JP5505973B2 - Method for producing thermoplastic resin - Google Patents

Description

The present invention relates to the production how the thermoplastic resin.

Since acrylic resins represented by polymethyl methacrylate (PMMA) have high transparency, various optical materials such as light guide plates and liquid crystal display films, lenses, household goods, OA equipment, Widely used in the field of lighting equipment.
In particular, in recent years, the acrylic resin has been used in optical materials such as light guide plates and liquid crystal display films, etc., to cope with the thinning of displays and to be used in high-temperature environments. And optical properties have been demanded.

  In the conventional acrylic resin production process, a plate-like or block-like resin is obtained by a cast polymerization method or a block polymerization method, and then pulverized in a size that is easy to process by removing the fine powder generated by pulverization with a pulverizer. I'm getting things.

  There has also been proposed a technique for pelletizing the pulverized product with an extruder or the like and using the pellets in various processes (for example, see Patent Document 1).

Japanese Examined Patent Publication No. 04-45522

However, if the fine powder generated in the pulverization step is removed, the recovery rate of the desired pulverized product is reduced accordingly.
On the other hand, when a lot of fine powder is contained in the pulverized product, it becomes a lump at the feed location during the pellet granulation process, and the workability deteriorates. Therefore, it is necessary to sieve and remove the fine powder generated in the pulverization of the acrylic resin, and the recovery rate is inevitably lowered as described above.

  Therefore, an object of the present invention is to reduce the amount of fine powder generated during pulverization of a thermoplastic resin, to improve production efficiency, and to improve workability in a subsequent process.

  As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventor has reduced the generation amount of fine powder in the pulverization process by adding a specific compound during polymerization, and the pulverized product recovery rate In addition, the present invention has been completed by finding that the above-described problems can be solved by improving the workability in the subsequent process.

[1]
Having a polymerization step of copolymerizing the aromatic group-containing vinyl compound monomer (b) and the unsaturated carboxylic acid anhydride (c) with the unsaturated carboxylic acid ester monomer (a),
In the said polymerization process, when the monomer whole quantity is 100 mass parts, the manufacturing method of the thermoplastic resin which adds 0.001 mass part or more and 5 mass parts or less of the compound shown to following General formula (1).

In the formula (1), R ₁ represents H or a tertiary alkyl group having 4 to 10 carbon atoms, and R ₂ is represented by a tertiary alkyl group having 4 to 8 carbon atoms or the following general formula (2). R ₃ is a group having 1 to 72 carbon atoms containing 0 to 8 O and 0 to 2 S, or a group represented by the following general formula (3).

  In the formula (2), X represents H or halogen.

In the above formula (3), R ₄ represents an alkyl group having 1 to 18 carbon atoms, n represents an integer of 0 to 3.

[2]
The method for producing a thermoplastic resin according to [1] , wherein a bulk polymerization method or a cast polymerization method is used in the polymerization step.

[3]
The method for producing a thermoplastic resin according to [1] or [2] , further comprising a step of pulverizing the obtained thermoplastic resin after the polymerization step.

[4]
In the step of pulverizing the thermoplastic resin, the mass of the sheet-shaped thermoplastic resin before being applied to the pulverizer is “X”, and a coarse pulverizer Orient Mill VM manufactured by Seishin Enterprise Co., Ltd., to which a 10 mm mesh net is attached. After grinding with a -42D machine, when the mass of the pulverized product after removing the pulverized product through a sieve of 500 μm mesh is “Y”, the recovery rate of the thermoplastic resin calculated by the following formula is The method for producing a thermoplastic resin according to the above [3] , which is 90% by mass or more.
Recovery rate = (Y / X) × 100 (%)

  According to this invention, generation | occurrence | production of the fine powder at the time of the grinding | pulverization of a thermoplastic resin can be reduced, and the improvement of production efficiency can be aimed at effectively.

  Hereinafter, although the form for implementing this invention (henceforth "this embodiment") is demonstrated, this invention is not limited to the form shown below.

[Method for producing thermoplastic resin]
The manufacturing method of the thermoplastic resin of this embodiment has a superposition | polymerization process which superposes | polymerizes using the unsaturated carboxylic acid ester monomer (a) mentioned later.
In the polymerization step, the unsaturated carboxylic acid ester monomer (a) is added to the aromatic group-containing vinyl compound monomer (b), which will be described later, and the unsaturated carboxylic acid monomer, which will be described later, to the extent that the effects of the invention can be exerted. The acid anhydride (c) may be copolymerized.
Moreover, in the said polymerization process, you may copolymerize the other vinylic monomer (d) mentioned later in the range which does not impair the effect of invention.
In the polymerization step, when the total amount of monomers is 100 parts by mass, 0.001 part by mass or more and 5 parts by mass or less of a compound represented by the following general formula (1) is added.

In the general formula (1) (hereinafter also simply referred to as formula (1)), R ₁ represents H or a tertiary alkyl group having 4 to 10 carbon atoms, and R ₂ represents 3 having 4 to 8 carbon atoms. A secondary alkyl group or a group represented by the following general formula (2) (hereinafter also simply referred to as formula (2)) is shown.
R ₃ is a group having 1 to 72 carbon atoms containing 0 to 8 O and 0 to 2 S or a group represented by the following general formula (3) (hereinafter also simply referred to as formula (3)). is there.

  In the formula (2), X represents H or halogen.

In the above formula (3), R ₄ represents an alkyl group having 1 to 18 carbon atoms, n represents an integer of 0 to 3.

Hereinafter, the raw material used for a superposition | polymerization process is demonstrated.
(material)
<Unsaturated carboxylic acid ester monomer (a)>
Although it does not specifically limit as unsaturated carboxylic acid ester monomer (a), The monomer shown to the following general formula (4) (henceforth only a formula (4)) is preferable.

