KR20190035779A - METHACRYL RESIN COMPOSITION AND METHOD FOR PRODUCING THE SAME, MOLDED PRODUCT, FILM, MULTILAYER FILM, - Google Patents

Abstract

The present invention provides a methacrylic resin composition capable of obtaining a molded article having a high-temperature moldability and a high dimensional stability against heat. The methacrylic resin composition of the present invention comprises a methacrylic resin (M1) having an? Relaxation temperature T? ₁ of 137 占 폚 or more when measured in a tensile mode, dynamic viscoelasticity at 1 Hz and a methacrylic resin and a? relaxation temperature T _{? 2} of 132 占 폚 or lower. Η ₁ > η ₂ when the melt viscosity at 260 ° C. and the shear rate of 122 sec ^-1 of the methacrylic resin (M1) and the methacrylic resin (M2) are respectively η ₁ and η ₂ , and the methacrylic resin M1) / methacrylic resin (M2) is 2/98 to 30/70.

Description

METHACRYL RESIN COMPOSITION AND METHOD FOR PRODUCING THE SAME, MOLDED PRODUCT, FILM, MULTILAYER FILM,

TECHNICAL FIELD The present invention relates to a methacrylic resin composition, a method for producing the same, a molded article, a film, a laminated film, and a laminated molded article.

The methacrylic resin has high transparency and is preferable as a material for an optical member, an illuminating member, a signboard member, and a decorative member. However, since the general-purpose methacrylic resin has a low glass transition temperature (Tg) of about 110 캜 and is not so good in heat resistance, the dimensional stability of the molded article against heat is poor. As a methacrylic resin having a high Tg, a methacrylic resin having a high syndiotacticity (rr) is known. As a methacrylic resin having a high syndiotacticity (rr), an anionic polymerization method can be mentioned (see Patent Documents 1 and 2). However, the methacrylic resin having a high syndiotacticity (rr) obtained by this method has poor moldability, and the resulting molded article tends to have inferior surface smoothness and the like. Although the moldability can be improved by lowering the molecular weight, the mechanical strength of the resulting molded article tends to decrease. For this reason, a molded article made of a methacrylic resin having a high syndiotacticity (rr) has not been put to practical use.

Patent Document 3 discloses a methacrylic resin [1] having a syndiotacticity (rr) of 65% or more in triplet display and a methacrylic resin [2] having 45 to 58% of syndiotacticity (rr) Of methacrylic resin [1] / methacrylic resin [2] in a mass ratio of 40/60 to 70/30 (claim 1). By combining methacrylic resin [1] having high syndiotacticity (rr) [1] and atactic methacrylic resin [2] at the above mass ratio, improvement in heat resistance and good moldability can be achieved.

Japanese Patent Application Laid-Open No. 3-263412 Japanese Patent Application Laid-Open No. 2002-327012 International Publication No. 2014/185509

As described above, in general, in the case of methacrylic resins, heat resistance (dimensional stability against heat) and moldability are characteristic of defeating, and it is difficult to make them compatible. In recent years, there has been a growing demand for molded articles, such as complicated shapes and improved stability against heat. For this reason, it is demanded that a molded article having good moldability at a high temperature and having high dimensional stability against heat can be molded.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a methacrylic resin composition which is capable of obtaining a molded article having good high-temperature moldability and high dimensional stability to heat and a method of producing the same.

The present invention provides the following methacrylic resin composition, a process for producing the same, a molded article, a film, a laminated film, and a laminated molded article.

[1] A methacrylic resin (M1) having an α relaxation temperature T _α1 of 137 ° C. or higher when measured in a tensile mode, dynamic viscoelasticity at 1 Hz,

(M2) having an? Relaxation temperature T _{? 2} of 132 占 폚 or less when measured in a tensile mode, dynamic viscoelasticity at 1 Hz, and the methacrylic resin composition

Η ₁ > η ₂ when the melt viscosity of the methacrylic resin (M1) and the methacrylic resin (M2) at 260 ° C. and the shear rate of 122 sec ^-1 is respectively η ₁ and η ₂ ,

Wherein the mass ratio of methacrylic resin (M1) / methacrylic resin (M2) is 2/98 to 29/71.

[2] The methacrylic resin composition according to [1], wherein the methacrylic resin (M1) has a molecular weight distribution (Mw / Mn) of 1.0 to 1.4.

[3] The methacrylic resin composition according to [1] or [2], wherein the methacrylic resin (M1) has a weight average molecular weight (Mw) of 40,000 to 200,000.

[4] The methacrylic resin composition according to any one of [1] to [3], wherein the methacrylic resin (M2) has a methacrylate monomer unit content of 99 mass% or more.

[5] The methacrylic resin composition according to any one of [1] to [4], further comprising a polycarbonate resin (PC) and / or a phenoxy resin (PR).

[6] The methacrylic resin composition according to any one of [1] to [5], further comprising a crosslinked rubber (CR) and / or a block copolymer (BP).

[7] The methacrylic resin composition according to any one of [1] to [6], further comprising an ultraviolet absorber (LA).

[8] 260 ℃ of the methacrylic resin (M1) and methacrylic resin (M2), in the case where the melt viscosity at a shear rate of 122 sec ^-1 to η ₁ and η _2, η _1> η ₂ of,

A methacrylic resin (M1) having an? Relaxation temperature T? ₁ of 137 占 폚 or more when measured in a tensile mode, dynamic viscoelasticity at 1 Hz,

A tensile mode, a methacrylic resin (M2) having an? Relaxation temperature T _{? 2} of 132 占 폚 or less when measured at a dynamic viscoelasticity of 1 Hz,

Is melt-kneaded with a methacrylic resin (M1) / methacrylic resin (M2) in a mass ratio of 2/98 to 29/71.

[9] A molded article comprising the methacrylic resin composition according to any one of [1] to [7].

[10] A film comprising a methacrylic resin composition according to any one of [1] to [7].

[11] A film of [10] which is a stretched film.

[12] A laminated film having a layer comprising a film of [10] or [11].

[13] The laminated film of [12], further comprising a layer made of a metal and / or a metal oxide.

[14] A laminated film according to [12] or [13], further comprising an adhesive layer.

[15] A laminated molded article in which a laminated film of any one of [12] to [14] is laminated on a substrate.

In the present specification, "α relaxation temperature (T _α )", "melt viscosity (η)", "weight average molecular weight (Mw)" and "molecular weight distribution (Mw / Of the present invention.

According to the present invention, it is possible to provide a methacrylic resin composition capable of obtaining a molded article having a high-temperature moldability and a high dimensional stability against heat, and a method for producing the same.

&Quot; Methacrylic resin composition "

The methacrylic resin composition of the present invention comprises a methacrylic resin (M1) having an? Relaxation temperature T? ₁ of 137 占 폚 or more when measured in a tensile mode, dynamic viscoelasticity at 1 Hz and a methacrylic resin and a methacrylic resin (M2) having an? relaxation temperature T _{? 2} of 132 占 폚 or lower.

In the present specification, "? Relaxation temperature (T _? )" Is the temperature of the peak of the relaxation (? Relaxation) caused by the segment movement of the polymer main chain. The? relaxation temperature (T _? ) can be measured by the method described in [Example].

Further, in general, but the correlation is recognized between the glass transition temperature (Tg) and α relaxation temperature (T _α) as determined from a DSC curve in the present invention, with a Tg in place of α relaxation temperature (T _α) indicator is not used Do not.

(Methacrylic resin (M1))

The methacrylic resin (M1) is not particularly limited as long as the? Relaxation temperature T? ₁ when the dynamic viscoelasticity is measured in a tensile mode, sinusoidal wave 1 Hz is 137 ° C or more. The methacrylic resin (M1) may be used alone or in combination of two or more. The methacrylic resin (M1) includes at least one methacrylic acid ester monomer unit such as a methyl methacrylate (MMA) monomer unit. Examples of methacrylic acid esters include methacrylic acid alkyl esters such as MMA, ethyl methacrylate, and butyl methacrylate; Methacrylic acid aryl esters such as phenyl methacrylate; And methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate and methacrylic anhydride. Among them, methacrylic alkyl ester is preferable, and MMA is most preferable.

The content of the methacrylic acid ester monomer unit in the methacrylic resin (M1) is preferably 20% by mass or more, and more preferably 50% by mass or more. Examples of the methacrylic resin (M1) include a methacrylic copolymer (A1) comprising a monomer unit that increases the MMA monomer unit and an? Relaxation temperature (T _? ), A structural unit having a MMA monomer unit and a cyclic structure in the main chain , A methacrylic copolymer (A2) having a high syndiotacticity (rr) in triplet, and a methacrylic resin (A3) having a high syndiotacticity (rr) in a triplet state.

≪ Methacrylic copolymer (A1) >

Examples of the monomer unit for increasing the? Relaxation temperature (T _? ) In the methacrylic copolymer (A1) include 2-isobornyl methacrylate, 8-tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate, Methacrylic acid cycloalkyl esters such as 2-norbornyl methacrylate, and 2-adamantyl methacrylate; (Meth) acrylic acid such as acrylic acid and methacrylic acid; And structural units derived from monomers such as acrylamide, methacrylamide, N-methylmethacrylamide, and (meth) acrylamides such as N, N-dimethyl methacrylamide.

≪ Methacrylic copolymer (A2) >

Examples of the structural unit having a ring structure in the main chain of the methacrylic copolymer (A2) include a lactone ring unit, a maleic anhydride unit, an anhydroglutaric acid unit, a glutarimide unit, an N-substituted maleimide unit , Or a structural unit containing a tetrahydropyran ring unit is preferable. Examples of the method for producing the methacrylic copolymer (A2) include a method of copolymerizing a cyclic monomer having a polymerizable unsaturated carbon-carbon double bond such as maleic anhydride and N-substituted maleimide with MMA or the like; And a method in which a part of the molecular chain of the methacrylic resin obtained by polymerization is cyclized in the molecule.

The content of the MMA monomer unit in the methacrylic copolymer (A2) is preferably 20 to 99% by mass, more preferably 30 to 95% by mass, and particularly preferably 40 to 90% by mass, Is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, and particularly preferably from 10 to 60% by mass. The content of the MMA monomer units in the methacrylic copolymer (A2) does not include those converted to structural units having a cyclic structure in the main chain by intramolecular cyclization in the MMA monomer units.

Examples of the structural unit having a cyclic structure as a main chain include structural units containing a group of &gt; CH-OC (= O) - in the cyclic structure, a structure containing -C (= O) -OC Unit, a structural unit containing a -C (= O) -NC (= O) - group in the ring structure, or a structural unit containing> CH-O-CH <group in the ring structure.

Examples of the structural unit containing a &gt; CH-OC (= O) - group in the ring structure include a structural unit of? -Propiolactone diyl (nickname: oxooxetane diyl),? -Butyrolactone diyl (2-oxodihydropyranediyl) structural unit such as? -Valerolactone di (a-2-oxodihydropyranediyl) structural unit, and the like. In the formula, &quot; &gt; C &quot; means that the carbon atom C has two bonding hands.

The? -valero lactone diyl structural unit includes a structural unit represented by the following formula (I).

[Chemical Formula 1]

In the formula (I), it is preferable that R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms, R ¹⁴ is a hydrogen atom, and R ¹⁵ is a methyl group. R ¹⁶ is -COOR, R is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, preferably a methyl group. "*" Means a combined hand.

Examples of the organic residue 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. &Quot; Ac &quot; represents an acetyl group. The carbon number of the organic residue is preferably 1 to 10, more preferably 1 to 5.

The 隆 -valerolactone diyl structural unit can be contained in the methacrylic resin by, for example, intramolecular cyclization of two adjacent MMA monomer units.

Examples of the structural unit containing a -C (= O) -OC (= O) - group in the cyclic structure include 2,5-dioxodihydrofurandiyl structural unit, 2,6-dioxodihydropyranyl structural unit, And 2,7-dioxooxepanediyl structural units.

As the 2,5-dioxodihydrofurandiyl structural unit, a structural unit represented by the following formula (II) is exemplified.

(2)

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

Examples of the organic residue 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. &Quot; Ac &quot; represents an acetyl group. The carbon number of the organic residue is preferably 1 to 10, more preferably 1 to 5.

It is preferable that R ²¹ and R ²² are both hydrogen atoms. In this case, from the viewpoints of ease of manufacture and control of intrinsic birefringence, it is preferable that styrene or the like is copolymerized. Specifically, there can be mentioned a copolymer having a styrene monomer unit, an MMA monomer unit and a maleic anhydride monomer unit described in International Publication No. 2014/021264.

The 2,5-dioxodihydrofurandiyl structural unit may be contained in the methacrylic resin by copolymerization using maleic anhydride.

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

(3)

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

Examples of the organic residue 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. &Quot; Ac &quot; represents an acetyl group. The organic residue preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group.

The 2,6-dioxo-dihydropyranediyl structural unit can be contained in the methacrylic resin by, for example, intramolecular cyclization of two adjacent MMA monomers.

A structural unit containing a -C (= O) -NC (= O) - group in the ring structure (and the other of the N bonds is omitted) is preferably a 2,5-dioxopyrrolidinediyl structural unit , A 2,6-dioxo-piperidinediyl structural unit, and a 2,7-dioxo-formaldehyde structural unit.

Examples of the 2,6-dioxopiperidinyl diyl structural unit include a structural unit represented by the following formula (IV).

