JP6852997B2 - Impact resistance improver, thermoplastic resin composition and film - Google Patents

Description

The present invention relates to impact resistance improvers, thermoplastic resin compositions and films. More specifically, the present invention relates to a molded product such as a film having a high refractive index and excellent thermodegradability, transparency and impact resistance, a thermoplastic resin composition suitable for obtaining such a molded product, and a thermoplastic resin composition. The present invention relates to an impact resistance improving agent which is hard to be thermally decomposed even when it is melt-kneaded with a thermoplastic resin and exposed to high heat in order to obtain such a thermoplastic resin composition.

Optical devices such as light emitting diodes and image sensors; optical members such as lenses and prisms; optical control films such as antireflection films and antiglare films are required to have a high refractive index resin material. A resin having a high refractive index can be obtained, for example, by introducing a substituent exhibiting high molecular refraction into the molecular chain, or adjusting the molecular chain structure or molecular weight to reduce the molar volume. Further, a resin composition having a high refractive index can be obtained, for example, by blending nanoparticles having a high refractive index with the resin.

As a methacrylic resin having a high refractive index, polymethylmethacrylate having a halogenated carbazole ring is known (Patent Document 1). However, the use of halogen elements in electronic components is restricted from the viewpoint of preventing environmental pollution.

Patent Document 2 discloses a cured product having a high refractive index obtained by polymerizing a composition containing a (meth) acrylic acid ester having a spiro ring structure in which a cyclic structure is bonded to fluorene via a spiro carbon. There is. Patent Document 3 discloses a cured product having a high refractive index obtained by polymerizing a composition containing a monomer having a substituent on (meth) acryloxymethylbenzyloxynaphthalene. Patent Document 4 discloses an optical resin material obtained by copolymerizing tricyclo (meth) acrylate [5.2.1.0 ^{2,6] -deca-8-yl with another monomer.} .. Patent Document 5 discloses a cured product having a high refractive index obtained by polymerizing a composition containing a (meth) acrylate having a dithia ring structure. Since these resin materials are hard and brittle, their uses are limited.

It has been proposed to blend an elastomer in order to improve the impact resistance of a hard and brittle resin material.
For example, Patent Document 6 contains a polymer moiety obtained from a monomer containing a (meth) acrylic acid ester of an aromatic thioalkyl alcohol as a main component and a (meth) acrylic acid ester of an aromatic thioalkyl alcohol as a main component. High-refractive index elastomer and thermoplastic containing a polymer moiety obtained from a non-polymer, having an overall refractive index n of 1.570 or more, insoluble in methyl ethyl ketone, and having a glass transition temperature of -10 ° C or less A resin composition containing a resin is disclosed.

Patent Document 7 discloses a resin composition containing a copolymer obtained by graft-polymerizing a monomer such as (meth) acrylic acid ester to a non-conjugated diene rubber containing an aromatic vinyl polymer. ing.

Patent Document 8 describes a core layer formed by polymerizing a monomer mainly composed of a styrene compound, an intermediate layer formed by polymerizing a monomer mainly composed of an alkyl acrylate, and a single amount mainly composed of methyl methacrylate. Disclosed is a resin composition obtained by blending a three-layer core-shell structure particle having a refractive index of 1.547 to 1.574 with a shell layer formed by polymerizing a body into a polyethylene terephthalate-based resin.

Patent Document 9 is a rubber graft copolymer composed of a rubber-like polymerized portion and a graft polymerized portion, wherein the rubber graft copolymer contains a unit obtained from aryl (meth) acrylate as an essential structural unit. A rubber graft copolymer in which the rubber-like polymerized portion has a multi-step layer structure, the innermost layer has a refractive index of 1.58 or more, and the entire rubber-like polymerized portion has a refractive index of 1.56 or more. Discloses a thermoplastic resin composition containing one or more resins selected from the group consisting of aromatic polycarbonate resins, aliphatic polyester resins, aromatic polyester resins, and poly (meth) acrylate resins. There is.

US 5132430 A Japanese Unexamined Patent Publication No. 2011-225488 Japanese Unexamined Patent Publication No. 2015-67796 Japanese Unexamined Patent Publication No. 61-73705 Japanese Unexamined Patent Publication No. 2003-183334 Japanese Unexamined Patent Publication No. 2011-252146 Japanese Unexamined Patent Publication No. 7-48496 Japanese Unexamined Patent Publication No. 2001-31852 Japanese Unexamined Patent Publication No. 2014-162878

The toughness and transparency of elastomers and rubber tend to decrease as the refractive index increases by adjusting the molecular structure, and when exposed to high heat during melting and kneading, they thermally decompose and form silver streaks, bubbles, etc. in films and the like. It may cause poor appearance due to coloring or foreign matter, or decrease in transparency.
An object of the present invention is a molded product such as a film having a high refractive index and excellent heat decomposition resistance, transparency and impact resistance, a thermoplastic resin composition suitable for obtaining such a molded product, and such. It is an object of the present invention to provide an impact resistance improving agent which is hard to be thermally decomposed even when it is melt-kneaded with a thermoplastic resin and exposed to high heat in order to obtain a thermoplastic resin composition.

As a result of studies for solving the above problems, the present invention including the following aspects has been completed.

[1] Containing core particles having an inner shell surrounding the center core and the center core, and core-shell crosslinked rubber particles having an outer shell surrounding the core particles.
At least one of the polymers constituting the center core and the inner shell is a crosslinked rubber polymer.
The ratio of the mass of the sulfur component contained in the polymer constituting the center core to the mass of the polymer constituting the center core or the mass of the sulfur component contained in the polymer constituting the inner shell with respect to the mass of the polymer constituting the inner shell. one of the mass ratio is much larger than the ratio of the mass of the sulfur component contained in the polymer constituting the outer shell relative to the mass of the polymer constituting the outer shell,
The average particle size D of the core particles is 150 nm or more and 300 nm or less.
Refractive index n _dIS of polymer constituting the refractive index n _DCC and the inner shell of the polymer constituting the center core is 0 nm ≦ | meet × D ≦ 9 nm relation, | _n dCC -n _dIS
Co Asher Ri refractive index n _d 1.50 to 1.55 der crosslinked rubber particles, and
Nitrogen flow rate 10 ml / min, 1.0% heating loss temperature measured at a heating rate of 20 ° C. / min, Ru der 310 ° C. or higher, the impact modifier.

[2] The crosslinked rubber polymer is a polymer (i) containing a structural unit derived from an acrylic acid ester or a conjugated diene.
The polymer other than the crosslinked rubber polymer constituting the center core and the inner shell is a polymer (ii) containing a structural unit derived from a methacrylate ester, and the polymer constituting the outer shell is derived from methyl methacrylate. The impact resistance improving agent according to [1], which is a polymer (iii) containing a structural unit.
[3] The crosslinked rubber polymer is a polymer (i) containing 50% by mass or more of structural units derived from an acrylic acid ester.
A polymer (ii) in which a polymer other than the crosslinked rubber polymer constituting the center core and the inner shell contains a total of 50% by mass or more of a structural unit derived from aromatic vinyl and a structural unit derived from methyl methacrylate. The impact resistance improving agent according to [1], wherein the polymer constituting the outer shell is a polymer (iii) containing 50% by mass or more of a structural unit derived from methyl methacrylate.

[4] The polymer (i) contains less than 10% by mass of a structural unit derived from a methacrylic acid ester.
The impact resistance improving agent according to [2] or [3], wherein the polymer (ii) contains 10% by mass or more of a structural unit derived from a methacrylic acid ester.
[5] The content of the structural unit derived from the acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the polymer (i) is less than 50% by mass with respect to the mass of the polymer (i). The impact resistance improving agent according to any one of [2] to [4].

[ 6 ] Seed particles are obtained by emulsion polymerization of a monomer for obtaining a polymer constituting the center core.
In the presence of seed particles, a monomer for obtaining a polymer constituting an inner shell was seed-emulsified and polymerized to obtain core particles.
Including seed emulsion polymerization of a monomer for obtaining a polymer constituting an outer shell in the presence of core particles to obtain core-shell crosslinked rubber particles.
The method for producing an impact resistance improving agent according to any one of the above [1] to [ 5].

[ 7 ] A thermoplastic resin composition containing the thermoplastic resin (A) and the impact resistance improving agent (B) according to any one of the above [1] to [5].

[ 8 ] The thermoplastic resin (A) has a ring structure containing> CH-OC (= O) -group, a ring structure containing -C (= O) -OC (= O) -group, and-. A structure having at least one ring structure in the main chain selected from the group consisting of a ring structure containing a C (= O) -NC (= O) -group and a ring structure containing> CH-O-CH <group. It contains a unit and a structural unit derived from methyl methacrylate.
The thermoplastic resin composition according to [7 ], wherein the mass ratio (A) / (B) of the thermoplastic resin (A) to the impact resistance improving agent (B) is 95/5 to 10/90.

（式(2)中、Ｘは炭素数６以上の環式炭化水素基を表す。）
〔１１〕 炭素数６以上の環式炭化水素基が、イソボルナン−２−イル基、トリシクロ［５．２．１．０^2,6］デカン−８−イル基、または置換基を有していてもよいシクロヘキシル基である、〔１０〕に記載の熱可塑性樹脂組成物。 [ 9 ] The thermoplastic resin (A) has a structural unit of 10 to 50% by mass derived from a methacrylic acid ring hydrocarbon ester and a structural unit of 50 to 90% by mass derived from a methacrylic acid ester other than the methacrylic acid ring hydrocarbon ester. %, And the thermoplastic resin composition according to [7 ], which contains 0 to 20% by mass of a structural unit derived from an acrylic acid ester.
[ 10 ] The thermoplastic resin composition according to [9 ], wherein the methacrylic acid cyclic hydrocarbon ester is a compound represented by the formula (2).

(In formula (2), X represents a cyclic hydrocarbon group having 6 or more carbon atoms.)
[ 11 ] A cyclic hydrocarbon group having 6 or more carbon atoms has an isobornan-2-yl group, a tricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, or a substituent. The thermoplastic resin composition according to [10 ], which is also a good cyclohexyl group.

[ 12 ] The thermoplastic resin composition according to [7 ], wherein the thermoplastic resin (A) contains a polycarbonate resin in an amount of 2 to 50% by mass with respect to the thermoplastic resin (A).
[13] A molded product made of the thermoplastic resin composition according to any one of the above [7] to [12].

[14] The center core and the inner shell are composed of a thermoplastic resin (A), core particles having an inner shell surrounding the center core and the center core, and core-shell crosslinked rubber particles having an outer shell surrounding the core particles. At least one of the constituent polymers is a crosslinked rubber polymer, and the ratio of the mass of the sulfur component contained in the polymer constituting the center core to the mass of the polymer constituting the center core or the ratio of the mass of the sulfur component contained in the polymer constituting the center core or the polymer constituting the inner shell One of the ratios of the mass of the sulfur component contained in the polymer constituting the inner shell to the mass is larger than the ratio of the mass of the sulfur component contained in the polymer constituting the outer shell to the mass of the polymer constituting the outer shell. large, the average particle diameter D of the core particles is at 150nm than 300nm or less, the refractive index n _dIS of polymer constituting the refractive index n _DCC and the inner shell of the polymer constituting the center core is 0nm ≦ | _n dCC -n _dIS | × meets D ≦ 9 nm relationship, and the refractive index n _d of the core-shell crosslinked rubber particles are 1.50 to 1.55 impact modifier (B) and the thermoplastic resin composition comprising A film consisting of.
[15] The thermoplastic resin (A) has a ring structure containing> CH-OC (= O) -group, a ring structure containing -C (= O) -OC (= O) -group, and-. A structure having at least one ring structure selected from the group consisting of a ring structure containing a C (= O) -NC (= O) -group and a ring structure containing> CH-O-CH <group in the main chain. A unit containing a unit and a structural unit derived from methyl methacrylate, or
Structural units derived from methacrylic acid cyclic hydrocarbon esters 10 to 50% by mass, structural units derived from methacrylic acid esters other than methacrylic acid cyclic hydrocarbon esters 50 to 90% by mass, and structural units derived from acrylic acid esters. The film according to [14], which contains 0 to 20% by mass .
[16] The film according to [14] or [15], which has a thickness of 10 to 50 μm.
[17] A polarizer protective film comprising the film according to the above [14], [15] or [16].
[18] A retardation film comprising the film according to the above [14], [15] or [16].
[19] An illumination or display device having the film according to the above [14], [15] or [16] and an organic light emitting diode.
[20] A display device having the film and the liquid crystal cell according to the above [14], [15] or [16].

The impact resistance improving agent of the present invention is hardly thermally decomposed even when it is melt-kneaded with a thermoplastic resin and exposed to high heat. A molded product such as a film obtained by molding a thermoplastic resin composition containing the impact resistance improving agent of the present invention and a thermoplastic resin has a high refractive index and is resistant to heat decomposition, transparency and impact resistance. Excellent.

The impact resistance improving agent of the present invention contains core-shell crosslinked rubber particles. The core-shell crosslinked rubber particles have a core particle and an outer shell surrounding the core particle. The core particles have a center core and an inner shell surrounding the center core. It is preferable that the center core, the inner shell and the outer shell are in close contact with each other. The inner shell between the center core and the outer shell may have only one layer or two or more layers.

In the core-shell crosslinked rubber particles, at least one of the polymers constituting the center core and the inner shell is a crosslinked rubber polymer (hereinafter, may be referred to as a polymer (i)). In the core-shell crosslinked rubber particles, all of the polymers constituting the center core and the inner shell may be the polymer (i), or only the polymer constituting the center core may be the polymer (i). However, only all the polymers constituting the inner shell may be the polymer (i), or at least one of the polymers constituting the inner shell may be the polymer (i). Of the polymers constituting the center core and the inner shell, the polymer constituting the portion other than the polymer (i) can be the polymer (ii). The polymer constituting the outer shell is the polymer (iii).

That is, in the core-shell crosslinked rubber particles, the combination mode of the polymers constituting [center core] / [inner shell] / [outer shell] is [polymer (i)] / [polymer (ii)] / [heavy]. Combined (iii)], [Polymer (i)] / [Polymer (i)] / [Polymer (iii)], [Polymer (ii)] / [Polymer (i)] / [Polymer (iii)] One layer of inner shell such as [iii)]; [polymer (ii)] / [polymer (i) / polymer (ii)] / [polymer (iii)], [polymer (i)] / [Polymer (ii) / Polymer (i)] / [Polymer (iii)], [Polymer (ii)] / [Polymer (i) / Polymer (ii) / Polymer (i)] / It includes those having two or more inner shell layers such as [polymer (iii)]. Of these, the aspect of [polymer (ii)] / [polymer (i)] / [polymer (iii)] is preferable. Two or more polymers (i) used in different parts such as [polymer (ii)] / [polymer (i) / polymer (ii) / polymer (i)] / [polymer (iii)] ) Or the polymer (ii) may have the same or different physical properties such as monomer composition.

The core-shell crosslinked rubber particles have an average particle diameter D of 150 nm or more and 300 nm or less, preferably 190 nm or more and 270 nm or less. When the average particle size D of the core particles is within the above range, it is likely to be effective in improving the impact resistance and reducing the haze.
The average particle size D of the core particles is determined as follows.
First, the core particle aqueous dispersion generated in the middle of producing the core-shell crosslinked rubber particles is sampled and diluted with ion-exchanged water so that the core particles have a concentration of 0.05% by mass. Spread the diluent on a glass plate and dry. In this way, the core particles are dispersed and exist on the glass plate without agglomeration. Next, platinum and palladium are vapor-deposited on the surface of the dried glass plate, which is observed with an electron microscope and a photograph is taken. From the electron micrographs, 100 particles were randomly selected, the particle size of each particle was measured, and the value obtained by arithmetically averaging these measured values was defined as the average particle size D.

