TW201811909A - Methacrylic resin composition and shaped product - Google Patents

Abstract

A thermoplastic methacrylic resin composition comprising 70 to 99.99 % by mass of a methacrylic resin [A] and 0.01 to 30 % by mass of a compound [B] having a molecular weight of 2 thousand to 300 thousand and containing at least three phenolic hydroxyl groups per molecule, examples of the methacrylic resin [A] include a resin comprising a structural unit derived from methyl methacrylate and a structural unit having a ring structure in a main chain, and examples of the compound [B] include polyvinylphenol, terpene phenol resin, novolac-type phenolic resin and the like. A shaped product comprising the resin composition.

Description

   Methacrylic resin composition and formed body   

The present invention relates to a methacrylic resin composition and a molded body. More specifically, the present invention relates to a methacrylic resin composition and a molded body comprising the methacrylic resin composition, wherein the methacrylic resin composition can inhibit thermal decomposition of methacrylic resin and mold pollution on the one hand On the one hand, melt molding is performed, and it is suitable for obtaining a molded body that is less prone to bleedout.

As a material for a polarizer protective film, a methacrylic resin which can be expected to have low moisture permeability instead of triethylfluorene cellulose having high moisture permeability is being explored. However, when the methacrylic resin is melt-formed, it is liable to decompose if it is overheated. Substances generated by this thermal decomposition may cause bubbles (silver streak) in the formed body, or mold contamination may occur.

In order to suppress the thermal decomposition of methacrylic resin, Patent Document 1 discloses that pentaerythritol-tetra [3- (3 ', 5'-di-third-butyl-4'-hydroxyphenyl) propionate], bis- [ Aromatic hydroxy compounds such as 3,3'-bis- (4'-hydroxy-3'-third butylphenyl) butanoic acid] alcohol ester are added to 50% by weight or more of methyl methacrylate units and other A methyl methacrylate copolymer of an unsaturated vinyl unit. However, even if the thermal decomposition of the methacrylic resin can be suppressed by adding the aromatic hydroxy compound shown in Patent Document 1, the mold may be contaminated by the aromatic hydroxy compound or the aromatic hydroxy compound may overflow.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Laid-Open No. 5-209102

The subject of the present invention is to provide a methacrylic resin composition, which can suppress the thermal decomposition of the methacrylic resin and mold contamination while performing melt molding, and is suitable for obtaining a molded body that is less prone to overflow.

In order to solve the above problems, as a result of intensive studies, the present invention including the following aspects has been completed.

[1] A thermoplastic methacrylic resin composition comprising: 70 to 99.99% by mass of a methacrylic resin [A]; and 0.01 to 30% by mass of a molecular weight of 2,000 to 300,000 and three or more in one molecule Phenolic hydroxyl compound [B].

[2] The methacrylic resin composition according to [1], wherein the methacrylic resin [A] contains 90% by mass or more of a structural unit derived from methyl methacrylate.

[3] The methacrylic resin composition according to [1] or [2], wherein the methacrylic resin [A] contains a structural unit derived from methyl methacrylate and a structural unit having a ring structure on the main chain.

[4] The methacrylic resin composition as described in [3], wherein the structural unit having a ring structure on the main chain, the ring structure includes a> CH-OC (= O) -group structural unit, and the ring structure includes -C (= O) -OC (= O) -based structural units, ring structures containing -C (= O) -NC (= O) -based structural units, or ring structures containing> CH-O- CH <basic structural unit.

[5] The methacrylic resin composition according to any one of [1] to [4], wherein the compound [B] is a polyvinyl phenol, a terpene phenol resin, a soluble phenol resin (resol) type phenol resin, or Novolac phenol resin.

[6] The methacrylic resin composition according to any one of [1] to [5], further comprising an ultraviolet absorber [C].

[7] The methacrylic resin composition according to any one of [1] to [6], further comprising a crosslinked rubber [D].

[8] The methacrylic resin composition according to any one of [1] to [7], further comprising a block copolymer [E] or a graft copolymer [F].

[9] The methacrylic resin composition according to any one of [1] to [8], further comprising a polycarbonate resin [G].

[10] A formed body comprising the methacrylic resin composition according to any one of the above [1] to [9].

[11] A film comprising the methacrylic resin composition according to any one of the above [1] to [9].

[12] An optical film comprising the thin film as described in [11] above.

[13] A polarizer protective film comprising the film as described in [11] above.

[14] A retardation film comprising the film as described in [11] above.

[15] A polarizing plate, which is formed by laminating at least one film according to any one of [11] to [14] above.

[16] A method for producing a molded article, comprising: 70 to 99.99% by mass of a methacrylic resin [A] and 0.01 to 30% by mass of a molecular weight of 2,000 to 300,000 and three or more phenols in one molecule The compound [B] of a hydroxyl group is melt-kneaded to obtain a thermoplastic methacrylic resin composition, and the methacrylic resin composition is further melt-molded.

Even if the methacrylic resin composition of the present invention is overheated during melt molding, thermal decomposition is unlikely to occur, and mold contamination is unlikely to occur. The formed body containing the methacrylic resin composition of the present invention is less likely to overflow. The molded body, particularly a film, containing the methacrylic resin composition of the present invention has high transparency, low moisture permeability, and high heat resistance, and thus can be used in fields that exhibit such characteristics, such as the optical field.

Since the methacrylic resin composition of the present invention is thermoplastic, it can be easily formed into a desired shape by melt molding. The methacrylic resin composition of the present invention can be used, for example, in a field exposed to light or a field exposed to thermal energy.

Forms used to implement the invention

The methacrylic resin composition of the present invention contains a methacrylic resin [A] and a compound [B].

    [Methacrylic resin [A]]    

The methacrylic resin [A] may be a polymer formed by containing only a structural unit derived from methyl methacrylate (hereinafter sometimes referred to as a methacrylic resin [A0]), or it may contain a polymer derived from A random copolymer formed by the structural unit of methyl methacrylate and a structural unit derived from another monomer (hereinafter, this random copolymer is sometimes referred to as a methacrylic resin [A1]), and may also be a source containing A random copolymer from a structural unit of methyl methacrylate and a structural unit having a ring structure in the main chain (hereinafter, this random copolymer is sometimes referred to as a methacrylic resin [A2]). A commercially available methacrylic resin can be used as the methacrylic resin [A0] or [A1].

The methacrylic resin [A] is a polystyrene-equivalent weight average molecular weight Mw _A calculated from a chromatogram obtained by a gel permeation chromatography, preferably 50,000 to 200,000, and more preferably 55,000 to 160,000, and even better 60,000 to 120,000. The higher the Mw _{A, the} higher the strength of the molded body obtained from the methacrylic resin [A]. The lower the Mw _{A, the} better the moldability of the methacrylic resin [A], and the smoothness of the surface of the obtained molded body tends to be improved.

The ratio of the weight average molecular weight Mw _A of the methacrylic resin [A] to the number average molecular weight Mn _A in terms of polystyrene calculated from the chromatogram obtained with a gel permeation chromatography, Mw _A / Mn _A It is preferably 1.0 or more and 5.0 or less, more preferably 1.2 or more and 3.0 or less, even more preferably 1.2 or more and 2.5 or less, and particularly preferably 1.3 or more and 1.7 or less. The lower Mw _A / Mn _A tends to have better impact resistance and toughness. The higher Mw _A / Mn _{A is, the} higher the melt fluidity of the methacrylic resin [A] is, and the smoothness of the surface of the obtained molded body tends to be improved.

The methacrylic resin [A1] used in the present invention has a total content of structural units derived from methyl methacrylate from the viewpoint of heat resistance and the like, preferably 90% by mass or more, and more preferably 95% by mass % Or more, more preferably 98% by mass or more, and even more preferably 99% by mass or more.

The methacrylic resin [A1] may contain a structural unit derived from a monomer other than methyl methacrylate. Examples of monomers other than methyl methacrylate include alkyl methacrylates other than methyl methacrylate such as ethyl methacrylate and butyl methacrylate; and methyl groups such as phenyl methacrylate. Aryl acrylate; Cycloalkyl methacrylate, cyclohexyl methacrylate, norbornene methacrylate, etc .; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-vinyl hexyl acrylate, etc. Alkyl acrylates; aryl acrylates, such as phenyl acrylate; cyclohexyl acrylates, norbornene acrylates, etc .; aromatic vinyl compounds such as styrene, α-methylstyrene; acrylonitrile; Acrylonitrile; vinyl monomers having only one polymerizable carbon-carbon double bond in one molecule. The methacrylic resin [A1] preferably does not contain a structural unit derived from a monomer having two or more polymerizable carbon-carbon double bonds in one molecule.

For methacrylic resin [A0] or methacrylic resin [A1], the three molecules indicate the lower limit of the regularity (rr), preferably 50%, more preferably 52%, and even more preferably 53%. Although the upper limit of the syndiotacticity (rr) represented by the three molecules of the methacrylic resin [A0] or the methacrylic resin [A1] is not particularly limited, it is preferably 99% from the viewpoint of film forming property, and more 85% is preferred, 77% is even better, 65% is even better, and 64% is best.

The syndiotacticity (rr) represented by the three molecules (hereinafter sometimes referred to simply as "syntacticity (rr)") is two of the three consecutive structural unit bonds (triads) ( The two molecules, diad), are all racemic (represented as rr) ratios. In addition, the same three-dimensional arrangement in the bond (two molecules, diad) of the structural unit in the polymer molecule is called meso, and the opposite is called racemo, which are denoted as m and r, respectively. .

The three-molecule syndiotacticity (rr) can be measured in deuterated chloroform at 30 ° C for ¹ H-NMR spectrum, and the area (X) and the area of 0.6 to 0.95 ppm when TMS is taken as 0 ppm from this spectrum can be measured. The area (Y) of the region from 0.6 to 1.35 ppm is calculated by the formula: (X / Y) × 100.

The content of the methacrylic resin [A0] or the methacrylic resin [A1] used in the present invention is preferably from 0.1 to 10%, more preferably from 0.5 to 5 as the content of the component (high molecular weight component) having a molecular weight of 200,000 or more. %. In addition, the methacrylic resin [A0] or the methacrylic resin [A1] used in the present invention has a content of a component (low molecular weight component) having a molecular weight of less than 15,000, preferably 0.1 to 5%, and more preferably 0.2. ~ 3%. When the methacrylic resin [A0] or the methacrylic resin [A1] contains a high-molecular weight component and a low-molecular weight component within this range, film forming properties can be improved, and a film having a uniform film thickness can be easily obtained.

