JP2007262396A - Thermoplastic resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has not only excellent transparency and heat resistance but also desired characteristics such as mechanical strength and moldability, does cause a foaming phenomenon, especially when thermally processed, and can give molded articles free from bubbles and silver streaks, and to provide a method for producing the same. <P>SOLUTION: This thermoplastic resin composition comprising a methacrylic resin having a glass transition temperature of ≥110°C and at least one metal compound selected from metal salts, metal complexes and metal oxides is characterized in that the content of the metal compound in the composition is 10 to 10,000 ppm converted into metal atom on the basis of the mass of the methacrylic resin. The method for producing the thermoplastic resin composition is characterized by forming ring structures by a cyclization condensation reaction using a catalyst and then adding an agent for inactivating the catalyst, when producing the methacrylic resin having the ring structures in the main chain and having a glass transition temperature of ≥110°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition and a method for producing the same, and more specifically, a thermoplastic resin composition containing a methacrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher, and It relates to the manufacturing method.

  Conventionally, a methacrylic resin is known as a resin having transparency. Methacrylic resins are not only transparent, but also have excellent surface gloss and weather resistance, and have a good balance of mechanical strength, moldability, and surface hardness, so they are widely used in optical-related applications such as automobiles and home appliances. in use. However, since the glass transition temperature of methacrylic resins is around 100 ° C., it has been difficult to use in fields where heat resistance is required.

  As a transparent heat-resistant resin having transparency and heat resistance, and also having various properties such as mechanical strength and moldability, a polymer having a hydroxyl group and an ester group in a molecular chain has recently been used as a lactone ring. Several lactone ring-containing polymers obtained by a polycondensation reaction have been proposed. For example, by subjecting 2- (hydroxymethyl) acrylic acid alkyl ester / methyl methacrylate copolymer or α-hydroxymethylstyrene / methyl methacrylate copolymer to a dealcoholization reaction which is a kind of transesterification, It is a polymer in which a lactone ring is produced by the condensation of an existing hydroxyl group and an ester group. However, in the conventional method, an esterification catalyst or a transesterification catalyst such as sulfuric acid or p-toluenesulfonic acid is used for the dealcoholization reaction. However, in order to increase the dealcoholization reaction rate, There is a problem that the obtained polymer is colored, and conversely, if the dealcoholization rate is low, the dealcoholization reaction proceeds when the obtained polymer is thermally processed, and bubbles or silver streaks are formed in the molded product. There was a problem of entering.

Therefore, in Patent Document 1, in the dealcoholization reaction, by using an organophosphorus compound as a catalyst, coloring is reduced, good transparency is ensured, and bubbles and silver streaks enter the molded product. A technique for suppressing the above is disclosed. In Patent Document 2, the dealcoholization reaction is performed in the presence of a solvent, and the dealcoholization step is used in combination with the dealcoholization reaction, whereby the dealcoholization reaction rate is extremely high and can be obtained. There has been disclosed a technique in which the residual volatile content of the polymer is small, and therefore, foam and silver streak are prevented from entering the molded product. Furthermore, Patent Document 3 prevents the dealcoholization reaction from proceeding during thermal processing by converting an unreacted hydroxyl group to a group that does not act as a dealcoholization reaction point during the dealcoholization reaction, Therefore, a technique for preventing bubbles and silver streaks from entering the molded article is disclosed.
JP 2001-151814 A JP 2002-230016 A JP 2002-138106 A

  However, all of the above conventional techniques are still insufficient to suppress the foaming phenomenon of the polymer, particularly at the time of heat processing, and it has been difficult to obtain a molded product free from bubbles and silver streaks. .

  Under the circumstances described above, the problem to be solved by the present invention is not only excellent in transparency and heat resistance, but also has desired characteristics such as mechanical strength and moldability, and causes a foaming phenomenon particularly during thermal processing. An object of the present invention is to provide a thermoplastic resin composition capable of providing a molded product free from bubbles and silver streaks and a method for producing the same.

  As a result of various studies, the present inventors have generally found that the catalyst used for the transesterification remains in the methacrylic resin having a ring structure formed by transesterification. Of the copolymerized units constituting the molecular chain, the hydroxyl group of an unreacted ring-forming unit (that is, a unit that has not yet formed a ring), or active hydrogen such as water present in a small amount in the system, and an alkyl ester group Alcohol generated by transesterification is considered to be the main cause of the foaming phenomenon, and when the catalyst deactivator used for transesterification was added, it was found that the foaming phenomenon was difficult to occur during heat processing. Completed the invention. Hereinafter, “transesterification” may be referred to as “cyclization condensation reaction”.

  That is, the present invention provides a methacrylic resin having a ring structure in the main chain and having a glass transition temperature of 110 ° C. or higher, and at least one metal compound selected from a metal salt, a metal complex, and a metal oxide. The content of the metal compound in the composition is 10 to 10,000 ppm in terms of metal atom based on the mass of the methacrylic resin. A thermoplastic resin composition is provided.

  In the thermoplastic resin composition of the present invention, the metal compound is preferably a salt of a typical metal element. Here, the typical metal element is preferably calcium, magnesium or zinc.

  The thermoplastic resin composition of the present invention may contain an organic acid. In this case, the metal compound is preferably a metal salt of an organic acid, more preferably a metal salt of a carboxylic acid or an organic phosphorus compound.

  In the thermoplastic resin composition of the present invention, the foaming amount generated when the composition is heated at 260 ° C. for 20 minutes is preferably 20 pieces / g or less.

  In the thermoplastic resin composition of the present invention, the methacrylic resin is preferably a lactone ring structure, more preferably the following formula (1):

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
Having a lactone ring structure.

  Further, the present invention is a method for producing a thermoplastic resin composition as described above, in producing a methacrylic resin having a ring structure in the main chain and having a glass transition temperature of 110 ° C. or higher. Provided is a production method comprising adding a catalyst deactivator after forming the ring structure by a cyclization condensation reaction using a catalyst.

  According to the thermoplastic resin composition of the present invention and the method for producing the same, since most of the catalyst used in the cyclization condensation reaction is deactivated by the deactivator, not only is it excellent in transparency and heat resistance, In addition to providing desired properties such as mechanical strength and molding processability, a molded product free from bubbles and silver streaks can be provided without causing a foaming phenomenon particularly during thermal processing.

<< Thermoplastic resin composition and method for producing the same >>
The thermoplastic resin composition of the present invention has at least one selected from a methacrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher, a metal salt, a metal complex, and a metal oxide. The metal compound in the composition, wherein the content of the metal compound in the composition is 10 to 10,000 ppm in terms of metal atom based on the mass of the methacrylic resin. It is characterized by being. Here, “at least one metal compound selected from metal salts, metal complexes and metal oxides” means a quencher added after a cyclization condensation reaction for introducing a ring structure into the main chain of the methacrylic resin Or a product produced by the reaction of the catalyst used in the cyclocondensation reaction for introducing a ring structure into the main chain of the methacrylic resin with the deactivator added after the cyclocondensation reaction or its modification Means a thing. This product or its modified product is not particularly limited because it depends on the type of catalyst and deactivator, the conditions of the cyclization condensation reaction and the devolatilization step, and the like. Since the metal is contained in either the catalyst or the deactivator, the content of the metal compound can be expressed in terms of metal atoms.

  The content of the metal compound in the thermoplastic resin composition of the present invention is usually 10 to 10,000 ppm in terms of metal atom based on the mass of the methacrylic resin, and the upper limit is preferably 5,000 ppm. Preferably, it is 3,000 ppm, more preferably 1,000 ppm, and the lower limit is preferably 30 ppm, more preferably 50 ppm, still more preferably 100 ppm. When the content of the metal compound is less than 10 ppm, the amount of the catalyst or the deactivator is small, so that the action is insufficient, and a sufficient ring structure is not introduced into the main chain, resulting in a decrease in heat resistance. Or foam or silver streaks may enter the molded product. On the contrary, when the content of the metal compound exceeds 10,000 ppm, the amount of the catalyst or the deactivator added is large, so that the action is saturated and the catalyst or the deactivator is used more than necessary. In addition, problems such as resin coloring may occur and manufacturing costs may increase. In addition, content of a metal compound can be measured by ICP (ICP-AES, ICP-MS), an atomic absorption spectrum, ion chromatography, elemental analysis, GC, GC / MS, LC etc., for example.

  In the thermoplastic resin composition of the present invention, the metal compound is preferably a salt of a typical metal element. Here, the typical metal element is preferably calcium, magnesium or zinc.

  The thermoplastic resin composition of the present invention may contain an organic acid. The metal compound is preferably a metal salt of an organic acid, more preferably a metal salt of a carboxylic acid or an organic phosphorus compound. Here, the organic acid is a product produced by decomposition of a catalyst used in a cyclization condensation reaction for introducing a ring structure into the main chain of a methacrylic resin or a deactivator added after the cyclization condensation reaction, or a modification thereof. Means a thing. The organic acid and its content are not particularly limited because it depends on the type and amount of the catalyst and the quenching agent, the conditions of the cyclization condensation reaction and the devolatilization step, and the like. In addition, content of this organic acid can be measured by ion chromatography, for example.

