JPWO2017200032A1 - Methacrylic resin composition and molded body - Google Patents

Abstract

A methacrylic resin [A] such as a resin containing a structural unit derived from methyl methacrylate and a structural unit having a ring structure in the main chain, and a polyvinylphenol, a terpenephenol resin, a novolac type Thermoplastic methacrylic resin composition containing 0.01 to 30% by mass of a compound [B] having a molecular weight of 2,000 to 300,000 and having three or more phenolic hydroxyl groups in one molecule, such as phenol resin object. A molded body comprising the resin composition.

Description

  The present invention relates to a methacrylic resin composition and a molded body. More specifically, the present invention relates to a methacrylic resin composition suitable for obtaining a molded article that can be melt-molded while suppressing thermal decomposition of the methacrylic resin and mold contamination, and hardly causes bleeding out, and the methacrylic resin. The present invention relates to a molded article comprising the composition.

  As a material for the polarizer protective film, a methacrylic resin that can be expected to have low moisture permeability instead of high moisture permeability triacetylcellulose has been studied. However, methacrylic resin is easily decomposed when it is overheated during melt molding. Substances generated by this thermal decomposition may cause bubbles (silver streaks) in the molded body or mold contamination.

  In order to suppress thermal decomposition of methacrylic resin, Patent Document 1 discloses pentaerythritol-tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], bis- [3, Aromatic hydroxy compounds such as 3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester and the like containing methyl methacrylate units of 50% by weight or more and other unsaturated vinyl units And adding to a methyl methacrylate copolymer comprising: However, even if the thermal decomposition of the methacrylic resin can be suppressed by the addition of the aromatic hydroxy compound shown in Patent Document 1, mold contamination by the aromatic hydroxy compound or bleeding out of the aromatic hydroxy compound may be caused. .

JP-A-5-209102

  An object of the present invention is to provide a methacrylic resin composition suitable for obtaining a molded article that can be melt-molded while suppressing thermal decomposition of methacrylic resin and mold contamination, and hardly causes bleeding out.

  As a result of intensive studies in order to solve the above problems, the present invention including the following modes has been completed.

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

[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 in the main chain. .
[4] A structural unit having a ring structure in the main chain, a structural unit containing a> CH—O—C (═O) — group in the ring structure, —C (═O) —O—C (═O) — group Is a structural unit containing a —C (═O) —N—C (═O) — group in the ring structure, or a structural unit containing a> CH—O—CH <group in the ring structure. The methacrylic resin composition according to [3].

[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 resol type phenol resin, or a novolac type phenol resin.
[6] The methacrylic resin composition according to any one of [1] to [5], further containing an ultraviolet absorber [C].
[7] The methacrylic resin composition according to any one of [1] to [6], further containing a crosslinked rubber [D].
[8] The methacrylic resin composition according to any one of [1] to [7], further containing a block copolymer [E] or a graft copolymer [F].
[9] The methacrylic resin composition according to any one of [1] to [8], further containing a polycarbonate resin [G].

[10] A molded article comprising the methacrylic resin composition according to any one of [1] to [9].
[11] A film comprising the methacrylic resin composition according to any one of [1] to [9].
[12] An optical film comprising the film according to [11].
[13] A polarizer protective film comprising the film according to [11].
[14] A retardation film comprising the film according to [11].
[15] A polarizing plate obtained by laminating at least one film according to any one of [11] to [14].

[16] Methacrylic resin [A] 70 to 99.99 mass%, compound having a molecular weight of 2,000 to 300,000 and having three or more phenolic hydroxyl groups in one molecule [B] 0.01 to 30 mass% And kneading to obtain a thermoplastic methacrylic resin composition,
The manufacturing method of a molded object which has melt-molding this methacrylic resin composition.

  Even if the methacrylic resin composition of the present invention is overheated in melt molding, it is difficult to thermally decompose and hardly cause mold contamination. The molded body made of the methacrylic resin composition of the present invention hardly causes bleeding out. Since the molded body, particularly the film, comprising the methacrylic resin composition of the present invention has high transparency, low moisture permeability, and high heat resistance, it can be used in fields where such features can be utilized, for example, in the optical field. .

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

  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 containing only a structural unit derived from methyl methacrylate (hereinafter, this may be referred to as methacrylic resin [A0]), or methyl methacrylate. Even a random copolymer containing a structural unit derived from (2) and a structural unit derived from another monomer (hereinafter, this random copolymer may be referred to as a methacrylic resin [A1]). Alternatively, a random copolymer containing a structural unit derived from methyl methacrylate and a structural unit having a ring structure in the main chain (hereinafter, this random copolymer may be referred to as a methacrylic resin [A2]). It may be. A commercially available methacrylic resin can be used as the methacrylic resin [A0] or [A1].

The methacrylic resin [A] has a polystyrene-equivalent weight average molecular weight Mw _A calculated based on a chromatogram obtained by gel permeation chromatography, preferably 50,000 to 200,000, more preferably 550,000 to 160,000. More preferably, it is 60,000 to 120,000. As Mw _A increases, the strength of the molded product obtained from the methacrylic resin [A] tends to increase. The lower the Mw _{A, the} better the processability of the methacrylic resin [A] and the better the surface smoothness of the resulting molded product.

In the methacrylic resin [A], the ratio Mw _A / Mn _A of the weight average molecular weight Mw _{A to} the number average molecular weight Mn _{A in} terms of polystyrene calculated based on a chromatogram obtained by gel permeation chromatography is preferably 1.0. It is 5.0 or more, more preferably 1.2 or more and 3.0 or less, further preferably 1.2 or more and 2.5 or less, and particularly preferably 1.3 or more and 1.7 or less. The lower the Mw _A / Mn _{A, the} better the impact resistance and toughness. As Mw _A / Mn _A increases, the melt fluidity of the methacrylic resin [A] increases and the surface smoothness of the resulting molded product tends to improve.

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

  The methacrylic resin [A1] may contain structural units derived from monomers other than methyl methacrylate. Examples of monomers other than methyl methacrylate include, for example, alkyl methacrylates other than methyl methacrylate such as ethyl methacrylate and butyl methacrylate; aryl methacrylates such as phenyl methacrylate; cyclohexyl methacrylate, and methacrylic acid. Methacrylic acid cycloalkyl esters such as norbornenyl; acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; aryl acrylates such as phenyl acrylate; acrylic Acrylic acid cycloalkyl esters such as cyclohexyl acid and norbornenyl acrylate; Aromatic vinyl compounds such as styrene and α-methylstyrene; Acrylonitrile; Methacrylonitrile Polymerizable carbon in one molecule, such as a - can be exemplified a vinyl monomer having only one carbon-carbon double bond. 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.

  In the methacrylic resin [A0] or the methacrylic resin [A1], the lower limit of the triplet syndiotacticity (rr) is preferably 50%, more preferably 52%, and still more preferably 53%. The upper limit of the tridentated syndiotacticity (rr) of the methacrylic resin [A0] or the methacrylic resin [A1] is not particularly limited, but is preferably 99%, more preferably 85% from the viewpoint of film forming properties. More preferably 77%, even more preferably 65%, and most preferably 64%.

A triplet display syndiotacticity (rr) (hereinafter sometimes simply referred to as "syndiotacticity (rr)") is a chain of three consecutive structural units (triplet, triad). The two chains (doublet, diad) are both racemo (represented as rr). In the chain of molecular units (doublet, diad) in the polymer molecule, those having the same configuration are referred to as “meso”, and those opposite to each other are referred to as “racemo”, which are expressed as m and r, respectively.
The tridentate syndiotacticity (rr) was measured in 0.6-0.95 ppm when the ¹ H-NMR spectrum was measured at 30 ° C. in deuterated chloroform and the TMS was 0 ppm. The area (X) of the region and the area (Y) of the region of 0.6 to 1.35 ppm can be measured and calculated by the formula: (X / Y) × 100.

In the methacrylic resin [A0] or methacrylic resin [A1] used in the present invention, the content of a component having a molecular weight of 200,000 or more (high molecular weight component) is preferably 0.1 to 10%, more preferably 0.5 to 5%. The methacrylic resin [A0] or methacrylic resin [A1] used in the present invention preferably has a content of a component having a molecular weight of less than 15,000 (low molecular weight component), preferably 0.1 to 5%, more preferably 0.2 to 3%. When the methacrylic resin [A0] or the methacrylic resin [A1] contains the high molecular weight component and the low molecular weight component in this range, the film forming property is improved and a film having a uniform film thickness is easily obtained.
The content of the component having a molecular weight of 200,000 or more is the chromatogram detected before the retention time of the standard polystyrene having a molecular weight of 200,000 in the area surrounded by the chromatogram measured by GPC and the baseline. Calculated as the ratio of the area surrounded by the baseline. The content of a component having a molecular weight of less than 15,000 is a chromatogram detected after the retention time of standard polystyrene having a molecular weight of 15,000 in the area surrounded by the chromatogram obtained by GPC and the baseline. Calculated as the ratio of the area of the portion surrounded by the gram and the baseline.

