JP2011042764A - Method for producing acrylic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing acrylic resins by an extruder for greatly improving reactivity and reaction uniformity by reducing extrusion fluctuation and for suppressing foreign matter and defects derived from a resin in the acrylic resin. <P>SOLUTION: In the method for producing acrylic resins, an acrylic resin is produced by means of a tandem type reactive extruder having a first extruder 1 wherein a solid resin material is plasticized, and a reagent of a first step reaction is fed 5 for performing a reaction; a second extruder 2 wherein a reagent (auxiliary material) of a second step reaction is fed 10 to a molten resin supplied from the first extruder for performing reaction and/or devolatilization, and equipment connecting a resin discharge port 6 of the first extruder and a second extruder material supply port 7 together. A temperature Q of an extruder highest temperature portion in the first extruder and/or the second extruder is set to 180-320&deg;C, and a reaction time t is set to 0.2-60 minutes. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an acrylic resin by a reactive 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 an acrylic resin can be manufactured.

  However, the conventional production method in which a thermoplastic resin is melted and reacted cannot control the reaction efficiency and the reaction uniformity, and there is room for improvement.

  Until now, as a method of improving reaction efficiency and reaction uniformity, there is a method of improving reaction efficiency by using carbon dioxide as a reaction medium in a method for producing a modified thermoplastic resin using an extruder (for example, Patent Document 1). However, since such a method uses a reaction medium, there are problems that the equipment becomes complicated and expensive, and the manufacturing cost is high.

  In addition, in order to improve the heat resistance of the acrylic resin, a copolymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit is produced, and further, intramolecular by dehydration and / or dealcoholization reaction in a later step. There exists a manufacturing method which suppresses foaming at the time of processing by performing a cyclization reaction, and obtains a thermoplastic copolymer excellent in thermal stability (for example, patent documents 2). However, there is a problem that productivity cannot be significantly improved because time is required for the intramolecular cyclization reaction in the subsequent step.

JP2002-256042 JP2008-106248

  The present invention has been made in view of the problems of such conventional techniques. In the method of producing an acrylic resin by an extruder, the extrusion fluctuation is suppressed and the reactivity and reaction uniformity are reduced. An object of the present invention is to provide a method for producing an acrylic resin capable of greatly improving and suppressing foreign matters and defects derived from the resin in the acrylic resin.

  According to the present invention, a solid resin raw material is plasticized, a reaction agent for the first stage reaction is supplied to perform the reaction, and the molten resin supplied from the first extruder is subjected to the second stage. A second extruder for supplying a reaction reagent (secondary raw material) for the eye reaction and performing reaction and / or devolatilization, and a part for connecting a resin discharge port of the first extruder and a second extruder raw material supply port, preferably In the reaction extruder with the pressure control mechanism in the first extruder, by controlling the maximum temperature of the extruder and the reaction time within the appropriate range, the fluctuation of extrusion is suppressed and the reactivity and reaction uniformity are greatly increased. Further, by controlling the imide group and / or the contained acid amount / containing acid component in the acrylic resin, it is possible to suppress the occurrence of foreign matters and defects derived from the resin during molding.

That is, the present invention relates to the following (i) to (VI).
(I) plasticizing a solid resin raw material, supplying a reaction reagent for the first-stage reaction to perform the reaction, and the second-stage reaction of the molten resin supplied from the first extruder Tandem reactive extrusion having a second extruder for supplying a reaction reagent (sub-raw material) for reaction and / or devolatilization, and a facility for connecting a resin discharge port of the first extruder and a second extruder raw material supply port In the method for producing an acrylic resin with a machine, when the maximum temperature of the extruder in the first extruder and / or the second extruder is Q ° C. and the reaction time is t minutes, the following formulas (1) and (2 The method for producing an acrylic resin characterized by satisfying

180 ≦ Q ≦ 320 (1)
0.2 ≦ t ≦ 60 (2)
(Ii) The method for producing an acrylic resin according to (i), which is a tandem reaction extruder provided with a pressure control mechanism in a connected facility.
(Iii) The method for producing an acrylic resin according to (i) or (ii), wherein the reaction reagent is an imidizing agent and / or an esterifying agent.
(Iv) A unit in which the acrylic resin is represented by the following general formula (1) and the following general formula (2
) And / or a unit represented by the following general formula (3) and / or a unit represented by the general formula (4), (i) ~ (
The manufacturing method of acrylic resin as described in any one of iii).