  In producing the thermoplastic resin composition of the present invention, a methacrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher is produced by a cyclization condensation reaction using a catalyst. After forming the ring structure, a deactivator may be added to deactivate the catalyst. That is, the method for producing the thermoplastic resin composition of the present invention is a cyclocondensation using a catalyst in producing a methacrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher. After the formation of the ring structure by reaction, the catalyst deactivator is added. Regarding the method for producing the thermoplastic resin composition of the present invention, hereinafter, the case where the methacrylic resin is a lactone ring-containing polymer will be described in detail. When the methacrylic resin is other than the lactone ring-containing polymer, for example, In the case of a polymer having a ring structure composed of glutaric anhydride, a 2,5-dioxotetrahydrofuran ring-containing polymer, and a 2,6-dioxotetrahydropyran ring-containing polymer, the main chain is also formed by a cyclization condensation reaction. By appropriately selecting the monomer component so that these ring structures are formed, it can be carried out in the same manner as in the case of the lactone ring-containing polymer.

≪Methacrylic resin≫
In the thermoplastic resin composition of the present invention, examples of the methacrylic resin having a ring structure in the main chain and having a glass transition temperature of 110 ° C. or higher include, for example, a lactone ring-containing polymer, the following formula (2):

And a polymer having a ring structure composed of glutaric anhydride, a 2,5-dioxotetrahydrofuran ring-containing polymer, and a 2,6-dioxotetrahydropyran ring-containing polymer. These methacrylic resins may be used alone or in combination of two or more. Among these methacrylic resins, a lactone ring-containing polymer is particularly preferable because it has not only excellent transparency and heat resistance but also desired properties such as mechanical strength and moldability.

  The glass transition temperature of the methacrylic resin is usually 110 ° C. or higher, preferably 115 ° C. or higher, more preferably 120 ° C. or higher, more preferably 125 ° C. or higher, and the upper limit is not particularly limited, Preferably it is 170 degreeC, More preferably, it is 160 degreeC, More preferably, it is 150 degreeC. In addition, the glass transition temperature of methacrylic resin is the value calculated | required by the midpoint method based on ASTM-D-3418.

  Hereinafter, the lactone ring-containing polymer, which is a particularly preferred methacrylic resin, will be described in detail as an example for the thermoplastic resin composition of the present invention and the production method thereof.

<Configuration of lactone ring-containing polymer>
The lactone ring-containing polymer used in the thermoplastic resin composition of the present invention preferably has the following formula (1) as the ring structure formed by the cyclization condensation reaction:

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
Having a lactone ring structure. Here, the “organic residue” means an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or a substituted aryl group. Specific examples thereof include, for example, a methyl group, an ethyl group, and a propyl group. Isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, cyclohexyl group, phenyl group, methoxyphenyl group, benzyl group, naphthyl group, octyl group, 2-ethylhexyl group, lauryl group, stearyl group, etc. It is done.

  The content of the lactone ring structure represented by the above formula (1) in the structure of the lactone ring-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60% by mass. Especially preferably, it is 10-50 mass%. When the content of the lactone ring structure is less than 5% by mass, the heat resistance, solvent resistance, and surface hardness of the obtained polymer may be lowered. On the contrary, when the content of the lactone ring structure exceeds 90% by mass, the moldability of the obtained polymer may be deteriorated.

  The lactone ring-containing polymer may have a structure other than the lactone ring structure represented by the above formula (1). The structure other than the lactone ring structure represented by the above formula (1) is not particularly limited. For example, a (meth) acrylic acid ester, which will be described later as a method for producing a lactone ring-containing polymer, Hydroxyl group-containing monomer, unsaturated carboxylic acid, and the following formula (3):

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or —CO —O—R ⁶ group, Ac represents an acetyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms]
A polymer structural unit (repeated structural unit) formed by polymerizing at least one monomer selected from the group consisting of the monomers represented by

  The content ratio of the structure other than the lactone ring structure represented by the above formula (1) in the structure of the lactone ring-containing polymer is a polymer structural unit (repeated structural unit) formed by polymerizing (meth) acrylic acid ester. In this case, it is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, further preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass, and is formed by polymerizing a hydroxyl group-containing monomer. In the case of a polymer structural unit (repeating structural unit), preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, particularly preferably 0 to 10% by mass. . In the case of a polymer structural unit (repeating structural unit) formed by polymerizing an unsaturated carboxylic acid, it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and still more preferably 0 to 15% by mass. Especially preferably, it is 0-10 mass%. Furthermore, in the case of a polymer structural unit (repeating structural unit) formed by polymerizing the monomer represented by the formula (3), preferably 0 to 30% by mass, more preferably 0 to 20% by mass, Preferably it is 0-15 mass%, Most preferably, it is 0-10 mass%.

<Production of lactone ring-containing polymer>
The method for producing the lactone ring-containing polymer is not particularly limited. For example, the polymer obtained after obtaining the polymer (a) having a hydroxyl group and an ester group in the molecular chain by a polymerization step. It is obtained by carrying out a lactone cyclization condensation step for introducing a lactone ring structure into the polymer by heat-treating (a).
In the polymerization step, for example, the following formula (4):

[Wherein, R ⁷ and R ⁸ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms]
The polymer which has a hydroxyl group and an ester group in a molecular chain is obtained by performing the polymerization reaction of the monomer component which mix | blended the monomer shown by.

  Examples of the monomer represented by the formula (4) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, and 2- (hydroxy Examples include methyl) n-butyl acrylate, t-butyl 2- (hydroxymethyl) acrylate, and the like. These monomers may be used alone or in combination of two or more. Among these monomers, 2- (hydroxymethyl) methyl acrylate and 2- (hydroxymethyl) ethyl acrylate are preferable, and since the effect of improving heat resistance is high, methyl 2- (hydroxymethyl) acrylate Is particularly preferred.

  The content ratio of the monomer represented by the above formula (4) in the monomer component to be subjected to the polymerization step is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and further preferably 10 to 60% by mass. %, Particularly preferably 10 to 50% by mass. When the content ratio of the monomer represented by the above formula (4) is less than 5% by mass, the heat resistance, solvent resistance and surface hardness of the obtained polymer may be lowered. On the contrary, when the content ratio of the monomer represented by the above formula (4) exceeds 90% by mass, gelation may occur in the polymerization step or the lactone cyclization condensation step, and the moldability of the obtained polymer may be increased. May decrease.

  You may mix | blend monomers other than the monomer shown by the said Formula (4) with the monomer component with which it uses for a superposition | polymerization process. Such a monomer is not particularly limited. For example, a (meth) acrylic acid ester, a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and the following formula (3):

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or —CO —O—R ⁶ group, Ac represents an acetyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms]
And the like. These monomers may be used alone or in combination of two or more.

  The (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer represented by the formula (4). For example, methyl acrylate, ethyl acrylate Acrylates such as n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid And methacrylic acid esters such as isobutyl, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. These (meth) acrylic acid esters may be used alone or in combination of two or more. Among these (meth) acrylic acid esters, methyl methacrylate is particularly preferable because the obtained polymer has excellent heat resistance and transparency.

  When using a (meth) acrylic acid ester other than the monomer represented by the above formula (4), the content ratio in the monomer component to be subjected to the polymerization step is sufficient to exert the effect of the present invention. Preferably it is 10-95 mass%, More preferably, it is 10-90 mass%, More preferably, it is 40-90 mass%, Most preferably, it is 50-90 mass%.

  The hydroxyl group-containing monomer is not particularly limited as long as it is a hydroxyl group-containing monomer other than the monomer represented by the above formula (4). For example, α-hydroxymethylstyrene, α-hydroxy And 2- (hydroxyalkyl) acrylic acid esters such as ethyl styrene and methyl 2- (hydroxyethyl) acrylate; 2- (hydroxyalkyl) acrylic acids such as 2- (hydroxyethyl) acrylic acid; and the like. These hydroxyl group-containing monomers may be used alone or in combination of two or more.

  In the case of using a hydroxyl group-containing monomer other than the monomer represented by the above formula (4), the content ratio in the monomer component to be subjected to the polymerization step is preferable in order to sufficiently exhibit the effects of the present invention. Is 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, and particularly preferably 0 to 10% by mass.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, α-substituted methacrylic acid and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more. Among these unsaturated carboxylic acids, acrylic acid and methacrylic acid are particularly preferable because the effects of the present invention are sufficiently exhibited.

  When using an unsaturated carboxylic acid, the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, in order to sufficiently exhibit the effects of the present invention. %, More preferably 0 to 15% by mass, particularly preferably 0 to 10% by mass.

  Examples of the monomer represented by the above formula (3) include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. These monomers may be used alone or in combination of two or more. Of these monomers, styrene and α-methylstyrene are particularly preferable because the effects of the present invention are sufficiently exhibited.

  When the monomer represented by the above formula (3) is used, the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass in order to sufficiently exhibit the effects of the present invention. More preferably, it is 0-20 mass%, More preferably, it is 0-15 mass%, Most preferably, it is 0-10 mass%.

  The form of the polymerization reaction for polymerizing the monomer components to obtain a polymer having a hydroxyl group and an ester group in the molecular chain is preferably a polymerization form using a solvent, and solution polymerization is particularly preferred.

  The polymerization temperature and the polymerization time vary depending on the type and ratio of the monomer used. For example, the polymerization temperature is preferably 0 to 150 ° C., the polymerization time is 0.5 to 20 hours, and more Preferably, the polymerization temperature is 80 to 140 ° C. and the polymerization time is 1 to 10 hours.

