JP2008274186A - Method for producing thermoplastic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing thermoplastic resin with suppressed thermal deterioration of the resin, by improving reaction efficiency and sharply improving reaction uniformity by suppressing fluctuation of extrusion in a tandem type reaction extruder. <P>SOLUTION: The invention relates to a method for producing thermoplastic resin by using a tandem type reaction extruder provided with a first extruder, a second extruder and a part connecting the resin delivery of the first extruder and the supply port of the second extruder, and a pressure controlling mechanism in the part connecting the resin delivery of the first extruder and the supply port of the second extruder, and setting "the distance between the supply port of the second extruder and the pressure controlling mechanism" shorter than "the distance between the resin delivery of the first extruder and the pressure controlling mechanism", and a first step reaction treating the main raw materials and auxiliary material is carried out in the first extruder, and a second step reaction further reacting the reaction product in the first extruder with the other auxiliary material or volatilizing is carried out in the second extruder, wherein a single screw extruder is used as the first extruder. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a thermoplastic resin by a tandem reaction extruder.

  The reaction extrusion method, in which the resin is heated and melted using an extruder and the molten resin and the reactant are reacted continuously, is superior in productivity to the batch method performed in a reaction vessel, etc., and is low cost and efficient. It has the characteristic that a thermoplastic resin can be manufactured.

  However, the conventional production method in which a thermoplastic resin is melted and reacted has a problem that the reaction efficiency and the reaction uniformity are low.

  From this, as a method for improving the reaction efficiency and reaction uniformity, there is a method for improving the reaction efficiency by using carbon dioxide as a reaction medium with respect to the method for producing a modified thermoplastic resin using an extruder (for example, Patent Document 1). Since such a method uses a reaction medium, the facilities are complicated and expensive, and the manufacturing cost is high.

  In contrast, monomers and copolymers selected from the group consisting of (meth) acrylate homopolymers or (meth) acrylate esters and styrene, substituted styrene, maleic anhydride, itaconic anhydride and mixtures thereof. Regarding the imidization method, a method of reacting amine or ammonia under a certain pressure using a cavity transfer mixer and then continuously degassing with a degas extruder is disclosed (for example, see Patent Document 2). ). However, in such a tandem reaction extruder having a first extruder and a second extruder that are different in shape from the extruder, the inside of the component that connects the resin discharge port of the first extruder and the raw material supply port of the second extruder As a result, the resin and the reaction by-product are separated, the fluctuations in extrusion of the first extruder and the second extruder increase, and the reaction becomes non-uniform. Further, in order to reduce the extrusion fluctuation, a part that includes a pressure control device immediately after the resin discharge port of the first extruder and connects the first extruder and the second extruder material supply port, and the second extrusion Although it is conceivable to reduce the extrusion fluctuation of the machine, in this case, the resin and the reaction by-product foam in the parts to be connected, or the separation and extrusion fluctuate, resulting in a non-uniform reaction.

In general, reactive extrusion is performed using a twin screw extruder with high kneading / dispersibility, and high kneading / high screwing using screw elements having various kneading / dispersing mechanisms of the twin screw extruder. There is a method of promoting the reaction by imparting a dispersing ability and / or increasing the residence time in the extruder by increasing the extruder L / D. However, the twin-screw extruder has a structure with many small staying parts in the screw / barrel, and since the reaction proceeds by kneading / dispersing in the extruder screw until the reaction is completed, the resin is altered by heat in the extruder. However, there is a possibility of becoming a foreign substance in the resin molded product.
JP2002-256042 JP-A-7-214552

  The present invention has been made in view of the problems of such a conventional technique. In a tandem type reaction extruder, the reaction efficiency is improved and the variation in extrusion is suppressed and the reaction uniformity is greatly improved. It is an object of the present invention to provide a method for producing a thermoplastic resin that can be improved and that can prevent resin thermal degradation due to resin retention in an extruder.

  In order to solve the above problems, the present inventors have conducted intensive studies. As a result, the first extruder, the second extruder, and a tandem type extruder having a resin discharge port of the first extruder and a component connecting the raw material supply port of the second extruder, It discovered that the said subject could be solved by performing different reaction with a 2nd extruder, and completed this invention.

That is, the present invention
(I) The first extruder, the second extruder, the parts connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, and the resin discharge port of the first extruder and the second extruder The internal pressure control mechanism for connecting the raw material supply ports is provided, and the “distance between the second extruder raw material supply port and the pressure control mechanism” is shorter than the “distance between the first extruder discharge port and the pressure control mechanism”. Using the tandem type extruder characterized in that, the first stage reaction in which the main raw material and the auxiliary raw material are processed in the first extruder is performed, and in the second extruder, the reaction product in the first extruder is Furthermore, it is a manufacturing method of the thermoplastic resin which performs the 2nd stage reaction processed with another auxiliary material, Comprising: A manufacturing method characterized by using a single screw extruder for a 1st extruder.

  (Ii) The first extruder, the second extruder, the parts connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, and the resin discharge port of the first extruder and the second extruder The internal pressure control mechanism for connecting the raw material supply ports is provided, and the “distance between the second extruder raw material supply port and the pressure control mechanism” is shorter than the “distance between the first extruder discharge port and the pressure control mechanism”. The manufacturing method of the thermoplastic resin which performs the 1st step | paragraph reaction which processes a main raw material and an auxiliary | assistant raw material in a 1st extruder, and devolatilizes in a 2nd extruder using the tandem type | mold extruder characterized by the above-mentioned A manufacturing method characterized by using a single screw extruder as the first extruder.

  (Iii) The first extruder that is a single-screw extruder has an L / D that is a ratio of an extruder length Lcm to a diameter Dcm of 50 or less, and is described in (i) or (ii) A method for producing a thermoplastic resin.

  (Iv) The internal pressure of the component connecting the resin discharge port of the first extruder and the second extruder raw material supply port is 20 MPa or more and 100 MPa or less, and any one of (i) to (iii) Of manufacturing thermoplastic resin.