The measurement by gel permeation chromatography is performed as follows. Tetrahydrofuran is used as the eluent, and TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 are connected in series as the column. As an analyzer, HLC-8320 (product number) manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) was used. 4 mg of the methacrylic resin to be tested was dissolved in 5 ml of tetrahydrofuran to prepare a test solution. The column oven temperature was set to 40 ° C., 20 μl of the test solution was injected at an eluent flow rate of 0.35 ml / min, and the chromatogram was measured.
The chromatogram is a chart in which the electric signal value (intensity Y) derived from the difference in refractive index between the test solution and the reference solution is plotted against the retention time X.
A standard polystyrene having a molecular weight in the range of 400 to 5000000 was measured by gel permeation chromatography, and a calibration curve showing the relationship between retention time and molecular weight was prepared. When the chromatogram shows a single peak, it is based on a line connecting the point where the slope on the high molecular weight side of the chromatogram changes from zero to positive and the point where the slope of the peak on the low molecular weight side changes from negative to zero. Line. If the chromatogram shows multiple peaks, connect the line connecting the point where the slope of the highest molecular weight peak changes from zero to positive and the point where the slope of the lowest molecular weight peak changes from negative to zero. Baseline.

  The methacrylic resin [A0] or methacrylic resin [A1] has a melt flow rate determined by measurement under conditions of 230 ° C. and 3.8 kg load, preferably 0.1 to 30 g / 10 min or more, more preferably 0. .5 to 20 g / 10 min, more preferably 1 to 15 g / 10 min.

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

  The glass transition temperature is an intermediate glass transition temperature obtained from a DSC curve. In the DSC curve, the resin to be measured is subjected to the first temperature increase (1st run) at 10 ° C./min to 250 ° C. using a differential scanning calorimeter in accordance with JIS K7121, and then cooled to room temperature. Thereafter, the glass transition temperature is the midpoint glass transition temperature of the second run detected when the second temperature rise (2nd run) is performed from room temperature to 250 ° C. at a rate of temperature rise of 10 ° C./min.

  The methacrylic resin [A2] contains a structural unit having a ring structure in the main chain. This improves the heat resistance of the methacrylic resin composition. Therefore, in the methacrylic resin [A2] containing a structural unit derived from methyl methacrylate and a structural unit having a ring structure in the main chain, the total content of structural units derived from methyl methacrylate is more than the above-mentioned range. Can be lowered. For example, the total content of the structural units derived from methyl methacrylate in the methacrylic resin [A2] containing a structural unit derived from methyl methacrylate and a structural unit having a ring structure in the main chain is preferably 20 to 99. It is 30 mass%, More preferably, it is 30-95 mass%, More preferably, it is 40-90 mass%. The total content of structural units having a ring structure in the main chain is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and still more preferably 10 to 60% by mass. A methacrylic resin [A2] containing a structural unit derived from methyl methacrylate and a structural unit having a ring structure in the main chain is other than the structural unit derived from methyl methacrylate and the structural unit having a ring structure in the main chain. You may have a structural unit. Such a structural unit can be a structural unit derived from a monomer exemplified as a monomer other than methyl methacrylate as described 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 the structural unit having a ring structure in the main chain, a structural unit containing a> CH—O—C (═O) — group in the ring structure, and a —C (═O) —O—C (═O) — group as a ring A structural unit containing a structure, a structural unit containing a —C (═O) —N—C (═O) — group in the ring structure, or a structural unit containing a> CH—O—CH <group in the ring structure is preferable.
A structural unit having a ring structure in the main chain is obtained by copolymerizing a cyclic monomer having a polymerizable unsaturated carbon-carbon double bond such as maleic anhydride and N-substituted maleimide with methyl methacrylate. Alternatively, a part of the molecular chain of the methacrylic resin obtained by polymerization can be contained in the methacrylic resin by intramolecular condensation cyclization.

  As the structural unit containing> CH—O—C (═O) — group in the ring structure, β-propiolactone diyl (also known as oxooxetanediyl) structural unit, γ-butyrolactone diyl (also known as 2-oxodihydrofurandi) Yl) structural units, and lactone diyl structural units such as δ-valerolactone diyl (also known as 2-oxodihydropyrandiyl) structural units. In the formula, “> C” means that the carbon atom C has two bonds.

  For example, examples of the δ-valerolactone diyl structural unit include the structural unit represented by the formula (I).

式（I）中、Ｒ¹⁴およびＲ¹⁵はそれぞれ独立に水素原子または炭素数１〜２０の有機残基であり、Ｒ¹⁴が水素原子、Ｒ¹⁵がメチル基であることが好ましい。Ｒ¹⁶は−ＣＯＯＲであり、Ｒは水素原子または炭素数１〜２０の有機残基であり、好ましくはメチル基である。＊は結合手を意味する。
なお、式（I）における、有機残基としては、直鎖若しくは分岐状のアルキル基、直鎖若しくは分岐状のアルキレン基、アリール基、−ＯＡｃ基、および−ＣＮ基等を挙げることができる。有機残基は酸素原子を構成原子として含んでいてもよい。「Ａｃ」はアセチル基を示す。有機残基は、その炭素数が、好ましくは１〜１０、より好ましくは１〜５である。

In the 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, preferably a methyl group. * Means a bond.
In addition, as an organic residue in Formula (I), a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, -OAc group, -CN group, etc. can be mentioned. The organic residue may contain an oxygen atom as a constituent atom. “Ac” represents an acetyl group. The organic residue preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

  The δ-valerolactone diyl structural unit can be contained in a methacrylic resin by intramolecular cyclization of structural units derived from two adjacent methyl methacrylates.

  As the structural unit containing a —C (═O) —O—C (═O) — group in the ring structure, a 2,5-dioxodihydrofurandiyl structural unit, a 2,6-dioxodihydropyrandiyl structural unit, Examples include 2,7-dioxooxepanediyl structural unit.

  For example, examples of the 2,5-dioxodihydrofurandiyl structural unit include a structural unit represented by the formula (II).

式（II）中、Ｒ²¹およびＲ²²はそれぞれ独立に水素原子または炭素数１〜２０の有機残基である。
なお、式（II）における、有機残基としては、直鎖若しくは分岐状のアルキル基、直鎖若しくは分岐状のアルキレン基、アリール基、−ＯＡｃ基、および−ＣＮ基等を挙げることができる。有機残基は酸素原子を含んでいてもよい。「Ａｃ」はアセチル基を示す。有機残基は、その炭素数が、好ましくは１〜１０、より好ましくは１〜５である。

In the formula (II), R ²¹ and R ²² are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
In addition, as an organic residue in Formula (II), a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, -OAc group, -CN group, etc. can be mentioned. The organic residue may contain an oxygen atom. “Ac” represents an acetyl group. The organic residue preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

R ²¹ and R ²² are more preferably hydrogen atoms. In that case, from the viewpoint of ease of production and adjustment of intrinsic birefringence, it is usually preferable that styrene or the like is copolymerized. Specific examples include a copolymer having a structural unit derived from styrene, a structural unit derived from methyl methacrylate, and a structural unit derived from maleic anhydride, as described in WO2014 / 021264A1. .
The 2,5-dioxodihydrofurandiyl structural unit can be contained in the methacrylic resin by copolymerization of maleic anhydride or the like.

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

式（III）中、Ｒ³³およびＲ³⁴はそれぞれ独立に水素原子または炭素数１〜２０の有機残基である。
なお、式（III）における、有機残基としては、直鎖若しくは分岐状のアルキル基、直鎖若しくは分岐状のアルキレン基、アリール基、−ＯＡｃ基、および−ＣＮ基等を挙げることができる。有機残基は酸素原子を含んでいてもよい。「Ａｃ」はアセチル基を示す。有機残基は、その炭素数が、好ましくは１〜１０、より好ましくは１〜５であり、さらに好ましくはメチル基である。

In the formula (III), R ³³ and R ³⁴ are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
In addition, as an organic residue in Formula (III), a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, -OAc group, -CN group, etc. can be mentioned. The organic residue may contain an oxygen atom. “Ac” represents an acetyl group. The organic residue preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably a methyl group.

  The 2,6-dioxodihydropyrandiyl structural unit can be contained in the methacrylic resin by intramolecular cyclization of structural units derived from two adjacent methyl methacrylates.

  As a structural unit containing a —C (═O) —N—C (═O) — group in a ring structure (note that another bond of N is omitted), 2,5- Examples thereof include a dioxopyrrolidinediyl structural unit, a 2,6-dioxopiperidinediyl structural unit, and a 2,7-dioxoazepandiyl structural unit.

  For example, examples of the 2,6-dioxopiperidinediyl structural unit include a structural unit represented by the formula (IV).

式（IV）中、Ｒ⁴¹およびＲ⁴²はそれぞれ独立に水素原子または炭素数１〜８のアルキル基であり、Ｒ⁴³は水素原子、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、または炭素数６〜１０のアリール基である。
原料入手の容易さ、費用、耐熱性などの観点から、Ｒ⁴¹およびＲ⁴²はそれぞれ独立に水素原子またはメチル基であることが好ましく、Ｒ⁴¹がメチル基でありＲ⁴²が水素原子であることがより好ましい。Ｒ⁴³は水素原子、メチル基、ｎ−ブチル基、シクロへキシル基またはベンジル基であることが好ましく、メチル基であることがより好ましい。

In formula (IV), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴³ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. A cycloalkyl group or an aryl group having 6 to 10 carbon atoms.
From the viewpoint of easy availability of raw materials, cost, heat resistance, etc., R ⁴¹ and R ⁴² are preferably each independently a hydrogen atom or a methyl group, R ⁴¹ is a methyl group, and R ⁴² is a hydrogen atom. Is more preferable. 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.