[Chemical Formula 4]

In formula (IV), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Lt; / RTI &gt;"*" Means a combined hand.

In terms of ease of raw material availability, cost, and heat resistance, R ⁴¹ and R ⁴² are each independently preferably a hydrogen atom or a methyl group, and R ⁴¹ is a methyl group, more preferably R ⁴² is a hydrogen atom. R ⁴³ is preferably a hydrogen atom, a methyl group, a n-butyl group, a cyclohexyl group, or a benzyl group, more preferably a methyl group.

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

[Chemical Formula 5]

In the formula (V), R ⁵² and R ⁵³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 6 to 14 carbon atoms. R ⁵¹ is an arylalkyl group having 7 to 14 carbon atoms or an aryl group having 6 to 14 carbon atoms and having no substituent or substituent. The substituent mentioned here 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 combined hand. R ⁵¹ is preferably a phenyl group or a cyclohexyl group, and it is preferable that R ⁵² and R ⁵³ are both hydrogen atoms.

The 2,5-dioxo pyrrolidinyl diyl structural unit may be contained in the methacrylic resin by copolymerization using N-substituted maleimide or the like.

Examples of the structural unit containing> CH-O-CH <group in the ring structure include an oxetanediyl structural unit, a tetrahydrofurandiyl structural unit, a tetrahydropyranediyl structural unit, and an oxepanediyl structural unit. In the formula, &quot; &gt; C &quot; means that the carbon atom C has two bonding hands.

As the tetrahydropyranyl structural unit, a structural unit represented by the following formula (VI) may be mentioned.

[Chemical Formula 6]

In formula (VI), R ⁶¹ and R ⁶² each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms and a cyclic structure. "*" Means a combined hand. R ⁶¹ and R ⁶² each independently represent a tricyclo [5.2.1.0 ^2,6 ] decanyl group, a 1,7,7-trimethylbicyclo [2.2.1] heptan-3-yl group, a t- A t-butylcyclohexanyl group is preferred.

Among the structural units having the above ring structure in the main chain, 隆 -valerolactone diyl structural units and 2,5-dioxodihydrofurandiyl structural units are preferable from the viewpoints of raw materials and easiness of production.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of the methacrylic copolymers (A1) and (A2) is preferably 1.2 to 5.0, 1.3 to 3.5. The lower the Mw / Mn is, the better the impact resistance and toughness of the obtained molded article tend to be. The higher the Mw / Mn, the higher the melt flowability of the methacrylic resin composition and the better the surface smoothness of the resulting molded article.

In the present specification, Mw and Mn are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene. Mw and Mw / Mn can be measured by the method described in [Example].

The glass transition temperature (Tg) of the methacrylic copolymer (A2) is preferably 120 占 폚 or higher, more preferably 123 占 폚 or higher, particularly preferably 124 占 폚 or higher. The upper limit of the Tg of the methacrylic copolymer (A2) is preferably 160 占 폚.

In the present specification, the glass transition temperature (Tg) is measured according to JIS K7121 at room temperature or higher. (1st run) at a heating rate of 10 ° C / min to 230 ° C. After cooling to room temperature, the second temperature rise (2nd run) was carried out from room temperature to 230 ° C at a heating rate of 10 ° C / Conduct. The midpoint glass transition temperature of the 2nd run is obtained as Tg.

&Lt; Methacrylic resin (A3) &gt;

The methacrylic resin (A3) has a syndiotacticity (rr) in the triplet display of 65% or more, preferably 70 to 90%, and more preferably 72 to 85%. When the syndiotacticity (rr) is 65% or more, the? Relaxation temperature (T _? ) Becomes significantly higher, and the surface hardness of the resulting molded article becomes significantly higher.

The molecular weight distribution (Mw / Mn) of the methacrylic resin (A3) is preferably 1.0 to 1.8, more preferably 1.0 to 1.4, and particularly preferably 1.03 to 1.3. When the methacrylic resin (A3) having a molecular weight distribution (Mw / Mn) within this range is used, the obtained methacrylic resin composition has excellent mechanical strength. Mw and Mw / Mn can be controlled by adjusting the type and / or amount of the polymerization initiator used in the production.

The methacrylic resin (M1) may contain one or more monomer units other than the above monomer units from the methacrylic copolymers (A1), (A2) and the methacrylic resin (A3). Examples of other monomer units include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; Acrylic acid aryl esters such as phenyl acrylate; Cycloalkyl acrylate esters such as cyclohexyl acrylate and norbornenyl acrylate; Aromatic vinyl compounds such as styrene and? -Methylstyrene; And nitriles such as acrylonitrile and methacrylonitrile. These structural units include structural units derived from vinyl monomers having only one polymerizable carbon-carbon double bond in one molecule.

The Mw of the methacrylic resin (M1) is preferably 40,000 to 200,000, more preferably 40,000 to 150,000, and particularly preferably 50000 to 120000. When the Mw is 40,000 or more, the mechanical strength (impact resistance and toughness) of the obtained molded article tends to be improved. When the Mw is 200,000 or less, the flowability of the methacrylic resin composition is improved and the moldability tends to be improved.

The melt flow rate (MFR) of the methacrylic resin (M1) measured under the conditions of 230 캜 and a load of 3.8 kg is preferably 0.1 g / 10 min or more, more preferably 0.2 to 30 g / 10 min, Preferably 0.5 to 20 g / 10 min, and most preferably 1.0 to 15 g / 10 min.

The methacrylic resin (M1) can be produced by a known polymerization method of a radical polymerization method and an anionic polymerization method. As the radical polymerization method, a polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method may be used, and as the anionic polymerization method, a polymerization method such as a bulk polymerization method and a solution polymerization method may be selected .

The radical polymerization can be carried out in the absence of a solvent or in a solvent, and it is preferable that the methacrylic resin (M1) having a low impurity concentration can be obtained. From the viewpoint of the silverification or inhibition of the coloring of the molded article, the polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas while reducing the amount of dissolved oxygen.

Examples of the polymerization initiator used in the radical polymerization method include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexa Butyl peroxypivalate, t-butyl peroxy neodecanoate, t-hexyl peroxyneodecanoate, 1,1,3,3-tetramethyl butyl Peroxyneodecanoate, 1,1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), and dimethyl 2,2'-azobis (2-methylpropionate). Among them, t-hexylperoxy 2-ethylhexanoate, 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2'-azobis (2-methylpropionate) . The polymerization initiator may be used alone or in combination of two or more.

The one-hour half-life temperature of the polymerization initiator is preferably 60 to 140 占 폚, more preferably 80 to 120 占 폚. The hydrogenating ability of the polymerization initiator is preferably 20% or less, more preferably 10% or less, particularly preferably 5% or less. The amount of the polymerization initiator to be used is preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.01 parts by mass, particularly preferably 0.005 to 0.007 parts by mass based on 100 parts by mass of the at least one monomer to be polymerized.

In addition, the hydrogen-withdrawing ability can be known from the technical data of the polymerization initiator manufacturer (for example, the technical data of "Nitto Kasei Co., Ltd." hydrogen peroxide ability and initiator efficiency "(April 2003)). Further, it can be measured by a radical trapping method (? -Methylstyrene dimer trapping method) using? -Methylstyrene dimer. This measurement is generally carried out as follows. First, the polymerization initiator is cleaved under the coexistence of? -Methylstyrene dimer as a radical trapping agent to generate a radical fragment. Among the resulting radical fragments, a radical fragment having a low hydrogen-withdrawing ability is added in addition to the double bond of? -Methylstyrene dimer. On the other hand, a hydrogen scavenging radical fragment generates hydrogen from cyclohexane to generate a cyclohexyl radical, which is then added to the double bond of the? -Methylstyrene dimer to form a cyclohexane entrapped product . Thus, the ratio (molar fraction) of the radical fragment having a high hydrogen-withdrawing ability to the theoretical amount of the radical fragment produced, which is obtained by quantitatively determining the cyclohexane or cyclohexane trapping product, is obtained as the hydrogen-withdrawing ability.

Examples of the chain transfer agent used in the radical polymerization method include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butane dithiol, 1,6-hexane dithiol, (Β-thiopropionate), and pentaerythritol bis (thiopropionate), butanediol bisthioglycolate, butanediol bisthiourethionate, hexanediol bisthioglycolate, hexanediol bisthiouropionate, trimethylolpropane tris And alkyl mercaptans such as lithol tetrakisthiopropionate. Of these, monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferable. The chain transfer agent may be used alone or in combination of two or more.

From the viewpoints of the moldability of the resin and the mechanical strength of the molded article, the amount of the chain transfer agent to be used is preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.8 part by mass, relative to 100 parts by mass of the at least one monomer provided in the polymerization reaction Particularly preferably 0.1 to 0.6 parts by mass, and most preferably 0.10 to 0.5 parts by mass. The amount of the chain transfer agent to be used is preferably 2,500 to 10,000 parts by mass, more preferably 3,000 to 9,000 parts by mass, and particularly preferably 3,500 to 6,000 parts by mass based on 100 parts by mass of the polymerization initiator.

As the solvent used in the radical polymerization method, aromatic hydrocarbons such as benzene, toluene, and ethylbenzene are preferable. The solvent may be used alone or in combination of two or more. The amount of the solvent to be used is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, based on 100 parts by mass of the polymerization reaction raw material, from the viewpoints of viscosity and productivity of the reaction liquid.

The polymerization reaction temperature is preferably 100 to 200 占 폚, more preferably 110 to 180 占 폚. When the polymerization temperature is 100 占 폚 or higher, the productivity tends to be improved by improving the polymerization rate and lowering the viscosity of the polymerization liquid. When the polymerization temperature is 200 占 폚 or less, the control of the polymerization rate is facilitated, the production of by-products is suppressed, and the coloring of the resin can be suppressed. From the viewpoint of production efficiency, the polymerization reaction time is preferably 0.5 to 4 hours, more preferably 1.5 to 3.5 hours, particularly preferably 1.5 to 3 hours. The polymerization reaction time in the case of the continuous flow type reaction apparatus is an average residence time in the reactor.

The polymerization conversion rate in the radical polymerization method is preferably 20 to 80 mass%, more preferably 30 to 70 mass%, and particularly preferably 35 to 65 mass%. When the polymerization conversion rate is 20 mass% or more, the remaining unreacted monomer tends to be easily removed, and the appearance of the obtained molded article tends to be improved. When the polymerization conversion rate is 70 mass% or less, the viscosity of the polymerization solution is lowered and the productivity tends to be improved.

The reaction apparatus may be either a batch reaction apparatus or a continuous flow type reaction apparatus, and a continuous flow type reaction apparatus is preferable from the viewpoint of productivity. In the continuous flow type reaction, a polymerization reaction raw material (a mixed liquid containing one or more kinds of monomers, a polymerization initiator, a chain transfer agent and the like) is prepared in an inert atmosphere such as nitrogen and the mixture is supplied to the reactor at a constant flow rate, The liquid in the reactor is withdrawn at a flow rate. As the reactor, there can be mentioned a tubular reactor which can be brought close to a current (plug flow), or a molding reactor which can be brought into a state close to complete mixing. The number of reactors may be one or two or more, and at least one reactor may preferably employ a continuous flow type molding reactor. The amount of the liquid in the molding reactor in the polymerization reaction is preferably 1/4 to 3/4, more preferably 1/3 to 2/3 of the volume of the molding reactor. The reactor is usually equipped with a stirrer. Examples of the stirring apparatus include a static stirring apparatus and a dynamic stirring apparatus. Examples of the dynamic stirring apparatus include a max blend type stirring apparatus, a stirring apparatus having lattice-shaped blades for rotating the circumference of a vertically disposed rotary shaft, a propeller type stirring apparatus, and a screw type stirring apparatus . Among them, from the viewpoint of uniform mixing property, a max blend type stirring apparatus is preferable.

After completion of the polymerization, volatile components such as unreacted monomers are removed, if necessary. As the removing method, a heating and degreasing method is preferable. Examples of the devolatilization method include a balanced flash method and an adiabatic flash method. The devolatilization temperature by the adiabatic flash method is preferably 200 to 280 ° C, more preferably 220 to 260 ° C. The heating time of the resin in the adiabatic flash system is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and particularly preferably 0.5 to 2 minutes. By devolatilization in such a temperature range and heating time, it is easy to obtain a methacrylic resin (M1) which is less colored. The unreacted monomers thus removed can be recovered and used for the polymerization reaction. The yellow index of the recovered monomers may be increased by the heat applied to the recovery operation or the like. The recovered monomers are preferably purified by a known method to reduce the yellow index.

As a control method of the molecular weight distribution (Mw / Mn), a control polymerization method is exemplified, and a living radical polymerization method and a living anionic polymerization method are preferable. Examples of the living radical polymerization method include an atom transfer radical polymerization (ATRP) method, a reversible addition fragmented chain transfer polymerization (RAFT) method, a nitroxide interposition polymerization (NMP) method, a boron interposition polymerization method, Laws and the like. (Living) Anion polymerization is a method in which an anionic polymerization is carried out in the presence of a mineral acid salt such as a salt of an alkali metal or an alkaline earth metal using an organic alkali metal compound as a polymerization initiator (see JP-A No. 7-25859) A method in which an anionic polymerization is carried out in the presence of an organoaluminum compound using an organic alkali metal compound as a polymerization initiator (see JP-A-11-335432), and a method in which an anionic polymerization is carried out using an organic rare earth metal complex as a polymerization initiator Japanese Unexamined Patent Application Publication No. 6-93060).