The molecular weight can be calculated by measuring the ratio of the area of the part enclosed by the baseline and the chromatogram and baseline measured by GPC to the area of the part surrounded by the baseline by measuring the standard polystyrene with a molecular weight of 200,000 before the retention time. Content of more than 200,000 ingredients. By using the GPC chromatogram and the area enclosed by the baseline, the ratio between the chromatogram obtained by measuring standard polystyrene with a molecular weight of 15,000 after the retention time and the area enclosed by the baseline can be calculated to be less than Content of ingredients with a molecular weight of 15,000.

The measurement by a gel permeation chromatography was performed in the following manner. Tetrahydrofuran was used as the eluent, and a device in which two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 were connected in series was used as a column. As the analysis device, HLC-8320 (product number) manufactured by Tosoh Corporation with a differential refractive index detector (RI detector) was used. 4 mg of a methacrylic resin as a test object was dissolved in 5 ml of tetrahydrofuran to prepare a test solution. The column oven temperature was set to 40 ° C., and 20 μl of the test object solution was injected at a flow rate of 0.35 ml / min of the eluent, and the chromatography was measured.

The chromatographic system is a graph in which the electronic signal value (intensity Y) derived from the refractive index difference between the test solution and the reference solution is plotted against the retention time X.

The standard polystyrene with a molecular weight in the range of 400 to 5000000 was measured by a gel permeation chromatography, and a calibration line showing the relationship between the retention time and the molecular weight was prepared. When the chromatogram shows a sharp peak, the line connecting the point where the slope of the high molecular weight side changes from zero to positive and the point where the slope of the low molecular weight side peak changes from negative to zero is used as a reference line. When a plurality of peaks are displayed in the chromatogram, a line connecting the point where the slope of the peak on the highest molecular weight side changes from zero to the point where the slope of the peak on the lowest molecular weight side changes from negative to zero is used as a reference line.

The methacrylic resin [A0] or methacrylic resin [A1] is preferably measured at 230 ° C and a load of 3.8 kg, and the melt flow rate is preferably 0.1 to 30 g / 10 minutes or more, and more preferably 0.5 to 20 g. / 10 minutes, preferably 1-15g / 10 minutes.

The glass transition temperature of the methacrylic resin [A0] or the methacrylic resin [A1] is preferably 100 ° C or higher, more preferably 110 ° C or higher, even more preferably 115 ° C or higher, and particularly preferably 120 ° C or higher. Although the upper limit of the glass transition temperature of the methacrylic resin [A0] or the methacrylic resin [A1] is not particularly limited, it is preferably 131 ° C.

The glass transition temperature is an intermediate point glass transition temperature obtained from a DSC curve. The DSC curve is based on JIS K7121, using a differential scanning calorimeter, and heating the resin to be measured for the first time (first time) to 250 ° C at 10 ° C / min, then cooling to room temperature, and then increasing the temperature from room temperature. The intermediate point glass transition temperature was detected at the rate of 10 ° C./min for the second temperature rise (second time) to 250 ° C.

The methacrylic resin [A2] contains a structural unit having a ring structure in the main chain. This can improve the heat resistance of the methacrylic resin composition. Thereby, the total content of structural units derived from methyl methacrylate in the methacrylic resin [A2] containing structural units derived from methyl methacrylate and structural units having a ring structure on the main chain can be combined , To lower than the above range. For example, the total content of structural units derived from methyl methacrylate in a methacrylic resin [A2] containing structural units derived from methyl methacrylate and structural units having a ring structure in the main chain is preferably 20 to 99% by mass, more preferably 30 to 95% by mass, and even more preferably 40 to 90% by mass. The total content of structural units having a ring structure on the main chain is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass. The methacrylic resin [A2] containing a structural unit derived from methyl methacrylate and a structural unit having a ring structure on the main chain may also contain a structural unit derived from methyl methacrylate and having A structural unit other than a structural unit of a ring structure. This structural unit may be a structural unit derived from a monomer as a monomer other than methyl methacrylate as exemplified above. The methacrylic resin [A2] preferably does not contain a structural unit derived from a monomer having two or more polymerizable carbon-carbon double bonds in one molecule.

As a structural unit having a ring structure in the main chain, a ring structure containing a> CH-OC (= O)-group is preferred, and a ring structure contains -C (= O) -OC (= O)- The structural unit of the base, the structural unit containing the -C (= O) -NC (= O) -group in the ring structure, or the structural unit containing the> CH-O-CH <group in the ring structure.

The cyclic monomer having a polymerizable unsaturated carbon-carbon double bond such as maleic anhydride, N-substituted maleimine, and the like can be copolymerized with methyl methacrylate or the like, or can be obtained by polymerization Part of the molecular chain of the methacrylic resin is subjected to intramolecular cyclization condensation, so that the methacrylic resin contains a structural unit having a ring structure in the main chain.

As the structural unit whose ring structure contains> CH-OC (= O)-group, β-propiolactone diyl (alias: oxopropylene oxide diyl) structural unit, γ-butyrolactone diyl ( Alias: 2-oxo dihydrofuran diyl) structural unit, lactone diyl structural unit such as δ-valerolactone diyl (alias: 2-oxo dihydropyran diyl) structural unit. In addition, "> C" in the formula means that the carbon atom C has two atomic bonds.

For example, as a delta-valerolactone diyl structural unit, the structural unit represented by Formula (I) is mentioned.

In formula (I), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms. Preferably, R ¹⁴ is a hydrogen atom and R ¹⁵ is a methyl group. R ¹⁶ is -COOR, R is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and is preferably a methyl group. * Indicates an atomic bond.

In the formula (I), examples of the organic residue include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, an -OAc group, and a -CN group. The organic residue may also contain an oxygen atom as a constituent atom. "Ac" represents ethenyl. The carbon number of the organic residue is preferably 1 to 10, and more preferably 1 to 5.

By intramolecular cyclization of two adjacent structural units derived from methyl methacrylate, the methacrylic resin can be made to contain a δ-valerolactone diyl structural unit.

Examples of the structural unit containing a -C (= O) -OC (= O)-group in the ring structure include a 2,5-dioxodihydrofurandiyl structural unit and a 2,6-dioxodihydro Pyranyldiyl structural unit, 2,7-dioxoepoxydiyldiyl structural unit, etc.

For example, a structural unit represented by formula (II) can be cited as a 2,5-dioxodihydrofurandiyl structural unit.

In formula (II), R ²¹ and R ²² are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms.

Examples of the organic residue in the formula (II) include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, an -OAc group, and a -CN group. Organic residues may also contain oxygen atoms. "Ac" represents ethenyl. The carbon number of the organic residue is preferably 1 to 10, and more preferably 1 to 5.

Both R ²¹ and R ²² are more preferably a hydrogen atom. In this case, it is generally preferred to copolymerize styrene or the like from the viewpoints of ease of production, adjustment of intrinsic birefringence, and the like. Specific examples include copolymers having a structural unit derived from styrene, a structural unit derived from methyl methacrylate, and a structural unit derived from maleic anhydride described in WO2014 / 021264A1.

The methacrylic resin can contain 2,5-dioxodihydrofurandiyl structural unit by copolymerization of maleic anhydride and the like.

Examples of the 2,6-dioxodihydropyrandiyl structural unit include a structural unit represented by formula (III).

In formula (III), R ³³ and R ³⁴ are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms.

Examples of the organic residue in the formula (III) include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, an -OAc group, and a -CN group. Organic residues may also contain oxygen atoms. "Ac" represents ethenyl. The carbon number of the organic residue is preferably 1 to 10, more preferably 1 to 5, and even more preferably methyl.

By intramolecular cyclization of two adjacent structural units derived from methyl methacrylate, the methacrylic resin can contain 2,6-dioxodihydropyrandiyl structural units.

As a structural unit including a -C (= O) -NC (= O)-group in the ring structure (wherein the other atomic bond that N has is omitted), there can be listed: 2,5-dioxopyrrolidine diyl Structural unit, 2,6-dioxopyridine diyl structural unit, 2,7-dioxo nitrogen Second base structural unit and so on.

For example, a structural unit represented by formula (IV) can be cited as a 2,6-dioxopyridinediyl structural unit.

In formula (IV), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ⁴³ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms Or an aryl group having 6 to 10 carbon atoms.

From the viewpoints of easy availability of raw materials, cost, heat resistance, and the like, it is preferred that R ⁴¹ and R ⁴² are each independently a hydrogen atom or a methyl group, and more preferably that R ⁴¹ is a methyl group and R ⁴² is a hydrogen atom. R ^{43 is} preferably a hydrogen atom, a methyl group, an n-butyl group, a cyclohexyl group, or a benzyl group, and more preferably a methyl group.

Due to intramolecular cyclization of two adjacent structural units derived from methyl methacrylate in the presence of an amine, the methacrylic resin can contain a 2,6-dioxopyridine diyl structural unit.

Examples of the 2,5-dioxopyrrolidine diyl structural unit include a structural unit represented by formula (V).

In formula (V), R ⁵² and R ⁵³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkyl group having 6 to 14 carbon atoms; R ⁵¹ is an aralkyl group having 7 to 14 carbon atoms, or An unsubstituted or substituted aryl group having 6 to 14 carbon atoms. The group substituted in the aryl group is preferably a halogen group, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms. . R ^{51 is} preferably phenyl or cyclohexyl; R ⁵² and R ^{53 are} preferably both hydrogen atoms.

The methacrylic resin can contain 2,5-dioxopyrrolidine diyl structural units by copolymerization of N-substituted maleimidine imine and the like.

Examples of the structural unit including the> CH-O-CH <group in the ring structure include a propylene oxide diyl structural unit, a tetrahydrofuran diyl structural unit, a tetrahydropyran diyl structural unit, and an epoxy hexane diyl structure. Unit, etc. In addition, "> C" in the formula means that the carbon atom C has two atomic bonds.

For example, a structural unit represented by the formula (VI) can be cited as a tetrahydropyranediyl structural unit.

In formula (VI), R ⁶¹ and R ⁶² are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms having a ring structure.

As R ⁶¹ and R ⁶² , it is preferably independently tricyclic [5.2.1.0 ^2,6 ] decyl, 1,7,7-trimethylbicyclo [2.2.1] hept-3-yl, and tert-butyl Or 4-tert-butylcyclohexyl.