The average particle size D of the core particles can be easily estimated by the following method.
1) Prepare a plurality of core particle aqueous dispersions (core particle concentration: 0.05% by mass) having a known average particle diameter D, and draw a calibration line showing the relationship between the absorbance of the core particle aqueous dispersion and the average particle diameter D. The average particle size D can be estimated from the measured absorbance of the core particle aqueous dispersion (core particle concentration: 0.05% by mass) having an unknown average particle size. As the absorbance, for example, a value measured at a wavelength of 590 nm in a quartz cell having an optical path length of 10 mm can be used.
2) Core-shell Cross-linked rubber particles are kneaded with a thermoplastic resin (A), dyed, and observed with an electron microscope. The outline of the particles is observed to be dark. Therefore, a plurality of core-shell crosslinked rubber particles containing core particles having a known average particle diameter D are prepared, and the size of each of the dark contours is measured as described above. Create a calibration curve showing the relationship between the size of the dark contour and the average particle size D, and estimate the average particle size D from the size of the dark contour in the core-shell crosslinked rubber particles containing core particles whose average particle size is unknown. Can be done.

Shell cross-linked rubber particles, the refractive index n _dIS of polymer constituting the refractive index n _DCC and the inner shell of the polymer constituting the center core is, in view of _{transparency, 0nm ≦ | n dCC -n dIS} | × D The relationship of ≦ 9 nm, preferably 0 nm ≦ | n _{dCC −ndIS} | × D ≦ 8 nm is satisfied. _{Further, the absolute value of the difference between the refractive index ndIS} of the polymer constituting the inner shell and the refractive index _{ndOS of} the polymer constituting the outer shell is preferably less than 0.005, more preferably less than 0.004. More preferably, it is less than 0.003.
The refractive index n _dOS of polymer constituting the refractive index n _DCC of the polymer constituting the center core, the refractive index n _dIS of the polymer constituting the inner shell, and the outer shell, constituting each polymer It is the sum of the values obtained by multiplying the refractive index of the homopolymer in the monomer unit by the mass ratio of the monomer unit in the polymer.
When there are two or more polymers constituting the inner shell, the refractive index n _dIS is the mass ratio (x) of each polymer in the inner shell to the refractive index ( _{ndIS (i)) of each polymer. It is a value calculated by multiplying i} ) by the sum of the values.

The polymer (i) is a rubber elastic polymer having a structural unit derived from a crosslinkable monomer and having a structure in which the structural unit bridges a polymer chain. The elastic modulus of the rubber elastic polymer at room temperature (Young's modulus) is preferably 1 to 10 MPa.

A crosslinkable monomer is a monomer having two or more polymerizable functional groups in one molecule. Examples of the crosslinkable monomer include allyl acrylate, allyl methacrylate, 1-acryloxy-3-butene, 1-methacryloxy-3-butene, 1,2-diacryloxy-ethane, 1,2-dimethacryloxy-ethane, and the like. 1,2-Diacryloxy-propane, 1,3-diacryloxy-propane, 1,4-diacryloxy-butane, 1,3-dimethacryloxy-propane, 1,2-dimethacryloxy-propane, 1,4-dimethacryloxy-butane, triethylene Glycoldimethacrylate, polyethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, 1.9-nonanediol dimethacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, 1.9-nonanediol diacrylate , Divinylbenzene, 1,4-pentadiene, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate and the like. These may be used individually by 1 type or in combination of 2 or more type.

The amount of the structural unit derived from the crosslinkable monomer contained in the polymer (i) is preferably 0.05 to 10% by mass, more preferably 0.5, based on the total mass of the polymer (i). It is ~ 7% by mass, more preferably 1-5% by mass.

The polymer (i) is not particularly limited as long as the polymer chain exhibits rubber elasticity. The polymer (i) preferably has a polymer chain having either or both of a structural unit derived from an acrylic acid ester and a structural unit derived from a conjugated diene.
Examples of the acrylic acid ester used for the polymer (i) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and acrylate. Acrylic acid acyclic alkyl esters such as tert-butyl, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate; acrylics such as cyclohexyl acrylate and isobornyl acrylate Acrylic acid cyclic alkyl ester; Acrylic acid aryl ester such as phenyl acrylate and naphthyl acrylate; Functional group-containing acrylic acid non-cyclic alkyl ester such as 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate; Examples thereof include a monomer represented by 1a) (hereinafter, may be referred to as a monomer (1a)). The monomer (1a) is preferably used from the viewpoint of increasing the refractive index.

（式(1a)中、Ｒ¹⁸は芳香環を含む炭素数６〜２０の有機基を表す。Ｙは炭素数１〜６のアルキレン基又は炭素数２〜６のアルキレンオキシ基を表し、該アルキレン基及び該アルキレンオキシ基は、水酸基、オキソ基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜４のアシル基又はハロゲン原子で置換されていてもよい。ｍは１〜６の整数を表し、ｍが２以上の整数である場合、Ｙは相互に同じでも異なってもよい。）

(In the formula (1a), R ¹⁸ represents an organic group having 6 to 20 carbon atoms including an aromatic ring. Y represents an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group having 2 to 6 carbon atoms, and the alkylene group. The group and the alkyleneoxy group are a hydroxyl group, an oxo group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and glycidyl. It may be substituted with an oxy group, an acyl group having 2 to 4 carbon atoms or a halogen atom. M represents an integer of 1 to 6, and when m is an integer of 2 or more, Y is the same as or different from each other. May be good.)

Examples of the organic group having 6 to 20 carbon atoms including an aromatic ring include a pyridylmethyl group, a phenyl group, a benzyl group, a phenylethyl group, a pyrazino [2,3-b] pyrazil group, and a pyrido [2,3-b] pyrazil group. , Kinoxalyl group, quinolyl group, naphthalenyl group, pyrido [3,4-b] quinoxalyl group, pyrido [3,4-b] [1.7] naphthyldinyl group, phenazinyl group, phenanthrolyl group phenyltridinyl group, acridinyl group , Anthracenyl group, phenanthrenyl group, pyrido [3,2-f] [1.7] phenanthrolinyl group, biphenyl group and the like.

Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 1,3-butandyl group, a 1,2-butandyl group, a pentamethylene group and a hexamethylene group. Can be mentioned.
Examples of the alkyleneoxy group having 2 to 6 carbon atoms include an ethyleneoxy group, a propyleneoxy group, a trimethyleneoxy group, a tetramethyleneoxy group, and a hexamethyleneoxy group. For the alkyleneoxy group having 2 to 6 carbon atoms, it is preferable that the ^{oxy group is bonded to R 18.}

Examples of the monomer (1a) used in the present invention include acryloyloxymethylbenzene, 2- (acryloyloxy) ethylbenzene, 2- (acryloyloxy) ethyloxybenzene, and 2- (acryloyloxy) ethyloxy-4-α-c. Milphenol, 2- (acryloyloxy) ethyloxy-2-o-phenylphenol; 2- (acryloyloxy) ethyloxy-1-benzyloxynaphthalene; 2- [2'-hydroxy- 5'-(Acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(acryloyloxyethyl) phenyl] -2H-benzotriazole, 2-[ 2'-hydroxy-3'-t-butyl-5'-(acryloyloxypropyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5- (2'-acryloyl) Oxyethyl) -2H-benzotriazole, 2-[(2'-hydroxy-5'-(acryloyloxyethyl) phenyl) -5-chloro] -2H-benzotriazole and other benzotriazole structure-containing acrylates; 2-benzoyl- 5- (2'-hydroxy-3'-acryloyloxypropoxy) -phenol, 2-benzoyl-5- (2'-acryloyloxyethoxy) -phenol, 2-benzoyl-5- (2'-acryloyloxyethoxy)- Benzophenone structure-containing acrylates such as 6-tert-butyl-phenol; 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-1,3,5-triazine, 2,4- Bis (2-methylphenyl) -6- [2-hydroxy-4- (3-acryloyloxy-2-hydroxypropioxy)]-1,3,5-triazine, 2,4-diphenyl-6- [2-] Hydroxy-4- (11-acryloyloxy-undecyloxy) phenyl] -1,3,5-triazine and other triazine structure-containing acrylates; (acryloyloxymethyl) benzyloxy-naphthalene described in JP-A-2015-67796. 1- (Acryloyloxy) ethyl-naphthalene described in JP2013-209573; 1 (acryloyloxy) ethyl-biphenyl etc. described in JP2013-209572; JP2013-18 9-Acryloyloxy-9-alkylfluorene and the like described in JP-A No. 1097; acrylates and the like having a terphenyl structure described in JP-A-2013-112744; and 9-dithiaspiro described in JP-A-2011-225488. Acrylate having a fluorene structure and the like; phenylphenol ethoxyacrylate and the like described in JP-A-2001-124904 can be mentioned.

（式(D-1a)〜(D-3a)中、Ｙ¹は炭素数１〜６のアルキレン基を表す。該アルキレン基は、炭素数１〜６のアルキル基、水酸基又はオキソ基で置換されていてもよい。Ｒ¹⁹は、水酸基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、またはグリシジルオキシ基を表す。ｎは０〜５の整数、ｐは０〜４の整数、ｑは０〜５の整数を表す。ｍは、式(1a)におけるものと同じ意味を表す。ｍが２以上の整数である場合、複数のＹ¹は、同じであっても異なってもよい。ｐ及びｑが２以上の整数である場合、複数のＲ¹⁹は、同一であっても異なってもよい。） Among the monomers (1a), the monomers represented by the formulas (D-1a) to (D-3a) are preferable, and the formula (D-1-1), the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) or the formula (D-2-1) is preferable. The monomer represented by (D-3-1) is more preferable.

(In formulas (D-1a) to (D-3a), Y ¹ represents an alkylene group having 1 to 6 carbon atoms. The alkylene group is substituted with an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or an oxo group. R ¹⁹ represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a glycidyloxy group. N is an integer of 0 to 5, and p is 0 to 4. integer, .m q is an integer of 0 to 5, when .m represent the same meaning as in formula (1a) is an integer of 2 or more, plural Y ¹ is different even with the same If p and q are integers of 2 or more, the plurality of R ^19s may be the same or different.)

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

The total amount of the structural unit derived from the acrylic acid ester and the structural unit derived from the conjugated diene that can be contained in the polymer (i) is preferably 40% by mass or more with respect to the total mass of the polymer (i). It is more preferably 45 to 99% by mass, still more preferably 50 to 98% by mass. The polymer chain preferably does not contain a structural unit derived from a conjugated diene from the viewpoint of enhancing light resistance. The amount of the structural unit derived from the acrylic acid ester that can be contained in the polymer (i) is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 45% by mass or more, based on the total mass of the polymer (i). Is 50% by mass or more.
The content of the structural unit derived from the acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the polymer (i) is preferably less than 99% by mass with respect to the mass of the polymer (i). It is more preferably less than 98% by mass, still more preferably less than 90% by mass.

The polymer (i) may have structural units derived from other vinyl-based monomers in addition to the acrylic ester, conjugated diene, and crosslinkable monomer.
Examples of other vinyl-based monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and tert-methacrylate. Acyclic alkyl esters of methacrylic acid such as butyl, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate; cyclic methacrylate such as cyclohexyl methacrylate and isobornyl methacrylate. Alkyl esters; methacrylic acid aryl esters such as phenyl methacrylate and naphthyl methacrylate; 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate; monomers represented by the formula (1b) (hereinafter, simply). Meth (1b)); Aromatic vinyl monomers such as styrene, p-methylstyrene, o-methylstyrene; N-propylmaleimide, N-cyclohexylmaleimide, NO-chlorophenylmaleimide, etc. Maleimide-based monomers; examples thereof include acrylonitrile, methacrylic acid, acrylamide, methacrylic acid, acrylic acid, and methacrylic acid. Of these, aromatic vinyl monomer or monomer (1b) is preferable, and styrene is more preferable, from the viewpoint of increasing the refractive index. These may be used alone or in combination of two or more. The amount of structural units derived from other vinyl-based monomers that can be contained in the polymer (i) is preferably 60% by mass or less, more preferably 50% by mass, based on the total mass of the polymer (i). It is less than or equal to 40% by mass or more.

The polymer (i) is a copolymer having a structural unit derived from an acrylic acid ester, a structural unit derived from a crosslinkable monomer, and, if necessary, a structural unit derived from another vinyl-based monomer. , A copolymer having a structural unit derived from a conjugated diene, a structural unit derived from a crosslinkable monomer, and a structural unit derived from another vinyl-based monomer, if necessary, a structure derived from an acrylic acid ester. Examples thereof include a copolymer having a structural unit derived from a unit and a conjugated diene, a structural unit derived from a crosslinkable monomer, and, if necessary, a structural unit derived from another vinyl-based monomer. Of these, the polymer (i) has a structural unit derived from an acrylic acid ester, a structural unit derived from a crosslinkable monomer, and, if necessary, a structural unit derived from another vinyl-based monomer. Copolymers are preferred.

The polymer (ii) is not particularly limited as long as it is a polymer other than the polymer (i). The polymer (ii) preferably has a structural unit derived from a methacrylic acid ester. Examples of the methacrylic acid ester used in the polymer (ii) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate and methacrylic acid. Acyclic alkyl esters of methacrylic acid such as tert-butyl, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate; methacrylics such as cyclohexyl methacrylate and isobornyl methacrylate. Cyclic acid cyclic alkyl ester; aryl methacrylate ester such as phenyl methacrylate; functional group-containing non-cyclic alkyl ester methacrylate such as 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate; monomer (1b) And so on. The monomer (1b) is preferably used from the viewpoint of increasing the refractive index. These may be used alone or in combination of two or more. Of these, methyl methacrylate is preferable.

（式(1b)中、Ｒ¹⁸は芳香環を含む炭素数６〜２０の有機基を表す。Ｙは炭素数１〜６のアルキレン基又は炭素数２〜６のアルキレンオキシ基を表し、該アルキレン基及び該アルキレンオキシ基は、水酸基、オキソ基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜４のアシル基又はハロゲン原子で置換されていてもよい。ｍは１〜６の整数を表し、ｍが２以上の整数である場合、Ｙは相互に同じでも異なってもよい。）

(In the formula (1b), R ¹⁸ represents an organic group having 6 to 20 carbon atoms including an aromatic ring. Y represents an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group having 2 to 6 carbon atoms, and the alkylene group. The group and the alkyleneoxy group are a hydroxyl group, an oxo group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and glycidyl. It may be substituted with an oxy group, an acyl group having 2 to 4 carbon atoms or a halogen atom. M represents an integer of 1 to 6, and when m is an integer of 2 or more, Y is the same as or different from each other. May be good.)

The organic group having 6 to 20 carbon atoms including the aromatic ring, the alkylene group having 1 to 6 carbon atoms, and the alkyleneoxy group having 2 to 6 carbon atoms are as described in the description of the formula (1a).

Examples of the monomer (1b) used in the present invention include methacryloyloxymethylbenzene, 2- (methacryloyloxy) ethylbenzene, 2- (methacryloyloxy) ethyloxybenzene, and 2- (methacryloyloxy) ethyloxy-4-α-c. Milphenol, 2- (methacryloyloxy) ethyloxy-2-o-phenylphenol; 2- (methacryloyloxy) ethyloxy-1-benzyloxynaphthalene; 2- [2'-hydroxy-as described in JP-A-2014-201735. 5'-(Methylloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2-[ 2'-Hydroxy-3'-t-butyl-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5- (2'-methacryloyl) Oxyethyl) -2H-benzotriazole, 2-[(2'-hydroxy-5'-(methacryloyloxyethyl) phenyl) -5-chloro] -2H-benzotriazole and other benzotriazole structure-containing methacrylates; 2-benzoyl- 5- (2'-Hydroxy-3'-methacryloyloxypropoxy) -phenol, 2-benzoyl-5- (2'-methacryloyloxyethoxy) -phenol, 2-benzoyl-5- (2'-methacryloyloxyethoxy)- Benzene structure-containing methacrylates such as 6-tert-butyl-phenol; 2,4-diphenyl-6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]-1,3,5-triazine, 2,4- Bis (2-methylphenyl) -6- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropioxy)]-1,3,5-triazine, 2,4-diphenyl-6- [2- Hydroxy-4- (11-methacryloyloxy-undecyloxy) phenyl] -1,3,5-triazine and other triazine structure-containing methacrylates; (methacryloyloxymethyl) benzyloxy-naphthalene described in JP-A-2015-67796. 1- (Methylloyloxy) ethyl-naphthalen described in JP2013-209573; 1 (methacryloyloxy) described in JP2013-209572. B) Ethyl-biphenyl and the like; 9-methacryloyloxy-9-alkylfluorene and the like described in JP2013-181997A; methacrylates and the like having a terphenyl structure described in JP2013-112744A; JP2011-2011- Examples thereof include methacrylate having a 9-dithiaspirofluorene structure described in Japanese Patent Application Laid-Open No. 225488.