As the polymerization initiator used in the anion polymerization method, alkyl lithium such as n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium is preferable. From the viewpoint of productivity, it is preferable to coexist the organoaluminum compound.

As the organoaluminum compound, a compound represented by the formula: AlR ¹ R ² R ³ (wherein R ¹ to R ³ each independently represents an alkyl group having an unsubstituted or substituted group, a cycloalkyl group having an unsubstituted or substituted group, An unsubstituted or substituted aryl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkoxyl group, an unsubstituted or substituted aryloxy group, or an N, N-2 substituted amino group And R ² and R ³ may be an unsubstituted or substituted arylenedioxy group in which they are bonded to each other).

Examples of the organoaluminum compound include isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6- 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum.

In an anionic polymerization method, an ether and a nitrogen-containing compound may be coexisted to control the polymerization reaction.

(Methacrylic resin (M2))

The methacrylic resin (M2) is not particularly limited as long as the? Relaxation temperature T _{? 2} when the dynamic viscoelasticity is measured in a tensile mode, sinusoidal wave 1 Hz is 132 占 폚 or lower. The methacrylic resin (M2) may be used alone or in combination of two or more. The methacrylic resin (M2) includes at least one methacrylic acid ester monomer unit such as an MMA monomer unit. Examples of methacrylic acid esters include methacrylic acid alkyl esters such as MMA, ethyl methacrylate, and butyl methacrylate; Methacrylic acid aryl esters such as phenyl methacrylate; And methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate and methacrylic anhydride. Among them, methacrylic alkyl ester is preferable, and MMA is most preferable.

The content of methacrylic acid ester monomer units in the methacrylic resin (M2) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, particularly preferably 99% Or more, and most preferably 100 mass%.

The content of the MMA monomer unit in the methacrylic resin (M2) is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, particularly preferably 99% And preferably 100% by mass.

The methacrylic resin (M2) may contain at least one monomer unit other than the methacrylic acid ester monomer unit. Examples of other monomer units include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; Acrylic acid aryl esters such as phenyl acrylate; Cycloalkyl acrylate esters such as cyclohexyl acrylate and norbornenyl acrylate; Aromatic vinyl compounds such as styrene and? -Methylstyrene; Acrylamide and methacrylamide; And nitriles such as acrylonitrile and methacrylonitrile. These structural units include structural units derived from vinyl monomers having only one polymerizable carbon-carbon double bond in one molecule.

The Mw of the methacrylic resin (M2) is preferably 40,000 to 200,000, more preferably 50,000 to 150,000, and particularly preferably 50000 to 120000. The mechanical strength (impact resistance and toughness) of the molded article obtained by Mw of 40,000 or more tends to be improved. When the Mw is 200,000 or less, the flowability of the methacrylic resin composition is improved and the moldability tends to be improved.

The molecular weight distribution (Mw / Mn) of the methacrylic resin (M2) is preferably 1.6 to 5.0, more preferably 1.7 to 4.0, and particularly preferably 1.7 to 3.0. When a methacrylic resin (M2) having a molecular weight distribution (Mw / Mn) within this range is used, the resulting molded article has excellent mechanical strength. Mw and Mw / Mn can be controlled by adjusting the type and / or amount of the polymerization initiator used in the production of the methacrylic resin (M2).

The melt flow rate (MFR) of the methacrylic resin (M2) measured at 230 캜 under a load of 3.8 kg is preferably 0.1 g / 10 min or more, more preferably 0.2 to 30 g / 10 min, Preferably 0.5 to 20 g / 10 min, and most preferably 1.0 to 15 g / 10 min.

The method for producing the methacrylic resin (M2) is preferably a method for adjusting the polymerization temperature, the polymerization time, the kind and / or amount of the chain transfer agent, the kind and / or the amount of the polymerization initiator in the radical polymerization method Method is preferable. Details of the radical polymerization method are as described above.

(Mass ratio)

In the methacrylic resin composition of the present invention, the mass ratio of methacrylic resin (M1) / methacrylic resin (M2) is 2/98 to 29/71, preferably 5/95 to 28/72, 90 to 25/75. The methacrylic resin (M1) having a high? -dilution temperature (T _? ) and low thermal decomposition resistance improves the heat resistance of the resin composition. However, when the methacrylic resin (M1) having a high? -Retarding temperature (T _? ) Is excessively high, the viscosity of the resin composition at the time of molding becomes high and the moldability is deteriorated. Further, since the methacrylic resin (M1) having a high? -Dilution temperature (T _? ) Has a low thermal decomposition resistance, if it is excessive, decomposition and foaming may occur during high-temperature molding, and the appearance of the obtained molded article may be deteriorated. When the methacrylic resin (M1) is excessively low, the dimensional stability with respect to the desired heat is not obtained. The methacrylic resin (M2) having a low α-relaxation temperature (T _α ) improves the moldability of the resin composition. When the mass ratio of the methacrylic resin (M1) or (M2) is within the above range, a methacrylic resin composition having good high-temperature moldability and high dimensional stability against heat of the molded article are obtained.

Methacrylic resin composition of the present invention, methacrylic resin (M1) and the metadata 260 ℃, melt viscosity at a shear rate of 122 sec ^-1 of the methacrylic resin (M2) in each case to a η ₁ and η _2, η ₁ Gt; ₂ . As the methacrylic resin (M2) than the α relaxation temperature is higher methacrylic resin (M1) the melt viscosity η ₁ The methacrylic resin (M2) melt viscosity higher than η ₂ of, at the time of molding the methacrylic resin composition is a methacrylic resin (M1) is liable to be oriented and difficult to be relaxed, the resulting molded article can exhibit good mechanical strength and high dimensional stability. In addition, such an action effect can be expressed even when the content ratio of the methacrylic resin (M1) is small.

The total amount of the methacrylic resin (M1) and the methacrylic resin (M2) in the methacrylic resin composition of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, particularly preferably 90% By mass is not less than 92% by mass.

The methacrylic resin composition comprising only the methacrylic resins (M1) and (M2) has a Mw of preferably 50,000 to 200,000, more preferably 52,000 to 150,000, particularly preferably 55,000 to 1200,000, and a molecular weight distribution (Mw / Mn ) Is preferably 1.2 to 2.0, more preferably 1.3 to 1.8. When the Mw and the molecular weight distribution (Mw / Mn) are in this range, the moldability of the methacrylic resin composition becomes good, and a molded article excellent in mechanical strength (impact resistance and toughness) is easily obtained.

The methacrylic resin composition comprising only the methacrylic resin (M1) or (M2) has a melt flow rate (MFR) of preferably 0.1 g / 10 min or more, more preferably 0.1 g / Is 0.2 to 30 g / 10 min, particularly preferably 0.5 to 20 g / 10 min, and most preferably 1.0 to 10 g / 10 min.

(Other polymer)

The methacrylic resin composition of the present invention may contain one or more other polymers other than the methacrylic resins (M1) and (M2), if necessary. The other polymer may be added during or after the polymerization of the methacrylic resin (M1) and / or the methacrylic resin (M2), or may be added at the time of kneading the methacrylic resins (M1) and (M2).

Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and polynorbornene; Ethylenic ionomers; Styrene resins such as polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin and MBS resin; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Nylon 6, nylon 66, and polyamide elastomer; Polycarbonate; Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl phenol, and ethylene-vinyl alcohol copolymer; Polyacetal; Polyurethane ; Modified polyphenylene ether and polyphenylene sulfide; Silicone modified resins; Acrylic rubber, acrylic thermoplastic elastomer, and silicone rubber; Styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; And olefin rubbers such as IR, EPR, and EPDM. The amount of the other polymer in the methacrylic resin composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 0% by mass.

(Preferred Embodiment)

In a preferred embodiment, the methacrylic resin composition of the present invention may include methacrylic resins (M1) and (M2) and a polycarbonate resin (PC) and / or a phenoxy resin (PR). The polycarbonate resin (PC) and the phenoxy resin (PR) may all be used alone or in combination. By including the polycarbonate resin (PC) and / or the phenoxy resin (PR), it is possible to obtain a methacrylic resin composition which can easily adjust the retardation. The amount of the polycarbonate resin (PC) and / or the phenoxy resin (PR) is preferably 1.0 to 10 parts by mass, more preferably 1.5 to 10 parts by mass, per 100 parts by mass of the total amount of the methacrylic resin (M1) 7 parts by mass, particularly preferably 2.0 to 6 parts by mass.

&Lt; Polycarbonate resin (PC) &gt;

Examples of the polycarbonate resin (PC) include a polymer obtained by a reaction between a polyfunctional hydroxy compound and a carbonic acid ester-forming compound. From the viewpoint of compatibility with the methacrylic resin and transparency of the obtained molded article, an aromatic polycarbonate resin is preferable.

 The polycarbonate resin (PC) preferably has a melt volume flow rate (MVR) measured under the conditions of 300 占 폚 and 1.2 Kg load in view of compatibility with the methacrylic resin and transparency and surface smoothness of the resulting molded article, Is in the range of 130 to 250 cm 3/10 min, more preferably 150 to 230 cm 3/10 min, particularly preferably 180 to 220 cm 3/10 min.

The polycarbonate resin (PC) preferably has a Mw in terms of polystyrene of preferably 15,000 to 28,000, more preferably 18,000 to 27,000, particularly preferably 20,000 to 30,000, from the viewpoint of compatibility with the methacrylic resin and transparency and surface smoothness of the obtained molded article. And preferably 20,000 to 24,000.

Further, MVR and Mw of the polycarbonate resin (PC) can be controlled by adjusting the amount of the terminal terminator and / or branching agent.

The Tg of the polycarbonate resin (PC) is preferably 130 占 폚 or higher, more preferably 135 占 폚 or higher, particularly preferably 140 占 폚 or higher. The upper limit of the Tg is usually 180 ° C.

Examples of the method for producing the polycarbonate resin (PC) include a phosgene method (interfacial polymerization method) and a melt polymerization method (ester exchange method). The aromatic polycarbonate resin can be produced by subjecting a polycarbonate resin raw material produced by a melt polymerization method to a treatment for adjusting the amount of a terminal hydroxy group.

The polycarbonate resin (PC) may contain other structural units such as a polyester, a polyurethane, a polyether, or a polysiloxane in addition to the polycarbonate structural unit.

&Lt; Phenoxy resin (PR) &gt;

The phenoxy resin (PR) is a thermoplastic polyhydroxypolyether resin. The phenoxy resin (PR) may contain at least 50 mass% of one or more structural units represented by the following formula (1).

(7)

In the formula (1), X is divalent containing at least one benzene ring, and R is a linear or branched alkylene group having 1 to 6 carbon atoms. The structural unit represented by the formula (1) may be connected in any form of random, alternating, or block.

The phenoxy resin (PR) preferably contains 10 to 1000, more preferably 15 to 500, particularly preferably 30 to 300 structural units represented by the formula (1).

It is preferable that the phenoxy resin (PR) does not have an epoxy group at the terminal, since it is easy to obtain a molded article with few gel defects.

The Mn of the phenoxy resin (PR) in terms of polystyrene is preferably 3000 to 2000000, more preferably 5000 to 100000, and particularly preferably 10000 to 50000. When the Mn is in this range, a methacrylic resin composition having high heat resistance and high strength can be obtained.

The Tg of the phenoxy resin (PR) is preferably 80 占 폚 or higher, more preferably 90 占 폚 or higher, and particularly preferably 95 占 폚 or higher. When the Tg of the phenoxy resin (PR) is excessively high, the heat resistance of the methacrylic resin composition tends to be low. The upper limit of the Tg is preferably 150 占 폚. When the Tg of the phenoxy resin (PR) is excessively high, the obtained molded article tends to be easily broken.

The phenoxy resin (PR) can be obtained, for example, from a condensation reaction of a divalent phenol compound and epihalohydrin, or a condensation reaction between a divalent phenol compound and a bifunctional epoxy resin. This reaction can be carried out in the absence of a solvent or in a solvent.

Examples of the divalent phenol compound include hydroquinone, resorcin, 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ketone, 2,2-bis (4-hydroxyphenyl) , 1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis Bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, Bis (2- (4-hydroxyphenyl) propyl) benzene, 2- (4-hydroxyphenyl) 2-bis (4-hydroxyphenyl) -1,1,1-3,3,3-hexafluoropropane, and 9,9'-bis (4-hydroxyphenyl) fluorene. Among them, 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ketone, 2,2-bis (4-hydroxyphenyl) propane, and 9,9 ' -Bis (4-hydroxyphenyl) fluorene is preferable.

Examples of bifunctional epoxy resins include epoxy oligomers obtained by the condensation reaction of the above-mentioned dihydric phenol compound and epihalohydrin. Specific examples of the epoxy resin include hydroquinone diglycidyl ether, resorcine diglycidyl ether, bisphenol S type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, methylhydroquinone diglycidyl ether, Dihydroxydiphenyl oxide diglycidyl ether, 4,4'-dihydroxydiphenyl oxide diglycidyl ether, 2,6-dihydroxynaphthalene diglycidyl ether, dichlorobisphenol A diglycidyl ether, and tetrabromobis Phenol A type epoxy resin, and 9,9'-bis (4-hydroxyphenyl) fluorene diglycidyl ether. Among them, bisphenol A type epoxy resin, bisphenol S type epoxy resin, hydroquinone diglycidyl ether, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, and 9,9'- Bis (4-hydroxyphenyl) fluorene diglycidyl ether is preferable.