(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.)

(R ⁹ and R ¹⁰ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.)

(V) The main raw material is a thermoplastic resin having a unit represented by the following general formula (2) or a unit represented by the following general formula (2) and a unit represented by the following general formula (3). The method for producing an acrylic resin according to any one of (i) to (iv), wherein:

(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.)

(Vi) The units represented by the following general formula (5) and the following general formula (4) are each X mm.
The method for producing an acrylic resin according to any one of (i) to (v), wherein, when ol / g and Ymmol / g, the following mathematical formulas (3) and (4) are satisfied.

0 ≦ X ≦ 0.25 (3)
0 ≦ X + Y ≦ 0.80 (4)

(However, R ¹¹ and R ¹² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.)

(R ⁹ and R ¹⁰ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.)

  According to the present invention, a solid resin raw material is plasticized, a reaction agent for the first stage reaction is supplied to perform the reaction, and the molten resin supplied from the first extruder is subjected to the second stage. A tandem having a second extruder for supplying a reaction reagent (secondary raw material) for the reaction and / or devolatilization, and a facility for connecting the resin discharge port of the first extruder and the second extruder raw material supply port In the method of producing acrylic resin with a mold-type reactive extruder, the extrusion fluctuation is suppressed and the reactivity and reaction uniformity are greatly improved, and the imide group and / or the contained acid amount and content in the acrylic resin By controlling the acid component, it is possible to provide a method for producing an acrylic resin capable of suppressing the generation of foreign matters and defects derived from the resin.

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

  In the method for producing an acrylic resin with a tandem type reaction extruder, the present invention is as follows when the highest temperature of the extruder in the first extruder and / or the second extruder is Q ° C. and the reaction time is t minutes. It is the manufacturing method of acrylic resin characterized by satisfy | filling numerical formula (1) and (2).

180 ≦ Q ≦ 320 (1)
0.2 ≦ t ≦ 60 (2)
First, a tandem type extruder is, for example, two units, a first extruder and a second extruder, which are components that connect a resin discharge port of the first extruder and a raw material supply port of the second extruder (hereinafter simply referred to as a tandem type extruder). Abbreviated 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. A first extruder, a second extruder, and a tandem-type extruder having a resin discharge port of the first extruder and a component connecting a raw material supply port of the second extruder, the first extruder and the second extruder It is also possible to carry out different reactions on the machine.

  FIG. 1 shows an example of a tandem reaction extruder, 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).

  Next, a tandem type extruder having a pressure control mechanism will be described. An extruder having a pressure control mechanism is a device that can control the pressure loss by changing the resin flow path volume. A preferable pressure control mechanism can be exemplified by a valve, such as a constant flow pressure valve, and other gear pumps, orifices, etc., but may be incorporated in the extruder itself.

  The position where the pressure control mechanism is attached is not particularly limited as long as it is a position on the downstream side from the reaction reagent supply port, but it is preferably installed near the second extruder. Further, in a tandem type extruder having a second extruder, etc., depending on the type of the pressure control mechanism, 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 as an entity may be referred to as the position of the pressure control mechanism.

  As a connection between the extruders, it is possible to connect only by a short pipe having no pressure control mechanism.

  As the extruder in the present invention, a single screw extruder, a co-directional meshing type twin screw extruder, a co-directional non-meshing type twin screw extruder, a different direction meshing type twin screw extruder, a different direction non-meshing type 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.

  The tandem reaction extruder according to the present invention has a filter between components connecting the discharge port (6) of the first extruder (1) and the raw material supply port (7) of the second extruder (2). May be. Moreover, you may have a filter between the components which connect the discharge port of a 2nd extruder (2), and a strand die. It is preferable to install a gear pump for boosting the resin before the filter. As the type of filter, it is preferable to use a stainless steel leaf disc filter capable of removing foreign substances from the molten polymer, and it is preferable to use a fiber type, a powder type, or a composite type thereof as the filter element.