  In the case of a polymerization form using a solvent, the polymerization solvent is not particularly limited. For example, aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran And ether solvents such as These solvents may be used alone or in combination of two or more. Moreover, since the residual volatile matter of the lactone ring containing polymer finally obtained will increase when the boiling point of a solvent is too high, the solvent whose boiling point is 50-200 degreeC is preferable.

  During the polymerization reaction, a polymerization initiator may be added as necessary. The polymerization initiator is not particularly limited. For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl Organic peroxides such as carbonate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2 ′ -Azo compounds such as azobis (2,4-dimethylvaleronitrile); These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers and reaction conditions.

  When performing the polymerization, it is preferable to control the concentration of the polymer produced in the polymerization reaction mixture to be 50% by mass or less in order to suppress gelation of the reaction solution. Specifically, when the concentration of the polymer formed in the polymerization reaction mixture exceeds 50% by mass, it is preferable that the polymerization solvent is appropriately added to the polymerization reaction mixture and controlled to be 50% by mass or less. . The concentration of the polymer formed in the polymerization reaction mixture is more preferably 45% by mass or less, and further preferably 40% by mass or less. In addition, since productivity will fall when the density | concentration of the polymer produced | generated in the polymerization reaction mixture is too low, the density | concentration of the polymer produced | generated in the polymerization reaction mixture becomes like this. Preferably it is 10 mass% or more, More preferably, it is 20 mass%. That's it.

  The form in which the polymerization solvent is appropriately added to the polymerization reaction mixture is not particularly limited, and for example, the polymerization solvent may be added continuously or the polymerization solvent may be added intermittently. By controlling the concentration of the polymer formed in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, to increase the lactone ring content and improve the heat resistance. Even when the ratio between the hydroxyl group and the ester group in the molecular chain is increased, gelation can be sufficiently suppressed. The polymerization solvent to be added may be, for example, the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent. Moreover, the polymerization solvent to be added may be only one kind of single solvent or two or more kinds of mixed solvents.

  The polymerization reaction mixture obtained when the above polymerization step is completed usually contains a solvent in addition to the obtained polymer, but it is necessary to completely remove the solvent and take out the polymer in a solid state. Rather, it is preferably introduced into the subsequent lactone cyclization condensation step in a state containing a solvent. If necessary, after taking out in a solid state, a solvent suitable for the subsequent lactone cyclization condensation step may be added again.

  The polymer obtained in the polymerization step is a polymer (a) having a hydroxyl group and an ester group in the molecular chain, and the weight average molecular weight of the polymer (a) is preferably 1,000 to 2,000,000. 000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably 50,000 to 500,000. The polymer (a) obtained in the polymerization step is subjected to heat treatment in the subsequent lactone cyclization condensation step, whereby a lactone ring structure is introduced into the polymer to become a lactone ring-containing polymer.

  The reaction for introducing a lactone ring structure into the polymer (a) is a reaction in which a hydroxyl group and an ester group present in the molecular chain of the polymer (a) are cyclized and condensed to form a lactone ring structure by heating. Yes, by the cyclocondensation, alcohol is by-produced. By forming the lactone ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted. If the reaction rate of the cyclization condensation reaction leading to the lactone ring structure is insufficient, the heat resistance will not be improved sufficiently, or a condensation reaction will occur during the molding due to the heat treatment during molding, and the resulting alcohol will be contained in the molded product. May exist as bubbles or silver streaks.

  The lactone ring-containing polymer obtained in the lactone cyclization condensation step preferably has the following formula (1) as the ring structure formed by transesterification:

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
Having a lactone ring structure.

  The method for heat-treating the polymer (a) is not particularly limited, and a conventionally known method may be used. For example, you may heat-process the polymerization reaction mixture containing the solvent obtained by the superposition | polymerization process as it is. Or you may heat-process using a ring-closure catalyst as needed in presence of a solvent. Or heat processing can also be performed using the heating furnace and reaction apparatus provided with the vacuum apparatus or devolatilization apparatus for removing a volatile component, the extruder provided with the devolatilization apparatus, etc.

  In carrying out the cyclization condensation reaction, in addition to the polymer (a), another thermoplastic resin may coexist. When performing the cyclization condensation reaction, if necessary, an esterification catalyst or a transesterification catalyst such as p-toluenesulfonic acid generally used as a catalyst for the cyclization condensation reaction may be used. Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid, and methacrylic acid may be used as a catalyst. Furthermore, as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 61-254608 and 61-261303, basic compounds, organic carboxylates, carbonates, and the like may be used.

  Alternatively, an organophosphorus compound may be used as a catalyst for the cyclization condensation reaction. By using an organic phosphorus compound as a catalyst, the cyclization condensation reaction rate can be improved, and coloring of the resulting lactone ring-containing polymer can be greatly reduced. Furthermore, by using an organophosphorus compound as a catalyst, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.

  Examples of the organic phosphorus compound that can be used include alkyl (aryl) phosphonous acids such as methyl phosphonous acid, ethyl phosphonous acid, and phenyl phosphonous acid (however, these are tautomers such as alkyl (aryl)). And optionally mono- or diesters thereof; dialkyl (aryl) phosphinic acids such as dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid and their esters Alkyl (aryl) phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, trifluoromethylphosphonic acid, phenylphosphonic acid and their monoesters or diesters; methylphosphinic acid, ethylphosphinic acid, Alkyl (aryl) phosphinic acids such as phenylphosphinic acid and esters thereof; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, phosphorous Phosphorous acid monoester, diester or triester such as trimethyl phosphate, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate, isodecyl phosphate, phosphoric acid Lauryl, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate, diisostearyl phosphate, Diphenyl phosphate, trimethyl phosphate, triethyl phosphate Phosphoric monoesters, diesters or triesters such as triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, dimethylphosphine, diethylphosphine, Mono-, di- or tri-alkyl (aryl) phosphine such as diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, diethylchlorophosphine, diphenylchloro Alkyl (aryl) halogen phosphines such as phosphine; Mono-, di- or tri-alkyl (aryl) phosphines such as nylphosphine, dimethylphosphine oxide, diethylphosphine oxide, diphenylphosphine oxide, trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide; tetramethylphosphonium chloride, chloride And halogenated tetraalkyl (aryl) phosphoniums such as tetraethylphosphonium and tetraphenylphosphonium chloride. These organic phosphorus compounds may be used alone or in combination of two or more. Among these organophosphorus compounds, since the catalytic activity is high and the colorability is low, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester, and alkyl (aryl) phosphonic acid Preferably, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester is more preferable, and alkyl (aryl) phosphonous acid, phosphoric acid monoester or diester is particularly preferable.

  Although the usage-amount of the catalyst used in the case of a cyclization condensation reaction is not specifically limited, For example, Preferably it is 0.001-5 mass% with respect to a polymer (a), More preferably, it is 0.01. -2.5 mass%, More preferably, it is 0.01-1 mass%, Most preferably, it is 0.05-0.5 mass%. When the amount of the catalyst used is less than 0.001% by mass, the reaction rate of the cyclization condensation reaction may not be sufficiently improved. On the other hand, when the amount of the catalyst used exceeds 5% by mass, the obtained polymer may be colored or the polymer may be cross-linked to make melt molding difficult.

  The addition timing of the catalyst is not particularly limited. For example, the catalyst may be added at the beginning of the reaction, may be added during the reaction, or may be added in both of them.

  It is preferable to carry out the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction. In this case, a mode in which the devolatilization step is used throughout the cyclization condensation reaction and a mode in which the devolatilization step is not used over the entire cyclization condensation reaction but only in a part of the process. In the method using the devolatilization step in combination, the alcohol produced as a by-product in the cyclization condensation reaction is forcibly devolatilized and removed, so that the equilibrium of the reaction is advantageous for the production side.

  The devolatilization process means a process of removing volatile components such as solvents and residual monomers and alcohol by-produced by a cyclization condensation reaction leading to a lactone ring structure under reduced pressure heating conditions as necessary. To do. If this removal treatment is insufficient, residual volatile components in the obtained polymer increase, and coloring may occur due to deterioration during molding, and molding defects such as bubbles and silver streaks may occur.

  In the case of using a devolatilization step throughout the cyclization condensation reaction, the apparatus to be used is not particularly limited. It is preferable to use a devolatilizing device or vented extruder consisting of a tank, or a devolatilizing device and an extruder arranged in series, and a devolatilizing device or vented extruder consisting of a heat exchanger and a devolatilizing tank More preferably, it is used.

  The reaction treatment temperature in the case of using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. Conversely, when the reaction treatment temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  The reaction treatment pressure in the case of using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 798 to 66.5 hPa (600 to 50 mmHg). When the reaction treatment pressure exceeds 931 hPa (700 mmHg), volatile components including alcohol may easily remain. Conversely, if the reaction treatment pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.

  When using an extruder with a vent, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.

  The reaction treatment temperature when using an extruder with a vent is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. Conversely, when the reaction treatment temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  The reaction processing pressure when using an extruder with a vent is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 798 to 13.3 hPa (600 to 10 mmHg). When the reaction treatment pressure exceeds 931 hPa (700 mmHg), volatile components including alcohol may easily remain. Conversely, if the reaction treatment pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.

  In the case of a form in which a devolatilization step is used throughout the cyclization condensation reaction, the physical properties of the lactone ring-containing polymer obtained may deteriorate under severe heat treatment conditions, as will be described later. It is preferable to carry out by using an extruder with a vent etc. on the conditions as mild as possible.

