Composition, polymer, cured product, molded body, and method for producing polymethyl methacrylate

Abstract

To provide a composition having excellent storage stability; a polymer, a cured product, and a molded body obtained by using the composition; and a method for producing polymethyl methacrylate using the composition.SOLUTION: The present invention pertains to a composition which contains methyl methacrylate and toluene, wherein the concentration of toluene is more than 0 mass ppm but less than 1000 mass ppm of the entire composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a composition, a polymer, a cured product, a molded article, and a method for producing polymethyl methacrylate. [Background technology]

[0002] Poly(methyl(meth)acrylate) obtained by polymerizing methyl(meth)acrylate is used in various fields as a resin material with excellent transparency and weather resistance. In recent years, due to the rise in resource prices and the growing awareness of environmental issues, products (molded articles) containing poly(methyl(meth)acrylate) used for various applications as described above are being collected and recycled.

[0003] Methods for recycling polymethyl(meth)acrylate include, for example, material recycling, in which the recovered molded bodies are subjected to a molding process again to produce new molded bodies; chemical recycling, in which the recovered molded bodies are heat-treated to thermally decompose (depolymerize) the polymethyl(meth)acrylate to recover the methyl(meth)acrylate, and the recovered methyl(meth)acrylate (sometimes referred to as recycled MMA or recycled MA) is used to produce new molded bodies; and thermal recycling, in which the recovered molded bodies are burned as fuel and the combustion energy is used directly as a heat source and further to generate electricity.

[0004] Furthermore, in response to the recent diversification of applications of poly(methyl (meth)acrylate), techniques for improving the quality of poly(methyl (meth)acrylate have been investigated. For example, as a polymerization apparatus suitable for obtaining high-quality polymethyl(meth)acrylate, a polymerization apparatus that suppresses the formation of gelled matter in a reaction tank in which raw material monomers react with a polymerization initiator has been proposed (see Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2012-102190 A Summary of the Invention [Problem to be solved by the invention]

[0006] In addition to improving the polymerization process of raw material monomers as described in Patent Document 1, measures for improving the quality of polymethyl(meth)acrylate include measures for suppressing deterioration in quality of raw material monomers during storage. In view of the above circumstances, an object of one embodiment of the present disclosure is to provide a composition having excellent storage stability, particularly excellent storage stability when stored for a long period of time, a polymer, a cured product, and a molded product obtained using the composition, and a method for producing polymethyl methacrylate using the composition. [Means for solving the problem]

[0007] Means for solving the above problems include the following embodiments. <1> A composition comprising methyl methacrylate and toluene, wherein the concentration of the toluene is greater than 0 ppm by mass and less than 1000 ppm by mass of the total composition. <2> The content of methyl methacrylate in the entire composition is 85% by mass or more. <1> The composition described in <3> The content of methyl methacrylate in the entire composition is 90% by mass or more. <1> or <2> The composition described in <4> The concentration of toluene is 5 ppm by mass to 700 ppm by mass of the total composition. <1> ~ <3> The composition according to any one of claims 1 to 5. <5> The concentration of toluene is 100 ppm by mass to 600 ppm by mass of the total composition. <1> ~ <4> The composition according to any one of claims 1 to 5. <6> The methyl methacrylate comprises recycled methyl methacrylate or bio-derived methyl methacrylate; <1> ~ <5> The composition according to any one of claims 1 to 5. <7> Further containing (meth)acrylic acid esters other than methyl methacrylate, <1> ~ <6> The composition according to any one of claims 1 to 5. <8> Further comprising a polymer containing a structural unit derived from methyl methacrylate; <1> ~ <7> The composition according to any one of claims 1 to 5. <9> <1> ~ <8> A polymer comprising a structural unit derived from methyl methacrylate contained in the composition according to any one of claims 1 to 5. <10> <9> A molded article comprising the polymer according to claim 1. <11> <1> ~ <8> 2. A cured product of the composition according to claim 1. <12> <11> A molded article comprising the cured product according to claim 1. <13> <1> ~ <8> 2. A method for producing polymethyl methacrylate, comprising a step of polymerizing methyl methacrylate contained in the composition according to any one of claims 1 to 11. Effect of the Invention

[0008] According to one embodiment of the present disclosure, there are provided a composition having excellent storage stability, particularly excellent storage stability when stored for a long period of time, a polymer, a cured product, and a molded product obtained using the composition, and a method for producing polymethyl methacrylate using the composition. [Brief description of the drawings]

[0009] [Figure 1] 1 is a graph showing the relationship between the toluene concentration and the average transmittance of the compositions prepared in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present invention will be described, however, the present invention is not limited to the following embodiment. In this specification, the numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples.