(V) When the internal volume of the part connecting the resin discharge port of the first extruder and the second extruder raw material supply port is Vcm ³ , and the resin supply amount per minute to the first extruder is Qcm ³ In addition, the residence time V / Q in the connection component is set to 1 minute or more and 15 minutes or less by arbitrarily changing the internal volume of the component, and the production of the thermoplastic resin according to any one of (i) to (iv) Method.

  (Vi) The thermoplastic resin according to any one of (i) to (v), wherein a resin dispersion mechanism is provided in a component connecting the resin discharge port of the first extruder and the second extruder material supply port. Manufacturing method.

  (Vii) A first stage reaction is performed in which the acrylic resin and the imidizing agent are treated in the first extruder, and the reaction product in the first extruder is further treated with the esterifying agent in the second extruder. The method for producing a thermoplastic resin according to any one of (i), (iii), (iv), (v), and (vi), wherein a stage reaction is performed.

  (Viii) An imide resin in which the thermoplastic resin has a unit represented by the following general formula (1), a unit represented by the following general formula (2) and / or a unit represented by the following general formula (3) The method for producing a thermoplastic resin according to any one of (i) to (vii), wherein

（但し、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ^３は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）

(However, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

（但し、Ｒ^４及びＲ^５は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ^６は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）

(However, R ⁴ and R ⁵ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

（但し、Ｒ^７は、水素又は炭素数１〜８のアルキル基を示し、Ｒ^８は、炭素数６〜１０のアリール基を示す。）
に関する。

(However, R ⁷ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.)
About.

  According to the present invention, a tandem extrusion having a first extruder, a second extruder, which are single-screw extruders, and a component connecting a resin discharge port of the first extruder and a raw material supply port of the second extruder. It is possible to significantly improve reaction uniformity by suppressing extrusion fluctuations and to prevent resin deterioration due to resin stagnation in the extruder by performing different reactions between the first extruder and the second extruder. In addition, it is possible to provide a production method capable of producing a thermoplastic resin easily and efficiently at low cost.

  Further, according to the present invention, a thermoplastic resin useful as an optical material or a heat-resistant material, particularly an imide resin, can be produced with low equipment cost and high productivity by using a tandem extrusion reactor. Become.

  Furthermore, according to the present invention, by suppressing the pressure fluctuation, it is possible to obtain a thermoplastic resin, in particular, an imide resin, having very small characteristic variation and few resin-deteriorating foreign substances in the resin.

  The present invention uses a tandem type extruder having a first extruder, a second extruder, and a component connecting a resin discharge port of the first extruder and a raw material supply port of the second extruder, and the first extruder And a second extruder, which are different from each other, wherein a single screw extruder is used as the first extruder.

  The tandem type extruder of the present invention is, for example, two parts, a first extruder and a second extruder, which are components that connect the resin discharge port of the first extruder and the raw material supply port of the second extruder (hereinafter referred to as “the second extruder”). In some cases, they are simply connected as connecting parts). If necessary, the third extruder may be connected with a connecting component. If there are at least two or more, the number of connected devices can be set as appropriate.

  Further, the tandem extruder has a second internal pressure control mechanism (which may be simply abbreviated as a pressure control mechanism) connecting the resin discharge port of the first extruder and the second extruder raw material supply port. The “distance between the extruder raw material supply port and the pressure control mechanism” is shorter than the “distance between the first extruder discharge port and the pressure control mechanism”. Furthermore, the internal pressure of the component connecting the resin discharge port of the first extruder and the second extruder material supply port is preferably 20 MPa or more and 100 MPa or less. Specifically, pressure gauges are respectively installed on the resin discharge port of the first extruder and the parts connecting the resin discharge port of the first extruder and the second extruder material supply port, and both values are the above values. Just point. The lower limit is particularly preferably 25 MPa or more, and more preferably 30 MPa or more. The upper limit is particularly preferably 90 MPa or less, and further preferably 80 MPa or less.

  If the internal pressure of the component connecting the resin discharge port of the first extruder and the second extruder raw material supply port is less than 20 MPa, the reaction efficiency in the first extruder is lowered, which is not preferable. Further, when the internal pressure of the component is less than 5 MPa, the reaction efficiency in the first extruder is lowered, and the resin and the reaction by-product are foamed and separated in the connection component, the fluctuation of extrusion is increased, and the reaction is not uniform. Therefore, it is not preferable.

  Also, when the internal pressure of the part connecting the resin discharge port of the first extruder and the second extruder raw material supply port is higher than 100 MPa, especially when the pressure resistance specification of the extruder speed reducer is exceeded, the extruder may be damaged. There is also not preferable.

  FIG. 1 shows an example of a tandem reaction extruder according to the present invention, but the present invention is not limited to this. As shown in the figure, the first extruder (1) and the second extruder (2) are arranged in a tandem type. The tandem type may be either a parallel arrangement as shown in FIG. 1 or an orthogonal arrangement in which the first extruder (1) and the second extruder (2) are arranged at right angles. The discharge port (6) of the first extruder (1) is connected to the raw material supply port (7) of the second extruder (2) via the connection component (3).

  In the present invention, a single screw extruder is used as the first extruder. The single-screw extruder has a higher pressure resistance than a multi-screw extruder such as a twin-screw extruder, so that the pressure in the extruder can be increased, and the first-stage reaction efficiency can be significantly increased. Since there are few resin residence parts in an extruder, it becomes possible to prevent the thermal deterioration of the resin in reaction extrusion, and since equipment cost is cheap, it is preferable.

  In the present invention, as the second extruder, a single-screw extruder, a same-direction meshing twin-screw extruder, a same-direction non-meshing twin-screw extruder, a different-direction meshing twin-screw extruder, a different-direction non-meshing twin-screw Various extruders such as an extruder and a multi-screw extruder can be applied. Among them, in particular, various twin screw extruders are preferably applied from the viewpoint of high kneading / dispersing ability, and the same direction meshing twin screw extruder is more preferred because of high kneading / dispersing ability and productivity.