（式(D-1b)〜(D-3b)中、Ｙ¹は炭素数１〜６のアルキレン基を表す。該アルキレン基は、炭素数１〜６のアルキル基、水酸基又はオキソ基で置換されていてもよい。Ｒ¹⁹は、水酸基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、またはグリシジルオキシ基を表す。ｎは０〜５の整数、ｐは０〜４の整数、ｑは０〜５の整数を表す。ｍは、式(1a)におけるものと同じ意味を表す。ｍが２以上の整数である場合、複数のＹ¹は、同じであっても異なってもよい。ｐ及びｑが２以上の整数である場合、複数のＲ¹⁹は、同一であっても異なってもよい。） Among the monomers (1b), the monomers represented by the formulas (D-1b) to (D-3b) are preferable, and the monomers represented by the formula (D-1-2) are more preferable.

(In formulas (D-1b) to (D-3b), Y ¹ represents an alkylene group having 1 to 6 carbon atoms. The alkylene group is substituted with an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or an oxo group. R ¹⁹ represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a glycidyloxy group. N is an integer of 0 to 5, and p is 0 to 4. integer, .m q is an integer of 0 to 5, when .m represent the same meaning as in formula (1a) is an integer of 2 or more, plural Y ¹ is different even with the same If p and q are integers of 2 or more, the plurality of R ^19s may be the same or different.)

The amount of the structural unit derived from the methacrylic acid ester that can be contained in the polymer (ii) is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and further, based on the mass of the polymer (ii). It is preferably 25 to 50% by mass.

The polymer (ii) may have a structural unit derived from a crosslinkable monomer. Examples of the crosslinkable monomer used for the polymer (ii) include those exemplified as the crosslinkable monomer used for the polymer (i). The amount of the structural unit derived from the crosslinkable monomer in the polymer (ii) is preferably 0 to 5% by mass, more preferably 0.01 to 3% by mass, based on the mass of the polymer (ii). More preferably, it is 0.02 to 2% by mass.

The polymer (ii) may have a structural unit derived from another vinyl-based monomer or a structural unit derived from a conjugated diene, in addition to the methacrylic acid ester and the crosslinkable monomer. From the viewpoint of enhancing light resistance, those containing no structural unit derived from conjugated diene are preferable.
Examples of other vinyl-based monomers include acrylic acid acyclic alkyl ester, acrylic acid cyclic alkyl ester, acrylic acid aryl ester, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, and a single amount. Body (1a); aromatic vinyl monomers such as styrene, p-methylstyrene, o-methylstyrene; maleimide-based monomers such as N-propylmaleimide, N-cyclohexylmaleimide, NO-chlorophenylmaleimide; acrylonitrile , Methacrylic acid, acrylamide, methacrylic acid, acrylic acid, methacrylic acid, crotonic acid and the like. Of these, aromatic vinyl monomers are preferable, and styrene is more preferable, from the viewpoint of increasing the refractive index. These may be used alone or in combination of two or more. The amount of structural units derived from other vinyl-based monomers that can be contained in the polymer (ii) is preferably 98% by mass or less, more preferably 96% by mass or less, based on the mass of the polymer (ii). , More preferably 70% by mass or less, and preferably 40% by mass or more. The total amount of the structural unit derived from the aromatic vinyl monomer and the structural unit derived from methyl methacrylate that can be contained in the polymer (ii) is preferably 50 mass by mass with respect to the mass of the polymer (ii). % Or more, more preferably 70% by mass or more, still more preferably 80% by mass or more.

The polymer (ii) is a copolymer having a structural unit derived from a methacrylic acid ester and, if necessary, a structural unit derived from another vinyl-based monomer, and conjugate with a structural unit derived from a methacrylic acid ester. A copolymer having a structural unit derived from diene and, if necessary, a structural unit derived from other vinyl-based monomers, a structural unit derived from a methacrylic acid ester, and a structural unit derived from a crosslinkable monomer. If necessary, a copolymer having a structural unit derived from other vinyl-based monomers, a structural unit derived from a methacrylic acid ester, a structural unit derived from a conjugated diene, and a structural unit derived from a crosslinkable monomer. And, if necessary, a copolymer having a structural unit derived from other vinyl-based monomers, and the like can be mentioned. Of these, the polymer (ii) has a structural unit derived from a methacrylic acid ester, a structural unit derived from a crosslinkable monomer, and, if necessary, a structural unit derived from another vinyl-based monomer. Copolymers are preferred.

At least one of the polymers constituting the center core and the inner shell preferably contains a monomer (1a) or a structural unit derived from the monomer (1b). The amount of the monomer (1a) or the structural unit derived from the monomer (1b) that can be contained in at least one of the polymers constituting the center core and the inner shell is the amount of the polymer constituting the center core and the inner shell. Of these, preferably 1 to 70% by mass, more preferably 2 to 65% by mass, still more preferably, with respect to the mass of the polymer containing the structural unit derived from the monomer (1a) or the monomer (1b). Is 5 to 60% by mass.
Further, the amount of the structural unit derived from the monomer (1a) or the monomer (1b) contained in at least one of the polymers constituting the center core and the inner shell is based on the total mass of the core-shell crosslinked rubber particles. It is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and even more preferably 20 to 35% by mass.

The polymer (iii) is not particularly limited as long as it is a polymer other than the polymer (i) and the polymer (ii) selected as the polymer constituting the center core and the inner shell. The polymer (iii) is preferably a thermoplastic polymer compatible with the thermoplastic resin (A) to which the impact resistance improving agent of the present invention is added and melt-kneaded.

The polymer (iii) is preferably a thermoplastic polymer having a structural unit derived from a methacrylic acid ester and, if necessary, a structural unit derived from another vinyl-based monomer.

The methacrylic acid ester used in the polymer (iii) is a methacrylic acid alkyl ester monomer having an alkyl group having 1 to 8 carbon atoms, or a methacrylic acid aromatic ester having an aromatic group having 6 to 24 carbon atoms. Is preferable. Examples of the methacrylic acid ester monomer include methyl methacrylate, butyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like. These may be used individually by 1 type or in combination of 2 or more type. Of these, methyl methacrylate is preferable.
The amount of the structural unit derived from the methacrylic acid ester monomer contained in the polymer (iii) is preferably 40% by mass or more, more preferably 50% by mass or more, and further, with respect to the mass of the polymer (iii). It is preferably 70% by mass or more, and most preferably 90% by mass or more.

Examples of other vinyl-based monomers that can be used for the polymer (iii) include the same vinyl-based monomers as those exemplified in the above-mentioned polymer (ii). The amount of structural units derived from other vinyl-based monomers that can be contained in the polymer (iii) is preferably 60% by mass or less, more preferably 50% by mass or less, based on the mass of the polymer (iii). , More preferably 40% by mass or less.

The amount of the outer shell of the core-shell crosslinked rubber particles is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 20 to 40% by mass with respect to the mass of the particles. The amount of the polymer (i) is preferably 20 to 100% by mass, more preferably 30 to 70% by mass, based on the total mass of the center core and the inner shell.

In the core-shell crosslinked rubber particles, it is preferable that at least one of the polymers constituting the center core and the inner shell contains a sulfur component, and it is more preferable that the polymer constituting the center core contains a sulfur component. ..
Further, the ratio of the mass of the sulfur component contained in the polymer constituting the center core to the mass of the polymer constituting the center core or the sulfur contained in the polymer constituting the inner shell with respect to the mass of the polymer constituting the inner shell. either the ratio of the weight of component is greater than the ratio of the mass of the sulfur component contained in the polymer constituting the outer shell relative to the mass of the polymer constituting the outer shell.
The ratio of the mass of the sulfur component contained in the polymer constituting the center core to the mass of the polymer constituting the center core or the mass of the sulfur component contained in the polymer constituting the inner shell with respect to the mass of the polymer constituting the inner shell. Any of the mass ratios is preferably 0.05 to 2% by mass, more preferably 0.1 to 1.5% by mass.
The ratio of the mass of the sulfur component contained in the polymer constituting the outer shell to the mass of the polymer constituting the outer shell is preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.4. It is mass%.
The amount of the sulfur component contained in the polymer can be adjusted by the type and amount of the sulfur-containing compound used at each stage in producing the core-shell crosslinked rubber particles. Examples of the sulfur-containing compound include emulsifiers, chain transfer agents, polymerization initiators and the like.

The ratio of the mass of the sulfur component contained in the polymer to the mass of the polymer is determined as follows.
First, 0.2 g of each of the sample polymer, specifically the seed particles, core particles or core-shell cross-linked rubber particles obtained at each stage in producing the core-shell cross-linked rubber particles, is precisely weighed and placed in a container. To this, 10 ml of concentrated nitric acid is added, the container is sealed, and the decomposition treatment is carried out with a microwave sample decomposition apparatus (ETHOS-1600 type manufactured by Milestone General Co., Ltd.) at an output of 500 to 1000 W for 55 minutes. Next, the sulfur component (mass%) is quantified with an ICP emission spectroscopic analyzer (CCD multi-element simultaneous ICP emission spectroscopic analyzer manufactured by Seiko Instruments, ICP-OES VISTA-PRO). The amount of sulfur component contained in the polymer constituting the outer shell is the amount of sulfur component contained in the polymer (core particles) constituting the center core and the inner shell from the amount of sulfur component contained in the core shell crosslinked rubber particles. It can be calculated by subtracting, and the amount of sulfur component contained in the polymer constituting the inner shell is the amount of sulfur contained in the polymer (seed particle) constituting the center core from the amount of sulfur component contained in the core particles. It can be calculated by subtracting the amount of components.

In the impact resistance improving agent of the present invention, the average particle size of the core-shell crosslinked rubber particles is preferably 0.16 to 1 μm, more preferably 0.18 to 0.5 μm, and further preferably 0.2 to 0.4 μm. is there. In this specification, the average particle size is a value calculated based on electron microscope observation. Impact resistance of the present invention from the viewpoint that the core-shell crosslinked rubber particles can be easily uniformly dispersed in the thermoplastic resin (A) in the melt-kneading of the thermoplastic resin (A) and the impact resistance improving agent (B) of the present invention. The improving agent is preferably one in which the core-shell crosslinked rubber particles as described above are granulated to a size of 1000 μm or less, and more preferably one in which the core-shell crosslinked rubber particles are granulated to a size of 500 μm or less. The granulated product of the core-shell crosslinked rubber particles may be agglomerated in a state where the outer shells are fused to each other. The granulated product of the core-shell crosslinked rubber particles may be in the form of pellets, granules, powder or the like.

The acid value of the core-shell crosslinked rubber particles measured in JIS K 0070: 1992 is preferably 10 mg / g or less, more preferably 7 mg / g or less, still more preferably 5 mg / g or less, still more preferably 3 mg / g or less. Most preferably, it is 1 mg / g or less. The acid value of the core-shell crosslinked rubber particles can be adjusted, for example, by washing with water. The acid value of the core-shell crosslinked rubber particles is measured using a sample solution obtained by stirring the core-shell crosslinked rubber particles in chloroform at room temperature for 12 hours or more. Since the core-shell crosslinked rubber particles may not be completely dissolved in chloroform, the sample solution may contain undissolved components. The undissolved component may be removed from the sample solution immediately before the measurement.

The core-shell crosslinked rubber particles have a refractive index (nd ²³ ) of 1.50 to 1.55, preferably 1.50 to 1.54, and more preferably 1.51 to 1.54. From the viewpoint of enhancing the transparency of the thermoplastic resin composition containing the core-shell crosslinked rubber particles and the thermoplastic resin (A), the difference in refractive index between the thermoplastic resin (A) and the core-shell crosslinked rubber particles is preferably 0. It is preferably 0.05 or less, more preferably 0.02 or less, still more preferably 0.01 or less, and most preferably 0.005 or less.

Further, the impact resistance improving agent of the present invention has a 1.0% heating weight loss temperature measured at a nitrogen flow rate of 10 ml / min and a heating rate of 20 ° C./min, preferably 310 ° C. or higher, more preferably 315 to 350 ° C. Is. When the 1.0% heat loss temperature is in this range, stains on the roll and the mold are suppressed, and air bubbles can be prevented from being mixed into the film obtained by molding.

The method for producing the impact resistance improving agent of the present invention is not particularly limited as long as it is a method capable of obtaining the core-shell crosslinked rubber particles as described above. A preferred method for producing the impact resistance improving agent of the present invention is to obtain seed particles by emulsion polymerization (first stage polymerization) of a monomer for obtaining a polymer constituting the center core, and in the presence of the seed particles. In order to obtain core particles by seed emulsion polymerization (second stage polymerization) of the monomer for obtaining the polymer constituting the inner shell, and to obtain the polymer constituting the outer shell in the presence of the core particles. It includes seed emulsion polymerization (third stage polymerization) of a monomer to obtain core-shell crosslinked rubber particles. Since the emulsification polymerization method or the seed emulsification polymerization method is a well-known technique in the art as a method for obtaining general core-shell particles, detailed explanations can be referred to in other documents. When the number of polymers constituting the inner shell is 2 or more, the second stage polymerization is performed twice or more.

Examples of the emulsifier used for emulsification polymerization or seed emulsification polymerization include dialkyl sulfosuccinates such as anionic emulsifiers sodium dioctyl sulfosuccinate and sodium dilauryl sulfosuccinate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, and dodecyl. Alkyl sulfate such as sodium sulfate; polyoxyethylene alkyl ether which is a nonionic emulsifier, polyoxyethylene nonylphenyl ether, etc .; polyoxyethylene nonylphenyl ether which is a nonionic / anionic emulsifier Polyoxyethylene nonylphenyl ether such as sodium sulfate Sulfate, polyoxyethylene alkyl ether sulfate such as polyoxyethylene alkyl ether sodium sulfate, alkyl ether carboxylate such as polyoxyethylene tridecyl ether sodium acetate; can be mentioned. These 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.

The polymerization initiator used for emulsion polymerization or seed emulsion polymerization is not particularly limited. For example, persulfate-based initiators such as potassium persulfate and ammonium persulfate; redox-based initiators such as persulfoxylate / organic peroxide and persulfate / sulfite can be mentioned.

The chain transfer agent used for emulsion polymerization or seed emulsion polymerization is not particularly limited. For example, monofunctional thiol compounds such as n-butyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, t-tetradecyl mercaptan, n-tetradecyl mercaptan, 1,4- Butanedithiol, 1,6-hexanedithiol, 1,10-decandiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane Tristhioglycolate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimetylolpropan trithiopropionate, trimethylolpropanthithiopropionate, pentaerythritol tetrakis (3) -Mercaptobutyrate), pentaerythritol tetraxthiopropionate, pentaerythritol tetraxthioglycolate, trishydroxyethyl tristhiopropionate, polyfunctional thiol compounds such as 1,4-bis (3-mercaptobutyryloxy) butane , Thiolphenol, tetraethylthiuram disulfide, pentanphenylethane, achlorein, metachlorine, allyl alcohol, carbon tetrachloride, ethylene bromide and the like. Of these, n-octyl mercaptan, n-dodecyl mercaptan, and pentaerythritol tetrakis (3-mercaptobutyrate) are preferable. The chain transfer agent can be used alone or in combination of two or more.
The amount of chain transfer agent used in the first or second stage polymerization is preferably relative to the total weight of the monomers provided in the first or second stage polymerization, respectively. Is 0.05 to 2% by mass, more preferably 0.1 to 1.5% by mass. The amount of the chain transfer agent used in the third-stage polymerization is preferably 0.05 to 0.5% by mass, based on the total weight of the monomers used in the third-stage polymerization. It is preferably 0.1 to 0.4% by mass.
In particular, by using a chain transfer agent in the first stage polymerization, the 1.0% heating weight loss temperature of the impact resistance improving agent of the present invention measured at a nitrogen flow rate of 10 ml / min and a heating rate of 20 ° C./min can be obtained. Can be high.