Examples of the solvent used in the production of the phenoxy resin (PR) include methyl ethyl ketone, dioxane, tetrahydrofuran, acetophenone, N-methylpyrrolidone, dimethylsulfoxide, N, N- And protonic organic solvents such as propane.

Examples of the catalyst used in the production of the phenoxy resin (PR) include alkali metal hydroxides, tertiary amine compounds, quaternary ammonium compounds, tertiary phosphine compounds, and quaternary phosphonium compounds.

X in the formula (1) is preferably a divalent radical derived from the compounds represented by the following formulas (2) to (4). In addition, the positions of the two bonding hands constituting the two tails are not particularly limited as long as they are chemically possible positions. X in the formula (1) is preferably a divalent group having two bonding hands generated by drawing two hydrogen atoms from a benzene ring image in the compounds represented by the formulas (2) to (4). In particular, it is preferable that the compound is a divalent group having two bonding hands generated by drawing out one hydrogen atom from any two benzene rings of the compounds represented by the formulas (3) to (4).

[Chemical Formula 8]

In the formula (2), R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms. p is an integer of 1 to 4;

[Chemical Formula 9]

In the formula (3), R ¹ is a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a cycloalkylidene group having 3 to 20 carbon atoms. In the formulas (3) and (4), R ² and R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms . n and m are each independently an integer of 1 to 4;

In formula (1), X may be a divalent group derived from a compound in which a plurality of benzene rings are condensed with an alicyclic ring or a heterocyclic ring. For example, a divalent group derived from a compound having a fluorene structure or a carbazole structure.

The structural unit represented by the formula (1) is preferably a structural unit represented by the following formula (5) or (6), more preferably a structural unit represented by the following formula (7). The phenoxy resin (PR) of the preferred embodiment preferably contains 10 to 1000 such structural units.

[Chemical formula 10]

In formula (5), R ⁹ is a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a cycloalkylidene group having 3 to 20 carbon atoms. In the formulas (5) and (6), R ¹⁰ is a linear or branched alkylene group having 1 to 6 carbon atoms.

Examples of the commercially available phenoxy resin (PR) include YP-50 and YP-50S manufactured by Shinnitetsu Sumikin Chemical Industry, jER series manufactured by Mitsubishi Chemical Corporation, PKFE and PKHJ manufactured by InChem.

(Another preferred embodiment)

In another preferred embodiment, the methacrylic resin composition of the present invention may include methacrylic resins (M1) and (M2) and a crosslinked rubber (CR) and / or a block copolymer (BP). The crosslinking rubber (CR) and the block copolymer (BP) may all be used alone or in combination of two or more.

<Cross-linked rubber (CR)>

 The crosslinked rubber (CR) is a polymer having rubber elasticity in which a plurality of polymer chains are crosslinked by a crosslinkable monomer having a plurality of polymerizable functional groups in one monomer. Examples of the crosslinked rubber (CR) include an acrylic crosslinked rubber containing an acrylic acid alkyl ester monomer unit and a crosslinkable monomer unit, a diene crosslinked rubber containing a conjugated diene monomer unit and a crosslinkable monomer unit, a conjugated diene monomer unit containing an acrylic acid alkyl ester monomer unit and a conjugated diene And cross-linked rubbers containing a monomer unit and a cross-linking monomer unit. These crosslinked rubbers may contain other vinyl-based monomer units, if necessary.

 The crosslinked rubber (CR) is preferably in the form of particles. The crosslinked rubber particles (CRp) may be single-layer particles consisting solely of a crosslinked rubber polymer or multilayer particles of two or more layers made of a crosslinked rubber polymer and another polymer. As the multilayered particle, a core-shell-type particle composed of a core portion made of a crosslinked rubber polymer and a shell portion made of another polymer is preferable. In the core-shell type particle, the core portion may have one or more inner shell layers covering the center core portion and, if necessary, the center core portion, and the shell portion may have one outer shell layer covering the core portion. It is preferable that there is no gap between each layer. As the core-shell type particles, acrylic multi-layer polymer particles (CRa) are particularly preferable.

In the core-shell-type particle, at least a part of the core portion composed of the center core portion and optionally one or more inner shell layers includes the crosslinked rubber polymer (i). In the core portion, when the remaining portion that does not include the crosslinked rubber polymer (i) is present, the remaining portion includes the other polymer (iii). When the plurality of portions of the core portion include the crosslinked rubber polymer (i), the kinds and physical properties of the crosslinked rubber polymer (i) contained in them may be the same or may not be the same. Similarly, when a plurality of the remainders of the core portion include another polymer (iii), the kind and physical properties of the other polymer (iii) contained in them may be the same or may not be the same.

 The crosslinked rubber polymer (i) preferably contains an acrylic acid alkyl ester monomer unit and / or a conjugated diene monomer unit and a crosslinkable monomer unit. The alkyl group of the alkyl acrylate monomer used in the crosslinked rubber polymer (i) preferably has 1 to 8 carbon atoms. Examples of such acrylic acid alkyl ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. These may be used alone or in combination of two or more. Examples of the conjugated diene-based monomer include butadiene and isoprene. These may be used alone or in combination of two or more. The amount of the alkyl acrylate monomer unit and / or the conjugated diene monomer unit in the crosslinked rubber polymer (i) is preferably 60% by mass or more, more preferably 70 to 99% by mass, and particularly preferably 80 to 98% by mass, to be.

Examples of the crosslinkable monomer include allyl acrylate, allyl methacrylate, 1-acryloxy-3-butene, 1-methacryloxy-3-butene, 1,2-diacryloxy- Diacryloxypropane, 1,3-diacryloxypropane, 1,4-diacryloxy-butane, 1,3-dimethacryloxy-propane, 1,2-di Methacryloxypropane, 1,4-dimethacryloxy-butane, triethylene glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, hexanediol diacrylate, divinylbenzene, 1 , 4-pentadiene, and triallyl isocyanate. These may be used alone or in combination of two or more. The amount of the crosslinkable monomer units in the crosslinked rubber polymer (i) is preferably 0.05 to 10% by mass, more preferably 0.5 to 7% by mass, and particularly preferably 1 to 5% by mass.

The crosslinked rubber polymer (i) may contain other vinyl-based monomer units, if necessary. Other vinyl monomers include methacrylic acid ester monomers such as MMA, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate; Aromatic vinyl monomers such as styrene, p-methylstyrene, and o-methylstyrene; Maleimide-based monomers such as N-propylmaleimide, N-cyclohexylmaleimide, and N-o-chlorophenylmaleimide. These may be used alone or in combination of two or more.

As the other polymer (iii), it is preferable to have a methacrylic acid alkyl ester monomer unit. The other polymer (iii) may comprise a crosslinkable monomer unit and / or another vinyl monomer unit, if necessary.

 The number of carbon atoms in the methacrylic acid alkyl ester monomer used in the other polymer (iii) is preferably 1 to 8. Examples of such methacrylic acid alkyl ester monomers include MMA, ethyl methacrylate, and butyl methacrylate, and MMA is preferable. These may be used alone or in combination of two or more. The amount of the methacrylic acid alkyl ester monomer unit in the other polymer (iii) is preferably 80 to 100% by mass, more preferably 85 to 99% by mass, and particularly preferably 90 to 98% by mass.

As the crosslinkable monomer used for the other polymer (iii), the same crosslinking monomer as exemplified in the crosslinked rubber polymer (i) can be used. The amount of the crosslinkable monomer unit in the other polymer (iii) is preferably 0 to 5% by mass, more preferably 0.01 to 3% by mass, and particularly preferably 0.02 to 2% by mass.

Examples of other vinyl monomers to be used for the other polymer (iii) include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate and 2-ethylhexyl acrylate Monomers; Vinyl acetate; Styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, and aromatic vinyl monomers such as? -Methylstyrene and vinylnaphthalene; Nitriles such as acrylonitrile and methacrylonitrile; Alpha, beta -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Maleimide-based monomers such as N-ethylmaleimide and N-cyclohexylmaleimide. These may be used alone or in combination of two or more.

In the core-shell type particles, the shell portion composed of one or more outer shell layers preferably comprises a thermoplastic polymer (ii). As the thermoplastic polymer (ii), it is preferable to contain a methacrylic acid alkyl ester monomer unit and, if necessary, other vinyl monomer units. It is preferable that at least a part of the thermoplastic polymer (ii) is grafted to the center core layer or the inner shell layer adjacent to the inside.

The number of carbon atoms in the methacrylic acid alkyl ester monomer unit in the thermoplastic polymer (ii) is preferably 1 to 8. Examples of such methacrylic acid alkyl ester monomers include MMA and butyl methacrylate, and MMA is preferable. These may be used alone or in combination of two or more. The amount of the methacrylic acid alkyl ester monomer unit in the thermoplastic polymer (ii) is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more.

As the other vinyl monomer used in the thermoplastic polymer (ii), the same vinyl monomer other than those exemplified in the other polymer (iii) described above can be used. The amount of other vinyl-based monomer units in the thermoplastic polymer (ii) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

The constitution of the core portion and the shell portion in the core shell-type particle includes two-layer polymer particles in which the center core portion is composed of the crosslinked rubber polymer (i) and the outer shell layer is composed of the thermoplastic polymer (ii); A three-layer polymer particle wherein the center core portion is made of another polymer (iii), the inner shell layer is made of a crosslinked rubber polymer (i), and the outer shell layer is made of a thermoplastic polymer (ii); A three-layer polymer particle in which the center core portion is made of one kind of crosslinked rubber polymer (i), the inner shell layer is made of another kind of crosslinked rubber polymer (i), and the outer shell layer is made of thermoplastic polymer (ii); A three-layer polymer particle composed of a center core portion of a crosslinked rubber polymer (i), an inner shell layer of another polymer (iii) and an outer shell layer of a thermoplastic polymer (ii); Wherein the center core part comprises a crosslinked rubber polymer (i), the first inner shell layer comprises another polymer (iii), the second inner shell layer comprises a crosslinked rubber polymer (i), the outer shell layer comprises a thermoplastic polymer (ii) , And the like.

Above all, the acrylic three-layer polymer particles in which the center core portion is made of another polymer (iii), the inner shell layer is made of the crosslinked rubber polymer (i) and the outer shell layer is made of the thermoplastic polymer (ii) is preferable. The other polymer (iii) of the center core portion is a copolymer of an acrylic acid alkyl ester monomer unit having 0 to 19.95 mass% of an alkyl group having 1 to 8 carbon atoms and 0.05 to 2 mass% of a crosslinkable monomer unit, Wherein the crosslinked rubber polymer (i) of the inner shell layer is a copolymer of an acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms in an amount of 80 to 98 mass%, an aromatic vinyl monomer unit of 1 to 19 mass% and a crosslinkable monomer unit 1 Wherein the thermoplastic polymer (ii) of the outer shell layer is a copolymer of acrylic acid alkyl ester monomer units having an MMA monomer unit of 80 to 100 mass% and an alkyl acrylate monomer unit having an alkyl group of 1 to 8 carbon atoms in an amount of 0 to 20 mass% Layer polymer particles are particularly preferred.

From the viewpoint of transparency of the core-shell type particles, it is preferable to select the polymer of each layer so that the difference in refractive index between adjacent layers is preferably less than 0.005, more preferably less than 0.004, particularly preferably less than 0.003 .

The proportion of the outer shell layer in the core shell-type particles is preferably 10 to 60 mass%, more preferably 15 to 50 mass%, and particularly preferably 20 to 40 mass%. The proportion of the portion containing the crosslinked rubber polymer (i) in the core portion is preferably 20 to 100% by mass, more preferably 30 to 70% by mass.

The volume-based average particle diameter of the crosslinked rubber particles (CRp) is preferably 0.02 to 1 占 퐉, more preferably 0.05 to 0.5 占 퐉, and particularly preferably 0.1 to 0.3 占 퐉. By using the crosslinked rubber particles (CRp) having such a volume-based mean particle diameter, the appearance defects of the resulting molded article can be remarkably reduced. In the present specification, the &quot; volume-based mean particle diameter &quot; is a value calculated based on particle diameter distribution data measured by light scattering light method.

As the method of producing the crosslinked rubber particles (CRp), the emulsion polymerization method or the seed emulsion polymerization method is preferable from the viewpoints of particle size control and ease of production of a multilayer structure. The emulsion polymerization method is a method for producing an emulsion containing polymer particles by emulsion polymerization of at least one raw material monomer. In the seed emulsion polymerization method, core-shell polymer particles comprising seed particles and a shell layer covering the seed particles are obtained by emulsion-polymerizing one or more raw material monomers to obtain seed particles, followed by emulsion polymerization of the other raw monomers in the presence of the seed particles Emulsions can be produced. An emulsion including core-shell multilayer polymer particles composed of seed particles and a plurality of shell layers covering the seed particles can be produced by repeating the step of emulsion-polymerizing one or more raw monomers in the presence of the obtained core-shell polymer particles .