  The main raw material of the acrylic resin obtained in the present invention is 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 , Maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid and other α, β-ethylenically unsaturated carboxylic acids, (meth) acrylic esters and other acrylic monomers and at least one of them The polymer (acrylic resin) etc. which superposed | polymerized can be mentioned. Among them, (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): A polymer or a (meth) acrylic acid ester polymer such as a methyl methacrylate polymer composed of a repeating unit represented by the general formula (2) is preferred.

(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.)

In the formula (2), R ⁴ is preferably a hydrogen atom, and R ⁵ is preferably a methyl group. R ⁶ is preferably a methyl group. In the formula (3), R ⁷ is preferably hydrogen, and R ⁸ is preferably a phenyl group.

  In the present invention, a (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer or a (meth) acrylic acid ester polymer such as methyl methacrylate polymer is polymerized, and this is imide. When the resin is formed, the (meth) acrylic acid ester-aromatic vinyl copolymer and (meth) acrylic acid ester polymer that can be used in the present invention are linear (linear) if imidization reaction is possible. The polymer 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.

  The reaction reagent in the present invention is not particularly limited as long as it reacts with the main raw material to give an acrylic resin.

  Next, the following formula (1) and the following formula (2) in the present invention will be described.

180 ≦ Q ≦ 320 (1)
0.2 ≦ t ≦ 60 (2)
The extruder maximum temperature of the extruder of the present invention is the temperature of the highest temperature portion of the extruder in the reaction section from the extruder reaction reagent press-fitting section (8) to the raw material supply port (7) of the second extruder. Here, the temperature at the highest temperature point is the barrel temperature, the temperature analyzed from the indication value of the resin thermometer installed in the extruder, and the value of the measured temperature of the resin, such as the measured value of the reaction part temperature in the extruder, the most. Refers to high temperature.

  The value of the maximum temperature QQ ° C. of the extruder of the present invention needs to be 180 ° C. or higher and 320 ° C. or lower. Preferably they are 200 degreeC or more and 310 degrees C or less, More preferably, they are 220 degreeC or more and 300 degrees C or less.

  The reaction time of the present invention is the time from when the resin and the reaction reagent are supplied into the extruder until the resin and the reaction reagent are separated.

  The value of the reaction time t of the present invention needs to be 0.2 minutes or more and 60 minutes or less. Preferably they are 0.3 minutes or more and 45 minutes or less, More preferably, they are 0.4 minutes or more and 30 minutes or less.

  If the value of the extruder maximum temperature Q ° C. and the value of the reaction time t are within the above ranges, the fluctuation in extrusion can be suppressed and the reactivity and reaction uniformity can be greatly improved.

  If the value of the extruder maximum temperature Q ° C is less than 180 ° C, the reaction efficiency tends to decrease and the productivity tends to deteriorate, and if it exceeds 320 ° C, the resin tends to be thermally deteriorated.

  Further, if the value of the reaction time t is less than 0.2 minutes, the reaction efficiency tends to be low, and if it exceeds 60 minutes, the resin tends to be thermally deteriorated.

  The reaction system internal pressure (maximum pressure in the reaction part in the extruder) at this time can be carried out at 0.5 MPa or more and 50 MPa or less. The pressure in the reaction system is the highest pressure in pressure measuring equipment installed in an extruder or pressure control mechanism, pressure measuring equipment installed in a reaction reagent press-fitting part or line, and other measuring equipment that can analyze the pressure in the extruder. . The internal pressure of the reaction system is preferably 0.5 MPa or more and 50 MPa or less. More preferably, it is 1 MPa or more and 20 MPa or less, More preferably, it is 2 MPa or more and 15 MPa or less. When the internal pressure of the reaction system is less than 0.5 MPa, the reaction efficiency in the extruder becomes low, and the reaction by-product foams and separates in the reaction part, the fluctuation of extrusion increases, and the reaction becomes non-uniform. Therefore, it is not preferable.

  Further, when the internal pressure of the reaction system is higher than 50 MPa, particularly when the pressure resistance specification of the extruder speed reducer is exceeded, the extruder may be damaged, which is not preferable.

  Further, the number of parts added of the reaction reagent at this time (reaction reagent supply weight part when the amount of the supplied resin is 100 parts by weight) may be appropriately determined according to necessary physical properties. Preferably, it is 0.5 to 30 parts by weight with respect to 100 parts by weight of the supplied resin. More preferably, it is 0.8-25 weight part, More preferably, it is 1-20 weight part. If the amount is less than 0.5 parts by weight, the reaction rate decreases, and if it exceeds 50 parts by weight, the production cost increases, which is not preferable.