[0011] <Composition> The composition of the present disclosure comprises methyl methacrylate and toluene, The composition has a toluene concentration of more than 0 ppm by mass and less than 1000 ppm by mass of the total composition. As shown in the examples described below, the composition of the present disclosure has excellent storage stability.

[0012] (Methyl methacrylate) The compositions of the present disclosure include methyl methacrylate. In the present disclosure, "methyl methacrylate" refers to methyl methacrylate that is essentially free of impurities such as by-products generated during the synthesis of methyl methacrylate. However, the methyl methacrylate in the present disclosure is not limited thereto, provided that the purpose of the invention is not impaired. In other words, "methyl methacrylate" may contain impurities that cannot be completely removed by conventional purification methods, or may contain impurities at a content that cannot be detected by conventional detection methods.

[0013] The content of methyl methacrylate in the composition is not particularly limited and can be selected depending on the application of polymethyl methacrylate obtained using the composition, etc. The content of methyl methacrylate may be, for example, 85 mass% or more, 90 mass% or more, 95 mass% or more, or 99 mass% or more of the entire composition. When the content of methyl methacrylate in the composition is within the above range, it is preferable from the viewpoint of at least the heat resistance or transparency (light transmittance) of a polymer obtained by polymerizing the composition and a molded article containing the same.

[0014] The methyl methacrylate contained in the composition may be synthesized by a known synthesis method. The synthesis method is not particularly limited, and may be the ACH method, the C4 direct acid method, or the alpha method.

[0015] The methyl methacrylate contained in the composition may include recycled methyl methacrylate. In this disclosure, recycled methyl methacrylate means methyl methacrylate obtained by depolymerization of polymethyl methacrylate (a reaction in which a polymer is decomposed to produce a monomer). Depolymerization of polymethyl methacrylate can be effected, for example, by subjecting polymethyl methacrylate to a heat treatment. The source of polymethyl methacrylate, which is a raw material for regenerated methyl methacrylate, is not particularly limited as long as it is possible to recover methyl methacrylate. For example, the source of polymethyl methacrylate may be a molded body containing polymethyl methacrylate.

[0016] The methyl methacrylate included in the composition may include bio-derived methyl methacrylate. In the present disclosure, bio-derived methyl methacrylate means methyl methacrylate synthesized from a raw material of biological origin. The raw material of biological origin may be a raw material of plant origin or an animal origin, and is preferably a raw material derived from vegetable oil.

[0017] (toluene) The compositions of the present disclosure include toluene. The concentration of toluene contained in the composition is greater than 0 ppm by mass and less than 1,000 ppm by mass of the entire composition. From the viewpoint of long-term storage stability of the composition, the concentration of toluene contained in the composition is preferably 5 ppm by mass or more of the total composition, more preferably 50 ppm by mass or more, and even more preferably 100 ppm by mass or more. From the viewpoint of the optical stability of the composition, the concentration of toluene contained in the composition is preferably 700 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 500 ppm by mass or less, of the entire composition.

[0018] If necessary, the composition may contain a component other than methyl methacrylate and toluene. For example, the composition may contain a (meth)acrylic acid ester other than methyl methacrylate, a polymer containing a structural unit derived from methyl methacrylate, a low content component, or an additive, which will be described later.

[0019] ((Meth)acrylic acid ester) The composition may contain, in addition to methyl methacrylate, a (meth)acrylic acid ester other than methyl methacrylate (hereinafter also simply referred to as a (meth)acrylic acid ester). Specific examples of (meth)acrylic acid esters include methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and cyclopentanyl (meth)acrylate. Among these, methyl acrylate or ethyl acrylate is preferred, and methyl acrylate is more preferred. These may be used alone or in combination of two or more. In the present disclosure, "(meth)acrylic acid ester" indicates that it may be either an acrylic acid ester or a methacrylic acid ester. The (meth)acrylic acid ester may be included in the composition as a by-product produced during the production of methyl methacrylate or during the regeneration treatment of polymethyl methacrylate, or may be intentionally mixed into the composition.