  In the case where the devolatilization step is used in combination throughout the cyclization condensation reaction, the polymer (a) obtained in the polymerization step is preferably introduced into the cyclization condensation reaction device together with a solvent. Depending on the situation, it may be passed once again through a cyclocondensation reaction apparatus such as a vented extruder.

  You may perform the form used together only in a part of process, without using a devolatilization process over the whole process of cyclization condensation reaction. For example, the apparatus for producing the polymer (a) is further heated, and if necessary, a part of the devolatilization step is used together to advance the cyclization condensation reaction to some extent in advance, followed by the devolatilization step. Is a form in which a cyclization condensation reaction is simultaneously used to complete the reaction.

  In the form of using the devolatilization step throughout the cyclization condensation reaction described above, for example, when the polymer (a) is heat-treated at a high temperature of about 250 ° C. or higher using a twin-screw extruder. Depending on the thermal history, partial decomposition or the like may occur before the cyclization condensation reaction occurs, and the physical properties of the resulting lactone ring-containing polymer may deteriorate. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before the cyclization condensation reaction using the devolatilization process at the same time, the latter reaction conditions can be relaxed, and the physical properties of the resulting lactone ring-containing polymer deteriorated. Is preferable. As a particularly preferred form, for example, a form in which the devolatilization step is started after a lapse of time from the start of the cyclization condensation reaction, that is, a hydroxyl group and an ester present in the molecular chain of the polymer (a) obtained in the polymerization step A mode in which a group is preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent and then a cyclization condensation reaction using a devolatilization step simultaneously is performed. Specifically, for example, a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle reactor, and then a reactor equipped with a devolatilizer, for example, heat exchange Preferred is a mode in which the cyclization condensation reaction is completed with a devolatilizer comprising a vessel and a devolatilization tank, an extruder with a vent, or the like. In particular, in the case of this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.

  As described above, the hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. The method of carrying out the cyclization condensation reaction simultaneously using the volatilization process is a preferred form in obtaining the lactone ring-containing polymer in the present invention. With this form, a lactone ring-containing polymer having a higher glass transition temperature, a higher cyclization condensation reaction rate, and excellent heat resistance can be obtained. In this case, as a measure of the cyclization condensation reaction rate, for example, the mass reduction rate within the range of 150 to 300 ° C. in the dynamic TG measurement shown in the examples is preferably 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.

  The reactor that can be employed in the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization process at the same time is not particularly limited. For example, an autoclave, a kettle reactor, a heat exchanger And a devolatilizer comprising a devolatilization tank, and a vented extruder suitable for a cyclization condensation reaction using a devolatilization step at the same time can also be used. Of these reactors, an autoclave and a kettle reactor are particularly preferable. However, even when a reactor such as an extruder with a vent is used, the autoclave or kettle can be adjusted by adjusting the temperature conditions, barrel conditions, screw shape, screw operating conditions, etc. It is possible to carry out the cyclization condensation reaction in the same state as the reaction state in the type reactor.

  In the case of the cyclization condensation reaction carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time, for example, a mixture containing the polymer (a) and the solvent obtained in the polymerization step is used as (i) a catalyst. And (ii) a method of performing a heat reaction without a catalyst, a method of performing the above (i) or (ii) under pressure, and the like.

  The “mixture containing the polymer (a) and the solvent” introduced into the cyclization condensation reaction in the lactone cyclization condensation step refers to the polymerization reaction mixture obtained in the polymerization step itself or once the solvent is removed. It means a mixture obtained by re-adding a solvent suitable for the cyclization condensation reaction later.

  The solvent that can be re-added in the cyclization condensation reaction that is carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time is not particularly limited. For example, aromatic carbonization such as toluene, xylene, ethylbenzene, etc. Hydrogens; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, dimethyl sulfoxide, tetrahydrofuran; and the like. These solvents may be used alone or in combination of two or more. It is preferable to use the same type of solvent as that used in the polymerization step.

  Examples of the catalyst to be added in the method (i) include commonly used esterification catalysts such as p-toluenesulfonic acid or transesterification catalysts, basic compounds, organic carboxylates, and carbonates. In the invention, it is preferable to use the aforementioned organophosphorus compound. The addition timing of the catalyst is not particularly limited. For example, the catalyst may be added at the beginning of the reaction, may be added during the reaction, or may be added in both of them. The addition amount of the catalyst is not particularly limited, but for example, is preferably 0.001 to 5% by mass, more preferably 0.01 to 2.5% by mass with respect to the mass of the polymer (a). More preferably, it is 0.01-1 mass%, Most preferably, it is 0.05-0.5 mass%. Although the heating temperature and heating time of method (i) are not particularly limited, for example, the heating temperature is preferably room temperature to 300 ° C., more preferably 50 to 250 ° C., and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is less than room temperature or the heating time is less than 1 hour, the cyclization condensation reaction rate may be lowered. Conversely, when the heating temperature exceeds 300 ° C. or the heating time exceeds 20 hours, the resin may be colored or decomposed.

  In the method (ii), for example, the polymerization reaction mixture obtained in the polymerization step may be heated as it is using a pressure-resistant kettle reactor or the like. Although the heating temperature and heating time of method (ii) are not particularly limited, for example, the heating temperature is preferably 100 to 350 ° C., more preferably 150 to 300 ° C., and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. When the heating temperature is less than 100 ° C. or the heating time is less than 1 hour, the cyclization condensation reaction rate may be lowered. Conversely, when the heating temperature exceeds 350 ° C. or the heating time exceeds 20 hours, the resin may be colored or decomposed.

  In any method, there is no problem even under pressure depending on conditions.

  In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization step at the same time, there is no problem even if part of the solvent volatilizes spontaneously during the reaction.

  The mass reduction rate within the range of 150 to 300 ° C. in the dynamic TG measurement at the end of the cyclization condensation reaction performed in advance before the cyclization condensation reaction simultaneously used in combination with the devolatilization step, ie, immediately before the start of the devolatilization step is Preferably it is 2% or less, More preferably, it is 1.5% or less, More preferably, it is 1% or less. When the mass reduction rate exceeds 2%, the cyclization condensation reaction rate does not rise to a sufficiently high level even if the cyclization condensation reaction is performed simultaneously with the devolatilization step, and the physical properties of the resulting lactone ring-containing polymer. May deteriorate. In addition, when performing said cyclization condensation reaction, in addition to a polymer (a), you may coexist other thermoplastic resins.

  The hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. In the case of the form in which the cyclized condensation reaction is performed, the polymer obtained by the cyclized condensation reaction performed in advance (the polymer in which at least a part of the hydroxyl group and the ester group present in the molecular chain is subjected to the cyclized condensation reaction) and the solvent May be introduced into the cyclization condensation reaction using the devolatilization step at the same time, and if necessary, the polymer (at least a part of the hydroxyl group and ester group present in the molecular chain is cyclized and condensed). You may introduce | transduce into the cyclocondensation reaction which used the devolatilization process together, after passing through other processes, such as adding a solvent again after isolating the polymer which reacted.

  The devolatilization step is not limited to being completed at the same time as the cyclization condensation reaction, and may be completed after a lapse of time from the completion of the cyclization condensation reaction.

<Physical properties of lactone ring-containing polymer>
The lactone ring-containing polymer preferably has a weight average molecular weight of 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably. 50,000 to 500,000.

  The lactone ring-containing polymer preferably has a mass reduction rate in the range of 150 to 300 ° C. in dynamic TG measurement of 1% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

  Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, the disadvantage that bubbles and silver streaks enter the molded product can be avoided. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to the high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has sufficiently high heat resistance.

  The lactone ring-containing polymer has a coloring degree (YI) of preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1 or less when a chloroform solution having a concentration of 15% by mass is used. . When the coloring degree (YI) exceeds 6, transparency may be impaired due to coloring, and may not be used for the intended purpose.

  The lactone ring-containing polymer has a 5% mass reduction temperature in thermal mass spectrometry (TG) of preferably 330 ° C. or higher, more preferably 350 ° C. or higher, and still more preferably 360 ° C. or higher. The 5% mass reduction temperature in thermal mass spectrometry (TG) is an index of thermal stability, and if it is less than 330 ° C., sufficient thermal stability may not be exhibited.

  The lactone ring-containing polymer has a glass transition temperature (Tg) of preferably 115 ° C. or higher, more preferably 125 ° C. or higher, and further preferably 130 ° C. or higher. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is preferably 170 ° C, more preferably 160 ° C, and further preferably 150 ° C. In addition, the glass transition temperature (Tg) of a lactone ring containing polymer is the value calculated | required by the midpoint method based on ASTM-D-3418.

  The total amount of residual volatile components contained in the lactone ring-containing polymer is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. When the total amount of residual volatile components exceeds 1,500 ppm, it may be colored due to alteration during molding, foaming, or molding defects such as silver streak.

  In applications where transparency is required, the lactone ring-containing polymer preferably has a total light transmittance of 85% or more, more preferably measured by a method based on ASTM-D-1003 for a molded product obtained by injection molding. Is 88% or more, more preferably 90% or more. The total light transmittance is an index of transparency, and if it is less than 85%, the transparency may be lowered and may not be used for applications requiring transparency.