  The acrylic resin of the present invention is not particularly limited, and examples thereof include those obtained by further polymerizing, modifying or reacting an acrylic monomer and a polymer obtained by polymerizing at least one of them. Methyl methacrylate resin, polystyrene resin, cellulose resin, vinyl chloride resin, polysulfone resin, polyethersulfone resin, maleimide / olefin resin, glutarimide resin, lactone ring-containing polymer, glutaric anhydride Examples thereof include a copolymer resin such as a product-containing resin or a resin composition obtained by mixing these. A glutarimide resin is preferable.

  Here, a method for producing a glutarimide resin (hereinafter referred to as an imide resin) as an acrylic resin will be described as an example. Specifically, a reaction in which a raw acrylic resin (hereinafter referred to as a main raw material) and an imidizing agent are processed in a first extruder using a tandem reaction extruder having a pressure control mechanism will be described.

  An example of the reaction agent 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. Further, urea compounds such as urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea that generate these amines or ammonia 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.

  In the glutarimide resin, the imidation rate is preferably 3% or more and 95% or less, more preferably 5% or more and 90% or less, and further preferably 8% or more and 80% or less. When not satisfy | filling above-mentioned numerical formula (1), the imide resin which has the imidation ratio of the said range cannot be obtained.

  In the first extruder of the tandem type reaction extruder, first, a raw material acrylic resin (main raw material) is used, and this is used as a secondary raw material for the first stage reaction such as ammonia or substituted amine (hereinafter referred to as an imidizing agent). ) Can be obtained (hereinafter referred to as imide resin intermediate 1).

  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 (mono derived from the carboxyl group and the acid anhydride group) remaining in the resin can be controlled (hereinafter sometimes referred to as “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 temperature is in the range of 180 to 320 ° C. in order to suppress the decomposition, coloring, etc. of the resin due to excessive heat history. 200-310 degreeC is preferable and 220-300 degreeC is more preferable. 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 30 parts by weight with respect to 100 parts by weight of the imide resin intermediate 1.

  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, and benzyl glycidyl ether. Examples of the reaction accelerator include base catalysts such as trimethylamine, triethylamine, benzyldimethylamine, and tetramethylammonium hydroxide, and acid catalysts such as p-toluenesulfonic acid, tetrabutyltitanate, and manganese tetraacetate, and Lewis catalysts. Among these, a base catalyst is preferable, and from the viewpoint of physical properties of the obtained resin, a tertiary amine such as trimethylamine, triethylamine, and benzyldimethylamine is more preferable, and triethylamine is more preferable.

  Further, the esterifying agent contained in the imide resin intermediate 2 may be removed by devolatilization under reduced pressure or the like.

  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 180 to 320 ° C. 200-310 degreeC is preferable and 220-300 degreeC is more preferable. The reaction time is 0.2 to 60 minutes. 0.3 to 45 minutes are preferable, and 0.4 to 30 minutes are more preferable.

  Next, the following mathematical formulas (3) and (4) in the present invention will be described.

0 ≦ X ≦ 0.25 (3)
0 ≦ X + Y ≦ 0.80 (4)
X value in Formula (3) is content of the unit shown by following General formula (5) contained in acrylic resin. Y value in Formula (4) is content of the unit shown by following General formula (4) contained in acrylic resin.

(However, R ¹¹ and R ¹² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.)

(R ⁹ and R ¹⁰ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.)

  The X value is preferably 0 mmol / g or more and 0.25 mmol / g or less. More preferably, they are 0 mmol / g or more and 0.23 mmol / g or less, More preferably, they are 0 mmol / g or more and 0.20 mmol / g or less. When the X value exceeds 0.25 mmol / g, the resin-derived foreign matter and defects tend to increase.

  The (X + Y) value is preferably 0 mmol / g or more and 0.80 mmol / g or less. More preferably, they are 0 mmol / g or more and 0.77 mmol / g or less, More preferably, they are 0 mmol / g or more and 0.75 mmol / g or less. If the (X + Y) value exceeds 0.80 mmol / g, the moldability tends to be lowered.