Among the above-mentioned structural units having a ring structure in the main chain, δ-valerolactone diyl structural unit or 2,5-dioxodihydrofurandi is preferred from the viewpoint of raw materials and ease of production. Base building unit.

The melt flow rate of the methacrylic resin [A2] determined at 230 ° C and a load of 3.8 kg is preferably 0.1 to 20 g / 10 minutes or more, more preferably 0.5 to 15 g / 10 minutes, and even more preferably 1 ~ 10g / 10 minutes.

The glass transition temperature of the methacrylic resin [A2] is preferably 110 ° C or higher, more preferably 115 ° C or higher, even more preferably 120 ° C or higher, and particularly preferably 125 ° C or higher. Although the upper limit of the glass transition temperature of the methacrylic resin [A2] is not particularly limited, it is preferably 140 ° C.

The methacrylic resin [A] used in the present invention may be formed by one type of methacrylic resin that satisfies the above-mentioned characteristics, or may be formed by a mixture of a plurality of types of methacrylic resins that satisfies the above-mentioned characteristics.

One or two or more methacrylic resins constituting the methacrylic resin [A] used in the present invention can be obtained by any production method. For example, a methacrylic resin can be obtained by polymerizing methyl methacrylate or by polymerizing methyl methacrylate with other monomers. Polymerization can be performed in a conventional manner. Examples of the polymerization method include classification in the form of chain transfer, such as radical polymerization and anion polymerization. In addition, classification in the form of a reaction solution includes block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Each characteristic of the methacrylic resin [A] can be achieved by adjusting polymerization conditions such as polymerization temperature, polymerization time, type, amount and timing of addition of a chain transfer agent, and type, amount, and timing of addition of a polymerization initiator. . Controlling characteristics under such polymerization conditions is a technique well known to those skilled in the art, and it is not difficult for those skilled in the art to manufacture resins having the desired characteristics.

In addition, a methacrylic resin [A2] can be obtained by subjecting the resin obtained by the above polymerization to the above-mentioned intramolecular cyclization.

The amount of the methacrylic resin [A] contained in the methacrylic resin composition is 70 to 99.99% by mass, preferably 90 to 99.98% by mass, and more preferably 95 to 99.96% by mass.

    [Compound [B]]    

The compound [B] is a compound having 3 or more, preferably 10 or more phenolic hydroxyl groups in one molecule. When the number of phenolic hydroxyl groups is less than 3, the effect of suppressing thermal decomposition of a methacrylic resin may not be obtained.

The lower limit of the molecular weight of the compound [B] is 2,000, preferably 3,000, more preferably 5,000, even more preferably 10,000, and the upper limit of the molecular weight thereof is 300,000. The compound [B] having a molecular weight within the above range does not cause defects such as mold contamination or overflow during molding, and can obtain molded products such as films having good appearance.

The compound [B] may be a compound having a single molecular weight or a polymer having a molecular weight distribution. The molecular weight of a compound having a single molecular weight can be determined by various mass analysis. The molecular weight of a polymer having a molecular weight distribution is a weight average molecular weight in terms of polystyrene obtained by measurement with a gel permeation chromatography.

Specific examples of the compound [B] include polyvinyl phenols such as poly-o-hydroxystyrene, poly-m-hydroxystyrene, and poly-p-hydroxystyrene; terpene phenol resins, bisphenol A novolac resins, and the like Novolac phenol resin; soluble phenol resin phenol resin; phenol resin having a hydroxynaphthalene structure (see WO2014 / 208132A1); phenol resin having an aralkyl group on an aromatic ring (see WO2014 / 073557A1) and the like. Among these, polyvinyl phenol, terpene phenol resin, novolac type phenol resin, or soluble phenol resin type phenol resin is preferred; from the viewpoint of high effect of suppressing thermal decomposition, polyvinyl phenol is the most good.

The amount of the compound [B] contained in the methacrylic resin composition is 0.01 to 30% by mass, preferably 0.02 to 10% by mass, and more preferably 0.04 to 5% by mass.

In addition, the mass ratio of the compound (B) to the methacrylic resin (A) ((B) / (A)) is preferably 0.01 / 99.99 to 30/70, more preferably 0.02 / 99.98 to 10/90, and It is preferably 0.04 / 99.96 ~ 5/95.

    [Ultraviolet absorbent [C]]    

The ultraviolet absorber [C] used in the present invention is a conventional ultraviolet absorber that may be blended with a thermoplastic resin. The molecular weight of the ultraviolet absorber [C] is preferably more than 200, more preferably 300 or more, even more preferably 500 or more, even more preferably 600 or more. The upper limit of the molecular weight of the ultraviolet absorber [C] is preferably 2,000.

Generally, an ultraviolet absorber is a compound having the ability to absorb ultraviolet rays. The ultraviolet absorber mainly refers to a compound having a function of converting light energy into heat energy.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, Type, benzoate type, salicylate type, cyanoacrylate type, aniline oxalate type, malonic ester type, formamidine type and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, benzotriazoles (compounds having a benzotriazole skeleton), three Class (with three Skeletal compound). Benzotriazoles or tris The effect of suppressing deterioration of the resin (for example, yellowing, etc.) by ultraviolet rays is high.

Examples of the benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name) TINUVIN329), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethylene) phenol (manufactured by BASF; trade name TINUVIN234), 2,2 ' -Methylenebis [6- (2H-benzotriazol-2-yl) -4-third octylphenol] (manufactured by ADEKA Corporation; LA-31), 2- (5-octylthio-2H- Benzotriazol-2-yl) -6-tert-butyl-4-methylphenol and the like.

As three Class, including: 2,4,6-ginseng (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-tris (Manufactured by ADEKA Corporation; LA-F70) or its analog UV absorber (manufactured by BASF; CGL777, TINUVIN460, TINUVIN479, etc.), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-tris Wait.

Others can preferably use the maximum Moire absorption coefficient ε _max at a wavelength of 380 ~ 450nm is 1200dm ³ . UV absorber below mol ^-1 cm ^-1 . Examples of such an ultraviolet absorber include 2-ethylene-2'-ethoxy-anilide (manufactured by Clariant Japan; trade name: Sandeyuboa VSU).

As the ultraviolet absorber [C], WO2011 / 089794A1, WO2012 / 124395A1, Japanese Patent Application Publication No. 2012-012476, Japanese Patent Application Publication No. 2013-023461, Japanese Patent Application Publication No. 2013-112790, and Japanese Patent Application Publication No. 2013- Metal complexes having a ligand having a heterocyclic structure disclosed in Japanese Unexamined Patent Publication No. 194037, Japanese Unexamined Patent Publication No. 2014-62228, Japanese Unexamined Patent Publication No. 2014-88542, and Japanese Unexamined Patent Publication No. 2014-88543.

The amount of the ultraviolet absorber [C] that can be contained in the methacrylic resin composition of the present invention is preferably from 0.1 to 10 parts by mass, more preferably from 0.2 to 5 based on 100 parts by mass of the methacrylic resin [A]. Mass parts, even more preferably 0.3 to 3 mass parts.

    [Crosslinked rubber [D]]    

The crosslinked rubber [D] used in the present invention is a polymer having rubber elasticity, in which a polymer chain is crosslinked by a structural unit derived from a crosslinkable monomer. The crosslinkable monomer is one having two or more polymerizable functional groups in one monomer.

Examples of the crosslinkable monomer include allyl acrylate, allyl methacrylate, 1-propenyloxy-3-butene, 1-methacryloxy-3-butene, 1 2,2-Dipropenyloxy-ethane, 1,2-Dipropenyloxy-ethane, 1,2-Dipropenyloxy-propane, 1,3-Dipropenyloxy-propane , 1,4-dipropenyloxy-butane, 1,3-dimethylpropenyloxy-propane, 1,2-dimethylpropenyloxy-propane, 1,4-dimethylpropene Methoxy-butane, triethylene glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, hexanediol diacrylate, divinylbenzene, 1,4-pentane Diene, triallyl isocyanate, etc. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the crosslinked rubber include acrylic crosslinked rubber, diene crosslinked rubber, and the like, and more specifically, copolymerization of an alkyl acrylate monomer, a crosslinkable monomer, and other vinyl monomers Copolymer rubber, conjugated diene monomer and cross-linkable monomer and other vinyl-based monomer copolymer rubber, alkyl acrylate monomer and conjugated diene-based monomer and cross-linkable monomer and other ethylene Copolymer rubber based on monomers, etc.

In the present invention, the crosslinked rubber is preferably contained in the form of particles in the methacrylic resin composition.

The crosslinked rubber particles may be single-layer particles containing only crosslinked rubber, or may be multilayer particles containing crosslinked rubber and other polymers. The form of the multilayer particles containing a crosslinked rubber and other polymers is preferably a core-shell type particle, which is composed of a core made of a crosslinked rubber and a shell made of other polymers.

The crosslinked rubber particles suitable for the present invention are acrylic multilayer polymer particles. The acrylic multilayer polymer particles have a core portion and a shell portion. The core part has a core and an inner shell of more than one layer formed by covering the core with a slightly concentric circle shape according to demand. The shell part has a single-layer shell formed by covering the core part with a substantially concentric circle shape. It is preferable that the acrylic multilayer polymer particles are connected without a gap between the core, the inner shell and the outer shell.

The acrylic multilayer polymer particles are preferably those in which at least one of the core and the inner shell contains a crosslinked rubber polymer (i), and the remainder is in which the polymer (iii) is contained.

When at least two of the core and the inner shell are made of a crosslinked rubber polymer (i), the crosslinked rubber polymer (i) contained therein may have the same polymer physical properties or may have Different polymer properties. In addition, when there are two or more remaining parts in the core and the inner shell, the polymers (iii) contained therein may have the same physical properties of the polymers, or may have different physical properties of the polymers.

The above-mentioned crosslinked rubber polymer (i) preferably has at least a structural unit derived from an alkyl acrylate monomer and / or a structural unit derived from a conjugated diene monomer and a crosslinkable monomer derived Building blocks.

The alkyl acrylate monomer is preferably an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-vinylhexyl acrylate, and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the conjugated diene-based monomer include butadiene and isoprene. These can be used individually by 1 type or in combination of 2 or more types.

The amount of the structural unit derived from the alkyl acrylate monomer and / or the structural unit derived from the conjugated diene monomer in the crosslinked rubber polymer (i) is relative to the total mass of the crosslinked rubber polymer (i). It is preferably 60% by mass or more, more preferably 70 to 99% by mass, and even more preferably 80 to 98% by mass.