Examples of the emulsifier used in the emulsion polymerization method include anionic emulsifiers, nonionic emulsifiers, and nonionic emulsifiers and anionic emulsifiers. Examples of the anionic emulsifier include dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dilaurylsulfosuccinate; Alkylbenzene sulfonic acid salts such as sodium dodecylbenzenesulfonate; And alkylsulfates such as sodium dodecylsulfate. Examples of the nonionic emulsifier include polyoxyethylene alkyl ethers and polyoxyethylene nonylphenyl ethers. Examples of the nonionic / anionic emulsifier include polyoxyethylene nonylphenyl ether sulfate such as polyoxyethylene nonylphenyl ether sodium sulfate; Polyoxyethylene alkyl ether sulfates such as polyoxyethylene alkyl ether sulfates and alkyl ether carboxylates such as polyoxyethylene tridecyl ether sodium acetate. These may be used alone or in combination of two or more. The average number of repeating units of the ethylene oxide (EO) units in the exemplified compounds of the nonionic emulsifier and the nonionic emulsifier is preferably not more than 30, more preferably not more than 30 Preferably 20 or less, particularly preferably 10 or less.

As the polymerization initiator used in the emulsion polymerization, persulfate-based initiators such as potassium persulfate and ammonium persulfate; Persulfoxylate / organic peroxides, and redox-type initiators such as persulfate / sulfite.

Examples of the separation method of the crosslinked rubber particles (CRp) from the emulsion obtained by the emulsion polymerization include a salting-out solidification method, a freezing solidification method and a spray drying method. Among them, the salting-out solidification method and the freeze-solidification method are preferable, and the freeze-solidification method is more preferable in that the impurities contained in the crosslinked rubber particles (CRp) can be easily removed by washing. According to the freeze-solidification method without using a flocculant, a resin composition having excellent water resistance is easily obtained. Further, if the emulsion is filtered with a wire mesh or the like having an opening of 50 mu m or less before the solidification step, the foreign matter mixed in the emulsion can be removed, which is preferable.

From the viewpoint of the particle dispersibility in the melt kneading of the methacrylic resin (M1), (M2) and the crosslinked rubber particle (CRp), the crosslinked rubber particle (CRp) preferably has a diameter of 1000 탆 or less, more preferably 500 탆 Of the diameter of the aggregate. In the coagulated form, the shell portions are mutually fusion-bonded. Examples of the shape of the crosslinked rubber particle agglomerate include pellet, powder, granule and the like.

The amount of the crosslinking rubber (CR) in the methacrylic resin composition of the present invention is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, per 100 parts by mass of the total amount of the methacrylic resins (M1) and (M2) Particularly preferably 15 to 20 parts by mass.

To the methacrylic resin composition of the present invention, dispersion auxiliary particles (DA) such as methacrylic resin particles may be added in order to enhance the uniform dispersibility of the crosslinked rubber particles (CRp). The volume-based average particle diameter of the dispersion auxiliary particles DA is preferably smaller than that of the crosslinked rubber particles (CRp), preferably 0.04 to 0.12 mu m, more preferably 0.05 to 0.1 mu m. The mass ratio of the dispersion auxiliary particles (DA) / crosslinked rubber particles (CRp) is preferably 0/100 to 60/40, more preferably 10/90 to 50/50, particularly Preferably 20/80 to 40/60.

<Block Copolymer (BP)>

The block copolymer (BP) is a copolymer in which plural kinds of polymer molecular chains (polymer blocks) are entirely linked in a chain or radial manner. It is preferable that at least one of the polymer blocks constituting the block copolymer (BP) is a polymer comprising at least 90% by mass of methacrylic acid ester monomer units, a polymer comprising a styrene monomer unit And polymers comprising acrylonitrile monomer units, polymers comprising styrene monomer units and maleic anhydride monomer units, polymers comprising styrene monomer units, maleic anhydride monomer units and MMA monomer units, or polyvinyl butyral .

From the viewpoint of improving the strength of the molded article, the block copolymer (BP) is preferably at least one polymer block (bl) (methacrylate ester polymer block) comprising a polymethacrylic acid ester such as polymethyl methacrylate (PMMA) , And a block copolymer (BPa) comprising at least one polymer block (b2) (acrylic acid ester polymer block) composed of a polyacrylic ester.

As a method for producing the block copolymer (BPa), there can be used a method in which a starting point of polymerization is formed at the end of one polymer block using living polymerization, and a monomer is polymerized from the starting point to connect the other polymer block; A method of preparing a plurality of polymer blocks and subjecting them to an addition reaction or a condensation reaction, and the like.

The amount of the block copolymer (BP) is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 25 parts by mass, and particularly preferably from 1 to 100 parts by mass, based on 100 parts by mass of the total amount of the methacrylic resins (M1) and To 20 parts by mass.

(Other optional components)

The methacrylic resin composition of the present invention may contain other optional components as needed. Other optional components include fillers, antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants, salt pigments, light diffusing agents, , And various additives such as phosphors. The total amount of these various additives is preferably 7 mass% or less, more preferably 5 mass% or less, particularly preferably 4 mass% or less.

&Lt; Ultraviolet absorber (LA) &gt;

When the molecular weight of the ultraviolet absorber (LA) is too low, foaming may occur at the time of molding the methacrylic resin composition. Therefore, the molecular weight of the ultraviolet absorber (LA) is preferably more than 200, more preferably 300 or more, particularly preferably 500 or more, and most preferably 600 or more.

The ultraviolet absorber (LA) is a compound which is said to have a function of converting light energy into thermal energy. Examples of the ultraviolet absorber (LA) include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, anilides oxalic acid, malonic acid esters, and formamidines have. These may be used alone or in combination of two or more. Benzotriazoles (compounds having a benzotriazole skeleton) and triazines (compounds having a triazine skeleton) are preferable from the standpoint that the effect of suppressing degradation (yellowing, etc.) of the resin by ultraviolet rays is high.

Examples of benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name: TINUVIN329, Methyl-1-phenylethyl) phenol (trade name: TINUVIN234, manufactured by BASF), 2,2'-methylenebis [6- (2H-benzotriazole (5-octylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4- -Methylphenol and the like.

As the triazine stream, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (LA-F70 manufactured by ADEKA) (CGL777, TINUVIN460, TINUVIN479, etc.) and 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5- Triazine, and the like.

In addition, an ultraviolet absorber having a maximum value? _Max of the molar extinction coefficient at a wavelength of 380 to 450 nm of not more than 1200 dm ³ .mol ^-1 cm ^-1 can be mentioned. Examples of such an ultraviolet absorber include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd., trade name: Sandubore VSU).

In addition, International Publication No. 2011/089794, International Publication No. 2012/124395, Japanese Patent Application Laid-Open No. 2012-012476, Japanese Laid-Open Patent Publication No. 2013-023461, Japanese Laid-Open Patent Publication No. 2013-112790, Japanese Laid- 2013-194037, 2014-62228, 2014-88542, and 2014-88543, and the like can be given as examples of the metal complex having a ligand of a heterocyclic structure. Examples of such a metal complex include compounds represented by the following formula (A).

(11)

In the formula (A), M is a metal atom. Y ¹ to Y ⁴ are each independently a divalent group other than a carbon atom (oxygen atom, sulfur atom, NH, and NR ^5, etc.). R ⁵ is a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, and an aralkyl group. The substituent may further have a substituent. Z ¹ and Z ² are each independently a triple bond (nitrogen atom, CH 3, and CR ⁶ ). R ⁶ is a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, and an aralkyl group. The substituent may further have a substituent. R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, an alkoxyl group, a halogeno group, an alkylsulfonyl group, a monopolinosulfonyl group, a piperidinosulfonyl group, a thiomorpholinosulfonyl group, And a piperadinosulfonyl group. The substituent may further have a substituent. a to d each represent the number of R ¹ to R ⁴ , each independently an integer of 1 to 4;

Examples of the ligand of the heterocyclic structure in the above metal complex include 2,2'-iminobisbenzothiazole, 2- (2-benzothiazolylamino) benzoxazole, 2- (2-benzothiazolylamino) Imidazole, bis (2-benzothiazolyl) methane, bis (2- benzoimidazolyl) methane, bis (2- Imidazolyl] methane, and derivatives thereof. As the central metal of the metal complex, copper, nickel, cobalt, and zinc are preferable. The metal complex is preferably dispersed in a medium such as a low molecular weight compound or a polymer. The addition amount of the metal complex is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass based on 100 parts by mass of the methacrylic resin composition of the present invention. Since the metal complex has a large molar extinction coefficient at a wavelength of 380 to 400 nm, the amount of the metal complex to be added is small in order to obtain a desired ultraviolet absorption effect. Therefore, deterioration of the appearance of the molded article due to bleed-out or the like can be suppressed. In addition, since the metal complex has high heat resistance, deterioration and decomposition during molding are small. Further, since the metal complex has high light resistance, the ultraviolet absorption performance can be maintained for a long time.

The maximum value? _Max of the molar extinction coefficient of the ultraviolet absorber can be measured in the following manner. 10.00 mg of an ultraviolet absorber is added to 1 L of cyclohexane, and dissolved by naked eyes so that there is no undissolved product. The solution is poured into a 1 cm x 1 cm x 3 cm quartz glass cell and absorbance is measured at a wavelength of 380-450 nm using a U-3410 spectrophotometer manufactured by Hitachi, Ltd. From the molecular weight (M _UV ) of the ultraviolet absorber and the maximum value (A _max ) of the measured absorbance, the maximum value? _Max of the molar extinction coefficient is calculated from the following formula.

ε _max = [A _max / (10 × 10 ^-3 )] × M _UV

<Polymer Processing Aids (PA)>

As the polymer processing aid (PA), polymer particles (non-crosslinked rubber particles) having a particle diameter of 0.05 to 0.5 mu m which can be produced by emulsion polymerization can be used. The polymer particles may be single-layer particles composed of a polymer having a single composition and a single extreme viscosity, or may be multi-layered particles of two or more layers composed of two or more polymers having different compositions or intrinsic viscosities. Particularly, a two-layer structure particle having a polymer layer having a low intrinsic viscosity in an inner layer and a polymer layer having an intrinsic viscosity of 5 dl / g or more in an outer layer is preferable. The polymer processing aid (PA) preferably has an intrinsic viscosity of 3 to 6 dl / g. If the extreme viscosity is too low, the effect of improving the moldability may be insufficient, and in the extreme case, the moldability of the methacrylic resin composition may be deteriorated. Specific examples include Metablen-P series manufactured by Mitsubishi Rayon Co., Ltd. and Paraboloid series manufactured by Dow Chemical Company. The amount of the polymer processing aid (PA) is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the methacrylic resins (M1) and (M2). When the compounding amount is too low, good processing characteristics can not be obtained, and when the compounding amount is too large, there is a fear that the appearance of the formed article is deteriorated.

<Other additives>

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 in the methacrylic resin composition of the present invention is preferably 3 mass% or less, more preferably 1.5 mass% or less.

Examples of the antioxidant include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. The antioxidant may be used alone or in combination of two or more. Among them, a phosphorus-based antioxidant and a hindered phenol-based antioxidant are preferable from the viewpoint of an effect of preventing deterioration of optical characteristics due to coloring, and a phosphorus-based antioxidant and a hindered phenol-based antioxidant are more preferably used in combination. When the phosphorus antioxidant and the hindered phenol antioxidant are used in combination, the mass ratio of the phosphorus antioxidant: hindered phenol antioxidant is preferably 1: 5 to 2: 1, more preferably 1: 2 to 1: 1 Do.

Examples of the phosphorus antioxidant include 2,2-methylenebis (4,6-ditetylphenyl) octyl phosphite (trade name: Adekastab HP-10 manufactured by ADEKA), tris (2,4- Butylphenyl) phosphite (trade name: IRGAFOS 168), and 3,9-bis (2,6-di-tert- And 3,9-diphosphaspiro [5.5] undecane (trade name: Adecastab PEP-36, manufactured by ADEKA).

Examples of hindered phenol antioxidants include pentaerythrityl-tetrakis [3- (3,5-ditbutyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, manufactured by BASF) Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name IRGANOX1076, manufactured by BASF).

The thermal deterioration inhibitor can prevent the thermal degradation of the resin by capturing the polymer radical which is generated when the resin is exposed to high heat under substantially anoxic conditions. Examples of the thermal deterioration preventing agent include 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate (SumilTomo Chemical Co., , 4-di-t-amyl-6- (3 ', 5'-di-t-amyl-2'-hydroxy- alpha -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., have.

The light stabilizer is a compound which is said to have a function of capturing a radical generated by oxidation by light. And hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

Examples of the lubricant include stearic acid, behenic acid, stearoamidic acid, methylenebisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hydrogenated oil.

Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; Higher fatty acid esters of glycerin such as stearic acid monoglyceride and stearic acid diglyceride, and the like. The combination of higher alcohol and glycerin fatty acid monoester is preferable. The mass ratio of the higher alcohol / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1, more preferably 2.8 / 1 to 3.2 / 1.

As the organic dye, a compound that converts ultraviolet rays to visible light is preferably used.

Examples of the light-diffusing agent and the gloss-removing agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.

Examples of the fluorescent substance include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent whitening agent, and a fluorescent whitening agent.

(Physical Properties of Methacrylic Resin Composition)

The methacrylic resin composition of the present invention preferably has a Mw of 50,000 to 200,000, more preferably 55,000 to 160,000, particularly preferably 60,000 to 1,200,000, and most preferably 70,000 to 100,000, and a molecular weight distribution (Mw / Mn) Is preferably 1.0 to 5.0, more preferably 1.2 to 3.0, particularly preferably 1.3 to 2.0, and most preferably 1.3 to 1.7. When the Mw and the molecular weight distribution (Mw / Mn) are in this range, the moldability of the methacrylic resin composition becomes good, and a molded article excellent in mechanical strength (impact resistance and toughness) is easily obtained.

