CN109563328A

CN109563328A - Methacrylic resin composition and its manufacturing method, film, stacked film, are laminated into body at formed body

Info

Publication number: CN109563328A
Application number: CN201780046768.4A
Authority: CN
Inventors: 福原直人; 川北展史; 中原淳裕; 阿部达
Original assignee: Kuraray Co Ltd
Current assignee: Kuraray Co Ltd
Priority date: 2016-07-29
Filing date: 2017-07-27
Publication date: 2019-04-02
Also published as: JPWO2018021449A1; TWI767924B; JP7045994B2; KR20190035779A; WO2018021449A1; TW201815945A; KR102346225B1

Abstract

The present invention provides the methacrylic resin composition that formed body of the hot forming well and to heat with high-dimensional stability can be obtained.Methacrylic resin composition of the invention is α relaxation temperature T when carrying out Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz_α1For 137 DEG C or more of methacrylic resins (M1) and the α relaxation temperature T at stretch mode, 1Hz when progress Measurement of Dynamic Viscoelasticity_α2For the methacrylic resin composition of 132 DEG C of methacrylic resins (M2) below.By methacrylic resin (M1) and methacrylic resin (M2) at 260 DEG C, shear velocity 122 seconds^‑1Under melt viscosity be set to η₁And η₂When, η₁> η₂, methacrylic resin (M1)/methacrylic resin (M2) mass ratio is 2/98~30/70.

Description

Methacrylic resin composition and its manufacturing method, formed body, film, stacked film, It is laminated into body

Technical field

The present invention relates to methacrylic resin composition and its manufacturing method, formed body, film, stacked film, it is laminated into Body.

Background technique

Methacrylic resin has high transparency, is suitable as optical component, illuminating member, billboard component and dress Adorn the material of component etc..But the glass transition temperature (Tg) of widely used methacrylic resin is down to about 110 DEG C, heat resistance is not so good, therefore, formed body to heat dimensional stability it is bad.As the methacrylic resin of Tg high, The high methacrylic resin of known degree of syndiotacticity (rr).The metering system high as degree of syndiotacticity (rr) The manufacturing method of acid resin can enumerate anionic polymerization (referenced patent document 1,2).But it is obtained by this method The high methacrylic resin of degree of syndiotacticity (rr) formability it is bad, the surface with obtained formed body The tendency of flatness equal difference.Although formability can be improved by reducing molecular weight, the machine with obtained formed body The tendency of tool strength reduction.Therefore, status is the forming comprising degree of syndiotacticity (rr) high methacrylic resin Body is not yet practical.

Patent Document 3 discloses a kind of methacrylic resin compositions, wherein between making in terms of three unit groups The degree of syndiotacticity for methacrylic resin [1] He Yisan unit group meter that same steric regularity (rr) is 65% or more (rr) methacrylic resin [2] for being 45~58% is with methacrylic resin [1]/methacrylic resin [2] Mass ratio 40/60~70/30 contain (claim 1).By high with above-mentioned mass ratio cooperation degree of syndiotacticity (rr) Methacrylic resin [1] and atactic methacrylic resin [2], heat resistance can be taken into account and improved and good Formability.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 3-263412 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2002-327012 bulletin

Patent document 3: International Publication No. 2014/185509

Summary of the invention

Problem to be solved by the invention

As described above, generally in methacrylic resin, heat resistance (to the dimensional stability of heat) is with formability Both conflicting characteristic, it is difficult to take into account.In addition, in recent years, the complication of shape and the high-dimensional stability etc. to heat Requirement to formed body is increasingly increased.It is therefore desirable to which can shape at high temperature has good formability and has to heat The formed body of high-dimensional stability.

The present invention is to complete in view of the above problems, good and right its purpose is to provide hot forming can be obtained Heat has the methacrylic resin composition and its manufacturing method of the formed body of high-dimensional stability.

The method for solving problem

The present invention provide methacrylic resin composition below and its manufacturing method, formed body, film, stacked film, It is laminated into body.

[1] a kind of methacrylic resin composition is that Measurement of Dynamic Viscoelasticity is carried out at stretch mode, 1Hz When α relaxation temperature T_α1It is viscous that dynamic is carried out for 137 DEG C or more of methacrylic resins (M1) and at stretch mode, 1Hz α relaxation temperature T when elasticity measurement_α2For the methacrylic resin group of 132 DEG C of methacrylic resins (M2) below Object is closed,

By methacrylic resin (M1) and methacrylic resin (M2) at 260 DEG C, shear velocity 122 seconds^-1 Under melt viscosity be set to η₁And η₂When, η₁> η₂,

Methacrylic resin (M1)/methacrylic resin (M2) mass ratio is 2/98~29/71.

[2] methacrylic resin composition as described in [1], wherein the molecule of methacrylic resin (M1) Amount distribution (Mw/Mn) is 1.0~1.4.

[3] methacrylic resin composition as described in [1] or [2], wherein methacrylic resin (M1) Weight average molecular weight (Mw) is 40000~200000.

[4] methacrylic resin composition as described in any one of [1]~[3], wherein methacrylic tree The content of the methyl methacrylate monomer unit of rouge (M2) is 99 mass % or more.

[5] methacrylic resin composition as described in any one of [1]~[4], wherein further contain poly- carbon Acid ester resin (PC) and/or phenoxy resin (PR).

[6] methacrylic resin composition as described in any one of [1]~[5], wherein further containing crosslinking Rubber (CR) and/or block copolymer (BP).

[7] methacrylic resin composition as described in any one of [1]~[6], wherein further containing ultraviolet Light absorbers (LA).

[8] a kind of manufacturing method of methacrylic resin composition, wherein by methacrylic resin (M1) with Methacrylic resin (M2) with methacrylic resin (M1)/methacrylic resin (M2) mass ratio 2/98~ 29/71 carries out melting mixing, and methacrylic resin (M1) carries out α when Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz Relaxation temperature T_α1It is 137 DEG C or more, methacrylic resin (M2) carries out Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz When α relaxation temperature T_α2For 132 DEG C hereinafter,

By methacrylic resin (M1) and methacrylic resin (M2) at 260 DEG C, shear velocity 122 seconds^-1 Under melt viscosity be set as η₁And η₂When, η₁> η₂。

[9] a kind of formed body, the methacrylic resin composition described in any one of [1]~[7] are constituted.

[10] a kind of film, the methacrylic resin composition described in any one of [1]~[7] are constituted.

[11] film as described in [10] is stretched film.

[12] a kind of stacked film has the layer being made of the film of [10] or [11].

[13] stacked film as described in [12], wherein further there is the layer being made of metal and/or metal oxide.

[14] stacked film as described in [12] or [13], wherein further there is adhesive layer.

[15] one kind is laminated into body, and stacked film described in any one of [12]~[14] is laminated on substrate.

In the present specification, " α relaxation temperature (T_α) ", " melt viscosity (η) ", " weight average molecular weight (Mw) " and " molecular weight Method that distribution (Mw/Mn) " is recorded in item by [embodiment] measures.

Invention effect

In accordance with the invention it is possible to provide the forming that hot forming can be obtained well and there is high-dimensional stability to heat The methacrylic resin composition and its manufacturing method of body.

Specific embodiment

" methacrylic resin composition "

Methacrylic resin composition of the invention contains carries out Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz When α relaxation temperature T_α1It is viscous that dynamic is carried out for 137 DEG C or more of methacrylic resins (M1) and at stretch mode, 1Hz α relaxation temperature T when elasticity measurement_α2For 132 DEG C of methacrylic resins (M2) below.

In the present specification, " α relaxation temperature (T_α) " refer to relaxation (α relaxation caused by the sub-chain motion because of main polymer chain Henan) summit temperature.α relaxation temperature (T_α) method that can record in the item by [embodiment] measures.

It should be noted that it is generally acknowledged that the glass transition temperature (Tg) and α relaxation temperature (T that are found out by DSC curve_α) Between it is related, but in the present invention, replace α relaxation temperature (T without using Tg_α) it is used as index.

(methacrylic resin (M1))

Methacrylic resin (M1) if at stretch mode, sine wave 1Hz carry out Measurement of Dynamic Viscoelasticity when α Relaxation temperature T_α1It is then not particularly limited for 137 DEG C or more.Methacrylic resin (M1) can be used it is one or two kinds of with On.Methacrylic resin (M1) contains more than one the methacrylic acid such as methyl methacrylate (MMA) monomeric unit Ester monomer unit.It as methacrylate, can enumerate: the methyl such as MMA, ethyl methacrylate and butyl methacrylate Alkyl acrylate；The arylmethacrylates such as phenyl methacrylate；Ice drops in cyclohexyl methacrylate and methacrylic acid Cycloalkyl methacrylates such as piece alkenyl esters etc..Wherein, preferably alkyl methacrylate, most preferably MMA.

The content of methacrylate monomers unit in methacrylic resin (M1) is preferably 20 mass % or more, More preferably 50 mass % or more.As methacrylic resin (M1), it can enumerate containing MMA monomeric unit and improve α Relaxation temperature (T_α) monomeric unit methacrylic acid based copolymer (A1), containing MMA monomeric unit and main chain there is ring knot The high first of the degree of syndiotacticity (rr) of methacrylic acid based copolymer (A2) He Yisan unit group meter of the structural unit of structure Base acrylic resin (A3) etc..

< methacrylic acid based copolymer (A1) >

As the raising α relaxation temperature (T in methacrylic acid based copolymer (A1)_α) monomeric unit, can enumerate come Derived from methacrylic acid 2- isobornyl thiocyanoacetate, methacrylic acid 8- tricyclic [5.2.1.0^2,6] last of the ten Heavenly stems ester, methacrylic acid 2- norbornyl ester With the cycloalkyl methacrylates such as methacrylic acid 2- Buddha's warrior attendant alkyl ester；Acrylic acid and methacrylic acid etc. (methyl) acrylic acid Class；(methyl) third such as acrylamide, Methacrylamide, N- methyl methacrylamide and N, N- dimethylmethacryl amide The structural unit of the monomers such as acrylamide.

