WO2021020426A1 - Methacryl resin composition, resin modifier, molded body, film, and film manufacturing method - Google Patents

Abstract

Provided is a methacryl resin that contains: a methacryl polymer (A) having a weight-average molecular weight Mw_A of at least 30,000, a ratio of the weight-average molecular weight Mw_A to the number average molecular weight Mn_A of 1.0 to 1.4, and a glass transition temperature of 125 °C; and a methacryl polymer (B) having a weight-average molecular weight Mw_B of 80,000 to 3,000,000 and at least 2.5 times the weight-average molecular weight Mw_A. The melt viscosity η_B of the methacryl polymer (B) at a shear rate of 122 s^-1 and a temperature of 260 °C is higher than the melt viscosity η_A of the methacryl polymer (A) at a shear rate of 122 s^-1 and a temperature of 260 °C; the mass ratio of the methacryl polymer (A) with respect to the methacryl polymer (B) is 2/98 to 39/61; and a peak top molecular weight M_{P t} at which a weight fraction derivative value of a weight-basis differential molecular weight distribution curve is highest is 100,000 to 2,000,000.

Description

Methacrylic resin composition, resin modifier, molded product and film, and method for producing film

The present invention relates to a methacrylic resin composition, a resin modifier, a molded product and a film, and a method for producing a film.

Methacrylic resin (a polymer mainly containing structural units derived from methacrylic acid ester) is excellent in transparency, light resistance, surface hardness and the like. Various optical members such as a light guide plate, a lens, a sheet, and a film can be obtained by molding a resin composition containing a methacrylic resin.

Patent Document 1 describes a (meth) acrylic resin A having a weight average molecular weight of preferably 200,000 or less, and a glass transition temperature lower than that of the (meth) acrylic resin A, and a weight average molecular weight of preferably 100,000 or more and 1,000,000 or less. A (meth) acrylic resin B contains a (meth) acrylic resin A in a weight ratio of preferably 80/20 to 40/60 of the (meth) acrylic resin B. The composition and the film containing the composition are disclosed. Patent Document 1 states that if the content of the (meth) acrylic resin B is excessively large, the heat shrinkage rate of the obtained (meth) acrylic resin film tends to increase.

In Patent Document 2, the α relaxation temperature Tα1 when measured in dynamic viscoelasticity at 1 Hz in a tensile mode is 137 ° C. or higher, the molecular weight distribution is preferably 1.0 to 1.4, and the weight average molecular weight is 40,000 to 40,000. A methacrylic resin (M1) having a weight average of 200,000 and a methacrylic resin (M2) having an α relaxation temperature Tα ₂ of 132 ° C. or lower and a weight average molecular weight of preferably 40,000 to 200,000 when measured in a tensile mode and dynamic viscoelasticity at 1 Hz. ), And η ₁ > η ₂ when the melt viscosities of the methacrylic resin (M1) and the methacrylic resin (M2) at 260 ° C. and a shear rate of 122 seconds- ¹ are η ₁ and η ₂ , respectively. A methacrylic resin composition having a molecular weight ratio of methacryl resin (M1) / methacryl resin (M2) of 2/98 to 29/71 is disclosed.

Patent Document 3 discloses a dope composition containing a methacrylic resin having a weight average molecular weight of 250,000 or more and additives such as a phenolic compound having a weight average molecular weight of less than 50,000, a styrene copolymer, and a novolak resin. doing.

JP-A-2015-10757 WO2018 / 021449A1 WO2015 / 09876A1

An object of the present invention is to provide a novel methacrylic resin composition, resin modifier, molded product and film, and a method for producing a film.

The present invention includes the following forms.

[1] Polymer having a weight average molecular weight Mw _A of 30,000 or more, a ratio of weight average molecular weight Mw _{A to} a number average molecular weight Mn _A of 1.0 to 1.4, and a glass transition temperature of 125 ° C. or more. The polymer (A) and the methacrylic polymer (B) having a weight average molecular weight Mw _B of 80,000 to 3,000, which is 2.5 times or more the weight average molecular weight Mw _A , and the methacrylic polymer (B) shear rate 122 sec ^-1 and melt viscosity eta _B at a temperature 260 ° C. is higher than the melt viscosity eta _a at a shear rate of 122 sec ^-1 and a temperature 260 ° C. methacrylic polymer (a),
The peak top molecular weight M _Pt having the mass ratio of the methacrylic polymer (A) to the methacrylic polymer (B) of 2/98 to 39/61 and having the highest weight fraction differential value in the weight-based differential molecular weight distribution curve is 100,000 to 2000,000,
Methacrylic resin.

[2] In the weight-based differential molecular weight distribution curve, the sum of the weight fraction differential values of the components having a molecular weight of 1/20 or less of the peak top molecular weight M _Ph having the highest molecular weight is the sum of the weight fraction differential values of all the components. [1], wherein the total of the weight fraction derivative values of the components having a molecular weight of 15,000 or less is 2% or less with respect to the total weight fraction derivative values of all the components. Methyl resin.

[3] The methacrylic resin according to [1] or [2], wherein the weight average molecular weight Mw _A is 40,000 to 140000 and the weight average molecular weight Mw _B is 160000 to 2000000.
[4] The absolute value of the difference between the refractive index n _dA of the methacrylic polymer (A) and the refractive index n _dB of the methacrylic polymer (B) | n _dA −n _dB | is 0.005 or less, [1]. The methacrylic resin according to any one of [3].
[5] A resin composition containing the methacrylic resin according to any one of [1] to [4] and an elastomer.

[6] has a weight average molecular weight Mw of from 40,000 to 140,000, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of 1.0-1.4, the refractive index n _d be from 1.485 to 1.495 , A methacrylic polymer (A) having a triad syndiotacticity (rr) of 63 to 80%, a glass transition temperature of 125 ° C. or higher, and containing 100% by mass of a structural unit derived from methyl methacrylate. Resin modifier.
[7] In the methacrylic polymer (A), the total weight fraction differential values of the components having a molecular weight of 15,000 or less in the weight-based differential molecular weight distribution curve is 2% of the total weight fraction differential values of all the components. The resin modifier according to [6] below.

[8] A molded product containing the methacrylic resin according to any one of [1] to [4].

[9] A film containing the methacrylic resin according to any one of [1] to [4] and having a thickness of 20 μm or more and 200 μm or less.
[10] The film according to [9], which is for optics.

[11] A doping containing the methacrylic resin according to any one of [1] to [4] and an organic solvent.

[12] The doping according to [11] is cast on a casting support, and the doping is cast.
A method for producing a film, which comprises then removing the organic solvent.
[13] The production method according to [12], wherein the thickness of the film is 20 μm or more and 200 μm or less.

The methacrylic resin or resin composition of the present invention has high transparency and high heat resistance. The molded product of the present invention, for example, a film, has high transparency, high heat resistance, and high mechanical strength, and is also excellent in surface smoothness, surface hardness, or impact resistance. The method for producing a film of the present invention has a short time required for evaporation of an organic solvent, and has high production efficiency for a film having excellent surface smoothness, surface hardness, or impact resistance.

The methacrylic resin of the present invention contains a methacrylic polymer (A) and a methacrylic polymer (B).

The methacrylic polymer (A) is a random polymer mainly containing a structural unit derived from a methacrylic acid ester. This methacrylic polymer (A) can be used as a resin modifier.

Examples of the methacrylic acid ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; aryl methacrylate esters such as phenyl methacrylate; and cycloalkyl methacrylates such as cyclohexyl methacrylate and norbornenyl methacrylate. ; Can be mentioned. Of these, alkyl methacrylate esters are preferred, and methyl methacrylate is most preferred.

The amount of the structural unit derived from the methacrylic acid ester contained in the methacrylic polymer (A) is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total structural units of the methacrylic polymer (A). It is more preferably 98% by mass or more, even more preferably 99% by mass or more, and most preferably 100% by mass.
Among the structural units derived from methacrylic acid ester, the content of the structural unit derived from methyl methacrylate of the methacrylic acid polymer (A) is preferably 90% by mass with respect to all the structural units of the methacrylic acid polymer (A). % Or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more, and most preferably 100% by mass.

The methacrylic polymer (A) may contain a structural unit derived from a monomer other than the methacrylic acid ester. Examples of the monomer other than the methacrylic acid ester include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; acrylic acids such as phenyl acrylate. Acrylic ester; Acrylic acid cycloalkyl ester such as cyclohexyl acrylate and norbornenyl acrylate; Aromatic vinyl compounds such as styrene and α-methylstyrene; acrylamide; Methalamide; Acrylonitrile; Methacronitrile; Examples thereof include vinyl-based monomers having only one polymerizable carbon-carbon double bond.

The weight average molecular weight Mw _A of the methacrylic polymer (A) is usually 30,000 or more, preferably 40,000 to 200,000, more preferably 40,000 to 140,000, and further preferably 40,000 to 100,000. When Mw _A is 30,000 or more, the impact resistance and toughness of the molded product tend to be improved. The upper limit of Mw _A is not particularly limited, the Mw _A is 200,000 or less, the flowability of the methacrylic resin or resin composition, to provide good moldability tends to be a sufficient level.

The methacrylic polymer (A) has a ratio of weight average molecular weight Mw _{A to} number average molecular weight Mn _A (Mw _A / Mn _A ) of usually 1.0 to 1.4, preferably 1.01 to 1.4. It is more preferably 1.05 to 1.4, still more preferably 1.05 to 1.3. When a methacrylic polymer (A) having Mw _A / Mn _A within this range is used, it is easy to obtain a molded product having excellent mechanical strength. In addition, Mw _A and Mn _A are values calculated by converting into the molecular weight of standard polystyrene based on the chromatogram measured by gel permeation chromatography.