The melt flow rate (MFR) of the methacrylic resin composition of the present invention measured under the conditions of 230 占 폚 and 3.8 kg load is preferably 0.1 to 30 g / 10 min, more preferably 0.5 to 20 g / 10 min, Particularly preferably 1.0 to 15 g / 10 min.

The methacrylic resin composition of the present invention is preferably 3.0% or less, more preferably 2.0% or less, and particularly preferably 1.5% or less in haze when processed into a film having a thickness of 3.2 mm.

(Method for producing methacrylic resin composition)

The methacrylic resin composition of the present invention may be produced by melt-kneading methacrylic resin (M1), (M2) and, if necessary, other polymer. The melt kneading can be carried out using a melt kneader such as a kneader rudder, an extruder, a mixing roll, and a Banbury mixer. The kneading temperature can be appropriately adjusted according to the softening temperature of the methacrylic resin (M1), (M2) and, if necessary, other polymers used, and is usually within the range of 150 to 300 占 폚. The shear rate at the time of kneading can be adjusted within a range of 10 to 5000 sec ^-1 .

Another method for producing the methacrylic resin composition of the present invention is to polymerize the other methacrylic resin in the presence of one of the methacrylic resins (M1) and (M2) and, if necessary, another polymer There is a way. This production method has a shorter thermal history to be applied to the methacrylic resin as compared with the above-mentioned production method, so that thermal decomposition of the methacrylic resin is suppressed, and a methacrylic resin composition having little coloring and foreign matters is easily obtained.

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

"Molded body"

The molded article of the present invention is obtained by molding the methacrylic resin composition of the present invention. Examples of the molding method include a T die method (such as a lamination method and a co-extrusion method), an inflation method (a co-extrusion method, etc.), a compression molding method, a blow molding method, a calender molding method, a vacuum molding method, an injection molding method (an insert method, A core backing method, and a sandwich method); Solution casting method and the like. Among them, T-die method, inflation method, injection molding method and the like are preferable from the viewpoint of productivity and cost.

"film"

The shape of the molded body may be arbitrary, and may be a film or the like. The film of the present invention is a film made of the methacrylic resin composition of the present invention. In general, a planar formed body having a thickness of 5 to 250 占 퐉 is mainly classified as a &quot; film &quot;, and a planar formed body thicker than 250 占 퐉 is classified mainly as a &quot; sheet &quot;

Examples of the film forming method include a melt film forming method and a solution film forming method, and a melt film forming method is preferable from the viewpoint of productivity. Examples of the melt film forming method include an inflation method, a T-die method, a calender method, and a cutting method. Among them, the T-die method is preferable. Examples of the melt film forming apparatus include an extruder type melt extrusion apparatus having a single shaft or a biaxial extrusion screw. The melt extrusion temperature is preferably 150 to 350 占 폚, more preferably 200 to 300 占 폚. In the case of melt-kneading using a melt extrusion apparatus, it is preferable to perform melt kneading under reduced pressure or in an inert atmosphere such as nitrogen from the viewpoint of suppressing coloring. In the melt extrusion apparatus, it is preferable to provide a polymer filter for removing foreign matter and a gear pump for increasing the thickness precision.

It is preferable that the methacrylic resin composition is extruded from a T-die in a molten state, and this is extruded into one or more cooling mirror-surface rolls or mirror-surface belts in order to obtain a film of good surface smoothness, good mirror gloss and low haze in the extrusion- A method of cooling by contacting or holding is preferable. It is preferable that the mirror-surface roll or the mirror-surface belt is made of at least a mirror-finished chromium-plated metal.

The thickness of the methacrylic resin film (unstretched film) formed by the above method is preferably 10 to 500 占 퐉, more preferably 20 to 200 占 퐉 in view of mechanical strength, film uniformity, and winding property. The thickness distribution is preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3%, of the average value. If the thickness distribution exceeds 10%, there is a possibility that stretching unevenness may occur when the stretching treatment is performed.

The methacrylic resin film (unstretched film) formed by the above method may be subjected to stretching treatment. By the stretching treatment, mechanical strength (impact resistance and toughness) and thermal properties are increased, and a film hardly causing cracks is obtained. The stretching treatment includes a stretching process, a heat fixing process, and a relaxation process. Examples of the stretching method include a sequential biaxial stretching method, a simultaneous biaxial stretching method, and a tubular stretching method.

In the case of the sequential biaxial stretching method, the stretching speed is preferably 1 to 8,000% / min, more preferably 100 to 6,000% / min in any stretching direction. In addition, the stretching speed may be the same or not in the two directions. In the case of the simultaneous biaxial stretching method, the stretching speed is preferably 1 to 8,000% / min, more preferably 50 to 6,000% / min. In any of these methods, productivity is poor at a low elongation speed, and film breakage may occur at an elongation speed.

The stretching temperature is preferably Tg to (Tg + 30 deg. C), more preferably (Tg + 5 deg. C) in any of the sequential / simultaneous biaxial stretching methods based on the Tg of the methacrylic resin composition of the present invention. ° C) to (Tg + 25 ° C). In this range, thickness irregularity is suppressed. When the stretching temperature is too high, there is a fear that the film is broken, and in the case of over-stretching, there is a fear that the effect of improving the mechanical strength and thermal properties by the stretching treatment becomes insufficient.

The area multiplication factor of the stretched film to the undrawn film is preferably 1.01 to 12.25 times, more preferably 1.10 to 9 times. When the draw ratio is less than 1.01 times, the effect of improving the mechanical strength of the film becomes insufficient. When the draw ratio exceeds 12.25 times, there is a fear that the mechanical strength is lowered. In the case of biaxial stretching, the stretching magnification in each axial direction is preferably 1.01 to 3.5 times.

The film of the present invention can be used as a polarizing film, a polarizer protective film, a retardation film, a liquid crystal protective film, a surface material of a portable information terminal, a protective film for a display window of a portable information terminal, a transparent conductive film coated with silver nanowires or carbon nanotubes, And a front film of various displays, and is particularly preferable for a polarizer protective film and the like.

In addition, the film of the present invention can be used for IR (infrared) cut film, crime prevention film, shatterproof film, edible film, metal edible film, back sheet for solar cell, front sheet for flexible solar battery, Films, and gas barrier films.

The film of the present invention is also preferable for an optical film for an organic electroluminescence (EL) illumination device.

&Quot; Laminated film &quot;

The film (unstretched film or stretched film) of the present invention may be in the form of a laminated film in which other layers are laminated on at least one surface. The laminated film of the present invention has a layer made of the above-mentioned film (unstretched film or stretched film) of the present invention.

The other layers include various functional layers. Examples of the functional layer include a hard coat layer, an antiglare layer, an antireflection layer, a sticking prevention layer, a diffusion layer, an antiglare layer, an antistatic layer, an antifouling layer and a slippery layer including fine particles.

The other layer may be a polarizer made of a polyvinyl alcohol film doped with iodine. A polarizing plate which is one embodiment of the laminated film of the present invention has the polarizer and a polarizer protective film comprising the above-mentioned film of the present invention laminated on at least one surface of the polarizer. In the embodiment in which the film of the present invention is laminated on one surface of the polarizer, an optional optical film other than the film of the present invention can be laminated on the other surface of the polarizer, if necessary. Examples of the optional optical film include a polarizer protective film other than the film of the present invention, a viewing angle adjusting film, a retardation film, and a luminance improving film. The lamination may be carried out through an adhesive layer as required.

The polarizing plate of the above embodiment can be used in an image display apparatus. Examples of the image display device include a self-emission type display device such as an (organic) electroluminescence display (ELD), a plasma display (PD), and a field emission display (FED) A liquid crystal display (LCD), and the like. The LCD has a liquid crystal cell and a polarizing plate disposed on at least one side thereof.

The other layer may be a layer composed of a metal and / or a metal oxide. Examples of the metal include aluminum, silicon, magnesium, palladium, zinc, tin, nickel, silver, copper, gold, indium, stainless steel, chromium, and titanium. Examples of the metal oxide include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide, cobalt oxide, zirconium oxide, tin oxide, , Copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, and barium oxide. These metals and metal oxides can be used alone or in combination of two or more. Among them, indium is preferable because it has excellent luster and is excellent in luster. It is preferable that the laminated film laminated with a metal layer by vapor deposition or the like on the film of the present invention is difficult to lose gloss even when it is subjected to deep drawing. In addition, aluminum is excellent in gloss and has excellent designability and can be obtained industrially at low cost, and is particularly preferable for applications in which deep drawing molding is not required. As a method for forming a layer composed of a metal and / or a metal oxide, a vacuum deposition method is usually used, but ion plating, sputtering, and CVD (Chemical Vapor Deposition) may also be used. Before forming the layer composed of the metal and / or the metal oxide, the film of the present invention may be subjected to surface treatment such as corona treatment in advance. The thickness of the layer made of the metal and / or the metal oxide is generally about 5 to 100 nm, and preferably 5 to 250 nm when deep drawing is performed after the layer is formed.

The other layer may be a layer made of another thermoplastic resin. Examples of other thermoplastic resins suitable for lamination include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, other (meth) acrylic resin, ABS (acrylonitrile- Butadiene-styrene copolymer) resin, ethylene vinyl alcohol resin, polyvinyl butyral resin, polyvinyl acetal resin, styrene thermoplastic elastomer, olefin thermoplastic elastomer, and acrylic thermoplastic elastomer. The thickness of the thermoplastic resin layer is suitably designed according to the application and is not particularly limited and is preferably 500 탆 or less from the viewpoint of secondary processability.

The production method of the laminated film having the layer made of the other thermoplastic resin is not particularly limited. For example, (1) a method of continuously laminating a film of the present invention prepared separately and another thermoplastic resin film between a pair of heating rolls; (2) a method of thermocompression bonding the thermoplastic resin film and the thermoplastic resin film of the present invention separately prepared using a hot press; (3) a method in which a film of the present invention and another thermoplastic resin film are separately prepared, one of the films is pressure-formed or vacuum-formed, and another film is laminated; (4) a method of laminating the film of the present invention prepared separately and another thermoplastic resin film through an adhesive layer (wet lamination method); (5) a method of laminating another thermoplastic resin melt-extruded from a T die to a film of the present invention prepared in advance; (6) A method of co-extruding the methacrylic resin composition of the present invention and another thermoplastic resin.

&Quot; Laminated formed article &quot;

The laminated molded article of the present invention is obtained by laminating the film of the present invention or the laminated film of the present invention on a substrate. The base material is not particularly limited, and other thermoplastic resin base materials, thermosetting resin base materials, wood base materials, and non-wood fiber base materials can be mentioned. Examples of other thermoplastic resins used for the base material are the same as those described above as materials for the other layers constituting the laminated film. Other thermosetting resins used for the substrate include epoxy resins, phenol resins, and melamine resins.

The production method of the laminated molded article is not particularly limited. For example, a laminated molded article can be obtained by subjecting the (laminated) film of the present invention to vacuum molding, pressure molding, compression molding or the like under heating with an adhesive layer interposed therebetween, if necessary.

In the other manufacturing method, the (laminated) film of the present invention is inserted between the male molds for injection molding, and the molten thermoplastic resin is injected into one side of the (laminated) film in the mold to form the injection- , And an injection molding simultaneous injection method in which the injection-molded body and the (laminated) film are simultaneously subjected to bonding. The (laminated) film of the present invention used in this method may be a flat film, or it may be preliminarily formed by vacuum molding, pressure molding or the like, and may be formed into an arbitrary uneven shape. The preforming of the (laminated) film of the present invention may be carried out in a mold of an injection molding machine used in the injection molding simultaneous injection method, or may be carried out using another molding machine. (Lamination) A method of preliminarily molding a film and then injecting a molten resin into the one surface is called an insert molding method.

In the laminated molded article of the present invention, it is preferable that the layer comprising the film of the present invention is the outermost layer. The laminated molded article of the present invention is excellent in surface smoothness, surface hardness, and surface gloss. When the laminated film of the present invention has a print layer, a pattern or the like is clearly displayed. When a laminated film having a layer made of a metal or a metal oxide is used, mirror-like luster like metal can be obtained.

INDUSTRIAL APPLICABILITY As described above, the present invention can provide a methacrylic resin composition capable of obtaining a molded article having a high-temperature moldability and a high dimensional stability against heat. The methacrylic resin composition of the present invention has satisfactory moldability even when exposed to high temperatures, for example, when passing through a polymer filter, even when a thermal history of, for example, about 280 DEG C is obtained, have. Further, the obtained molded article can have high dimensional stability even for heat of about 130 캜.

According to the present invention, it is possible to provide a methacrylic resin composition which is capable of obtaining a molded article having good moldability at a high temperature and excellent in transparency, dimensional stability against heat, and mechanical strength (impact resistance and toughness).

Example

Hereinafter, examples and comparative examples related to the present invention will be described.

[Evaluation Items and Evaluation Methods]

The evaluation items and evaluation methods are as follows.