< methacrylic acid based copolymer (A2) >

There is the structural unit of ring structure as the main chain in methacrylic acid based copolymer (A2), preferably comprise lactonic ring Unit, maleic anhydride units, glutaric anhydride unit, glutarimide unit, N- substituted maleimide amine unit or oxinane Structural unit of the ring element as ring structure.As the manufacturing method of methacrylic acid based copolymer (A2), it can enumerate: make horse Come the side of the copolymerization such as the cyclic monomer and MMA with polymerism unsaturation carbon-to-carbon double bond such as acid anhydrides and N- substituted maleimide amine Method；Make the method etc. that intramolecular cyclization is carried out by a part for the strand for polymerizeing obtained methacrylic resin.

The content of the MMA monomeric unit of methacrylic acid based copolymer (A2) is preferably 20~99 mass %, more preferably 30~95 mass %, particularly preferably 40~90 mass %, it is preferably 1~80 that main chain, which has the content of the structural unit of ring structure, Quality %, more preferably 5~70 mass %, particularly preferably 10~60 mass %.It should be noted that metha crylic is total The content of MMA monomeric unit in polymers (A2), which does not include in MMA monomeric unit, is converted into main chain tool by intramolecular cyclization The monomeric unit of the structural unit of circular structure.

There is the structural unit of ring structure as main chain, the structure list of > CH-O-C (=O)-base is contained preferably in ring structure Contain-C (=O)-N-C (=O)-base in structural unit, ring structure in member, ring structure containing-C (=O)-O-C (=O)-base Structural unit or ring structure in the structural unit containing > CH-O-CH < base.

As in ring structure contain > CH-O-C (=O)-base structural unit, can enumerate beta-propiolactone diyl (alias: Oxo oxetanes diyl) structural unit, gamma-butyrolacton diyl (alias: 2- oxo-dihydro furans diyl) structural unit and The lactones diyl structural units such as δ-valerolactone diyl (alias: 2- oxo-dihydro pyrans diyl) structural unit.It should be noted that " > C " in formula refers to that there are two be bonded hand for tool on carbon atom C.

As δ-valerolactone diyl structural unit, structural unit represented by following formula (I)s can be enumerated.

In formula (I), R¹⁴And R¹⁵It is each independently the organic residue of hydrogen atom or carbon atom number 1~20, preferably R¹⁴For hydrogen Atom, R¹⁵For methyl.R¹⁶It is the organic residue of hydrogen atom or carbon atom number 1~20, preferably methyl for-COOR, R." * " is Digital closes hand.

As above-mentioned organic residue, the alkyl of straight or branched, the alkylidene of straight or branched, virtue can be enumerated Base ,-OAc base and-CN base etc..Organic residue can contain oxygen atom." Ac " indicates acetyl group.The carbon atom number of organic residue is excellent It is selected as 1~10, more preferably 1~5.

δ-valerolactone diyl structural unit can pass through the intramolecular cyclization etc. of two MMA monomeric units adjacent to each other Containing in methacrylic resin.

As the structural unit for containing-C (=O)-O-C (=O)-base in ring structure, 2,5- dioxo dihydro can be enumerated Two based structures of furans diyl structural unit, 2,6- dioxo dihydropyran diyl structural unit and 2,7- dioxo oxepane Unit etc..

As 2,5- dioxo dihydrofuran diyl structural unit, structure list represented by following formula (II)s can be enumerated Member.

In formula (II), R²¹And R²²It is each independently the organic residue of hydrogen atom or carbon atom number 1~20." * " is digital Close hand.

R²¹And R²²Both preferably hydrogen atom.In this case, from the viewpoints such as ease of manufacturing and intrinsic birefringent adjusting Consider, it is usually preferred to which copolymerization has styrene etc..Specifically, can enumerate recorded in International Publication No. 2014/021264 etc. , copolymer with styrenic monomer units, MMA monomeric unit and maleic anhydride monomer units.

2,5- dioxo dihydrofuran diyl structural unit can be by using copolymerization of maleic anhydride etc. and containing in first In base acrylic resin.

As 2,6- dioxo dihydropyran diyl structural unit, structure list represented by following formula (III)s can be enumerated Member.

In formula (III), R³³And R³⁴It is each independently the organic residue of hydrogen atom or carbon atom number 1~20." * " refers to It is bonded hand.

As above-mentioned organic residue, the alkyl of straight or branched, the alkylidene of straight or branched, virtue can be enumerated Base ,-OAc base and-CN base etc..Organic residue can contain oxygen atom." Ac " indicates acetyl group.The carbon atom number of organic residue is excellent It is selected as 1~10, more preferably 1~5, particularly preferably methyl.

2,6- dioxo dihydropyran diyl structural unit can pass through the molecule inner ring of two MMA monomers adjacent to each other Change etc. and containing in methacrylic resin.

As the structural unit in ring structure containing-C (=O)-N-C (=O)-base (it should be noted that possessed by N Label is omitted in another bonding hand), 2,5- dioxo pyrrolidin diyl structural unit, 2,6- dioxopiperidine two can be enumerated Based structures unit and 2,7- dioxo a word used for translation ring in heptan diyl structural unit etc..

As 2,6- dioxopiperidine diyl structural unit, structural unit represented by following formula (IV)s can be enumerated.

In formula (IV), R⁴¹And R⁴²It is each independently the alkyl of hydrogen atom or carbon atom number 1~8, R⁴³For hydrogen atom, carbon The aryl of the alkyl of atomicity 1~18, the naphthenic base of carbon atom number 3~12 or carbon atom number 6~10." * " refers to bonding hand.

The viewpoints consideration such as easiness, cost and heat resistance obtained from raw material, preferably R⁴¹And R⁴²It is each independently hydrogen original Son or methyl, more preferable R⁴¹For methyl, R⁴²For hydrogen atom.R⁴³Preferably hydrogen atom, methyl, normal-butyl, cyclohexyl or benzyl, More preferably methyl.

As 2,5- dioxo pyrrolidin diyl structural unit, structural unit represented by following formula (V)s can be enumerated.

In formula (V), R⁵²And R⁵³It is each independently hydrogen atom, the alkyl of carbon atom number 1~12 or carbon atom number 6~14 Alkyl.R⁵¹For the aryl alkyl of carbon atom number 7~14 or the virtue of unsubstituted or carbon atom number 6~14 with substituent group Base.Substituent group described herein is halogen group, hydroxyl, nitro, the alkoxy of carbon atom number 1~12, carbon atom number 1~12 The aryl alkyl of alkyl or carbon atom number 7~14." * " refers to bonding hand.R⁵¹Preferably phenyl or cyclohexyl, R⁵²And R⁵³It is excellent It is selected as hydrogen atom.

2,5- dioxo pyrrolidin diyl structural unit can be contained by using copolymerization of N- substituted maleimide amine etc. Have in methacrylic resin.

As the structural unit containing > CH-O-CH < base in ring structure, two based structures list of oxetanes can be enumerated Member, tetrahydrofuran diyl structural unit, oxinane diyl structural unit and oxepane diyl structural unit etc..It needs Bright, " > C " in formula refers to that there are two be bonded hand for tool on carbon atom C.

As oxinane diyl structural unit, structural unit represented by following formula (VI)s can be enumerated.

In formula (VI), R⁶¹And R⁶²It is each independently the hydrocarbon of hydrogen atom, the straight-chain of carbon atom number 1~20 or branched The alkyl of base or the carbon atom number 3~20 with ring structure." * " refers to bonding hand.As R⁶¹And R⁶², preferably respectively independent Ground is tricyclic [5.2.1.0^2,6] decyl, bicyclic [2.2.1] heptane -3- base of 1,7,7- trimethyl, tert-butyl and 4- t-butylcyclohexyl Alkynyl.

Above-mentioned main chain has in the structural unit of ring structure, from the viewpoint of raw material and ease of manufacturing, preferably δ- Valerolactone diyl structural unit and 2,5- dioxo dihydrofuran diyl structural unit.

(weight average molecular weight (Mw) is relative to several average marks for the molecular weight distribution of methacrylic acid based copolymer (A1) and (A2) Ratio, the Mw/Mn of son amount (Mn)) it is preferably 1.2~5.0, more preferably 1.3~3.5.Mw/Mn is lower, then have it is obtained at The better tendency of the impact resistance and toughness of body.Mw/Mn is higher, then with the melting of methacrylic resin composition The better tendency of the surface smoothness of higher, the obtained formed body of mobility.

In the present specification, Mw and Mn is that the chromatogram measured by gel permeation chromatography (GPC) is converted into standard The value of the molecular weight of polystyrene.Method that Mw and Mw/Mn can be recorded in the item by [embodiment] measures.

The glass transition temperature (Tg) of methacrylic acid based copolymer (A2) is preferably 120 DEG C or more, more preferably 123 DEG C or more, particularly preferably 124 DEG C or more.The upper limit of the Tg of methacrylic acid based copolymer (A2) is preferably 160 DEG C.

In the present specification, glass transition temperature (Tg) be more than room temperature at a temperature of carried out according to JISK7121 Measurement.Until 230 DEG C, implemented heating for the first time (operation (1st-run) for the first time) with 10 DEG C/min of heating rate, it is cold But to after room temperature, from room temperature until 230 DEG C, second of heating is implemented with 10 DEG C/min of heating rate and (is run for second (2nd-run)).The intermediate point glass transition temperature of second of operation is found out as Tg.

< methacrylic resin (A3) >

The degree of syndiotacticity (rr) in terms of three unit groups of methacrylic resin (A3) is 65% or more, preferably It is 70~90%, more preferably 72~85%.In the case where degree of syndiotacticity (rr) is 65% or more, α relaxation temperature (T_α) significantly improve, the surface hardness of obtained formed body significantly improves.