The crosslinkable monosystem has two or more polymerizable functional groups in one monomer. Examples of the crosslinkable monomer include allyl acrylate, allyl methacrylate, 1-propenyloxy-3-butene, 1-methacryloxy-3-butene, 1 2,2-Dipropenyloxy-ethane, 1,2-Dipropenyloxy-ethane, 1,2-Dipropenyloxy-propane, 1,3-Dipropenyloxy-propane , 1,4-dipropenyloxy-butane, 1,3-dimethylpropenyloxy-propane, 1,2-dimethylpropenyloxy-propane, 1,4-dimethylpropene Methoxy-butane, triethylene glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, hexanediol diacrylate, divinylbenzene, 1,4- Pentadiene, triallyl isocyanate, etc. These can be used individually by 1 type or in combination of 2 or more types.

The amount of the structural unit derived from a crosslinkable monomer in the crosslinked rubber polymer (i) is preferably 0.05 to 10% by mass, and more preferably 0.5 relative to the total mass of the crosslinked rubber polymer (i). ~ 7 mass%, and even better is 1 to 5 mass%.

The crosslinked rubber polymer (i) may have a structural unit derived from another vinyl-based monomer. The other vinyl-based monomer in the crosslinked rubber polymer (i) is not particularly limited as long as it can be copolymerized with the alkyl acrylate monomer and the crosslinkable monomer. Examples of other vinyl-based monomers in the crosslinked rubber polymer (i) include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and formic acid such as cyclohexyl methacrylate. Acrylate monomers; aromatic vinyl monomers such as styrene, p-styrene, ortho-styrene; and N-propylmaleimide, N-cyclohexylmaleimide, N-o-chloro Maleimide-based monomers such as phenylmaleimide. These can be used individually by 1 type or in combination of 2 or more types.

In the crosslinked rubber polymer (i), the amount of the structural unit derived from another vinyl-based monomer is relative to the structural unit derived from an alkyl acrylate monomer and the structural unit derived from a conjugated diene monomer. And the balance of the total amount of the structural units derived from the crosslinkable monomer.

The polymer (iii) is not particularly limited as long as it is other than the crosslinked rubber polymer (i), but it is preferably one having a structural unit derived from an alkyl methacrylate monomer. The polymer (iii) may contain a structural unit derived from a crosslinkable monomer and / or a structural unit derived from another vinyl-based monomer as another structural unit.

The alkyl methacrylate monomer used in the polymer (iii) is preferably an alkyl methacrylate monomer having an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. These can be used individually by 1 type or in combination of 2 or more types. Among these, methyl methacrylate is preferable.

The amount of the structural unit derived from the alkyl methacrylate monomer in the polymer (iii) is preferably 80 to 100% by mass, more preferably 85 to 99% by mass, and even more preferably 90 to 98% by mass.

Examples of the crosslinkable monomer used in the polymer (iii) are the same as those exemplified for the crosslinkable rubber polymer (i). The amount of the structural unit derived from the crosslinkable monomer in the polymer (iii) is preferably 0 to 5% by mass, more preferably 0.01 to 3% by mass, and even more preferably 0.02 to 2% by mass.

The other vinyl-based monomer in the polymer (iii) is not particularly limited as long as it is copolymerizable with the alkyl methacrylate monomer and the crosslinkable monomer. Examples of other vinyl-based monomers in the polymer (iii) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate. , Acrylic acid monomers such as 2-vinylhexyl acrylate; ethyl acetate; aromatic vinyl monomers such as styrene, p-methylstyrene, m-styrene, o-methylstyrene, α-methylstyrene, vinylnaphthalene; Nitriles such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and N-ethylene maleimide, N-cyclohexyl maleimide And other maleimide-based monomers. These can be used individually by 1 type or in combination of 2 or more types.

The amount of the structural unit derived from the other vinyl-based monomer in the polymer (iii) is relative to the total amount of the structural unit derived from the alkyl methacrylate monomer and the structural unit derived from the crosslinkable monomer. The rest.

It is preferable that the acrylic multilayer polymer particle has a shell made of a thermoplastic polymer (ii).

The above-mentioned thermoplastic polymer (ii) has a structural unit derived from an alkyl methacrylate monomer. The thermoplastic polymer (ii) may have a structural unit derived from another vinyl-based monomer.

The alkyl methacrylate monomer in the thermoplastic polymer (ii) is preferably an alkyl methacrylate monomer having an alkyl group having 1 to 8 carbon atoms.

Examples of the alkyl methacrylate monomer include methyl methacrylate and butyl methacrylate. These can be used individually by 1 type or in combination of 2 or more types. Among these, methyl methacrylate is preferable.

The amount of the structural unit derived from the alkyl methacrylate monomer in the thermoplastic polymer (ii) is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

Examples of the other vinyl-based monomer in the thermoplastic polymer (ii) include the same ones as the other vinyl-based monomers exemplified in the polymer (iii).

The amount of the structural unit derived from another vinyl-based monomer in the thermoplastic polymer (ii) is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

Examples of the configuration of the core portion and the shell portion of the acrylic multilayer polymer particles include, for example, two-layer polymer particles whose core is a crosslinked rubber polymer (i) and whose shell is a thermoplastic polymer (ii); the core is Polymer (iii), the inner shell is a cross-linked rubber polymer (i), the outer shell is a thermoplastic polymer (ii), a three-layer polymer particle; the core is a certain cross-linked rubber polymer (i), the inner shell Is another type of crosslinked rubber polymer (i), the outer layer is a three-layer polymer particle of thermoplastic polymer (ii); the core is a crosslinked rubber polymer (i), the inner shell is a polymer (iii), and the outer shell Is a three-layer polymer particle of thermoplastic polymer (ii); the core is crosslinked rubber polymer (i), the inner inner shell is polymer (iii), the outer inner shell is crosslinked rubber polymer (i), and the outer shell is 4-layer polymer particles and the like of the thermoplastic polymer (ii).

Among these, three-layer polymer particles whose core is polymer (iii), whose inner shell is a crosslinked rubber polymer (i), and whose outer shell is a thermoplastic polymer (ii) are preferred.

The three-layer polymer particles are more preferably: the core polymer (iii) is 80 to 99.95 mass% of methyl methacrylate, and 0 to 19.95 mass% of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms. Copolymer of a monomer and 0.05 to 2% by mass of a crosslinkable monomer; the crosslinked rubber polymer (i) of the inner shell is 80 to 98% by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms A copolymer of a monomer, an aromatic vinyl monomer of 1 to 19 mass%, and a crosslinkable monomer of 1 to 5 mass%; and the thermoplastic polymer (ii) of the shell is 80 to 100 mass% of methacrylic acid A copolymer of a methyl ester and 0 to 20% by mass of an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms.

From the viewpoint of the transparency of the acrylic multilayer polymer particles, the difference in refractive index between adjacent layers is preferably less than 0.005, more preferably less than 0.004, and even more preferably less than 0.003. In this way, the content of each layer is selected. Polymers are preferred.

The proportion of the outer shell portion in the acrylic multilayer polymer particles is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass. In the core part, the proportion of the layered body containing the crosslinked rubber polymer (i) is preferably 20 to 100% by mass, and more preferably 30 to 70% by mass.

The volume-based average particle diameter of the crosslinked rubber particles used in the present invention is preferably 0.02 to 1 μm, more preferably 0.05 to 0.5 μm, and even more preferably 0.1 to 0.3 μm.

If a crosslinked rubber particle component having such a volume-based average particle diameter is used, it is possible to significantly reduce defects in the appearance of the molded article. The volume-based average particle diameter in the present specification is a value calculated from the particle size distribution data measured by a light scattering light method.

The crosslinked rubber particles can be obtained by any manufacturing method. From the viewpoints of controlling the particle size, making it easy to produce a multilayer structure, and the like, an emulsion polymerization method or a seed emulsion polymerization method is suitably used. The emulsion polymerization method is a method for producing an emulsion containing polymer particles by emulsifying and polymerizing a predetermined monomer. The seed emulsification polymerization method is to emulsify a predetermined monomer and polymerize to obtain seed particles, and then emulsify and polymerize other predetermined monomers in the presence of the seed particles, thereby producing "containing seed particles and coating the same in a substantially concentric circle. Seed particle shell polymer core-shell polymer particle emulsion "method. In the presence of the core-shell polymer particles, it is possible to repeatedly emulsify and polymerize other predetermined monomers as many times as desired, thereby making it possible to manufacture Emulsion of core-shell multilayer polymer particles.

Examples of the emulsifier used in the emulsification polymerization method include dioctyl sodium sulfosuccinate, anionic emulsifiers, and dialkyl sulfosuccinates such as sodium dilauryl sulfosuccinate; twelve Alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium dodecyl sulfate; polyoxyethylene alkyl ethers and polyoxyethylene nonylphenyl non-ionic emulsifiers Ethers, etc .; polyoxyethylene nonylphenyl ether sulfates, such as polyoxyethylene nonylphenyl ether sulfate, nonionic / anionic emulsifiers, polyoxyethylene, etc. Alkyl ether carboxylates such as vinyl alkyl ether sulfates and polyoxyethylene tridecyl ether sodium acetate. These can be used individually by 1 type or in combination of 2 or more types. In order to prevent the foaming property of the emulsifier from becoming extremely large, the number of repeating units of the ethylene oxide unit in the exemplary compounds of the nonionic emulsifier and the nonionic / anionic emulsifier is preferably 30 or less, and more preferably 20 Hereinafter, it is more preferably 10 or less.

The polymerization initiator used in the emulsion polymerization is not particularly limited. Examples include persulfate-based initiators such as potassium persulfate and ammonium persulfate; redox-based initiators such as per sulfoxylate / organic peroxide, persulfate / sulfite, and the like .

The crosslinked rubber particles can be separated from the emulsion obtained by the emulsion polymerization by a conventional method such as a salting out coagulation method, a freeze coagulation method, and a spray drying method. Among these, from the viewpoint that impurities contained in the crosslinked rubber particles can be easily removed by washing with water, the salt-out solidification method and the freeze-solidification method are preferable, and the freeze-solidification method is more preferable. In the freeze coagulation method, an acrylic resin film having excellent water resistance is easily obtained because no coagulant is used.

In addition, before the coagulation step, if the emulsion is filtered with a gold mesh or the like having an opening of 50 μm or less, it is preferable to remove foreign matter mixed in the emulsion.