Separation and acquisition of the core-shell crosslinked rubber particles from the emulsion obtained by seed emulsion polymerization can be carried out by a known method such as a salting out coagulation method, a freeze coagulation method, or a spray drying method. The salting-out coagulation method and the freeze-coagulation method are preferable, and the freeze-coagulation method is more preferable, because impurities contained in the core-shell crosslinked rubber particles can be easily removed by washing with water. Since no flocculant is used in the freeze-coagulation method, it is easy to obtain a molded product having excellent water resistance. Since foreign substances that may be contained in the emulsion can be removed, it is preferable to filter the emulsion with a wire mesh having a mesh size of 50 μm or less before the coagulation step.

By adding the impact resistance improving agent of the present invention to the thermoplastic resin and kneading it, a thermoplastic resin composition having excellent transparency, impact resistance and the like can be obtained.

The thermoplastic resin composition of the present invention contains the thermoplastic resin (A) and the impact resistance improving agent (B) of the present invention.

The thermoplastic resin (A) used in the present invention is not particularly limited. For example, methacrylic resin; polyester resin such as polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin; polyamide resin such as polyamide 6 resin, polyamide 66 resin, polyamide elastomer; polyethylene resin, polypropylene resin, polybutene-1 resin, poly-4. -Methylpentene-1 resin, polynorbornene resin, norbornene-based ring-opening polymer or its hydrogenated product, norbornene-based addition polymer or its hydrogenated product and other polyolefin resins; ethylene-based ionomer; polystyrene resin, styrene-maleic anhydride Polystyrene-based resins such as copolymers, high-impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, Polyvinyl butyral resin, polyvinyl acetal resin, polyvinylidene fluoride, polyurethane, phenoxy resin, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin, silicone rubber; styrene-based thermoplastic elastomers such as SEPS, SEBS, SIS, IR, EPR, EPDM, etc. Examples thereof include olefin-based thermoplastic elastomers and acrylic-based thermoplastic elastomers such as acrylic block copolymers. The thermoplastic resin (A) preferably has a refractive index n ²⁵ _d of 1.5 to 1.6. Of these, it is preferable to use only the methacrylic resin as the thermoplastic resin (A), and it is more preferable to use the methacrylic resin and the polycarbonate resin in combination. Even when only the methacrylic resin is used or when the methacrylic resin and the polycarbonate resin are used in combination, the thermoplastic resin other than these is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 0% by mass. It may be used together depending on the situation.

In the thermoplastic resin composition of the present invention, the mass ratio of the thermoplastic resin (A) and the impact resistance improving agent (B) of the present invention is not particularly limited. The mass ratio (A) / (B) of the thermoplastic resin (A) and the impact resistance improving agent (B) of the present invention is preferably 95/5 to 10/90, more preferably 90/10 to 30/70. , More preferably 85/15 to 40/60, and even more preferably 80/20 to 50/50.
The total amount of the thermoplastic resin (A) contained in the thermoplastic resin composition of the present invention and the impact resistance improving agent (B) of the present invention is preferably 40 to 40 to the mass of the thermoplastic resin composition. It is 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, and most preferably 80 to 100% by mass.

One of the thermoplastic resins (A) preferably used in the present invention is derived from a polymer containing only a structural unit derived from methyl methacrylate or a structural unit derived from methyl methacrylate and another monomer. It is a random copolymer containing a structural unit having no ring structure in the main chain (hereinafter, these are referred to as methacrylic resin [Aa]). Other monomers thereof include acrylic acid acyclic alkyl ester; acrylic acid aryl ester; acrylic acid aralkyl ester; acrylic acid cyclic alkyl ester; 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, and the like. Allyl acrylate; Non-cyclic alkyl methacrylic acid ester other than methyl methacrylate; Aryl methacrylate ester; Aralkyl methacrylate ester; Cyclic alkyl methacrylate ester; 2-Hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, Allyl methacrylate; unsaturated carboxylic acid; olefin; conjugated diene; aromatic vinyl compound; acrylamide, methacrylicamide, acrylonitrile, methacrylic nitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, etc. be able to.
In the methacrylic resin [Aa], the amount of structural units derived from methyl methacrylate is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, based on the total structural units. It is more preferably 95% by mass or more, and most preferably 99.5% by mass or more. The amount of structural units derived from other monomers and having no ring structure in the main chain is not limited as long as it is balanced with the amount of structural units derived from methyl methacrylate, and is preferably 50% by mass or less, more preferably. Is 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and most preferably 0.5% by mass or less.

The methacrylic resin [Aa] is not particularly limited by the conformation of asymmetric carbons on the molecular chain. Structures with the same conformation in the duplex (diad) (isotactic diad structure or mesostructure [m]), structures with different conformations in the duplex (diad) (syndiotactic diad structure or racemo) Structure [r]), structure in which isotactic diad structures are lined up in triplets (triads) (isotactic triad structure, [m, m]), syndiotactic diad structures in triplets (triads) Lined structure (syndiotactic triad structure, [r, r]), structure in which an isotactic diad structure and a syndiotactic diad structure are lined up in a triplet (triad) (heterotactic triad structure, [m, r] ] Or [r, m]) and so on. The methacrylic resin [Aa] used in the present invention preferably has many syndiotactic triad structures from the viewpoint of heat resistance.

The lower limit of syndiotacticity (rr) of the methacrylic resin [Aa] is preferably 58%, more preferably 59%, and even more preferably 60%. The upper limit of the syndiotacticity (rr) of the methacrylic resin [Aa] is not particularly limited, but from the viewpoint of film forming property, it is preferably 99%, more preferably 85%, still more preferably 77%, still more preferably. 65%, most preferably 64%.

Syndiotacticity (rr) is the ratio of syndiotactic triad structures to total triad structures. Syndiotacticity (rr) (%) is ^{measured in 1} H-NMR spectrum at 30 ° C. in deuterated chloroform, and is in the region of 0.6 to 0.95 ppm when TMS is 0 ppm. The area (X) and the area (Y) in the region of 0.6 to 1.35 ppm can be measured and calculated by the formula: (X / Y) × 100.

The polystyrene-equivalent weight average molecular weight Mw of the methacrylic resin [Aa] calculated based on the chromatogram obtained by gel permeation chromatography is preferably 50,000 to 200,000, more preferably 55,000 to 160,000. More preferably, it is 60,000 to 120,000. The higher the Mw, the higher the strength of the molded product obtained from the methacrylic resin [Aa] tends to be. The lower the Mw, the better the molding processability of the tacryl resin [Aa], and the smoother the surface of the obtained molded product tends to be.

The methacrylic resin [Aa] has a ratio Mw / Mn of weight average molecular weight Mw to polystyrene-equivalent number average molecular weight Mn calculated based on a chromatogram obtained by gel permeation chromatography, preferably 1.05 or more and 3 or less. It is preferably 1.3 or more and 2.5 or less, and more preferably 1.3 or more and 1.7 or less. The lower the Mw / Mn, the better the impact resistance and toughness tend to be. The higher the Mw / Mn, the higher the melt fluidity of the methacrylic resin [Aa], and the smoother the surface of the obtained molded product tends to be.

The measurement by gel permeation chromatography is performed as follows. Tetrahydrofuran is used as the eluent, and TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 are connected in series as the column. As an analyzer, HLC-8320 (product number) manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) was used. A solution to be tested is prepared by dissolving 4 mg of the methacrylic resin to be tested in 5 ml of tetrahydrofuran. The temperature of the column oven is set to 40 ° C., the eluent flow rate is 0.35 ml / min, 20 μl of the solution to be tested is injected, and the chromatogram is measured.
The chromatogram is a chart in which the electric signal value (intensity Y) derived from the difference in refractive index between the test target solution and the reference solution is plotted against the retention time X.
Standard polystyrene with a molecular weight in the range of 400 to 500000 is measured by gel permeation chromatography to prepare a calibration curve showing the relationship between retention time and molecular weight. The baseline is the line connecting the point where the slope of the high molecular weight side of the chromatogram changes from zero to positive and the point where the slope of the peak on the low molecular weight side changes from negative to zero. If the chromatogram shows multiple peaks, draw a line connecting the point where the slope of the peak on the highest molecular weight side changes from zero to plus and the point where the slope of the peak on the lowest molecular weight side changes from minus to zero. Use as a baseline.

The melt flow rate of the methacrylic resin [Aa], which is determined by measuring at 230 ° C. and a load of 3.8 kg, is preferably 0.1 to 30 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes. , More preferably 1 to 15 g / 10 minutes.

The methacrylic resin [Aa] has a glass transition temperature of preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, and particularly preferably 123 ° C. or higher. The upper limit of the glass transition temperature of the methacrylic resin [Aa] is not particularly limited, but is preferably 131 ° C.

The glass transition temperature (Tg) is the intermediate point glass transition temperature obtained from the DSC curve. The DSC curve shows that the resin to be measured is heated once from room temperature to 230 ° C (1 ^st run) at a temperature rise rate of 10 ° C / min using a differential scanning calorimeter according to JIS K7121, and then to room temperature. cooling, then it is obtained by differential scanning calorimetry, during heating of the 2 ^nd run when warmed (2 ^nd run) at 10 ° C. / min up to 230 ° C. from room temperature.

Another type of thermoplastic resin (A) preferably used in the present invention is a methacrylic resin [Ab] containing a structural unit having a ring structure in the main chain and a structural unit derived from methyl methacrylate. Methacrylic resin [Ab] is characterized by high glass transition temperature, low water absorption, and small shrinkage at high temperature and high humidity.

The methacrylic resin [Ab] has a ring structure in which the content of the structural unit derived from methyl methacrylate is preferably 20 to 99% by mass, more preferably 30 to 95% by mass, still more preferably 40 to 90% by mass. The content of the structural unit having the above in the main chain is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and further preferably 10 to 60% by mass. The content of the structural unit derived from methyl methacrylate in the methacrylic resin [Ab] is converted into a structural unit having a ring structure in the main chain by intramolecular cyclization among the structural units derived from methyl methacrylate. Does not include acrylic.

The methacrylic resin [Ab] may have a structural unit derived from methyl methacrylate and a structural unit other than the structural unit having a ring structure in the main chain. Examples of the monomer from which the other structural unit is derived include an alkyl methacrylate ester other than methyl methacrylate such as ethyl methacrylate and t-butyl methacrylate; an aryl methacrylate ester such as phenyl methacrylate; and methacrylic acid. 1-Methylcyclopentyl, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, norbornenyl methacrylate, isobornyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid Cycloalkyl methacrylate esters such as 4-t-butylcyclohexyl; methacrylic acid aralkyl esters such as benzyl methacrylate; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylate Acrylic acid alkyl esters such as isobutyl, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate; glycidyl acrylate; allyl acrylate; acrylate Acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate; 3-dimethylaminoethyl acrylate; Acrylic acid aryl esters such as phenylacrylic acid and toluyl acrylate; Acrylic acid Acrylic acid aralkyl ester such as benzyl; Acrylic acid cycloalkyl ester such as cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate; Aromatic vinyl compounds such as styrene and α-methylstyrene; acrylamide; methacrylicamide; Examples thereof include vinyl-based monomers having only one polymerizable carbon-carbon double bond in one molecule such as lonitrile.

As a structural unit having a ring structure in the main chain, a structural unit containing> CH-OC (= O) -group in the ring structure and -C (= O) -OC (= O) -group as a ring. Structural units included in the structure, -C (= O) -NC (= O) -groups in the ring structure, or> CH-O-CH <groups in the ring structure are preferred.
The structural unit having a ring structure in the main chain is obtained by copolymerizing a cyclic monomer having a polymerizable unsaturated carbon-carbon double bond such as maleic anhydride or N-substituted maleimide with methyl methacrylate or the like. , Or a part of the molecular chain of the methacrylic resin obtained by polymerization can be contained in the methacrylic resin [Ab] by intramolecular condensation cyclization.

> CH-OC (= O) -groups are included in the ring structure as structural units such as β-propiolactone diyl (also known as oxooxetane diyl) structural unit and γ-butyrolactone diyl (also known as 2-oxodihydrofuran). Il) structural unit, lactone diyl structural unit such as δ-valerolactone diyl (also known as 2-oxodihydropyrandiyl) structural unit can be mentioned. In addition, "> C" in the formula means that the carbon atom C has two bonds.

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

In formula (I), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an organic residue having 1 to 20 carbon ^{atoms, and it is preferable that R 14} is a hydrogen atom and R ¹⁵ is a methyl group. R ¹⁶ is −COOR, and R is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, preferably a methyl group. * Means a bond.
Examples of the organic residue in the formula (I) include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, a -OAc group, and a -CN group. The organic residue may contain an oxygen atom. "Ac" indicates an acetyl group. The organic residue has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

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

As the structural unit containing the −C (= O) -OC (= O) − group in the ring structure, 2,5-dioxodihydrofrangyl structural unit, 2,6-dioxodihydropyrandiyl structural unit, 2,7-Dioxooxepangyl structural units and the like can be mentioned.

式（II）中、Ｒ²¹およびＲ²²はそれぞれ独立に水素原子または炭素数１〜２０の有機残基である。＊は結合手を意味する。
なお、式（II）における、有機残基としては、直鎖若しくは分岐状のアルキル基、直鎖若しくは分岐状のアルキレン基、アリール基、−ＯＡｃ基、および−ＣＮ基等を挙げることができる。有機残基は酸素原子を含んでいてもよい。「Ａｃ」はアセチル基を示す。有機残基は、その炭素数が、好ましくは１〜１０、より好ましくは１〜５である。 For example, examples of the 2,5-dioxodihydrofurandiyl structural unit include a structural unit represented by the formula (II).

In formula (II), R ²¹ and R ²² are independent hydrogen atoms or organic residues having 1 to 20 carbon atoms, respectively. * Means a bond.
Examples of the organic residue in the formula (II) include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, a -OAc group, and a -CN group. The organic residue may contain an oxygen atom. "Ac" indicates an acetyl group. The organic residue has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

It is more preferable that both ^{R 21} and R ^{22 are hydrogen atoms.} In that case, it is usually preferable that styrene or the like is copolymerized from the viewpoint of ease of production and adjustment of natural birefringence. Specifically, a copolymer having a structural unit derived from styrene, a structural unit derived from methyl methacrylate, and a structural unit derived from maleic anhydride, as described in WO2014 / 021264A, can be mentioned. it can.
The 2,5-dioxodihydrofrangyl structural unit can be contained in the methacrylic resin by copolymerization of maleic anhydride or the like.

式（III）中、Ｒ³³およびＲ³⁴はそれぞれ独立に水素原子または炭素数１〜２０の有機残基である。＊は結合手を意味する。
なお、式（III）における、有機残基としては、直鎖若しくは分岐状のアルキル基、直鎖若しくは分岐状のアルキレン基、アリール基、−ＯＡｃ基、および−ＣＮ基等を挙げることができる。有機残基は酸素原子を含んでいてもよい。「Ａｃ」はアセチル基を示す。有機残基は、その炭素数が、好ましくは１〜１０、より好ましくは１〜５、もっとも好ましくは１である。最も好ましい有機残基はメチル基である。 Examples of the 2,6-dioxodihydropyrandiyl structural unit include a structural unit represented by the formula (III).

In formula (III), R ³³ and R ³⁴ are independently hydrogen atoms or organic residues having 1 to 20 carbon atoms, respectively. * Means a bond.
Examples of the organic residue in the formula (III) include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, a -OAc group, and a -CN group. The organic residue may contain an oxygen atom. "Ac" indicates an acetyl group. The organic residue has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and most preferably 1. The most preferred organic residue is the methyl group.