The molecular weight distribution (Mw/Mn) of methacrylic resin (A3) is preferably 1.0~1.8, more preferably 1.0~ 1.4, particularly preferably 1.03~1.3.Use the methacrylic resin with the molecular weight distribution (Mw/Mn) within the scope of this (A3) when, the mechanical strength of obtained methacrylic resin composition is excellent.Mw and Mw/Mn can be by adjusting manufacture When the type of polymerization initiator that uses and/or amount controlled.

Methacrylic resin (M1) can contain methacrylic acid based copolymer (A1), (A2) and methacrylic Cited monomeric unit other more than one monomeric unit other than the above in resin (A3).As other monomers unit, It can enumerate from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-EHA etc. Alkyl acrylate；The aryl acrylates such as phenyl acrylate；The acrylic acid such as cyclohexyl acrylate and acrylic acid norbornene base ester Cycloalkyl ester；The aromatic ethenyl compounds such as styrene and α-methylstyrene；Nitriles such as acrylonitrile and methacrylonitrile etc. Only there is the structural unit of the vinyl monomer of a polymerism carbon-to-carbon double bond in a molecule.

The Mw of methacrylic resin (M1) is preferably 40000~200000, and more preferably 40000~150000, it is special It You Xuanwei 50000~120000.Mw be 40000 or more when, with obtained formed body mechanical strength (impact resistance and Toughness etc.) improve tendency, Mw be 200000 or less when, with methacrylic resin composition mobility improve, at The tendency that shape improves.

The melt flow rate (MFR) of methacrylic resin (M1) measured under conditions of 230 DEG C and 3.8kg load It (MFR) is preferably 0.1g/10 minutes or more, more preferably 0.2~30g/10 minutes, particularly preferably 0.5~20g/10 minutes, Most preferably 1.0~15g/10 minutes.

Methacrylic resin (M1) can pass through radical polymerization and anionic polymerization polymerization well known in this way Method manufactures.It should be noted that can choose mass polymerization, solution polymerization process as radical polymerization, suspending and gather The polymerizations such as legal and emulsion polymerization can choose mass polymerization and solution polymerization process etc. as anionic polymerization Polymerization.

Radical polymerization can be solvent-free lower or in a solvent carry out, from obtaining the methacrylic acid of low impurity concentration From the viewpoint of resinoid (M1), preferably in solvent-free lower progress.From the viewpoint of the crazing or coloring for inhibiting formed body, Polymerization reaction is preferably reducing dissolved oxygen content and is carrying out under the inactive gas atmospheres such as nitrogen.

As polymerization initiator used in radical polymerization, tert-hexyl peroxide isopropyl single carbon acid can be enumerated Ester, tert-hexyl peroxide 2 ethyl hexanoic acid ester, 1,1,3,3- tetramethyl butyl peroxidating 2 ethyl hexanoic acid ester, tert-butyl hydroperoxide Pivalate, tert-hexyl peroxide pivalate, tert-butyl hydroperoxide neodecanoic acid ester, tert-hexyl peroxide neodecanoic acid ester, 1,1, Bis- (tert-hexyl peroxide) hexamethylenes of 3,3- tetramethyl butyl new decanoate ester peroxide, 1,1-, benzoyl peroxide, peroxidating 3, 5,5- trimethyl acetyl, lauroyl peroxide, 2,2 '-azos bis- (2- methyl propionitrile), 2,2 '-azos bis- (2- methylbutyronitriles) and Dimethyl 2,2 '-azo bis- (2 Methylpropionic acid esters) etc..Wherein, preferred bis- (uncles of tert-hexyl peroxide 2 ethyl hexanoic acid ester, 1,1- Hexyl peroxidating) hexamethylene and dimethyl 2,2 '-azo it is bis- (2 Methylpropionic acid ester).One kind or two can be used in polymerization initiator Kind or more.

1 hour half life temperature of polymerization initiator is preferably 60~140 DEG C, and more preferably 80~120 DEG C.Polymerization causes The hydrogen-taking capacity of agent is preferably 20% hereinafter, more preferably 10% hereinafter, particularly preferably 5% or less.Polymerization initiator makes Dosage is relative to being preferably 0.0001~0.02 mass parts by more than one 100 mass parts of monomer for polymerization reaction, more Preferably 0.001~0.01 mass parts, particularly preferably 0.005~0.007 mass parts.

It should be noted that hydrogen-taking capacity can be by the technical data of polymerization initiator manufacturer (for example, Japanese grease The technical data " hydrogen-taking capacity and efficiency of initiator of organic peroxide " (in April, 2003 is made) of Co., Ltd.) etc. know. Furthermore it is possible to by using α-methylstyrenedimer free radical capture method (α-methylstyrenedimer prize law) into Row measurement.The measurement usually carries out in the following manner.Firstly, in the α-methylstyrenedimer as radical scavenger Coexisting down makes polymerization initiator crack and generate free radical segment.The low free substrate of hydrogen-taking capacity in the free radical segment of generation Section and the double bond addition of α-methylstyrenedimer and be captured.On the other hand, the high free radical segment of hydrogen-taking capacity is from ring Take hydrogen in hexane by force, make cyclohexyl free radical generate, the double bond addition of the cyclohexyl free radical and α-methylstyrenedimer and It is captured, it generates hexamethylene and captures product.Therefore, it will be found out by being captured and product quantifies to hexamethylene or hexamethylene , ratio (molar percentage) conduct that the free radical segment that hydrogen-taking capacity is high is relative to theoretic free radical segment yield Hydrogen-taking capacity is found out.

As chain-transferring agent used in radical polymerization, n octylmercaptan, n-dodecyl mercaptan, uncle can be enumerated The double thiopropionates of lauryl mercaptan, 1,4- succinimide mercaptans, 1,6- ethanthiol, ethylene glycol, the double thioglycolic acids of butanediol The double thiopropionates of ester, butanediol, the double thioglycolic acid esters of hexylene glycol, hexylene glycol double thiopropionates, trimethylolpropane tris- Alkyl sulfides alcohols such as (β-thiopropionate) and pentaerythrite tetrathio propionic ester etc..Wherein, preferred n octylmercaptan and positive ten The monofunctional alkyls mercaptan such as dialkyl group mercaptan.One or more can be used in chain-transferring agent.

From the viewpoint of the formability of resin and the mechanical strength of formed body, the usage amount of chain-transferring agent is relative to being supplied In more than one 100 mass parts of monomer of polymerization reaction be preferably 0.01~1 mass parts, more preferably 0.05~0.8 mass Part, particularly preferably 0.1~0.6 mass parts, most preferably 0.10~0.5 mass parts.The usage amount of chain-transferring agent is relative to poly- Closing 100 mass parts of initiator is preferably 2500~10000 mass parts, more preferably 3000~9000 mass parts, particularly preferably 3500~6000 mass parts.

As solvent used in radical polymerization, the preferably aromatic hydrocarbons such as benzene, toluene and ethylbenzene.Solvent can be used It is one or more kinds of.From the viewpoint of the viscosity and productivity of reaction solution, the usage amount of solvent is relative to polymerization reaction original Expect that 100 mass parts are preferably that 100 below the mass, more preferably 90 below the mass.

Polymeric reaction temperature is preferably 100~200 DEG C, and more preferably 110~180 DEG C.By making 100 DEG C of polymerization temperature More than, there is the tendency for improving productivity by the raising of polymerization speed and the lowering viscousity of polymer fluid.By making to polymerize Temperature is 200 DEG C hereinafter, the control of polymerization speed becomes easy, and then the generation of by-product is inhibited, and is able to suppress resin Coloring.From the viewpoint of production efficiency, polymerization reaction time is preferably 0.5~4 hour, and more preferably 1.5~3.5 is small When, particularly preferably 1.5~3 hours.It should be noted that the polymerization reaction time in the case where continuous flow general formula reaction unit For the mean residence time in reactor.

Polymerisation conversion in radical polymerization is preferably 20~80 mass %, more preferably 30~70 mass %, special It You Xuanwei not 35~65 mass %.By making 20 mass % of polymerisation conversion or more, removing with remaining unreacted monomer It goes to become easy, the appearance of obtained formed body becomes good tendency.By making 70 mass % of polymerisation conversion hereinafter, The tendency that viscosity, productivity with polymer fluid improve.

Reaction unit can be any one in intermittent reaction device and continuous flow general formula reaction unit, from productivity From the viewpoint of, preferred continuous flow general formula reaction unit.In the reaction of continuous flow general formula, prepared under the torpescence atmosphere such as nitrogen Polymerization reaction raw material (mixed liquor of monomer, polymerization initiator and chain-transferring agent containing more than one etc.), by it with a constant current Amount supply into reactor, with the liquid in the comparable flow extraction device of supply amount.As reactor, energy can be enumerated Enough tube-type reactors for forming the state for being similar to plug flow or the tank reactor for being capable of forming the state for being similar to be thoroughly mixed. The quantity of reactor can be one or two or more, preferably at least one tank reactor using continuous flow general formula.Polymerization The liquid measure in tank reactor when reaction is preferably 1/4~3/4 relative to the volume of tank reactor, more preferably 1/3~ 2/3.Agitating device is usually mounted in reactor.As agitating device, static agitation device and dynamic agitation dress can be enumerated It sets.As dynamic agitation device, MAXBLEND formula agitating device can be enumerated, in the longitudinal type rotary shaft rotation for being configured at center Agitating device, propeller device and the screw agitating device of latticed blade etc. turned.Wherein, from uniform Combination From the viewpoint of, preferred MAXBLEND formula agitating device.