  Examples of the connecting parts include those in which the resin flow path shape is a circular pipe or an L-shaped pipe. The connection component according to the present invention preferably has a gentle volume change of the resin flow path. Particularly preferred is a connecting part having a resin flow path with no volume change. In a connecting part having a resin flow path whose volume has changed rapidly, the resin and the reaction by-product are foamed and separated, the extrusion is fluctuated, and the reaction becomes non-uniform, which is not preferable. The resin residence time in the connection component can be set appropriately by changing the connection component volume V with respect to the resin supply amount Q per hour to the first extruder. The connecting part volume V can be appropriately set by changing the connecting part cross-sectional area and / or the connecting part length. However, changing the connecting part cross-sectional area affects the resin fluidity in the flow path, so the connecting part length is changed. Thus, it is preferable to set the connection component volume. The resin residence time V / Q in the connection part is preferably 1 minute or more and 15 minutes or less. Especially preferably, it is 2 minutes or more and 13 minutes or less, More preferably, it is 3 minutes or more and 10 minutes or less.

  When the resin residence time in the connection part is less than 1 minute, the resin reaches the raw material supply port of the second extruder although the reaction does not proceed sufficiently, which is not preferable.

  If the resin residence time in the connection part is 15 minutes or more, the resin is still in the connection pipe even though the reaction has progressed sufficiently, and there is a possibility of resin heat deterioration, Since production efficiency deteriorates, it is not preferable.

  The tandem type extruder of the present invention can suppress fluctuations in extrusion by providing the connecting part with the pressure control mechanism (4), and the resin of the first extruder (1) -first extruder. The internal pressure of the component (3) connecting the discharge port and the second extruder raw material supply port can be controlled. The pressure control mechanism is a device that can control the pressure loss by changing the resin flow path volume. A preferable pressure control mechanism according to the present invention can be exemplified by a constant flow pressure valve, a gear pump, an orifice, and the like. If the volume of the resin flow path in the pressure control mechanism is changed suddenly, the resin and reaction by-products may foam and separate, resulting in fluctuations in extrusion and non-uniform reaction. Therefore, a constant flow pressure valve, an orifice and the like are particularly preferable.

  In addition, the tandem type extruder of the present invention preferably includes a resin dispersion mechanism in the connection part in order to allow the reaction to proceed efficiently even in the connection part. Examples of the resin dispersion mechanism provided in the connection component include a static mixer, and a plurality of pins arranged at random positions perpendicular to the flow direction in the component.

Thus, by providing a sufficient resin residence time in the connection pipe, preferably by providing a resin dispersion mechanism in the connection part, and by sufficiently raising the pressure in the first extruder and in the connection pipe to greatly improve the reaction efficiency. By shortening the length of the first extruder, the facility cost can be reduced at a low cost. The ratio between the length L of the first extruder and the diameter D is preferably L / D50 or less, particularly preferably 40 or less, and further preferably 30 or less.
Further, in the present invention, it is possible to suppress the extrusion fluctuation with higher accuracy by appropriately adjusting the position where the pressure control mechanism is attached. The position where the pressure control mechanism according to the present invention is attached is particularly limited if the “distance between the second extruder raw material supply port and the pressure control mechanism” is shorter than the “distance between the first extruder discharge port and the pressure control mechanism”. However, it is preferable that the “distance between the second extruder raw material supply port and the pressure control mechanism” is as short as possible, and it is most preferable that the distance is directly connected to the second extruder raw material supply port. When the pressure control mechanism is equal to the “distance between the second extruder raw material supply port and the pressure control mechanism” and the “distance between the first extruder discharge port and the pressure control mechanism” or “the second extruder raw material supply port and the pressure When the “distance between the first extruder discharge port and the pressure control mechanism” is shorter than the “distance with the control mechanism” or when the first extruder discharge port and the pressure control mechanism are directly connected, the connection after the pressure control mechanism Since the resin and reaction by-product are foamed in the parts or separated and the extrusion is fluctuated, the reaction becomes non-uniform. Also, depending on the type of pressure control mechanism, when the pressure control mechanism and the connecting part or the second extruder raw material supply port (position where kneading is started in the second extruder) are integrated, The portion where the pressure difference occurs is sometimes referred to as the position of the pressure control mechanism.

  The extrusion fluctuation in the present invention is the pressure fluctuation in the component connecting the resin discharge port of the first extruder and the second extruder raw material supply port. Specifically, when pressure gauges are respectively installed in the resin discharge port of the first extruder and the parts connecting the resin discharge port of the first extruder and the second extruder material supply port, the pressure in each pressure gauge More specifically, it is the difference between the maximum value and the minimum value of pressure per unit time (1 minute). Preferably, this extrusion fluctuation is within 1 MPa.

  In the present invention, the raw material can be a solid resin, and is supplied from the hopper to the raw material supply port (5) of the first extruder (1), which is a single screw extruder, and is heated and melted in the extruder. Is done. From the auxiliary raw material supply port (8) of the first stage reaction provided in the part after the resin is melted in the extruder, the auxiliary raw material in a solid, liquid or gaseous state is supplied using a supply device such as a pump. The first stage reaction of the resin and the auxiliary material is performed.

  The first-stage reaction product in the first extruder is guided to the second extruder raw material supply port via a connecting part connected to the resin discharge port without being isolated from the resin discharge port. It is thrown into.

  Next, the first stage reaction in the reaction product in the first extruder supplied from the first extruder at the vent port (9) provided after the second extruder (2) raw material supply port (7). Unreacted by-products, reaction by-products and decomposition products are removed. Examples of the pressure at the vent port include atmospheric pressure, vacuum, and the like, and preferably vacuum. A plurality of vent openings may be provided as necessary.

  The secondary raw material in the second stage reaction to the second extruder (2) is supplied from the secondary raw material supply port (10) of the second stage reaction using a pump or the like. Then, the second stage reaction is performed with the reaction product and the auxiliary material in the first extruder.

  Next, a vent port (11) is provided downstream from the by-material feed port (10) of the second extruder (2), and unreacted by-products, reaction by-products, decomposition in the second stage reaction product Remove things. What is necessary is just to set the distance to a vent port suitably from the reaction rate etc. of the reaction to implement. Examples of the pressure at the vent port include atmospheric pressure, vacuum, and the like, and preferably vacuum. A plurality of vent openings may be provided as necessary.