From the viewpoint of easily dispersing the crosslinked rubber particles evenly during the melt-kneading of the crosslinked rubber particles and the methacrylic resin [A], it is preferable to take out the crosslinked rubber particles in an aggregate of 1000 μm or less, more Preferably, the crosslinked rubber particles are taken out of the aggregates of 500 μm or less. The form of the crosslinked rubber particle aggregate is not particularly limited, and may be, for example, a pellet shape in a state where the shell portions are fused to each other, or may be a powder shape or a granule shape.

The amount of the crosslinked rubber [D] contained in the methacrylic resin composition according to the embodiment of the present invention is preferably 5 to 30 parts by mass, more preferably 10 to 100 parts by mass of the methacrylic resin [A]. ~ 25 parts by mass, and even more preferably 15 to 20 parts by mass.

In the methacrylic resin composition of the present invention, when the methacrylic resin composition contains the crosslinked rubber particles, in order to prevent the crosslinked rubber particles from agglomerating due to sticking or the like, each particle can be uniformly dispersed, but can be added and dispersed. Auxiliary particles. Examples of the dispersion auxiliary particles include methacrylic resin particles. The dispersion auxiliary particles are preferably those having an average particle diameter smaller than the average particle diameter of the crosslinked rubber particles. Specifically, the volume-based average particle diameter of the dispersed auxiliary particles is preferably 0.04 to 0.12 μm, and more preferably 0.05 to 0.1 μm.

From the viewpoint of dispersion effect and the like, the amount of the dispersion auxiliary particles relative to the mass ratio of the crosslinked rubber particles [D] is preferably 0/100 to 60/40, and more preferably 10/90 to 50/50. Even better is 20/80 ~ 40/60.

    [Block copolymer [E]]    

The block copolymer [E] used in the present invention, for example, the end of the molecular chain of polymer B (sometimes referred to as polymer block B) and the molecular chain of polymer A (sometimes referred to as polymer embedding) The ends of segment A) are connected, and the whole bonds are chained or radial.

The polymer blocks constituting the block copolymer are not particularly limited. For example, a block copolymer formed of a polymer block such as polymethyl methacrylate and a polymer block such as polyacrylate can change the compatibility of a methacrylic resin with an aromatic low-molecular compound and the like. Well.

The block copolymer can be produced, for example, by using living polymerization to prepare a polymerization starting point at the end of the polymer block A, and polymerizing the monomers from the starting point to produce a polymer block B. Method [i]; Method [ii] in which polymer block A and polymer block B are separately prepared, and these are subjected to addition or condensation reaction.

At least one of the polymer blocks constituting the block copolymer used in the present invention is preferably selected from the group consisting of 90% by mass or more from the viewpoint of compatibility with the methacrylic resin [A]. Polymers derived from structural units derived from methacrylate; polymers containing structural units derived from styrene and structural units derived from acrylonitrile; structures containing structural units derived from styrene and maleic anhydride Polymers of units; polymers containing structural units derived from styrene, structural units derived from maleic anhydride and structural units derived from methyl methacrylate; or polyvinyl butyraldehyde.

The amount of the block copolymer [E] contained in the methacrylic resin composition according to the embodiment of the present invention is preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass of the methacrylic resin [A]. 0.5 to 25 parts by mass, and even more preferably 1 to 20 parts by mass.

    [Graft copolymer [F]]    

The graft copolymer [F] used in the present invention is, for example, the end of a molecular chain (sometimes referred to as a graft side chain) of the polymer B is connected to a molecular chain (also sometimes referred to as a polymerization) of the polymer A The main chain), and the overall bonding component is branched.

The main chain and the graft side chain constituting the graft copolymer are not particularly limited. For example, a graft copolymer having a main chain including a polyolefin, a polycarbonate, an acrylic copolymer, and the like, and a graft side chain including a polystyrene, a styrene-acrylonitrile copolymer, and an acrylic copolymer. It has characteristics such that the compatibility between a methacrylic resin and an aromatic low-molecular compound becomes good.

The graft copolymer can be produced, for example, by a chain transfer method [i] of polymerizing a monomer as polymer B in the presence of polymer A, and by end of polymer B as a graft side chain Method for copolymerizing a polymer compound into which a polymerizable group is introduced and a monomer as polymer A [ii]; preparing a polymer A as a main chain and a polymer B as a graft side chain, and adding these Formation or condensation reaction method [iii] and so on.

From the viewpoint of compatibility with the methacrylic resin [A], the main chain or at least one graft side chain constituting the graft copolymer used in the present invention is preferably selected from the group consisting of: 90% by mass Polymers derived from the structural units derived from methacrylate above; polymers containing structural units derived from styrene and structural units derived from acrylonitrile; polymers containing structural units derived from styrene and maleic anhydride Polymers of structural units; polymers containing structural units derived from styrene, structural units derived from maleic anhydride and structural units derived from methyl methacrylate; polyvinyl butyral; polycarbonate.

The amount of the graft copolymer [F] contained in the methacrylic resin composition according to the embodiment of the present invention is preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass of the methacrylic resin [A]. 0.5 to 25 parts by mass, and even more preferably 1 to 20 parts by mass.

    [Polycarbonate resin [G]]    

The polycarbonate resin [G] that can be added to the methacrylic resin composition of the present invention is not particularly limited, and examples thereof include polymers obtained by the reaction of a polyfunctional hydroxyl compound and a carbonate-forming compound. In the present invention, an aromatic polycarbonate resin is preferred in terms of compatibility with the methacrylic resin [A] and the transparency of the obtained film.

The polycarbonate resin [G] used in the present invention is, at the point of compatibility with the methacrylic resin [A], the transparency of the obtained film, surface smoothness, etc., at 300 ° C and 1.2Kg. a melt volume flow rate (the MVR) values, preferably 130 ~ 250cm ^3/10 min and more preferably 150 ~ 230cm ^3/10 minutes, and then the best of 180 ~ 220cm ^3/10 min.

In addition, the polycarbonate resin [G] used in the present invention will penetrate through the gel from the viewpoints of compatibility with the methacrylic resin [A], transparency of the resulting film, surface smoothness, and the like. The weight average molecular weight calculated by converting the chromatogram measured by a chromatograph (GPC) into the molecular weight of standard polystyrene is preferably 15,000 to 28,000, more preferably 18,000 to 27,000, and even more preferably 20,000 to 2.4. Million. The MVR value and weight average molecular weight of the polycarbonate resin [G] can be adjusted by adjusting the amounts of the blocking agent and the branching agent.

The glass transition temperature of the polycarbonate resin [G] used in the present invention is preferably 130 ° C or higher, more preferably 135 ° C or higher, and even more preferably 140 ° C or higher. The upper limit of the glass transition temperature of this polycarbonate resin is generally 180 ° C. Here, the glass transition temperature refers to the temperature rise above the room temperature in accordance with JIS K7121, the first temperature increase (first cycle) to 250 ° C at a temperature increase rate of 10 ° C / min, and then cooling to room temperature. When the temperature rise rate was 10 ° C./min from room temperature (second time) to 250 ° C., the intermediate point glass transition temperature of the second time.

The manufacturing method of a polycarbonate resin [G] is not specifically limited. Examples thereof include a phosgene method (interfacial polymerization method) and a melt polymerization method (transesterification method). In addition, the aromatic polycarbonate resin suitable for the present invention may be one obtained by subjecting a polycarbonate resin raw material produced by a melt polymerization method to a treatment for adjusting the amount of terminal hydroxyl groups. In addition, as the polycarbonate resin [G], a commercially available product or other known items can be used.

The polycarbonate resin [G] may include a structural unit having a polyester, polyurethane, polyether, or polysiloxane structure in addition to the polycarbonate structural unit.

The amount of the polycarbonate resin [G] contained in the methacrylic resin composition according to the embodiment of the present invention is preferably 0.1 to 15 parts by mass, and more preferably 100 parts by mass of the methacrylic resin [A]. 0.5 to 10 parts by mass, and even more preferably 1 to 8 parts by mass. Within this range, the compatibility between the methacrylic resin (A) and the polycarbonate resin [G] is good, so a film having high transparency, high refractive index, and good surface smoothness can be easily obtained. In particular, when the amount of the polycarbonate resin [G] is 1 to 4 parts by mass relative to 100 parts by mass of the methacrylic resin [A], the absolute value of the retardation of the film can be reduced.

The methacrylic resin composition used in the present invention may contain other polymers as long as the effects of the present invention are not impaired. Examples of other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionic polymers; polystyrene Styrene resins such as styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, etc .; methyl methacrylate -Styrene copolymer; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, etc .; Polyamides such as nylon 6, nylon 66, polyamide elastomers; phenoxy resins, Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene benzene Base sulfide, silicon modified resin; silicone rubber; styrene-based thermoplastic elastomers such as SEPS, SEBS, SIS; olefin-based rubbers such as IR, EPR, EPDM, etc. The content of these polymers in the methacrylic resin composition is preferably 20% by mass or less, and more preferably 10% by mass or less.

The methacrylic resin composition of the present invention may contain a polymer processing aid. Examples of the polymer processing aid include polymer particles having a particle diameter of 0.05 to 0.5 μm that can be produced by an emulsion polymerization method. The polymer particles may be single-layer particles containing a polymer having a single composition ratio and a single limiting viscosity, or may be multilayer particles containing two or more polymers having different composition ratios or limiting viscosities. Among them, the following can be cited as preferred examples: particles having a double-layered structure in which the inner layer includes a polymer layer having a low limiting viscosity and the outer layer includes a polymer layer having a high limiting viscosity of 5 dl / g or more. As a polymer processing aid, the limiting viscosity is preferably 3 to 6 dl / g.

The amount of the polymer processing aid contained in the methacrylic resin composition according to the embodiment of the present invention is preferably 0.1% by mass or more and 7% by mass or less with respect to 100 parts by mass of the methacrylic resin [A]. It is 0.2 mass% or more and 5 mass% or less, and more preferably 0.5 mass% or more and 4 mass% or less.