(Polymerization conversion ratio)

A gas chromatograph GC-14A manufactured by Shimadzu Corporation, GL Sciences Inc. Manufactured by Inert CAP 1 (df = 0.4 탆, I.D. = 0.25 mm, length = 60 m). The injection temperature was 180 ° C and the detector temperature was 180 ° C. The column temperature was maintained at 60 占 폚 for 5 minutes, then raised from 60 占 폚 to 200 占 폚 at a heating rate of 10 占 폚 / minute, and maintained at 200 占 폚 for 10 minutes. Measurement was carried out under these conditions, and the polymerization conversion rate was calculated based on the obtained results.

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

4 mg of the resin to be measured was dissolved in 5 ml of tetrahydrofuran (THF), and the solution was filtered with a filter having a pore diameter of 0.1 탆 to prepare a sample solution. As the GPC apparatus, &quot; HLC-8320 &quot; manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) was used. As a column, two TSKgel Super Multipore HZM-M manufactured by Tosoh Corporation and a Super HZ4000 connected in series were used. Tetrahydrofuran (THF) was used as the eluent. The temperature of the column oven was set at 40 占 폚, and 20 占 퐇 of the sample solution was injected into the apparatus at an eluent liquid flow rate of 0.35 ml / min, and the chromatogram was measured. The chromatogram is a chart plotting the electric signal value (intensity Y) derived from the difference in refractive index between the sample solution and the reference solution with respect to the retention time X. FIG.

10 polystyrene standards each having a molecular weight in the range of 400 to 5,000,000 were subjected to GPC measurement to prepare a calibration curve showing the relationship between the retention time and the molecular weight. Based on this calibration curve, Mw and Mw / Mn of the resin to be measured were determined. The baseline of the chromatogram is different from the baseline in that the slope of the peak on the high molecular weight side of the GPC chart changes from zero to positive as seen from the fast retention time and from the point where the slope of the peak on the low molecular weight side becomes fast As a result, a line connecting minus and zero changes the line. When the chromatogram indicates a plurality of peaks, 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 As a baseline.

(Syndiotacticity (rr) of three consecutive characters)

¹ H-NMR measurement was performed on the resin to be measured. As a measuring device, a nuclear magnetic resonance apparatus ("ULTRA SHIELD 400 PLUS" manufactured by Bruker) was used. For 10 mg of sample, 1 mL of deuterated chloroform was used as a deuterated solvent. The measurement temperature was room temperature (20 ~ 25 ℃) and the number of integration was 64 cycles. The area X of the area of 0.6 to 0.95 ppm and the area Y of the area of 0.6 to 1.35 ppm when the reference material TMS is 0 ppm are calculated and calculated by the formula: (X / Y) x 100 One value was defined as the syndiotacticity (rr) (%) of the three-digit display.

(Dynamic viscoelasticity measurement)

A test piece of a short width of 5 mm in width was cut out from a hot press formed film having a thickness of 1 mm and subjected to dynamic viscoelasticity measurement. As the measuring apparatus, a forced vibration type dynamic viscoelasticity measuring apparatus (&quot; Rheogel-E4000 &quot; manufactured by Ubiteo Co., Ltd.) was used. The specimens were set in the apparatus at a chuck distance of 20 mm. Temperature raising rate from 3O &lt; 0 &gt; C / minute to 50 &lt; 0 &gt; C to 230 [deg.] C under the condition of automatic frequency control, basic frequency: 1 Hz, measurement mode: tensile mode, Were measured. The storage elastic modulus (E '), the loss elastic modulus (E' '), and tan delta were plotted, and the peak of tan delta appearing at 100 deg. The peak top temperature of this? Relaxation was set as? Relaxation temperature.

(Melt flow rate (MFR))

The MFR of the resin to be measured was measured in accordance with JIS K7210 under the conditions of 230 占 폚, 3.8 kg load, and 10 minutes.

(Melt viscosity?)

The resin to be measured was dried at 80 DEG C for 12 hours, and then the melt viscosity? Was measured under the conditions of 260 DEG C and a shear rate of 122 sec &lt; ^-1 &gt; using &quot; CAPILLOGRAPH 1D &quot; manufactured by TOYO SEIKI Co.,

(High-temperature moldability (hot weight retention))

As a measuring apparatus, a thermogravimetric analyzer ("TGA-50" manufactured by Shimadzu Corporation) was used. The thermogravimetric reduction of the resin to be measured was measured with a temperature profile in which the temperature was raised from 50 DEG C to 290 DEG C at a temperature raising rate of 20 DEG C / min and kept at 290 DEG C for 20 minutes. The weight retention rate after holding at 290 占 폚 for 20 minutes was determined based on the weight at the time point of 50 占 폚 (retention rate 100%), and the high temperature moldability (heat decomposability) was evaluated according to the following criteria. Further, it can be said that the higher the thermogravimetric retentivity is, the higher the thermal decomposability is, and the higher the temperature moldability is.

 <Criteria>

A (good): The thermogravimetric retentivity is 80% or more,

B (poor): The thermal weight retention rate is less than 80%.

(Hayes)

The haze of the biaxially oriented film was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) in accordance with JIS K7136.

(Total light transmittance)

The total light transmittance of the biaxially oriented film was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) according to JIS K7361-1.

(Dimensional stability (coefficient of linear thermal expansion))

A test piece having a width of 4 mm, a length of 20 mm and a thickness of 40 占 퐉 was cut out from the biaxially stretched film. As a measuring apparatus, thermomechanical analysis TMA ("Q400EM" manufactured by TA Instrument) was used. The chuck distance was 8 mm and the load was 0.01 N, the temperature was raised from 25 캜 to 130 캜 at a rate of 10 캜 / min, and the dimensional change of the test piece was measured. The linear thermal expansion coefficient was calculated from the slope of the dimensional change amount in the temperature range of 50 to 90 캜.

(Impact resistance (impact value))

Test specimens of 80 mm x 80 mm x 40 m thickness were cut out from the biaxially stretched film. The impact resistance value was measured when the test piece was broken with a sphere having a diameter of 12.7 ± 0.2 mmφ using a film impact tester (manufactured by Yasuda Seiki).

(Retardation in the film thickness direction Rth)

From the obtained biaxially stretched film, a test piece of 40 mm x 30 mm was cut out. This test piece was set in an automatic birefringence system ("KOBRA-WR" manufactured by Prince Instrument Co., Ltd.). The retardation in the oblique direction at 40 ° was measured under the conditions of a temperature of 23 ± 2 ° C, a humidity of 50 ± 5% and a wavelength of measurement light of 590 nm. The refractive indices n _x , n _y and n _z were calculated from this value and the average refractive index n and the retardation Rth in the thickness direction (= ((n _x + n _y ) / 2 - n _z ) x d) was calculated. N _x is the refractive index in the in-plane slow axis direction, n _y is the refractive index in the in-plane slow axis orthogonal direction, n _z is the refractive index in the thickness direction, and d is the thickness of the test piece [nm]. The thickness d [nm] of the test piece was measured using a dezymatic indicator (manufactured by Mitsutoyo Co., Ltd.). The average refractive index n was measured using a digital precision refractometer (&quot; KPR-20 &quot; manufactured by Carl Zeiss Optics KK).

(Production Example 1) (Production of methacrylic resin (M1-1)) [

The inside of an autoclave equipped with a stirring blade and a three-chamber cock was replaced with nitrogen. To this were added 73.3 kg of a toluene solution of isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 1,600 kg of toluene, 80 kg of 1,2-dimethoxyethane and a concentration of 0.45 M (42.3 mol) of sodium carbonate and 8.44 kg (14.1 mmol) of a 1.3 M solution of sec-butyllithium (solvent: 95% by mass of cyclohexane / 5% by mass of n-hexane). While stirring, 550 kg of distilled and purified MMA was added dropwise thereto at 15 占 폚 over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 15 캜 for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion rate of MMA at this point was 100%. To the obtained solution, 1500 kg of toluene was added and diluted. Subsequently, the diluted solution was poured into a large amount of methanol to obtain a precipitate. The resulting precipitate was dried at 80 DEG C and 140 Pa for 24 hours to obtain a methacrylic resin (M1-1).

The methacrylic resin (M1-1) had a Mw of 70000, a melt viscosity? Of 1200 Pa 占 퐏, a Mw / Mn of 1.06, a syndiotacticity (rr) of 75% and an? , And the content of the MMA monomer unit was 100 mass% (polymethyl methacrylate (PMMA)). Table 1 shows the physical properties of the methacrylic resin (M1-1).

(Production Example 2) (Production of methacrylic resin (M1-2)

The inside of an autoclave equipped with a stirring blade and a three-chamber cock was replaced with nitrogen. To this were added 73.3 kg of a toluene solution of isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 1,600 kg of toluene, 60 kg of 1,2-dimethoxyethane and a concentration of 0.45 M And 4.22 kg (7.1 mmol) of a solution of sec-butyllithium (solvent: cyclohexane 95 mass% / n-hexane 5 mass%). While stirring, 550 kg of distilled and purified MMA was added dropwise thereto at 15 占 폚 over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 15 캜 for 90 minutes. The color of the solution changed from yellow to colorless. The polymerization conversion rate of MMA at this point was 100%. To the obtained solution, 1500 kg of toluene was added and diluted. Subsequently, the diluted solution was poured into a large amount of methanol to obtain a precipitate. The resulting precipitate was dried at 80 DEG C and 140 Pa for 24 hours to obtain a methacrylic resin (M1-2).

The methacrylic resin (M1-2) had Mw of 36000, a melt viscosity? Of 400 Pa.s, a Mw / Mn of 1.07, a syndiotacticity (rr) of 75% and an? , And the content of the MMA monomer unit was 100 mass% (polymethyl methacrylate (PMMA)). Table 1 shows the physical properties of the methacrylic resin (M1-2).

(Production Example 3) (Production of methacrylic resin (M2-1)) [

The inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen. To this were added 100 parts by mass of purified MMA, 0.0054 parts by mass of 2,2'-azobis (2-methylpropionitrile (hydrogen-releasing ability: 1%, 1 hour half-life temperature: 83 ° C), and n-octylmercaptan 0.200 parts by mass was added and stirred to obtain a raw material liquid. Nitrogen was sent to the raw material liquid to remove dissolved oxygen.

The raw material liquid was introduced into a plastic reactor connected with an autoclave and a pipe by 2/3 of the capacity. While maintaining the temperature at 140 占 폚, the polymerization reaction was first initiated in a batch mode. When the polymerization conversion rate reached 55% by mass, the raw material liquid was supplied from the autoclave to the molding reactor at a flow rate of 150 minutes with an average residence time of 150 minutes while maintaining the temperature at 140 占 폚. At the same time, The reaction liquid was withdrawn from the molding reactor and converted to a continuous flow polymerization reaction. After the conversion, the polymerization conversion rate in the steady state was 48 mass%.

The reaction liquid withdrawn from the shaping reactor in a steady state was supplied to a shell-and-tube heat exchanger having an internal temperature of 230 DEG C at a flow rate of an average residence time of 2 minutes, and then heated. Subsequently, the warmed reaction liquid was introduced into a flash evaporator, and volatile matter containing an unreacted monomer as a main component was removed to obtain a molten resin. The molten resin from which the volatile components were removed was fed to a twin-screw extruder having an internal temperature of 260 占 폚, discharged into strands, and cut into pelletizers to obtain methacrylic resin (M2-1) on pellets.

The methacrylic resin (M2-1) had a Mw of 112000, a melt viscosity? Of 1000 Pa.s, a Mw / Mn of 1.86, a syndiotacticity (rr) of 52% and an? , And the content of the MMA monomer unit was 100 mass% (polymethyl methacrylate (PMMA)). Table 1 shows the physical properties of the methacrylic resin (M2-1).

(Production Example 4) (Production of methacrylic resin (M2-2)

The inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen. To this were added 100 parts by mass of purified MMA, 0.0065 parts by mass of 2,2'-azobis (2-methylpropionitrile (hydrogen-releasing ability: 1%, 1 hour half-life temperature: 83 ° C), and n-octylmercaptan And 0.290 parts by mass were added and stirred to obtain a raw material liquid. Nitrogen was sent to the raw material liquid to remove dissolved oxygen.

The raw material liquid was added to the plastic reactor connected with the autoclave and the piping up to 2/3 of the capacity. While keeping the temperature at 120 占 폚, the polymerization reaction was initiated in a batch method. When the polymerization conversion rate reached 55% by mass, the raw material liquid was supplied from the autoclave to the molding reactor at a flow rate of 120 minutes with an average residence time of 120 minutes while maintaining the temperature at 120 占 폚. At the same time, The reaction liquid was withdrawn from the molding reactor and converted to a continuous flow polymerization reaction. After the conversion, the polymerization conversion rate in the steady state was 45 mass%.

The reaction liquid withdrawn from the shaping reactor in a steady state was supplied to a shell-and-tube heat exchanger having an internal temperature of 230 DEG C at a flow rate of an average residence time of 2 minutes, and then heated. Subsequently, the warmed reaction liquid was introduced into a flash evaporator, and volatile matter containing an unreacted monomer as a main component was removed to obtain a molten resin. The molten resin from which the volatile components were removed was fed to a twin screw extruder having an internal temperature of 230 캜 and discharged into a strand shape and cut into pelletizers to obtain a methacrylic resin (M2-2) on pellets.