Further, in the second extruder (2), the second-stage reaction of the first-stage reaction product and the second-stage auxiliary material is not performed, and the first-stage is made with a plurality of vents as necessary. Volatilization of unreacted by-products, reaction by-products and decomposition products of the eye reaction, and heat treatment are also possible.
Various additives such as catalysts, antioxidants, heat stabilizers, plasticizers, lubricants, UV absorbers, antistatic agents, colorants, shrinkage inhibitors, etc. are fed from the first extruder (1) raw material supply port (5). Can be supplied with resin. Moreover, various additives can also be supplied from the additive supply port (12) of the second extruder (2) as required. Examples of a method for supplying various additives from the additive supply port (12) include a side feed method, an individual feed method for adding from the upper part of the extruder, and the like.

  In the present invention, different reactions can be carried out between the first extruder and the second extruder using the tandem extruder.

  Specifically, the first stage reaction in which the main raw material and the auxiliary raw material are processed in the first extruder is performed, and the reaction product in the first extruder is further processed with another auxiliary raw material in the second extruder. A second stage reaction can be performed.

  As an example, a first stage reaction in which an acrylic resin and an imidizing agent are treated in a first extruder, and a reaction product in the first extruder is further treated with an esterifying agent in a second extruder. A reaction for obtaining an imide resin as a thermoplastic resin by performing a stage reaction can be mentioned.

  In the first extruder of the tandem reaction extruder, first, an acrylic resin is used as a raw material resin (main raw material), and this is used as a secondary raw material for the first-stage reaction such as ammonia or substituted amine (hereinafter, imidization). It is possible to obtain a resin (hereinafter sometimes referred to as an imide resin intermediate 1) that has been treated.

  This imide resin intermediate 1 is treated with a secondary raw material of the second stage reaction (hereinafter sometimes referred to as an esterifying agent) in the second extruder of the tandem type reaction extruder, and heated if necessary. By performing the treatment or the like, the ratio of the acid component (derived from the carboxy group and the acid anhydride) remaining in the resin can be controlled (hereinafter sometimes referred to as the imide resin intermediate 2). At this time, it is possible to perform only heat treatment or the like without treatment with an esterifying agent. In the second extruder, when only heat treatment (mixing / dispersion of molten resin in the extruder) is performed, dehydration reaction between carboxyl groups in the imide resin intermediate 1 and / or desorption of carboxyl groups and alkyl ester groups. Some or all of the carboxyl groups can be converted into acid anhydride groups by alcohol reaction or the like. The heat treatment is carried out at a reaction temperature in the range of 150 to 400 ° C. in order to suppress decomposition, coloring, etc. of the resin due to excessive heat history. 180-320 degreeC is preferable and 200-280 degreeC is more preferable.

  Furthermore, the imide resin intermediate 2 can be removed by removing the esterifying agent contained in the resin by devolatilization under reduced pressure or the like, thereby obtaining the imide resin of the present invention.

  In order to obtain the imide resin intermediate 1 and the imide resin intermediate 2 of the present invention, the reaction temperature is increased in order to proceed with imidization or acid component control and to suppress decomposition, coloring, etc. of the resin due to excessive thermal history. Is performed in the range of 150 to 400 ° C. 180-320 degreeC is preferable and 200-280 degreeC is more preferable.

  In addition to the production method as described above, the production method is not particularly limited as long as the imide resin can be obtained by the tandem reaction extruder of the present invention.

  In this case, as the acrylic resin as the main raw material, an acid anhydride such as maleic anhydride or a half ester of them with a linear or branched alcohol having 1 to 20 carbon atoms; acrylic acid, methacrylic acid, maleic acid, Mention may be made of α, β-ethylenically unsaturated carboxylic acids such as maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid and citraconic acid. Further, (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer comprising a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3): And (meth) acrylic acid ester polymers such as methyl methacrylate polymers composed of repeating units represented by general formula (2).

（但し、Ｒ^４及びＲ^５は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ^６は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）

(However, R ⁴ and R ⁵ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

（但し、Ｒ^７は、水素又は炭素数１〜８のアルキル基を示し、Ｒ^８は、炭素数６〜１０のアリール基を示す。）
本発明のイミド樹脂を製造する際に、先ずメチルメタクリレート−スチレン共重合体等の（メタ）アクリル酸エステル−芳香族ビニル共重合体、又はメタクリル酸メチル重合体等の（メタ）アクリル酸エステル重合体を重合し、これをイミド樹脂化する場合、本発明で用いる事ができる（メタ）アクリル酸エステル−芳香族ビニル共重合体、（メタ）アクリル酸エステル重合体は、イミド化反応が可能であれば、リニアー（線状）ポリマーであっても、またブロックポリマー、コアシェルポリマー、分岐ポリマー、ラダーポリマー、架橋ポリマーであっても構わない。ブロックポリマーはＡ−Ｂ型、Ａ−Ｂ−Ｃ型、Ａ−Ｂ−Ａ型、又はこれら以外のいずれのタイプのブロックポリマーであっても構わない。コアシェルポリマーはただ一層のコア及びただ一層のシェルのみからなるものであっても、それぞれが多層になっていても構わない。

(However, R ⁷ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.)
When producing the imide resin of the present invention, first, a (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer or a (meth) acrylic acid ester weight such as methyl methacrylate polymer is used. When a polymer is polymerized and converted into an imide resin, the (meth) acrylate-aromatic vinyl copolymer and (meth) acrylate polymer that can be used in the present invention can undergo an imidization reaction. As long as it is a linear polymer, it may be a block polymer, a core-shell polymer, a branched polymer, a ladder polymer, or a crosslinked polymer. The block polymer may be an A-B type, an A-B-C type, an A-B-A type, or any other type of block polymer. The core-shell polymer may be composed of only one core and only one shell, or each may be a multilayer.