The method for preparing the methacrylic resin composition of the present invention is not particularly limited. Examples thereof include a method of polymerizing a monomer mixture containing methyl methacrylate in the presence of the compound [B] to produce a methacrylic resin [A]; a method of combining the methacrylic resin [A] with a compound [B] Methods of melt-kneading and the like. Among these, the steps of the melt-kneading method are simple and therefore preferable. When melt-kneading, other polymers and additives can be mixed according to demand. After mixing the methacrylic resin [A] with other polymers and additives, it can be mixed with the compound [B]; the compound [B] can also be mixed with other After the polymer and additives are mixed, they are mixed with the methacrylic resin [A]; other methods may also be used. The kneading can be performed using a known mixing device or kneading device such as a kneader-ruder, a single-shaft or multi-shaft extruder, a mixing drum, and a Banbury mixer. Among these, a biaxial extruder is preferred. The temperature at the time of mixing / kneading can be appropriately adjusted according to the melting temperature of the methacrylic resin [A] and the compound [B] used, but it is preferably 110 ° C to 300 ° C.

The methacrylic resin composition of the present invention preferably contains methacrylic resin [A] 70 to 99.99% by mass, more preferably 90 to 99.98% by mass, and even more preferably 95 to 99.96% by mass. When a methacrylic resin [A] is included in this range, transparency and heat resistance will be excellent.

The methacrylic resin composition of the present invention preferably contains the compound [B] in an amount of 0.01 to 30% by mass, more preferably 0.02 to 10% by mass, and even more preferably 0.04 to 5% by mass. Within this range, the effect of suppressing thermal decomposition is obtained, and the obtained methacrylic resin composition is excellent in transparency.

The methacrylic resin composition of the present invention preferably has a glass transition temperature of 100 ° C or higher, more preferably 105 ° C or higher, and even more preferably 110 ° C or higher. Although the upper limit of the glass transition temperature of the methacrylic resin composition is not particularly limited, it is preferably 130 ° C.

The weight average molecular weight (Mw) determined by measuring the methacrylic resin composition of the present invention by GPC is preferably 50,000 to 200,000, more preferably 55,000 to 160,000, and even more preferably 60,000 to 120,000. It is preferably 70,000 to 100,000. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) determined by measuring the methacrylic resin composition by GPC is preferably 1.0 to 5.0, more preferably 1.2 to 3.0, even more preferably 1.3 to 2.0, and particularly preferably 1.3 ~ 1.7. When the Mw and molecular weight distribution (Mw / Mn) are within this range, the moldability of the methacrylic resin composition is good, and a molded body excellent in impact resistance and toughness is easily obtained.

The melt flow rate determined by the methacrylic resin composition of the present invention is measured at 230 ° C and a load of 3.8 kg, preferably 0.1 to 30 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes, and most preferably 1.0 to 15g / 10 minutes.

The haze of the methacrylic resin composition of the present invention under a thickness of 3.2 mm is preferably 3.0% or less, more preferably 2.0% or less, and even more preferably 1.5% or less.

In order to improve convenience during storage, transportation, or molding, the methacrylic resin composition of the present invention may be in the form of pellets or the like.

The methacrylic resin composition of the present invention can be used as a molded body by a conventional molding method. Examples of the molding method include a T-die method (lamination method, coextrusion method, etc.), an inflation method (coextrusion method, etc.), a compression molding method, a blow molding method, a calendering method, a vacuum molding method, and an injection molding method. Methods (embedding method, two-color method, pressure method, core-back method, sandwich method, etc.), melt forming methods, and solution casting methods.

In such a molding method, a mold or the like is generally used for molding a resin composition. Examples thereof include a roll for sheet forming, a roll for film forming, a calender roll, a mold for compression molding, a mold for blow molding, a mold for vacuum forming, a mold for injection molding, and a mold for casting polymerization. The mold or the like used for forming is not necessarily made of metal, and may be, for example, made of rubber or reinforced glass. Since the methacrylic resin composition of the present invention is less prone to mold contamination, it can be applied to production in which continuous molding is performed for a long time, production in which repeated molding is performed multiple times, and the like.

Examples of uses of the molded article of the present invention include signboard parts such as advertising columns, standing signs, outdoor signboards, door signboards, and roof signboards; display parts such as display cases, dividers, and storefront displays Fluorescent lampshade, atmosphere lighting lampshade, lampshade, luminous ceiling, light wall, chandelier and other lighting parts; interior parts such as chandelier and mirror; door, vault, safety window glass, partition wall, stair guard, balcony Fenders, construction parts such as roofs of leisure buildings; aircraft windshields, driving sunshades, locomotives, motorboat windshields, bus sunshades, automobile side sunshades, rear sunshades, and head wings And related parts of transportation devices such as headlights and lampshades; electronic equipment parts such as nameplates for audio and video, sound covers, TV protection covers, display covers for vending machines; medical equipment such as heat preservation boxes and X-ray equipment parts Parts; mechanical housings, instrument covers, experimental devices, scales, dials, observation windows and other equipment-related parts; light guide plates and films for surface light of display devices Optical components such as light guide plates and films for backlights, liquid crystal protection plates, Fresnel lenses, lenticular lenses, front panels for various displays, diffusers, reflective materials, etc .; road signs, guide plates, convex mirrors, soundproof walls And other transportation-related parts; surface materials for automobile interiors, surface materials for mobile phones, and film members such as film; cover materials for washing machines; components for home appliances such as control panels and top panels for electronic pots; others such as greenhouses , Large water tanks, water tanks, clock panels, bathtubs, sanitary equipment, table mats, game parts, toys, masks for face protection when welding, etc.

The molded article of the present invention is particularly suitable for use in, for example, various cover plates, various terminal boards, printed wiring boards, speakers, microscopes, binoculars, and cameras, from the viewpoint of excellent weather resistance and suppressing the overflow of ultraviolet absorbers. , Clocks, and other optical equipment; In addition, as image, optical recording, optical communication, information equipment related parts, such as cameras, VTRs, projection TVs and other finder, filter, Mikasa, Fresnel Ear lenses, protective films for various optical disc (VD, CD, DVD, MD, LD, etc.) substrates, optical switches, optical connectors, liquid crystal displays, light guide films / sheets for liquid crystal displays, flat displays, light guide films for flat displays / Sheet, plasma display, light guide film / sheet for plasma display, light guide film / sheet for electronic paper, retardation film / sheet, polarizing film / sheet, polarizer protective film / sheet, polarizer protective film / sheet , Wavelength plate, light diffusing film / sheet, diaphragm film / sheet, reflective film / sheet, anti-reflection film / sheet, viewing angle expanding film / sheet, anti-glare film / sheet, brightness enhancement film / sheet, liquid crystal and electroluminescence Display element substrate and touch surface , A touch panel light directing film / sheet, various front side panel and the spacer or the like between the various modules for various optical purposes.

Specifically, it can be used for various liquid crystal display elements such as mobile phones, digital information terminal equipment, navigation, automotive liquid crystal displays, liquid crystal monitors, dimming panels, OA equipment displays, AV equipment displays, and electroluminescence. Display elements or touch panels. In addition, from the viewpoint of excellent weather resistance, it is also particularly suitable for use in, for example, building interior and exterior components, curtain walls, roof components, roof materials, window components, rainwater pipes, exteriors, wall materials, and floor materials. , Structural materials, components for road construction, retro-reflective films / sheets, agricultural films / sheets, lighting covers, kanbans, light-transmitting sound-proof walls and other known building materials.

The formed body of the present invention can be used as a solar cell, and can also be used for a solar cell surface protective film, a solar cell packaging film, a solar cell back surface protective film, a solar cell base film, a gas barrier film, and the like.

The method of producing the film of the present invention as an aspect of the molded body is not particularly limited. For example, the film of the methacrylic resin composition can be formed by a conventional method such as a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, and a blow molding method to obtain the film of the present invention. . Among these, the extrusion molding method is preferred. By extrusion molding, a film having improved toughness, excellent handleability, and excellent balance between toughness and surface hardness and rigidity can be obtained. The temperature of the methacrylic resin composition discharged from the extruder is preferably set to 160 to 270 ° C, and more preferably 220 to 260 ° C.

In the extrusion molding method, from the viewpoint of obtaining a film with good surface smoothness, good specular gloss, and low haze, it is preferable to include the above-mentioned methacrylic resin composition extruded from a T-shaped die in a molten state. Method, which is then clamped into two or more mirror rollers or mirror tapes to perform the forming step. The mirror roller or mirror belt is preferably made of metal. The linear pressure between a pair of mirror rollers or mirror belts is preferably 2 N / mm or more, more preferably 10 N / mm or more, and even more preferably 30 N / mm or more.

In addition, the surface temperature of the mirror roller or the mirror belt is preferably 130 ° C or lower. In addition, the surface temperature of at least one of the pair of mirror rollers or mirror belts is preferably 60 ° C or higher. When set to such a surface temperature, the methacrylic resin composition discharged from the extruder can be cooled faster than natural cooling, and it is easy to produce a film having excellent surface smoothness and low haze.

The film of the present invention may be subjected to a stretching treatment. By the stretching treatment, a film with improved mechanical strength and less cracking can be obtained. The stretching method is not particularly limited, and examples thereof include a uniaxial stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method. From the viewpoint of uniformly stretching and obtaining a high-strength film, the temperature during stretching is preferably 100 to 200 ° C, and more preferably 110 to 160 ° C. Under normal length basis, it is extended at 100 ~ 5000% / min. It is preferable to extend so that the area ratio becomes 1.5 to 8 times. After stretching, a film with little heat shrinkage can be obtained by heat fixing.

The thickness of the film of the present invention is not particularly limited, and when used as an optical film, the thickness is preferably 1 to 300 μm, more preferably 10 to 100 μm, and even more preferably 15 to 80 μm.

The haze of the film of the present invention in a thickness of 40 μm is preferably 0.2% or less, and more preferably 0.1% or less. The film of the present invention having a haze in the above range has excellent surface gloss and transparency. When the film of the present invention is used as an optical member such as a liquid crystal protective film and a light guide film, the utilization efficiency of light from a light source is improved, which is preferable. Furthermore, since the film of the present invention is excellent in processability, fine and dense surface shaping can be applied.

The film of the present invention is suitable for a polarizer protective film, a retardation film, a liquid crystal protective plate, a surface material of a mobile information terminal device, a display window protective film of a mobile information terminal device, a light guide film, a silver nanometer wire and a nanometer. The carbon tube is coated on the surface of the transparent conductive film, the front panel of various displays, etc., and is especially suitable for polarizer protective films.

The film of the present invention can also be used in fields other than the optical field, such as IR filter film, anti-crime film, anti-shatter film, decorative film, metal decorative film, back sheet for solar cells, front sheet for flexible solar cells, shrinkage Film, film for in-mold label, gas barrier substrate film, etc.