[0020] When the composition contains a (meth)acrylic acid ester, the concentration thereof is preferably 50,000 ppm by mass or less, more preferably 40,000 ppm by mass or less, and even more preferably 30,000 ppm by mass or less, of the entire composition. When the composition contains another (meth)acrylic acid ester, the concentration thereof may be 1 ppm by mass or more, 2 ppm by mass or more, or 5 ppm by mass or more of the total composition.

[0021] The composition may contain, in addition to methyl methacrylate, a polymer containing a structural unit derived from methyl methacrylate. This polymer may be a homopolymer of methyl methacrylate, or a copolymer of methyl methacrylate and other (meth)acrylic acid esters polymerizable therewith, as long as it contains a structural unit derived from methyl methacrylate. Examples of other (meth)acrylic acid esters polymerizable with methyl methacrylate include the same as those mentioned above.

[0022] (low content ingredients) The composition may contain minor components other than toluene, which may be present in the composition as by-products produced during the manufacture of methyl methacrylate or during the regeneration process of polymethyl methacrylate. In the present disclosure, low content components refer to components that are included in the composition at concentrations of less than 1000 ppm by mass.

[0023] Examples of low content components other than toluene that may be contained in the composition include carboxylic acid esters, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, alcohols, and butyl acrylate. The composition may contain only one type of low content component other than toluene, or two or more types of low content components other than toluene.

[0024] Specific examples of carboxylate esters include methyl isobutyrate, methyl propionate, methyl 2,4-dimethyl-4-pentenoate, methyl 2-methyl-3-butenoate, methyl tiglate, methyl 3-methyl-3-butenoate, methyl 3-methyl-2-butenoate, dimethyl itaconate, and dimethyl 2-methyl-5-methylenehexanedioate. A specific example of the aromatic hydrocarbon compound is styrene. Specific examples of the aliphatic hydrocarbon compounds include 1-octene and 1-octadecene.

[0025] When the composition contains low content components other than toluene, the concentration of each low content component is preferably 700 ppm by mass or less of the total composition, and may be 1 ppm by mass or more, 2 ppm by mass or more, or 5 ppm by mass or more of the total composition.

[0026] (Additives) If necessary, the composition may contain additives, such as a release agent, a polymerization regulator, a polymerization initiator, an ultraviolet absorber, and a colorant. The composition may contain only one type of additive, or two or more types of additives.

[0027] Examples of release agents that the composition may contain include higher fatty acid esters, higher fatty alcohols, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, and fatty acid derivatives. Specific examples of release agents include sodium di-(2-ethylhexyl)sulfosuccinate, stearyl alcohol, methyl stearate, and stearic acid amide.

[0028] The composition may contain one type of release agent or two or more types of release agents. The content of the release agent in the composition can be, for example, 0.01% by mass to 1.0% by mass of the entire composition.

[0029] The polymerization regulator (additive for controlling the polymerization rate in the polymerization reaction) that may be contained in the composition may be any suitable polymerization regulator known in the art. For example, a compound capable of controlling the polymerization rate in the direction of decreasing the polymerization rate may be used as such a polymerization regulator. Specific examples of the polymerization regulator include mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, and α-methylstyrene dimer.

[0030] The composition may contain one or more types of polymerization regulator. The content of the polymerization regulator in the composition can be, for example, 0.001% by mass to 0.5% by mass of the entire composition.

[0031] Polymerization initiators that the composition may contain include radical polymerization initiators, diacyl peroxide initiators, dialkyl peroxide initiators, peroxyester initiators, percarbonate initiators, and peroxyketal initiators.

[0032] Specific examples of radical polymerization initiators include azo compounds such as 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4,4-trimethylpentene), 2,2'-azobis(2-methylpropane), 2-cyano-2-propylazoformamide, 2,2'-azobis(2-hydroxymethylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and dimethyl 2,2'-azobis(2-methylpropionate).

[0033] Specific examples of diacyl and dialkyl peroxide initiators include dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, and lauroyl peroxide.

[0034] Specific examples of peroxyester initiators include tert-butylperoxy-3,3,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and tert-amylperoxy-2-ethylhexanoate.