<Amount of lactone ring-containing polymer>
The blending amount of the lactone ring-containing polymer in the thermoplastic resin composition of the present invention may be appropriately adjusted according to the use of the composition, and is not particularly limited, but is preferably 50 to 100 mass, for example. %, More preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass. When the blending amount of the lactone ring-containing polymer is less than 50% by mass, desired properties such as mechanical strength and molding processability may not be exhibited in addition to excellent transparency and heat resistance.

<Other ingredients>
The thermoplastic resin composition of the present invention may contain a polymer other than the lactone ring-containing polymer (hereinafter sometimes referred to as “other polymer”) as other components. Examples of other polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); polyvinyl chloride, polyvinylidene chloride, chlorinated vinyl resins, and the like. Acrylic polymers such as polymethyl methacrylate; Styrenes such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer Polymers: Polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polylactic acid, polybutylene succinate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetals; Polyphenylene oxide; Polyphenylene sulfide; Polyetheretherketone; Polysulfone; Polyethersulfone; Polyoxybenzylene; Polyamideimide; Rubber polymer such as ABS resin and ASA resin blended with polybutadiene rubber and acrylic rubber; Etc.

  The blending amount of the other polymer in the thermoplastic resin composition of the present invention may be appropriately adjusted according to the use of the composition, and is not particularly limited. For example, it is preferably 0 to 50% by mass. More preferably, it is 0-40 mass%, More preferably, it is 0-30 mass%, Most preferably, it is 0-20 mass%.

  The thermoplastic resin composition of the present invention may contain various additives. Examples of additives include antioxidants such as hindered phenols, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; phenyls UV absorbers such as salicylate, (2,2′-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide, etc. Flame retardants; Antistatic agents such as anionic, cationic and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers; Resin modifiers; Organic fillers and inorganic fillers Agents, plasticizers, lubricants, and the like.

  The blending amount of each additive in the thermoplastic resin composition of the present invention may be appropriately adjusted according to the use of the composition, and is not particularly limited, but is preferably 0 to 5% by mass, for example. More preferably, it is 0-2 mass%, More preferably, it is 0-0.5 mass%.

≪Deactivator≫
For example, when a lactone ring-containing polymer is used as the methacrylic resin, as described above, in the lactone cyclization condensation step, the hydroxyl group and ester group present in the molecular chain of the polymer (a) are cyclized and condensed. Thus, a lactone ring structure is formed in the molecular chain of the polymer (in the main skeleton of the polymer) by causing a dealcoholization reaction which is a kind of transesterification. Generally, when the catalyst used for transesterification is an acidic substance, the catalyst remaining after the reaction can be deactivated by neutralization with a basic substance. Therefore, the quenching agent used in this case is not particularly limited as long as it is a basic substance and does not generate a substance that inhibits the resin composition during heat processing. And metal compounds such as metal complexes and metal oxides. Here, the metal constituting the metal compound is not particularly limited as long as it does not inhibit the physical properties of the resin composition and does not cause environmental pollution at the time of disposal. For example, lithium, sodium, potassium And alkaline metals such as magnesium, calcium, strontium and barium; amphoteric metals such as zinc, aluminum, tin and lead; zirconium; and the like. Of these metals, typical metal elements are preferred because of less coloring of the resin, alkaline earth metals and amphoteric metals are particularly preferred, and calcium, magnesium and zinc are most preferred. The metal salt is preferably an organic acid metal salt, particularly preferably an organic carboxylic acid, an organic phosphorus compound, or an acidic organic sulfur compound because of its dispersibility in a resin and solubility in a solvent. The organic carboxylic acid constituting the metal salt of the organic carboxylic acid is not particularly limited. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, Examples include adipic acid. Examples of the organophosphorus compound constituting the metal salt of the organophosphorus compound include alkyl (aryl) phosphonous acids such as methylphosphonous acid, ethylphosphonous acid, and phenylphosphonous acid (however, these are tautomers) Alkyl (aryl) phosphinic acid) and their monoesters or diesters; dialkyl (aryl) phosphinic acids such as dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid And alkyl (aryl) phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, trifluoromethylphosphonic acid, phenylphosphonic acid and their monoesters or diesters; methylphosphinic acid, Alkyl (aryl) phosphinic acids such as sphinic acid and phenylphosphinic acid and esters thereof; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, diphenyl phosphite Phosphorous acid monoester, diester or triester such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate, isodecyl phosphate Lauryl phosphate, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate, diphosphate Isostearyl, diphenyl phosphate, trimethyl phosphate, lithium Phosphoric acid monoesters, diesters or triesters such as triethyl acid phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, dimethylphosphine, Mono-, di- or tri-alkyl (aryl) phosphine such as diethylphosphine, diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, diethylchlorophosphine Alkyl (aryl) halogen phosphines such as diphenylchlorophosphine; methylphosphine oxide, ethylphosphine oxide Phosphine oxide, phenyl phosphine oxide, dimethyl phosphine oxide, diethyl phosphine oxide, diphenyl phosphine oxide, trimethyl phosphine oxide, triethyl phosphine oxide, triphenyl phosphine oxide, mono-, di- or tri-alkyl (aryl) phosphine oxides; And halogenated tetraalkyl (aryl) phosphonium such as methylphosphonium chloride, tetraethylphosphonium chloride, tetraphenylphosphonium chloride; and the like. Examples of the acidic organic sulfur compound constituting the metal salt of the acidic organic sulfur compound include p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, and dodecylbenzenesulfonic acid. The organic component in the metal complex is not particularly limited, and examples thereof include acetylacetone. On the other hand, when the catalyst used for transesterification is a basic substance, for example, an acidic substance such as an organic phosphorus compound may be used to deactivate the catalyst remaining after the reaction. In any case, these deactivators may be used alone or in combination of two or more. The quenching agent may be added in any form such as a solid, powder, granule, dispersion, suspension, and aqueous solution, and is not particularly limited.

  The addition amount of the deactivator may be appropriately adjusted according to the amount of the catalyst used for transesterification, and is not particularly limited, but is preferably 10 based on the mass of the methacrylic resin, for example. It is -10,000 ppm, More preferably, it is 50-5,000 ppm, More preferably, it is 100-3,000 ppm. When the addition amount of the deactivator is less than 10 ppm, the action of the deactivator becomes insufficient, and bubbles and silver streaks may enter the molded product. On the other hand, if the addition amount of the deactivator exceeds 10,000 ppm, the action of the deactivator is saturated and the deactivator is used more than necessary, which may increase the production cost.

  The timing of adding the deactivator is, in particular, as long as it is after the ring structure is formed by the cyclization condensation reaction and before the obtained resin composition is heat-processed in producing the methacrylic resin. It is not limited. For example, a deactivator is added at a predetermined stage during the production of the methacrylic resin, or after the methacrylic resin is produced, the methacrylic resin, the deactivator and other components are simultaneously heated and melted and kneaded. A method of heating and melting a methacrylic resin and other components, adding a quencher thereto, and kneading; a melt of a methacrylic resin being heated and melting there, and other components And the like. In this case, it is preferable to provide a devolatilization step after kneading the thermoplastic resin composition. This is because the obtained thermoplastic resin composition hardly causes a foaming phenomenon during heat processing. Examples of the devolatilization step include the devolatilization step described above as the devolatilization step performed in the production of the lactone ring-containing polymer.

≪Characteristics of thermoplastic resin composition≫
Even if the catalyst used for the transesterification remains, the thermoplastic resin composition of the present invention is a very small amount and most of the catalyst is deactivated, so that the foaming phenomenon does not occur during heat processing. Actually, the foaming amount generated when this thermoplastic resin composition is heated at 260 ° C. for 20 minutes is preferably 20 pieces / g or less, more preferably 15 pieces / g or less, further preferably 10 pieces / g or less, particularly Preferably it is 5 pieces / g or less.

  In addition, the amount of foaming shall be measured using the melt indexer prescribed | regulated to JIS-K7210. More specifically, the amount of foaming is determined by filling the dried thermoplastic resin composition into a melt indexer cylinder, holding it at 260 ° C. for 20 minutes, and then extruding it into a strand. The number of bubbles generated between the bottom and the lower marked line is counted and expressed as the number per 1 g of the thermoplastic resin composition.

≪Use and molding of thermoplastic resin composition≫
The thermoplastic resin composition of the present invention is not only excellent in transparency and heat resistance, but also has desired properties such as mechanical strength and molding processability. Industrial parts, automotive parts such as automobiles, building materials / shopping, coating materials, protective films for depainting, lighting equipment, large water tanks, optical lenses, optical prisms, optical films, optical fibers, optical disks, other mirrors, stationery However, among these applications, optical lenses, optical prisms, optical films, optical fibers, optical disks, and the like are particularly preferable.

  The thermoplastic resin composition of the present invention can be molded into various shapes depending on the application. Examples of shapes that can be molded include films, sheets, plates, disks, blocks, balls, lenses, rods, strands, cords, fibers, and the like. The molding method may be appropriately selected from conventionally known molding methods according to the shape, and is not particularly limited.

  Hereinafter, a method for producing an optical film from the thermoplastic resin composition of the present invention will be described in detail by taking an optical film which is a particularly preferable application as an example.

<Manufacture of optical film>
In order to produce an optical film from the thermoplastic resin composition of the present invention, for example, a film raw material is pre-blended with a conventionally known mixer such as an omni mixer, and then the resulting mixture is extruded and kneaded. In this case, the mixer used for extrusion kneading is not particularly limited. For example, a conventionally known mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader can be used. .