  The 2,6-dioxopiperidinediyl structural unit can be contained in a methacrylic resin by, for example, intramolecular cyclization of a structural unit derived from two adjacent methyl methacrylates in the presence of an amine.

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

式（V）中、Ｒ⁵²およびＲ⁵³はそれぞれ独立に水素原子、炭素数１〜１２のアルキル基、または炭素数６〜１４のアルキル基であり、Ｒ⁵¹は、炭素数７〜１４のアリールアルキル基、または無置換の若しくは置換基を有する炭素数６〜１４のアリール基である。アリール基に置換される基は、ハロゲノ基、ヒドロキシル基、ニトロ基、炭素数１〜１２のアルコキシ基、炭素数１〜１２のアルキル基または炭素数７〜１４のアリールアルキル基である。Ｒ⁵¹はフェニル基またはシクロヘキシル基であることが好ましく、Ｒ⁵²およびＲ⁵³は共に水素原子であることが好ましい。

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, and R ⁵¹ is aryl having 7 to 14 carbon atoms. An alkyl group or an unsubstituted or substituted aryl group having 6 to 14 carbon atoms. The group substituted by the aryl group is a halogeno 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 arylalkyl group having 7 to 14 carbon atoms. R ⁵¹ is preferably a phenyl group or a cyclohexyl group, and both R ⁵² and R ⁵³ are preferably hydrogen atoms.

  The 2,5-dioxopyrrolidinediyl structural unit can be contained in the methacrylic resin by copolymerization of N-substituted maleimide or the like.

  Examples of the structural unit containing a> CH—O—CH <group in the ring structure include an oxetanediyl structural unit, a tetrahydrofurandiyl structural unit, a tetrahydropyrandiyl structural unit, and an oxepandiyl structural unit. In the formula, “> C” means that the carbon atom C has two bonds.

  For example, examples of the tetrahydropyrandiyl structural unit include a structural unit represented by the formula (VI).

式（VI）中、Ｒ⁶¹およびＲ⁶²はそれぞれ独立に水素原子、炭素数１〜２０の直鎖状若しくは分岐鎖状の炭化水素基、または環構造を有する炭素数３〜２０の炭化水素基である。
Ｒ⁶¹およびＲ⁶²としては、それぞれ独立に、トリシクロ［５．２．１．０^2,6］デカニル基、１，７，７−トリメチルビシクロ［２．２．１］ヘプタン−３−イル基、ｔ−ブチル基、または４−ｔ−ブチルシクロヘキサニル基が好ましい。

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. It is.
R ⁶¹ and R ⁶² are each independently a tricyclo [5.2.1.0 ^2,6 ] decanyl group, a 1,7,7-trimethylbicyclo [2.2.1] heptan-3-yl group, A t-butyl group or a 4-t-butylcyclohexanyl group is preferable.

  Among the structural units having the above ring structure in the main chain, from the viewpoint of raw materials and ease of production, δ-valerolactone diyl structural unit or 2,5-dioxodihydrofurandiyl structural unit is preferable.

  The methacrylic resin [A2] has a melt flow rate determined by measurement under conditions of 230 ° C. and a load of 3.8 kg, preferably 0.1 to 20 g / 10 min or more, more preferably 0.5 to 15 g / 10. Min, more preferably 1-10 g / 10 min.

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

  The methacrylic resin [A] used in the present invention may be one that satisfies the above characteristics with one kind of methacrylic resin, or one that satisfies the above characteristics with a mixture of a plurality of kinds of methacrylic resins. There may be.

The one or more methacrylic resins constituting the methacrylic resin [A] used in the present invention may be obtained by any manufacturing method. For example, a methacrylic resin can be obtained by polymerizing methyl methacrylate or by polymerizing methyl methacrylate and other monomers. The polymerization can be performed by a known method. Examples of the polymerization method include classification according to the form of chain transfer, and examples thereof include radical polymerization and anionic polymerization. The classification according to the form of the reaction liquid includes bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. Each characteristic of the methacrylic resin [A] described above can be realized by adjusting the polymerization conditions such as the polymerization temperature, the polymerization time, the type, amount and addition time of the chain transfer agent, the type, amount and addition time of the polymerization initiator. . Such characteristic control by 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 produce a resin having the desired characteristics.
Furthermore, the methacrylic resin [A2] can be obtained by intramolecular cyclization of the resin obtained by the polymerization as described above.

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

Compound [B] has a molecular weight lower limit of 2,000, preferably 3,000, more preferably 5,000, still more preferably 10,000, and a molecular weight upper limit of 300,000. The compound [B] having a molecular weight in the above range does not cause defects such as mold contamination and bleed out during molding, and gives a molded article such as a film having a good appearance.
Compound [B] may be a compound having a single molecular weight or a polymer having a distribution in molecular weight. The molecular weight of a compound having a single molecular weight can be measured by various mass spectrometry. The molecular weight of a polymer having a distribution in molecular weight is a weight average molecular weight in terms of polystyrene obtained by measurement by gel permeation chromatography.

  Specific examples of the compound [B] include polyphenols such as poly-o-hydroxystyrene, poly-m-hydroxystyrene, and poly-p-hydroxystyrene, novolac-type phenol resins such as terpenephenol resin and bisphenol A-type novolac resin, and resol-type. Examples thereof include phenol resins, phenol resins having a hydroxy naphthalene structure (see WO2014 / 208132A1), phenol resins 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 resol type phenol resin is preferable, and polyvinyl phenol is most preferable because of its high effect of suppressing thermal decomposition.

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, more preferably 0.04 to 5% by mass.
The mass ratio ((B) / (A)) between the compound (B) and the methacrylic resin (A) is preferably 0.01 / 99.99 to 30/70, more preferably 0.02 / 99. It is 98-10 / 90, More preferably, it is 0.04 / 99.96-5 / 95.

[Ultraviolet absorber [C]]
The ultraviolet absorbent [C] used in the present invention is a known ultraviolet absorbent that may be blended in a thermoplastic resin. The molecular weight of the ultraviolet absorber [C] is preferably more than 200, more preferably 300 or more, still more preferably 500 or more, and still more preferably 600 or more. The upper limit of the molecular weight of the ultraviolet absorber [C] is preferably 2000.

In general, an ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, benzotriazoles (compounds having a benzotriazole skeleton) and triazines (compounds having a triazine skeleton) are preferable. Benzotriazoles or triazines have a high effect of suppressing resin degradation (for example, yellowing) due to ultraviolet rays.

  Examples of 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-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2′-methylenebis [6- (2H-benzotriazole-2 -Yl) -4-tert-octylphenol] (manufactured by ADEKA; LA-31), 2- (5-octylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol be able to.

  Examples of triazines include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70) and its analogs. Certain hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; CGL777, TINUVIN460, TINUVIN479, etc.), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, etc. Can be mentioned.

In addition, an ultraviolet absorber having a maximum molar extinction coefficient ε _max at a wavelength of 380 to 450 nm of 1200 dm ³ · mol ⁻¹ cm ⁻¹ or less can be preferably used. Examples of such an ultraviolet absorber include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan, Inc .; trade name “Sandyuboa VSU”).

  WO2011 / 089794A1, WO2012 / 124395A1, JP2012-012476, JP2013-023461, JP2013-112790, JP2013-194037, JP201462228, JP A metal complex having a heterocyclic ligand disclosed in JP 2014-88542 A, JP 2014-88543 A, or the like can be used as the ultraviolet absorber [C].

  The amount of the ultraviolet absorber [C] that can be contained in the methacrylic resin composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the methacrylic resin [A]. It is 5 mass parts, More preferably, it is 0.3-3 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 crosslinking 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-acryloxy-3-butene, 1-methacryloxy-3-butene, 1,2-diacryloxy-ethane, 1,2-dimethacryloxy-ethane, 1,2-diacryloxy-propane, 1,3-diacryloxy-propane, 1,4-diacryloxy-butane, 1,3-dimethacryloxy-propane, 1,2-dimethacryloxy-propane, 1,4-dimethacryloxy-butane, triethylene Examples include glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, hexanediol diacrylate, divinylbenzene, 1,4-pentadiene, triallyl isocyanate, and the like. You may use these individually by 1 type or in combination of 2 or more types.

  Examples of the cross-linked rubber include acrylic cross-linked rubber, diene cross-linked rubber, and the like, and more specifically, an acrylic acid alkyl ester monomer, a cross-linkable monomer, and other vinyl monomers. Copolymer rubber, copolymer rubber of conjugated diene monomer, crosslinkable monomer and other vinyl monomer, alkyl acrylate monomer, conjugated diene monomer and crosslinkable monomer Examples thereof include copolymer rubbers of a monomer and other vinyl monomers.

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

  The crosslinked rubber particles may be single-layer particles composed only of the crosslinked rubber, or may be multilayer particles composed of the crosslinked rubber and another polymer. As a form of the multilayer particle composed of the crosslinked rubber and other polymer, core-shell type particles comprising a core composed of the crosslinked rubber and a shell composed of the other polymer are preferable.