[0035] Specific examples of percarbonate initiators include tert-butyl peroxy allyl carbonate, and tert-butyl peroxy isopropyl carbonate.

[0036] Specific examples of peroxyketal initiators include 1,1-di-tert-butylperoxycyclohexane, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, and 1,1-di-tert-hexylperoxy-3,3,5-trimethylcyclohexane.

[0037] The composition may contain one type of polymerization initiator or two or more types of polymerization initiators. The content of the polymerization initiator in the composition can be, for example, 0.01% by mass to 5% by mass of the entire composition.

[0038] UV absorbers that the composition may contain include benzophenone UV absorbers, cyanoacrylate UV absorbers, benzotriazole UV absorbers, malonate UV absorbers, and oxalanilide UV absorbers.

[0039] Specific examples of ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-hydroxy-4-n-octylbenzophenone, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, and 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0040] The composition may contain one or more types of ultraviolet absorbents. The content of the ultraviolet absorber in the composition can be, for example, 0.001% by mass to 1% by mass of the entire composition.

[0041] Colorants that the composition may contain include perylene dyes, perinone dyes, pyrazolone dyes, methine dyes, coumarin dyes, quinophthalone dyes, quinoline dyes, anthraquinone dyes, asdolapyridone dyes, thioindigo dyes, coumarin dyes, isoindolinone pigments, sichetopyrrolopyrrole pigments, condensed azo pigments, benzimidazolone pigments, dioxazine pigments, copper phthalocyanine pigments, and quinacridone pigments.

[0042] The composition may contain only one type of colorant, or two or more types of colorants. The content of the colorant in the composition is, for example, 1.0×10 -8 The content can be 0.5% by mass to 0.5% by mass.

[0043] When the composition contains additives, the total content thereof may be 15 mass % or less, 10 mass % or less, 5 mass % or less, or 1 mass % or less of the total composition. When the composition contains additives, the total content thereof may be 0.01 mass % or more, 0.05 mass % or more, or 0.1 mass % or more of the total composition.

[0044] The storage conditions for the composition of the present disclosure are not particularly limited, and may be, for example, 0° C. to 45° C. From the viewpoint of ensuring good quality, the storage temperature is preferably selected from the range of 0° C. to 39° C., more preferably selected from the range of about 25° C.±10° C., and even more preferably selected from the range of about 25° C. to 30° C.

[0045] The composition of the present disclosure has excellent storage stability. Specifically, the transmittance of the composition after storage is improved compared to the case where toluene is not added. Therefore, the composition of the present disclosure can maintain high transmittance even after long-term storage. In the present disclosure, the storage stability of the composition was measured by measuring the transmittance of the composition stored under accelerated conditions. The following describes the method of measuring the transmittance used to evaluate storage stability.

[0046] In the examples described later, the storage stability of the composition was evaluated by (1) preparing a composition containing methyl methacrylate and toluene, (2) conducting a storage test including the following steps 1 to 7 in this order, and (3) measuring the transmittance of the composition stored under accelerated conditions.

[0047] Step 1: 25 mL of the composition is poured into the bottom of a pressure vessel ("TVS-N2" manufactured by Taiatsu Glass Industries Co., Ltd.). Step 2: Place a gasket between the top and bottom of the pressure vessel to seal it. Step 3: Feed nitrogen into the top tip of the pressure vessel and seal it at an internal pressure of 0.2 MPa. Check that the internal pressure does not change for one minute. Step 4: Release the internal pressure from the pressure vessel and install a stopcock at the top tip of the pressure vessel. Step 5: Place the pressure vessel in an oil bath set at 80°C. Step 6: Keep in oil bath for 24 hours. Step 7: After 24 hours, remove the pressure vessel from the oil bath and place it in ice-cold water to cool it down quickly.

[0048] In the examples described later, the transmittance of the composition stored under accelerated conditions is measured by measuring the transmittance of the composition after storage. Specifically, the average transmittance (%) of light having a wavelength of 300 nm to 370 nm when the optical path length is 10 mm is measured using the composition after storage. The average transmittance refers to the average value of the transmittance values ​​at each wavelength in 5 nm intervals in the measured wavelength range of 300 nm to 370 nm. A spectrophotometer (Hitachi Spectrophotometer U-4000 manufactured by Hitachi High-Tech Fielding Co., Ltd.) is used for the measurement, but any suitable commercially available spectrophotometer may be used. A higher transmittance of the composition means improved transparency. Furthermore, the higher the transmittance after storage, the more the composition can be judged to maintain its optical properties, such as transparency. The average transmittance of the composition stored under accelerated conditions is preferably 98.10% or more, more preferably 98.50% or more. Compositions containing methyl methacrylate are often used for molded articles that require transparency, and compositions that exhibit such a transmittance are useful for molded articles that require transparency.