In the formula (4), R ₅ represents a hydrogen atom or an alkyl group having a carbon number of 1-6, may have a hydroxyl group on the alkyl group.
R ₆ represents a group having 1 to 12 carbon atoms, and may have a hydroxyl group on the carbon.
Among these, an acrylate monomer in which R ₅ is a hydrogen atom or a methacrylic acid ester monomer in which a C 1 methyl group is preferable.
Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, acrylic acid (2-ethylhexyl), acrylic Examples include acid (t-butylcyclohexyl), benzyl acrylate, acrylic acid (2,2,2-trifluoroethyl), and the like.
Examples of the methacrylic acid ester monomer include butyl methacrylate, ethyl methacrylate, methyl methacrylate, propyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, methacrylic acid (2-ethylhexyl), and methacrylic acid (t-butylcyclohexyl). ), Methacrylic acid (2,2,2-trifluoroethyl), phenyl methacrylate, benzyl methacrylate and the like, and methyl methacrylate is particularly preferable.
The said (meth) acrylic acid ester monomer may be used independently and may be used in combination of 2 or more type.

<Aromatic group-containing vinyl compound monomer (b)>
As the aromatic group-containing vinyl compound monomer (b), a compound monomer represented by the following general formula (5) (hereinafter also simply referred to as formula (5)) can be used.

In the formula (5), R ₇ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. And R ₇ may be the same group or different groups. Further, R ₇ may form a ring structure.
R ₈ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may have a hydroxyl group on the alkyl group. Moreover, n in a formula represents the integer of 0-5.

Examples of the monomer represented by the formula (5) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4- Dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, о-ethylstyrene, p-tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, iso In this embodiment, propenyl benzene (α-methyl styrene), isopropenyl toluene, isopropenyl ethyl benzene, isopropenyl propyl benzene, isopropenyl butyl benzene, isopropenyl pentyl benzene, isopropenyl hexyl benzene, isopropenyl octyl benzene and the like can be mentioned. Purpose and It can be selected according to the characteristics required for the thermoplastic resin to be used.
Styrene and isopropenylbenzene are preferable, and styrene is more preferable.
The aromatic group-containing vinyl monomer (b) may be used alone or in combination of two or more.

  When the aromatic group-containing vinyl compound monomer (b) is used in the polymerization step, when the total of the component (a) and the component (b) described above is 100 parts by mass, the component (a) 10 mass. It is preferable to set it as 10 to 90 mass parts of (b) component.

<Unsaturated carboxylic acid anhydride (c)>
Examples of the unsaturated carboxylic acid anhydride (c) include maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, itaconic anhydride, aconitic anhydride, trimellitic anhydride, and the like. Maleic anhydride is particularly preferred.
Unsaturated carboxylic acid anhydride (c) may be used independently and may be used in combination of 2 or more type.

When the unsaturated carboxylic acid anhydride (c) is copolymerized, the blending ratio of each monomer component is appropriately determined according to the properties required for the target thermoplastic resin, and preferably (a ) Component is used in an amount of 10 to 90 parts by mass, (b) component is used in an amount of 1 to 90 parts by mass, and (c) component is used in an amount of 1 to 50 parts by mass.
Moreover, when it is set as 100 mass parts in total of the said (b) component and (c) component, (b) component is 40 mass parts or more and 99 mass parts or less, (c) component is 1 mass part or more and 60 mass parts or less. More preferably, (b) component 50 parts by mass or more and 90 parts by mass or less, (c) component 10 parts by mass or more and 50 parts by mass or less, more preferably (b) component 55 parts by mass or more and 85 parts by mass or less. , (C) component is 15 parts by mass or more and 45 parts by mass or less.

<Other vinyl monomers (d)>
In the polymerization step described above, other vinyl monomers may be used as long as the effects of the invention are not impaired.
Examples of other vinyl monomers (d) include vinyl cyanides such as acrylonitrile and methacrylonitrile, and maleimides such as N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Amides such as acrylamide, methacrylamide and the like.
The other vinyl monomer (d) is 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the total monomer amount in consideration of the balance of optical properties, heat resistance and processability of the target thermoplastic resin. It is preferably used in the range of 50 parts by mass, more preferably 0.1 to 40 parts by mass, still more preferably 0.5 to 35 parts by mass, even more preferably 1 to 30 parts by mass, and even more preferably 1 to 25 parts. Used in the range of parts by mass.

<Compound shown in general formula (1)>
In the polymerization step in the method for producing the thermoplastic resin of the present embodiment, the compound represented by the general formula (1) is added.
By causing the compound represented by the above formula (1) to be present in the polymerization system, the generation of fine powder when the finally obtained thermoplastic resin is pulverized can be reduced, and the effect of improving the yield can be obtained.

Examples of the compound represented by the above formula (1) include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1 -Methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4-tert-butylphenol, 2- (2H-benzotriazol-2-yl) -4-bis (1,1, 3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (t-butyl) phenol, 2- (2H-benzotriazole-2 -Yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6 − -Tert-butylphenol, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, hexadecyl-3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate, heptadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate and the like.
In particular, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2 -(2H-benzotriazol-2-yl) -4-t-butylphenol, 2- (2H-benzotriazol-2-yl) -4-bis (1,1,3,3-tetramethylbutyl) phenol, isooctyl -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, hexadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, heptadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydro Roxyphenyl) propionate is preferred, and isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, hexadecyl-3- (3,5-di-tert-butyl-4-hydroxy) More preferred are phenyl) propionate, heptadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate .

The addition amount of the compound represented by the above formula (1) is 0.001 part by mass or more and 5 parts by mass or less, preferably 0.001 part by mass or more and 3 parts by mass when the total amount of monomers to be copolymerized is 100 parts by mass. Parts or less, more preferably 0.02 parts by mass or more and 2 parts by mass or less, further preferably 0.03 parts by mass or more and 2 parts by mass or less, and even more preferably more than 0.03 parts by mass and 2 parts by mass or less.
By making the addition amount 0.001 part by mass or more, the effect of reducing the generation of fine powder at the time of pulverization can be sufficiently obtained, and by making the addition amount 5 parts by mass or less, thermoplasticity can be achieved with a practically preferable polymerization time. Resin is obtained, good productivity can be secured, and sufficient heat resistance required for the thermoplastic resin can be obtained.
The compounds represented by the above formula (1) may be used alone or in combination of two or more.

(Polymerization method)
The above-mentioned unsaturated carboxylic acid ester monomer (a), if necessary, aromatic group-containing vinyl compound monomer (b), unsaturated carboxylic acid anhydride (c), other vinyl monomers ( d) is appropriately mixed, and the compound represented by the above formula (1) is added, and a chain transfer agent and a polymerization initiator described later are added as necessary to carry out polymerization.
At that time, the order of adding the monomer and the compound represented by the formula (1) is not particularly limited as long as the effect of the present application can be exhibited. In order to obtain the effect of the present application sufficiently, the compound represented by the formula (1) is preferably added simultaneously with the monomer to initiate polymerization.
As the polymerization method, any conventionally known method such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like can be applied.
In order to obtain a copolymer having a high degree of polymerization, bulk polymerization or cast polymerization is particularly preferable.

(Polymerization temperature, polymerization time)
In the polymerization step of the (co) polymer constituting the thermoplastic resin of the present embodiment, the polymerization temperature may be a temperature at which the polymerization proceeds, but preferably from 50 ° C. to 200 ° C. from the viewpoint of realizing high productivity. It is 50 degreeC or less, More preferably, it is 50 degreeC or more and 180 degrees C or less. When a bulk polymerization method or a cast polymerization method is selected, the temperature is preferably 50 ° C. or higher and 160 ° C. or lower, and more preferably 50 ° C. or higher and 130 ° C. or lower.
The polymerization time is not particularly limited as long as the degree of polymerization required in the selected polymerization method can be obtained, but from the viewpoint of securing practically sufficient productivity and the like, 0.5 hours to 30 hours The following is preferable. When the solution polymerization method is selected, it is preferably 0.5 hours or longer and 10 hours or shorter, more preferably 0.5 hours or longer and 5 hours or shorter.
When bulk polymerization or cast polymerization is selected, it is preferably 2 hours or longer and 30 hours or shorter, and more preferably 2 hours or longer and 25 hours or shorter.

(Dissolved oxygen concentration)
In the polymerization step of the (co) polymer constituting the thermoplastic resin of the present embodiment, the degree of polymerization can be increased as the dissolved oxygen concentration in the polymerization solution is lower. Specifically, it is preferably 10 ppm or less.
The dissolved oxygen concentration can be measured using, for example, a dissolved oxygen meter DO meter B-505 (manufactured by Iijima Electronics Co., Ltd.).
As a method for lowering the dissolved oxygen concentration, a method of bubbling an inert gas in the polymerization solution, and an operation of releasing the pressure after pressurizing the container containing the polymerization solution with an inert gas to about 0.2 MPa before the polymerization are repeated. The method, the method of passing an inert gas in the container containing a polymerization solution, etc. are mentioned.

(Polymerization initiator)
When polymerizing the thermoplastic resin of the present embodiment, a polymerization initiator may be used for the purpose of adjusting the degree of polymerization.
Examples of the polymerization initiator are listed below.
Examples of the radical polymerization initiator include di-t-butyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, t-butyl peroxyneodecanate, t-butyl peroxypivalate, and dilauroyl peroxide. , Dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butyl Peroxy) cyclohexane and other organic peroxides, azobisisobutyronitrile, azobisisovaleronitrile, 1,1-azobis (1-cyclohexanecarbonitrile), 2,2′-azobis-4-methoxy-2, 4-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethyl Le valeronitrile, general radical polymerization initiator azo such as 2,2'-azobis-2-methylbutyronitrile and the like. These may be used alone or in combination of two or more.

  The above-described radical initiator may be used as a redox initiator in combination with a predetermined reducing agent.

  The above-mentioned polymerization initiator is generally used in the range of 0 to 1 part by mass with respect to 100 parts by mass of the monomer mixture used for the polymerization, taking into consideration the polymerization temperature and the half-life of the initiator. Can be selected as appropriate.

When selecting a bulk polymerization method or a cast polymerization method, from the viewpoint of preventing coloring of the desired thermoplastic resin and improving water resistance, the peroxide-based initiators lauroyl peroxide, decanoyl peroxide and t-Butylperoxy-2-ethylhexanoate and the like are particularly suitable.
In addition, when the solution polymerization method is performed at a high temperature of 90 ° C. or higher, a peroxide, an azobis initiator or the like that has a 10-hour half-life temperature of 80 ° C. or higher and is soluble in the organic solvent to be used is preferable. Specifically, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, , 1-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile and the like.
These polymerization initiators are preferably used, for example, in the range of 0 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers.