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

  In the present invention, the raw material can be a solid-state resin, which is supplied from the raw material supply port (5) of the first extruder (1) by a feeder device or the like, and is heated and melted in the extruder. Examples of the feeder device include a constant weight feeder and a constant volume feeder. 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 (1) is not isolated from the resin discharge port (6), but passes through the connecting part (3) connected to the resin discharge port (6). It is led to the machine raw material supply port (7) and charged into the second extruder (2).

  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.

  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 the imide resin obtained as described above, for example, various types can be produced by appropriately setting the type and amount of the main raw material and the auxiliary raw material by the above-described method. What has the unit represented by (1) and the unit represented by the following general formula (2) and / or the following general formula (3) and / or (4) is preferable.

(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.)

(R ⁹ and R ¹⁰ each independently represent hydrogen or an alkyl group having 1 to 8 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)). (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 preferred.

The glutarimide unit may be 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) is 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) is 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 glutarimide 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 3 to 95% by weight, more preferably 5 to 90% by weight, and still more preferably 8 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.

  What is necessary is just to set content of the aromatic vinyl unit represented by General formula (3) of an imide resin according to the required physical property. Although not particularly limited, it is preferably 1% by weight or more based on the total repeating unit of the imide resin. The preferred content of the aromatic vinyl unit is 1 to 40% by weight, more preferably 1 to 30% by weight, and still more preferably 1 to 50% 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 resin that has the unit represented by the general formula (2), the resin that has the unit represented by the general formula (3), and the imidizing agent that is the auxiliary material, which is the main raw material, An imide resin containing the unit represented by the general formula (1) and the unit represented by the general formula (2) and / or the unit represented by the general formula (3) in an arbitrary ratio can be obtained. By adjusting the ratios of the general formulas (1), (2) and (3), 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 be set to 0), and the addition ratio of the imidizing agent during imidization is further determined. 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 the amount of each structural unit and glutarimide in the methyl methacrylate-styrene copolymer or (meth) acrylic acid ester polymer. By adjusting the content of the unit, it is possible to give a characteristic that does not substantially have orientation birefringence. Moreover, it has positive orientation birefringence by reducing the content of the general formula (3), not including the general formula (3), or increasing the content of the general formula (1). An imide resin can also be produced. 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 refers to birefringence that develops when uniaxially 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. In the said imide resin, it is possible to adjust the value of orientation birefringence according to the use to be used.

The value of the orientation birefringence of the imide resin having substantially no orientation birefringence is preferably −0.1 × 10 ^{−3 to} 0.1 × 10 ⁻³ , and −0.01 × 10 ^It is more preferable that it is ^{−3 to} 0.01 × 10 ⁻³ .

  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, Further, 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 0.5: 1.0 to 10.0 in weight ratio. Is preferably in the range of 1.0, more preferably in the range of 2.0: 1.0 to 9.0: 1.0, and in the range of 3.0: 1.0 to 7.0: 1.0. Is more preferable, and the range of 4.0: 1.0 to 6.5: 1.0 is particularly 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 an imide resin, if an excessive thermal 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 . In addition, extremely low molecular weight substances resulting from thermal decomposition and the crosslinked polymer itself may become foreign substances in the product. When the method for producing an imide resin in the present invention is applied, the thermal history of the resin can be reduced during the production process of the imide resin, and the above weight average molecular weight range can be achieved. In addition, the above-described foreign matter is less likely to occur. When the weight average molecular weight is less than 1 × 10 ⁴ , the mechanical strength in the case of 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, ultraviolet 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.

  As the ultraviolet absorber that can be used in the present invention, a known ultraviolet absorber can be used. Preferred ultraviolet absorbers are one or more ultraviolet absorbers selected from triazine ultraviolet absorbers, benzotriazole ultraviolet absorbers, and benzophenone ultraviolet absorbers.

  Although the heat stabilizer used in the present invention is not particularly limited, for example, those comprising at least one compound selected from hindered phenol compounds, lactone compounds, phosphorus compounds, hindered amine compounds, and thioether compounds are preferable. .