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

The structural unit containing the −C (= O) -NC (= O) − group in the ring structure (note that the other bond possessed by N is omitted) is 2,5-. Examples thereof include a dioxopyrrolidine diyl structural unit, a 2,6-dioxopiperidine diyl structural unit, and a 2,7-dioxoazepandiyl structural unit.

式（IV）中、Ｒ⁴¹およびＲ⁴²はそれぞれ独立に水素原子または炭素数１〜８のアルキル基であり、Ｒ⁴³は水素原子、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、または炭素数６〜１０のアリール基である。＊は結合手を意味する。
原料入手の容易さ、費用、耐熱性などの観点から、Ｒ⁴¹およびＲ⁴²はそれぞれ独立に水素原子またはメチル基であることが好ましく、Ｒ⁴¹がメチル基でありＲ⁴²が水素原子であることがより好ましい。Ｒ⁴³は水素原子、メチル基、ｎ−ブチル基、シクロへキシル基またはベンジル基であることが好ましく、メチル基であることがより好ましい。 For example, examples of the 2,6-dioxopiperidinediyl structural unit include a structural unit represented by the formula (IV).

In formula (IV), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴³ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and 3 to 12 carbon atoms. It is a cycloalkyl group or an aryl group having 6 to 10 carbon atoms. * Means a bond.
From the viewpoint of easy availability of raw materials, cost, heat resistance, etc., ^{it is preferable that R 41} and R ⁴² are independently hydrogen atoms or methyl groups, R ⁴¹ is a methyl group and R ⁴² is a hydrogen atom. Is more preferable. R ⁴³ is preferably a hydrogen atom, a methyl group, an n-butyl group, a cyclohexyl group or a benzyl group, and more preferably a methyl group.

式（V）中、Ｒ⁵²およびＲ⁵³はそれぞれ独立に水素原子、炭素数１〜１２のアルキル基、または炭素数６〜１４のアルキル基であり、Ｒ⁵¹は、炭素数７〜１４のアリールアルキル基、または無置換の若しくは置換基を有する炭素数６〜１４のアリール基である。アリール基に置換される基は、ハロゲノ基、ヒドロキシル基、ニトロ基、炭素数１〜１２のアルコキシ基、炭素数１〜１２のアルキル基または炭素数７〜１４のアリールアルキル基である。＊は結合手を意味する。Ｒ⁵¹はフェニル基またはシクロヘキシル基であるのが好ましく、Ｒ⁵²およびＲ⁵³は共に水素原子であるのが好ましい。
２，５−ジオキソピロリジンジイル構造単位は、Ｎ−置換マレイミドの共重合などによって、メタクリル樹脂に含有させることができる。 Examples of the 2,5-dioxopyrrolidinediyl structural unit include a structural unit represented by the formula (V).

In formula (V), R ⁵² and R ⁵³ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or alkyl groups having 6 to 14 carbon atoms, and R ⁵¹ is an aryl having 7 to 14 carbon atoms. It is an alkyl group, or an aryl group having 6 to 14 carbon atoms having an unsubstituted or substituent. The group substituted with the aryl group is a halogeno group, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 14 carbon atoms. * Means a bond. R ⁵¹ is preferably a phenyl group or a cyclohexyl group, ^{and both R 52} and R ⁵³ are preferably hydrogen atoms.
The 2,5-dioxopyrrolidinediyl structural unit can be contained in the methacrylic resin by copolymerization of N-substituted maleimide or the like.

Examples of the structural unit containing the> CH-O-CH <group in the ring structure include an oxetane diyl structural unit, a tetrahydrofuran diyl structural unit, a tetrahydropyran diyl structural unit, and an oxepandyl structural unit. In addition, "> C" in the formula means that the carbon atom C has two bonds.

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

In formula (VI), R ⁶¹ and R ⁶² are independently hydrogen atoms, linear or branched hydrocarbon groups having 1 to 20 carbon atoms, or hydrocarbon groups having 3 to 20 carbon atoms having a ring structure, respectively. Is. * Means a bond.
R ⁶¹ and R ⁶² are independently tricyclo [5.2.1.0 ^2,6 ] decanyl group, 1,7,7-trimethylbicyclo [2.2.1] heptane-3-yl group, respectively. A t-butyl group or a 4-t-butylcyclohexanyl group is preferable.

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

The polystyrene-equivalent weight average molecular weight Mw of the methacrylic resin [Ab] calculated based on the chromatogram obtained by gel permeation chromatography is preferably 40,000 to 200,000, more preferably 40,000 to 150,000, and even more preferably. Is 50,000 to 120,000. The higher the Mw, the higher the strength of the molded product obtained from the methacrylic resin [Ab] tends to be. The lower the Mw, the better the molding processability of the methacrylic resin [Ab], and the smoother the surface of the obtained molded product tends to be.

The methacrylic resin [Ab] has a ratio Mw / Mn of weight average molecular weight Mw to polystyrene-equivalent number average molecular weight Mn calculated based on a chromatogram obtained by gel permeation chromatography, preferably 12 or more and 5.0 or less. It is preferably 1.3 or more and 3.5 or less. The lower the Mw / Mn, the better the impact resistance and toughness tend to be. The higher the Mw / Mn, the higher the melt fluidity of the methacrylic resin [Ab], and the smoother the surface of the obtained molded product tends to be.

The melt flow rate of the methacrylic resin [Ab] determined by measuring at 230 ° C. and a load of 3.8 kg is preferably 0.1 to 20 g / 10 minutes, more preferably 0.5 to 15 g / 10 minutes. , More preferably 1.0 to 10 g / 10 minutes.

Further, the methacrylic resin [Ab] has a glass transition temperature of preferably 120 ° C. or higher, more preferably 123 ° C. or higher, still more preferably 124 ° C. or higher. The upper limit of the glass transition temperature of the methacrylic resin [Ab] is not particularly limited, but is preferably 160 ° C.

Another one of the thermoplastic resins (A) preferably used in the present invention is a structural unit derived from a methacrylic acid ring hydrocarbon ester and a structural unit derived from a methacrylic acid ester other than the methacrylic acid ring hydrocarbon ester. A methacrylic acid resin [Ac] containing a structural unit derived from an acrylic acid ester, if necessary. The methacrylic resin [Ac] has a structure in which the ring structure is bonded to the main chain in a pendant shape. Methacrylic resin [Ac] is characterized by high glass transition temperature, low water absorption, and small shrinkage at high temperature and high humidity.

Examples of the cyclic hydrocarbon group constituting the methacrylic acid cyclic hydrocarbon ester include octahydropentalene-1-yl group, octahydropentalene-2-yl group, and octahydro-1-1H-inden-4-yl group. Il group, octahydro-1-1H-inden-5-yl group, hexahydro-1,5-methano-pentalene-3A-yl group, decahydronaphthalene-1-yl group, decahydronaphthalen-2-yl group, octa Hydrocyclopenta [c, d] pentalene-2A-2a (2H) -yl group, 3a, 6a-dimethyloctahydropentalene-2-yl group, tetradecahydroanthracene-9-yl group, androstan-4- Condensed polycyclic hydrocarbon group such as yl group, cholesterol-2-yl group, cholesterol-5-yl group; norbornan-2-yl group, 2-methylnorbornan-2-yl group, 2-ethylnorbornan-2- Il group, 1,3,3-trimethylnorbornan-2-yl group, 1,2,3,3-tetramethylnorbornan-2-yl group, 1,3,3-trimethylnorbornan-2-yl group, isobornan- 2-Il group, 2-methylisobornan-2-yl group, 2-ethylisobornan-2-yl group, decahydro-2,5-methano-7,10-methanonaphthalene-1-yl group, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yl group, 8-methyltricyclo [5.2.1.0 ^2,6 ] Decane-8-yl group, 8-ethyltricyclo [5] 2.1.0 ^2,6 ] Decane-8-yl group, adamantan-1-yl group, adamantan-2-yl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group , Decahydro-3,6-methano-2,2,7,7-tetramethylnaphthalene-1-yl group and other bridging ring hydrocarbon groups; spirobicyclopentane-2-yl group, spirobicyclopentane-3-3 Polycyclic hydrocarbon group having spiro structure such as yl group, spirobicyclohexane-2-yl group, spirobicyclohexane-3-yl group; cyclopentyl group, cyclopentyl group substituted with alkyl group, cyclohexyl group, alkyl group Aromatic charcoal such as monocyclic hydrocarbon groups such as cyclohexyl group, cycloheptyl group and cyclooctyl group substituted with, phenyl group, phenyl group substituted with alkyl group, naphthyl group and naphthyl group substituted with alkyl group. Hydrogen group; etc. can be mentioned. The alkyl group in the "substituted with an alkyl group" is preferably an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or isobutyl. Groups, tert-butyl groups and the like can be mentioned. As the cyclic hydrocarbon group, an aliphatic cyclic hydrocarbon group is preferable.

式(2)中、Ｘは、炭素数６以上の環式炭化水素基、好ましくは炭素数１０以上の橋かけ環式炭化水素基である。なお、橋かけ環式炭化水素基は、環を構成する隣り合わない二つの炭素原子が１以上の炭素原子からなる炭素鎖で結ばれた構造を有する脂環式炭化水素基である。係る橋かけ環式炭化水素基は、炭素鎖で結ばれた構造以外に、縮合環構造、スピロ環構造を有してもよい。橋かけ環式炭化水素基を構成する炭素原子の数は、１０〜２０であることがより好ましい。アルキルなどの非環式炭化水素基にシクロへキシル基やフェニル基などが置換したものは環式炭化水素基に含まない。 The methacrylic acid cyclic hydrocarbon ester is preferably a compound represented by the formula (2).

In the formula (2), X is a cyclic hydrocarbon group having 6 or more carbon atoms, preferably a bridging cyclic hydrocarbon group having 10 or more carbon atoms. The bridging ring hydrocarbon group is an alicyclic hydrocarbon group having a structure in which two non-adjacent carbon atoms constituting a ring are connected by a carbon chain composed of one or more carbon atoms. The crosslinked cyclic hydrocarbon group may have a fused ring structure or a spiro ring structure in addition to the structure connected by a carbon chain. The number of carbon atoms constituting the crosslinked cyclic hydrocarbon group is more preferably 10 to 20. Cyclic hydrocarbon groups in which an acyclic hydrocarbon group such as alkyl is substituted with a cyclohexyl group or a phenyl group are not included.

Examples of the cyclic hydrocarbon group having 6 or more carbon atoms include octahydrocyclopenta [c, d] pentalen-2A-2a (2H) -yl group, 3a, 6a-dimethyloctahydropentalene-2-yl group, and tetra. Decahydroanthracene-9-yl group, androstan-4-yl group, cholesterol-2-yl group, cholesterol-5-yl group, 1,3,3-trimethylnorbornan-2-yl group, 1,2,3 , 3-Tetramethylnorbornan-2-yl group, 1,3,3-trimethylnorbornenan-2-yl group, isobornan-2-yl group, 2-methylisobornan-2-yl group, 2-ethylisobol Nan-2-yl group, decahydro-2,5-methano-7,10-methanonaphthalene-1-yl group, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, 8-methyl Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, adamantan-1-yl Group, adamantan-2-yl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, decahydro-3,6-methano-2,2,7,7-tetramethylnaphthalene-1 -Il group, spirobicyclohexane-2-yl group, spirobicyclohexane-3-yl group and the like can be mentioned.
Among these, 1,3,3-trimethylnorbornan-2-yl group, 1,2,3,3-tetramethylnorbornan-2-yl group, 1,3,3-trimethylnorbornenan-2-yl group, isobornan -2-yl group, 2-methylisobornan-2-yl group, 2-ethylisobornan-2-yl group, decahydro-2,5-methano-7,10-methanonaphthalene-1-yl group, Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, 8-methyltricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, 8-ethyltricyclo [ 5.2.1.0 ^2,6 ] Decane-8-yl group, adamantan-1-yl group, adamantan-2-yl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group Group, cyclohexyl group, cyclohexyl group substituted with alkyl group, phenyl group, phenyl group substituted with alkyl group, naphthyl group, naphthyl group substituted with alkyl group are preferable, isobornan-2-yl group, tricyclo [5 The 2.1.0 ^2,6 ] decane-8-yl group is more preferred, and the tricyclo [5.2.1.0 ^2,6 ] decane-8-yl group (common name: dicyclopentanyl group) is preferred. Especially preferable.

The amount of the structural unit derived from the methacrylic acid cyclic hydrocarbon ester contained in the methacrylic resin [Ac] is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, based on the methacrylic resin [Ac]. It is preferably 20 to 30% by mass.

Examples of the methacrylic acid ester other than the methacrylic acid ring-type hydrocarbon ester used in the methacrylic acid resin [Ac] include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and the like. Acyclic methacrylic acid such as isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, etc. Carbide ester: 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate and the like can be mentioned. Among these, methacrylic acid acyclic hydrocarbon ester is preferable from the viewpoint of improving transparency and heat resistance, and more than methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-butyl methacrylate. Preferably, methyl methacrylate is most preferred.
The amount of the structural unit derived from the methacrylic acid ester other than the methacrylic acid cyclic hydrocarbon ester contained in the methacrylic acid resin [Ac] is preferably 50 to 90% by mass, more preferably 60 to 60% with respect to the methacrylic acid resin [Ac]. It is 85% by mass, more preferably 70 to 80% by mass.

Acrylic acid esters used in methacrylic acid [Ac] include acrylic acid acyclic hydrocarbon esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic. Acrylic acid aromatic hydrocarbon ester such as phenyl acid; Acrylic acid alicyclic hydrocarbon ester such as cyclohexyl acrylate and norbornenyl acrylate can be mentioned. Among these, methyl acrylate, ethyl acrylate, and butyl acrylate are preferable, and methyl acrylate is particularly preferable, from the viewpoint of suppressing thermal decomposition and improving moldability.
The amount of the structural unit derived from the acrylic acid ester contained in the methacrylic resin [Ac] is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 0, based on the methacrylic resin [Ac]. It is 5% by mass.

The methacrylic resin [Ac] may have a structural unit derived from a monomer other than the methacrylic acid ester and the acrylic acid ester. Examples of such a monomer include a monomer having only one polymerizable carbon-carbon double bond in one molecule such as acrylamide; methacrylamide; acrylonitrile; methacrylnitrile and styrene. It is preferable not to include structural units derived from monomers having an acidic functional group such as acrylic acid, methacrylic acid, and 4-vinylbenzenesulfonic acid because they increase the acid value and increase the water absorption. ..
The amount of structural units derived from the methacrylic acid ester and the monomer other than the acrylic acid ester that may be contained in the methacrylic acid resin [Ac] is preferably 0 to 10% by mass with respect to the mass of the methacrylic acid resin [Ac]. It is more preferably 0 to 5% by mass, still more preferably 0 to 2% by mass.

The methacrylic resin [Ac] has a weight average molecular weight (hereinafter, may be referred to as “Mw”) of preferably 60,000 to 200,000, more preferably 80,000 to 160,000, and further preferably 90,000 to 150,000. , Particularly preferably 100,000 to 130,000. When the Mw of the methacrylic resin [Ac] is large, the strength of the film made of the resin composition of the present invention is high, it is difficult to crack, and it is easy to stretch, so that a thinner film can be obtained. Further, when the Mw of the methacrylic resin [Ac] is small, the methacrylic resin [Ac] has a high molding processability, so that the film made of the resin composition of the present invention tends to have a uniform thickness and excellent surface smoothness.

The methacrylic resin [Ac] has a ratio of Mw to a number average molecular weight (hereinafter, may be referred to as “Mn”) (Mw / Mn: hereinafter, this value may be referred to as “molecular weight distribution”). It is preferably 1.2 to 5.0, more preferably 1.5 to 3.5. When the molecular weight distribution is 1.2 or more, the fluidity of the methacrylic resin [Ac] is improved, and the film made of the resin composition of the present invention tends to have excellent surface smoothness. When the molecular weight distribution is 5.0 or less, the film made of the resin composition of the present invention tends to have excellent impact resistance and toughness. In addition, Mw and Mn are values which converted the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.