(Control of molecular weight)
In the polymerization step of the thermoplastic resin in the present embodiment, the molecular weight can be controlled within a range that does not impair the effects of the invention.
Examples of the method for controlling the molecular weight include a method of adding chain transfer agents such as alkyl mercaptans, dimethylacetamide, dimethylformamide, and triethylamine, and iniferters such as dithiocarbamates, triphenylmethylazobenzene, and tetraphenylethane derivatives. . The molecular weight can be controlled by adjusting these addition amounts.
Among these additives, alkyl mercaptans are preferable from the viewpoint of handling properties and stability. For example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, 2-ethylhexyl thioglycolate, ethylene glycol dithioglycolate, trimethylolpropane tris (Thioglycolate), pentaerythritol tetrakis (thioglycolate) and the like. The additive for controlling the molecular weight can be appropriately added according to the required molecular weight, but generally in the range of 0.001 to 3 parts by mass with respect to 100 parts by mass of the total monomer mixture. Use.
Other molecular weight control methods include the method of changing the polymerization method, the method of adjusting the amount of the polymerization initiator, and the method of changing the polymerization temperature.
For the various molecular weight control methods described above, only one type of method may be used, or two or more types may be used in combination.

(Molecular weight)
About the molecular weight of the copolymer which comprises the thermoplastic resin obtained in this embodiment, ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is 1.5-3.0. The range is preferably 1.6 to 2.7, more preferably 1.6 to 2.4.
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is determined by gel permeation chromatography (GPC) and converted to PMMA (polymethyl methacrylate).
The weight average molecular weight (Mw) measured by GPC is preferably 50,000 to 300,000 in order to achieve a good balance of fluidity, heat resistance, stretch stability and the like of the thermoplastic resin of this embodiment. More preferably, it is 5 to 250,000, more preferably 7 to 220,000, and still more preferably 80 to 200,000.

〔Thermoplastic resin〕
(Constitution)
The thermoplastic resin of the present embodiment is a polymer obtained by polymerization using the unsaturated carboxylic acid ester monomer (a) described above. In the polymerization step, the compound represented by the above formula (1) is used for the purpose. It is produced by adding 0.001 part by mass to 5 parts by mass with respect to 100 parts by mass of the polymer.
The thermoplastic resin of the present embodiment includes the above-described aromatic group-containing vinyl compound monomer (b) in addition to the unsaturated carboxylic acid ester monomer (a), and the unsaturated carboxylic acid anhydride (c) described above. ) May be copolymerized. Furthermore, what copolymerized the other vinylic monomer (d) mentioned above may be used.
In the thermoplastic resin composition of the present embodiment, the compound represented by the general formula (1) is dissolved or finely dispersed in the (co) polymer.

(Other resins that can be combined)
The thermoplastic resin of the present embodiment described above can be used in combination with a conventionally known resin.
The resin to be combined is not particularly limited, and any known thermoplastic resin and curable resin can be used.
Examples of the thermoplastic resin include polypropylene resin, polyethylene resin, polystyrene resin, syndiotactic polystyrene resin, ABS resin, acrylic resin, AS resin, BAAS resin, MBS resin, AAS resin, raw resin, and the like. Decomposable resin, polycarbonate-ABS resin alloy, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate and other polyalkylene arylate resins, polyamide resins, polyphenylene ether resins, polyphenylene sulfide resins And phenolic resins.
In particular, AS resin and BAAS resin are suitable for improving fluidity, ABS resin and MBS resin are suitable for improving impact resistance, and polyester resin is suitable for improving chemical resistance. It is.
In addition, polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, and the like can achieve the effect of improving flame retardancy.
Examples of the curable resin include unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, epoxy resin, cyanate resin, xylene resin, triazine resin, urea resin, melamine resin, benzoguanamine resin, urethane resin, oxetane resin, Examples include ketone resins, alkyd resins, furan resins, styrylpyridine resins, silicone resins, and synthetic rubbers.
These resins may be used alone or in combination of two or more.

(Additive)
In order to impart other characteristics such as rigidity and dimensional stability to the thermoplastic resin of the present embodiment, a predetermined additive may be added within a range not impairing the effects of the invention.
Additives include antioxidants, UV absorbers, heat stabilizers, light stabilizers, plasticizers (paraffinic process oil, naphthenic process oil, aromatic process oil, paraffin, organic polysiloxane, Mineral oil, etc.), flame retardants (eg, phosphorus compounds such as organic phosphorus compounds, red phosphorus, inorganic phosphates, halogens, silicas, silicones, etc.), flame retardant aids (eg, antimony oxides, metals) Oxides, metal hydroxides, etc.), curing agents (diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diethylaminopropylamine, 3,9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane, mensendiamine, isophoronediamine, N-aminoethylpi Amines such as azine, m-xylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, phenol resins such as phenol novolac resin and cresol novolac resin, liquid polymercaptan, polysulfide, etc. Polymercaptan, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, methylcyclohexenetetracarboxylic anhydride , Succinic anhydride, trimellitic anhydride, chlorendic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydride) Acid anhydrides such as rotrimate), curing accelerators (2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole, organic phosphines such as triphenylphosphine and tributylphosphine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol , Tertiary amines such as tetramethylhexanediamine, boron salts such as triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylaminetetraphenylborate, 1,4-benzoquinone, 1 Quinoid compounds such as 4-naphthoquinone, 2,3-dimethyl-1,4-benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-1,4-benzoquinone), antistatic agents (for example, polyamide elastomers, Quaternary ammonium salt system, pyridine derivative, aliphatic sulfonate, aromatic sulfonate, aromatic sulfonate copolymer, sulfate ester salt, polyhydric alcohol partial ester, alkyldiethanolamine, alkyldiethanolamide, polyalkylene glycol Derivatives, betaines, imidazoline derivatives, etc.), conductivity imparting agents, stress relieving agents, mold release agents (alcohols, esters of alcohols and fatty acids, esters of alcohols and dicarboxylic acids, silicone oils, etc.), crystallization accelerators, Hydrolysis inhibitors, lubricants (eg steer Acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate and higher fatty acids, and metal salts thereof, higher fatty acid amides such as ethylene bisstearamide, etc.), impact imparting agents, slidability improvers ( Hydrocarbons such as low molecular weight polyethylene, higher alcohols, polyhydric alcohols, polyglycols, polyglycerols, higher fatty acids, higher fatty acid metal salts, fatty acid amides, esters of fatty acids and fatty alcohols, full of fatty acids and polyhydric alcohols Esters or partial esters, full or partial esters of fatty acids and polyglycols, silicones, fluororesins, etc., compatibilizers, nucleating agents, reinforcing agents, flow control agents, dyes (nitroso dyes, nitro dyes, azo dyes) , Stilbene azo dye, ketoimine dye, triphenylmethane dye, oxa Nthene dye, acridine dye, quinoline dye, methine / polymethine dye, thiazole dye, indamine / indophenol dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone / oxyketone dye, anthraquinone dye, indigoid dye, phthalocyanine dye, etc. Dyes), sensitizers, colorants (titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine, cobalt blue, chromium oxide, spinel green, lead chromate pigments, cadmium pigments and other inorganic pigments, azo lakes Pigments, benzimidazolone pigments, diarylide pigments, azo pigments such as condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, perylene faces , Organic pigments such as condensed polycyclic pigments such as anthraquinone pigments, perinone pigments, dioxazine violet, scaly aluminum metallic pigments, spherical aluminum pigments used to improve weld appearance, pearl tone Mica powder for metallic pigments, other metallic pigments such as glass coated with inorganic polyhedral particles such as glass, etc.), rubber polymer, thickener, anti-settling agent, anti-sagging agent, filling Agents (glass fibers, fibrous reinforcing agents such as carbon fibers, glass beads, calcium carbonate, talc, clay, etc.), antifoaming agents (silicone antifoaming agents, surfactants, polyethers, higher alcohols, etc.) Antifoaming agents, etc.), coupling agents, rust inhibitors, antibacterial / antifungal agents, antifouling agents, conductive polymers and the like.