  An example of the auxiliary material is an imidizing agent. Examples of imidizing agents include amines containing aliphatic hydrocarbon groups such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, tert-butylamine, n-hexylamine, and aniline. Aromatic hydrocarbon group-containing amines such as benzylamine, toluidine, and trichloroaniline, alicyclic hydrocarbon group-containing amines such as cyclohexylamine, and ammonia. In addition, urea compounds such as urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea that generate these amines by heating can also be used. Of these imidizing agents, methylamine, ammonia, and cyclohexylamine are preferable from the viewpoint of cost and physical properties, and methylamine is particularly preferable.

  What is necessary is just to determine suitably the addition amount of an imidation agent by the imidation rate for expressing a required physical property. Preferably, it is 1 to 100 parts by weight with respect to 100 parts by weight of the main raw material.

  Examples of esterifying agents include dimethyl carbonate, 2,2-dimethoxypropane, dimethyl sulfoxide, triethyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, diphenyl carbonate, dimethyl sulfate, methyl toluene sulfonate, methyl trifluoromethyl sulfonate. , Methyl acetate, methanol, ethanol, methyl isocyanate, p-chlorophenyl isocyanate, dimethylcarbodiimide, dimethyl-t-butylsilyl chloride, isopropenyl acetate, dimethylurea, tetramethylammonium hydroxide, dimethyldiethoxysilane, tetra-N-butoxy Silane, dimethyl (trimethylsilane) phosphite, trimethyl phosphite Trimethyl phosphate, tricresyl phosphate, diazomethane, ethylene oxide, propylene oxide, cyclohexene oxide, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether.

  The addition amount of the esterifying agent is determined by the ratio of the acid component in the resin for expressing necessary physical properties. Preferably, it is 1 to 100 parts by weight with respect to 100 parts by weight of the imide resin intermediate 1.

  When the imide resin intermediate 1 is treated with an esterifying agent and / or heat-treated, or for the imide resin intermediate 2, generally used catalysts, antioxidants, heat stabilizers, plasticizers, lubricants, UV absorption An agent, an antistatic agent, a coloring agent, an anti-shrinkage agent and the like may be added as long as the object of the present invention is not impaired.

  As described above, examples of the thermoplastic resin that can be synthesized by effectively applying the present invention include imide resins.

  As the imide resin, for example, various types can be produced by appropriately setting the kind and amount of the main raw material and the auxiliary raw material by the above-described method. Specifically, the imide resin is represented by the following general formula (1). And a unit represented by the general formula (2) and / or a unit represented by the general formula (3).

（但し、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ^３は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）
本発明のイミド樹脂を構成する、第一の構成単位は、前記一般式（１）で表されるものであり、一般的にグルタルイミド単位と呼ばれる事が多い（以下、一般式（１）をグルタルイミド単位と省略して示す事がある。）。

(However, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
The first structural unit constituting the imide resin of the present invention is represented by the general formula (1) and is generally called a glutarimide unit (hereinafter referred to as the general formula (1)). Sometimes abbreviated as glutarimide unit.)

As a preferable glutarimide unit, R ¹ and R ² are hydrogen or a methyl group, and R ³ is hydrogen, a methyl group, a butyl group, or a cyclohexyl group. The case where R ¹ is a methyl group, R ² is hydrogen, and R ³ is a methyl group is particularly preferable.

The glutarimide unit may be of a single type or may include a plurality of types in which R ¹ , R ² and R ³ are different.

  In addition, a glutarimide unit can be formed by imidizing the main raw material demonstrated in the method to manufacture the imide resin mentioned above.

  The second structural unit constituting the imide resin is represented by the general formula (2) and is generally called a (meth) acrylic acid ester unit (here, (meth) Acrylic acid ester refers to acrylic acid ester and methacrylic acid ester.Hereinafter, general formula (2) may be abbreviated as (meth) acrylic acid ester unit).

  When manufacturing an imide resin, when (meth) acrylic acid ester-aromatic vinyl copolymer or (meth) acrylic acid ester polymer is first polymerized and then imidized, it is specifically ( The raw material for giving a meth) acrylic acid ester unit as a residue is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. are mentioned. Of these, methyl methacrylate is particularly preferred.

These second structural units may be of a single type or may include a plurality of types in which R ⁴ , R ⁵ , and R ⁶ are different. Similarly, a plurality of types of raw materials that give the (meth) acrylic acid ester unit as a residue may be used.

The third structural unit contained in the imide resin of the present invention as needed is represented by the general formula (3), and is generally called an aromatic vinyl unit (hereinafter referred to as general vinyl). (Formula (3) may be abbreviated as an aromatic vinyl unit.)
Preferred aromatic vinyl structural units include styrene in which R ⁷ is hydrogen and R ⁸ is a phenyl group, and α-methylstyrene in which R ⁷ is a methyl group and R ⁸ is a phenyl group. Of these, styrene is particularly preferred.

These third structural units may be of a single type, or may include a plurality of types in which R ⁷ and R ⁸ are different.

The content of the glutarimide unit represented by the general formula (1) in the imide resin depends on, for example, the structure of R ³ , but is preferably 20% by weight or more of the imide resin. The preferable content of the glutarimide unit is 20% to 95% by weight, more preferably 40 to 90% by weight, and still more preferably 50 to 80% by weight. When the ratio of the glutarimide unit is smaller than this range, the resulting imide resin may have insufficient heat resistance or the transparency may be impaired. On the other hand, if it exceeds this range, the heat resistance and melt viscosity are unnecessarily increased, the moldability becomes worse, the mechanical strength of the resulting film becomes extremely brittle, and the transparency may be impaired.

  The content of the aromatic vinyl unit represented by the general formula (3) in the imide resin is preferably 1% by weight or more based on the total repeating unit of the imide resin. The content of the aromatic vinyl unit is preferably 1 to 40% by weight, more preferably 1 to 30% by weight, and still more preferably 1 to 25% by weight. When the aromatic vinyl unit is larger than this range, the resulting imide resin has insufficient heat resistance. If it is smaller than this range, the mechanical strength of the resulting film may be lowered.