Gel permeation chromatography can be performed as follows. Tetrahydrofuran is used as the eluent, and two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and Super HZ4000 are connected in series as the column. As an analyzer, HLC-8320 (product number) manufactured by Tosoh Corporation equipped with RI (differential refractometer) is used. 4 mg of the sample resin is dissolved in 5 ml of tetrahydrofuran and further filtered through a 0.1 μm filter to obtain a sample solution. The temperature of the column oven is set to 40 ° C., 20 μl of the sample solution is injected at an eluent flow rate of 0.35 ml / min, and the chromatogram is measured. The chromatogram is a chart obtained by plotting an electric signal (detection intensity Y) derived from the difference in refractive index between the sample solution and the reference solution with respect to the elution time (retention time).
Conversion of standard polystyrene to molecular weight is performed based on the calibration curve. A calibration curve is created by measuring the chromatogram by gel permeation chromatography for each standard polystyrene in the range of 400 to 500000 molecular weight and plotting the elution time and the logarithmic value of the molecular weight.

In the methacrylic polymer (A), the sum of the weight fraction differential values of the components (M ≤ 15,000) having a molecular weight of 15,000 or less is the sum of the weight fraction differential values of all the components in the weight-based differential molecular weight distribution curve. On the other hand, it is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less. The smaller the total weight fraction derivative of the components having a molecular weight of 15,000 or less, the higher the strength of the methacrylic resin composition tends to be.
In the weight-based differential molecular weight distribution curve, the horizontal axis is the logarithmic log (M) of the molecular weight, and the vertical axis is the weight fraction differential value (the value dw obtained by differentiating the weight fraction W with the logarithmic log (M) of the molecular weight). It is a plot of / d (log (M))), and is obtained by converting the horizontal axis to the molecular weight of standard polystyrene based on the chromatogram used in calculating Mw _A and Mn _A. .. In particular,
1) Draw a baseline on the chromatogram to identify the peak and
2) Using the logarithmic value of the molecular weight of standard polystyrene-elution time calibration curve (calibration curve), convert the elution time to the molecular weight,
3) Calculate the peak area, calculate the weight fraction for each elution time,
4) Plot the logarithmic value of molecular weight on the horizontal axis and the weight fraction on the vertical axis.
5) Sequentially integrate the weight fractions and plot the logarithmic value of the molecular weight on the horizontal axis and the integrated value of the weight fractions on the vertical axis to obtain the integrated molecular weight distribution curve.
6) Calculate the differential value (weight fraction differential value dw / d (log (M))) of the integrated molecular weight distribution curve for each molecular weight.
7) Plot the logarithmic log (M) of molecular weight on the horizontal axis and the weight fraction differential value dw / d (log (M)) on the vertical axis to obtain a differential molecular weight distribution curve.
For the total of the weight fraction differential values in the predetermined molecular weight range, the area surrounded by the differential molecular weight distribution curve and the line where the weight fraction differential value is zero in the predetermined molecular weight range can be used as a representative value.

The glass transition temperature of the methacrylic polymer (A) is preferably 125 ° C. or higher, more preferably 127 ° C. or higher, and even more preferably 129 ° C. or higher. The upper limit of the glass transition temperature of the methacrylic polymer (A) is preferably 140 ° C. The higher the glass transition temperature of the methacrylic polymer (A), the higher the heat resistance of the methacrylic resin or resin composition of the present invention, and the less likely it is that deformation such as heat shrinkage will occur.

The lower limit of the triad syndiotacticity (rr) of the methacrylic polymer (A) is 63%, preferably 65%, more preferably 72%, and the upper limit is preferably 90%, more preferably 85%. More preferably, it is 80%. When the triad syndiotacticity (rr) of the methacrylic polymer (A) is 63% or more, the methacrylic resin or resin composition of the present invention has high heat resistance and tends to be less likely to be deformed such as heat shrinkage. is there. Further, when the triad syndiotacticity (rr) of the methacrylic polymer (A) is in the above range, the strength of the methacrylic resin or the resin composition of the present invention is particularly improved. It is considered that this is because the carbonyl-carbonyl interaction between the methacrylic polymer (A) and the methacrylic polymer (B) is improved.

Here, in triad syndiotacticity (rr), two chains (doubles, diad) of a chain of three consecutive structural units (triple, triad) are both racemo (denoted as rr). Is the ratio. In the chain of structural units (doubles, diads) in the polymer molecule, those having the same configuration are referred to as meso, and the opposite ones are referred to as racemo, which are referred to as m and r, respectively.
The triad syndiotacticity (rr) (%) is a region of 0.6 to 0.95 ppm when ^{1 1} H-NMR spectrum is measured at 30 ° C. in deuterated chloroform and TMS is 0 ppm. The area (X) of the above 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.

The method for producing the methacrylic polymer (A) is not particularly limited as long as the methacrylic polymer (A) satisfying the above physical characteristics can be obtained. From the viewpoint of productivity, the anion polymerization method is preferable. More preferably, in the anion polymerization method, the polymerization temperature, the polymerization time, the type and amount of the chain transfer agent, the type and amount of the polymerization initiator, and the like are appropriately set so as to satisfy the above-mentioned physical property values. Produces methacrylic polymer (A).

Examples of the anionic polymerization method include a method in which an organic alkali metal compound is used as a polymerization initiator and anionic polymerization is carried out in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt (see Special Fair 7-25859), and organic. A method of anionic polymerization using an alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see JP-A-11-335432) and a method of anionic polymerization using an organic rare earth metal complex as a polymerization initiator (see JP-A-6-93060). ) And so on.

In the anion polymerization method, it is preferable to use alkyllithium such as n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium as the polymerization initiator. Further, from the viewpoint of productivity, it is preferable that the organoaluminum compound coexists. As the organic aluminum, the compound represented by Al R ¹ R ² R ³ (R ¹ , R ² and R ³ may have an alkyl group or a substituent which may independently have a substituent, respectively. A good cycloalkyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent. Alternatively, it represents an N, N-disubstituted amino group. Further, R ² and R ³ may be an arylenoxy group which may have a substituent formed by binding them.) be able to. Specific examples of the organoaluminum compound include isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, and isobutyl [2,2]. '-Methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum and the like can be mentioned. Further, in the anion polymerization method, an ether, a nitrogen-containing compound, or the like can coexist in order to control the polymerization reaction.

The methacrylic polymer (A) is useful as a resin modifier, and is particularly useful as a modifier for the methacrylic polymer (B).

The methacrylic polymer (B) is a random polymer mainly containing a structural unit derived from a methacrylic acid ester.

Examples of the methacrylic acid ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; aryl methacrylate esters such as phenyl methacrylate; and cycloalkyl methacrylates such as cyclohexyl methacrylate and norbornenyl methacrylate. ; Can be mentioned. Of these, alkyl methacrylate esters are preferred, and methyl methacrylate is most preferred.
The amount of the structural unit derived from the methacrylic acid ester contained in the methacrylic polymer (B) is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total structural units of the methacrylic polymer (B). ..

The methacrylic polymer (B) may contain a structural unit derived from an acrylic acid ester. Examples of the acrylic acid ester include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic acid aryl esters such as phenyl acrylate; to cyclo acrylate. Examples thereof include acrylic acid cycloalkyl esters such as xyl and norbornenyl acrylate. The amount of the structural unit derived from the acrylic acid ester contained in the methacrylic polymer (B) is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the total structural units of the methacrylic polymer (B). %.

The methacrylic polymer (B) may contain a structural unit derived from a monomer other than the methacrylic acid ester and the acrylic acid ester. Examples of monomers other than methacrylic acid ester and acrylic acid ester include α, β-unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; unsaturated group-containing divalent carboxylic acids such as maleic anhydride, fumaric acid and itaconic acid. Aromatic vinyl compounds such as styrene and α-methylstyrene; α and β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like can be mentioned. .. The amount of structural units derived from monomers other than methyl methacrylate and acrylic acid ester contained in the methacrylic polymer (B) is preferably 20% by mass or less based on the total structural units of the methacrylic polymer (B). , More preferably 10% by mass or less.

The weight average molecular weight Mw _B of the methacrylic polymer (B) is preferably 80,000 or more, more preferably 80,000 to 3,000, more preferably 120,000 to 2,500,000, still more preferably 16,000 to 20,000,000. When Mw _B is 80,000 or more, the impact resistance and toughness of the methacrylic resin or the resin composition tend to be improved. The upper limit of Mw _B is not particularly limited from the viewpoint of impact resistance and toughness, but the methacrylic polymer (B) having Mw _B exceeding 3,000,000 tends to be difficult to produce. When Mw _B is 160,000 or more, the strength of the methacrylic resin or the resin composition is particularly improved. It is considered that this is because the carbonyl-carbonyl interaction between the methacrylic polymer (A) and the methacrylic polymer (B) is improved.

The ratio (Mw _B / Mn _B ) of the weight average molecular weight Mw _{B to} the number average molecular weight Mn _B of the methacrylic polymer (B) is preferably 1.7 to 2.6, more preferably 1.7 to 2. 5, more preferably 1.7 to 2.3. When a methacrylic polymer (B) having Mw _B / Mn _B within this range is used, it is easy to obtain a molded product having excellent mechanical strength. In addition, Mw _B and Mn _B are values calculated by converting into the molecular weight of standard polystyrene based on the chromatogram measured by gel permeation chromatography.