[0049] The composition of the present disclosure, which is made by mixing toluene and methyl methacrylate in a predetermined ratio, has improved transmittance after storage compared to a composition that does not contain toluene, and exhibits high transmittance even after storage. This effect can be said to be an unexpected and surprising effect. Although the reason is unclear, it is believed that some action (e.g., interaction between monomers) occurs during storage due to the addition of a small amount of toluene to methyl methacrylate.

[0050] <Polymer, cured product and molded product> The polymer of the present disclosure is a polymer containing structural units derived from methyl methacrylate contained in the composition of the present disclosure. Here, the polymer refers to a polymer that is involved in polymerization contained in the composition. The polymer of the present disclosure is a polymer obtained by polymerizing components, and has a structural unit derived from a component involved in the polymerization. The polymer of the present disclosure may contain a structural unit derived from methyl methacrylate contained in the composition of the present disclosure and a structural unit derived from another polymerization component. The weight average molecular weight of the polymer of the present disclosure is not particularly limited and can be selected according to the application of the polymer. The cured product of the present disclosure is a cured product of the composition of the present disclosure described above. Here, the cured product is a cured composition, and may contain components that are not involved in polymerization. However, depending on the method for curing the composition, it may be considered to be the same as the above-mentioned polymer (i.e., it does not contain components that are not involved in polymerization). The molded article of the present disclosure includes the polymer or cured product of the present disclosure. When the cured product can be regarded as the same as the polymer, the molded article includes a polymer of the composition of the present disclosure. The molded article is preferably a molded article including a cured product obtained by curing only the composition of the present disclosure. The molded article may be an object obtained by molding the polymer or the cured product into any shape.

[0051] (Physical properties of polymer and cured product) The polymer and cured product of the present disclosure have excellent optical properties. Specifically, they tend to have excellent optical properties such as transparency, compared with polymers or cured products obtained from compositions containing methyl methacrylate but not containing toluene. Polymers and cured products of methyl methacrylate compositions are often required to have high transparency for their applications. Therefore, the composition of the present application can provide a polymer or cured product with higher transparency than a polymer or cured product of a composition not containing toluene. In addition, the composition of the present application exhibits a higher transmittance than a composition not containing toluene even after the composition is stored for a long period of time. Therefore, the composition of the present application can provide a polymer or cured product with high transparency even after the composition is stored for a long period of time.

[0052] The transparency of the polymer and the cured product can be judged by measuring the transmittance. In the present disclosure, the transmittance may be measured on the produced polymer or cured product, or may be measured after the polymer or cured product is subjected to an accelerated aging treatment. This method can efficiently evaluate the transparency of the polymer or cured product after long-term use.

[0053] The transmittance of the polymer or the cured product can be measured, for example, by the following method. First, a test piece of 50 mm×50 mm×3 mm made from the polymer or the cured product is subjected to accelerated aging treatment by leaving it for 200 hours in an incubator ("Vacuum Oven VOS-301SD" manufactured by Tokyo Rikakikai Co., Ltd.) set at 80° C. Next, the test piece after the accelerated aging treatment is used to measure the average transmittance (%) of light rays having a wavelength of 380 nm to 780 nm when the optical path length is set to 50 mm. The measurement is performed with a spectrophotometer ("Hitachi Spectrophotometer U-4000" manufactured by Hitachi High-Tech Fielding Co., Ltd.). From the viewpoint of optical properties, the average transmittance of the polymer or the cured product after the accelerated aging treatment is preferably 81% or more, more preferably 81.5% or more.

[0054] Whether the polymer and cured product of the present disclosure contain methyl methacrylate, toluene, or other components can be determined by known analytical methods, such as gas chromatography and liquid chromatography.

[0055] <Production method of polymethyl methacrylate> The method for producing polymethyl methacrylate of the present disclosure includes a step of polymerizing the methyl methacrylate contained in the composition of the present disclosure. Here, the polymethyl methacrylate of the present disclosure includes a polymer obtained from the composition of the present disclosure and a cured product obtained from the composition.