The methacrylic resin M2-2 had a Mw of 83,000, a melt viscosity? Of 700 Pa 占 퐏, a Mw / Mn of 1.87, a syndiotacticity rr of 55%, an? , And the content of the MMA monomer unit was 100 mass% (polymethyl methacrylate (PMMA)). Table 1 shows the physical properties of the methacrylic resin (M2-2).

(Polycarbonate resin (PC))

(PC) were prepared.

Polycarbonate resin ("SD POLYCA TR-2201", manufactured by Sumika Sutron Polycarbonate Co., Ltd., MVR (measured according to JIS K7210 at 300 ° C under a load of 1.2 Kg for 10 minutes) 210 cm 3/10 min, Mw = 22000, Mw / Mn = 2.0).

(Preparation Example 5) (Preparation of crosslinked rubber particle composition (CD-1)) [

&Lt; Production example 5-1 &gt;

48 kg of ion-exchanged water was charged into a reaction vessel of 100 L capacity equipped with a glass lining equipped with a condenser, a thermometer and a stirrer. Subsequently, 416 g of sodium stearate, 128 g of sodium lauryl sarcosinate and 16 g of sodium carbonate Lt; / RTI &gt; Subsequently, 11.2 kg of MMA and 110 g of allyl methacrylate were charged, and the mixture was heated to 70 DEG C while stirring. Thereafter, 560 g of a 2% potassium persulfate aqueous solution was added to initiate emulsion polymerization. The internal temperature rises due to the heat generated by polymerization, and then the internal temperature starts to fall. After the temperature was lowered to 70 캜, the mixture was stirred at 70 캜 for 30 minutes for emulsion polymerization to obtain an emulsion containing the seed particles.

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

To the emulsion containing the core-shell two-layer particles, 320 g of a 2% aqueous potassium persulfate solution was added and a mixture consisting of 6.2 kg of MMA, 0.2 kg of methyl acrylate and 200 g of n-octylmercaptan was added over 30 minutes Respectively. After completion of the addition, the mixture was stirred for 60 minutes to effect emulsion polymerization, and then cooled to room temperature. Thus, an emulsion containing 40 mass% of crosslinked rubber particles (acrylic three-layer polymer particles) (CR-1) having a core shell three-layer structure having an average particle diameter of 0.23 mu m as a volume basis was obtained.

&Lt; Production example 5-2 &gt;

 48 kg of ion-exchanged water was charged into a reaction vessel of 100 L capacity equipped with a glass lining equipped with a condenser, a thermometer and a stirrer, and then 252 g of a surfactant ("Pelex SS-H" manufactured by Kao Corporation) . After raising the temperature of the reaction vessel to 70 캜, 160 g of a 2% potassium persulfate aqueous solution was added thereto, and then a mixture consisting of 3.04 kg of MMA, 0.16 kg of methyl acrylate and 15.2 g of n-octylmercaptan was added in a batch, To initiate emulsion polymerization. Stirring was continued for 30 minutes from the point at which heat generation due to the polymerization reaction disappeared.

After adding 160 g of a 2% potassium persulfate aqueous solution thereto, a mixture of 27.4 kg of MMA, 1.44 kg of methyl acrylate and 98 g of n-octylmercaptan was continuously added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 60 minutes to effect emulsion polymerization. The resulting emulsion was cooled to room temperature. Thus, an emulsion containing 40 mass% of acrylic polymer particles (dispersion auxiliary particles) (DA-1) having an average particle diameter of 0.12 mu m and an intrinsic viscosity of 0.44 g / dl was obtained.

&Lt; Production Example 5-3 &

The emulsion containing the crosslinked rubber particles (acrylic three-layer polymer particles) (CR-1) obtained in Production Example 5-1 and the emulsion containing the acrylic polymer particles (dispersion auxiliary particles) (DA-1) obtained in Production Example 5-2 The emulsion was mixed so that the mass ratio of the particles (CR-1): particles (DA-1) was 2: 1. The mixed emulsion was frozen at -20 占 폚 for 2 hours. The frozen mixed emulsion was poured into two times the amount of hot water at 80 DEG C and was ice-cooled to obtain a slurry. The slurry was maintained at 80 DEG C for 20 minutes, dehydrated, and dried at 70 DEG C to be pulverized. Thus, a crosslinked rubber particle composition (CD-1) comprising the crosslinked rubber particles (CR-1) and the dispersion auxiliary particles (DA-1) was obtained.

(Production Example 6) (Production of block copolymer (BP-1)) [

735 kg of dry toluene, 36.75 kg of 1,2-dimethoxyethane and 30.0 g of isobutyl bis (2,6-di-t-butyl) were added to a three-necked flask whose inside was replaced with nitrogen at room temperature -4-methylphenoxy) aluminum (20 mol) in toluene. To this was added 1.17 mol of sec-butyllithium. Further, 39.0 kg of MMA was added and the mixture was reacted at room temperature for 1 hour to obtain an MMA polymer (methacrylic acid ester polymer) (b1-1). The Mw of the MMA polymer (b1-1) was 45,800.

Subsequently, the reaction solution was cooled to -25 캜, and a mixture of 29.0 kg of n-butyl acrylate and 10.0 kg of benzyl acrylate was added dropwise over 0.5 hours, and the polymerization reaction was continued from the terminal of the MMA polymer (b1-1). Thereafter, 4 kg of methanol was added to the reaction solution to terminate the polymerization reaction, and the reaction solution was poured into a large amount of methanol to precipitate the block copolymer (BP-1). The resulting precipitate was filtered and dried at 80 DEG C and 1 torr (about 133 Pa) for 12 hours.

Thus, a diblock copolymer (BP-1) comprising an MMA polymer block (b1-1) and an acrylic acid ester polymer block (b2-1) comprising n-butyl acrylate unit and benzyl acrylate unit was obtained. The block copolymer (BP-1) had Mw of 92000 and Mw / Mn of 1.06. Since the Mw of the MMA polymer (b1-1) was 45800, the Mw of the acrylic acid ester polymer (b2-1) was determined to be 46200. The proportion of benzyl acrylate units in the acrylic acid ester polymer (b2-1) was 25.6% by mass. The mass ratio of (b1-1) / (b2-1) was 50/50.

(Ultraviolet absorber (LA))

Of ultraviolet absorber (LA) were prepared.

(LA-31): 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4-t-octylphenol]

(LA-F70): 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA).

(Polymer Processing Aids (PA))

The following polymer processing aid (PA) was prepared.

(Average polymerization degree: 7734, content of MMA monomer unit: 88 mass%, content of acrylic monomer unit: 12 mass%) manufactured by Mitsubishi Rayon Co., Ltd. (PA-1).

(Example 1)

20 parts by mass of a methacrylic resin (M1-1), 80 parts by mass of a methacrylic resin (M2-1), 1.0 part by mass of a block copolymer (BP-1), 0.9 parts by mass of an ultraviolet absorber (LA- And 2 parts by mass of the auxiliary agent (PA-1) were mixed and melted and kneaded at 250 占 폚 using a twin-screw extruder ("KZW20TW-45MG-NH-600" To prepare a methacrylic resin composition (R11). The physical properties of the methacrylic resin composition (R11) were evaluated. The composition and evaluation results of the methacrylic resin composition (R11) are shown in Table 2.

The obtained methacrylic resin composition (R11) was dried at 80 DEG C for 12 hours. The methacrylic resin composition (R11) was extruded from a 150 mm wide T-die at a resin temperature of 260 占 폚 using a 20 mm? Single-axis extruder (manufactured by OCS) and passed through a roll having a surface temperature of 100 占 폚, An undrawn film having a thickness of 160 mu m was obtained.

The resulting unstretched film was cut into 100 mm x 100 mm. This film was subjected to biaxial stretching using a biaxial (tanks) arrangement biaxial stretching tester. In the first step, simultaneous biaxial stretching was carried out under the conditions of a stretching temperature Tg + 20 占 폚, a stretching rate of 860% / min and a stretching magnification of 2 占 2. Then, in the second step, , And then quenched to obtain a biaxially oriented film (F11) having a thickness of 40 占 퐉. Table 3 shows the stretching conditions and the evaluation results of the biaxially stretched film. Further, corona discharge treatment was performed on one side of the obtained biaxially oriented film (F11), and then aluminum was vapor deposited to a thickness of 30 nm by vacuum deposition. The laminated film thus obtained was excellent in mirror-surface luster.

(Examples 2 to 4)

In each of Examples 2 to 4, methacrylic resin compositions (R12) to (R14) and biaxially oriented films (F12) to (F14) were obtained in the same manner as in Example 1 except that the composition and the stretching conditions were changed. ) Was obtained and evaluated. The composition, stretching conditions and evaluation results are shown in Tables 2 and 3.

(Comparative Examples 1 to 4)

In each of Examples 1 to 4, methacrylic resin compositions (R21) to (R24) and biaxially oriented films (F21) to (F24) were obtained in the same manner as in Example 1 except that the composition and the stretching conditions were changed. ) Was obtained and evaluated. The composition, stretching conditions and evaluation results are shown in Tables 2 and 3.

(result)

In Examples 1 to 4, a methacrylic resin (M1) having an? Relaxation temperature of 137 占 폚 or more and a methacrylic resin (M2) having an? Relaxation temperature of 132 占 폚 or less and a melt viscosity? ₁ Methacrylic resin compositions (R11) to (R14) wherein the methacrylic resin (M2) has a melt viscosity? ₂ and a methacrylic resin (M1) / methacrylic resin (M2) mass ratio of 2/98 to 29/71 ). All of the methacrylic resin compositions (R11) to (R14) obtained in Examples 1 to 4 had high thermogravimetric retention and good moldability at high temperature. All of the biaxially stretched films (F11) to (F14) obtained in Examples 1 to 4 had high transparency, a low coefficient of linear thermal expansion, good dimensional stability, and good impact resistance.

In Comparative Example 1 using only the methacrylic resin (M2) as the methacrylic resin, the obtained biaxially oriented film (F21) had a large coefficient of linear thermal expansion and poor dimensional stability and poor impact resistance. The methacrylic resin (M1) and the methacrylic resin (M2) were used in combination as the methacrylic resin. In Comparative Examples 2 and 3 in which the amount of the methacrylic resin (M1) was larger than those in Examples 1 to 3, (R22) to (R23) all had low thermogravure retention and poor moldability at high temperature. In Comparative Example 4 in which the melt viscosity? ₁ of the methacrylic resin (M1) was smaller than the melt viscosity? ₂ of the methacrylic resin (M2), the dimensional stability was poor and the impact resistance was inferior because of the large linear expansion coefficient.

The present invention is not limited to the above-described embodiments and examples, and it is possible to appropriately change the design without departing from the gist of the present invention.

This application claims priority based on Japanese Patent Application No. 2016-150205 filed on July 29, 2016, and hereby accepts all of its disclosure.

Claims (15)

A methacrylic resin (M1) having an? Relaxation temperature T? ₁ of 137 占 폚 or more when measured in a tensile mode, dynamic viscoelasticity at 1 Hz,
(M2) having an? Relaxation temperature T _{? 2} of 132 占 폚 or less when measured in a tensile mode, dynamic viscoelasticity at 1 Hz, and the methacrylic resin composition
Η ₁ > η ₂ when the melt viscosity of the methacrylic resin (M1) and the methacrylic resin (M2) at 260 ° C. and the shear rate of 122 sec ^-1 is respectively η ₁ and η ₂ ,
Wherein the mass ratio of methacrylic resin (M1) / methacrylic resin (M2) is 2/98 to 29/71. The method according to claim 1,
Wherein the methacrylic resin (M1) has a molecular weight distribution of 1.0 to 1.4. 3. The method according to claim 1 or 2,
Wherein the methacrylic resin (M1) has a weight average molecular weight of 40,000 to 200,000. 4. The method according to any one of claims 1 to 3,
Wherein the methacrylic resin (M2) has a methacrylate monomer unit content of 99 mass% or more. 5. The method according to any one of claims 1 to 4,
Wherein the methacrylic resin composition further comprises a polycarbonate resin and / or a phenoxy resin. 6. The method according to any one of claims 1 to 5,
Wherein the methacrylic resin composition further comprises a crosslinked rubber and / or a block copolymer. 7. The method according to any one of claims 1 to 6,
A methacrylic resin composition, further comprising an ultraviolet absorber. 260 ℃ of the methacrylic resin (M1) and methacrylic resin (M2), in the case where the melt viscosity at a shear rate of 122 sec ^-1 to η ₁ and η _2, η _1> η ₂ of,
A methacrylic resin (M1) having an? Relaxation temperature T? ₁ of 137 占 폚 or more when measured in a tensile mode, dynamic viscoelasticity at 1 Hz,
A tensile mode, a methacrylic resin (M2) having an? Relaxation temperature T _{? 2} of 132 占 폚 or less when measured at a dynamic viscoelasticity of 1 Hz,
Is melt-kneaded with a methacrylic resin (M1) / methacrylic resin (M2) in a mass ratio of 2/98 to 29/71. A molded article comprising the methacrylic resin composition according to any one of claims 1 to 7. A film comprising the methacrylic resin composition according to any one of claims 1 to 7. 11. The method of claim 10,
Stretched film. A laminated film having a layer made of the film according to claim 10 or 11. 13. The method of claim 12,
Further comprising a layer comprising a metal and / or a metal oxide. The method according to claim 12 or 13,
Further comprising an adhesive layer. A laminated molded article, wherein the laminated film according to any one of claims 12 to 14 is laminated on a substrate.