  By adjusting the ratio of the general raw materials, general formulas (2) and (3), and the imidizing agent, which is a secondary raw material, the unit represented by general formula (1) and the general formula (2) Can be obtained, and an imide resin containing the unit represented by the general formula (3) in an arbitrary ratio can be obtained, and the ratios of the general formulas (1), (2), and (3) are adjusted. Therefore, it is possible to adjust to various required physical properties. For example, when the imide resin of the present invention is first formed by polymerizing a (meth) acrylic ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer, for example, a (meth) acrylic ester is used. The ratio of the general formula (3) is determined by adjusting the polymerization ratio of the aromatic vinyl and the aromatic vinyl (the ratio of the general formula (3) can also be set to 0). By adjusting, the ratios of the general formulas (1) and (2) can be further adjusted.

  The imide resin may further be copolymerized with a fourth structural unit as necessary. A constitution obtained by copolymerizing nitrile monomers such as acrylonitrile and methacrylonitrile, and maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide as the fourth structural unit Units can be used. These may be directly copolymerized in a thermoplastic resin or may be graft copolymerized. The fourth structural unit is preferably contained in the main raw material.

  In the imide resin obtained in the production method of the present invention, the type containing the general formula (3) is obtained by adjusting the content of each constituent unit and glutarimide unit in the methyl methacrylate-styrene copolymer. It is also possible to impart a feature that does not substantially have orientation birefringence. Oriented birefringence refers to birefringence that develops when stretched at a predetermined temperature and a predetermined draw ratio. In this specification, unless otherwise specified, it means birefringence that develops when stretched 100% at a temperature 5 ° C. higher than the glass transition temperature of the imide resin.

Here, the orientation birefringence is the product of the intrinsic birefringence derived from the polymer structure and the orientation distribution function derived from the molecular orientation state. The refractive index (nx) in the stretching axis direction and the axial refractive index (ny) orthogonal thereto. ) From the following formula: Δn _or = nx−ny
The phase difference Re (nm) measured by a phase meter is divided by the thickness d (μm).
Oriented birefringence Δn _or = Re / d
As described above, the orientation birefringence is the difference between the refractive index (nx) in the stretching axis direction and the refractive index (ny) in the axial direction perpendicular thereto, and therefore, when nx is larger than ny, it shows a positive value and vice versa. When nx is smaller than ny, a negative value is indicated.

The value of orientation birefringence is preferably −0.1 × 10 ^{−3 to} 0.1 × 10 ⁻³ , and preferably −0.01 × 10 ^{−3 to} 0.01 × 10 ^−3. More preferred. When the orientation birefringence is out of the above range, the birefringence is likely to occur during the molding process with respect to the environmental change, and it becomes difficult to obtain stable optical characteristics.

  In order to obtain an imide resin having substantially no orientation birefringence, the amount of each structural unit in the (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer is adjusted, Furthermore, it is necessary to prepare the degree of imidization, and the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (3) are 2.0: 1.0 to 4.0 by weight ratio. Is preferably in the range of 1.0, more preferably in the range of 2.5: 1.0 to 4.0: 1.0, and in the range of 3.0: 1.0 to 3.5: 1.0. Is more preferable.

The imide resin of the present invention preferably has a weight average molecular weight of 1 × 10 ⁴ to 5 × 10 ⁵ . In the process of producing a thermoplastic resin, if an excessive heat history is given to the resin, thermal decomposition occurs, and the weight average molecular weight is less than 1 × 10 ⁴ . Furthermore, crosslinking may occur and the weight average molecular weight may exceed 5 × 10 ⁵ . When the method for producing a thermoplastic resin according to the present invention is applied, the heat history for the resin can be reduced in the process of producing the thermoplastic resin, and the range of the weight average molecular weight can be achieved. When the weight average molecular weight is less than 1 × 10 ⁴ , the mechanical strength when formed into a film is insufficient, and when it exceeds 5 × 10 ⁵ , the viscosity at the time of melt extrusion is high, and the molding processability is lowered. , Productivity of molded products may decrease.

  The glass transition temperature in the imide resin of the present invention is preferably 110 ° C. or higher, and more preferably 120 ° C. or higher. When the glass transition temperature is lower than the above value, the application range is limited in applications where heat resistance is required.

If necessary, other thermoplastic resins can be added to the imide resin of the present invention. When molding, generally used antioxidants, heat stabilizers, plasticizers, lubricants, UV absorbers, antistatic agents, colorants, shrinkage inhibitors, etc. are added within the range that does not impair the purpose of the present invention. You may do it.
Molded articles obtained from the imide resin of the present invention include, for example, imaging fields such as cameras, VTRs, projector lenses, viewfinders, filters, prisms, and Fresnel lenses, optical disc pickups such as CD players, DVD players, and MD players. Information equipment such as lens fields such as lenses, optical recording fields for optical disks such as CD players, DVD players, and MD players, liquid crystal light guide plates, liquid crystal display films such as polarizer protective films and retardation films, and surface protective films Fields, optical communication fields such as optical fiber, optical switch, optical connector, etc., automotive headlights, tail lamp lenses, inner lenses, instrument covers, sunroofs, and other vehicle fields, glasses, contact lenses, internal vision lenses, need for sterilization Medical supplies Appliances field, road translucent plates, pair glass lenses, lighting windows and carports, lighting lenses and covers, building material sizing, etc., microwave cooking containers (tableware), home appliance housings, toys , Sunglasses, stationery, etc.

The present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, each measuring method of the physical property measured in the following Examples and Comparative Examples is as follows.
(1) Measurement of imidation rate 1 g of the product pellets was dissolved in 5 cc of dichloromethane, and IR spectrum was measured at room temperature using Travel IR manufactured by SensIR Technologies. From the obtained spectrum, determined with the absorption intensity (Abs _Ester) attributed to the ester carbonyl group of 1720 cm ^-1, the imidization ratio from the ratio of the absorption intensity assignable to an imide carbonyl group of 1660cm ^-1 (Abs _imide) It was. Here, the imidation rate refers to the proportion of the imide carbonyl group in all carbonyl groups.
(2) Measurement of ratio of acid component remaining in resin 0.3 g of product pellets were dissolved in 37.5 ml of dichloromethane, and 37.5 ml of methanol was added. To this solution, 2 drops of 1 wt% phenolphthalein ethanol solution was added, 5 ml of 0.1N sodium hydroxide aqueous solution was added, and the mixture was stirred for 1 hour. 0.1N hydrochloric acid was added dropwise to this solution, and the amount of 0.1N hydrochloric acid added (Aml) until the reddish purple color of the solution disappeared was measured.