The methacrylic polymer (B) has a glass transition temperature of preferably 100 ° C. or higher, more preferably 105 ° C. or higher. The upper limit of the glass transition temperature of the methacrylic polymer (B) is preferably 140 ° C. When the glass transition temperature of the methacrylic polymer (B) is in this range, the heat resistance of the methacrylic resin or the resin composition becomes high, and deformation such as heat shrinkage tends to be difficult to occur.

The methacrylic polymer (B) has a triad syndiotacticity (rr) of preferably 45 to 63%, more preferably 49 to 60%. When the triad syndiotacticity (rr) of the methacrylic polymer (B) is in the above range, the heat resistance of the methacrylic resin or the resin composition and the moldability tend to be well balanced.

The method for producing the methacrylic polymer (B) is not particularly limited as long as the methacrylic polymer (B) satisfying the above physical characteristics can be obtained. Examples of the method for producing the methacrylic polymer (B) include radical polymerization and anionic polymerization from the viewpoint of the reaction active site. In addition, the method for producing the methacrylic polymer (B) includes emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like from the viewpoint of the form of the polymerization reaction solution. Of these, radical emulsion polymerization, radical bulk polymerization, or radical suspension polymerization is preferable, and radical bulk polymerization is more preferable, from the viewpoint of high productivity and ease of polymerization.

Specific examples of the polymerization initiator used in bulk polymerization or suspension polymerization include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy2-ethylhexanoate, and 1,1,3,3-tetramethylbutyl. Peroxy2-ethylhexanoate, t-butylperoxypivarate, t-hexylperoxypivalate, t-butylperoxyneodecanoeate, t-hexylperoxyneodecanoeate, 1,1 , 3,3-Tetramethylbutylperoxyneodecanoate, 1,1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, etc. Peroxides: 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), etc. Azo compounds and the like can be mentioned. Of these, t-hexyl peroxy2-ethylhexanoate, 1,1-bis (t-hexyl peroxy) cyclohexane, and dimethyl 2,2'-azobis (2-methylpropionate) are preferable. Specific examples of the polymerization initiator used in emulsion polymerization are persulfate-based initiators such as potassium persulfate and ammonium persulfate; and redox-based initiators such as persulfoxylate / organic peroxide and persulfate / sulfite. Agents can be mentioned. The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator used may be set so that a methacrylic polymer (B) satisfying the above physical property values can be obtained. For example, with respect to 100 parts by mass of the monomer to be subjected to the polymerization reaction. It can be appropriately set within the range of preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.01 parts by mass, and further preferably 0.005 to 0.007 parts by mass. it can.

The polymerization initiator used in bulk polymerization is one that generates reactive radicals. The polymerization initiator has a 1-hour half-life temperature of preferably 60 to 140 ° C, more preferably 80 to 120 ° C. Further, the polymerization initiator has a hydrogen extraction ability of preferably 20% or less, more preferably 10% or less, still more preferably 5% or less.

The hydrogen abstraction ability can be known from the technical data of the polymerization initiator manufacturer (for example, the technical data of Nippon Oil & Fats Co., Ltd. "Hydrogen extraction ability of organic peroxide and initiator efficiency" (created in April 2003)). .. Further, the hydrogen extraction ability can be measured by a radical trapping method using an α-methylstyrene dimer, that is, an α-methylstyrene dimer trapping method. The measurement is generally performed as follows. First, the polymerization initiator is cleaved in the coexistence of α-methylstyrene dimer as a radical trapping agent to generate a radical fragment. Among the generated radical fragments, the radical fragment having a low hydrogen abstraction force is added to the double bond of the α-methylstyrene dimer and captured. On the other hand, a radical fragment having a high hydrogen abstraction force abstracts hydrogen from cyclohexane to generate a cyclohexyl radical, and the cyclohexyl radical is added to and trapped in the double bond of α-methylstyrene dimer to generate a cyclohexane trapping product. Therefore, cyclohexane or cyclohexane capture product is quantified, the ratio (mole fraction) of radical fragments having high hydrogen abstraction power to the theoretical amount of radical fragment generation is calculated, and this is used as the hydrogen abstraction ability.

Chain transfer agents used in massive polymerization include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol. Bisthioglycolate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropanthris- (β-thiopropionate), pentaerythritol tetraxthiopropionate, etc. Alkyl mercaptans and the like can be mentioned. Of these, monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferable. These chain transfer agents may be used alone or in combination of two or more.
The amount of the chain transfer agent used may be set so that the methacrylic polymer (B) satisfying the above physical property values can be obtained. For example, with respect to 100 parts by mass of the monomer subjected to the polymerization reaction. It can be appropriately set within the range of preferably 0 to 0.5 parts by mass, more preferably 0.05 to 0.4 parts by mass, and further preferably 0.06 to 0.25 parts by mass. The amount of the chain transfer agent used can be appropriately set within the range of preferably 2500 to 10000 parts by mass, more preferably 3000 to 9000 parts by mass with respect to 100 parts by mass of the polymerization initiator.

A suspension stabilizer can be used in suspension polymerization. Examples of the suspension stabilizer include an organic colloidal polymer substance, an inorganic colloidal polymer substance, inorganic fine particles, and a combination thereof with a surfactant.

An emulsifier can be used in emulsion polymerization. Examples of the emulsifier include dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dilauryl sulfosuccinate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, and alkyl sulfates such as sodium dodecyl sulphate; nonions. Polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, etc., which are system emulsifiers; polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene alkyl ether sulfate, etc., which are nonionic and anionic emulsifiers, such as polyoxyethylene nonylphenyl ether sulfate. Polyoxyethylene alkyl ether sulfate such as sodium, alkyl ether carboxylate such as polyoxyethylene tridecyl ether sodium acetate; can be mentioned. These emulsifiers may be used alone or in combination of two or more. The average number of repeating units of ethylene oxide units in the examples of the nonionic emulsifier and the nonionic / anion 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.

In emulsion polymerization or suspension polymerization, the resin is taken out from the reaction product solution by a known method after the completion of the polymerization reaction. In emulsion polymerization, the resin can be taken out from the reaction product liquid (emulsion) by a salting out coagulation method, a freeze coagulation method, a spray drying method or the like. Among these, the salting out coagulation method and the freeze coagulation method are preferable from the viewpoint that impurities contained in the resin can be easily removed by washing with water. It is preferable to filter the emulsion with a wire mesh having a mesh size of 50 μm or less before the coagulation step because foreign substances mixed in the emulsion can be removed.

In the methacrylic resin of the present invention, the methacrylic polymer (B) has a shear rate of 122 seconds- ¹ and a melt viscosity η _{B at a} temperature of 260 ° C., and the methacrylic polymer (A) has a shear rate of 122 seconds- ¹ and a temperature of 260 ° C. Higher than viscosity η _A. The difference between the melt viscosity η _B and the melt viscosity η _A is preferably 1000 Pa · s or more, and more preferably 1500 Pa · s or more.
Further, in the methacrylic resin of the present invention, the weight average molecular weight Mw _B of the methacrylic polymer (B) is 2.5 times or more, preferably 3 times or more the weight average molecular weight Mw _A.

The methacrylic resin of the present invention has an absolute value of the difference between the refractive index n _dA of the methacrylic polymer (A) and the refractive index n _dB of the methacrylic polymer (B) | n _dA −n _dB |, preferably 0.005. It is as follows.

The amount of the methacrylic polymer (A) contained in the methacrylic resin of the present invention is preferably 2 to 39 with respect to the methacrylic resin from the viewpoint of achieving both heat resistance and molding processability or surface smoothness in a good state. It is by mass, more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and most preferably 5 to 16% by mass.

The amount of the methacrylic polymer (B) contained in the methacrylic resin of the present invention is preferably 61 to 98 mass with respect to the methacrylic resin from the viewpoint of achieving both heat resistance or mechanical strength and molding processability in a good state. %, More preferably 70 to 95% by mass, still more preferably 80 to 95% by mass, and most preferably 84 to 95% by mass.

The methacrylic resin of the present invention has a mass ratio of the methacrylic polymer (A) to the methacrylic polymer (B) of 2/98 to 39/61, more preferably 5/95 to 30/70, still more preferably 5/95. ~ 20/80.

Methacrylic resin of the present invention, the highest peak top molecular weight M _Pt weight fraction differential value in the differential molecular weight distribution curve of the weight is preferably from 100000 to 2000000, more preferably 120000 to 2000000, more preferably at from 160,000 to 2,000,000 is there. When the peak top molecular weight _MPt is in this range, a molded product having excellent strength, hardness, and surface smoothness can be obtained.

The methacrylic resin of the present invention has a weight fraction differential value of a component (M ≤ 1/20 M _Ph ) having a molecular weight of 1/20 or less of the peak top molecular weight M _Ph having the highest molecular weight in the weight-based differential molecular weight distribution curve. The total is preferably 2% or less, more preferably 1.5% or less, based on the total weight fraction derivative values of all the components.
In the methacrylic resin of the present invention, in the weight-based differential molecular weight distribution curve, the total of the weight fraction differential values of the components having a molecular weight of 15,000 or less (M ≤ 15,000) is relative to the total weight fraction differential values of all the components. It is preferably 2% or less, more preferably 1.75% or less.
The effect of the methacrylic resin or resin composition of the present invention is further improved by the small amount of the low molecular weight component as described above.