[0056] The method for polymerizing methyl methacrylate contained in the composition is not particularly limited, and may be carried out by a known method, such as bulk polymerization, cell cast polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

[0057] Specifically, the composition of the present disclosure can be used to obtain a sheet (molded product) of a methyl methacrylate polymer by bulk polymerization, for example. In cell cast polymerization, the composition is heated under a predetermined heating condition to cause a polymerization reaction to proceed, thereby obtaining a cured product (molded product) of the composition.

[0058] In the method for polymerizing methyl methacrylate contained in the composition of the present disclosure or the method for producing a molded body, the heating temperature and heating time among the heating conditions can be set, for example, taking into consideration the type and content of the selected polymerization regulator, polymerization initiator, and / or other components.

[0059] In the cell cast polymerization, the heating temperature for producing the cured product and its molded article can be, for example, 50° C. to 120° C. The heating time for the production can be, for example, 1 hour to 20 hours. The heat treatment can be a heat treatment including a plurality of steps with different heating temperatures and / or heating times.

[0060] The cured product obtained by cell cast polymerization and its molded article can be produced, for example, by carrying out a heat treatment under heating conditions including the following steps 1 to 7.

[0061] Step 1: Raise the temperature from room temperature to 68°C over 20 minutes. Step 2: Hold at 68°C for 90 minutes. Step 3: Reduce the temperature from 68°C to 64°C over 20 minutes. Step 4: Hold at 64°C for 90 minutes. Step 5: Increase temperature from 64°C to 123°C over 10 minutes. Step 6: Hold at 123°C for 120 minutes. Step 7: The temperature is reduced from 123°C to room temperature over 78 minutes.

[0062] In the method for producing a cured product and a molded article thereof, by carrying out the above steps 1 to 7 in this order, heat generation during the polymerization reaction can be suppressed and the polymerization can be stably completed.

[0063] When the composition of the present disclosure is subjected to a heat treatment, for example, a cell casting method (cell casting polymerization) using a cell capable of defining an enclosed space of a predetermined shape inside can be applied to form a molded body of a predetermined shape. The manufacturing method of a molded body by the cell casting method will be specifically described below.

[0064] In manufacturing a green body by the cell casting method, a cell is first prepared. Here, an example of forming a green body that is a plate-like body (sometimes called a cast plate) will be described. Such a cell can be composed of at least two flat plate-like members and a sealing material (gasket) that is arranged so as to be sandwiched between the two flat plate-like members and can seal the gap between the two opposing flat plate-like members as an airtight space.

[0065] The flat plate member may be in the form of a sheet or a belt. The flat plate member is made of a material that is not dissolved by the composition of the present disclosure, does not inhibit the polymerization reaction of the composition, and has sufficient heat resistance to the heating temperature in the heat treatment. Examples of suitable materials for the flat plate member include glass and metal.

[0066] As the sealing material, any suitable sealing material known in the art can be used. The sealing material is made of a material that is not dissolved by the composition of the present disclosure, does not inhibit the polymerization reaction of the composition, and has sufficient heat resistance to the heating temperature in the heat treatment. A specific example of a suitable sealing material is a gasket made of vinyl chloride resin.

[0067] Next, the composition of the present disclosure is injected into the gap (void) defined by the prepared cell by any suitable conventional method. After that, the cell is heat-treated under the heating conditions already described. The method of heat-treating the cell into which the composition of the present disclosure is injected is not particularly limited. The method of heat-treating the cell can be, as in the conventional cell casting method, a method of directly heat-treating the cell from the outside using a hot air circulating oven, an infrared heater, or the like, or a method of further providing any suitable conventional jacket on the outside of the cell and introducing a heat medium such as hot air, hot water, or water vapor into the jacket.

[0068] <Uses of polymethyl methacrylate and its molded bodies> The polymethyl methacrylate obtained from the composition of the present disclosure and its molded article are excellent in light transmittance, heat resistance, and weather resistance. Therefore, the composition of the present disclosure can be suitably applied to various applications that may be exposed to the external environment and further to heat and light sources, such as lighting fixtures, automobile parts, signs, and building materials. EXAMPLES

[0069] Hereinafter, embodiments of the present disclosure will be described based on examples. The following examples are not intended to limit the present disclosure.