  The crosslinked rubber particles suitably used in the present invention are acrylic multilayer polymer particles. The acrylic multilayer polymer particles have a core part and a shell part. The core portion includes a center core and, if necessary, one or more inner shells that cover the center core in a substantially concentric shape. The shell portion has a one-layer outer shell that covers the core portion substantially concentrically. In the acrylic multilayer polymer particles, it is preferable that the center core, the inner shell, and the outer shell are connected to each other without a gap.

Acrylic multilayer polymer particles are those in which at least one of the center core and the inner shell contains the crosslinked rubber polymer (i) and the remaining part contains the polymer (iii). It is preferable that
When at least two of the center core and the inner shell contain the crosslinked rubber polymer (i), the crosslinked rubber polymer (i) contained in them has the same polymer physical properties. Alternatively, it may have different polymer properties. Further, when the remaining part of the center core and the inner shell is two or more, the polymer (iii) contained in them may have the same polymer properties or different polymer properties. It may be a thing.

The crosslinked rubber polymer (i) includes a structural unit derived from an alkyl acrylate monomer and / or a structural unit derived from a conjugated diene monomer, and a structural unit derived from a crosslinkable monomer. It is preferable that it has at least.
The acrylic acid alkyl ester monomer is preferably an acrylic acid alkyl ester 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, and 2-ethylhexyl acrylate. You may use these individually by 1 type or in combination of 2 or more types.
Examples of the conjugated diene monomer include butadiene and isoprene. You may use these 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 based on the total mass of the crosslinked rubber polymer (i). And preferably 60% by mass or more, more preferably 70 to 99% by mass, and still more preferably 80 to 98% by mass.

  The crosslinkable monomer has two or more polymerizable functional groups in one monomer. Examples of the crosslinkable monomer include allyl acrylate, allyl methacrylate, 1-acryloxy-3-butene, 1-methacryloxy-3-butene, 1,2-diacryloxy-ethane, 1,2-dimethacryloxy-ethane, 1,2-diacryloxy-propane, 1,3-diacryloxy-propane, 1,4-diacryloxy-butane, 1,3-dimethacryloxy-propane, 1,2-dimethacryloxy-propane, 1,4-dimethacryloxy-butane, triethylene Examples include glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, hexanediol diacrylate, divinylbenzene, 1,4-pentadiene, triallyl isocyanate, and the like. You may use these individually by 1 type or in combination of 2 or more types.

  The amount of the structural unit derived from the crosslinkable monomer in the crosslinked rubber polymer (i) is preferably 0.05 to 10% by mass, more preferably 0, relative to the total mass of the crosslinked rubber polymer (i). .5-7% by mass, more preferably 1-5% by mass.

The crosslinked rubber polymer (i) may have a structural unit derived from another vinyl monomer. The other vinyl monomer in the crosslinked rubber polymer (i) is not particularly limited as long as it is copolymerizable with the above-mentioned alkyl acrylate monomer and the crosslinkable monomer. Examples of other vinyl monomers in the crosslinked rubber polymer (i) include methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate; styrene, p-methylstyrene. And aromatic vinyl monomers such as o-methylstyrene; and maleimide monomers such as N-propylmaleimide, N-cyclohexylmaleimide, and N-o-chlorophenylmaleimide. You may use these individually by 1 type or in combination of 2 or more types.
The amount of structural units derived from other vinyl monomers in the crosslinked rubber polymer (i) includes structural units derived from alkyl acrylate monomers, structural units derived from conjugated diene monomers, and cross-linking. It is the remainder with respect to the total amount of the structural unit derived from the sex monomer.

The polymer (iii) is not particularly limited as long as it is other than the crosslinked rubber polymer (i), but preferably has a structural unit derived from a methacrylic acid alkyl ester monomer. The polymer (iii) may contain, as other structural units, structural units derived from a crosslinkable monomer and / or structural units derived from other vinyl monomers.
The methacrylic acid alkyl ester monomer used in the polymer (iii) is preferably a methacrylic acid alkyl ester monomer having an alkyl group having 1 to 8 carbon atoms. Examples of the methacrylic acid alkyl ester monomer include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. You may use these individually by 1 type or in combination of 2 or more types. Of these, methyl methacrylate is preferred.
The amount of the structural unit derived from the methacrylic acid alkyl ester monomer in the polymer (iii) is preferably 80 to 100% by mass, more preferably 85 to 99% by mass, and further preferably 90 to 98% by mass.

  Examples of the crosslinkable monomer used in the polymer (iii) include the same crosslinkable monomers exemplified in the above-mentioned crosslinked 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 still more preferably 0.02 to 2% by mass. is there.

The other vinyl monomer in the polymer (iii) is not particularly limited as long as it can be copolymerized with the above-mentioned methacrylic acid alkyl ester monomer and the crosslinkable monomer. Other vinyl monomers in the polymer (iii) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid Acrylic acid ester monomers such as 2-ethylhexyl; vinyl acetate; aromatic vinyl monomers such as styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, α-methylstyrene, vinylnaphthalene; acrylonitrile; Nitriles such as methacrylonitrile; α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; and maleimide monomers such as N-ethylmaleimide and N-cyclohexylmaleimide. You may use these individually by 1 type or in combination of 2 or more types.
The amount of the structural unit derived from the other vinyl monomer in the polymer (iii) is based on the total amount of the structural unit derived from the alkyl methacrylate monomer and the structural unit derived from the crosslinkable monomer. The rest.

  The acrylic multilayer polymer particles preferably have an outer shell containing the thermoplastic polymer (ii).

  The thermoplastic polymer (ii) has a structural unit derived from a methacrylic acid alkyl ester monomer. The thermoplastic polymer (ii) may have a structural unit derived from another vinyl monomer.

The methacrylic acid alkyl ester monomer in the thermoplastic polymer (ii) is preferably a methacrylic acid alkyl ester monomer having an alkyl group having 1 to 8 carbon atoms.
Examples of the methacrylic acid alkyl ester monomer include methyl methacrylate and butyl methacrylate. You may use these individually by 1 type or in combination of 2 or more types. Of these, methyl methacrylate is preferred.
The amount of the structural unit derived from the methacrylic acid alkyl ester monomer in the thermoplastic polymer (ii) is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more.

Examples of the other vinyl monomers in the thermoplastic polymer (ii) include the same vinyl monomers as those exemplified in the polymer (iii).
The amount of the structural unit derived from the other vinyl monomer in the thermoplastic polymer (ii) is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

Examples of the configuration of the core part and the shell part of the acrylic multilayer polymer particle include, for example, a two-layer polymer particle in which the center core is a crosslinked rubber polymer (i) and the outer shell is a thermoplastic polymer (ii); Three-layer polymer particles in which the center core is the polymer (iii), the inner shell is the crosslinked rubber polymer (i), and the outer shell is the thermoplastic polymer (ii); A three-layer polymer particle in which the inner shell is another type of crosslinked rubber polymer (i) and the outer shell is a thermoplastic polymer (ii); the center core is a crosslinked rubber polymer (i ) In which the inner shell is a polymer (iii) and the outer shell is a thermoplastic polymer (ii); three-layer polymer particles; the center core is a crosslinked rubber polymer (i), and the inner inner shell is a polymer ( In iii), the outer inner shell is a crosslinked rubber polymer (i) and the outer shell is heatable. And 4-layer polymer particles that are a plastic polymer (ii).
Of these, three-layer polymer particles in which the center core is the polymer (iii), the inner shell is the crosslinked rubber polymer (i), and the outer shell is the thermoplastic polymer (ii) are preferable.
In the three-layer polymer particle, the center core polymer (iii) is an alkyl acrylate monomer having an alkyl group of 80 to 99.95% by mass of methyl methacrylate and an alkyl group of 1 to 8 carbon atoms. .95% by mass and a crosslinkable monomer of 0.05-2% by mass, wherein the crosslinked rubber polymer (i) of the inner shell has an alkyl group having 1-8 carbon atoms. Thermoplastic polymer of outer shell (ii), which is a copolymer of 80 to 98% by weight of ester monomer, 1 to 19% by weight of aromatic vinyl monomer and 1 to 5% by weight of crosslinkable monomer Is more preferably a copolymer of 80 to 100% by mass of methyl methacrylate and 0 to 20% by mass of an acrylic acid alkyl ester 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. It is preferable to select a polymer contained in

  The ratio of the outer shell part in the acrylic multilayer polymer particles is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and still more preferably 20 to 40% by mass. The ratio of the layer containing the crosslinked rubber polymer (i) in the core part is preferably 20 to 100% by mass, 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 still more preferably 0.1 to 0.3 μm.
When a crosslinked rubber particle component having such a volume-based average particle size is used, defects in the appearance of the molded product can be significantly reduced. In addition, the volume reference average particle diameter in this specification is a value calculated based on the particle size distribution data measured by the light scattering light method.

  The crosslinked rubber particles may be obtained by any manufacturing method. From the viewpoints of particle size control, ease of production of the multilayer structure, the emulsion polymerization method or the seed emulsion polymerization method is preferred. The emulsion polymerization method is a method capable of producing an emulsion containing polymer particles by emulsifying a predetermined monomer and polymerizing it. In the seed emulsion polymerization method, seed particles are obtained by emulsifying and polymerizing a predetermined monomer, and by emulsifying and polymerizing another predetermined monomer in the presence of the seed particles, This is a method capable of producing an emulsion containing core-shell polymer particles having a shell polymer coated in a substantially concentric shape. A core-shell having seed particles and a plurality of shell polymers covering them substantially concentrically by repeating emulsification and polymerization of another predetermined monomer in the presence of the core-shell polymer particles a desired number of times Emulsions containing multi-layer polymer particles can be produced.