The methacrylic resin composition of the present invention contains the methacrylic resin of the present invention. The methacrylic resin composition of the present invention may contain the methacrylic resin of the present invention and a resin other than the methacrylic resin (additional resin).
Examples of other resins include olefin-based thermoplastic resins such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-1-pentene); halogen-containing heat such as vinyl chloride and vinyl chlorinated resins. Plastic resin; Acrylic thermoplastic resin; Polystyrene-based thermoplastic resin such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer; polyethylene terephthalate, polybutylene terephthalate, Polyesters such as polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetals; polycarbonates; polyphenylene oxides; polyphenylene sulfides; polyether ether ketones; polysulphons; polyether salphons; Examples thereof include rubbery polymers such as ABS resin and ASA resin containing acrylic rubber, and cellulose resins such as polyvinyl butyral and cellulose acylate. In the methacrylic resin composition of the present invention, these other resins may be in a compatible state or a phase-separated state with the methacrylic resin of the present invention.

The methacrylic resin composition of the present invention may contain the methacrylic resin of the present invention, an elastomer, and if necessary, the other resin described above.

Elastomer is a mixture of methacrylic resin in a compatible state or a phase-separated state. The elastomer is preferably mixed with a methacrylic resin in a phase-separated state to form a dispersed phase. The shape of the dispersed phase is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, a rod shape, a flat body shape, and a string shape. The size of the dispersed phase is not particularly limited, but for example, the average particle size is preferably 0.05 to 1 μm, more preferably 0.07 to 0.5 μm, and further preferably 0.10 to 0.4 μm.

The elastomer is preferably a polymer containing a structural unit derived from an acrylic acid ester. Examples of the acrylic acid ester include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; acrylic acids such as cyclohexyl acrylate and norbornenyl acrylate. Acrylic acid cycloalkyl ester; Of these, alkyl acrylate esters are preferred, and butyl acrylate is most preferred.
The amount of the structural unit derived from the acrylic acid ester contained in the elastomer is preferably 30% by mass or more, more preferably 35% by mass or more and 90% by mass or less, and further preferably 40% by mass or more and 80% by mass or less.

In addition to the structural unit derived from the acrylic acid ester, the elastomer may have a structural unit derived from a vinyl-based monomer having only one polymerizable carbon-carbon double bond in one molecule. Examples of the vinyl-based monomer include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; and aryl methacrylates such as phenyl methacrylate; Cycloalkyl methacrylic acid esters such as cyclohexyl methacrylate and norbornenyl methacrylate; aralkyl esters of methacrylic acid such as benzyl methacrylate, aromatic vinyl compounds such as styrene and α-methylstyrene; acrylamide; methacrylicamide; acrylonitrile; methacrylic nitrile ; And so on.

The amount of elastomer contained in the methacrylic resin composition of the present invention is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and further preferably 0 to 30% by mass with respect to the methacrylic resin composition. .. The amount of elastomer can be appropriately set from the viewpoints of chemical resistance, heat resistance, flexural modulus, workability, and the like.

The elastomer is not particularly limited by the form of its molecular chain, and is, for example, a linear polymer elastomer (for example, a random copolymer elastomer, a block copolymer elastomer, etc.), a branched chain polymer elastomer (for example, a graft elastomer). Elastomer, star-type block copolymer elastomer), and the like. Of these, the elastomer preferably contains a block copolymer elastomer composed of a polymer block mainly having a structural unit derived from a methacrylic acid ester and a polymer block having a structural unit derived from an acrylic acid ester. ..

The elastomer may be particles containing a crosslinked rubber polymer containing a structural unit derived from an acrylic acid ester (hereinafter, referred to as crosslinked rubber particles).

The crosslinked rubber particles have an average particle diameter of preferably 0.05 to 1 μm, more preferably 0.07 to 0.5 μm, and even more preferably 0.10 to 0.4 μm. When crosslinked rubber particles having an average particle size within such a range, particularly an average particle size of 0.15 to 0.3 μm, are used, toughness can be exhibited with a small amount of compounding without impairing rigidity and surface hardness. Can be done. The average particle size is an average value in a volume-based particle size distribution measured by a light scattering method.

The crosslinked rubber particles are preferably composed of an inner layer and an outermost layer covering the inner layer. The inner layer may be composed of only a core layer, or may be composed of a core layer and an intermediate layer covering the core layer. The intermediate layer may be a single layer made of one polymer, or may be a multilayer made of different polymers.
From the viewpoint of transparency, the crosslinked rubber particles have a difference in refractive index _nd between the two adjacent layers, preferably less than 0.01, more preferably less than 0.008, and further preferably less than 0.005. Is preferable.

The mass ratio of the inner layer to the outermost layer of the crosslinked rubber particles is preferably 60/40 to 95/5, more preferably 70/30 to 90/10.

The crosslinked rubber particles include, for example, two-layer particles of a core layer made of a crosslinked rubber polymer (II) and an outermost layer made of a thermoplastic polymer (III) covering the core layer; the crosslinked polymer (I). Three-layer particles consisting of a core layer composed of, an intermediate layer composed of a crosslinked rubber polymer (II) covering the core layer, and an outermost layer composed of a thermoplastic polymer (III) covering the intermediate layer; a crosslinked rubber polymer. A core layer composed of (II), a first intermediate layer composed of a crosslinked polymer (I) covering the core layer, and a second intermediate layer composed of a crosslinked rubber polymer (II) covering the first intermediate layer. Examples thereof include four-layer particles with the outermost layer made of the thermoplastic polymer (III) covering the second intermediate layer.

The thermoplastic polymer (III) is a structural unit derived from a methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and, if necessary, a structural unit derived from a monofunctional monomer other than the methacrylic acid alkyl ester. It is a polymer composed of. The thermoplastic polymer (III) preferably does not contain structural units derived from the polyfunctional monomer.

The amount of the structural unit derived from the methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms constituting the thermoplastic polymer (III) is 80 to 100 mass with respect to the mass of the thermoplastic polymer (III). %, Preferably 85-95% by mass.

Examples of the methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter, may be referred to as methacrylic acid C1-8 alkyl ester) include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2 methacrylic acid. -Ethylhexyl, propyl methacrylate, cyclohexyl methacrylate and the like can be mentioned. Of these, methyl methacrylate is preferable.

The amount of the structural unit derived from the monofunctional monomer other than the methacrylic acid C1-8 alkyl ester constituting the thermoplastic polymer (III) is 0 to 20 mass with respect to the mass of the thermoplastic polymer (III). %, Preferably 5 to 15% by mass.
Examples of the monofunctional monomer other than the methacrylic acid C1-8 alkyl ester include acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate; styrene and p-methylstyrene. , Α-Methylstyrene and other aromatic vinyl compounds; examples thereof include maleimide compounds such as N-propyl maleimide, N-cyclohexyl maleimide and NO-chlorophenyl maleimide.

The amount of the thermoplastic polymer (III) is preferably 40 to 75% by mass, more preferably 50 to 70% by mass, and further preferably 55 to 65% by mass with respect to the mass of the crosslinked rubber particles.

The crosslinked polymer (I) is composed of a structural unit derived from methyl methacrylate, a structural unit derived from a monofunctional monomer other than methyl methacrylate, and a structural unit derived from a polyfunctional monomer.

The amount of the structural unit derived from methyl methacrylate constituting the crosslinked polymer (I) is 40 to 98.5% by mass, preferably 45 to 95% by mass, based on the mass of the crosslinked polymer (I). ..

The amount of the structural unit derived from the monofunctional monomer other than methyl methacrylate constituting the crosslinked polymer (I) is 1 to 59.5% by mass, preferably 1 to 59.5% by mass, based on the mass of the crosslinked polymer (I). It is 5 to 55% by mass.
Examples of the monofunctional monomer other than methyl methacrylate include methacrylic ester other than methyl methacrylate such as ethyl methacrylate, butyl methacrylate and cyclohexyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, and 2 acrylate. Acrylic esters such as ethylhexyl and propyl acrylate; aromatic vinyl compounds such as styrene, p-methylstyrene and α-methylstyrene; maleimide compounds such as N-propylmaleimide, N-cyclohexylmaleimide and No-chlorophenylmaleimide Can be mentioned.

The amount of the structural unit derived from the polyfunctional monomer constituting the crosslinked polymer (I) is 0.05 to 0.4% by mass, preferably 0.1, based on the mass of the crosslinked polymer (I). It is about 0.3% by mass.
Examples of the polyfunctional monomer include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallyl. Isocyanurate and the like can be mentioned.

The amount of the crosslinked polymer (I) is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and further preferably 10 to 30% by mass with respect to the mass of the crosslinked rubber particles.

The crosslinked rubber polymer (II) is a structural unit derived from an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and / or a structural unit derived from a conjugated diene, and a structural unit derived from a polyfunctional monomer. Consists of.

The amount of the structural unit derived from the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and / or the structural unit derived from the conjugated diene constituting the crosslinked rubber polymer (II) is determined by the crosslinked rubber polymer (II). It is 98.3 to 99% by mass, preferably 95 to 98% by mass, based on the mass of.

Examples of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate.

Examples of the conjugated diene include 1,3-butadiene, isoprene and the like.

The amount of the structural unit derived from the polyfunctional monomer constituting the crosslinked rubber polymer (II) is 1 to 1.7% by mass, preferably 1.2, based on the mass of the crosslinked rubber polymer (II). It is ~ 1.6% by mass, more preferably 1.3 to 1.5% by mass.
Examples of the polyfunctional monomer include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallyl. Isocyanurate and the like can be mentioned.