Examples of the heat stabilizer include antioxidants such as hindered phenol antioxidants and phosphorus processing stabilizers, and hindered phenol antioxidants are preferred.
Specifically, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl) -4-hydroxyphenylpropionamide, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6- Triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5 -Tert-butyl-4-hydroxy-m-tolyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl -3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- ( 4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol, etc. In particular, pentaerythritol terakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate Masui.

Examples of ultraviolet absorbers include benzotriazole compounds, benzotriazine compounds, benzoate compounds, benzophenone compounds, oxybenzophenone compounds, phenol compounds, oxazole compounds, malonic ester compounds, cyanoacrylate compounds, Examples include lactone compounds, salicylic acid ester compounds, benzoxazinone compounds, and the like. Particularly preferred are benzotriazole compounds and benzotriazine compounds. These may be used alone or in combination of two or more.
The ultraviolet absorber preferably has a vapor pressure (P) at 20 ° C. of 1.0 × 10 ⁻⁴ Pa or less from the viewpoint of ensuring good molding processability of the thermoplastic resin obtained in the present embodiment. It is more preferably 1.0 × 10 ⁻⁶ Pa or less, and further preferably 1.0 × 10 ⁻⁸ Pa or less.
Here, good moldability means that, for example, when a film is formed, the low molecular compound adheres less to the roll. When it adheres to the roll, it reattaches to the surface, which causes the appearance to deteriorate and the optical characteristics to deteriorate.
The melting point (Tm) of the ultraviolet absorber is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 130 ° C. or higher, and even more preferably 160 ° C. or higher. .
The ultraviolet absorber preferably has a weight reduction rate of 50% or less, more preferably 30% or less, and more preferably 15% or less when the temperature is increased from 23 ° C. to 260 ° C. at a rate of 20 ° C./min. More preferably, it is still more preferably 10% or less, and particularly preferably 5% or less.

(Processing and kneading of thermoplastic resin)
When the thermoplastic resin of this embodiment is processed or kneaded in combination with various additives or other resins, a conventionally known method can be applied and is not particularly limited.
For example, kneading can be performed using a kneader such as an extruder, a heating roll, a kneader, a roller mixer, a Banbury mixer, and the like.
In particular, use of an extruder is preferable because of high productivity.
The kneading temperature may be in accordance with the preferred processing temperature of the base resin, and is generally in the range of 140 to 300 ° C, preferably in the range of 180 to 280 ° C.

(Handling method of thermoplastic resin)
The solid material of the thermoplastic resin of the present embodiment may be used in a predetermined process as it is, but from the viewpoint of ensuring good handling, as a pulverized product pulverized using a predetermined pulverizer or the like It is preferable to use it.
When the thermoplastic resin is pulverized by a pulverizer, it is preferable to attach a mesh of a predetermined size in order to reduce the handleability of the pulverized product and the amount of fine powder after pulverization.
The mesh size is preferably 1 mm to 30 mm, more preferably 3 mm to 30 mm, and still more preferably 5 mm to 20 mm.
If the pulverized product contains a lot of fine powder, it may be deteriorated when processing such as extrusion using the pulverized product, so remove the fine powder from the pulverized product. Is preferred.
As a method for removing the fine powder, a known method can be applied. For example, a method of passing through a sieve having a roughness of 0.1 mm to 1 mm is mentioned. In that case, you may wash | clean with the solvent in which the obtained thermoplastic resin does not melt | dissolve. Water is preferably used as the solvent that does not dissolve the thermoplastic resin.
When the thermoplastic resin of the present embodiment is pulverized by a predetermined pulverizer, the recovery rate after removing fine powder is 90% by mass or more compared with that before pulverization.