  In general, the foreign matters in the resin may be those mixed from the environment, those generated during molding, those generated during resin synthesis (for example, scale), and the like. The foreign matters and defects derived from the resin here are components different from the surrounding imide resin and the shape is not particularly limited, but the foreign matters have long sides of 10 μm or more. These can be observed with an optical microscope. For example, many of them appear yellow or colorless and transparent. In general, (meth) acrylic acid ester resins are copolymerized with acrylic acid esters such as methyl acrylate in order to suppress a zipping reaction caused by high temperature heating. Conditions such as the high reaction temperature during the reaction and the presence of amines affect the tertiary hydrogen of the main chain of (meth) acrylic acid esters to generate carbon radicals. . It can be considered that this carbon radical is the starting point, and a heterogeneous resin is produced by main chain cleavage or intermolecular coupling reaction. The component different from the imide resin thus produced is considered to be a foreign substance or a defect derived from the resin. Moreover, when there are many carboxylic acid components in acrylic resin, aggregation by a hydrogen bond will generate | occur | produce and it may become a foreign material and a defect derived from resin.

  When the acrylic resin of the present invention is used for optical applications, for example, in a molded body having a length of 210 mm, a width of 300 mm, and a thickness of 3 mm so that foreign matters and defects derived from the resin do not become fatal defects. The number is preferably 100 or less, and more preferably 50 or less. More preferably, it is 20 or less.

  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 ratio 1 g of product pellets were dissolved in 5 cc of dichloromethane, and an IR spectrum was measured at room temperature using an IR meter manufactured by JASCO Corporation. 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.

  The variation in imidization rate was obtained by collecting a sample resin for every 500 kg of imidized resin to be obtained, measuring the imidization rate by the above method, and displaying the maximum value of the difference from the average value of the imidization rate.

(2) Measurement of ratio of acid component remaining in resin (2-1)
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 10 minutes. 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 (mono derived from a carboxyl group and an acid anhydride group) remaining in the resin was defined as Cmmol / g, and the following formula was used.

    C = 0.1 × ((5-AB) /0.3)

(2-2)
0.3 g of product pellets were dissolved in 37.5 ml of dichloromethane and 37.5 ml of dimethyl sulfoxide was added. To this solution, add 2 drops of 1 wt% phenolphthalein ethanol solution, add 5 ml of 0.1N sodium hydroxide aqueous solution and stir. Add 0.1N hydrochloric acid dropwise to this solution until the reddish purple color of the solution disappears. The dropping amount (Dml) of 0.1N hydrochloric acid was measured.

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

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

    F = 0.1 × ((5-DE) /0.3)

(2-3)
The carboxyl group (X) and the acid anhydride amount (Y) were determined by the following formula.

X = F−Y
Y = (F−C) × 2

(3) Inspection of foreign matter After the produced resin is dried at 100 ° C. for 5 hours, it is extruded at a discharge rate of 20 kg / hr at a cylinder and T die temperature of 270 ° C. using a 40 mmφ single-screw extruder and a 400 mm wide T die. The molten resin was cooled with a cooling drum to obtain a sheet-like molded body having a width of about 400 mm and a thickness of 150 μm. A test piece having a size of 210 mm in length and 300 mm in width was cut out from the obtained sheet-like molded product having a thickness of 150 μm. While this test piece was irradiated with light from a desk stand (National SQ948H, fluorescent lamp 27W) in a dark room, the periphery of the visually observed foreign matter was checked with an oil pen. Next, the checked foreign matter was observed with a transmission optical microscope (digital microscope (VH-Z75), manufactured by Keyence Corporation) with a magnification of 50 times. The above observation was performed on both sides of the sheet-like molded body, and the total number and type of foreign matters were measured. As a method of distinguishing the resin-derived foreign matter or defect from the general foreign matter, it was judged by the color of the foreign matter when observed with a transmission optical microscope having a magnification of 50 times or more. It was judged that the resin-derived foreign matters and defects looked yellow and colorless and transparent, and the general foreign matters looked other colors. The size of foreign matters and defects derived from the resin was set to 20 μm or more.