The methacrylic resin [Ac] is measured in accordance with JIS K7210 under the condition of 230 ° C. and a load of 3.8 kg, and has a melt flow rate of preferably 0.1 to 15 g / 10 minutes, more preferably 0.5. It is ~ 5 g / 10 minutes, more preferably 0.8 ~ 3 g / 10 minutes.

The acid value of the methacrylic resin [Ac] is measured by JIS K 0070: 1992. The acid value is preferably 7 mg / g or less, preferably 5 mg / g or less, more preferably 3 mg / g or less, further preferably 1.0 mg / g or less, and most preferably 0.5 mg / g or less. When the acid value is in this range, thermal decomposition derived from the structural unit derived from the methacrylic acid cyclic hydrocarbon ester in the methacrylic resin [Ac] can be suppressed.

The glass transition temperature of the methacrylic resin [Ac] is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher. The upper limit of the glass transition temperature of the methacrylic resin [Ac] is usually 140 ° C. The glass transition temperature can be controlled by adjusting the proportion of structural units derived from the cyclic hydrocarbon ester of methacrylic acid. When the glass transition temperature is in this range, the heat resistance of the obtained film is improved, and deformation such as heat shrinkage is unlikely to occur.
Here, the glass transition temperature (Tg) is measured in a region above room temperature in accordance with JIS K7121, and is once raised from room temperature to 230 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter. temperature (1 ^st run) and then cooled to room temperature, then when the temperature was raised (2 ^nd run) at 10 ° C. / min up to 230 ° C. from room temperature, 2 ^nd differential scanning calorimetry during heating of the run It is obtained at.

The methacrylic resin [Aa], [Ab] or [Ac] is not particularly limited by the method for producing the methacrylic resin [Aa], [Ab] or [Ac]. For example, it can be produced by a known polymerization method such as a radical polymerization method or an anion polymerization method. The radical polymerization can be carried out by a suspension polymerization method, a lump polymerization method, a solution polymerization method or an emulsion polymerization method, and among these, from the viewpoint of productivity and heat-degradability, the suspension polymerization method or the lump polymerization method is used. Is preferable. The bulk polymerization method is preferably carried out by a continuous flow method.
The characteristic values of the methacrylic resin [Aa], [Ab] or [Ac] can be adjusted by adjusting the polymerization conditions, specifically, the polymerization temperature, the polymerization time, the type and amount of the chain transfer agent, and the type of the polymerization initiator. It can be done by adjusting the amount and amount.

Yet another one of the thermoplastic resins (A) preferably used in the present invention is a polycarbonate resin. In particular, the aromatic polycarbonate resin may exhibit high compatibility, high transparency and excellent surface smoothness when used in combination with a methacrylic resin. The thermoplastic resin (A) preferably contains a polycarbonate resin in an amount of 2 to 50% by mass with respect to the thermoplastic resin (A).

Polycarbonate resin, 300 ° C., the melt volume flow rate (MVR) at 1.2 Kg, and preferably from 1~250cm ^3/10 min, more preferably 3~230cm ^3/10 min.
The polycarbonate resin has a weight average molecular weight of preferably 18,000 to 75,000, more preferably 20,000, which is calculated by converting a chromatogram measured by gel permeation chromatography (GPC) into a molecular weight of standard polystyrene. ~ 60,000. The MVR value and weight average molecular weight of the polycarbonate resin can be adjusted by adjusting the amount of the terminal terminator or the branching agent.

The glass transition temperature of the polycarbonate resin is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, still more preferably 140 ° C. or higher. The upper limit of the glass transition temperature of the polycarbonate resin is usually 180 ° C.
Here, the glass transition temperature (Tg) is measured in a region above room temperature in accordance with JIS K7121, and is once raised from room temperature to 230 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter. temperature (1 ^st run) and then cooled to room temperature, then when the temperature was raised (2 ^nd run) at 10 ° C. / min up to 230 ° C. from room temperature, 2 ^nd differential scanning calorimetry during heating of the run It is obtained at.

The polycarbonate resin is not particularly limited depending on the production method thereof. For example, a phosgene method (interfacial polymerization method) and a melt polymerization method (transesterification method) can be mentioned. Further, the aromatic polycarbonate resin preferably used in the present invention may be obtained by subjecting a polycarbonate resin raw material produced by the melt polymerization method to a treatment for adjusting the amount of terminal hydroxy groups. Further, as the polycarbonate resin, a commercially available product or other known one can be used.

The polycarbonate resin may contain a unit having a polyester, polyurethane, polyether or polysiloxane structure, or the like, in addition to the polycarbonate unit.

In the combined use of the aromatic polycarbonate resin and the methacrylic resin, the mass ratio (PMMA) / (PC) of the methacrylic resin (PMMA) and the polycarbonate resin (PC) is preferably 98/2 to 50/50 from the viewpoint of compatibility. , More preferably 98/2 to 60/40. High compatibility tends to provide high transparency, high refractive index and good surface smoothness. Further, when the mass ratio (PMMA) / (PC) of the methacrylic resin (PMMA) and the polycarbonate resin (PC) is set to 98/2 to 90/10, it is easy to obtain a molded product having a small phase difference (retalysis) due to birefringence. ..

The thermoplastic resin composition of the present invention may contain a filler, if necessary, as long as the effects of the present invention are not impaired. Examples of the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate and the like. The amount of the filler that can be contained in the thermoplastic resin composition of the present invention is preferably 3% by mass or less, more preferably 1.5% by mass or less.

The thermoplastic resin composition of the present invention is an antioxidant, a heat deterioration inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, and a charge, as long as the effects of the present invention are not impaired. It may contain additives such as an inhibitor, a flame retardant, a dye pigment, a light diffusing agent, an organic dye, a matting agent, and a phosphor.

These additives may be used alone or in combination of two or more. Further, these additives may be added at the time of producing the thermoplastic resin (A) or the impact resistance improving agent (B) of the present invention, or the produced thermoplastic resin (A) or the present invention. It may be added to the impact resistance improving agent (B) of the above, or may be added when preparing the thermoplastic resin composition of the present invention. The total amount of the additives contained in the thermoplastic resin composition of the present invention is preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass, based on the thermoplastic resin (A). It is as follows.

The method for preparing the thermoplastic resin composition of the present invention is not particularly limited. For example, a method comprising polymerizing a monomer for obtaining a thermoplastic resin (A) in the presence of the impact resistance improving agent (B) of the present invention to obtain a thermoplastic resin composition in situ. Examples thereof include a method including kneading the thermoplastic resin (A) and the impact resistance improving agent (B) of the present invention.
Examples of the device that can be used for kneading include a kneader ruder, an extruder, a mixing roll, and a Banbury mixer. Of these, a twin-screw extruder is preferable. The temperature at the time of kneading can be appropriately adjusted according to the softening temperature of the thermoplastic resin (A), the softening temperature of the impact resistance improving agent (B) of the present invention, and the like, but is preferably 110 ° C. to 280 ° C. More preferably, it is 200 ° C. to 270 ° C. If the melting temperature is too high, the acid value of the thermoplastic resin composition may increase.

The thermoplastic resin composition of the present invention has a glass transition temperature of preferably 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 122 ° C. or higher, and particularly preferably 125 ° C. or higher. The upper limit of the glass transition temperature of the thermoplastic resin composition of the present invention is not particularly limited, but is preferably 135 ° C.
Here, the glass transition temperature (Tg) is measured in a region above room temperature in accordance with JIS K7121, and is once raised from room temperature to 230 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter. temperature (1 ^st run) and then cooled to room temperature, then when the temperature was raised (2 ^nd run) at 10 ° C. / min up to 230 ° C. from room temperature, 2 ^nd differential scanning calorimetry during heating of the run It is obtained at.

The Mw determined by gel permeation chromatography (GPC) measurement of the solvent-soluble component of the thermoplastic resin composition of the present invention is preferably 70,000 to 200,000, more preferably 72,000 to 180,000, and further. It is preferably 75,000 to 150,000. The Mw / Mn determined by gel permeation chromatography (GPC) measurement of the solvent-soluble component of the thermoplastic resin composition of the present invention is preferably 1.2 to 5.0, more preferably 1.5 to 3. It is .5. When Mw and Mw / Mn are in this range, the molding processability of the resin composition becomes good, and it becomes easy to obtain a molded product having excellent impact resistance and toughness. Here, tetrahydrofuran is used as the solvent.

In the thermoplastic resin composition of the present invention, the melt flow rate (MFR) determined by measurement under the conditions of 230 ° C. and a 3.8 kg load is preferably 0.1 to 15 g / 10 minutes, more preferably 0. It is 5 to 5 g / 10 minutes, most preferably 1.0 to 3 g / 10 minutes.

The thermoplastic resin composition of the present invention has a haze of 1.0 mm thickness of preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.

The thermoplastic resin composition according to the present invention has an acid value of preferably 7 mg / g or less, more preferably 5 mg / g or less, still more preferably 3 mg / g, from the viewpoints of low yellow index, suppression of discoloration or suppression of foreign matter formation. It is g or less, more preferably 1.0 mg / g or less, and most preferably 0.5 mg / g or less. The acid value can be measured according to JIS K 0070: 1992.

The thermoplastic resin composition of the present invention can be subjected to a molding step into a film or the like in any form such as pellets, granules and powders.

The thermoplastic resin composition of the present invention can be molded by a known method to obtain various molded bodies. Examples of the molding method include an extrusion molding method, an injection molding method, a calender molding method, a blow molding method, a compression molding method, a solution casting method and the like. Further, in order to obtain a composite molded body with another material, a known manufacturing method of the composite molded body such as an insert molding method and a coating molding method can be adopted.

The film of the present invention comprises the thermoplastic resin composition of the present invention. The method for producing the film of the present invention is not particularly limited, and examples thereof include a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, and a blow molding method. Of these, the extrusion molding method is preferable. According to the extrusion molding method, it is possible to obtain a film having excellent transparency, improved toughness, excellent handleability, and an excellent balance between toughness, surface hardness and rigidity. The temperature of the thermoplastic resin composition according to the present invention discharged from the extruder is preferably set to 160 to 270 ° C, more preferably 220 to 260 ° C. When the temperature of the thermoplastic resin composition is high, the acid value of the obtained film tends to be high.

From the viewpoint of surface smoothness and thickness uniformity of the film, it is preferable to take and press the extruded film-like molten resin composition between the mirror surface rolls or the mirror surface belts. It is preferable that the mirror surface roll or the mirror surface belt is made of metal. The linear pressure between the mirror surface roll or the mirror surface belt is preferably 10 N / mm or more, more preferably 30 N / mm or more. From the viewpoint of surface smoothness, haze, appearance, etc., the surface temperature of the mirror surface roll or the mirror surface belt has a lower limit of preferably 60 ° C., more preferably 70 ° C., and an upper limit of preferably 130 ° C., more preferably 100 ° C. ℃.
After molding the thermoplastic resin composition into a film, a stretching treatment may be performed. The stretching treatment may improve the mechanical strength and make it less likely to crack. The stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, a tuber stretching method, and a rolling method. The lower limit of the stretching temperature is 5 ° C. higher than the glass transition temperature of the thermoplastic resin (A), and the upper limit is 40 ° C. higher than the glass transition temperature of the thermoplastic resin (A). The stretching rate is preferably 100-5000% / min. In the stretching treatment, it is more preferable to carry out a heat fixing step after the stretching step. By heat fixing, a film with less heat shrinkage can be obtained.

The film of the present invention has a thickness of preferably 1 to 200 μm, more preferably 10 to 50 μm, and even more preferably 15 to 40 μm.

The film of the present invention has a haze at a thickness of 40 μm, preferably 0.3% or less, more preferably 0.2% or less.

When the film of the present invention is used as an optical film having a low retardation, the in-plane directional retardation Re at a thickness of 40 μm with respect to light having a wavelength of 590 nm is preferably 19 nm or less, more preferably 15 nm or less, still more preferably 10 nm or less, particularly. It is preferably 5 nm or less, and most preferably 1 nm or less.
Film of the present invention, when used as an optical film of low retardation, thickness retardation R _th in the thickness 40μm with respect to light having a wavelength of 590nm is preferably -12nm than 12nm or less, more preferably -5nm least 5nm less, It is more preferably -3 nm or more and 3 nm or less, particularly preferably -2 nm or more and 2 nm or less, and most preferably -1 nm or more and 1 nm or less.
The in-plane direction phase difference Re and the thickness direction phase difference R _th are values defined by the following equations, respectively.
Re = (n _{x −} n _y ) × d
R _th = ((n _x + n _y ) /2- _nz ) x d
Here, n _x is the refractive index in the slow axis direction of the _{film, n y} is the refractive index in the phase advance axis direction of the _{film, n z} is the refractive index in the thickness direction of the film, and d [nm. ] Is the thickness of the film. The slow-phase axis is the axis in the direction in which the refractive index in the film surface is maximized. The phase-advancing axis is the axis in the plane in the direction perpendicular to the slow-phase axis.

The film of the present invention has a photoelastic coefficient β with respect to light having a wavelength of 590 nm, preferably −3.0 × 10 ^-12 Pa ^-1 or more and 3.0 × 10 ^-12 Pa ^-1 or less, more preferably −2.0. × 10 ^-12 Pa ^-1 or more and 2.0 × 10 ^-12 Pa ^-1 or less, more preferably −1.0 × 10 ^-12 Pa ^-1 or more and 1.0 × 10 ^-12 Pa ^-1 or less. The photoelastic coefficient β [10 ^-12 Pa ^-1 ] is the in-plane direction phase difference R _in [nm] when the stress σ [Pa] is applied and the film thickness d [nm] as shown in the following equation. It can be calculated from the relationship with.
R _in = β × σ × d

When the in-plane direction phase difference Re, the thickness direction phase difference R _th, and the photoelastic coefficient β are in the above ranges, the influence of the phase difference on the display characteristics of the image display device can be remarkably suppressed. More specifically, interference unevenness and distortion of a 3D image when used in a liquid crystal display device for a 3D display can be remarkably suppressed.

When the film of the present invention is used as a retardation film, the in-plane retardation Re per 40 μm thickness is preferably 10 to 200 nm, more preferably 10 to 180 nm, and even more preferably 10 to 150 nm. .. Then, it is preferable that the thickness direction retardation R _th is -10 to-250 nm, more preferably from -20 to-230 nm, more preferably from -30 to-200 nm.

A functional layer may be provided on the surface of the film of the present invention. The functional layers include a hard coat layer, an anti-glare layer, an anti-reflection layer, an anti-sticking layer, a diffusion layer, an anti-glare layer, an anti-static layer, an anti-fouling layer, a slippery layer made of fine particles, a gas barrier layer, and silver. Examples thereof include a transparent conductive layer made of nanowires, carbon nanotubes, and the like.

Since the film of the present invention has excellent heat decomposition resistance, impact resistance and transparency, it is a retardation film, a polarizer protective film, a liquid crystal protective plate, a surface material of a portable information terminal, and a display window of a portable information terminal. It is suitable for optical applications such as protective films, light guide films, optical gas barrier films, front plates of various displays, and transparent conductive films. Further, the film of the present invention includes an IR cut film, a security film, a shatterproof film, a decorative film, a metal decorative film, a solar cell back sheet, a flexible solar cell front sheet, a shrink film, an in-mold label film, and the like. It is also suitable for applications other than optical applications.

The polarizing plate according to the present invention has at least a polarizing element and a film of the present invention laminated on the polarizing element. The film of the present invention may be laminated on both sides of the polarizer or may be laminated on one side. When the film of the present invention is laminated as a polarizer protective film on one side of the polarizer, an optical film other than the film of the present invention can be laminated on the other side. Examples of such an optical film include a polarizer protective film, a viewing angle adjusting film, a retardation film, and a brightness improving film. Lamination can also be done via an adhesive layer.