[Molded body]
The molded body of the thermoplastic resin of the present embodiment is obtained by molding the thermoplastic resin obtained by the above-described manufacturing method using various molding methods.
Examples of the molding method include known methods such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, T-die molding, press molding, extrusion molding, foam molding, and film molding by casting. Applicable. Furthermore, secondary processing molding methods such as pressure forming and vacuum forming can be applied.

In addition, when the thermoplastic resin produced by the production method of the present embodiment is blended with a predetermined curable resin to obtain a resin composition, the components for producing the resin composition are mixed without solvent. The resin mixture is mixed with a solvent that can be mixed uniformly as necessary, and then the solvent is removed to form a resin mixture. These are cast into a predetermined mold and cured, and then cooled. The desired molded body can be obtained by taking out from.
Alternatively, it may be cast into a predetermined mold and cured by hot pressing.

The solvent for dissolving each component is not particularly limited as long as various materials can be mixed uniformly and the effects of the invention are not impaired by use.
For example, toluene, xylene, acetone, methyl ethyl ketone, methyl butyl ketone, diethyl ketone, cyclopentanone, cyclohexanone, dimethylformamide, methyl cellosolve, methanol, ethanol, n-propanol, iso-propanol, n-butanol, n-pentanol , N-hexanol, cyclohexanol, n-hexane, n-pentane and the like.

  Another example is a method in which a resin composition is kneaded and manufactured using a kneader such as a heating roll, kneader, Banbury mixer, extruder, etc., then cooled, pulverized, and further molded by transfer molding, injection molding, compression molding, or the like. Can be mentioned.

Moreover, although the hardening method of a molded object changes with hardeners to be used, it is not specifically limited.
For example, heat curing, light curing, UV curing, curing by pressure, curing by moisture, and the like can be given. The order of mixing the components is not particularly limited as long as the effect of the present invention can be achieved.

[Use]
The thermoplastic resin molded body produced by the thermoplastic resin production method of the present embodiment is a household product, OA equipment, AV equipment, battery electrical equipment, lighting equipment, automotive parts use, housing use, sanitary use, liquid crystal Light guide plate, diffuser plate, polarizing plate protective film, 1/4 wavelength plate, 1/2 wavelength plate, viewing angle control film used in displays such as displays, plasma displays, organic EL displays, field emission displays, rear projection televisions, It can be suitably used for a phase difference film such as a liquid crystal optical compensation film, a display front plate, a display substrate, a lens, a touch panel, and other transparent substrates used for solar cells. In addition, in the fields of optical communication systems, optical switching systems, and optical measurement systems, they can also be used for waveguides, lenses, optical fibers, optical fiber coating materials, LED lenses, lens covers, and the like.
It can also be used as a modifier for other resins.
Further, the molded body made of the thermoplastic resin produced by the method for producing a thermoplastic resin in the present embodiment is subjected to surface functionalization treatment such as antireflection treatment, transparent conductive treatment, electromagnetic wave shielding treatment, gas barrier treatment, etc. It can be used as various functional molded bodies.
Moreover, the thermoplastic resin obtained by this embodiment has high transparency, and is used for various films such as an optical film such as a polarizing plate protective film and a retardation film, an antiglare film, and a decorative film. Applicable.

  Examples of the present invention and comparative examples will be specifically described below, but the present invention is not limited to the examples described below.

First, measurement methods and evaluation methods of physical properties applied to examples and comparative examples described later are shown below.
[(1) Calculation of recovery rate]
When the weight of the sheet-shaped resin before being applied to the pulverizer is “X”, and after pulverization by the pulverizer, the pulverized product is passed through a 500 μm mesh sieve to remove the fine powder, the weight of the pulverized product is “Y”. Calculated by
Recovery rate = (Y / X) × 100 (%)

[Example 1]
Using a container equipped with a stirrer, 70 parts by mass of methyl methacrylate, 20 parts by mass of styrene, 10 parts by mass of maleic anhydride, and 1 part by mass of the following compound (A) were mixed, and 0.05 mass of lauroyl peroxide was added thereto. And 0.3 parts by mass of n-octyl mercaptan were added and dissolved to prepare a monomer compounding solution.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm are used, and the vicinity of the outer periphery is bonded with a flexible vinyl chloride gasket, and the distance between the two glass plates is 3.5 mm. A cell was prepared and prepared.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr.
Thereafter, the reduced pressure was released to restore the normal pressure, and the glass cell was immediately poured into the glass cell to fill it.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. A sheet-like resin was obtained.
The sheet-like resin obtained as described above was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve, Fine powder was removed to obtain a pulverized composition.
The recovery rate of the pulverized composition was 93.2%.

[Example 2]
Using a container equipped with a stirrer, 64 parts by weight of methyl methacrylate, 2 parts by weight of methyl acrylate, 22 parts by weight of styrene, 12 parts by weight of maleic anhydride, and 0.7 part by weight of the following compound (B) were mixed. In addition, 0.05 part by mass of lauroyl peroxide and 0.3 part by mass of n-octyl mercaptan were added and dissolved to prepare a monomer compounding solution.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm are used, and the vicinity of the outer periphery is bonded with a flexible vinyl chloride gasket, and the distance between the two glass plates is 3.5 mm. A cell was prepared and prepared.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released to restore the normal pressure, and the glass cell was immediately poured into the glass cell to fill it.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. A sheet-like resin was obtained.
The sheet-like resin obtained as described above was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve, Fine powder was removed to obtain a pulverized composition.
The recovery rate of the pulverized composition was 93.1%.