The surface of the film of the present invention may be provided with a functional layer. Examples of the functional layer include a hard coating layer, an anti-glare layer, an anti-reflection layer, an anti-adhesion layer, a diffusion layer, an anti-glare layer, an antistatic layer, an antifouling layer, and a slippery layer containing fine particles.

The polarizing plate using the film of the present invention includes at least a polarizer and the film of the present invention laminated on the polarizer. The film of the present invention may be laminated on both sides of a polarizer, or may be laminated on one side. When a single-area layer of the polarizer is used as the polarizer protective film, an optical film other than the film of the present invention can be laminated on the other side. Examples of the optical film include a polarizer protective film, a viewing angle adjustment film, a retardation film, and a brightness-up film. Lamination can be performed via an adhesive layer.

The polarizing plate using the film of the present invention can be used in an image display device. Specific examples of the image display device include a self-luminous display device such as an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED: Field Emission Display), and a liquid crystal display (LCD). . A liquid crystal display device includes a liquid crystal cell and the above-mentioned polarizing plate arranged on at least one side of the liquid crystal cell.

Since the film of the present invention is excellent in thermal decomposition resistance and has impact resistance, it is suitable as a film used in an organic electroluminescence lighting device or an organic electroluminescence display device.

Examples

Hereinafter, the present invention will be specifically described by examples and comparative examples, but the present invention is not limited to the following examples. The measurement of physical properties and the like was performed by the following method.

    (Polymerization conversion rate)    

A column (Inert CAP 1 (df = 0.4 μm, 0.25 mm I.D. × 60 m) manufactured by GL Sciences Inc.) was attached to a gas chromatograph GC-14A manufactured by Shimadzu Corporation, and the injection temperature was set to 180 ° C. The detector temperature was set to 180 ° C, and the column temperature was increased from 60 ° C (for 5 minutes) to 200 ° C at a heating rate of 10 ° C / minute, and then held at 200 ° C for 10 minutes. The polymerization conversion was calculated.

    (Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution)    

A gel permeation chromatography (GPC) was used to measure the chromatogram under the following conditions to calculate a value converted to the molecular weight of standard polystyrene. In the GPC chart, the point at which the slope of the peak on the high molecular weight side changes from zero when the retention time is shorter and the point where the slope of the peak on the low molecular weight side changes from negative to zero when the retention time is shorter As the baseline.

GPC device: made by Tosoh Corporation, HLC-8320

Detector: Differential refractive index detector

Tubular string: A device formed by connecting two TSKgel SuperMultipore HZM-Ms made by Tosoh Corporation and SuperHZ4000 in series.

Eluent: Tetrahydrofuran

Dissolving agent flow rate: 0.35ml / min

Column temperature: 40 ℃

Correction line drawing: made using 10 points of standard polystyrene

    (Glass transition temperature Tg)    

In accordance with JIS K7121, a differential scanning calorimeter (DSC-50 (Product No.), manufactured by Shimadzu Corporation) was used to raise the temperature of the methacrylic resin and the methacrylic resin composition to 250 ° C for the first time, and then After cooling to room temperature, the temperature was raised from room temperature to 250 ° C for a second time at 10 ° C / minute, and the DSC curve was measured under these conditions. The intermediate-point glass transition temperature was determined from the DSC curve measured at the second temperature increase (second round), and this was used as the glass transition temperature in the present invention.

    (Thermal weight retention)    

Using a thermogravimetric measuring device (TGA-50, manufactured by Shimadzu Corporation), the weighed methacrylic resin composition was heated from room temperature to 290 at a rate of 20 ° C / minute in an air environment (flow rate 50ml / min). ℃. Weighing was performed at a time point of reaching 290 ° C and a time point of 30 minutes thereafter, and the thermal weight retention was calculated by the following formula. The larger the thermogravimetric retention, the better the thermal decomposition resistance.

Thermal weight retention (%) = (weight at the time point at 290 ° C for 30 minutes) / (weight at the time point at 290 ° C) × 100

    (Total transmittance)    

Test pieces were cut from unstretched film or biaxially stretched film. In accordance with JIS K7361-1, the total transmittance of the test piece was measured using a haze meter (manufactured by Murakami Color Research Institute, HM-150). The methacrylic resin composition was hot-pressed to obtain a molded body having a thickness of 3.2 mm, and the total light transmittance was measured in the same manner as described above.

    (Haze)    

Test pieces were cut from unstretched film or biaxially stretched film. The haze was measured on the test piece in accordance with JIS K 7136 using a haze meter (manufactured by Murakami Color Research Institute, HM-150). The methacrylic resin composition was hot-pressed to obtain a molded body having a thickness of 3.2 mm, and the haze was measured in the same manner as described above.

    (Roller contamination)    

A film-making machine (type FS-5) manufactured by Optical Control System was used at a cylinder temperature of 290 ° C, a T-die temperature of 290 ° C, an edge gap (lip gap) of 0.5 mm, a discharge amount of 2.7 kg / hr, and a drum temperature of 85 ° C. The film was extruded into a methacrylic resin composition under the conditions of a film exit speed of 2.2 m / min to produce a film having a thickness of 100 μm. The surface of the metal roller through which the film passed was visually observed, and the time from the start of film formation to the time when white mist was slightly generated on the roller surface was measured. It was evaluated as [A] when it was more than 5 minutes, and "B" when it was less than 5 minutes. ".

    (Production Example 1) (Production of methacrylic resin [A-1])    

Nitrogen substitution was performed in an autoclave equipped with a stirring wing and a three-way cock. At room temperature, 1600 kg of toluene, 80 kg of 1,2-dimethoxyethane, and isobutyl bis (2,6-di-third-butyl-4-methylphenoxy) at a concentration of 0.45 M were placed therein. 73.3 kg (42.3 mol) of a toluene solution of aluminum and a solution of second butyl lithium (solvent: cyclohexane 95%, n-hexane 5%) at a concentration of 1.3 M (8.44 kg (14.1 mmol)). While stirring, 550 kg of distilled and purified methyl methacrylate was dripped at 15 ° C for 30 minutes. After completion of the dropping, the mixture was stirred at 15 ° C for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion rate of methyl methacrylate at this time point was 100%.

1500 kg of toluene was added to the obtained solution to perform dilution. Next, a large amount of methanol was poured into the diluted solution to obtain a precipitate. The obtained precipitate was dried at 80 ° C and 140Pa for 24 hours to obtain Mw of 70,000, molecular weight distribution of 1.06, syndiotacticity (rr) of 75%, glass transition temperature of 131 ° C, and origin of methyl methacrylate The content of the structural unit of the ester is 100% by mass of the methacrylic resin [A-1].

    (Production Example 2) (Production of methacrylic resin [A-2])    

Nitrogen substitution was performed in an autoclave equipped with a stirrer and a collecting tube. 100 parts by mass of purified methyl methacrylate, 2,2'-azobis (2-methylpropionitrile) (hydrogen removal capacity: 1%, 1-hour half-life temperature: 83 ° C), 0.0054 mass Parts and 0.200 parts by mass of n-octyl mercaptan, followed by stirring to obtain a raw material liquid. Nitrogen was sent to this raw material liquid to remove dissolved oxygen in the raw material liquid.

The raw material liquid was placed in a tank-type reactor connected to the autoclave by piping to 2/3 of the capacity. The temperature was maintained at 140 ° C, and the polymerization reaction was first performed in a batch manner. When the polymerization conversion rate was 55% by mass, the raw material liquid was supplied from the autoclave to the tank-type reactor at a flow rate of an average residence time of 150 minutes, and the reaction was excluded from the tank-type reactor at a flow rate equivalent to the supply flow rate of the raw material liquid. Liquid, maintaining the temperature at 140 ° C and switching to a continuous flow polymerization reaction. After the switching, the polymerization conversion rate in the normal state was 48% by mass.

At a flow rate with an average residence time of 2 minutes, the reaction liquid excluded from the tank reactor in a stable state was supplied to a multi-tube heat exchanger with an internal temperature of 230 ° C. to warm it. Next, the heated reaction solution was introduced into a flash evaporator to remove volatile components containing unreacted monomer as a main component, thereby obtaining a molten resin. The molten resin from which the volatile components were removed was supplied to a biaxial extruder with an internal temperature of 260 ° C., was discharged in a strand shape, and was cut with a pelletizer to obtain Mw of 112,000, molecular weight distribution of 1.86, and syndiotacticity ( Methacrylic resin [A-2] having a rr) of 52%, a glass transition temperature of 120 ° C., and a content of structural units derived from methyl methacrylate of 100% by mass.

    (Production Example 3) (Production of crosslinked rubber particles (m))    

In a 100-liter glass-lined reaction tank equipped with a condenser, a thermometer, and a stirrer, 48 kg of deionized water was placed, and then 416 g of sodium stearate, 128 g of sodium dodecylsarcosinate, and sodium carbonate were placed. 16g to dissolve it. Next, 11.2 kg of methyl methacrylate and 110 g of allyl methacrylate were placed, and the temperature was raised to 70 ° C while stirring. Thereafter, 560 g of a 2% potassium persulfate aqueous solution was added to start emulsion polymerization. The internal temperature rises due to the exothermic heat generated by the polymerization, and then the internal temperature starts to decrease. After lowering to 70 ° C, the mixture was stirred at 70 ° C for 30 minutes to emulsify and polymerize to obtain an emulsion containing seed particles.

To the emulsion containing the seed particles, 720 g of a 2% sodium persulfate aqueous solution was added. After 60 minutes, a mixture containing 12.4 kg of butyl acrylate, 1.76 kg of styrene, and 280 g of allyl methacrylate was dropped. After completion of the dropping, the mixture was stirred for 60 minutes to emulsify and polymerize to obtain an emulsion containing two core-shell particles.

To the emulsion containing the core-shell two-layer particles, 320 g of a 2% potassium persulfate aqueous solution was added, and it took another 30 minutes to add a mixture containing 6.2 kg of methyl methacrylate, 0.2 kg of methyl acrylate, and 200 g of n-octyl mercaptan. . After the addition was completed, the mixture was stirred for 60 minutes to emulsify and polymerize, and then cooled to room temperature to obtain an emulsion containing core-shell 3-layer crosslinked rubber particles (m) having a volume-based average particle diameter of 0.23 μm.