Example 1
An apparatus equivalent to that shown in FIG. 1 was used. As for the tandem type reactive extruder, the first extruder (1) and the second extruder (2) are both in the same direction meshing type with a diameter of 75 mm and L / D (ratio of the length L to the diameter D of the extruder) of 74. Using a twin screw extruder, the raw material resin was supplied to the first extruder raw material supply port (5) using a constant weight feeder (manufactured by Kubota Corporation). 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 38 mm and a length of 2 m (connection part (3)), and the resin discharge port (6) of the first extruder and the second extruder raw material supply port. A valve (pressure adjusting valve) was used for the in-part pressure control mechanism (4) connected to (7). The resin (strand) discharged from the second extruder was cooled by a cooling conveyor and then cut by a pelletizer to form pellets. 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, methyl methacrylate-styrene copolymer (Mw 95,000 styrene amount 11 mol%) is used as a raw material resin, and imide resin intermediate 1 is produced using monomethylamine as an imidizing agent. did. At this time, the maximum temperature of the extruder was 280 ° C., the screw rotation speed was 60 rpm, the raw material resin supply amount was 150 kg / hour, and the amount of monomethylamine added was 16 parts by weight with respect to 100 parts by weight of the raw material resin. The valve (pressure adjusting valve) was installed immediately before the second extruder raw material supply port, and the pressure of the first extruder monomethylamine press-fitting portion was adjusted to 8 MPa.

  For the second extruder, after devolatilizing the imidization reaction reagent and by-products remaining in the rear vent and vacuum vent, a mixed solution of dimethyl carbonate and triethylamine is added as an esterifying agent, and the esterification remaining after the reaction The imide resin intermediate 2 was produced by devolatilizing the agent and by-products. At this time, each barrel temperature of the extruder was 260 ° C. and the screw rotation speed was 55 rpm to obtain an imide resin.

  The reaction time was 8 minutes.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidation ratio of 70%, a variation of 1%, and a component X remaining in the resin of 0.25 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Example 2)
Regarding the second extruder, after devolatilizing the imidization reaction reagent and by-products remaining in the rear vent and vacuum vent, a mixed solution of dimethyl carbonate and triethylamine is added as an esterifying agent, and the esterification remaining after the reaction The imide resin intermediate 2 was produced by devolatilizing the agent and by-products. At this time, each barrel temperature of the extruder is 260 ° C., the screw rotation speed is 55 rpm, the addition amount of dimethyl carbonate is 2.4 parts by weight with respect to 100 parts by weight of the raw resin, and the addition amount of triethylamine is with respect to 100 parts by weight of the raw resin. 0.6 parts by weight. Otherwise, Example 1 was followed.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidation rate of 70%, a variation of 1%, and a component X remaining in the resin of 0.07 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Example 3)
An imide resin was produced in the same manner as in Example 1 except that the amount of the esterifying agent added was 5 parts by weight of dimethyl carbonate.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidation rate of 70%, a variation of 1%, and a component X remaining in the resin of 0.13 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

Example 4
An imide resin was produced in the same manner as in Example 1 except that the amount of the esterifying agent added was 5 parts by weight of dimethyl carbonate and a 5 μ cut fiber leaf disc filter was used.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidization rate of 70%, a variation of 1%, and a component X remaining in the resin of 0.01 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Example 5)
An imide resin was produced in the same manner as in Example 1 except that the amount of the imidizing agent added was 12 parts by weight.

  The imide resin was produced for about 7 days under the above conditions, and the obtained imide resin had a variation of 1% with respect to the imidization rate of 60%, and the component X remaining in the resin was 0.18 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Example 6)
An imide resin was produced in the same manner as in Example 1 except that the amount of the imidizing agent added was 12 parts by weight, the amount of dimethyl carbonate added was 1.8 parts by weight, and the amount of triethylamine added was 0.4 parts by weight.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidation ratio of 60%, a variation of 1%, and a component X remaining in the resin of 0.07 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Example 7)
An imide resin was produced in the same manner as in Example 1 except that the raw material resin supply rate was 200 kg / h.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidation rate of 63%, a variation of 1%, and a component X remaining in the resin of 0.20 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Example 8)
Polymethyl methacrylate polymer (Mw 105,000) is used as a raw material resin, 2 parts by weight of an imidizing agent, 4 parts by weight of dimethyl carbonate, and 1 part by weight of triethylamine (each 100% by weight of raw material resin) The imide resin was produced in the same manner as in Example 1 except that the reaction time was 7 minutes.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had a variation of 1% with respect to an imidization rate of 13.5%, and the component X remaining in the resin was 0.15 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