After polymerization, the volatile ingredients such as unreacted monomer are removed as needed.As the method for removing, preferably heating is de- Wave method.As devolatilization mode, equilibrium flash mode and adiabatic flash mode can be enumerated.Devolatilization temperature based on adiabatic flash mode Preferably 200~280 DEG C, more preferably 220~260 DEG C of degree.The heating time of resin in adiabatic flash mode is preferably 0.3 ~5 minutes, more preferably 0.4~3 minute, particularly preferably 0.5~2 minute.It is taken off with the temperature range and heating time When waving, it is easy to get and colours few methacrylic resin (M1).The unreacted monomer of removing can be by recycling again For polymerization reaction.Increase due to the heat that the yellow colour index of the monomer of recycling is applied when reclaimer operation etc. sometimes.The list of recycling Body is preferably purified by method appropriate to reduce yellow colour index.

As the control method of molecular weight distribution (Mw/Mn), control polymerization, preferably active free radical polymerization can be enumerated Method and active anionic polymerization.As living radical polymerization, atom transfer radical polymerization (ATRP) method can be enumerated, can Inverse addition fracture chain transfer polymerization (RAFT) method, NO free radical regulation polymerization (NMP) method, boron regulation polymerization and catalyst turn Move polymerization (CCT) method etc..It as (activity) anionic polymerization, can enumerate: use organic alkali metal compound as polymerization Initiator carries out the method for anionic polymerisation (with reference to Japan in the presence of the inorganic acid salts such as the salt of alkali or alkaline earth metal Fairness 7-25859 bulletin)；Use organic alkali metal compound as polymerization initiator, in the presence of organo-aluminum compound The lower method (referring to Japanese Unexamined Patent Publication 11-335432 bulletin) for carrying out anionic polymerisation；With use organic RE metalloid network Close the method (referring to Japanese Unexamined Patent Publication 6-93060 bulletin) etc. that object carries out anionic polymerisation as polymerization initiator.

As polymerization initiator used in anionic polymerization, preferably n-BuLi, s-butyl lithium, isobutyl group lithium and uncle The lithium alkylides such as butyl lithium.From the viewpoint of productivity, organo-aluminum compound preferably coexists.

It, can be with enumeration: AlR as organo-aluminum compound¹R²R³Represented compound (in formula, R¹~R³It is respectively independent Ground indicates unsubstituted or the alkyl with substituent group, naphthenic base that is unsubstituted or can having substituent group, unsubstituted or tool The aryl of substituted base, unsubstituted or alkoxy with substituent group, does not take unsubstituted or aralkyl with substituent group Generation or with substituent group aryloxy group or N, N- disubstituted amido.R²And R³Can be they be bonded made of, it is unsubstituted Or two oxygroup of arlydene with substituent group).

As organo-aluminum compound, isobutyl group bis- (2,6- di-t-butyl -4- methylphenoxy) aluminium, isobutyl group can be enumerated Bis- (2,6- di-t-butyl phenoxy group) aluminium and isobutyl group [2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert butyl phenoxy)] aluminium etc..

In anionic polymerization, in order to control polymerization reaction, ether and nitrogenous compound etc. can also be made to coexist.

(methacrylic resin (M2))

Methacrylic resin (M2) if at stretch mode, sine wave 1Hz carry out Measurement of Dynamic Viscoelasticity when α Relaxation temperature T_α2It is then not particularly limited for 132 DEG C or less.Methacrylic resin (M2) can be used it is one or two kinds of with On.Methacrylic resin (M2) contains more than one the methacrylate monomers unit such as MMA monomeric unit.As first Base acrylate can be enumerated: the alkyl methacrylates such as MMA, ethyl methacrylate and butyl methacrylate；Methyl The arylmethacrylates such as phenyl acrylate；The metering systems such as cyclohexyl methacrylate, norbornyl alkenyl esters Sour cycloalkyl ester etc..Wherein, preferably alkyl methacrylate, most preferably MMA.

The content of methacrylate monomers unit in methacrylic resin (M2) is preferably 90 mass % or more, More preferably 95 mass % or more, further preferably 98 mass % or more, particularly preferably 99 mass % or more, most preferably 100 mass %.

The content of MMA monomeric unit in methacrylic resin (M2) is preferably 90 mass % or more, more preferably 95 mass % or more, further preferably 98 mass % or more, particularly preferably 99 mass % or more, most preferably 100 matter Measure %.

Methacrylic resin (M2) can containing other other than methacrylate monomers unit more than one Monomeric unit.As other monomers unit, can enumerate from methyl acrylate, ethyl acrylate, propyl acrylate, propylene The alkyl acrylates such as acid butyl ester and 2-EHA；The aryl acrylates such as phenyl acrylate；Cyclohexyl acrylate and The acrylates base esters such as acrylic acid norbornene base ester；The aromatic ethenyl compounds such as styrene and α-methylstyrene； Acrylamide and Methacrylamide；Nitriles such as acrylonitrile and methacrylonitrile etc. only have a polymerism in a molecule The structural unit of the vinyl monomer of carbon-to-carbon double bond.

The Mw of methacrylic resin (M2) is preferably 40000~200000, and more preferably 50000~150000, it is special It You Xuanwei 50000~120000.By making 40000 or more Mw, the mechanical strength (impact resistance with obtained formed body Property and toughness etc.) tendency that improves, by making Mw 200000 hereinafter, having the mobility of methacrylic resin composition It improves, the tendency that formability improves.

The molecular weight distribution (Mw/Mn) of methacrylic resin (M2) is preferably 1.6~5.0, more preferably 1.7~ 4.0, particularly preferably 1.7~3.0.Use the methacrylic resin with the molecular weight distribution (Mw/Mn) within the scope of this (M2), the mechanical strength of obtained formed body is excellent.Mw and Mw/Mn can be by adjusting methacrylic resin (M2) The type and/or amount of the polymerization initiator used when manufacture is controlled.

The melt flow rate (MFR) of methacrylic resin (M2) measured under conditions of 230 DEG C and 3.8kg load It (MFR) is preferably 0.1g/10 minutes or more, more preferably 0.2~30g/10 minutes, particularly preferably 0.5~20g/10 minutes, Most preferably 1.0~15g/10 minutes.

As the manufacturing method of methacrylic resin (M2), from the viewpoint of productivity, preferably free radical polymerization Polymerization temperature, polymerization time, the type of chain-transferring agent and/or amount, the type of polymerization initiator and/or amount etc. are adjusted in method Whole method.Radical polymerization it is detailed as previously described.

(mass ratio)

In methacrylic resin composition of the invention, methacrylic resin (M1)/methacrylic tree The mass ratio of rouge (M2) is 2/98~29/71, preferably 5/95~28/72, particularly preferably 10/90~25/75.α relaxation temperature Spend (T_α) heat resistance of resin combination can be improved in high, resistance to pyrolytic is low methacrylic resin (M1).But α relaxes Henan temperature (T_α) high methacrylic resin (M1) it is excessive when, the viscosity of resin combination when forming increases, formability It is deteriorated.In addition, α relaxation temperature (T_α) high methacrylic resin (M1) resistance to pyrolytic it is low, therefore, amount is excessive When, it decomposes, blister in hot forming, the appearance of obtained formed body is also possible to be deteriorated.Methacrylic tree When rouge (M1) is very few, it cannot get the desired dimensional stability to heat.α relaxation temperature (T_α) low methacrylic resin (M2) formability of resin combination can be improved.When making the mass ratio above range of methacrylic resin (M1), (M2), The methacrylic resin group of the available high-dimensional stability to heat for taking into account good hot forming and formed body Close object.

In methacrylic resin composition of the invention, by methacrylic resin (M1) and methacrylic Resin (M2) at 260 DEG C, shear velocity 122 seconds^-1Under melt viscosity be set to η₁And η₂When, η₁> η₂.By making α relax The melt viscosity η of the Henan temperature methacrylic resin (M1) higher than methacrylic resin (M2)₁Higher than metering system The melt viscosity η of acid resin (M2)₂, in the forming of methacrylic resin composition, methacrylic resin (M1) it is easy to be orientated and be not easy relaxation, therefore, obtained formed body can show good mechanical strength and high ruler Very little stability.It should be noted that even if the content ratio of methacrylic resin (M1) seldom can show the work Use effect.

Methacrylic resin (M1) in methacrylic resin composition of the invention, the total amount of (M2) are excellent It is selected as 80 mass % or more, more preferably 85 mass % or more, particularly preferably 90 mass % or more, most preferably 92 mass % More than.

Only it is preferably by the Mw of methacrylic resin (M1), (M2) methacrylic resin composition constituted 50000~200000, more preferably 52000~150000, particularly preferably 55000~120000, molecular weight distribution (Mw/Mn) Preferably 1.2~2.0, more preferably 1.3~1.8.Mw and molecular weight distribution (Mw/Mn) in the range when, methacrylic acid The formability of based resin composition becomes well to be easy to get the excellent formed body of mechanical strength (impact resistance and toughness etc.).

Only by methacrylic resin (M1), (M2) methacrylic resin composition constituted at 230 DEG C and The melt flow rate (MFR) (MFR) measured under conditions of 3.8kg load is preferably 0.1g/10 minutes or more, more preferably 0.2~ 30g/10 minutes, particularly preferably 0.5~20g/10 minutes, most preferably 1.0~10g/10 minutes.

(other polymers)

Methacrylic resin composition of the invention can according to need containing methacrylic resin (M1), (M2) more than one the other polymers other than.It should be noted that other polymers can be in methacrylic resin (M1) and/or when the polymerization of methacrylic resin (M2) or after polymerization it adds, it can also be in methacrylic resin (M1), it is added when the mixing of (M2).