  Next, 2 drops of 1 wt% phenolphthalein ethanol solution was added to a mixed solution of 37.5 ml of dichloromethane and 37.5 ml of methanol. To this, 5 ml of 0.1N sodium hydroxide aqueous solution was added and stirred for 1 hour. 0.1N hydrochloric acid was added dropwise to this solution, and the amount of 0.1N hydrochloric acid added (Bml) until the reddish purple color of the solution disappeared was measured.

  The ratio of the acid component (derived from a carboxyl group and an acid anhydride) remaining in the resin was defined as Cmmol / g, and the following formula was used.

C = 0.1 × ((5-AB) /0.3)
(3) Variation In this example and comparative example, pellets were collected every 1 minute from 1 hour after the start of production, and the imidization rate and the ratio of acid components were measured by the above methods. The difference between the maximum value and the minimum value of the measured values obtained was regarded as the variation in the imidization rate and the variation in the acid component, respectively.

(4) Evaluation of the number of resin-deteriorated foreign matter Foreign matter having a longitudinal length of 20 μm or more and less than 50 μm present in a single A4 size film was observed at 400 × magnification using a Keyence digital microscope, and SPECTRA -Using a micro-infrared spectroscopic analyzer manufactured by TECH, resin-degraded foreign matters and other foreign foreign matters in the film foreign matters were classified, and the number of resin-deteriorated foreign matters was counted.

Example 1
An apparatus equivalent to that shown in FIG. 1 was used. As for the tandem type reactive extruder, the first extruder (1) has a diameter of 15 mm and a L / D (the ratio of the length L of the extruder to the diameter D) of 30 and the second extruder (2) has a single screw extruder. A raw resin was supplied from the hopper to the raw material supply port of the first extruder using a same-direction meshing twin screw extruder having a diameter of 15 mm and L / D (ratio of the length L to the diameter D of the extruder) of 60. The amount of raw material resin supplied per hour was 5 kg. The supply positions of the first stage reaction auxiliary material (imidizing agent) and the second stage reaction auxiliary material (esterifying agent) were the same as those shown in FIG. The positions of the vents in the first extruder and the second extruder were also the same as those shown in FIG. 1, and the degree of vacuum of each vent was -0.095 MPa. Further, the first extruder and the second extruder are connected by a pipe having a diameter of 20 mm and a length of 2.0 m (connecting part (3)), and the resin discharge port of the first extruder and the second extruder raw material supply port are connected. A constant flow pressure valve was used for the in-part pressure control mechanism (4) to be connected. Taking into account the specific gravity of 1.1 g / cm ³ of the imidized resin, the residence time in the connecting pipe at this time is about 9 minutes. The resin (strand) discharged from the second extruder was cooled in a water tank and then cut into pellets by a pelletizer. Here, the outlet of the first extruder, the first extruder and the second extruder are used to adjust the pressure in the part connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, or to determine the fluctuation of the extrusion. A resin pressure gauge was provided at the center of the machine connecting part and at the outlet of the second extruder.

  Regarding the first extruder, a commercially available methyl methacrylate-styrene copolymer (MS-800 manufactured by Nippon Steel Chemical Co., Ltd.) is used as a raw material resin, and an intermediate imide resin using monomethylamine as an imidizing agent. Body 1 was produced. At this time, each barrel temperature of the extruder was 250 ° C., the screw rotation speed was 150 rpm, the raw material resin supply amount was 5 kg / hour, and the addition amount of monomethylamine was 20 parts with respect to 100 parts of the raw material resin. In addition, the constant flow pressure valve is installed immediately before the second extruder raw material supply port, and the pressure at the outlet of the first extruder and the pressure at the central part of the connecting part of the first extruder and the second extruder (pressure in the connecting part) is 40 MPa. Adjusted as follows.

  Regarding the second extruder, an imide resin intermediate 2 was produced using a mixed solution of dimethyl carbonate and triethylamine as an esterifying agent. At this time, each barrel temperature of the extruder was 250 ° C., the screw rotation speed was 150 rpm, the addition amount of dimethyl carbonate was 8 parts with respect to 100 parts of the raw material resin, and the addition amount of triethylamine was 2 parts with respect to 100 parts of the raw material resin. . Furthermore, the esterifying agent was removed with a vent to obtain an imide resin.

  The obtained imide resin was dried at 100 ° C. for 5 hours, and then 280 ° C. using a single screw extruder having a diameter of 40 mm, an extruder length L / diameter ratio (L / D) of 35, and a 400 mm wide T-die. The film was extruded to create a film having a thickness of 150 μm, and a single A4 size film was observed to confirm the number of resin-deteriorated foreign substances in the film.

  Production was carried out for about 2 hours under the above conditions, and the obtained imide resin had a variation of 1% with respect to an imidation rate of 75% and a variation of 0.10 mmol / g of the acid component remaining in the resin. It was 0.01 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 0 per A4 size sheet.

(Example 2)
An imide resin was produced in the same manner as in Example 1 except that a commercially available polymethyl methacrylate (Sumitex MG manufactured by Sumitomo Chemical Co., Ltd.) was used as the raw material resin.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidization rate of 75%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 0 per A4 size sheet.

(Example 3)
An imidized resin was produced in the same manner as in Example 1 except that the amount of raw material resin supplied per hour was 3 kg.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidization rate of 75%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 0 per A4 size sheet.

Example 4
An imidized resin was produced in the same manner as in Example 2 except that the supply amount of the raw material resin per hour was 3 kg.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidization rate of 75%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 0 per A4 size sheet.