From the viewpoint of improving bending resistance, the structural unit derived from the polyfunctional monomer in the crosslinked polymer (I) is relative to the mass of the structural unit derived from the polyfunctional monomer in the crosslinked rubber polymer (II). The mass ratio of is preferably 0.05 to 0.25, more preferably 0.1 to 0.2. The glass transition temperature of the crosslinked rubber polymer (II) is preferably lower than the glass transition temperature of the crosslinked polymer (I).

The amount of the crosslinked rubber polymer (II) is preferably 20 to 55% by mass, more preferably 25 to 45% by mass, and further preferably 30 to 40% by mass with respect to the mass of the crosslinked rubber particles.

It is preferable that the molecular chains of the crosslinked polymer (I) and the crosslinked rubber polymer (II) are connected by a graft bond. Further, it is preferable that the molecular chains of the crosslinked rubber polymer (II) and the thermoplastic polymer (III) are connected by a graft bond. The graft bond is generated by a polymerization method (graft polymerization method) in which a substituent bonded to the main chain of the already completed polymer is used as a reaction active point and a branch portion is newly extended from the reaction active point. It is a bond that connects the main chain and the branch part.

The resin composition of the present invention may contain a conventional additive as long as it does not impair physical properties such as transparency and strength. Additives include, for example, UV absorbers, stabilizers, mold release agents, antistatic agents, flame retardants, plasticizers, dispersants, flow modifiers, leveling agents, defoamers, surface modifiers, heat resistance improvements. Agents, water repellency improvers, optical expression agents and the like can be used.

Examples of the plasticizer include phthalate ester type, fatty acid ester type, trimellitic acid ester type, phosphoric acid ester type, polyester type, epoxy type and the like.

Examples of the ultraviolet absorber include benzotriazole-based, 2-hydroxybenzophenone-based, and salicylic acid phenyl ester-based agents. For example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3, Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone Benzophenones such as, etc. can be exemplified.

Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.

Examples of the flame retardant include organic halogen-based flame retardants such as tetrabromobisphenol A, decabromodiphenyl oxide, and brominated polycarbonate; non-halogen flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, and tricresyl phosphate. And so on.

Examples of the antistatic agent include stearoamide propyl dimethyl-β-hydroxyethylammonium nitrate.

Examples of the surface modifier include polybutadiene and CTBN (terminal carboxylic acid-modified nitrile butadiene rubber).

Examples of the stabilizer include 2,6-di-t-butyl-4-methylphenol, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline and the like.

Examples of the leveling agent include fluorine-based surfactants.

Examples of the defoaming agent include acrylic copolymers and silicones.

These additives can be used alone or in combination of two or more. The amount of the additive is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the methacrylic resin composition. May be good.

The resin composition of the present invention may be in the form of a solid or in the form of a liquid.
The solid resin composition can be produced by mixing the methacrylic polymer (A), the methacrylic polymer (B) and other components (additional components) such as other resins, elastomers and additives as required. Can be prepared. Mixing can be performed by, for example, melt-kneading using a mixer such as a ribbon blender, a tumble mixer, or a Henschel mixer, or a mixing means using a kneader such as an open roller, a kneader, a Banbury mixer, or an extruder. These mixing means may be used alone or in combination of two or more. The resin composition of the present invention is not limited by the mixing order of the methacrylic polymer (A), the methacrylic polymer (B) and other components to be mixed as needed. For example, the methacrylic polymer (A) and the methacrylic polymer (B) may be mixed to obtain the methacrylic resin of the present invention, and then other components may be mixed thereto to obtain the resin composition of the present invention. , The methacrylic polymer (A), the methacrylic polymer (B) and other components may be mixed together to obtain the resin composition of the present invention, or the methacrylic polymer (A) and other components may be mixed. The resin composition of the present invention may be obtained by mixing and then mixing the methacrylic polymer (B) with the methacrylic polymer (B), or the methacrylic polymer (B) and other components are mixed with the methacrylic polymer. (A) may be mixed to obtain the resin composition of the present invention.

The liquid resin composition is formed by dissolving or dispersing the methacrylic polymer (A), the methacrylic polymer (B) and, if necessary, other components in a liquid medium. Examples of the liquid medium include hydrocarbons (benzene, toluene, etc.), halogen-based solvents (dichloromethane, etc.), ethers (diethyl ether, tetrahydrofuran, etc.), esters (ethyl acetate, etc.), ketones (acetone, ethylmethyl, etc.). Examples include alcohols (methanol, ethanol, butanol, etc.) such as ketones, diisopropyl ketones, cyclohexanone, etc. These liquid media may be used alone or in combination of two or more. The procedure for adding the methacrylic polymer (A), the methacrylic polymer (B) and, if necessary, other components to the liquid medium is not particularly limited.

The molded product of the present invention contains the methacrylic resin or resin composition of the present invention.
The molded product of the present invention can be applied to the methacrylic resin or solid resin composition of the present invention, for example, injection molding method, injection compression molding method, extrusion molding method (for example, T-die method, inflation method, etc.), calendar method, heat. It can be obtained by performing molding using a molding method (particularly, a hot press method), a transfer molding method, a blow molding method, a melt casting method, or the like.
Further, the molded product of the present invention can be obtained by subjecting the liquid resin composition of the present invention (for example, doping) to molding using, for example, a solvent casting method.

The film or sheet which is one aspect of the molded product of the present invention may be one that has not been stretched (unstretched film) or may be a stretched film that has been stretched. The film of the present invention can be used as an optical film or an optical sheet. The stretching may be either uniaxial stretching (for example, longitudinal stretching or transverse stretching) or biaxial stretching (for example, iso-stretching or partial stretching). The draw ratio may be, for example, about 1.1 to 10 times in each direction (or one direction) in uniaxial stretching and biaxial stretching, preferably 1.2 to 5 times, and more preferably 1.3. It is about 3 times. The strength of the film of the present invention may be improved by the stretching treatment. The thickness of the film is, for example, 1 to 1000 μm, preferably 3 to 800 μm, more preferably 5 to 500 μm, and most preferably 20 to 200 μm.

The doping of the present invention contains the methacrylic resin of the present invention, an organic solvent, and, if necessary, other components. Halogenized hydrocarbons such as dichloromethane are preferably used for doping; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl- Alcohols such as 2-butanol and cyclohexanol can be mentioned. The amount of the methacrylic resin of the present invention contained in the dope is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 15 to 50% by mass. The amount of the organic solvent contained in the doping is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and further preferably 50 to 85% by mass.

The dope of the present invention may contain an additive for solvent casting. Additives for solvent casting include moisture permeability reducing compounds; peeling accelerators; retardation (Rth) control agents; inorganic fine particles (matting agents); plasticizers such as phthalates and phosphate ester compounds; Re-expressing agents; Ultraviolet absorbers; antioxidants and the like can be mentioned.

Doping is preferably prepared at a temperature of 0 ° C. or higher (normal temperature or high temperature). The doping can be prepared by mixing a methacrylic resin, an organic solvent, other components if necessary, and a solvent casting additive if necessary. The mixing procedure is not particularly limited, and for example, a mixture of each component may be added to an organic solvent to dissolve it, or each component may be sequentially added to and dissolved in an organic solvent being stirred. Solutions of each component may be prepared in advance and the solutions may be mixed. The methacrylic resin or resin composition of the present invention may be dissolved at normal pressure, below the boiling point of the main solvent, or pressurized above the boiling point of the main solvent. Further, a method of performing by a cooling dissolution method as described in JP-A-9-95544, JP-A-9-95557, or JP-A-9-95538, or at a high pressure as described in JP-A-11-21379. You may go. Of these, it is preferable to pressurize at a temperature equal to or higher than the boiling point of the main solvent to dissolve the methacrylic resin or resin composition of the present invention.

The method for producing a film of the present invention includes casting the doping of the present invention on a support to obtain a liquid film, and removing the organic solvent from the liquid film. Doping casting is performed, for example, by pumping the dope from the storage tank to the die, draining the dope from the die slit, and applying it to a rotating metal endless belt. The thickness of the liquid film is adjusted so that the thickness of the film is preferably 20 to 200 μm from the viewpoint of the strength and processability of the film. The thickness of the liquid film can be adjusted by changing the amount of doping supplied, the speed of the endless belt (support), and the like. Since the solid film is obtained on the support by removing the organic solvent, the solid film is peeled off from the support. Since the organic solvent may remain in the solid film peeled off from the support, the solid film can be dried. In the drying treatment, for example, the time from 20% by mass to 0.1% by mass of the organic solvent remaining on the solid film is preferably less than 40 minutes, more preferably 30 minutes or less, still more preferably 25 minutes or less. It can be done under the condition of. Further, the film after the drying treatment may be subjected to heat treatment, stretching treatment or the like. The structure of the casting die, decompression chamber, support, etc., co-casting, peeling method, stretching, drying conditions of each process, handling method, curl, winding method after flatness correction, solvent recovery method, film recovery. For the method and the like, the description of paragraphs [0617] to [0889] of JP-A-2005-104148 is cited here.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples. In addition, the present invention includes all aspects in which the above-mentioned matters representing technical features such as characteristic values, forms, manufacturing methods, and uses are arbitrarily combined.

The physical properties of the methacrylic polymer and the like, as well as the methacrylic resin, the methacrylic resin composition and the doping were evaluated as follows.