It as other polymers, can enumerate: polyethylene, polypropylene, PB Polybutene-1, poly- 4- methylpentene -1 and poly- drop The polyolefin resins such as bornylene；Ethylene system ionomer；Polystyrene, styrene-maleic anhydride copolymer, high-impact polyphenyl second The phenylethylene resin series such as alkene, AS resin, ABS resin, AES resin, AAS resin, ACS resin and MBS resin；Poly terephthalic acid The polyester resin such as glycol ester and polybutylene terephthalate (PBT)；The polyamide such as nylon 6, nylon66 fiber and polyamide elastomer Resin；Polycarbonate；Polyvinyl chloride, Vingon, Kynoar, polyvinyl alcohol, polyvinyl butyral, polyvinyl alcohol Acetal, polyvinylphenol and ethylene-vinyl alcohol copolymer；Polyacetals；Polyurethane；Noryl and polyphenylene sulfide；Have Machine Si modification resin；Acrylic rubber, acrylic acid series thermoplastic elastomer (TPE) and organic silicon rubber；The benzene second such as SEPS, SEBS and SIS Alkene based thermoplastic elastomer；Olefin-baseds rubber such as IR, EPR and EPDM etc..In methacrylic resin composition of the invention The amounts of other polymers be preferably 10 mass % hereinafter, more preferably 5 mass % are hereinafter, particularly preferably 0 mass %.

(a preferred mode)

In a preferred mode, methacrylic resin composition of the invention can contain methacrylic Resin (M1), (M2) and polycarbonate resin (PC) and/or phenoxy resin (PR).Polycarbonate resin (PC) and phenoxy group One or more can be used in resin (PR).By containing polycarbonate resin (PC) and/or phenoxy resin (PR), It can obtain the easy methacrylic resin composition of adjustment of phase difference.Polycarbonate resin (PC) and/or phenoxy group The amount of resin (PR) is preferably 1.0~10 mass relative to 100 mass parts of total amount of methacrylic resin (M1), (M2) Part, more preferably 1.5~7 mass parts, particularly preferably 2.0~6 mass parts.

< polycarbonate resin (PC) >

As polycarbonate resin (PC), can enumerate through multifunctional hydroxy compounds and carbonic ester formative compound The obtained polymer of reaction.From the viewpoint of the transparency of compatibility and obtained formed body with methacrylic resin Consider, optimization aromatic polycarbonate resin.

From viewpoints such as the transparency, the surface smoothnesss of compatibility and obtained formed body with methacrylic resin Consider, the melt volume-flow rate (MVR) of polycarbonate resin (PC) measured under conditions of 300 DEG C and 1.2Kg load Preferably 130~250cm³/ 10 minutes, more preferably 150~230cm³/ 10 minutes, particularly preferably 180~220cm³/ 10 points Clock.

It is seen from the transparency of compatibility and obtained formed body with methacrylic resin and surface smoothness etc. Point considers that the Mw of the polystyrene conversion of polycarbonate resin (PC) is preferably 15000~28000, more preferably 18000~ 27000, particularly preferably 20000~24000.

It should be noted that the MVR and Mw of polycarbonate resin (PC) can be by adjusting end-capping reagent and/or branching agents Amount is to be controlled.

The Tg of polycarbonate resin (PC) is preferably 130 DEG C or more, more preferably 135 DEG C or more, particularly preferably 140 DEG C More than.The upper limit of Tg is usually 180 DEG C.

As the manufacturing method of polycarbonate resin (PC), phosgenation (interfacial polymerization) and melt phase polycondensation can be enumerated (ester-interchange method) etc..Aromatic polycarbonate resin can be by the polycarbonate resin fat raw material using melt phase polycondensation manufacture Implement the processing of adjustment terminal hydroxyl amount to manufacture.

Polycarbonate resin (PC) can also contain polyester, polyurethane, gather other than containing polycarbonate structural units The other structures unit such as ether or polysiloxanes.

< phenoxy resin (PR) >

Phenoxy resin (PR) is thermoplasticity polyhydroxy polyether resin.Phenoxy resin (PR) can containing 50 mass % with On following formula (1) represented by more than one structural unit.

In formula (1), X is the bivalent group containing at least one phenyl ring, and R is the Asia of the linear chain or branched chain of carbon atom number 1~6 Alkyl.Structural unit represented by formula (1) can be connected in the form of any one in random, alternating or block.

Phenoxy resin (PR) contains preferably 10~1000,15~500 more preferable, particularly preferred 30~300 formulas (1) structural unit represented by.

From the viewpoint of being easy to get the few formed body of gels defects, phenoxy resin (PR) preferably end does not have ring Oxygroup.

The Mn of the polystyrene conversion of phenoxy resin (PR) is preferably 3000~2000000, more preferably 5000~ 100000, particularly preferably 10000~50000.By making Mn in the range, the first that heat resistance is high, intensity is high can be obtained Base acrylic resin composition.

The Tg of phenoxy resin (PR) is preferably 80 DEG C or more, more preferably 90 DEG C or more, particularly preferably 95 DEG C or more. When the Tg of phenoxy resin (PR) is too low, the heat resistance with methacrylic resin composition reduces tendency.The upper limit of Tg Preferably 150 DEG C.When the Tg of phenoxy resin (PR) is excessively high, the tendency that becomes fragile with obtained formed body.

Phenoxy resin (PR) for example can be by the condensation reaction or dihydric phenolic compounds of dihydric phenolic compounds and epihalohydrins Sudden reaction with two functional epoxy resins obtains.The reaction can carry out under solvent-free or in a solvent.

As dihydric phenolic compounds, quinhydrones, resorcinol, 4,4- dihydroxybiphenyl, 4,4 '-dihydroxy hexichol can be enumerated Bis- (4- hydroxy phenyl) propane of base ketone, 2,2-, 1,1-bis(4-hydroxyphenyl)-cyclohexane, bis- (the 4- hydroxy phenyls) -3,3 of 1,1-, 5- trimethyl-cyclohexane, bis- (4- hydroxy phenyl) methane, bis- (4- hydroxy phenyl) ethane of 1,1-, bis- (4- hydroxy phenyl) fourths of 2,2- Bis- (4- the hydroxy phenyl) -1- diphenylphosphino ethanes of alkane, 1,1-, bis- (4- hydroxy phenyl) diphenyl methanes, the bis- (4- hydroxyl -3- first of 2,2- Base phenyl) propane, bis- (3- phenyl -4- hydroxy phenyl) propane of 2,2-, 2,2- bis- (4- hydroxyl -3- tert-butyl-phenyl) propane, 1, Bis- (2- (4- hydroxy phenyl) propyl) benzene of 3-, bis- (2- (4- hydroxy phenyl) propyl) benzene of 1,4-, bis- (the 4- hydroxy phenyls) -1 of 2,2-, 1,1,3,3,3- hexafluoropropane and 9,9 '-bis- (4- hydroxy phenyl) fluorenes etc..Wherein, from the aspect of physical property and cost, preferably 4, Bis- (4- hydroxy phenyl) propane of 4- dihydroxybiphenyl, 4,4 '-dihydroxydiphenyl ketone, 2,2- and 9,9 '-bis- (4- hydroxy phenyls) Fluorenes.

As two functional epoxy resins' classes, the condensation reaction by above-mentioned dihydric phenolic compounds and epihalohydrins can be enumerated Obtained epoxy oligomer.Specifically, quinhydrones diglycidyl ether, resorcinolformaldehyde resin, bisphenol S can be enumerated Type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, methylnaphthohydroquinone diglycidyl ether, chlorohydroquinone two shrink Glycerin ether, 4,4 '-dihydroxy diphenyl ether diglycidyl ethers, 2,6- dihydroxy naphthlene diglycidyl ether, dichloro bisphenol-A two shrink Glycerin ether and tetrabromobisphenol A type epoxy resin, 9,9 '-bis- (4)-hydroxy phenyls) fluorenes diglycidyl ether etc..Wherein, from physical property From the aspect of cost, preferably bisphenol A type epoxy resin, bisphenol-s epoxy resin, quinhydrones diglycidyl ether, Bisphenol F type ring Oxygen resin, tetrabromobisphenol A type epoxy resin and 9,9 '-bis- (4)-hydroxy phenyls) fluorenes diglycidyl ether.

Solvent used in manufacture as phenoxy resin (PR) can enumerate methyl ethyl ketone, dioxane, tetrahydro The aprotics such as furans, acetophenone, N-Methyl pyrrolidone, dimethyl sulfoxide, DMAC N,N' dimethyl acetamide and sulfolane are organic molten Agent.

Catalyst used in manufacture as phenoxy resin (PR) can enumerate alkali metal hydroxide, tertiary-aminated Close object, quaternary ammonium compound, tertiary phosphine compounds and seasonCompound etc..

X in formula (1) preferably derives from following formula (2)~(4) compound represented bivalent group.It needs to illustrate It is, as long as the chemically possible position in position for constituting two bonding hands of bivalent group is not particularly limited.In formula (1) X be preferably seize two hydrogen atoms from the phenyl ring in formula (2)~(4) compound represented and the tool that is formed there are two bondings The bivalent group of hand.Particularly preferably one is seized respectively from any two phenyl ring in formula (3)~(4) compound represented There are two the bivalent groups of bonding hand for hydrogen atom and the tool that is formed.

In formula (2), R⁴For the straight of hydrogen atom, the alkyl of the linear chain or branched chain of carbon atom number 1~6 or carbon atom number 2~6 The alkenyl of chain or branch.The integer that p is 1~4.

In formula (3), R¹For singly-bound, the alkylidene of the linear chain or branched chain of carbon atom number 1~6, carbon atom number 3~20 sub- ring The secondary naphthenic base (cycloalkylidene) of alkyl (cycloalkylene) or carbon atom number 3~20.In formula (3) and (4), R²And R³Be each independently hydrogen atom, carbon atom number 1~6 linear chain or branched chain alkyl or carbon atom number 2~6 straight chain Or the alkenyl of branch.N and m is each independently 1~4 integer.

In formula (1), X can be the bivalent group of the compound made of multiple phenyl ring and alicyclic ring or heterocyclic condensation. For example, can enumerate from the bivalent group with fluorene structured or carbazole structure compound.