  Examples of the emulsifier used in the emulsion polymerization method include dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dilauryl sulfosuccinate which are anionic emulsifiers, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, and the like. Nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene nonylphenyl ethers; Nonionic and anionic emulsifiers such as polyoxyethylene nonylphenyl ether sulfates such as polyoxyethylene nonylphenyl ether sulfates, Polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene tridecyl ether And alkyl ether carboxylates such as sodium acetate. You may use these individually by 1 type or in combination of 2 or more types. The average number of repeating units of the ethylene oxide unit in the exemplified compounds of the nonionic emulsifier and the nonionic anionic emulsifier is preferably 30 or less, more preferably 20 or less, in order to prevent the foaming property of the emulsifier from becoming extremely large. More preferably, it is 10 or less.

  The polymerization initiator used for emulsion polymerization is not particularly limited. Examples thereof include persulfate initiators such as potassium persulfate and ammonium persulfate; redox initiators such as persulfoxylate / organic peroxide and persulfate / sulfite.

Separation and acquisition of the crosslinked rubber particles from the emulsion obtained by emulsion polymerization can be performed by a known method such as a salting out coagulation method, a freeze coagulation method, or a spray drying method. Among these, the salting out coagulation method and the freeze coagulation method are preferable, and the freeze coagulation method is more preferable because impurities contained in the crosslinked rubber particles can be easily removed by washing with water. In the freeze coagulation method, since an aggregating agent is not used, an acrylic resin film excellent in water resistance is easily obtained.
In addition, it is preferable to filter the emulsion with a wire mesh having an opening of 50 μm or less before the coagulation step because foreign matters mixed in the emulsion can be removed.

  From the viewpoint of easily dispersing the crosslinked rubber particles uniformly in the melt-kneading of the crosslinked rubber particles and the methacrylic resin [A], the crosslinked rubber particles are preferably taken out with an aggregate of 1000 μm or less, and taken out with an aggregate of 500 μm or less. Is more preferable. The form of the crosslinked rubber particle aggregate is not particularly limited. For example, the crosslinked rubber particle aggregate may be in the form of pellets fused to each other at the shell, or may be in the form of powder or granule.

  The amount of the crosslinked rubber [D] included 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 25 parts by mass with respect to 100 parts by mass of the methacrylic resin [A]. Parts, more preferably 15 to 20 parts by mass.

In the methacrylic resin composition of the present invention, when the crosslinked rubber particles are contained in the methacrylic resin composition, the crosslinked rubber particles are not aggregated due to sticking or the like, so that each particle is uniformly dispersed. Dispersion aid particles can be added. Examples of the dispersion auxiliary particles include methacrylic resin particles. The dispersion auxiliary particles preferably have an average particle size smaller than the average particle size of the crosslinked rubber particles. Specifically, the volume-based average particle diameter of the dispersion auxiliary particles is preferably 0.04 to 0.12 μm, more preferably 0.05 to 0.1 μm.
From the viewpoint of the dispersion effect and the like, the amount of the dispersion auxiliary particle is a mass ratio with respect to the crosslinked rubber particle [D], preferably 0/100 to 60/40, more preferably 10/90 to 50/50, still more preferably 20 /. 80-40 / 60.

[Block copolymer [E]]
The block copolymer [E] used in the present invention is, for example, the molecular chain of the polymer B (polymer block B) at the end of the molecular chain of the polymer A (sometimes referred to as polymer block A). ) Are joined together in a chain or radial form as a whole.
The polymer block constituting the block copolymer is not particularly limited. For example, a block copolymer comprising a polymer block such as polymethyl methacrylate and a polymer block such as polyacrylic acid ester has good compatibility between a methacrylic resin and an aromatic low-molecular compound. May be.
The block copolymer is, for example, a method in which a polymerization initiation point is created at the end of the polymer block A using living polymerization, and a monomer is polymerized from this initiation point to produce a polymer block B [i], polymer The block A and the polymer block B can be prepared, and can be produced by a method [ii] or the like of adding or condensing them.

  At least one of the polymer blocks constituting the block copolymer used in the present invention is a polymer containing 90% by mass or more of a structural unit derived from a methacrylic ester, a structural unit derived from styrene, and a structure derived from acrylonitrile. A polymer containing a unit, a polymer containing a structural unit derived from styrene and a structural unit derived from maleic anhydride, a structural unit derived from styrene, a structural unit derived from maleic anhydride, and methyl methacrylate. From the viewpoint of compatibility with the methacrylic resin [A], a polymer containing a derived structural unit or polyvinyl butyral is preferably selected.

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

[Graft copolymer [F]]
The graft copolymer [F] used in the present invention may be, for example, a polymer B molecular chain (also referred to as a graft side chain) in the middle of the polymer A molecular chain (sometimes referred to as a polymer main chain). )) Are connected to each other, and are connected in a branched manner as a whole.
The main chain and graft side chain constituting the graft copolymer are not particularly limited. For example, a graft copolymer having a main chain composed of polyolefin, polycarbonate, acrylic copolymer, etc. and a graft side chain composed of polystyrene, styrene-acrylonitrile copolymer, acrylic copolymer, etc. The compatibility between the methacrylic resin and the aromatic low molecular weight compound may be improved.
For example, the graft copolymer has a chain transfer method [i] in which a monomer that becomes the polymer B is polymerized in the presence of the polymer A, and a polymer group introduced at the end of the polymer B that becomes the graft side chain. A method in which a molecular compound and a monomer to be a polymer A are copolymerized [ii], a polymer A to be a main chain and a polymer B to be a graft side chain are respectively prepared, and an addition or condensation reaction thereof is performed [ iii] and the like.

  A polymer in which the main chain or at least one graft side chain constituting the graft copolymer used in the present invention contains 90% by mass or more of a structural unit derived from a methacrylic acid ester, a structural unit derived from styrene and acrylonitrile Polymers containing structural units derived from, polymers containing structural units derived from styrene and structural units derived from maleic anhydride, structural units derived from styrene, structural units derived from maleic anhydride and methacrylic It is preferable from the viewpoint of compatibility with the methacrylic resin [A] that it is selected from a polymer containing a structural unit derived from methyl acid, polyvinyl butyral, and polycarbonate.

  The amount of the graft copolymer [F] to be included in the methacrylic resin composition according to the embodiment of the present invention is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the methacrylic resin [A]. It is 0.5-25 mass parts, More preferably, it is 1-20 mass parts.

[Polycarbonate resin [G]]
The polycarbonate resin [G] that may be added to the methacrylic resin composition of the present invention is not particularly limited, and examples thereof include a polymer obtained by a reaction between a polyfunctional hydroxy compound and a carbonate ester-forming compound. In the present invention, an aromatic polycarbonate resin is preferred from the viewpoint of compatibility with the methacrylic resin [A] and excellent transparency of the resulting film.

The polycarbonate resin [G] used in the present invention has a melt volume flow rate at 300 ° C. and 1.2 kg from the viewpoint of compatibility with the methacrylic resin [A], transparency of the resulting film, surface smoothness and the like. MVR) values, preferably 130~250cm ^3/10 min, more preferably 150~230cm ^3/10 min, more preferably 180~220cm ^3/10 min.

  The polycarbonate resin [G] used in the present invention was measured by gel permeation chromatography (GPC) 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 to 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 24,000. The MVR value and the weight average molecular weight of the polycarbonate resin [G] can be adjusted by adjusting the amounts of the terminal terminator 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 further preferably 140 ° C. or higher. The upper limit of the glass transition temperature of the polycarbonate resin is usually 180 ° C. Here, the glass transition temperature is performed in accordance with JIS K7121 in a region of room temperature or higher. The first temperature rise (1st run) is performed at a temperature increase rate of 10 ° C./min up to 250 ° C., and then to room temperature. It is the midpoint glass transition temperature of the 2nd run when cooling and then raising the temperature from room temperature to 250 ° C. at a rate of temperature increase of 10 ° C./min (2nd run).

  The manufacturing method of 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 preferably used in the present invention may be obtained by subjecting a polycarbonate resin raw material produced by a melt polymerization method to a treatment for adjusting the amount of terminal hydroxy groups. As the polycarbonate resin [G], commercially available products or other known products can be used.