(Polymerization conversion rate)
A column (InertCap 1 manufactured by GL Sciences Inc.; df = 0.4 μm, 0.25 mm ID × 60 m) was connected to a gas chromatograph GC-14A manufactured by Shimadzu Corporation, and the injection temperature was set to 180 ° C. The column temperature was raised to 180 ° C. from 60 ° C. (holding for 5 minutes) to 200 ° C. at a heating rate of 10 ° C./min, and then held for 10 minutes, and measurement was performed. Based on this result, polymerization was performed. The conversion rate was calculated.

(Triad syndiotacticity (rr), imidization rate)
The ¹ H-NMR spectrum of the resin sample was measured under the following conditions.
Device: Nuclear magnetic resonance device (ULTRA SHIELD 400 PLUS manufactured by Bruker)
Solvent: Deuterated chloroform Measurement nuclide: ¹ H
Measurement temperature: Room temperature Number of integrations: 64 times ^{1 In the 1} H-NMR spectrum, the area of the region (X) of 0.6 to 0.95 ppm and the area of the region of 0.6 to 1.35 ppm when TMS is 0 ppm. (Y) was measured, and the value calculated by (X / Y) × 100 was defined as triad syndiotacticity (rr) (%).
^{1 In the} H-NMR spectrum, the area (A) of the peak derived from ₃ O-CH groups in the methyl methacrylate unit around 3.5 to 3.8 ppm and the N-methyl around 3.0 to 3.3 ppm. The area (B) of the peak derived from ₃ N-CH groups in the glutarimide unit was measured, and the value calculated by [B / (A + B)] × 100 was used as the imidization rate.

[Weight average molecular weight Mw, number average molecular weight Mn, peak top molecular weight _MPt ]
The chromatogram was measured by gel permeation chromatography (GPC) under the following conditions, and the values (Mw, Mn, _MPt ) converted into the molecular weight of standard polystyrene were calculated. The baseline is that the slope of the peak on the high molecular weight side of the GPC chart changes from zero to plus when viewed from the earliest retention time, and the slope of the peak on the low molecular weight side changes from minus to zero when viewed from the earliest retention time. It is a line connecting the points that change to.
GPC device: manufactured by Tosoh Corporation, HLC-8320
Detector: Differential refractive index detector Column: Two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 connected in series were used.
Eluent: Tetrahydrofuran Eluent flow rate: 0.35 ml / min Column temperature: 40 ° C
Calibration curve: Created using data of 10 standard polystyrene points

(Melting viscosity η)
After the resin sample was dried at 80 ° C. for 12 hours, the melt viscosity η was measured using “Capirograph 1D” manufactured by Toyo Seiki Co., Ltd. under the conditions of a temperature of 260 ° C. and a shear rate of 122 sec ^-1 .

(Refractive index _nd )
The refractive index of the resin sample at a wavelength of 587.6 nm (helium d-line) was measured using "KPR-200" manufactured by Carnew Optical Industry Co., Ltd.

(Average particle size)
The rubber particle dispersion sample was measured by a light scattering method (volume conversion) using a laser diffraction / scattering particle size distribution measuring device LA-910 manufactured by Horiba Seisakusho. A median diameter was adopted as the particle diameter.

(Glass transition temperature Tg)
In accordance with JIS K7121, using a differential scanning calorimetry device (manufactured by Shimadzu Corporation, DSC-50 (product number)), the resin sample is heated to 230 ° C., then cooled to room temperature, and then from room temperature to 230. The temperature was raised to 10 ° C./min and the DSC curve was measured. The intermediate point glass transition temperature obtained from the DSC curve measured at the time of the second temperature rise was defined as the glass transition temperature in the present invention.

(Charpy impact strength, Rockwell hardness, transparency I)
The resin sample was subjected to hot press molding at 260 ° C. to obtain a molded product sample of 80 mm × 10 mm × 4 mm. The notched Charpy impact strength of the molded product sample was measured using a digital impact tester manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7111 1eU. The measurement was performed 10 times, and the average value was taken as the Charpy impact strength.
The Rockwell hardness of the molded product sample was measured using a Rockwell hardness tester (Rockwell hardness tester manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K7202.
The haze of the molded product sample was measured using a haze meter (HM-150, manufactured by Murakami Color Research Institute) in accordance with JIS K7136, and the transparency I was judged according to the following criteria.
〇: Haze is less than 5%.
X: Haze is 5% or more.

(Drying time)
A dope having a solid content concentration of 16% by mass was cast on a metal support so that the thickness after drying was 56 μm. When the residual amount of the organic solvent reached 20% by mass by air drying, the solid film obtained on the support was peeled off from the support. The peeled solid film was trimmed to obtain a 6 cm × 6 cm solid film sample. The solid membrane sample was fixed to a metal frame and dried under normal pressure at a damper opening of 50% and 140 ° C. using a circulation type constant temperature bath PHH-202 manufactured by ESPEC. The residual amount of the organic solvent was measured every 5 minutes. The residual amount of solvent can be expressed by the following formula.
Residual solvent amount (mass%) = [(XY) / Y] × 100
Here, X is the mass of the solid film during drying, and Y is the mass of the solid film when drying is in equilibrium.
The measurement was performed twice and the average value was calculated. A drying characteristic curve was created by plotting the drying time on the horizontal axis and the residual amount of organic solvent on the vertical axis. From the drying characteristic curve, the drying time when the residual amount of the organic solvent was 0.1% by mass was determined.

(Surface smoothness)
The reflection image when the fluorescent lamp was reflected on the surface of the solid film sample in which the residual amount of the organic solvent was 0.1% by mass was visually observed, and the surface smoothness was judged by the following criteria.
×: Fluorescent lamp image fluctuates 〇: Fluorescent lamp image does not fluctuate

(Transparency II)
For a solid film sample in which the residual amount of the organic solvent is 0.1% by mass, the haze is measured using a haze meter (HM-150, manufactured by Murakami Color Research Institute) in accordance with JIS K7136, and the haze is measured according to the following criteria. Transparency II was judged.
〇: Haze is less than 1%.
X: Haze is 1% or more.

(Film impact resistance)
A solid film sample having a residual amount of the organic solvent of 0.1% by mass was trimmed to obtain a test piece having a length of 60 mm and a width of 10 mm. It was diffracted once so that the creases came out over the entire width direction of 30 mm from the end. At this time, it was observed whether or not the pieces were separated into two or more pieces. This was performed three times, and the film impact resistance was judged according to the following criteria.
◯: Can not break 3 times ×: Can break at least 1 time out of 3 times

Production Example 1 (Production of methacrylic polymer (A-1))
The inside of the autoclave equipped with the stirring blade and the three-way cock was replaced with nitrogen. To this, at room temperature, 1600 kg of toluene, 60 kg of 1,2-dimethoxyethane, and 42.1 kg of a toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.45 M (2,6-di-t-butyl-4-methylphenoxy) ( 24.3 mol) and a solution of sec-butyllithium having a concentration of 1.3 M (solvent: cyclohexane 95% by mass / n-hexane 5% by mass) were charged in an amount of 4.82 kg (8.1 mmol). With stirring, 550 kg of distillation-purified methyl methacrylate was added dropwise to this at 15 ° C. over 30 minutes. After completion of the dropping, the mixture was stirred at 15 ° C. for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion rate of methyl methacrylate at this time was 100%. 1500 kg of toluene was added to the obtained solution for dilution. The diluent was poured into a large amount of methanol to give a precipitate. The obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours to obtain a methacrylic polymer (A-1).
The methacrylic polymer (A-1) has a Mw of 70,000, a component having a molecular weight of 15,000 or less (M≤15,000) in an amount of 0.17% by mass, a melt viscosity η of 1200 Pa · s, and a Mw / Mn of 1. At .1, the triadosyndio tacticity (rr) was 75%, the Tg was 131 ° C., and the amount of structural units derived from methyl methacrylate was 100% by mass. Table 1 shows the physical characteristics of the methacrylic polymer (A-1).

Production Example 2 (Production of methacrylic polymer (A-2))
The inside of the autoclave equipped 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, and a toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.45 M (73.3 kg) ( 42.3 mol) and a solution of sec-butyllithium having a concentration of 1.3 M (solvent: cyclohexane 95% by mass / n-hexane 5% by mass) were charged at 8.44 kg (14.1 mmol). With stirring, 550 kg of distillation-purified methyl methacrylate was added dropwise to this at 15 ° C. over 30 minutes. After completion of the dropping, the mixture was stirred at 15 ° C. for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion rate of methyl methacrylate at this time was 100%. 1500 kg of toluene was added to the obtained solution for dilution. The diluent was poured into a large amount of methanol to give a precipitate. The obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours to obtain a methacrylic polymer (A-2).
The methacrylic polymer (A-2) has a Mw of 40,000, a component having a molecular weight of 15,000 or less (M≤15,000) in an amount of 1.52% by mass, a melt viscosity η of 450 Pa · s, and a Mw / Mn of 1. At .1, the triadosyndio tacticity (rr) was 75%, the Tg was 130 ° C., and the amount of structural units derived from methyl methacrylate was 100% by mass. Table 1 shows the physical characteristics of the methacrylic polymer (A-2).