(Comparative Example 1)
Except for using the same-direction meshing twin screw extruder with a diameter of 15 mm and L / D (ratio of the length L to the diameter D of the extruder) of 60 for the first extruder and setting the internal pressure of the connecting part to 3 MPa, An imide resin was produced in the same manner as in Example 1.

  As a result, the obtained imide resin had a variation of 1% with respect to the imidization ratio of 60% and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 15 per A4 size sheet.

(Comparative Example 2)
Except for using the same-direction meshing twin screw extruder with a diameter of 15 mm and L / D (ratio of the length L to the diameter D of the extruder) of 60 for the first extruder and setting the internal pressure of the connecting part to 3 MPa, An imide resin was produced in the same manner as in Example 2.

  As a result, the obtained imide resin had a variation of 1% with respect to the imidization ratio of 60% and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 15 per A4 size sheet.

(Comparative Example 3)
The test was performed under the same conditions as in Example 1 except that the connection component diameter was 10 mm, the connection component length was 0.5 m, and the residence time in the connection component was approximately 0.5 minutes.

  As a result, the obtained imide resin had a variation of 1% with respect to the imidization ratio of 60% and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 0 per A4 size sheet.

(Comparative Example 4)
The test was performed under the same conditions as in Example 2 except that the connection component diameter was 10 mm, the connection component length was 0.5 m, and the residence time in the connection component was approximately 0.5 minutes.

  As a result, the obtained imide resin had a variation of 1% with respect to the imidization ratio of 60% and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 0 per A4 size sheet.

(Comparative Example 5)
The test was performed under the same conditions as in Example 1 except that the connecting tube diameter was 20 mm, the connecting tube length was 5.0 m, and the residence time in the connecting component was approximately 20 minutes.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidization rate of 75%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 10 per A4 size sheet.

(Comparative Example 6)
The test was performed under the same conditions as in Example 2 except that the connection pipe diameter was 20 mm, the connection pipe length was 5.0 m, and the residence time in the connection part was about 20 minutes.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidization rate of 75%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 10 per A4 size sheet.

(Comparative Example 7)
Except for using the same-direction meshing twin screw extruder with a diameter of 15 mm and L / D (ratio of the length L to the diameter D of the extruder) of 60 for the first extruder and setting the internal pressure of the connecting part to 3 MPa, An imide resin was produced in the same manner as in Example 3.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidation ratio of 65%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 10 per A4 size sheet.

(Comparative Example 8)
Except for using the same-direction meshing twin screw extruder with a diameter of 15 mm and L / D (ratio of the length L to the diameter D of the extruder) of 60 for the first extruder and setting the internal pressure of the connecting part to 3 MPa, An imide resin was produced in the same manner as in Example 4.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidation ratio of 65%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the center of the first extruder and the second extruder connecting pipe was 0.1 MPa. The number of resin-deteriorated foreign matters in the film was 10 per A4 size sheet.

  The results of the comparative examples are summarized in the following table.

It is a block diagram of the tandem type | mold reaction extruder by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st extruder 2 2nd extruder 3 Connection component 4 Pressure control mechanism in components which connects the resin discharge port of a 1st extruder, and a 2nd extruder raw material supply port 5 1st extruder raw material supply port 6 1st extrusion Machine discharge port 7 Second extruder raw material supply port 8 Secondary raw material supply port for first stage reaction 9 Second extruder vent port 10 Secondary raw material supply port for second stage reaction 11 Second extruder vent port 12 Various additions Agent supply port

Claims (8)

  The first extruder, the second extruder, the parts connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, and the raw material supply of the resin discharge port of the first extruder and the second extruder It has an internal pressure control mechanism that connects the ports, and the “distance between the second extruder raw material supply port and the pressure control mechanism” is shorter than the “distance between the first extruder discharge port and the pressure control mechanism”. Using the tandem type extruder, the first stage reaction in which the main raw material and the auxiliary raw material are processed in the first extruder is performed, and in the second extruder, the reaction product in the first extruder is further converted into another A method for producing a thermoplastic resin that performs a second-stage reaction to be treated with an auxiliary material, wherein a single-screw extruder is used as the first extruder.   The first extruder, the second extruder, the parts connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, and the raw material supply of the resin discharge port of the first extruder and the second extruder It has an internal pressure control mechanism that connects the ports, and the “distance between the second extruder raw material supply port and the pressure control mechanism” is shorter than the “distance between the first extruder discharge port and the pressure control mechanism”. A tandem-type extruder, wherein a first stage reaction is performed in which a main raw material and a secondary raw material are processed in a first extruder, and devolatilization is performed in a second extruder. A production method using a single screw extruder for the first extruder.   The production of a thermoplastic resin according to claim 1 or 2, wherein the first extruder, which is a single-screw extruder, has a ratio L / D, which is a ratio of the length Lcm to the diameter Dcm, of 50 or less. Method.   The thermoplastic resin according to any one of claims 1 to 3, wherein the internal pressure of the component connecting the resin discharge port of the first extruder and the second extruder raw material supply port is 20 MPa or more and 100 MPa or less. Manufacturing method. When the internal volume of the part connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder is Vcm ³ , and the resin supply amount per minute to the first extruder is Qcm ³ , the part The method for producing a thermoplastic resin according to any one of claims 1 to 4, wherein the residence time V / Q in the connection component is set to 1 minute or more and 15 minutes or less by arbitrarily changing the internal volume. The method for producing a thermoplastic resin according to any one of claims 1 to 5, wherein a resin dispersion mechanism is provided in a component connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder.
The first stage reaction in which the acrylic resin and the imidizing agent are treated in the first extruder, and the reaction product in the first extruder is further treated with the esterifying agent in the second extruder. The method for producing a thermoplastic resin according to any one of claims 1, 3, 4, 5 and 6.
The thermoplastic resin is an imide resin having a unit represented by the following general formula (1), a unit represented by the following general formula (2) and / or a unit represented by the following general formula (3). The method for producing a thermoplastic resin according to claim 1, wherein:

(However, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R ⁴ and R ⁵ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R ⁷ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.)

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