Example 3
Using a container equipped with a stirrer, 75 parts by mass of methyl methacrylate, 15 parts by mass of styrene, 10 parts by mass of maleic anhydride, and 0.8 parts by mass of the following compound (C) were mixed. 05 parts by mass and 0.3 parts by mass of n-octyl mercaptan were added and dissolved to prepare a monomer mixture.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm were used, and the vicinity of the outer periphery was attached with a flexible vinyl chloride gasket, and the distance between the two glass plates was 3 The cell was assembled and prepared to be 5 mm.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released to restore the normal pressure, and the glass cell was immediately poured to fill.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 20 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours. A sheet-like resin was obtained.
The sheet-like resin obtained as described above was pulverized by a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd., to which a 10 mm mesh net was attached, and the pulverized product was passed through a 500 μm sieve to obtain a fine powder. Was removed to obtain a pulverized composition.
The recovery rate of the pulverized composition was 94.3%.
The pulverized composition obtained as described above was subjected to a T-die mounting extruder (KZW15TW-25MG-NH type / width 150 mm T die mounting / lip thickness 0.5 mm) manufactured by Technobel, and the resin temperature in the cylinder of the extruder. Was adjusted to the conditions of 255 ° C. and the temperature of the T-die was 255 ° C., and extrusion was performed to obtain a transparent unstretched film having a thickness of 200 μm.
When the glass transition temperature of the obtained film was measured by DSC, it was Tg = 128 ° C.

Example 4
Using a vessel equipped with a stirrer, 75 parts by weight of methyl methacrylate, 15 parts by weight of styrene, 10 parts by weight of maleic anhydride, 0.8 part by weight of the compound (C), and 0.05 part by weight of the following compound (D) Was mixed and 0.05 parts by mass of lauroyl peroxide and 0.3 parts by mass of n-octyl mercaptan were added and dissolved to prepare a monomer compounding solution.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm were used, and the vicinity of the outer periphery was attached with a flexible vinyl chloride gasket, and the distance between the two glass plates was 3 The cell was assembled and prepared to be 5 mm.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released, the pressure was restored to normal pressure, and immediately filled into a prepared glass cell.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 20 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. Thus, a sheet-like resin was obtained.
The sheet-like resin obtained as described above was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd., to which a 10 mm mesh was attached, and the pulverized product was passed through a 500 μm sieve to obtain a fine powder. Was removed to obtain a pulverized composition.
The recovery rate of the pulverized composition was 94.0%.

Example 5
Using a container equipped with a stirrer, 66 parts by mass of methyl methacrylate, 22 parts by mass of styrene, 12 parts by mass of maleic anhydride, 1 part by mass of the compound (C), and 0.05 part by mass of the following compound (E) are mixed. Then, 0.05 part by mass of lauroyl peroxide and 0.3 part by mass of n-octyl mercaptan were added and dissolved to prepare a monomer compounding solution.
On the other hand, the periphery of two glass plates having a size of 250 × 300 mm and a thickness of 6 mm is bonded with a flexible vinyl chloride gasket, and the distance between these two glass plates is 3 by using two glass plates. The cell was assembled and prepared to be 5 mm.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released, the pressure was restored to normal pressure, and immediately filled into a prepared glass cell.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 20 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. Thus, a sheet-like resin was obtained.
The obtained sheet-like resin was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve to remove fine powder and pulverized composition I got a thing.
The recovery rate of the pulverized composition was 94.4%.

Example 6
Using a container equipped with a stirrer, 70 parts by mass of methyl methacrylate, 20 parts by mass of styrene, 10 parts by mass of maleic anhydride, 1 part by mass of the above compound (A) and 0.1 part by mass of the following compound (F) were mixed. To this, 0.05 part by mass of lauroyl peroxide and 0.3 part by mass of n-octyl mercaptan were added and dissolved to prepare a monomer compounding solution.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm were used, and the vicinity of the outer periphery was attached with a flexible vinyl chloride gasket, and the distance between the two glass plates was 3 The cell was assembled and prepared to be 5 mm.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released, the pressure was restored to normal pressure, and immediately filled into a prepared glass cell.
Next, it is kept in a hot water bath adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. Thus, a sheet-like resin was obtained.
The obtained sheet-like resin was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve to remove fine powder and pulverized composition I got a thing.
The recovery rate of the pulverized composition was 93.7%.

Example 7
Using a container equipped with a stirrer, 70 parts by mass of methyl methacrylate, 20 parts by mass of styrene, 10 parts by mass of maleic anhydride, 0.7 parts by mass of the above compound (A), 0.5 parts by mass of the following compound (G) It mixed, 0.05 mass part of lauroyl peroxide and 0.3 mass part of n-octyl mercaptan were added and melt | dissolved in this, and the monomer compounding liquid was produced.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm were used, and the vicinity of the outer periphery was attached with a flexible vinyl chloride gasket, and the distance between the two glass plates was 3 The cell was assembled and prepared to be 5 mm.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr.
Thereafter, the reduced pressure was released, the pressure was restored to normal pressure, and immediately filled into a prepared glass cell.
Next, it is kept in a hot water bath adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool at room temperature to remove the glass plate. Thus, a sheet-like resin was obtained.
After the obtained sheet-like resin was pulverized by a coarse powder pulverizer Orient Mill VM-42D type machine manufactured by Seishin Enterprise Co., Ltd., to which a 10 mm mesh net was attached, the pulverized product was passed through a 500 μm sieve to remove fine powder, A ground composition was obtained.
The recovery rate of the pulverized composition was 94.2%.