A polarizing plate having a polarizing element protective film, which is the film of the present invention, can be used in an image display device. Specific examples of the image display device include a self-luminous image display device such as an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED), a liquid crystal display (LCD), and a liquid crystal projector. An image display device using various liquid crystal cells can be mentioned. In a liquid crystal display, for example, a linear polarizing plate formed by bonding a polarizing element protective film and a polarizing element (polarizing film) of the present invention to at least one of two polarizing plates sandwiching a liquid crystal cell can be used. In an electroluminescence display, for example, a polarizing film that transmits only one linearly polarized light of incident light through a film of the present invention adjusted to have a λ / 4 phase difference in order to prevent reflection of external light. A circularly polarizing plate formed by bonding to can be used. The film of the present invention can be preferably used in a lighting device or display device using an organic light emitting diode, or a display device using a liquid crystal cell.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples.
Physical property values and the like were determined by the following methods.

(Resin monomer composition)
^{Using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS manufactured by Bruker), 1} H-NMR spectrum was measured under the conditions of 1 mL of deuterated chloroform, room temperature, and 64 integration times for 10 mg of resin, and the spectrum was used. The composition of the monomer unit in the resin was calculated.

(Weight average molecular weight (Mw))
Mw was calculated from a value converted to the molecular weight of standard polystyrene by measuring a chromatogram by gel permeation chromatography (GPC) under the following conditions.
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

(Measurement of particle size)
The average particle size D of the core particles contained in the core-shell crosslinked rubber particles obtained in Examples 1 and 4 and Comparative Example 3 was determined as follows.
First, the core particle aqueous dispersion generated in the middle of producing the core-shell crosslinked rubber particles is sampled and diluted with ion-exchanged water so that the core particles have a concentration of 0.05% by mass. Spread the diluent on a glass plate and dry. In this way, the core particles are dispersed and exist on the glass plate without agglomeration. Next, platinum and palladium are vapor-deposited on the surface of the dried glass plate, which is observed with an electron microscope and a photograph is taken. From the electron micrographs, 100 particles were randomly selected, the particle size of each particle was measured, and the value obtained by arithmetically averaging these measured values was taken as the average particle size D of the core particles.

The average particle size D of the core particles contained in the core-shell crosslinked rubber particles obtained in Examples 2 to 3 and 5 to 9 and Comparative Examples 1 to 2 and 4 was measured as follows.
An aqueous dispersion of core particles (core particle concentration: 0.05% by mass) contained in the core-shell crosslinked rubber particles obtained in Examples 1 and 4 and Comparative Example 3 was poured into a quartz cell having an optical path length of 10 mm, and the wavelength was increased. The absorbance at 590 nm was measured respectively. A calibration curve showing the relationship between the absorbance of the core particle aqueous dispersion contained in the core-shell crosslinked rubber particles obtained in Examples 1 and 4 and Comparative Example 2 and the average particle size D was prepared.
Optical path the absorbance of the aqueous dispersion (core particle concentration: 0.05% by mass) of the core particles contained in the core-shell crosslinked rubber particles obtained in Examples 2 to 3 and 5 to 9 and Comparative Examples 1 to 2 and 4. It was measured with a quartz cell having a length of 10 mm at a wavelength of 590 nm. The average particle size D was obtained from the measured value using a calibration curve.

(Sulfur component content)
0.2 g each of seed particles, core particles or core-shell cross-linked rubber particles obtained at each stage in producing core-shell cross-linked rubber particles was precisely weighed and placed in a container. To this, 10 ml of concentrated nitric acid was added, the container was sealed, and decomposition treatment was carried out for 55 minutes at an output of 500 to 1000 W with a microwave sample decomposition apparatus (ETHOS-1600 type manufactured by Milestone General Co., Ltd.). Next, the sulfur component (mass%) was quantified by an ICP emission spectrophotometer (ICP-OES VISTA-PRO, CCD multi-element simultaneous ICP emission spectrophotometer manufactured by Seiko Instruments). The mass ratio of each sulfur component contained in the center core, inner shell and outer shell was calculated from the quantitative values for the seed particles, core particles or core-shell crosslinked rubber particles.
In Tables 1 and 2, the ratio of the mass of the sulfur component contained in the polymer constituting the center core to the mass of the polymer constituting the center core, and the weight constituting the inner shell with respect to the mass of the polymer constituting the inner shell. The ratio of the mass of the sulfur component contained in the coalescence and the ratio of the mass of the sulfur component contained in the polymer constituting the outer shell to the mass of the polymer constituting the outer shell are set in the order of center core / inner shell / outer shell. It is described.

(Total light transmittance)
Using an injection molding machine (SE-180DU-HP manufactured by Sumitomo Heavy Industries, Ltd.), the resin composition was injection-molded at a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 1 minute to a length of 50 mm. , A test piece having a width of 50 mm and a thickness of 1 mm was obtained. For the test piece having an optical path length of 1 mm, the total light transmittance measured using a haze meter (HM-150, manufactured by Murakami Color Research Institute) according to JIS K7361-1 is used as the total light transmittance of the resin composition (HM-150). T _tA ).

A haze meter (manufactured by Murakami Color Research Institute, HM-) for a test piece having an optical path length of 3 mm obtained by press-molding an impact resistance improving agent at 200 ° C. using a press molding machine according to JIS K7361-1. The total light transmittance measured using 150) was _{defined as} the total light transmittance (T tB) of the impact resistance improving agent.

(Haze)
Using an injection molding machine (SE-180DU-HP manufactured by Sumitomo Heavy Industries, Ltd.), the resin composition was injection molded at a cylinder temperature of 280 ° C., a mold temperature of 75 ° C., and a molding cycle of 1 minute to a length of 50 mm. , A test piece having a width of 50 mm and a thickness of 1 mm was obtained. The haze measured with a haze meter (HM-150, manufactured by Murakami Color Research Institute) in accordance with JIS K7136 for the test piece having an optical path length of 1 mm was defined as the haze ( _HA ) of the resin composition.

A haze meter (manufactured by Murakami Color Research Institute, HM-150) in accordance with JIS K7136 for a test piece having an optical path length of 3 mm obtained by press-molding an impact resistance improving agent at 200 ° C. using a press molding machine. The haze measured using) was defined as the haze (H _B ) of the impact resistance improving agent.

(Refractive index)
Using a press molding machine, the impact resistance improving agent or the resin composition was press-molded at 200 ° C. to obtain a plate having a thickness of 3 mm, and a test piece having a thickness of 30 mm × 30 mm was cut out from this plate. The refractive index of this test piece measured with a precision refractive index meter (Carnew KPR-20 manufactured by Shimadzu Corporation) at 25 ° C. and helium d-line (587.56 nm) was measured with an impact resistance improver or resin composition. Refractive index (n ²⁵ _dB or n ²⁵ _dA ).
The refractive index of the center core and inner shell (n ²⁵ _dCC and n ²⁵ _dIS ) is the mass ratio of the monomer unit to the polymer to the refractive index of the homopolymer of the monomer unit constituting each polymer. It is the sum of the multiplied values.

(Heating weight loss temperature)
Measured with a thermal weight measuring device (TGA-50 manufactured by Shimadzu Corporation) under the conditions of a nitrogen flow rate of 10 ml / min and a temperature rise rate of 20 ° C / min, and based on the weight at 150 ° C (100% by weight), 1 The temperature at the time of 0.0% weight loss is 1.0% heating weight loss temperature (T ^1.0 _HL ), the temperature at the time of 2.5% weight loss is 2.5% heating weight loss temperature (T ^2.5 _HL ), and 5 The temperature at which the weight was reduced by 0.0% by weight was defined as the 5.0% heating weight loss temperature (T ^5.0 _HL ).

(Impact resistance)
Using an injection molding machine (SE-180DU-HP manufactured by Sumitomo Heavy Industries, Ltd.), the resin composition is injection-molded at a cylinder temperature of 230 ° C., a mold temperature of 65 ° C., and a molding cycle of 0.5 minutes. A test piece having a size of 80 mm, a width of 10 mm, and a thickness of 4 mm was obtained, and the Charpy impact strength without a notch measured by performing a Charpy impact test in accordance with ISO179-1 was determined by the Charpy impact of the resin composition. It was defined as strength (I _c ).

(Film formation)
The resin composition was subjected to a film-forming machine (model FS-5) manufactured by Optical Control System, with a cylinder and T-die temperature of 300 ° C., a lip gap of 0.5 mm, a discharge rate of 2.7 kg / hr, and a roll temperature of 85 ° C. Extrusion molding was performed at a film take-up speed of 2.2 m / min to continuously produce a film having a thickness of 100 μm. The surface of the roll was visually observed 1 hour after the start of production. The evaluation of film-forming property was expressed by the following indexes.
A: There is no or almost no roll stain.
B: There is a slight amount of roll stain.
C: Roll stain is remarkable.

<Example 1>
[First stage polymerization]
480 parts by mass of ion-exchanged water was put into a glass-lined reaction vessel equipped with a condenser, a thermometer and a stirrer and having a capacity of 100 L, and then polyoxyethylene (EO = 3) sodium acetate (Nikkor 3NEX manufactured by Nikko Chemical Co., Ltd.). ) 0.06 parts by mass was added and dissolved. The liquid in the reaction vessel was raised to 80 ° C. with stirring to consist of 62.0% by mass of styrene, 33.5% by mass of methyl methacrylate, 3.3% by mass of divinylbenzene and 1.2% by mass of n-octyl mercaptan. A solution containing 176.4 parts by mass of the mixture and 0.78 parts by mass of polyoxyethylene (EO = 3) sodium acetate (Nikkor 3NEX manufactured by Nikko Chemical Co., Ltd.) (raw material of [polymer (ii)]) was prepared at 80 ° C. Added. Then, 4.26 parts by mass of a 3% potassium persulfate aqueous solution was added to initiate emulsion polymerization at 80 ° C. After the temperature rise in the reaction vessel due to the heat of reaction subsided, the mixture was held at 80 ° C. for 30 minutes to obtain an emulsion containing seed particles.
[Second stage polymerization]
5.32 parts by mass of a 3% aqueous sodium persulfate solution was added to the emulsion obtained in the first stage polymerization. Then, 80.2 parts by mass of a mixture consisting of 54.1% by mass of butyl acrylate, 43.9% by mass of styrene, and 2% by mass of allyl methacrylate and sodium polyoxyethylene (EO = 3) acetate (Nikkol manufactured by Nikko Chemical Co., Ltd.) A solution containing 0.375 parts by mass of 3NEX (raw material of [polymer (i)]) was added dropwise at 80 ° C. over 60 minutes to carry out seed emulsion polymerization. After completion of the dropping, the mixture was held at 80 ° C. for 60 minutes to obtain an emulsion containing core particles having an average particle diameter of 220 nm.
[Third stage polymerization]
2.72 parts by mass of a 3% potassium persulfate aqueous solution was added to the emulsion obtained by the second stage polymerization. Then, 64.1 parts by mass of a mixture consisting of 29% by mass of methyl methacrylate, 4.9% by mass of methyl acrylate, 65.9% by mass of benzyl methacrylate and 0.2% by mass of n-octyl mercaptan ([polymer (iii). )] Was added at 80 ° C. for 30 minutes to carry out seed emulsion polymerization. After completion of the addition, the mixture was held at 80 ° C. for 60 minutes to obtain an emulsion containing 40% of core-shell crosslinked rubber particles.
[Granulation]
The emulsion obtained by the third stage polymerization was cooled to room temperature. The emulsion was then allowed to stand at −20 ° C. for 2 hours to freeze. The frozen emulsion was put into twice the amount of warm water at 80 ° C. and thawed to obtain a slurry. The slurry was held at 80 ° C. for 20 minutes, then dehydrated, and the rest was dried at 70 ° C. to obtain a granule (impact resistance improver B1) composed of core-shell crosslinked rubber particles. The evaluation results of the impact resistance improving agent B1 are shown in Table 1.

<Example 2>
Granules composed of core-shell crosslinked rubber particles by the same method as in Example 1 except that the composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization was changed to the ratio shown in Table 1. Impact resistance improver B2) was obtained. Table 1 shows the evaluation results of the impact resistance improving agent B2.

<Example 3>
The composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization was changed to the ratio shown in Table 1, and the first-stage polymerization, the second-stage polymerization and the third-stage polymerization were performed. Granules (impact resistance) composed of core-shell crosslinked rubber particles by the same method as in Example 1 except that the amounts of the mixture added in 1 were changed to 121.9 parts by mass, 134.7 parts by mass and 64.1 parts by mass, respectively. A sex improver B3) was obtained. The evaluation results of the impact resistance improving agent B3 are shown in Table 1.

<Example 4>
The composition of the mixture added in the first-stage polymerization, the second-stage polymerization, and the third-stage polymerization is changed to the ratio shown in Table 1, and polyoxyethylene (EO = 3) added together with the mixture in the second-stage polymerization. The amount of sodium acetate (Nikkol 3NEX manufactured by Nikko Chemical Co., Ltd.) was changed to 0.24 parts by mass, and the amount of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization was 160, respectively. Granules (impact resistance improver B4) composed of core-shell crosslinked rubber particles were obtained by the same method as in Example 1 except that they were changed to 0.4 parts by mass, 96.2 parts by mass and 64.1 parts by mass. The evaluation results of the impact resistance improving agent B4 are shown in Table 1.

<Example 5>
The composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization was changed to the ratio shown in Table 1, and the first-stage polymerization, the second-stage polymerization and the third-stage polymerization were performed. Granules (impact resistance) composed of core-shell crosslinked rubber particles by the same method as in Example 1 except that the amounts of the mixture added in 1 were changed to 112.2 parts by mass and 144.3 parts by mass and 64.1 parts by mass, respectively. A sex improver B5) was obtained. The evaluation results of the impact resistance improving agent B5 are shown in Table 1.

<Comparative example 1>
Granules composed of core-shell crosslinked rubber particles by the same method as in Example 1 except that the composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization was changed to the ratio shown in Table 1. Impact resistance improver B6) was obtained. The evaluation results of the impact resistance improving agent B6 are shown in Table 1.

<Comparative example 2>
The composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization is changed to the ratio shown in Table 1, and polyoxyethylene (EO = 3) added together with the mixture in the second-stage polymerization. A granule (impact resistance improver B7) composed of core-shell crosslinked rubber particles was obtained by the same method as in Example 1 except that the amount of sodium acetate (Nikkor 3NEX manufactured by Nikko Chemical Co., Ltd.) was changed to 0.3 parts by mass. .. The evaluation results of the impact resistance improving agent B7 are shown in Table 1.

<Comparative example 3>
The composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization is changed to the ratio shown in Table 2, and the polyoxyethylene (EO = 3) added together with the mixture in the second-stage polymerization. A granule (impact resistance improver B8) composed of core-shell crosslinked rubber particles was obtained by the same method as in Example 1 except that the amount of sodium acetate (Nikkor 3NEX manufactured by Nikko Chemical Co., Ltd.) was changed to 0.045 parts by mass. .. Table 2 shows the evaluation results of the impact resistance improving agent B8.

<Comparative example 4>
The composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization is changed to the ratio shown in Table 2, and the polyoxyethylene (EO = 3) added together with the mixture in the second-stage polymerization. A granule (impact resistance improver B9) composed of core-shell crosslinked rubber particles was obtained by the same method as in Example 1 except that the amount of sodium acetate (Nikkor 3NEX manufactured by Nikko Chemical Co., Ltd.) was 0.05 parts by mass. Table 2 shows the evaluation results of the impact resistance improving agent B9.