  The polycarbonate resin [G] may contain 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] to be included in the methacrylic resin composition according to the embodiment of the present invention is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 100 parts by mass of the methacrylic resin [A]. It is 5-10 mass parts, More preferably, it is 1-8 mass parts. By being in this range, since the compatibility of the methacrylic resin (A) and the polycarbonate resin [G] is good, it is easy to obtain a film having high transparency, high refractive index, and good surface smoothness. In particular, when the amount of the polycarbonate resin [G] is 1 to 4 parts by mass with respect 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. Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, Styrenic resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, polyamide elastomer Polyamides such as: phenoxy resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane Tan, modified polyphenylene ether, polyphenylene sulfide, silicone-modified resins; can be mentioned IR, EPR, and olefin rubbers such as EPDM; silicone rubber; SEPS, SEBS, styrene-based thermoplastic elastomers such as SIS. 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, which can be usually produced by an emulsion polymerization method. The polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be. Among these, particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable. The polymer processing aid preferably has an intrinsic viscosity of 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, more preferably 100% by mass of the methacrylic resin [A]. Is 0.2 mass% or more and 5 mass% or less, More preferably, it is 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. For example, a method of polymerizing a monomer mixture containing methyl methacrylate in the presence of compound [B] to produce methacrylic resin [A]; a method of melt-kneading methacrylic resin [A] and compound [B], etc. Can be mentioned. Among these, the melt-kneading method is preferable because the process is simple. When melt-kneading, other polymers and additives may be mixed as necessary, or after mixing the methacrylic resin [A] with other polymers and additives and mixing with the compound [B]. Alternatively, the compound [B] may be mixed with other polymer and additive and then mixed with the methacrylic resin [A], or other methods may be used. The kneading can be performed using a known mixing apparatus or kneading apparatus such as a kneader ruder, a single-screw or multi-screw extruder, a mixing roll, a Banbury mixer, and the like. Of these, a twin screw extruder is preferred. The temperature during mixing and kneading can be appropriately adjusted according to the melting temperature of the methacrylic resin [A] and the compound [B] to be used, but is preferably 110 ° C to 300 ° C.

The methacrylic resin composition of the present invention contains methacrylic resin [A] preferably 70 to 99.99% by mass, more preferably 90 to 99.98% by mass, and still more preferably 95 to 99.96% by mass. When the methacrylic resin [A] is included in this range, the transparency and heat resistance are excellent.
The methacrylic resin composition of the present invention contains 0.01 to 30% by mass, more preferably 0.02 to 10% by mass, and further preferably 0.04 to 5% by mass of the compound [B]. Within this range, the effect of suppressing thermal decomposition is obtained, and the transparency of the resulting methacrylic resin composition is excellent.

  The glass transition temperature of the methacrylic resin composition of the present invention is preferably 100 ° C or higher, more preferably 105 ° C or higher, and further preferably 110 ° C or higher. The upper limit of the glass transition temperature of the methacrylic resin composition is not particularly limited, but 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 550,000 to 160,000, still more preferably 60,000 to 120,000, particularly 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, More preferably, it is 1.3-2.0, Most preferably, it is 1.3-1.7. When the Mw and molecular weight distribution (Mw / Mn) are in this range, the molding processability of the methacrylic resin composition becomes good, and it becomes easy to obtain a molded body excellent in impact resistance and toughness.

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

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

  The methacrylic resin composition of the present invention can be in the form of pellets or the like in order to enhance convenience during storage, transportation or molding.

The methacrylic resin composition of the present invention can be formed into a molded body by a known molding method. Examples of molding methods include T-die method (laminate method, coextrusion method, etc.), inflation method (coextrusion method, etc.), compression molding method, blow molding method, calendar molding method, vacuum molding method, injection molding method (insert). Method, two-color method, press method, core back method, sandwich method, etc.) and solution casting method.
In these molding methods, a mold or the like is generally used for molding a resin composition. Examples thereof include a sheet forming roll, a film forming roll, a calendar roll, a compression molding mold, a blow molding mold, a vacuum molding mold, an injection molding mold, and a cast polymerization mold. The mold used for molding is not necessarily made of metal, and may be made of rubber or tempered glass, for example. Since the methacrylic resin composition of the present invention hardly causes mold contamination, it can be preferably used in production in which continuous molding is performed for a long time, production in which molding is repeated many times, and the like.

  Applications of the molded article of the present invention include, for example, billboard parts such as advertising towers, stand signboards, sleeve signboards, billboard signs, and rooftop signs; display parts such as showcases, partition plates, and store displays; fluorescent lamp covers, mood lighting Lighting parts such as covers, lamp shades, light ceilings, light walls, and chandeliers; interior parts such as pendants and mirrors; architectures such as doors, domes, safety window glass, partitions, staircases, balcony waistboards, and roofs for leisure buildings Parts: Aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading plates, automotive side visors, rear visors, head wings, headlight covers, and other transport related parts; audio visual nameplates, stereo covers, TV protection Electronic devices such as masks and display covers for vending machines Products: Medical equipment parts such as incubators and X-ray parts; equipment-related parts such as machine covers, instrument covers, experimental equipment, rulers, dials, observation windows; light guide plates and films for display devices, backlight guides Optical components such as optical plates and films, LCD protective plates, Fresnel lenses, lenticular lenses, front panels of various displays, diffusers and reflectors; traffic-related components such as road signs, guide plates, curved mirrors, and noise barriers; automobile interiors Surface materials for mobile phones, surface materials for mobile phones, film members such as marking films; members for household appliances such as canopy materials and control panels for washing machines, top panels for rice cookers; other greenhouses, large tanks, box tanks, watches Panels, bathtubs, sanitary, desk mats, game parts, toys, masks for face protection when welding, etc. It is.

The molded body of the present invention is excellent in weather resistance and suppresses bleeding out of the ultraviolet absorber, so that, for example, in various covers, various terminal boards, printed wiring boards, speakers, microscopes, binoculars, cameras, watches, etc. Representative optical equipment and parts related to video / optical recording / optical communication / information equipment, such as cameras, VTRs, projection TVs, filters, prisms, Fresnel lenses, various optical disks (VD, CD, DVD, MD, LD) Etc.) Protective films for substrates, optical switches, optical connectors, liquid crystal displays, light guide films and sheets for liquid crystal displays, flat panel displays, light guide films and sheets for flat panel displays, plasma displays, light guide films and sheets for plasma displays , Light guide film for electronic paper Sheet, retardation film / sheet, polarizing film / sheet, polarizing plate protective film / sheet, polarizer protective film / sheet, wave plate, light diffusion film / sheet, prism film / sheet, reflective film / sheet, anti-reflective film・ Sheets, viewing angle expansion films / sheets, anti-glare films / sheets, brightness enhancement films / sheets, display element substrates for liquid crystal and electroluminescence, touch panels, light guide films / sheets for touch panels, various front plates, and various modules It can be particularly suitably applied to various optical applications such as spacers.
Specifically, for example, various liquid crystal display elements such as mobile phones, digital information terminals, navigation, liquid crystal displays for vehicles, liquid crystal monitors, light control panels, displays for OA equipment, displays for AV equipment, electroluminescence display elements, or touch panels. Can be used. Also, from the point of excellent weather resistance, for example, building interior and exterior members, curtain walls, roofing members, roofing materials, window members, gutters, exteriors, wall materials, flooring materials, construction materials, The present invention is particularly preferably applicable to known building materials such as road construction members, retroreflective films / sheets, agricultural films / sheets, lighting covers, signboards, and translucent sound insulation walls.

  The molded body of the present invention can also be applied to solar cell surface protective films, solar cell sealing films, solar cell back surface protective films, solar cell base films, gas barrier film protective films and the like for solar cell applications.

  The film of the present invention which is one form of the molded body is not particularly limited by the production method. The film of the present invention can be obtained, for example, by forming the methacrylic resin composition by a known method such as a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, or a blow molding method. it can. Of these, the extrusion method is preferred. According to the extrusion molding method, a film having improved toughness, excellent handleability, and excellent balance between toughness, 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, more preferably 220 to 260 ° C.

  Among the extrusion molding methods, from the viewpoint of obtaining a film having good surface smoothness, good specular gloss, and low haze, the methacrylic resin composition is extruded from a T die in a molten state, and then it is applied to two or more specular surfaces. A method including forming by sandwiching with a roll or a mirror belt is preferable. The mirror roll or the mirror belt is preferably made of metal. The linear pressure between the pair of mirror rolls or the mirror belt is preferably 2 N / mm or more, more preferably 10 N / mm or more, and even more preferably 30 N / mm or more.

  Moreover, it is preferable that the surface temperature of a mirror surface roll or a mirror surface belt is 130 degrees C or less. The pair of mirror rolls or mirror belts preferably have at least one surface temperature of 60 ° C. or higher. When the surface temperature is set to such a value, the methacrylic resin composition discharged from the extruder can be cooled at a speed faster than natural cooling, and a film having excellent surface smoothness and low haze can be easily produced.

  The film of the present invention may be subjected to a stretching treatment. By the stretching treatment, a film that has high mechanical strength and is difficult to crack 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 tuber stretching method. The temperature at the time of stretching is preferably from 100 to 200 ° C, more preferably from 110 to 160 ° C, from the viewpoint that the film can be stretched uniformly and a high-strength film can be obtained. Stretching is usually performed at 100 to 5000% / min on a length basis. The stretching is preferably performed so that the area ratio is 1.5 to 8 times. A film with less heat shrinkage can be obtained by heat setting after stretching.

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

  In the film of the present invention, the haze at a thickness of 40 μm is preferably 0.2% or less, more preferably 0.1% or less. The film of the present invention having haze in the above range is excellent in surface gloss and transparency. When the film of the present invention is used as an optical member such as a liquid crystal protective film or a light guide film, it is preferable because the light use efficiency from the light source is increased. Furthermore, since the film of this invention is excellent in workability, it can give a fine and precise surface shaping.