Example 8
Using a vessel equipped with a stirrer, 65 parts by mass of methyl methacrylate, 20 parts by mass of styrene, 15 parts by mass of maleic anhydride, and 1 part by mass of the following compound (H) were mixed, and 0.05 parts by mass of lauroyl peroxide was mixed therewith. Then, 0.25 part by mass of n-octyl mercaptan was added and dissolved to prepare a monomer mixture.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm were used, and the vicinity of the outer periphery was attached with a flexible vinyl chloride gasket, and the distance between the two glass plates was 3 The cell was assembled and prepared to be 5 mm.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the decompression was released to restore the normal pressure, and the mixture was immediately poured into a prepared glass cell to fill it.
Next, it is kept in a hot water bath adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. Thus, a sheet-like resin was obtained.
The obtained sheet-like resin was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve to remove fine powder and pulverized composition I got a thing.
The recovery rate of the pulverized composition was 92.7%.

Example 9
Using a container equipped with a stirrer, 70 parts by weight of methyl methacrylate, 16 parts by weight of styrene, 14 parts by weight of maleic anhydride, 0.07 parts by weight of the compound (B) and 0.03 parts by weight of the compound (D) Was added and dissolved in 0.04 parts by mass of lauroyl peroxide and 0.5 parts by mass of n-octyl mercaptan to prepare a monomer compounding solution.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm are used, and the vicinity of the outer periphery is bonded with a flexible vinyl chloride gasket, and the distance between the two glass plates is 3.5 mm. A cell was prepared and prepared.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the reduced pressure was released to restore the normal pressure, and the glass cell was immediately poured to fill.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 22 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. A sheet-like resin was obtained.
The sheet-like resin obtained as described above was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve, Fine powder was removed to obtain a pulverized composition.
The recovery rate of the pulverized composition was 92.1%.

[Comparative Example 1]
Using a vessel equipped with a stirrer, 70 parts by mass of methyl methacrylate, 20 parts by mass of styrene, 10 parts by mass of maleic anhydride and 0.0005 parts by mass of the above compound (A) were mixed, and 0.05% lauroyl peroxide was mixed therewith. Mass parts and 0.3 parts by mass of n-octyl mercaptan were added and dissolved to prepare a monomer mixture.
On the other hand, two glass plates having a size of 250 × 300 mm and a thickness of 6 mm were used, and the vicinity of the outer periphery was attached with a flexible vinyl chloride gasket, and the distance between the two glass plates was 3 The cell was assembled and prepared to be 5 mm.
A devolatilization operation for 2 minutes was performed while stirring the monomer blend solution described above under a reduced pressure of 50 torr. Thereafter, the decompression was released to restore the normal pressure, and the mixture was immediately poured into a prepared glass cell to fill it.
Next, it is kept in a hot water tank adjusted to 60 to 65 ° C. for 20 hours, and then kept in a hot-air circulating oven adjusted to 110 ° C. for 3 hours, and then allowed to stand and cool indoors to remove the glass plate. Thus, a sheet-like resin was obtained.
The obtained sheet-like resin was pulverized with a coarse pulverizer Orient Mill VM-42D machine manufactured by Seishin Enterprise Co., Ltd. equipped with a 10 mm mesh net, and then the pulverized product was passed through a 500 μm sieve to remove fine powder and pulverized composition I got a thing. The recovery rate of the pulverized composition was 89.9%.
In Comparative Example 1, since the amount of the compound (A) added was too small, the generation of fine powder could not be sufficiently reduced, and the recovery rate of the pulverized composition was inferior to the above examples.

  The present invention is used for displays such as household goods, OA equipment, AV equipment, battery electrical equipment, lighting equipment, automobile parts use, housing use, liquid crystal display, plasma display, organic EL display, field emission display, rear projection TV, etc. Light guide plate, diffuser plate, polarizing plate protective film, 1/4 wavelength plate, 1/2 wavelength plate, viewing angle control film, retardation film such as liquid crystal optical compensation film, display front plate, display substrate, lens, touch panel, etc. In addition, heat used as a material for waveguides, lenses, optical fibers, optical fiber coating materials, LED lenses, lens covers, etc. in the fields of transparent substrates used in solar cells, optical communication systems, optical switching systems, and optical measurement systems Industrial advantages as a manufacturing technology for plastic resins There is a possibility.

Claims (4)

Having a polymerization step of copolymerizing the aromatic group-containing vinyl compound monomer (b) and the unsaturated carboxylic acid anhydride (c) with the unsaturated carboxylic acid ester monomer (a),
In the said polymerization process, when the monomer whole quantity is 100 mass parts, the manufacturing method of the thermoplastic resin which adds 0.001 mass part or more and 5 mass parts or less of the compound shown to following General formula (1).

(In the general formula (1), R ₁ represents H or a tertiary alkyl group having 4 to 10 carbon atoms, and R ₂ represents
A tertiary alkyl group having 4 to 8 carbon atoms or a group represented by the following general formula (2) is shown, and R ₃ is a group having 1 to 72 carbon atoms containing 0 to 8 O and 0 to 2 S. Or it is group represented by following General formula (3). )

(In general formula (2), X represents H or halogen.)

(In General Formula (3), R ₄ represents an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 0 to 3)   The method for producing a thermoplastic resin according to claim 1, wherein a bulk polymerization method or a cast polymerization method is used in the polymerization step.   The manufacturing method of the thermoplastic resin of Claim 1 or 2 which further has the process of grind | pulverizing the obtained thermoplastic resin after passing through the said superposition | polymerization process. In the step of pulverizing the thermoplastic resin, the mass of the sheet-shaped thermoplastic resin before being applied to the pulverizer is “X”, and a coarse pulverizer Orient Mill VM manufactured by Seishin Enterprise Co., Ltd., to which a 10 mm mesh net is attached. After grinding with a -42D machine, when the mass of the pulverized product after removing the pulverized product through a sieve of 500 μm mesh is “Y”, the recovery rate of the thermoplastic resin calculated by the following formula is It is 90 mass% or more, The manufacturing method of the thermoplastic resin of Claim 3.
Recovery rate = (Y / X) × 100 (%)