Production Example 3 (Production of methacrylic polymer (A-3))
The inside of the autoclave equipped with the stirring blade and the three-way cock was replaced with nitrogen. To this, at room temperature, 1600 kg of toluene, 110 kg of 1,2-dimethoxyethane, and 119.0 kg of a toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.45 M ( 68.7 mol) and a solution of sec-butyllithium having a concentration of 1.3 M (solvent: cyclohexane 95% by mass / n-hexane 5% by mass) 13.71 kg (22.9 mmol) were charged. With stirring, 550 kg of distillation-purified methyl methacrylate was added dropwise to this at 15 ° C. over 30 minutes. After completion of the dropping, the mixture was stirred at 15 ° C. for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion rate of methyl methacrylate at this time was 100%. 1500 kg of toluene was added to the obtained solution for dilution. The diluent was then poured into a large amount of methanol to give a precipitate. The obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours to obtain a methacrylic polymer (A-3).
The methacrylic polymer (A-3) has a Mw of 25,000, a component having a molecular weight of 15,000 or less (M≤15,000) in an amount of 7.06% by mass, a melt viscosity η of 150 Pa · s, and a Mw / Mn of 1. At .1, the triadosyndio tacticity (rr) was 76%, the Tg was 130 ° C., and the amount of structural units derived from methyl methacrylate was 100% by mass. Table 1 shows the physical characteristics of the methacrylic polymer (A-3).

Production Example 4 (Production of methacrylic polymer (A-4))
The inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate, 0.0065 parts by mass of 2,2'-azobis (2-methylpropionitrile (hydrogen extraction capacity: 1%, 1-hour half-life temperature: 83 ° C.)), and 0.290 parts by mass of n-octyl mercaptan was added and stirred to obtain a raw material solution. Nitrogen was sent into this raw material solution to remove dissolved oxygen.
The raw material solution was put into a tank reactor connected to the autoclave by piping up to 2/3 of the capacity. While maintaining the temperature at 140 ° C., the polymerization reaction was first started by a batch method. 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 with an average residence time of 120 minutes while maintaining the temperature at 140 ° C., and at the same time, it corresponds to the supply flow rate of the raw material liquid. The reaction solution was withdrawn from the tank reactor at the desired flow rate, and the polymerization reaction was switched to the continuous flow method. After switching, the polymerization conversion rate in the steady state was 45% by mass.
The reaction solution extracted from the tank-type reactor in a steady state was supplied to a multi-tube heat exchanger having an internal temperature of 230 ° C. at a flow rate having an average residence time of 2 minutes for heating. Next, the heated reaction solution was introduced into a flash evaporator to remove volatile components containing unreacted monomers as a main component to obtain a molten resin. The molten resin from which the volatile matter had been removed was supplied to a twin-screw extruder having an internal temperature of 230 ° C., discharged in a strand shape, and cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (A-4).
The methacrylic polymer (A-4) has an Mw of 80,000, a component having a molecular weight of 15,000 or less (M≤15,000) in an amount of 6.92% by mass, a melt viscosity η of 700 Pa · s, and a Mw / Mn of 1. At .87, the triadosyndio tacticity (rr) was 52%, the Tg was 120 ° C., and the amount of structural units derived from methyl methacrylate was 100% by weight. Table 1 shows the physical characteristics of the methacrylic polymer (A-4).

Production Example 5 (Production of methacrylic polymer (A-5))
Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 120 rpm and a temperature of 250 ° C. The methacrylic polymer (A-4) was supplied at 2 kg / hr, and monomethylamine was injected into the melt-kneaded portion of the twin-screw extruder at 0.08 kg / hr, and the methacrylic polymer (A-4) and monomethylamine were injected. And reacted. A kneading block was installed in the melt-kneading section, and a reverse flight was installed in the screw at the end of the reaction zone.
In the volatilization section set to 20 Torr (about 2.7 kPa), by-products and excess monomethylamine were volatilized and discharged through the vent.
The strand-shaped molten resin extruded from the die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (A-5a). It was.

Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 230 ° C. A methacrylic polymer (A-5a) was supplied at 1 kg / hr, and a liquid consisting of 1.6 parts by mass of carbon dimethyl and 0.2 parts by mass of triethylamine was added to the melt-kneaded portion of the twin-screw extruder at 0.01 kg / hr. The carboxy group in the methacrylic polymer (A-5a) was reacted with carbon dimethyl. A kneading block was installed in the melt-kneading section, and a reverse flight was installed in the screw at the end of the reaction zone.
The by-product and excess dimethyl carbonate were volatilized and discharged through the vent in the volatilization section set to 20 Torr (about 2.7 kPa).
The strand-shaped molten resin extruded from the die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped methacrylic polymer [A-5b]. It was.

Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 230 ° C. A methacrylic resin (A-5b) was supplied at 1 kg / hr. In the volatilization section set to 20 Torr (about 2.7 kPa), volatile components such as unreactant were volatilized and discharged through the vent.
The strand-shaped molten resin extruded from the die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (A-5). It was.
The methacrylic polymer (A-5) has an Mw of 80,000, a Mw / Mn of 1.8, a molecular weight of 15,000 or less (M ≤ 15,000) in an proportion of 6.60% by mass, and an imidization ratio of 7. At 0.0 mol%, the glass transition temperature was 130 ° C. Table 1 shows the physical characteristics of the methacrylic polymer (A-5).

Production example 6
By the suspension polymerization method, a methacrylic polymer (B-1) having a structural unit derived from methyl methacrylate in an amount of 100.0% by mass and an Mw of 420,000 was obtained. The physical characteristics of the methacrylic polymer (B-1) are shown in Table 1.

Production Example 7 (Production of methacrylic polymer (B-2))
89 parts by mass of purified methyl methacrylate and 11 parts by mass of methyl acrylate were placed in an autoclave with a stirrer and a sampling tube to obtain a monomer mixture. Polymerization initiator (2,2'-azobis (2-methylpropionitrile (AIBN), hydrogen extraction capacity: 1%, 1 hour half-life temperature: 83 ° C.) 0.0026 parts by mass and chain transfer to the monomer mixture 0.09 part by mass of the agent (n-octyl mercaptan) was added and dissolved to obtain a raw material solution. Oxygen in the production apparatus was expelled with nitrogen. The raw material solution was discharged from the autoclave in a constant amount, and the temperature was 140. It was supplied to a continuous flow tank type reactor controlled at ° C. at a flow rate having an average residence time of 150 minutes for massive polymerization. The reaction solution was separated from the sampling tube of the reactor and measured by gas chromatography. As a result, the polymerization conversion rate was 43% by mass.

The liquid discharged from the reactor was heated to 240 ° C. and supplied to a twin-screw extruder controlled at 260 ° C. at a constant flow rate. In the twin-screw extruder, the volatile matter containing the unreacted monomer as a main component was removed, and the resin component was extruded into a strand shape. The strand was cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (B-2). Table 1 shows the physical characteristics of the methacrylic polymer (B-2).

Production Example 8 (Production of methacrylic polymer (B-3))
The inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen. To this, 98.9 parts by mass of purified methyl methacrylate, 1.1 parts by mass of methyl acrylate, 2,2'-azobis (2-methylpropionitrile (hydrogen extraction capacity: 1%, 1 hour half-life temperature). : 83 ° C.) 0.0050 parts by mass and 0.26 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material solution. Nitrogen was sent into the raw material solution to remove dissolved oxygen in the raw material solution. did.
The raw material liquid was put into the tank-type reactor connected to the autoclave by piping up to 2/3 of the reactor capacity. The raw material liquid supply port to the tank reactor and the reaction liquid discharge port from the tank reactor were closed, and the temperature was maintained at 140 ° C. to start the batch-type polymerization reaction. When the polymerization conversion rate reaches 55% by mass, open the raw material liquid supply port to the tank reactor and the reaction liquid discharge port from the tank reactor, and open the raw material liquid at a flow rate with an average residence time of 150 minutes. The reaction solution was withdrawn from the tank reactor at a flow rate corresponding to the supply flow rate of the raw material liquid and supplied from the autoclave to the tank reactor, maintained at a temperature of 140 ° C., and switched to a continuous flow type polymerization reaction. After switching, the polymerization conversion rate in the steady state was 55% by mass.

The liquid discharged from the reactor was heated to 230 ° C. and supplied to a twin-screw extruder controlled to 240 ° C. at a constant flow rate. In the twin-screw extruder, the volatile matter containing the unreacted monomer as a main component was removed, and the resin component was extruded into a strand shape. The strand was cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (B-3). The physical characteristics of the methacrylic polymer (B-3) are shown in Table 1.

Production Example 9 (Production of crosslinked rubber particles (C-1))
A reactor equipped with a stirrer, a thermometer, a nitrogen gas introduction part, a monomer introduction tube and a reflux condenser, 1050 parts by mass of deionized water, 1 part by mass of sodium alkyldiphenyl ether disulfonate and 0.05 parts by mass of sodium carbonate. Was charged, and the inside of the reactor was sufficiently replaced with nitrogen gas to make it substantially oxygen-free. After that, the internal temperature was set to 80 ° C. 0.01 part by mass of potassium persulfate was added thereto, and the mixture was stirred for 5 minutes. Next, 20 parts by mass of a monomer mixture consisting of 93.7% by mass of methyl methacrylate (MMA), 6.1% by mass of methyl acrylate (MA) and 0.2% by mass of allyl methacrylate (ALMA) was added. It was continuously added dropwise over a minute. After completion of the dropping, the polymerization reaction was further carried out for 30 minutes so that the polymerization conversion rate was 98% or more.
Next, 0.05 parts by mass of a 3% aqueous potassium persulfate solution was added to the reactor, and the mixture was stirred for 5 minutes. Then, 157.4 parts by mass of a monomer mixture composed of 79.1% by mass of n-butyl acrylate, 17.1% by mass of styrene and 3.8% by mass of allyl methacrylate was continuously added dropwise over 40 minutes. After completion of the dropping, the polymerization reaction was further carried out for 30 minutes so that the polymerization conversion rate was 98% or more.
Next, 0.5 parts by mass of a 3% aqueous potassium persulfate solution was added to the reactor and stirred for 5 minutes. Then, 341 parts by mass of a monomer mixture containing 93.7% by mass of methyl methacrylate, 6.0% by mass of methyl acrylate and 0.3% by mass of n-octyl mercaptan (nOM, chain transfer agent) was applied over 100 minutes. It was dropped continuously. After completion of the dropping, a polymerization reaction was further carried out for 60 minutes so that the polymerization conversion rate was 98% or more to obtain an emulsion containing crosslinked rubber particles (C-1) having an average particle diameter of 0.1 μm.
The emulsion was then frozen at −30 ° C. for 4 hours. The frozen emulsion was placed in warm water at 80 ° C., which was twice the amount of the frozen emulsion, and thawed to obtain a slurry. The slurry was kept at 80 ° C. for 20 minutes. Then, it was dehydrated and dried at 70 ° C. to obtain a powder composed of a coagulated product of crosslinked rubber particles (C-1).