  Examples of the film forming method include conventionally known film forming methods such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Of these film forming methods, the solution casting method (solution casting method) and the melt extrusion method are particularly suitable.

  Examples of the solvent used in the solution casting method (solution casting method) include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as cyclohexane and decalin; esters such as ethyl acetate and butyl acetate Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, methyl cellosolve, ethyl cellosolve and butyl cellosolve; ethers such as tetrahydrofuran and dioxane; dichloromethane, Halogenated hydrocarbons such as chloroform and carbon tetrachloride; dimethylformamide; dimethyl sulfoxide; These solvents may be used alone or in combination of two or more.

  Examples of the apparatus for performing the solution casting method (solution casting method) include a drum casting machine, a band casting machine, and a spin coater.

  Examples of the melt extrusion method include a T-die method and an inflation method, and the molding temperature at that time may be appropriately adjusted according to the glass transition temperature of the film raw material, and is not particularly limited. For example, it is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.

  When forming a film by the T-die method, a roll-shaped film can be obtained by attaching a T-die to the tip of a known single-screw extruder or twin-screw extruder and winding the film extruded into a film. it can. At this time, it is possible to perform uniaxial stretching by appropriately adjusting the temperature of the winding roll and adding stretching in the extrusion direction. Further, simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching the film in a direction perpendicular to the extrusion direction.

  The film made of the thermoplastic resin composition of the present invention may be either an unstretched film or a stretched film. In the case of a stretched film, either a uniaxially stretched film or a biaxially stretched film may be used. In the case of a biaxially stretched film, either a simultaneous biaxially stretched film or a sequential biaxially stretched film may be used. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved. The thermoplastic resin composition of the present invention can suppress an increase in retardation even when stretched by mixing with other thermoplastic resins, and can obtain a film having optical isotropy. .

  The stretching temperature is preferably in the vicinity of the glass transition temperature of the thermoplastic resin composition that is the film raw material, and specifically, preferably (glass transition temperature-30 ° C) to (glass transition temperature + 100 ° C), more preferably. Is within the range of (glass transition temperature−20 ° C.) to (glass transition temperature + 80 ° C.). If the stretching temperature is less than (glass transition temperature-30 ° C.), a sufficient stretching ratio may not be obtained. On the other hand, when the stretching temperature exceeds (glass transition temperature + 100 ° C.), the thermoplastic resin composition may flow, and stable stretching may not be performed.

  The draw ratio defined by the area ratio is preferably in the range of 1.1 to 25 times, more preferably 1.3 to 10 times. If the draw ratio is less than 1.1 times, the toughness accompanying the drawing may not be improved. On the other hand, when the draw ratio exceeds 25 times, the effect of increasing the draw ratio may not be recognized.

  The stretching speed is unidirectional, preferably 10 to 20,000% / min, more preferably 100 to 10,000% / min. When the stretching speed is less than 10% / min, it takes time to obtain a sufficient stretching ratio, and the production cost may increase. On the contrary, when the stretching speed exceeds 20,000% / min, the stretched film may be broken.

  In addition, the film comprising the thermoplastic resin composition of the present invention can be subjected to heat treatment (annealing) after the stretching treatment in order to stabilize the optical isotropy and mechanical properties thereof. The conditions for the heat treatment may be appropriately selected similarly to the conditions for the heat treatment performed on a conventionally known stretched film, and are not particularly limited.

  The film made of the thermoplastic resin composition of the present invention preferably has a thickness of 5 to 200 μm, more preferably 10 to 100 μm. When the thickness is less than 5 μm, not only the strength of the film is lowered, but also when the durability test is performed by sticking to other parts, the crimp may be increased. On the other hand, when the thickness exceeds 200 μm, not only the transparency of the film is lowered, but also the moisture permeability is reduced, and when a water-based adhesive is used when sticking to other parts, water that is the solvent is used. The drying speed may be slow.

  The film composed of the thermoplastic resin composition of the present invention has a surface wetting tension of preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more. When the surface wetting tension is at least 40 mN / m or more, the adhesive strength between the film made of the thermoplastic resin composition of the present invention and other components is further improved. In order to adjust the surface wetting tension, for example, corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other conventionally known surface treatments can be performed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

  First, a method for evaluating a methacrylic resin having a ring structure in the main chain (hereinafter sometimes referred to as “polymer”) will be described.

<Polymerization reaction rate, polymer composition analysis>
For the reaction rate during the polymerization reaction and the content of the specific monomer unit in the polymer, the amount of unreacted monomer in the obtained polymerization reaction mixture was measured using a gas chromatograph (GC17A, manufactured by Shimadzu Corporation). It was obtained by measuring using.

<Dynamic TG>
The polymer (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into excess hexane or methanol for reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (1.33 hPa), 80 ° C. Volatile components and the like were removed by conducting the reaction for 3 hours or more, and the obtained white solid resin was analyzed by the following method (dynamic TG method).
Measuring apparatus: differential type differential thermal balance (Thermo Plus 2 TG-8120 Dynamic TG, manufactured by Rigaku Corporation)
Measurement conditions: Sample amount 5-10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 200 mL / min
Method: Step-like isothermal control method (controlled to a mass reduction rate value of 0.005% / s or less in the range from 60 ° C to 500 ° C)

<Ratio of ring structure content>
First, based on the amount of mass loss that occurs when all hydroxyl groups are dealcoholated as methanol from the obtained polymer composition, the polymer before decomposition starts from 150 ° C. before the mass loss starts in dynamic TG measurement. The dealcoholization reaction rate was determined from the mass reduction due to the dealcoholization reaction up to 300 ° C.

That is, in the dynamic TG measurement of the polymer having a ring structure in the main chain, the mass reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual measurement value is defined as the actual mass reduction rate (X). On the other hand, from the composition of the polymer, the mass reduction rate when assuming that all the hydroxyl groups contained in the polymer composition become alcohol and de-alcoholate because they are involved in the formation of the ring structure (that is, 100 in the composition) % Mass reduction rate calculated assuming that the dealcoholization reaction occurred) is defined as the theoretical mass reduction rate (Y). The theoretical mass reduction rate (Y) is more specifically the molar ratio of raw material monomers having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material single amount in the polymer composition. It can be calculated from the body content. These values are calculated for the dealcoholization:
1- (actual mass reduction rate (X) / theoretical mass reduction rate (Y))
Substituting for, the value is obtained and expressed in percentage (%), the dealcoholization reaction rate is obtained.

  As an example, the content rate of the lactone ring structure in the pellet obtained in Production Example 1 described later is calculated. When the theoretical mass reduction rate (Y) of this polymer was determined, the molecular weight of methanol was 32, the molecular weight of methyl 2- (hydroxymethyl) acrylate was 116, and methyl 2- (hydroxymethyl) acrylate. Since the content (mass ratio) in the polymer is 20.0 mass% in terms of composition, (32/116) × 20.0% ≈5.52 mass%. On the other hand, the actual mass reduction rate (X) by dynamic TG measurement was 0.17% by mass. When these values are applied to the above-described dealcoholization calculation formula, 1− (0.17 / 5.52) ≈0.969, and the dealcoholization reaction rate is 96.9%. And the content rate (mass) in the said copolymer composition of the raw material monomer which has a structure (hydroxy group) in connection with lactone cyclization as what was predetermined | prescribed lactone cyclization was performed by this dealcoholization reaction rate The ratio of the lactone ring structure in the copolymer can be calculated by multiplying the ratio) by the dealcoholization reaction rate and converting it to the content (mass ratio) of the lactone ring structure. In the case of Production Example 1, 2- (hydroxymethyl) methyl 2- (hydroxymethyl) acrylate having a content of 20.0% by mass in the copolymer, a calculated dealcoholization reaction rate of 96.9%, and a molecular weight of 116 Since the formula amount of the lactone ring structure produced when methyl) methyl acrylate is condensed with methyl methacrylate is 170, the content of the lactone ring structure in the copolymer is 28.4 (20.0 × 0.969 × 170/116) mass%.

<Weight average molecular weight>
The weight average molecular weight of the polymer was determined in terms of polystyrene using a gel permeation chromatograph (GPC system, manufactured by Tosoh Corporation).

<Melt flow rate>
The melt flow rate was measured at a test temperature of 240 ° C. and a load of 10 kg in accordance with JIS-K6874.

<Thermal analysis of polymer>
The thermal analysis of the polymer was performed using a differential scanning calorimeter (DSC-8230, manufactured by Rigaku Corporation) under the conditions of about 10 mg of sample, a heating rate of 10 ° C./min, and a nitrogen flow of 50 mL / min. In addition, the glass transition temperature (Tg) was calculated | required by the midpoint method based on ASTM-D-3418.

<Measurement of foaming amount>
For the strand-shaped molded product, the amount of foaming was measured. The dried thermoplastic resin composition is loaded into a cylinder of a melt indexer specified in JIS-K7210, held at 260 ° C. for 20 minutes, extruded into a strand shape, and an upper marked line of the obtained strand. The number of bubbles generated between the lower marked line was counted and expressed as the number per 1 g of the thermoplastic resin composition.