<Example 6>
[First stage polymerization]
480 parts by mass of ion-exchanged water was put into a reaction vessel equipped with a condenser, a thermometer and a stirrer and having a glass lining and having a capacity of 100 L, and then polyoxyethylene (EO = 3) sodium acetate (Nikkor manufactured by Nikko Chemical Co., Ltd.). 3NEX) 0.06 parts by mass was added and dissolved. The liquid in the reaction vessel was raised to 80 ° C. with stirring to 64.5% by mass of styrene, 28.0% by mass of methyl methacrylate, 4.9% by mass of methyl acrylate, 1.4% by mass of allyl methacrylate and n. -A solution containing 112.1 parts by mass of a mixture consisting of 1.2% by mass of octyl mercaptan and 0.78 parts by mass of polyoxyethylene (EO = 3) sodium acetate (Nikkol 3NEX manufactured by Nikko Chemical Co., Ltd.) ([Polymer (ii) )] Raw material) was added. Then, 4.26 parts by mass of a 3% potassium persulfate aqueous solution was added to initiate an emulsion polymerization reaction at 80 ° C. After the temperature rise in the reaction vessel due to the heat of reaction subsided, the mixture was held at 80 ° C. for 30 minutes to obtain an emulsion containing seed particles.
[Second stage polymerization]
5.32 parts by mass of a 3% aqueous sodium persulfate solution was added to the emulsion obtained in the first stage polymerization. After that, 50.0% by mass of diethylhexyl acrylate, NK ester A-LEN-10 (ethoxylated o-phenylphenol acrylate; existing chemical substance number: 4-1693, CAS: 72009-) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. 86-0) 142.7 parts by mass of a mixture consisting of 49.0% by mass and 1.0% by mass of allyl methacrylate and 0.375 parts by mass of polyoxyethylene (EO = 3) sodium acetate (Nikkor 3NEX manufactured by Nikko Chemical Co., Ltd.) A solution containing the above (raw material of [polymer (i)]) was added dropwise at 80 ° C. over 60 minutes to carry out seed emulsification polymerization. After completion of the dropping, the mixture was held at 80 ° C. for 60 minutes to obtain an emulsion containing core particles having an average particle diameter of 220 nm.
[Third stage polymerization]
2.72 parts by mass of a 3% potassium persulfate aqueous solution was added to the emulsion obtained by the second stage polymerization. Then, 65.9 parts by mass ([weight]) of a mixture consisting of 38.0% by mass of methyl methacrylate, 4.8% by mass of benzyl methacrylate, 57.0% by mass of methyl acrylate and 0.2% by mass of n-octyl mercaptan. The material of the coalescence (iii)]) was added at 80 ° C. for 30 minutes to carry out seed emulsion polymerization. After completion of the addition, the mixture was held at 80 ° C. for 60 minutes to obtain an emulsion containing 40% of core-shell crosslinked rubber particles.
[Granulation]
The emulsion obtained by the third stage polymerization was cooled to room temperature. The emulsion was then allowed to stand at −20 ° C. for 2 hours to freeze. The frozen emulsion was put into twice the amount of warm water at 80 ° C. and thawed to obtain a slurry. The slurry was held at 80 ° C. for 20 minutes, then dehydrated and the rest dried at 70 ° C. to obtain granules (impact resistance improver B10) composed of core-shell crosslinked rubber particles. Table 2 shows the evaluation results of the impact resistance improving agent B10.

<Examples 7 and 8>
Granules composed of core-shell crosslinked rubber particles by the same method as in Example 6 except that the composition of the mixture added in the first-stage polymerization, the second-stage polymerization and the third-stage polymerization was changed to the ratio shown in Table 2. Impact resistance improvers B11 and B12) were obtained. Table 2 shows the evaluation results of the impact resistance improving agents B11 and B12.

<Example 9>
0.06 parts by mass of polyoxyethylene (EO = 3) sodium acetate (Nikkol 3NEX manufactured by Nikko Chemical Co., Ltd.) added to 480 parts by mass of ion-exchanged water in the first-stage polymerization was changed to 0.24 parts by mass, and the first Granules made of core-shell crosslinked rubber particles (impact resistance) by the same method as in Example 6 except that the composition of the mixture added in the step polymerization, the second step polymerization and the third step polymerization was changed to the ratio shown in Table 2. A sex improver B13) was obtained. The average particle size of the core particles was 150 nm. Table 2 shows the evaluation results of the impact resistance improving agent B13.

The meanings of the abbreviations in the table are as follows.
St: Styrene MMA: Methyl methacrylate BA: Butyl acrylate DVB: Divinylbenzene MA: Methyl acrylate ALMA: Allyl methacrylate n-OM: n-octyl mercaptan 2-EHA: 2-Ethylhexyl acrylate BzA: Benzyl acrylate BzMA : Benzyl methacrylate PTMB: Pentaerythritol tetrakis (3-mercaptobutyrate)
A-LEN-10: NK ester A-LEN-10 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (existing chemical substance number: 4-1693, CAS: 72009-86-0)
M110: Aronix M110 (Paracmilphenol EO modified acrylate) manufactured by Toagosei Co., Ltd.

<Thermoplastic resin (A1)>
Styrene-maleic anhydride-methyl methacrylate random copolymer as a thermoplastic resin (A1) (R-200 manufactured by Denki Kagaku Kogyo Co., Ltd .; 56% by mass of styrene unit, 18% by mass of maleic anhydride unit and 26% by mass of methyl methacrylate unit Mass% [ ¹³ C-NMR analysis]; Mw = 168,000, Mw / Mn = 2.49, Tg = 138 ° C., refractive index n ²³ _d = 1.5550) was prepared.

<Thermoplastic resin (A2)>
In an autoclave, 63 parts by mass of methyl methacrylate, 35 parts by mass of dicyclopentanyl methacrylate (TCDMA), 2 parts by mass of methyl acrylate, 0.47 parts by mass of pentaerythritol tetraxthiopropionate, 0 parts of azobisisobutyronitrile. .06 parts by mass, 1,1-bis (1,1-dimethylperoxy) cyclohexane 0.01 parts by mass, water 231 parts by mass, dispersant 1.4 parts by mass and pH adjuster 17.5 parts by mass were added. did.
The liquid in the autoclave was raised to 70 ° C. with stirring, held at 70 ° C. for 120 minutes, and then held at 120 ° C. for 60 minutes for polymerization. The liquid in the autoclave was cooled to room temperature and then withdrawn from the autoclave. The extracted liquid was filtered to remove the solid content, and the solid content was washed with water and then dried with hot air at 80 ° C. for 24 hours. The obtained dried product is kneaded with a twin-screw extruder at a cylinder temperature of 230 ° C., extruded into strands, cut with a pelletizer, Mw = 127,000, TCDMA unit 32.5% by mass, Tg = 126 ° C. , Pellets of methacrylic resin having an acid value of 0.1 mg / g and a refractive index of 1.500 (thermoplastic resin (A2)) were obtained.

<Thermoplastic resin (A3)>
As the thermoplastic resin (A3), a polycarbonate resin (manufactured by Sumika Stylon Polycarbonate Co., Ltd., trade name: Caliber 300-22, Mw = 42,000, refractive index = 1.585) was prepared.

<Thermoplastic resin (A4)>
As the thermoplastic resin (A4), a methacrylic resin (manufactured by Kuraray Co., Ltd., trade name: Parapet (registered trademark) HR-1000S) was prepared.

<Example 10>
51.8% by mass of the thermoplastic resin (A1), 30.0% by mass of the impact resistance improving agent (B1) and 18.2% by mass of the thermoplastic resin (A4) were dry-mixed with a tumbler.
The obtained mixture was subjected to a twin-screw extruder (manufactured by Technobel Co., Ltd., trade name: KZW20TW-45MG-NH-600; shaft diameter = 20 mm), a cylinder temperature of 200 to 250 ° C., a die temperature of 240 ° C., and a screw rotation speed. It was melt-kneaded under the condition of 100 rpm, extruded into a strand shape, and cut with a pelletizer to obtain pellets of a thermoplastic resin composition. The evaluation results of the thermoplastic resin composition are shown in Table 3.

<Examples 11 to 15 and Comparative Examples 5 to 6>
Pellets of the thermoplastic resin composition were obtained by the same method as in Example 10 except that the compounding ratios shown in Table 3 were changed. The evaluation results of the thermoplastic resin composition are shown in Table 3.

<Comparative Examples 7 to 8>
Pellets of the thermoplastic resin composition were obtained by the same method as in Example 10 except that the compounding ratios shown in Table 4 were changed. The evaluation results of the thermoplastic resin composition are shown in Table 4.

<Example 16>
52.5% by mass of the thermoplastic resin (A1), 30.0% by mass of the impact resistance improving agent (B10) and 17.5% by mass of the thermoplastic resin (A4) were dry-mixed with a tumbler.
The obtained mixture was subjected to a twin-screw extruder (manufactured by Technobel Co., Ltd., trade name: KZW20TW-45MG-NH-600) under the conditions of a cylinder temperature of 200 to 250 ° C., a die temperature of 240 ° C., and a screw rotation speed of 100 rpm. It was kneaded, extruded into strands, and cut with a pelletizer to obtain pellets of a thermoplastic resin composition. The evaluation results of the thermoplastic resin composition are shown in Table 4.

<Examples 17 to 20>
Pellets of the thermoplastic resin composition were obtained by the same method as in Example 16 except that the compounding ratios shown in Table 4 were changed. The evaluation results of the thermoplastic resin composition are shown in Table 4.

As shown by these results, the thermoplastic resin composition (Examples 10 to 20) containing the impact resistance improving agent (Examples 1 to 9) and the thermoplastic resin of the present invention has a high Charpy impact strength (I). _c ), high 1.0% heat loss temperature (T ^1.0 _HL ), high total light transmittance (T _tA ), low haze ( _HA ) and good film-forming properties, and excellent balance of each physical property. ..

Claims (17)

Containing core particles with a center core and an inner shell surrounding the center core, and core-shell crosslinked rubber particles with an outer shell surrounding the core particles.
At least one of the polymers constituting the center core and the inner shell is a crosslinked rubber polymer.
The crosslinked rubber polymer is a polymer (i) containing 50% by mass or more of a structural unit derived from an acrylic acid ester and less than 10% by mass of a structural unit derived from a methacrylic acid ester.
A polymer (ii) in which a polymer other than the crosslinked rubber polymer constituting the center core and the inner shell contains a total of 50% by mass or more of a structural unit derived from aromatic vinyl and a structural unit derived from methyl methacrylate. Yes,
The polymer constituting the outer shell is a polymer (iii) containing 50% by mass or more of structural units derived from methyl methacrylate.
The polymer (ii) contains 10% by mass or more of structural units derived from methacrylic acid ester, and contains 10% by mass or more.
The ratio of the mass of the sulfur component contained in the polymer constituting the center core to the mass of the polymer constituting the center core or the mass of the sulfur component contained in the polymer constituting the inner shell with respect to the mass of the polymer constituting the inner shell. One of the mass ratios is larger than the ratio of the mass of the sulfur component contained in the polymer constituting the outer shell to the mass of the polymer constituting the outer shell.
The average particle size D of the core particles is 150 nm or more and 300 nm or less.
Refractive index n _dIS of polymer constituting the refractive index n _DCC and the inner shell of the polymer constituting the center core is 0 nm ≦ | meet × D ≦ 9 nm relation, | _n dCC -n _dIS
The refractive index n _d of the core-shell crosslinked rubber particles 1.50 to 1.55, and a nitrogen flow rate of 10 ml / min, 1.0% heating loss temperature measured at a heating rate of 20 ° C. / min, at 310 ° C. or higher There is an impact resistance improver. The polymer (i) claims that the content of the structural unit derived from the acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group is less than 50% by mass with respect to the mass of the polymer (i). Item 2. The impact resistance improving agent according to Item 1. The monomer for obtaining the polymer constituting the center core is emulsion-polymerized to obtain seed particles.
In the presence of seed particles, a monomer for obtaining a polymer constituting an inner shell was seed-emulsified and polymerized to obtain core particles.
Including seed emulsion polymerization of a monomer for obtaining a polymer constituting an outer shell in the presence of core particles to obtain core-shell crosslinked rubber particles.
The method for producing an impact resistance improving agent according to claim 1 or 2. A thermoplastic resin composition comprising the thermoplastic resin (A) and the impact resistance improving agent (B ) according to claim 1 or 2. The thermoplastic resin (A) has a ring structure containing> CH-OC (= O) -group, a ring structure containing -C (= O) -OC (= O) -group, and -C (=). A structural unit having at least one ring structure in the main chain selected from the group consisting of a ring structure containing an O) -NC (= O) -group and a ring structure containing> CH-O-CH <group. It contains a structural unit derived from methyl methacrylate, and contains
The thermoplastic resin composition according to claim 4 , wherein the mass ratio (A) / (B) of the thermoplastic resin (A) to the impact resistance improving agent (B) is 95/5 to 10/90. The thermoplastic resin (A) has 10 to 50% by mass of a structural unit derived from a methacrylic acid ring hydrocarbon ester, 50 to 90% by mass of a structural unit derived from a methacrylic acid ester other than a methacrylic acid ring hydrocarbon ester, and The thermoplastic resin composition according to claim 4 , which contains 0 to 20% by mass of a structural unit derived from an acrylic acid ester. The thermoplastic resin composition according to claim 6 , wherein the methacrylic acid cyclic hydrocarbon ester is a compound represented by the formula (2).

(In formula (2), X represents a cyclic hydrocarbon group having 6 or more carbon atoms.) The cyclic hydrocarbon group having 6 or more carbon atoms may have an isobornan-2-yl group, a tricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, or a substituent. The thermoplastic resin composition according to claim 7 , which is a group. The thermoplastic resin composition according to claim 4 , wherein the thermoplastic resin (A) contains a polycarbonate resin in an amount of 2 to 50% by mass with respect to the thermoplastic resin (A). A molded product made of the thermoplastic resin composition according to any one of claims 4 to 9. Thermoplastic resin (A) and
It is composed of a center core and a core particle having an inner shell surrounding the center core, and a core shell crosslinked rubber particle having an outer shell surrounding the core particle, and at least one of the polymer constituting the center core and the inner shell is a crosslinked rubber weight. It is a polymer (i) in which the crosslinked rubber polymer contains 50% by mass or more of structural units derived from acrylic acid ester and less than 10% by mass of structural units derived from methacrylic acid ester, and is a center core and inner shell. is a polymer polymer other than a crosslinked rubber polymer constituting contains more than 50 wt% in total of a structural unit derived from structural units and methyl methacrylate derived from an aromatic vinyl and (ii), the outer shell The constituent polymer is a polymer (iii) containing 50% by mass or more of a structural unit derived from methyl methacrylate, and the polymer (ii) contains 10% by mass or more of a structural unit derived from a methacrylate ester. , The ratio of the mass of the sulfur component contained in the polymer constituting the center core to the mass of the polymer constituting the center core, or the sulfur component contained in the polymer constituting the inner shell with respect to the mass of the polymer constituting the inner shell. One of the mass ratios of is larger than the ratio of the mass of the sulfur component contained in the polymer constituting the outer shell to the mass of the polymer constituting the outer shell, and the average particle diameter D of the core particles is 150 nm or more and 300 nm or less. , and the refractive index n _dIS of polymer constituting the refractive index n _DCC and the inner shell of the polymer constituting the center core is 0nm ≦ | _n dCC -n _dIS | meet × D ≦ 9 nm relationship, and core-shell crosslinked film comprising a thermoplastic resin composition having a refractive index n _d of the rubber particles comprising an impact modifier (B) is 1.50 to 1.55. The thermoplastic resin (A) is
> CH-OC (= O) -group-containing ring structure, -C (= O) -OC (= O) -group-containing ring structure, -C (= O) -NC (=) A structural unit having at least one ring structure in the main chain selected from the group consisting of a ring structure containing an O) -group and a ring structure containing> CH-O-CH <group, and a structural unit derived from methyl methacrylate. 10 to 50% by mass of structural units derived from methacrylic acid ring hydrocarbon esters, 50 to 90% by mass of structural units derived from methacrylic acid esters other than methacrylic acid ring hydrocarbon esters, and acrylic acid. The film according to claim 11 , which contains 0 to 20% by mass of a structural unit derived from an ester. The film according to claim 11 or 12 , which has a thickness of 10 to 50 μm. A polarizer protective film comprising the film according to claim 11 , 12 or 13. A retardation film comprising the film according to claim 11 , 12 or 13. An illumination or display device comprising the film according to claim 11 , 12 or 13, and an organic light emitting diode. A display device comprising the film and a liquid crystal cell according to claim 11 , 12 or 13.