Structural unit represented by formula (1) is preferably following formula (5), structural unit represented by (6), more preferably following Structural unit represented by formula (7).The phenoxy resin (PR) of preferred embodiment preferably comprises 10~1000 structural units.

In formula (5), R⁹For singly-bound, the alkylidene of the linear chain or branched chain of carbon atom number 1~6, carbon atom number 3~20 sub- ring The secondary naphthenic base of alkyl or carbon atom number 3~20.In formula (5) and (6), R¹⁰For the Asia of the linear chain or branched chain of carbon atom number 1~6 Alkyl.

As commercially available phenoxy resin (PR), YP-50 and YP- that the manufacture of aurification company is lived by Nippon Steel can be enumerated 50S, the jER series of Mitsubishi Chemical Ind's manufacture, the PKFE and PKHJ of the manufacture of InChem company etc..

(preferred other modes)

In preferred other modes, methacrylic resin composition of the invention can contain methacrylic Resin (M1), (M2) and crosslinking rubber (CR) and/or block copolymer (BP).It is crosslinked rubber (CR) and block copolymer (BP) One or more can be used.

< is crosslinked rubber (CR) >

Crosslinking rubber (CR) is will be multiple using the cross-linkable monomer in a monomer with multiple polymerizable functional groups Obtained from the macromolecular chain crosslinking, polymer with caoutchouc elasticity.As crosslinking rubber (CR), can enumerate containing acrylic acid The acrylic acid series of alkyl ester monomer unit and cross-linking monomer units is crosslinked rubber, contains conjugated diene monomeric unit and crosslinking Property monomeric unit diene series crosslinking rubber, contain alkyl acrylate monomer units and conjugated diene monomeric unit and crosslinking The crosslinking rubber etc. of property monomeric unit.These crosslinking rubber, which can according to need, contains other vinyl monomer units.

Being crosslinked rubber (CR) is preferably particle shape.Crosslinked rubber particles (CRp) can be for only comprising crosslinking rubber polymerization The single layer particle of object, or two layers or more of the multilayered particles comprising being crosslinked rubber polymer and other polymers.As Multilayered particles, the hud typed grain being preferably made of the shell portion comprising the core portion for being crosslinked rubber polymer and comprising other polymers Son.In core shell partical, core portion can have centronucleus portion and as needed one layer or more of the hypostracum in covering centronucleus portion, Shell portion can have one layer of the outer shell in covering core portion.It is preferred that very close to each other in each interlayer.As core shell partical, preferably third Olefin(e) acid system multiple layer polymer particle (CRa).

In core shell partical, at least one of the core portion comprising centronucleus portion and 1 layer or more of hypostracum as needed Divide and contains crosslinking rubber polymer (i).In the case that there is the remainder without crosslinking rubber polymer (i) in core portion, The remainder contains other polymers (iii).It should be noted that the multiple portions in core portion contain crosslinking rubber polymer (i) when, the type and physical property of crosslinking rubber polymer (i) contained therein can be the same or different.Similarly, core portion When multiple remainders contain other polymers (iii), the type and physical property of other polymers contained therein (iii) can phases It is same to can also be different.

As crosslinking rubber polymer (i), alkyl acrylate monomer units and/or conjugated diene monomer are preferably comprised Unit and cross-linking monomer units.The carbon for being crosslinked the alkyl of alkyl acrylate monomer used in rubber polymer (i) is former Subnumber is preferably 1~8.As the alkyl acrylate monomer, methyl acrylate, ethyl acrylate, acrylic acid third can be enumerated Ester, butyl acrylate and 2-EHA etc..One or more can be used in these substances.As conjugated diene It is monomer, butadiene and isoprene etc. can be enumerated.One or more can be used in these substances.It is crosslinked rubber polymerization The amount of alkyl acrylate monomer units and/or conjugated diene monomeric unit in object (i) is preferably 60 mass % or more, more Preferably 70~99 mass %, particularly preferably 80~98 mass %.

As cross-linkable monomer, allyl acrylate, allyl methacrylate, 1- acryloxy -3- can be enumerated Butylene, 1- methacryloxy -3- butylene, bis- acryloxies of 1,2--ethane, 1,2- dimethacryloxy-ethane, Bis- acryloxies of 1,2--propane, bis- acryloxies of 1,3--propane, bis- acryloxies of 1,4--butane, 1,3- dimethyl Acryloxy-propane, 1,2- dimethacryloxy-propane, 1,4- dimethacryloxy-butane, triethylene glycol Dimethylacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, hexanediyl ester, diethyl Alkenyl benzene, 1,4- pentadiene and triallyl isocyanate etc..One or more can be used in these substances.It is crosslinked rubber The amount of cross-linking monomer units in polymer (i) is preferably 0.05~10 mass %, more preferably 0.5~7 mass %, especially Preferably 1~5 mass %.

Crosslinking rubber polymer (i), which can according to need, contains other vinyl monomer units.As other vinyl It is monomer, can enumerates: the metering system such as MMA, ethyl methacrylate, butyl methacrylate and cyclohexyl methacrylate Acid ester monomer；The aromatic vinyl monomers such as styrene, p-methylstyrene and o-methyl styrene；N- propyl maleimide The maleimides amine system monomer such as amine, N- N-cyclohexylmaleimide and N-o- chlorophenylmaleimide.These substances can make With one or more.

As other polymers (iii), preferably with the polymer of alkyl methacrylate monomer unit.Other polymerizations Object (iii) can according to need containing cross-linking monomer units and/or other vinyl monomer units.

The carbon atom number of alkyl methacrylate monomer used in other polymers (iii) is preferably 1~8.As The alkyl methacrylate monomer can enumerate MMA, ethyl methacrylate and butyl methacrylate etc., preferably MMA. One or more can be used in these substances.Alkyl methacrylate monomer unit in other polymers (iii) Amount is preferably 80~100 mass %, more preferably 85~99 mass %, particularly preferably 90~98 mass %.

As cross-linkable monomer used in other polymers (iii), can be used and institute in crosslinking rubber polymer (i) The same substance of the cross-linkable monomer of illustration.The amount of cross-linking monomer units in other polymers (iii) is preferably 0~5 matter Measure %, more preferably 0.01~3 mass %, particularly preferably 0.02~2 mass %.

It as other vinyl monomers used in other polymers (iii), can enumerate: methyl acrylate, propylene Acetoacetic ester, propyl acrylate, butyl acrylate, Hexyl 2-propenoate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate and The acrylate monomers such as 2-EHA；Vinyl acetate；Styrene, p-methylstyrene, m-methyl styrene, neighbour The aromatic vinyl monomers such as methyl styrene and α-methylstyrene, vinyl naphthalene；The nitriles such as acrylonitrile and methacrylonitrile； The alpha, beta-unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid；N-ethylmaleimide and N- cyclohexyl maleimide The maleimides amine system monomer such as amine.One or more can be used in these substances.

In core shell partical, the shell portion comprising 1 layer or more of outer shell preferably comprises thermoplastic polymer (ii).As heat Thermoplastic polymer (ii) preferably has alkyl methacrylate monomer unit and contains other vinyl monomers as needed Unit.At least part of thermoplastic polymer (ii) preferably grafts on the central core layer or hypostracum with inner abutment.

The carbon atom number of alkyl methacrylate monomer unit in thermoplastic polymer (ii) is preferably 1~8.As The alkyl methacrylate monomer can enumerate MMA and butyl methacrylate etc., preferably MMA.These substances can be used It is one or more kinds of.The amount of alkyl methacrylate monomer unit in thermoplastic polymer (ii) is preferably 80 mass % More than, more preferably 85 mass % or more, particularly preferably 90 mass % or more.

As other vinyl monomers used in thermoplastic polymer (ii), it can be used and polymerize with above-mentioned other The same substance of other vinyl monomers illustrated by object (iii).Other ethylene base systems in thermoplastic polymer (ii) The amount of monomeric unit is preferably 20 mass % hereinafter, more preferably 15 mass % are hereinafter, particularly preferably 10 mass % or less.

As the constituted mode in core portion and shell portion in core shell partical, can enumerate: centronucleus portion includes crosslinking rubber Polymer (i), outer shell include the two layers of polymers particle of thermoplastic polymer (ii)；Centronucleus portion includes other polymers (iii), hypostracum includes the three one polymer particles of crosslinking rubber polymer (i), outer shell comprising thermoplastic polymer (ii)； Centronucleus portion includes that a certain kind is crosslinked rubber polymer (i), hypostracum includes another crosslinking rubber polymer (i), outer shell The three one polymer particles comprising thermoplastic polymer (ii)；Centronucleus portion includes comprising crosslinking rubber polymer (i), hypostracum Other polymers (iii), outer shell include the three one polymer particles of thermoplastic polymer (ii)；Centronucleus portion includes crosslinking rubber Xanthan polymer (i), the first hypostracum include other polymers (iii), the second hypostracum include crosslinking rubber polymer (i), it is outer Shell includes the four one polymer particles etc. of thermoplastic polymer (ii).

Among the above, preferred center core portion include other polymers (iii), hypostracum include crosslinking rubber polymer (i), it is outer Shell includes the three one polymer particle of acrylic acid series of thermoplastic polymer (ii).In turn, particularly preferred centronucleus portion other Polymer (iii) is the alkyl acrylate of 80~99.95 mass % of MMA monomeric unit, alkyl with carbon atom number 1~8 The crosslinking rubber of the copolymer of 0.05~2 mass % of 0~19.95 mass % of monomeric unit and cross-linking monomer units, hypostracum Polymer (i) is 80~98 mass % of alkyl acrylate monomer units of the alkyl with carbon atom number 1~8, aromatic series second The thermoplasticity polymerization of the copolymer, outer shell of 1~5 mass % of 1~19 mass % of alkenyl monomer unit and cross-linking monomer units Object (ii) is the alkyl acrylate monomer list of MMA monomeric unit 80~100 mass % and the alkyl with carbon atom number 1~8 The three one polymer particle of acrylic acid series of the copolymer of 0~20 mass % of member.