<Content of metal compound>
The content of the metal compound is a 2.5 wt% solution obtained by dissolving the thermoplastic resin composition in methyl ethyl ketone as a sample, using an ICP emission spectroscopic analyzer (CIROS CCD, manufactured by Rigaku Corporation) in terms of metal atoms, That is, it measured as content of the metal atom contained in the added metal compound.

<Production Example 1>
First, in a reaction vessel having a capacity of 30 L equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen gas introduction pipe, 8 kg of methyl methacrylate, 2 kg of methyl 2- (hydroxymethyl) acrylate, 10 kg of methyl isobutyl ketone, n-dodecyl mercaptan 5 g was charged.

  While introducing nitrogen gas into the reaction vessel, the temperature was raised to 105 ° C. and refluxed. As a polymerization initiator, 5 g of t-butyl peroxyisopropyl carbonate (Kaya-Carbon BIC-75, manufactured by Kayaku Akzo Co., Ltd.) was added. At the same time as the addition, a solution prepared by dissolving 10 g of t-butylperoxyisopropyl carbonate (Kaya-Carbon BIC-75, manufactured by Kayaku Akzo Co., Ltd.) in 230 g of methyl isobutyl ketone was added dropwise over a period of 2 hours. Solution polymerization was performed at 120 ° C., and further aging was performed for 4 hours.

  To the obtained polymer solution, 30 g of stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added and cyclized at about 90 to 120 ° C. for 5 hours under reflux. A condensation reaction was performed. Next, the obtained polymer solution was a vent type screw twin screw extruder having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4. (Φ = 29.75 mm, L / D = 30) is introduced at a treatment rate of 2.0 kg / h in terms of resin amount, and is further subjected to cyclization condensation reaction and devolatilization in this extruder and extruded. As a result, a transparent pellet (A) of the lactone ring-containing polymer was obtained.

  The obtained lactone ring-containing polymer was measured for dynamic TG, and a mass loss of 0.17% by mass was detected. The lactone ring-containing polymer had a weight average molecular weight of 133,000, a melt flow rate of 6.5 g / 10 min, and a glass transition temperature of 131 ° C.

<Production Example 2>
First, 136 kg of methyl methacrylate, 34 kg of methyl 2- (hydroxymethyl) acrylate, and 166 kg of toluene were charged into a 1 m ³ reaction kettle equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen gas introduction pipe.

  When nitrogen gas was introduced into this reaction kettle and the temperature was raised to 105 ° C. and refluxed, 187 g of t-amyl peroxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Corp.) was added as a polymerization initiator. At the same time, a solution prepared by dissolving 374 g of t-amylperoxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Co., Ltd.) in 3.6 kg of toluene was added dropwise over 2 hours, and the solution was refluxed at about 105 to 110 ° C. Polymerization was performed, and further aging was performed for 4 hours.

  To the obtained polymer solution, 170 g of stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added and cyclized at about 90 to 110 ° C. for 5 hours under reflux. A condensation reaction was performed. Subsequently, the obtained polymer solution was a vent type screw twin screw extruder having a barrel temperature of 250 ° C., a rotation speed of 150 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4. (Φ = 42 mm, L / D = 42), introduced at a processing rate of 13 kg / h in terms of resin amount, and further subjected to cyclization condensation reaction and devolatilization in this extruder, and extruded to give lactone A transparent pellet (B) of a ring-containing polymer was obtained.

  When the obtained lactone ring-containing polymer was measured for dynamic TG, a mass loss of 0.15% by mass was detected. The lactone ring-containing polymer had a weight average molecular weight of 147,000, a melt flow rate of 11.0 g / 10 min, and a glass transition temperature of 130 ° C.

<Example 1>
Zinc oxide (Nanofine, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the pellet (A) obtained in Production Example 1 at 270 ° C. using a twin screw extruder (φ = 20 mm, L / D = 25). A transparent pellet (A1) of the thermoplastic resin composition was obtained by adding 500 ppm to the amount of the polymer, kneading, and extruding.

  The obtained pellet (A1) was supplied to a melt indexer set at 260 ° C., held for 20 minutes, and then extruded into a strand shape under a load of 10 kg. The foaming amount was 0 / g. The content of the metal compound was 377 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.

<Example 2>
In Example 1, a thermoplastic resin composition was prepared in the same manner as in Example 1 except that 1,000 ppm of calcium stearate (Die Wax C, manufactured by Dainichi Chemical Industry Co., Ltd.) was added instead of 500 ppm of zinc oxide. Pellet (A2) was obtained.

  When the obtained pellet (A2) was extruded in the same manner as in Example 1, the foaming amount was 1.3 pieces / g. Moreover, content of the metal compound was 58 ppm in conversion of the metal atom on the basis of the mass of a polymer. The results are shown in Table 1.

<Example 3>
In Example 1, in place of zinc oxide 500 ppm, except that 2,000 ppm of zinc 2-ethylhexylate (Nikka Octix zinc 18%, manufactured by Nippon Chemical Industry Co., Ltd.) was added, A pellet (A3) of the thermoplastic resin composition was obtained.

  When the obtained pellet (A3) was extruded in the same manner as in Example 1, the foaming amount was 2 / g. Moreover, content of the metal compound was 320 ppm in conversion of the metal atom on the basis of the mass of a polymer. The results are shown in Table 1.

<Comparative Example 1>
A pellet (A0) of a thermoplastic resin composition was obtained in the same manner as in Example 1 except that zinc oxide was not added.

  When the obtained pellet (A0) was extruded in the same manner as in Example 1, foaming occurred and a clean strand-shaped molded product could not be obtained. The foaming amount was 33.3 pieces / g. The content of the metal compound was 0 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.

<Example 4>
Using a twin screw extruder (φ = 30 mm, L / D = 30) having a vent port, zinc acetate was added to the pellet (A) obtained in Production Example 1 while performing suction from the vent port at 260 ° C. By adding 1,200 ppm with respect to the polymer amount, kneading and extruding, a transparent pellet (A4) of the thermoplastic resin composition was obtained.

  The obtained pellet (A4) was supplied to an injection molding machine (HM7 type, manufactured by Nissei Plastic Industry Co., Ltd.) set at a barrel temperature of 260 ° C., held for 20 minutes, then shot by injection, and had a diameter of 40 mm and thickness. A 3 mm disk-shaped molded product was obtained. The obtained molded product was transparent, and defects such as bubbles and silver streaks were not observed. Further, the content of the metal compound was 435 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.

<Comparative example 2>
In Example 4, except that zinc acetate was not added, in the same manner as in Example 4, using a twin screw extruder having a vent port (φ = 30 mm, L / D = 30) at 260 ° C. The pellets (A) obtained in Production Example 1 were kneaded and extruded while suctioning from the vent port to obtain thermoplastic resin composition pellets (A0).

  The obtained pellet (A0) was injection-molded in the same manner as in Example 4. As a result, foaming was severe and a clean disk-shaped molded product could not be obtained. The results are shown in Table 1.

<Example 5>
By using an extruder equipped with a T die having a lip opening of 0.4 mm and a width of 150 mm, the pellet (A4) obtained in Example 4 was extruded at 260 ° C. and taken up with a roll adjusted to 110 ° C. A transparent film having a thickness of 100 μm and substantially free from defects could be obtained. Moreover, content of the metal compound was 408 ppm in conversion of the metal atom on the basis of the mass of the polymer. The results are shown in Table 1.

<Comparative Example 3>
Using an extruder equipped with a T die having a lip opening of 0.4 mm and a width of 150 mm, the pellet (A0) obtained in Comparative Example 2 was extruded at 260 ° C. and taken up with a roll adjusted to 110 ° C., Streaks due to foaming occurred and a clean film could not be obtained.

<Example 6>
Pellets (B) and acrylonitrile-obtained in Production Example 2 while sucking from the vent port at 280 ° C. using a dalmage single-screw extruder having a vent port (φ = 50 mm, L / D = 32) A styrene (AS) resin (Stylac AS783, manufactured by Asahi Kasei Chemicals Corporation) is kneaded and extruded together with 400 ppm of zinc acetate at a mass ratio of 90/10 to obtain transparent pellets (B1) of the thermoplastic resin composition. )

  The obtained pellet (B1) was supplied to an injection molding machine (HM7 type, manufactured by Nissei Plastic Industry Co., Ltd.) set at a barrel temperature of 260 ° C., held for 20 minutes, then shot by injection, and had a diameter of 40 mm and a thickness. A 3 mm disk-shaped molded product was obtained. The obtained molded product was transparent, and defects such as bubbles and silver streaks were not observed. The content of the metal compound was 137 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.

<Example 7>
In Example 6, a pellet (B2) of a thermoplastic resin composition was obtained in the same manner as in Example 6 except that 550 ppm of calcium acetyl acetate was used instead of 400 ppm of zinc acetate.

  When the obtained pellet (B2) was injection-molded in the same manner as in Example 6, the obtained molded product was transparent, and defects such as bubbles and silver streaks were not observed. Moreover, content of the metal compound was 88 ppm in conversion of the metal atom on the basis of the mass of a polymer. The results are shown in Table 1.

<Comparative example 4>
In Example 6, except that zinc acetate was not added, in the same manner as in Example 6, using a dalmage single-screw extruder having a vent port (φ = 50 mm, L / D = 32), 280 ° C. Then, while sucking from the vent port, the pellet (B) obtained in Production Example 2 and the acrylonitrile-styrene (AS) resin (Stylac AS783, manufactured by Asahi Kasei Chemicals Corporation) at a mass ratio of 90/10 The pellets (B0) of the thermoplastic resin composition were obtained by kneading and extruding.