Example 9
Using polymethyl methacrylate polymer (Mw 105,000) as a raw material resin, 2 parts by weight of an imidizing agent, 3.2 parts by weight of dimethyl carbonate, 0.8 parts by weight of triethylamine, An imide resin was produced in the same manner as in Example 1 except that the maximum temperature of the extruder was 260 ° C. and the reaction time was 5 minutes.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidation rate of 13.5%, a variation of 1%, and a component X remaining in the resin of 0.05 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Example 10)
Polymethyl methacrylate polymer (Mw 105,000) is used as a raw material resin, 2 parts by weight of an imidizing agent, 3.2 parts by weight of dimethyl carbonate, 0.8 parts by weight of triethylamine, and a heat stabilizer Example 1 except that 0.1 part by weight was added from the side feeder part of the second extruder, a 5 μ cut fiber leaf disc filter was used, the maximum temperature of the extruder was 260 ° C., and the reaction time was 5 minutes. An imide resin was produced in the same manner.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had a variation of 1% with respect to an imidization rate of 13.5%, and the component X remaining in the resin was 0.01 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Comparative Example 1)
An imide resin was produced in the same manner as in Example 1 except that the system pressure was 5 MPa, the reaction reagent was 16 parts by weight, and the extruder maximum temperature was 330 ° C.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidization rate of 65%, a variation of 3%, and a component X remaining in the resin of 0.30 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Comparative Example 2)
The same as in Example 1 except that polymethyl methacrylate polymer (Mw 105,000) was used as the raw material resin, the internal pressure was 3 MPa, the imidizing agent was 2 parts by weight, and the maximum temperature of the extruder was 330 ° C. The imide resin was manufactured by the method.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidization rate of 13.5%, a variation of 3%, and a component X remaining in the resin of 0.30 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

(Comparative Example 3)
A polymethyl methacrylate polymer (Mw 105,000) was used as a raw material resin, the internal pressure was 3 MPa, the imidizing agent was 2 parts by weight, the maximum temperature in the extruder was 330 ° C., and the reaction time was 10 minutes. An imide resin was produced in the same manner as in Example 1.

  Production was carried out for about 7 days under the above conditions. The resulting imide resin had an imidation rate of 13.5%, a variation of 3%, and the component X remaining in the resin was 0.03 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 1st extruder 2 2nd extruder 3 Connection component 4 Component internal pressure control mechanism 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 13 Second Extruder Vent Port 14 Second Extruder Vent Port

Claims (6)

A first extruder for plasticizing a solid resin material and supplying a reaction reagent for the first stage reaction to react, and a reaction reagent for the second stage reaction on the molten resin supplied from the first extruder ( A tandem-type reaction extruder having a second extruder that performs reaction and / or devolatilization by supplying a secondary raw material) and a facility that connects the resin discharge port of the first extruder and the second extruder raw material supply port. In the method for producing a resin, the following formulas (1) and (2) are satisfied when the maximum temperature of the extruder in the first extruder and / or the second extruder is Q ° C. and the reaction time is t minutes. A method for producing an acrylic resin.
180 ≦ Q ≦ 320 (1)
0.2 ≦ t ≦ 60 (2) 2. The method for producing an acrylic resin according to claim 1, which is a tandem reaction extruder provided with a pressure control mechanism in a connected facility. The method for producing an acrylic resin according to claim 1 or 2, wherein the reaction reagent is an imidizing agent and / or an esterifying agent. The acrylic resin is 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) and / or the general formula (4). It is an imide resin which has a unit represented by this, The manufacturing method of the acrylic resin of any one of Claims 1-3 characterized by the above-mentioned.

(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.)

(R ⁹ and R ¹⁰ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.) The main raw material is a thermoplastic resin having a unit represented by the following general formula (2) or a unit represented by the following general formula (2) and a unit represented by the following general formula (3). The manufacturing method of the acrylic resin of any one of Claims 1-4.

(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.) The following formulas (3) and (4) are satisfied when the units represented by the following general formula (5) and the following general formula (4) are X mmol / g and Y mmol / g, respectively. The manufacturing method of acrylic resin of any one of 1-5.
0 ≦ X ≦ 0.25 (3)
0 ≦ X + Y ≦ 0.80 (4)

(However, R ¹¹ and R ¹² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.)

(R ⁹ and R ¹⁰ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms.)

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