From the viewpoint of the transparency of core shell partical, preferably so that the specific refractivity of layer adjacent to each other is preferably small The polymer of each layer is selected in 0.005, more preferably less than the mode of 0.004, particularly preferably less than 0.003.

The ratio of outer shell in core shell partical is preferably 10~60 mass %, more preferably 15~50 mass %, special It You Xuanwei not 20~40 mass %.The ratio of the part containing crosslinking rubber polymer (i) in core portion is preferably 20~100 matter Measure %, more preferably 30~70 mass %.

The volume-based average particle size of crosslinked rubber particles (CRp) is preferably 0.02~1 μm, more preferably 0.05~0.5 μ M, particularly preferably 0.1~0.3 μm.When using crosslinked rubber particles (CRp) with the volume-based average particle size, Neng Gouxian Write the open defect for reducing obtained formed body.It should be noted that " volume-based average particle size " is base in this specification In the value that the particle size distribution data using the measurement of light scattered light method calculates.

As the manufacturing method of crosslinked rubber particles (CRp), seen from ease of manufacturing of size controlling and multilayered structure etc. Point consideration, preferred emulsion polymerization or seed emulsion polymerization.Emulsion polymerization is that more than one starting monomer is made to carry out cream The method that liquid polymerize to manufacture the lotion containing polymer particle.In seed emulsion polymerization, make more than one starting monomer Emulsion polymerization is carried out after obtaining seed particles, other starting monomers is made to carry out emulsion polymerization in the presence of the seed particles, Thus, it is possible to manufacture the lotion containing the Core-Shell Polymer Particles being made of seed particles with the shell for covering the seed particles. Further make in the presence of obtained Core-Shell Polymer Particles more than one starting monomer carry out emulsion polymerization, repeat into Row above-mentioned operation, thus, it is possible to manufacture more containing the nucleocapsid being made of seed particles with the multiple shells for covering the seed particles The lotion of one polymer particle.

As emulsifier used in emulsion polymerization, can enumerate anionic system emulsifier, nonionic system emulsifier and Nonionic-anionic system emulsifier.It as anionic system emulsifier, can enumerate: dioctyl sodium sulphosuccinate and two laurels The dialkyl sulfosuccinates such as base sodium sulfosuccinate；The alkylbenzene sulfonates such as neopelex；Dodecyl sulphur Alkyl sulfates such as sour sodium etc..As nonionic system emulsifier, polyoxyethylene alkyl ether and ethylene nonyl benzene can be enumerated Base ether etc..It as nonionic-anionic system emulsifier, can enumerate: the polyoxyethylene such as ethylene nonyl phenyl ether sodium sulphate Nonylplenyl ether sulfate；The polyoxyethylene alkyl ether sulfate salts such as polyoxyethylene alkyl ether sodium sulphate: three decyl ethers of polyoxyethylene Alkyl ether carboxy acid salts such as sodium acetate etc..One or more can be used in these substances.It should be noted that about nonionic It is the average repeat unit of ethylene oxide (EO) unit in emulsifier and nonionic-anionic system emulsifier exemplary compounds Number, in order to become the foaming characteristic of emulsifier will not greatly, preferably 30 hereinafter, more preferably 20 hereinafter, particularly preferably 10 Below.

It as polymerization initiator used in emulsion polymerization, can enumerate: the persulfates such as potassium peroxydisulfate and ammonium persulfate Series initiators；Cross sulfoxylate (persulfoxylate)/redox such as organic peroxide and persulfate/sulphite Series initiators.

As the method for isolating crosslinked rubber particles (CRp) from the lotion obtained by emulsion polymerization, can enumerate Saltout freezing method, freeze freezing method and spray drying process etc..Wherein, from can by washing will be in crosslinked rubber particles (CRp) From the viewpoint of the impurity contained easily removes, freezing method of preferably saltouing and freeze freezing method, more preferably freezes freezing method.Root Freeze freezing method according to without using agglutinant, the resin combination having excellent water-resistance can be easy to get.It should be noted that When filtering lotion using 50 μm of metal meshes below of mesh etc. before solidification process, the foreign matter being mixed into lotion can be removed, Thus preferably.

Disperse from the particle in the melting mixing of methacrylic resin (M1), (M2) and crosslinked rubber particles (CRp) Property from the viewpoint of, be preferably preferably 1000 μm or less with diameter by crosslinked rubber particles (CRp), more preferably 500 μm or less Agglutination body form take out.It should be noted that the form that shell portion is merged each other can be enumerated as agglutination form. As the shape of crosslinked rubber particles agglutination body, pellet (pellet) shape, powdered and particle (granule) shape can be enumerated Deng.

The amount of crosslinking rubber (CR) in methacrylic resin composition of the invention is relative to methacrylic Resin (M1), (M2) 100 mass parts of total amount be preferably 5~30 mass parts, more preferably 10~25 mass parts, particularly preferably For 15~20 mass parts.

In methacrylic resin composition of the invention, in order to improve the evenly dispersed of crosslinked rubber particles (CRp) Property, the dispersion such as methacrylic resin particle auxiliary particle (DA) can be added.Disperse the volume reference of auxiliary particle (DA) Average grain diameter is preferably smaller than crosslinked rubber particles (CRp), preferably 0.04~0.12 μm, more preferably 0.05~0.1 μm.From point It dissipates the viewpoints such as property improvement effect to consider, the mass ratio of dispersion auxiliary particle (DA)/crosslinked rubber particles (CRp) is preferably 0/100 ~60/40, more preferably 10/90~50/50, particularly preferably 20/80~40/60.

< block copolymer (BP) >

Block copolymer (BP) is multiple polymers strand (polymer blocks) on the whole with chain or radial connection Made of copolymer.From with from the viewpoint of the compatibility of methacrylic resin (M1), (M2), block copolymerization is preferably comprised At least one polymerization comprising the methacrylate monomers unit containing 90 mass % or more of the polymer blocks of object (BP) Object, contains styrenic monomer units and maleic anhydride list at the polymer containing styrenic monomer units and acrylonitrile monomer unit The polymer of body unit, the polymer containing styrenic monomer units and maleic anhydride monomer units and MMA monomeric unit or poly- Vinyl butyral.

From the viewpoint of the intensity for improving formed body, as block copolymer (BP), preferably comprise comprising poly- methyl-prop (methacrylate polymers are embedding for more than one the polymer blocks (b1) of the polymethacrylates such as e pioic acid methyl ester (PMMA) Section) and more than one the polymer blocks (b2) (acrylate polymer block) comprising polyacrylate block copolymer (BPa)。

It as the manufacturing method of block copolymer (BPa), can enumerate: using living polymerization in polymer blocks End forms polymerization starting point, makes monomer polymerization from the starting point, the method for connecting another polymer blocks to generate；Prepare Multiple polymers block makes them carry out addition reaction or the method for condensation reaction etc..

The amount of block copolymer (BP) is excellent relative to 100 mass parts of total amount of methacrylic resin (M1), (M2) It is selected as 0.1~30 mass parts, more preferably 0.5~25 mass parts, particularly preferably 1~20 mass parts.

(other optional members)

Methacrylic resin composition of the invention, which can according to need, contains other optional members.As other It hanks point, filler, antioxidant, heat deterioration preventing agent, ultraviolet absorbing agent, light stabilizer, lubricant, demoulding can be enumerated Agent, polymer processing aid, antistatic agent, fire retardant, dyes/pigments, light diffusing agent, organic pigment, delustering agent, impact resistance The various additives such as modification agent and fluorophor.The total amount of above-mentioned various additives is preferably 7 mass % hereinafter, more preferably 5 Quality % is hereinafter, particularly preferably 4 mass % or less.

< ultraviolet absorbing agent (LA) >

When the molecular weight of ultraviolet absorbing agent (LA) is too small, it may be produced in the forming of methacrylic resin composition Raw blistering.Therefore, the molecular weight of ultraviolet absorbing agent (LA) is preferably greater than 200, more preferably 300 or more, particularly preferably 500 More than, most preferably 600 or more.

Ultraviolet absorbing agent (LA) is considered as having the function of converting light energy into the compound of thermal energy.As ultraviolet light Absorbent (LA), can enumerate: benzophenone, benzotriazole, triazines, benzoates, salicylic acid esters, cyano third Olefin(e) acid esters, oxanilide class, malonic acid esters and formamidine etc..One or more can be used in these substances.From purple From the viewpoint of the inhibitory effect of the deterioration (xanthochromia etc.) of resin caused by outside line is high, preferably benzotriazole (has benzo The compound of triazole skeleton) and triazines (compound with triazine skeleton).

As benzotriazole, 2- (2H- benzotriazole -2- base) -4- (1,1,3,3- tetramethyl butyl) benzene can be enumerated Phenol (BASF AG's manufacture；Trade name TINUVIN329), bis- (the 1- methyl-1s-phenyl second of 2- (2H- benzotriazole -2- base) -4,6- Base) phenol (BASF AG's manufacture；Trade name TINUVIN234), 2,2 '-di-2-ethylhexylphosphine oxides [6- (2H- benzotriazole -2- base) -4- Tert-octyl phenol] (ADEKA company manufacture；) and 2- (5- octylthio -2H- benzotriazole -2- base) -6- tert-butyl -4- LA-31 Methylphenol etc..

As triazines, 2,4,6- tri- (2- hydroxyl -4- hexyl oxygroup -3- aminomethyl phenyl) -1,3,5-triazines can be enumerated (ADEKA company manufacture；LA-F70), as (BASF AG's manufacture of the hydroxyphenyltriazinuv system ultraviolet absorbing agent of its analog； CGL777, TINUVIN460, TINUVIN479 etc.) and 2,4- diphenyl -6- (2- hydroxyl -4- hexyl phenyl) -1,3,5- Triazine etc..