  The obtained pellet (B0) was injection-molded in the same manner as in Example 6. As a result, foaming was intense and a clean disk-shaped molded product could not be obtained. The results are shown in Table 1.

<Example 8>
First, 136 kg of methyl methacrylate, 34 kg of methyl 2- (hydroxymethyl) acrylate, and 166 kg of toluene were charged into a 1 m ³ reaction kettle equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen gas introduction pipe.

  When nitrogen gas was introduced into this reaction kettle and the temperature was raised to 105 ° C. and refluxed, 187 g of t-amyl peroxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Corp.) was added as a polymerization initiator. At the same time, a solution prepared by dissolving 374 g of t-amylperoxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Co., Ltd.) in 3.6 kg of toluene was added dropwise over 2 hours, and the solution was refluxed at about 105 to 110 ° C. Polymerization was performed, and further aging was performed for 4 hours.

  To the obtained polymer solution, 170 g of stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added and cyclized at about 90 to 110 ° C. for 5 hours under reflux. A condensation reaction was performed. Subsequently, the obtained polymer solution was a vent type screw twin screw extruder having a barrel temperature of 250 ° C., a rotation speed of 150 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4. (Φ = 42 mm, L / D = 42) at a processing rate of 13 kg / h in terms of resin amount. In this extruder, cyclization condensation reaction and devolatilization are further carried out, and at the same time as extrusion, By injecting zinc acetate in the form of an aqueous solution in the middle of the forevent and the fourth forevent so as to be 400 ppm with respect to the amount of polymer obtained, transparent pellets of the thermoplastic resin composition (B3 )

  The lactone ring-containing polymer contained in the obtained thermoplastic resin composition was the same as in Production Example 2. When dynamic TG was measured, a mass loss of 0.15% by mass was detected. The lactone ring-containing polymer had a weight average molecular weight of 147,000, a melt flow rate of 11.0 g / 10 min, and a glass transition temperature of 130 ° C.

  The obtained pellet (B3) was supplied to an injection molding machine (HM7 type, manufactured by Nissei Plastic Industry Co., Ltd.) set at a barrel temperature of 260 ° C., held for 20 minutes, then shot by injection, and had a diameter of 40 mm and a thickness. A 3 mm disk-shaped molded product was obtained. The obtained molded product was transparent, and defects such as bubbles and silver streaks were not observed. Moreover, content of the metal compound was 131 ppm in conversion of the metal atom on the basis of the mass of a polymer. The results are shown in Table 1.

<Example 9>
First, 240 kg of methyl methacrylate, 60 kg of methyl 2- (hydroxymethyl) acrylate, and 294 kg of toluene were charged into a 1 m ³ reaction kettle equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen gas introduction pipe.

  When nitrogen gas was introduced into this reaction kettle, the temperature was raised to 105 ° C. and refluxed, and 309 g of t-amyl peroxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Corp.) was added as a polymerization initiator. At the same time, a solution prepared by dissolving 621 g of t-amylperoxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Co., Ltd.) in 3.7 kg of toluene was added dropwise over 2 hours, and the solution was refluxed at about 105 to 110 ° C. Polymerization was performed, and further aging was performed for 6 hours.

  To the resulting polymer solution, 300 g of octyl phosphate (Phoslex A-8, manufactured by Sakai Chemical Industry Co., Ltd.) was added, and a cyclization condensation reaction was performed at about 90 to 110 ° C. for 5 hours under reflux. Subsequently, the obtained polymer solution was a vent type screw twin screw extruder having a barrel temperature of 250 ° C., a rotation speed of 240 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4. (Φ = 42 mm, L / D = 42) at a treatment rate of 16 kg / h in terms of resin amount. In this extruder, cyclization condensation reaction and devolatilization are further carried out, and at the same time as extrusion, the third Between forevent and fourth forevent, zinc octylate (Nikka Octix zinc 18%, manufactured by Nippon Chemical Industry Co., Ltd.) in the form of a toluene solution and 1,470 ppm relative to the amount of polymer obtained By carrying out injection so that a transparent pellet (B4) of the thermoplastic resin composition was obtained.

  The lactone ring-containing polymer contained in the obtained thermoplastic resin composition had a weight average molecular weight of 148,000, a melt flow rate of 10.9 g / 10 min, and a glass transition temperature of 131 ° C.

  The obtained pellet (B4) was supplied to an injection molding machine (HM7 type, manufactured by Nissei Plastic Industry Co., Ltd.) set at a barrel temperature of 260 ° C., held for 20 minutes, then shot by injection, and had a diameter of 40 mm and a thickness. A 3 mm disk-shaped molded product was obtained. The obtained molded product was transparent, and defects such as bubbles and silver streaks were not observed. Moreover, content of the metal compound was 250 ppm in conversion of the metal atom on the basis of the mass of a polymer. The results are shown in Table 1.

<Example 10>
First, 7 kg of methyl methacrylate, 2 kg of methacrylic acid, 1 kg of styrene, and 10 kg of toluene were charged into a 30 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen gas introduction pipe.

  When nitrogen gas was introduced into the reaction vessel and the temperature was raised to 105 ° C. and refluxed, t-amyl peroxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Corp.) 12 g was added as a polymerization initiator. At the same time, a solution polymerization of 24 g of t-amylperoxyisononanoate (Lupazole 570, manufactured by Arkema Yoshitomi Co., Ltd.) in 136 g of toluene was added dropwise over 2 hours while solution polymerization was carried out at about 105 to 120 ° C. under reflux. Aged for another 4 hours.

  To the resulting polymer solution, 20 g of magnesium ethoxide was added, and a cyclization condensation reaction was performed at about 90 to 120 ° C. for 5 hours under reflux. Subsequently, the obtained polymer solution was a vent type screw twin screw extruder having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, and a forevent number of 4. (Φ = 29.75 mm, L / D = 30) is introduced at a treatment rate of 2.0 kg / h in terms of resin amount, and is further subjected to cyclization condensation reaction and devolatilization in this extruder and extruded. At the same time, a polymer obtained by mixing a stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) in the form of a toluene solution between the third and fourth forvents. The transparent pellet (C1) of the thermoplastic resin composition was obtained by performing injection so that the amount was 5,000 ppm.

  The polymer having a ring structure made of glutaric anhydride contained in the obtained thermoplastic resin composition has a weight average molecular weight of 140,000, a melt flow rate of 13.0 g / 10 min, and a glass transition temperature. It was 127 ° C.

  The obtained pellet (C1) was supplied to a ment indexer set at 260 ° C., held for 20 minutes, and then extruded into a strand shape under a load of 10 kg. The foaming amount was 0 / g. Further, the content of the metal compound was 430 ppm in terms of metal atom based on the mass of the polymer. The results are shown in Table 1.

  As can be seen from Table 1, the thermoplastic resin compositions of Examples 1 to 10 are transparent because of the addition of a quencher, and various molded products that do not contain bubbles or silver streaks during thermal processing. Obtained.

  On the other hand, in the thermoplastic resin compositions of Comparative Examples 1 to 4, since no quenching agent was added, foaming was severe during thermal processing, and a clean molded product could not be obtained.

  Thus, in producing a methacrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher, after forming the ring structure by a cyclization condensation reaction using a catalyst, The thermoplastic resin composition obtained by adding a deactivator not only has excellent transparency and heat resistance, but also has desired properties such as mechanical strength and molding processability. It can be seen that a molded product that does not contain bubbles or silver streaks is generated.

  The thermoplastic resin composition and the method for producing the same of the present invention can provide a molded product that does not contain bubbles or silver streaks particularly during thermal processing, and thus can be widely used in various applications that effectively utilize transparency and heat resistance. It can be used and makes a great contribution especially to the field related to methacrylic resins.

Claims (10)

  Thermoplastic resin containing a methacrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher, and at least one metal compound selected from metal salts, metal complexes, and metal oxides A thermoplastic resin characterized in that the content of the metal compound in the composition is 10 to 10,000 ppm in terms of metal atoms, based on the mass of the methacrylic resin. Composition.   The thermoplastic resin composition according to claim 1, wherein the metal compound is a salt of a typical metal element.   The thermoplastic resin composition according to claim 2, wherein the typical metal element is calcium, magnesium, or zinc.   The thermoplastic resin composition according to claim 1, wherein the composition contains an organic acid.   The thermoplastic resin composition according to claim 1, wherein the metal compound is a metal salt of an organic acid.   The thermoplastic resin composition according to claim 5, wherein the metal salt of the organic acid is a metal salt of a carboxylic acid or an organic phosphorus compound.   The thermoplastic resin composition according to claim 1, wherein the foaming amount generated when the composition is heated at 260 ° C for 20 minutes is 20 pieces / g or less.   The thermoplastic resin composition according to claim 1, wherein the methacrylic resin has a lactone ring structure. The methacrylic resin is represented by the following formula (1):

[Wherein, R ^1, R ² and R ³ are, independently of one another, represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms; The organic residue may contain an oxygen atom
The thermoplastic resin composition of Claim 1 which has a lactone ring structure shown by these.   A method for producing a thermoplastic resin composition according to claim 1, wherein a ring using a catalyst is used for producing a methacrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C or higher. A production method comprising adding a catalyst deactivator after forming the ring structure by a polycondensation reaction.