[0070] <Example 1> 0.005% by mass of toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to and mixed with 99.999% by mass of methyl methacrylate to prepare composition 1. The obtained composition 1 was in the form of a solution.

[0071] <Examples 2 and 3 and Comparative Examples 1 and 2> Compositions were prepared in the same manner as in Example 1, except that the toluene and its concentration (ppm by mass) added to methyl methacrylate were changed from Example 1 as shown in Table 1. All of the obtained compositions were in the form of a solution.

[0072] (1) Evaluation of storage stability of composition A storage test including the following steps 1 to 7 in this order was carried out on the compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2. The storage test was carried out under accelerated conditions (80°C) to evaluate the stability after long-term storage.

[0073] Step 1: 25 mL of the composition is poured into the bottom of a pressure vessel ("TVS-N2" manufactured by Taiatsu Glass Industries Co., Ltd.). Step 2: Place a gasket between the top and bottom of the pressure vessel to seal it. Step 3: Feed nitrogen into the top tip of the pressure vessel and seal it at an internal pressure of 0.2 MPa. Check that the internal pressure does not change for one minute. Step 4: Release the internal pressure from the pressure vessel and install a stopcock at the top tip of the pressure vessel. Step 5: Place the pressure vessel in an oil bath set at 80°C. Step 6: Keep in oil bath for 24 hours. Step 7: After 24 hours, remove the pressure vessel from the oil bath and place it in ice-cold water to cool it down quickly.

[0074] The composition (3 mL) after the storage test was placed in a quartz glass cell (T-1, Taiko Seisakusho Co., Ltd.) with dimensions of 10 mm length x 10 mm width x 45 mm height. Using the composition placed in the quartz glass cell, the average transmittance (%) of light in the wavelength range of 300 nm to 370 nm when the optical path length was set to 10 mm was measured. The average transmittance is the average value of the transmittance values ​​at each wavelength in 5 nm intervals in the wavelength range of 300 nm to 370 nm. A spectrophotometer (Hitachi Spectrophotometer U-4000, Hitachi High-Tech Fielding Co., Ltd.) was used for the measurement. It can be determined that the higher the average transmittance, the more the optical properties such as high transparency are maintained even after storage. The results are shown in Table 1 and FIG. 1.

[0075] [Table 1]

[0076] As shown in Table 1 and FIG. 1, the compositions of Examples 1 to 3, in which toluene was added to methyl methacrylate at a concentration of less than 1000 ppm by mass, had higher average transmittance after the storage test than Comparative Example 1, in which toluene was not added to methyl methacrylate, and Comparative Example 2, in which toluene was added to methyl methacrylate at a concentration of 1000 ppm by mass. The above results suggest that adding toluene to methyl methacrylate at a concentration of less than 1000 ppm by mass contributes to improving the storage stability of the composition.

Claims

1. Contains methyl methacrylate and toluene, A composition having a toluene concentration of greater than 0 ppm by mass and less than 1000 ppm by mass of the total composition.

2. The composition according to claim 1, wherein the content of methyl methacrylate is 85% by mass or more of the total composition.

3. The composition according to claim 1, wherein the content of methyl methacrylate is 90% by mass or more of the total composition.

4. The composition of claim 1, wherein the concentration of toluene is from 5 ppm by weight to 700 ppm by weight of the total composition.

5. The composition according to claim 1, wherein the concentration of toluene is from 100 ppm by weight to 600 ppm by weight of the total composition.

6. 2. The composition of claim 1, wherein the methyl methacrylate comprises recycled methyl methacrylate or bio-derived methyl methacrylate.

7. The composition of claim 1 further comprising a (meth)acrylic acid ester other than methyl methacrylate.

8. The composition of claim 1 further comprising a polymer comprising structural units derived from methyl methacrylate.

9. A polymer comprising a structural unit derived from methyl methacrylate contained in the composition according to any one of claims 1 to 8.

10. A molded article comprising the polymer according to claim 9.

11. A cured product of the composition according to any one of claims 1 to 8.

12. A molded article comprising the cured product according to claim 11.

13. A method for producing polymethyl methacrylate, comprising a step of polymerizing methyl methacrylate contained in the composition according to any one of claims 1 to 8.

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