Production Example 10 (Production of Block Copolymer (D-1))
After degassing the inside of a 20-liter reaction vessel and replacing it with nitrogen, dried toluene at room temperature 10.29 kg, hexamethyltriethylenetetramine 0.019 kg, isobutylbis (2,6-di-t-butyl-4-) 0.35 kg of a toluene solution containing 0.17 mol of (methylphenoxy) aluminum was added, and 0.077 mol of sec-butyllithium was further added. To this, 0.50 kg of methyl methacrylate was added, and the mixture was reacted at room temperature for 1 hour. Subsequently, the polymerization solution was cooled to −25 ° C., and a mixed solution of 1.21 kg of n-butyl acrylate and 0.48 kg of benzyl acrylate was added dropwise over 1 hour. Subsequently, 1.23 kg of methyl methacrylate was added, the reaction solution was returned to room temperature, and the mixture was stirred for 8 hours. Then, 0.30 kg of methanol was added to the reaction solution to terminate the polymerization. The reaction solution is poured into a large amount of methanol, and the precipitated precipitate is recovered. Methyl methacrylate polymer block (a1-1) -n-butyl acrylate / benzyl acrylate polymer block (a2) -methyl methacrylate. A block copolymer (D-1) having a triblock structure composed of a coalesced block (a1-2) was obtained. The mass ratio of (a1-1): (a2): (a1-2) was 14.6: 49.5: 35.9. Block co polymer (D-1) is, Mw is 62600, Mw / Mn is 1.11, the refractive index n _d 1.493, tensile modulus 612MPa, plotting the relationship between the storage modulus G 'and temperature In the graph shown above, the temperature at which G'decreased sharply (order-disorder transition temperature (ODTT); JISB0103-5113)) was 207 ° C.

Example 1
10 parts by mass of methacrylic polymer (A-1) and 90 parts by mass of methacrylic polymer (B-1) were used in a twin-screw kneading extruder (TEX-44α, L / D = 40, manufactured by Japan Steel Works, Ltd.). The mixture was kneaded and extruded at a cylinder temperature of 260 ° C. and a screw rotation speed of 100 rpm to obtain a pellet-shaped methacrylic resin [1]. The evaluation results of the methacrylic resin [1] are shown in Table 2.

Examples 2 to 3, Comparative Examples 1 to 7 and Reference Example 1
The methacrylic resin by the same method as in Example 1 except that the methacrylic polymers (A-1) to (A-5) and the methacrylic polymers (B-1) to (B-3) were changed to the mass ratios shown in Table 2. [2] to [11] were obtained. Table 2 shows the evaluation results of the methacrylic resins [2] to [11].

Example 4
100 parts by mass of methacrylic resin [1], 483 parts by mass of dichloromethane, and 42 parts by mass of methanol were put into a mixing tank and stirred at 25 ° C. to dissolve the methacrylic resin [1], and the solid content concentration was 16% by mass. Dope [1] was obtained. The evaluation results of the doping [1] are shown in Table 3.

Examples 5-6, Comparative Examples 8-15 and Reference Example 2
Dopings [2] to [11] having a solid content concentration of 16% by mass were obtained in the same manner as in Example 4 except that the methacrylic resin [1] was changed to the methacrylic resins [2] to [11]. The evaluation results of the dopings [2] to [11] are shown in Table 3.

Example 7
10 parts by mass of methacrylic polymer (A-1), 70 parts by mass of methacrylic polymer (B-1), and 20 parts by mass of crosslinked rubber particles (C-1) were used in a twin-screw kneading extruder (TEX-44α, L / D = 40, manufactured by Japan Steel Works, Ltd.) was kneaded and extruded at a cylinder temperature of 260 ° C. and a screw rotation speed of 100 rpm to obtain a pellet-shaped methacrylic resin composition [12]. The evaluation results of the methacrylic resin composition [12] are shown in Table 4.

Example 8, Comparative Example 16 and Reference Example 3
The mass ratios of methacrylic polymers (A-1) and (A-3), methacrylic polymers (B-1), crosslinked rubber particles (C-1) and block copolymers (D-1) are shown in Table 4. Polymer resin compositions [13] to [15] were obtained in the same manner as in Example 7 except that they were changed. Table 4 shows the evaluation results of the methacrylic resin compositions [13] to [15].

Example 9
100 parts by mass of methacrylic resin composition [12], 483 parts by mass of dichloromethane, and 42 parts by mass of methanol were put into a mixing tank and stirred at 25 ° C. to dissolve the methacrylic resin composition [12] and solid content. A dope [12] having a concentration of 16% by mass was obtained. The evaluation results of the doping [12] are shown in Table 5.

Example 10, Comparative Example 17 and Reference Example 4
Dopings [13] to [15] having a solid content concentration of 16% by mass were obtained in the same manner as in Example 9 except that the methacrylic resin composition [12] was changed to the methacrylic resin compositions [13] to [15], respectively. It was. The evaluation results of the dopings [13] to [15] are shown in Table 5.

As described above, the methacrylic resin or the methacrylic resin composition of the present invention can provide a molded product having high transparency, high strength, excellent surface smoothness, and excellent heat resistance. In addition, the dope of the present invention has a high drying rate and is excellent in manufacturing suitability by the casting method.

Claims (13)

1. _A methacrylic polymer having a weight average molecular weight Mw _A of 30,000 or more, a ratio of weight average molecular weight Mw _{A to} a number average molecular weight Mn _A of 1.0 to 1.4, and a glass transition temperature of 125 ° C. or more. A) and a methacrylic polymer (B) having a weight average molecular weight Mw _B of 80,000 to 3,000,000 and 2.5 times or more the weight average molecular weight Mw _A are contained, and the shear rate of the methacrylic polymer (B). 122 sec ^-1 and melt viscosity eta _B at a temperature 260 ° C. is higher than the melt viscosity eta _a at a shear rate of 122 sec ^-1 and a temperature 260 ° C. methacrylic polymer (a),
   The peak top molecular weight M _Pt having the mass ratio of the methacrylic polymer (A) to the methacrylic polymer (B) of 2/98 to 39/61 and having the highest weight fraction differential value in the weight-based differential molecular weight distribution curve is 100,000 to 2000,000,
   Methacrylic resin.
2. In the weight-based differential molecular weight distribution curve, the sum of the weight fraction differential values of the components having a molecular weight of 1/20 or less of the peak top molecular weight M _Ph having the highest molecular weight is the sum of the weight fraction differential values of all the components. The methacrylic resin according to claim 1, wherein the total weight fraction derivative values of the components having a molecular weight of 2% or less and 15,000 or less are 2% or less with respect to the total weight fraction derivative values of all the components. ..
3. The methacrylic resin according to claim 1 or 2, wherein the weight average molecular weight Mw _A is 40,000 to 140000 and the weight average molecular weight Mw _B is 160000 to 20000000.
4. The absolute value | n _dA −n _dB | of the difference between the refractive index n _dA of the methacrylic polymer (A) and the refractive index n _dB of the methacrylic polymer (B) is 0.005 or less, according to claims 1 to 3. The methacrylic resin described in any one.
5. A resin composition containing the methacrylic resin according to any one of claims 1 to 4 and an elastomer.
6. The weight average molecular weight Mw of from 40,000 to 140,000, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of 1.0-1.4, the refractive index n _d is 1.485 to 1.495, triad Shinji Resin modification consisting of a methacrylic polymer (A) having an octancy (rr) of 63 to 80%, a glass transition temperature of 125 ° C. or higher, and containing 100% by mass of a structural unit derived from methyl methacrylate. Agent.
7. In the methacrylic polymer (A), the total weight fraction differential values of the components having a molecular weight of 15,000 or less in the weight-based differential molecular weight distribution curve is 2% or less of the total weight fraction differential values of all the components. , The resin modifier according to claim 6.
8. A molded product containing the methacrylic resin according to any one of claims 1 to 4.
9. A film containing the methacrylic resin according to any one of claims 1 to 4 and having a thickness of 20 μm or more and 200 μm or less.
10. The film according to claim 9, which is for optics.
11. Doping containing the methacrylic resin according to any one of claims 1 to 4 and an organic solvent.
12. The dope according to claim 11 is cast on a support to obtain a liquid film.
    A method for producing a film, which comprises removing an organic solvent from a liquid film.
13. The manufacturing method according to claim 12, wherein the thickness of the film is 20 μm or more and 200 μm or less.