic vinyl polymers and optionally aromatic vinyl monomers, aromatic vinyl dimers and aromatic vinyl trimers, wherein the amount of said at least one compound A resin composition that is 1% by weight or less based on the weight of the resin composition. The pellet according to claim 1, wherein the mixing of the thermoplastic resin (A) and the non-polymerizable liquid substance (B) is carried out while heating at a temperature of 300 DEG C or lower, and after the mixing, the product is cooled and then pelletized by pelletizing. Resin composition characterized in that produced in the form of. The resin composition according to claim 1, wherein the mixing is carried out in the presence of a solvent (D), and after the mixing, the solvent (D) is removed. The resin composition of Claim 19 whose quantity of the said solvent (D) is 0.1-100 weight part with respect to 100 weight part of said thermoplastic resin (A). The resin composition according to claim 19 or 20, wherein the solvent (D) has a boiling point that is higher than or equal to 300 ° C or lower than the temperature at which the mixing is carried out. A method for producing a molded article comprising melt extrusion of the following (i) and (ii) in a weight ratio of 20/95 to 115/5: (i) the following (A) and (B): (A) polyphenylene ether resin, polystyrene resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyolefin resin, polyamide resin, polymethacrylate resin, polyacetal resin, polyarylate resin , Polysulfone resins, polyether imide resins, polyether sulfone resins, polyether ether ketone resins, or thermoplastic elastomers having the same backbone as the polymer backbone of the resin, wherein the number average particles are 0.01 to 10,000 μm. Thermoplastic resin which is a powder having a diameter; And (B) an additive for the thermoplastic resin (A), which is in a liquid state at a temperature in the range of 25 to 300 ° C .; Phthalic acid ester, phthalic acid containing ester, aliphatic dibasic acid ester, glycol ester, aliphatic acid ester, epoxy compound, trioctyl trimellitate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate, tributyl acetyl citrate, chlorination Plasticizers selected from paraffin, polypropylene adipate, polyethylene sebacate, triacetin, tributyrin, toluenesulfonamide, alkylbenzenes, biphenyls, partially hydrogenated terphenyls or camphors; Thermal stabilizers selected from metal soaps, lead stabilizers, organotin stabilizers, composite stabilizers or epoxy compounds; Light stabilizers selected from ultraviolet absorbers, hindered amine light stabilizers, antioxidants, active species trapping agents, light shielding agents, metal inerts or quenchers; Flame retardants selected from halogen-containing flame retardants or phosphorus-containing flame retardants; coloring agent; blowing agent; slush; Spices; Fuming inhibitors; Tackifiers; antiseptic; Warming agent; Impact strength improver; Repellents; Wetting agents; Surfactants; Emulsifiers; Destabilizing agents; coagulant; Antifoam; Cryoprotectants; Creaming agents; Thickeners; At least one non-polymeric liquid substance selected from the group consisting of heat-sensitive agents and foaming agents Thermoplastic resin (A) by mixing together at a weight ratio of 10/90 to 90/10, at a temperature in the range from 25 to 300 ° C., wherein the at least one non-polymeric liquid material (B) remains liquid at this temperature). ) Is substantially the same as the resin composition prepared by the process comprising dissolving in) at least one nonpolymerizable liquid material (B) or swelling with at least one nonpolymerizable liquid material (B); And (ii) polystyrene resin, polyphenylene ether resin, polyolefin resin, polyvinyl chloride resin, polyamide resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polymethacrylate resin, polyacetal resin Thermoplastic resins selected from the group consisting of polyarylate resins, polysulfone resins, or combinations thereof. 23. The method of claim 22, wherein said thermoplastic resin (ii) contains at least one thermoplastic elastomer. 23. The method according to claim 22, wherein the resin composition (i) and the thermoplastic resin (ii) are the same as or different from the non-polymerizable liquid substance (B) and are flame retardant, flame retardant aid, light stabilizer, mold release agent, flow improver, heat stabilizer, Melt extrusion with at least one additive (E) selected from the group consisting of antistatic agents, colorants and blowing agents. A molded article made by the method according to claim 22. Polyphenylene ether resin composition containing the following (A ') and (B'): (A ') Polyphenylenes containing a plurality of polymer chains, each polymer chain comprising a repeating oxyphenylene unit and containing a hydroxyl group in an amount of 0.5 mol or less with respect to 100 mol of the repeating oxyphenylene unit. Ether resins; And (B ') at least one additive for said polyphenylene ether resin (A'). 27. The resin composition of claim 26, wherein said at least one additive (B ') is selected from the group consisting of flame retardants, plasticizers, thermal stabilizers and light stabilizers. 27. The resin composition of claim 26, wherein the weight ratio of said polyphenylene ether resin (A ') to said at least one additive (B') is 10/90 to 90/10. 28. The resin composition of claim 27, wherein said at least one additive (B ') is a flame retardant. 30. The resin composition of claim 29, wherein said flame retardant contains at least one organophosphorus compound. 31. The resin composition of claim 30, wherein said organophosphorus compound is at least one aromatic phosphate ester. The resin composition according to claim 31, wherein the aromatic phosphate ester is a monomeric aromatic phosphate ester represented by the following general formula (1): [Formula 1] [In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is the same as each other and represents an integer of 0 to 3; 32. The resin composition of claim 31, wherein the aromatic phosphate ester is an oligomeric aromatic phosphate ester represented by the following formula (2): [Formula 2] [Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more]. 32. The resin composition of claim 31, wherein the at least one aromatic phosphate ester is a mixture of a monomeric aromatic phosphate ester represented by formula (1) and an oligomeric aromatic phosphate ester represented by formula (2): [Formula 1] [In the formula, each Ar ¹ and Ar ² independently represent a C ₆ -C ₂₀ aromatic group unsubstituted or substituted with one or more C ₁ -C ₁₀ hydrocarbon groups; Each n is identical to each other and represents an integer of 0 to 3; [Formula 2] [Wherein each Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ independently represents a C ₆ to C ₂₀ aromatic group unsubstituted or substituted with one or more C _{1 to} C ₁₀ hydrocarbon groups; m is an integer of 1 or more]. 35. The method of claim 34, wherein the mixture contains 1 to 99% by weight of the monomeric aromatic phosphate ester and 1 to 99% by weight of the oligomeric aromatic phosphate ester, and wherein the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100% by weight. Resin composition which is%. 36. The method of claim 35, wherein the mixture contains 1-50 wt% of the monomeric aromatic phosphate ester and 50-99 wt% of the oligomeric aromatic phosphate ester, wherein the total amount of the monomeric aromatic phosphate ester and the oligomeric aromatic phosphate ester is 100 wt%. Resin composition which is%. A molded article made from the resin composition of claim 1 which is a film, sheet or foamed article. The molded article manufactured from the resin composition of Claim 1 which is a component for OA machines, a component for electric machines, a component for electronic devices, or an automotive part. The resin composition of Claim 1 used as an injection molding material. The molded article according to claim 25, which is a film, sheet or foamed article. The molded article according to claim 25, which is a component for an OA device, a component for an electrical device, a component for an electronic device, or an automotive part. The molded article according to claim 25, which is a pellet used as an injection molding material. A molded article made from the resin composition of claim 26 which is a film, sheet or foamed article. A molded article produced from the resin composition of claim 26, which is a component for an OA device, a component for an electrical device, a component for an electronic device, or an automotive part. The resin composition of claim 26 used as an injection molding material.