The film of the present invention has a polarizer protective film, a retardation film, a liquid crystal protective plate, a surface material for a portable information terminal, a display window protective film for a portable information terminal, a light guide film, silver nanowires and carbon nanotubes on the surface. It is suitable for a coated transparent conductive film, a front plate of various displays, and the like, and is particularly suitable for a polarizer protective film.
The film of the present invention includes fields other than the optical field, such as IR cut film, security film, scattering prevention film, decorative film, metal decorative film, solar cell back sheet, flexible solar cell front sheet, shrink film, It can be used for a film for a mold label, a gas barrier substrate film and the like.

  A functional layer may be provided on the surface of the film of the present invention. Examples of the functional layer include a hard coat layer, an antiglare layer, an antireflection layer, an antisticking layer, a diffusion layer, an antiglare layer, an antistatic layer, an antifouling layer, and an easy-sliding layer containing fine particles.

  The polarizing plate in which the film of the present invention is used has 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 the polarizer or may be laminated on one side. When the film of the present invention is laminated on one side of the polarizer as a polarizer protective film, an optical film other than the film of the present invention can be laminated on another side. Examples of the optical film include a polarizer protective film, a viewing angle adjusting film, a retardation film, and a brightness enhancement film. Lamination can also be performed via an adhesive layer.

  The polarizing plate in which the film of the present invention is used can be used for 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), a field emission display (FED), and a liquid crystal display (LCD). be able to. The liquid crystal display device includes a liquid crystal cell and the polarizing plate disposed 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 also suitable as a film used in an organic electroluminescence lighting device or an organic electroluminescence display device.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to the following Example. The physical property values and the like were measured by the following method.

(Polymerization conversion)
A column (GL Sciences Inc. manufactured Inert CAP 1 (df = 0.4 μm, 0.25 mm ID × 60 m)) was attached to a gas chromatograph GC-14A manufactured by Shimadzu Corporation, and the injection temperature was detected at 180 ° C. The temperature is set to 180 ° C, the column temperature is raised from 60 ° C (holding for 5 minutes) to 200 ° C at a heating rate of 10 ° C / minute, and the conditions are set to hold 200 ° C for 10 minutes. The polymerization conversion rate was calculated based on this result.

(Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution)
The chromatogram was measured under the following conditions by gel permeation chromatography (GPC), and the value converted into the molecular weight of standard polystyrene was calculated. The baseline is that the slope of the peak on the high molecular weight side of the GPC chart changes from zero to positive when viewed from the earlier retention time, and the slope of the peak on the low molecular weight side is from negative to zero when viewed from the earlier retention time. A line connecting the points that change to.
GPC device: manufactured by Tosoh Corporation, HLC-8320
Detector: Differential refractive index detector Column: TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and Super HZ4000 connected in series were used.
Eluent: Tetrahydrofuran Eluent flow rate: 0.35 ml / min Column temperature: 40 ° C
Calibration curve: Created using 10 standard polystyrene data

(Glass transition temperature Tg)
Using methacrylic resin and methacrylic resin composition in accordance with JIS K7121, the first temperature rise (1st run) to 250 ° C using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50 (product number)) Then, it was cooled to room temperature, and then the DSC curve was measured under the condition of raising the temperature from room temperature to 250 ° C. at a rate of 10 ° C./min for the second time. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature increase (2nd run) was defined as the glass transition temperature in the present invention.

(Thermal weight retention)
Using a thermogravimetric measuring device (manufactured by Shimadzu Corporation, TGA-50), the weighed methacrylic resin composition was heated from room temperature to 290 ° C. at a rate of 20 ° C./min in an air atmosphere (flow rate 50 ml / min). Weighing was performed at the time when the temperature reached 290 ° C. and 30 minutes after that, and the thermogravimetric retention was calculated by the following formula. It shows that it is excellent in thermal decomposition resistance, so that a thermogravimetric retention rate is large.
Thermal weight retention (%) = (weight at the time when 30 minutes have passed at 290 ° C.) / (Weight when the temperature reaches 290 ° C.) × 100

(Total light transmittance)
A test piece was cut out from an unstretched film or a biaxially stretched film. The total light transmittance of the test piece was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) according to JIS K7361-1. The methacrylic resin composition was hot pressed to obtain a molded product having a thickness of 3.2 mm, and the total light transmittance was measured in the same manner as described above.

(Haze)
A test piece was cut out from an unstretched film or a biaxially stretched film. The haze of the test piece was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) according to JIS K 7136. The methacrylic resin composition was hot-pressed to obtain a molded product having a thickness of 3.2 mm, and haze was measured in the same manner as described above.

(Roll dirt)
Using a film forming machine (model FS-5) manufactured by Optical Control System, cylinder temperature 290 ° C, T die temperature 290 ° C, lip gap 0.5mm, discharge rate 2.7kg / hr, roll temperature 85 ° C and film The methacrylic resin composition was extruded at a take-up speed of 2.2 m / min to produce a film having a thickness of 100 μm. The surface of the metal roll through which the film passes is visually observed, and the time from when the production of the film is started until when a slight white haze occurs on the roll surface is measured. When it was less than 5 minutes, it was rated as “B”.

(Production Example 1) (Production of methacrylic resin [A-1])
The inside of the autoclave fitted with the stirring blade and the three-way cock was replaced with nitrogen. To this, at room temperature, 1600 kg of toluene, 80 kg of 1,2-dimethoxyethane, 73.3 kg of a toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.45 M ( 42.3 mol) and a solution of 1.3 M sec-butyllithium (solvent: cyclohexane 95%, n-hexane 5%) were charged in an amount of 8.44 kg (14.1 mmol). While stirring, 550 kg of distilled methyl methacrylate was added dropwise at 30 ° C. over 30 minutes. After completion of dropping, the mixture was stirred at 15 ° C. for 90 minutes. The color of the solution changed from yellow to colorless. At this time, the polymerization conversion rate of methyl methacrylate was 100%.
The resulting solution was diluted by adding 1500 kg of toluene. Next, the diluted solution was poured into a large amount of methanol to obtain a precipitate. The obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours. The Mw was 70000, the molecular weight distribution was 1.06, the syndiotacticity (rr) was 75%, and the glass transition temperature was 131 ° C. And the methacryl resin [A-1] whose content of the structural unit derived from methyl methacrylate is 100 mass% was obtained.

(Production Example 2) (Production of methacrylic resin [A-2])
The inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate, 0.002 parts by mass of 2,2′-azobis (2-methylpropionitrile (hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.), and 0.200 parts by mass of n-octyl mercaptan was added and stirred to obtain a raw material liquid, and nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid.
The raw material liquid was put to 2/3 of the capacity in a tank reactor connected to the autoclave by piping. First, the polymerization reaction was started in a batch mode while maintaining the temperature at 140 ° C. When the polymerization conversion rate reaches 55% by mass, the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate of an average residence time of 150 minutes, and the reaction liquid is supplied at a flow rate corresponding to the supply flow rate of the raw material liquid. It was extracted from the tank reactor, maintained at a temperature of 140 ° C., and switched to a continuous flow polymerization reaction. After switching, the polymerization conversion in the steady state was 48% by mass.

  The reaction liquid withdrawn from the tank reactor in a steady state was heated by supplying it to a multi-tubular heat exchanger having an internal temperature of 230 ° C. at a flow rate with an average residence time of 2 minutes. Next, the heated reaction liquid was introduced into a flash evaporator, and volatile components mainly composed of unreacted monomers were removed to obtain a molten resin. The molten resin from which volatile components have been removed is supplied to a twin-screw extruder having an internal temperature of 260 ° C., discharged into a strand, cut with a pelletizer, Mw is 112,000, molecular weight distribution is 1.86, and syndiotacticity A methacrylic resin [A-2] having a city (rr) of 52%, a glass transition temperature of 120 ° C., and a content of structural units derived from methyl methacrylate of 100% by mass was obtained.

(Production Example 3) (Production of crosslinked rubber particles (m))
48 kg of ion-exchanged water is charged into a 100-liter reaction tank equipped with a condenser, a thermometer and a stirrer, and then dissolved with 416 g of sodium stearate, 128 g of sodium lauryl sarcosinate and 16 g of sodium carbonate. I let you. Next, 11.2 kg of methyl methacrylate and 110 g of allyl methacrylate were added and the temperature was raised to 70 ° C. while stirring. Thereafter, 560 g of a 2% aqueous potassium persulfate solution was added to initiate emulsion polymerization. The internal temperature increased due to heat generated by the polymerization, and then the internal temperature began to decrease. After dropping to 70 ° C., the mixture was stirred at 70 ° C. for 30 minutes for emulsion polymerization to obtain an emulsion containing seed particles.
To the emulsion containing seed particles, 720 g of a 2% aqueous sodium persulfate solution was added. Thereafter, a mixture of 12.4 kg of butyl acrylate, 1.76 kg of styrene and 280 g of allyl methacrylate was dropped over 60 minutes. After completion of dropping, the mixture was stirred for 60 minutes for emulsion polymerization to obtain an emulsion containing core-shell bilayer particles.
320 g of 2% aqueous potassium persulfate solution was added to the emulsion containing core-shell bilayer particles, and a mixture of 6.2 kg of methyl methacrylate, 0.2 kg of methyl acrylate and 200 g of n-octyl mercaptan was added over 30 minutes. . After completion of the addition, the mixture was stirred for 60 minutes for emulsion polymerization, and then cooled to room temperature to obtain an emulsion containing 40% of core-shell three-layered crosslinked rubber particles (m) having a volume-based average particle size of 0.23 μm.