    (Production Example 4) (Production of polymer particles (n))    

In a 100-liter glass-lined reaction tank equipped with a condenser, a thermometer, and a stirrer, 48 kg of deionized water was placed, followed by 252 g of a surfactant ("PELEX SS-H" manufactured by Kao Corporation). Let it dissolve. The reaction tank was heated to 70 ° C. Thereafter, 160 g of a 2% potassium persulfate aqueous solution was added thereto, and then a mixture containing 3.04 kg of methyl methacrylate, 0.16 kg of methyl acrylate, and 15.2 g of n-octyl mercaptan was added at a time to start emulsion polymerization. The stirring was continued for 30 minutes from the time point when the exothermic heat generated by the polymerization reaction disappeared.

Then, 160 g of a 2% potassium persulfate aqueous solution was added thereto, and then a mixture containing 27.4 kg of methyl methacrylate, 1.44 kg of methyl acrylate, and 98 g of n-octyl mercaptan was continuously dripped over 2 hours. After completion of the dropping, the mixture was stirred for 60 minutes to perform emulsion polymerization. The resulting emulsion was cooled to room temperature. Thus, an emulsion containing (meth) acrylate-based polymer particles (n) having a volume-based average particle diameter of 0.12 μm and a limiting viscosity of 0.44 g / dl was obtained.

    (Production Example 5) (Production of crosslinked rubber particles (D-1))    

The emulsion containing the particles (m) obtained in Production Example 3 and the emulsion containing the particles (n) (dispersion assisting particles) obtained in Production Example 4 were determined by the mass of the particles (m): particles (n) The ratio becomes 2: 1 mixed. It took 2 hours to freeze the mixed emulsion at -20 ° C. The frozen mixed emulsion was placed in twice the amount of warm water at 80 ° C to thaw it to obtain a slurry. This slurry was held at 80 ° C for 20 minutes, followed by dehydration and drying at 70 ° C to obtain a powder containing crosslinked rubber particles (D-1).

    (Production Example 6) (Production of block copolymer [E-1])    

In a three-necked flask substituted with nitrogen inside, 735 kg of toluene dried at room temperature, 36.75 kg of 1,2-dimethoxyethane, and isobutylbis (2,6-di-third-butyl) 4-methylphenoxy) aluminum 20 mol in toluene solution 39.4 kg. Then, 1.17 mol of second butyl lithium was added thereto. Furthermore, 39.0 kg of methyl methacrylate was added, and it was made to react at room temperature for 1 hour, and the methyl methacrylate polymer [c1 ₁ ] was obtained. The weight average molecular weight Mw _c11 of the methyl methacrylate polymer [c1 ₁ ] contained in the reaction solution was 45,800.

Next, the reaction solution was adjusted to -25 ° C for 0.5 hour, and a mixed solution of 29.0 kg of n-butyl acrylate and 10.0 kg of benzyl acrylate was dropped, and the polymerization reaction was continued from the terminal of the methyl methacrylate polymer [c1 ₁ ]. A diblock copolymer [E-1] containing a methyl methacrylate polymer block [c1 ₁ ] and an acrylate polymer block [c2] having n-butyl acrylate and benzyl acrylate was obtained. The block copolymer [E-1] contained in the reaction solution had a weight average molecular weight Mw _CB-1 of 92,000, and a weight average molecular weight Mw _CB-1 / number average molecular weight Mn _CB-1 of 1.06. Since the weight average molecular weight of the methyl methacrylate polymer [c1 ₁ ] is 45800, the weight average molecular weight of the acrylate polymer [c2] including n-butyl acrylate and benzyl acrylate is determined to be 46200. The ratio of the benzyl acrylate contained in the acrylate polymer [c2] was 25.5% by mass.

Next, 4 kg of methanol was added to the reaction solution to stop the polymerization reaction. Thereafter, a large amount of methanol was poured into the reaction solution to precipitate the diblock copolymer [E-1], and the precipitate was filtered and dried at 80 ° C. and 1 torr (about 133 Pa) for 12 hours. The ratio of the mass of the methacrylate polymer block [c1 ₁ ] to the mass of the acrylate polymer block [c2] was 50/50.

    <Example 1>    

60 parts by mass of methacrylic resin [A-1], 40 parts by mass of methacrylic resin [A-2], 1.0 part by mass of phenolic hydroxyl-containing compound [KH-6021], and ultraviolet absorber [LA-F70] 0.9 parts by mass, 1 part by mass of the block copolymer [E-1] and 2 parts by mass of the processing aid [H-1], mixed in a biaxial extruder (manufactured by TECHNOVEL), product name: KZW20TW-45MG- NH-600), melt-kneading was performed at 250 ° C, and the melt-kneaded product was extruded to produce a methacrylic resin composition [1]. The glass transition temperature of the methacrylic resin composition [1] was measured. The results are shown in Table 1.

The methacrylic resin composition [1] was hot-pressed to obtain a plate-shaped formed body of 50 mm × 50 mm × 3.2 mm. This plate-shaped molded body was used to measure the total light transmittance and haze. The results are shown in Table 1.

The methacrylic resin composition [1] was dried at 80 ° C for 12 hours. Use 20mm A uniaxial extruder (manufactured by OCS) extrudes the methacrylic resin composition [1] from a T-die with a width of 150 mm at a resin temperature of 260 ° C and feeds it into a roller with a surface temperature of 85 ° C to obtain a width An unstretched film of 110 mm and a thickness of 160 μm. The smoothness and strength of the produced unstretched film were measured. The evaluation results are shown in Table 1.

From the unstretched film having a thickness of 160 μm, a small piece of 100 mm × 100 mm was cut so that both sides thereof were parallel to the extrusion direction. This small piece was set on a Pantograph type biaxial stretching tester (manufactured by Toyo Seiki Co., Ltd.) at a glass transition temperature + 10 ° C at 150% / min in a direction parallel to the extrusion direction, Perform uniaxial extension to twice the length. Next, at a temperature of glass transition temperature + 10 ° C, at 150% / min, in a direction perpendicular to the extrusion direction, uniaxial extension is performed to twice the length, followed by holding for 10 seconds, and finally taken out at room temperature. It was then rapidly cooled to obtain a biaxially stretched film having an area stretching ratio of 4 times and a thickness of 40 μm. About the obtained biaxially stretched film, the total light transmittance and haze were measured. The results are shown in Table 1.

    <Examples 2 to 8, Comparative Examples 1 to 2>    

A methacrylic resin composition [2] to [10] was produced in the same manner as in Example 1 except that the blending ratios shown in Tables 1 to 2 were used, and physical properties were measured in the same manner as in Example 1.

The evaluation results are shown in Tables 1 to 2.

An unstretched film and a biaxially stretched film were obtained in the same manner as in Example 1, except that the methacrylic resin composition [2] to [10] was used instead of the methacrylic resin composition [1]. The evaluation results are shown in Tables 1 to 2.

The meanings of the abbreviations in the table are as follows.

    Compound containing phenolic hydroxyl group [B]    

KH-6021: Bisphenol A novolac resin (manufactured by DIC, weight average molecular weight Mw = 3000, molecular weight distribution Mw / Mn = 3.33, number of phenolic hydroxyl groups in one molecule = average 7.5.

VP8000: Poly-p-hydroxystyrene (manufactured by Soda Co., Ltd., weight average molecular weight Mw = 9800, molecular weight distribution Mw / Mn = 1.09, the number of phenolic hydroxyl groups in one molecule = 75 on average.

    UV absorber [C]    

LA-31: 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4-third octylphenol] (made by ADEKA Corporation)

LA-F70: 2,4,6-ginseng (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-tris (Made by ADEKA)

    Polycarbonate resin [G]    

G-1: a polycarbonate resin (Sumika Styron Polycarbonate Corporation, SD POLYCA TR-2201 (product number) linear, MVR (300 ℃, 1.2Kg, 10 min; in accordance with JIS K7210) = 210cm ^3/10 min Mw = 22000, Mw / Mn = 2.0), and the number of phenolic hydroxyl groups in one molecule = 0 to two.

    Processing Aid [H]    

H-1: MITSUBISHI RAYON company METABLEN P550A (average degree of polymerization: 7734, 88% by mass of structural units derived from methyl acrylate, 12% by mass of structural units derived from butyl acrylate)

    Antioxidant [I]    

I-1: Hindered phenolic antioxidant (Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], molecular weight 1178, number of phenolic hydroxyl groups in one molecule = 4.

Claims (16)

    A thermoplastic methacrylic resin composition comprising 70 to 99.99% by mass of a methacrylic resin [A] and 0.01 to 30% by mass of a molecular weight of 2 to 300,000 and having 3 or more phenolic properties in one molecule It is composed of a hydroxy compound [B].         The methacrylic resin composition according to claim 1, wherein the methacrylic resin [A] contains 90% by mass or more of a structural unit derived from methyl methacrylate.         The methacrylic resin composition according to claim 1, wherein the methacrylic resin [A] contains a structural unit derived from methyl methacrylate and a structural unit having a ring structure in the main chain.         For example, the methacrylic resin composition of claim 3, in which the structural unit has a ring structure on the main chain, the ring structure includes a> CH-OC (= O) -group structural unit, and the ring structure includes -C ( = O) -OC (= O) -group structural unit, ring structure containing -C (= O) -NC (= O) -group, or ring structure containing> CH-O-CH <group Building blocks.         The methacrylic resin composition according to any one of claims 1 to 4, wherein the compound [B] is a polyvinyl phenol, a terpene phenol resin, a resol type phenol resin or a novolac type phenol resin .         The methacrylic resin composition according to any one of claims 1 to 4, further comprising an ultraviolet absorber [C].         The methacrylic resin composition according to any one of claims 1 to 4, further comprising a crosslinked rubber [D].         The methacrylic resin composition according to any one of claims 1 to 4, further comprising a block copolymer [E] or a graft copolymer [F].         The methacrylic resin composition according to any one of claims 1 to 4, further comprising a polycarbonate resin [G].         A formed body comprising the methacrylic resin composition according to any one of claims 1 to 4.         A film comprising the methacrylic resin composition according to any one of claims 1 to 4.         An optical film comprising the thin film as claimed in claim 11.         A polarizer protective film comprising the film as claimed in claim 11.         A retardation film comprising the thin film as claimed in claim 11.         A polarizing plate is formed by laminating at least one film as claimed in claim 11.         A method for producing a molded article, comprising: 70 to 99.99% by mass of a methacrylic resin [A]; 0.01 to 30% by mass; a molecular weight of 2 to 300,000; and 3 or more phenolic hydroxyl groups in one molecule. Compound [B] is melt-kneaded to obtain a thermoplastic methacrylic resin composition; the methacrylic resin composition is melt-molded.