(Production Example 4) (Production of polymer particles (n))
48 kg of ion-exchanged water is charged into a 100-liter reaction vessel equipped with a glass lining equipped with a condenser, thermometer and stirrer, and then 252 g of a surfactant (“Perex SS-H” manufactured by Kao Corporation) is charged. And dissolved. The reaction vessel was heated to 70 ° C. Thereafter, 160 g of 2% potassium persulfate aqueous solution was added thereto, and then a mixture consisting of 3.04 kg of methyl methacrylate, 0.16 kg of methyl acrylate and 15.2 g of n-octyl mercaptan was added all at once to start emulsion polymerization. I let you. Stirring was continued for 30 minutes after the exotherm due to the polymerization reaction disappeared.
Thereafter, 160 g of a 2% potassium persulfate aqueous solution was added thereto, and then a mixture consisting of 27.4 kg of methyl methacrylate, 1.44 kg of methyl acrylate and 98 g of n-octyl mercaptan was continuously added dropwise over 2 hours. After completion of dropping, the mixture was stirred for 60 minutes for emulsion polymerization. The resulting emulsion was cooled to room temperature. In this way, an emulsion containing 40% of (meth) acrylate polymer particles (n) having a volume-based average particle size of 0.12 μm and an intrinsic 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 auxiliary particles) obtained in Production Example 4 were used as the particles (m): mass of the particles (n). The mixture was mixed so that the ratio was 2: 1. The mixed emulsion was frozen at −20 ° C. for 2 hours. The frozen mixed emulsion was thrown into twice as much warm water at 80 ° C. and iced to obtain a slurry. The slurry was held at 80 ° C. for 20 minutes, then dehydrated and dried at 70 ° C. to obtain a powder composed of crosslinked rubber particles (D-1).

(Production Example 6) (Production of block copolymer [E-1])
In a three-necked flask with the inside replaced with nitrogen, 735 kg of dry toluene at room temperature, 36.75 kg of 1,2-dimethoxyethane, and 20 mol of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum were added. 39.4 kg of the contained toluene solution was added. To this was added 1.17 mol of sec-butyllithium. Further, 39.0 kg of methyl methacrylate was added thereto and reacted at room temperature for 1 hour to obtain a methyl methacrylate polymer [c1 ₁ ]. The weight average molecular weight Mw _c11 of the methyl methacrylate polymer [c1 ₁ ] contained in the reaction solution was 45800.

Next, the reaction solution was brought to −25 ° C., and a mixed solution of 29.0 kg of n-butyl acrylate and 10.0 kg of benzyl acrylate was added dropwise over 0.5 hours to prepare a methyl methacrylate polymer [c1 ₁ ]. The polymerization reaction is continued from the end, and a diblock copolymer [E2] comprising a methyl methacrylate polymer block [c1 ₁ ] and an acrylate polymer block [c2] consisting of n-butyl acrylate and benzyl acrylate -1]. The block copolymer [E-1] contained in the reaction solution had a weight average molecular weight Mw _CB-1 of 92000 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 ] was 45800, the weight average molecular weight of the acrylate polymer [c2] composed of n-butyl acrylate and benzyl acrylate was determined to be 46200. The proportion of benzyl acrylate contained in the acrylate polymer [c2] was 25.6% by mass.

Subsequently, 4 kg of methanol was added to the reaction solution to stop the polymerization reaction. Thereafter, the reaction solution was poured into a large amount of methanol to precipitate a 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 methacrylic ester polymer block [c1 ₁ ] to the mass of the acrylate polymer block [c2] was 50/50.

<Example 1>
Methacrylic resin [A-1] 60 parts by mass, Methacrylic resin [A-2] 40 parts by mass, phenolic hydroxyl group-containing compound [KH-6021] 1.0 part by mass, UV absorber [LA-F70] 0.9 parts by mass Part, block copolymer [E-1] 1 part by weight and processing aid [H-1] 2 parts by weight, twin screw extruder (manufactured by Technobel Co., Ltd., trade name: KZW20TW-45MG-NH- 600) 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 press molded to obtain a plate-like molded body of 50 mm × 50 mm × 3.2 mm. The total light transmittance and haze were measured using the plate-like molded product. The results are shown in Table 1.

The methacrylic resin composition [1] was dried at 80 ° C. for 12 hours. Using a 20 mmφ single-screw extruder (OCS), the methacrylic resin composition [1] is extruded from a 150 mm wide T-die at a resin temperature of 260 ° C., and is taken up by a roll having a surface temperature of 85 ° C. An unstretched film having a thickness of 110 mm and a thickness of 160 μm was obtained. The surface smoothness and strength of the produced unstretched film were measured. The evaluation results are shown in Table 1.
A small piece of 100 mm × 100 mm was cut out from an unstretched film having a thickness of 160 μm so that two sides were parallel to the extrusion direction. The small piece is set in a pantograph type biaxial stretching tester (manufactured by Toyo Seiki Co., Ltd.), and is uniaxially doubled in length in a direction parallel to the extrusion direction at a glass transition temperature of + 10 ° C. at 150% / min. Stretched. Next, it is uniaxially stretched twice in length in the direction perpendicular to the extrusion direction at a glass transition temperature + 10 ° C. at 150% / min, then held for 10 seconds, and finally taken out at room temperature and rapidly cooled. A biaxially stretched film having an area stretch ratio of 4 times and a thickness of 40 μm was obtained. About the obtained biaxially stretched film, the total light transmittance and haze were measured. The results are shown in Table 1.

<Examples 2-8, Comparative Examples 1-2>
The methacrylic resin compositions [2] to [10] were produced in the same manner as in Example 1 except that the blending ratios shown in Tables 1 and 2 were used, and the physical properties were measured in the same manner as in Example 1.
The evaluation results are shown in Tables 1 and 2.

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

The meanings of the abbreviations in the table are as follows.
Phenolic hydroxyl group-containing compound [B]
KH-6021: Bisphenol A type novolak resin (manufactured by DIC, weight average molecular weight Mw = 3000, molecular weight distribution Mw / Mn = 3.33, the number of phenolic hydroxyl groups in one molecule = average 7.5).
VP8000: polyparahydroxystyrene (manufactured by Nippon Soda Co., Ltd., weight average molecular weight Mw = 9800, molecular weight distribution Mw / Mn = 1.09, number of phenolic hydroxyl groups in one molecule = average 75).

UV absorber [C]
LA-31: 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4-t-octylphenol] (manufactured by ADEKA)
LA-F70: 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA)

Polycarbonate resin [G]
G-1: linear polycarbonate resin (manufactured by Sumika scan Tyrone polycarbonate Inc., SD POLYCA TR-2201 (product number), MVR (300 ℃, 1.2Kg , 10 minutes; JIS K7210 compliant) = 210cm ^3/10 min, Mw = 22000, Mw / Mn = 2.0) The number of phenolic hydroxyl groups in one molecule = 0-2.

Processing aid [H]
H-1: Metablene P550A manufactured by Mitsubishi Rayon Co., Ltd. (average polymerization degree: 7734, structural unit 88% by mass derived from methyl tacrylate, structural unit 12% by mass derived from butyl acrylate)

Antioxidant [I]
I-1: Hindered phenol 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)

  Methacrylic resin [A] 70 to 99.99% by mass and a compound having a molecular weight of 2,000 to 300,000 and having three or more phenolic hydroxyl groups in one molecule [B] 0.01 to 30% by mass A thermoplastic methacrylic resin composition.   The methacrylic resin composition according to claim 1, wherein the methacrylic resin [A] contains 90 mass% or more of a structural unit derived from methyl methacrylate.   A methacrylic resin composition according to claim 1 or 2, 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.   A structural unit having a ring structure in the main chain is a structural unit containing a> CH—O—C (═O) — group in the ring structure, and a —C (═O) —O—C (═O) — group is a ring structure. A structural unit containing a —C (═O) —N—C (═O) — group in the ring structure, or a structural unit containing a> CH—O—CH <group in the ring structure. 3. The methacrylic resin composition according to 3.   The methacrylic resin composition according to any one of claims 1 to 4, wherein the compound [B] is polyvinylphenol, 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 5, further comprising an ultraviolet absorber [C].   The methacrylic resin composition according to any one of claims 1 to 6, further comprising a crosslinked rubber [D].   The methacrylic resin composition according to any one of claims 1 to 7, further comprising a block copolymer [E] or a graft copolymer [F].   The methacrylic resin composition according to any one of claims 1 to 8, further comprising a polycarbonate resin [G].   The molded object which consists of a methacryl resin composition as described in any one of Claims 1-9.   The film which consists of a methacryl resin composition as described in any one of Claims 1-9.   An optical film comprising the film according to claim 11.   A polarizer protective film comprising the film according to claim 11.   A retardation film comprising the film according to claim 11.   The polarizing plate formed by laminating | stacking at least 1 sheet of the film as described in any one of Claims 11-14. Melting methacrylic resin [A] 70 to 99.99 mass% and compound [B] 0.01 to 30 mass% having a molecular weight of 2,000 to 300,000 and having three or more phenolic hydroxyl groups in one molecule Kneading to obtain a thermoplastic methacrylic resin composition,
The manufacturing method of a molded object which has melt-molding this methacrylic resin composition.