In addition to this, the maximum value ε of the molar absorption coefficient under 380~450nm of wavelength can be enumerated_maxFor 1200dm³· mol^-1cm^-1Ultraviolet absorbing agent below.As the ultraviolet absorbing agent, 2- ethyl -2 '-ethyoxyl-oxalyl benzene can be enumerated Amine (Clariant Japanese firm manufacture；Trade name サ Application デユボア VSU) etc..

In addition to this, International Publication No. 2011/089794, International Publication No. 2012/124395, Japan can be enumerated Special open 2012-012476 bulletin, Japanese Unexamined Patent Publication 2013-023461 bulletin, Japanese Unexamined Patent Publication 2013-112790 bulletin, day This special open 2013-194037 bulletin, Japanese Unexamined Patent Publication 2014-62228 bulletin, Japanese Unexamined Patent Publication 2014-88542 bulletin and day The metal complex for the ligand with multiring structure recorded in this special open 2014-88543 bulletin etc..As the metal network Object is closed, compound represented by following formula (A) can be enumerated.

In formula (A), M is metallic atom.Y¹~Y⁴Bivalent group (oxygen atom, sulphur original being each independently other than carbon atom Son, NH and NR⁵Deng).R⁵For substituent groups such as alkyl, aryl, heteroaryl, heteroarylalkyl and aralkyl (アラ Le リ Le base).This takes Can further have substituent group for base.Z¹And Z²It is each independently trivalent radical (nitrogen-atoms, CH and CR⁶Deng).R⁶For alkane The substituent groups such as base, aryl, heteroaryl, heteroarylalkyl and aralkyl.The substituent group can further have substituent group.R¹~R⁴Respectively From independently being hydrogen atom, alkyl, hydroxyl, carboxyl, alkoxy, halogen group, alkyl sulfobetaines, morpholinyl sulfo group, piperidyl sulphur The substituent groups such as base, sulfenyl morpholinyl sulfo group and piperazinyl sulfo group.The substituent group can further have substituent group.A~d distinguishes table Show R¹~R⁴Quantity and be each independently 1~4 integer.

As the ligand of the multiring structure in above-mentioned metal complex, can enumerate the double benzothiazoles of 2,2 '-imino groups, 2- (2-[4-morpholinodithio base amino) benzoAzoles, 2- (2-[4-morpholinodithio base amino) benzimidazole, (2-[4-morpholinodithio base) (2- benzene And imidazole radicals) methane, bis- (2- benzosOxazolyl) methane, bis- (2-[4-morpholinodithio base) methane, bis- [2- (N- substitution) benzimidazoles Base] methane and they derivative etc..As the central metal of above-mentioned metal complex, preferably copper, nickel, cobalt and zinc etc..It is above-mentioned Metal complex is preferably dispersed in the media such as low molecular compound or polymer and uses.The additive amount of above-mentioned metal complex It is preferably 0.01~5 mass parts, more preferably 0.1 relative to 100 mass parts of methacrylic resin composition of the invention ~2 mass parts.Molar absorption coefficient of the metal complex under the wavelength of 380~400nm is big, therefore, desired for obtaining Ultraviolet radiation absorption effect and the amount added is few good.Therefore, the appearance degradation of formed body caused by being able to suppress because of exudation etc..Separately Outside, the heat resistance of above-mentioned metal complex is high, therefore, deterioration and decomposition of little when forming.In addition, above-mentioned metal complex is resistance to Photosensitiveness is high, therefore, can keep UV absorbing properties for a long time.

The maximum value ε of the molar absorption coefficient of ultraviolet absorbing agent_maxIt can measure as follows.It is added in hexamethylene 1L purple Ultraviolet absorbers 10.00mg, by when observing by visual observation there is no undissolved object in a manner of make it dissolve.The solution is injected into In 1cm × 1cm × 3cm quartz glass pond, U-3410 type spectrophotometer is manufactured using company, Hitachi, measures wavelength Absorbance under 380~450nm.By the molecular weight (M of ultraviolet absorbing agent_UV) and the maximum value (A of absorbance that is measured_max) The maximum value ε of molar absorption coefficient is calculated using following formula_max。

ε_max=[A_max/(10×10^-3)]×M_UV

< polymer processing aid (PA) >

As polymer processing aid (PA), can be used can by emulsion polymerization manufacture, have 0.05~0.5 μm partial size polymer particle (non-crosslinked rubber particles).Polymer particle can be by single composition and single characteristic viscosity Polymer constitute single layer particle, be also possible to be made of the two or more polymer formed or inherent viscosity is different two Layer or more multilayered particles.Wherein, preferably internal layer has polymeric layer, outer layer with low inherent viscosity and has with 5dl/g The particle of the double-layer structure of the polymeric layer of above high inherent viscosity.The inherent viscosity of polymer processing aid (PA) is preferably 3~6dl/g.When inherent viscosity is too small, the improvement of formability may be become inadequate, and when excessive, may cause methyl-prop The reduction of the formability of olefin(e) acid based resin composition.Specifically, the メタ Block レ Application-of Mitsubishi's Li Yang company manufacture can be enumerated The パラロイ De series etc. of P series and the Dow Chemical Company's manufacture.The amount of polymer processing aid (PA) is relative to methacrylic acid Resinoid (M1), (M2) 100 mass parts of total amount be preferably 0.1~5 mass parts.When use level is very few, it cannot get good Processing characteristics, when use level is excessive, the appearance possible deviation of formed body.

Other additives of < >

As filler, calcium carbonate, talcum, carbon black, titanium oxide, silica, clay, barium sulfate and magnesium carbonate can be enumerated Deng.The amount of filler in methacrylic resin composition of the invention is preferably 3 mass % hereinafter, more preferably 1.5 matter Measure % or less.

As antioxidant, phosphorous antioxidant, hindered phenolic antioxidant and thioether antioxidant etc. can be enumerated. One or more can be used in antioxidant.Wherein, from the sight of the deterioration preventing effect because of optical characteristics caused by colouring Point considers that preferably phosphorous antioxidant and hindered phenolic antioxidant, more preferable phosphorous antioxidant and hindered phenolic are anti-oxidant Agent is applied in combination.In the case where phosphorous antioxidant and hindered phenolic antioxidant is applied in combination, phosphorous antioxidant: by The mass ratio for hindering phenolic antioxidant is preferably 1:5~2:1, more preferably 1:2~1:1.

As phosphorous antioxidant, 2,2- di-2-ethylhexylphosphine oxide (4,6- di-tert-butyl-phenyl) octyl phosphite ester can be enumerated (ADEKA company manufacture；Trade name: アデカスタ Block HP-10), (BASF is public for three (2,4- di-tert-butyl-phenyl) phosphite esters Department's manufacture；Trade name: IRGAFOS168) and bis- four oxygen of (2,6- di-t-butyl -4- methylphenoxy) -2,4,8,10- of 3,9- Miscellaneous -3,9- two phospha spiral shell [5.5] hendecane (ADEKA company manufacture；Trade name: アデカスタ Block PEP-36) etc..

As hindered phenolic antioxidant, [the 3- (3,5- di-tert-butyl-hydroxy phenyl) third of pentaerythrite four can be enumerated Acid esters] (BASF AG's manufacture；Trade name IRGANOX1010) and octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyl) third Acid esters (BASF AG's manufacture；Trade name IRGANOX1076) etc..

The polymer that heat deterioration preventing agent generates when can be by being exposed to high fever in the state of capture substantially anaerobic Free radical and the heat deterioration for preventing resin.As heat deterioration preventing agent, 2- tert-butyl -6- (3 '-tert-butyls -5 '-first can be enumerated Base-hydroxybenzyl) (the sumitomo chemical company manufacture of -4- aminomethyl phenyl acrylate；Trade name スミライザー GM) and 2,4- bis- (the sumitomo chemical company manufacture of tertiary pentyl -6- (3 ', 5 '-two tertiary pentyls -2 '-hydroxy-alpha-methyl benzyl) phenyl acrylate；Quotient Name of an article スミライザー GS) etc..

Light stabilizer is considered as having the function of the compound for the free radical that capture generates in the oxidation caused by because of light. Hindered amines such as the compound with 2,2,6,6- tetraalkyl piperidine skeleton etc. can be enumerated.

As lubricant, stearic acid, behenic acid, stearoyl amino acid, methylene bis stearamide, hydroxy stearate can be enumerated Acid glycerol three ester, paraffin, ketone wax, octanol and hydrogenated oil and fat etc..

It as release agent, can enumerate: the higher alcohols such as cetanol and stearyl alcohol；Glycerol stearate monoesters and stearic acid are sweet Glycerol high-grade aliphatic ester such as oily diester etc..It is preferred that higher alcohols and glycerol fatty acid monoester are applied in combination.Higher alcohols/sweet The mass ratio of fatty acid oil monoesters is preferably 2.5/1~3.5/1, and more preferably 2.8/1~3.2/1.

As organic pigment, it is preferable to use ultraviolet light to be converted to the compound of visible light.

As light diffusing agent and delustering agent, it is micro- that glass granules, polysiloxane series crosslinked fine particles, cross-linked polymer can be enumerated Grain, talcum, calcium carbonate and barium sulfate etc..

As fluorophor, fluorescent pigment, fluorescent dye, fluorescent white dyestuff, fluorescent whitening agent and fluorescence drift can be enumerated White dose etc..

(physical property of methacrylic resin composition)

The Mw of methacrylic resin composition of the invention is preferably 50000~200000, more preferably 55000~ 160000, particularly preferably 60000~120000, most preferably 70000~100000, molecular weight distribution (Mw/Mn) is preferably 1.0~5.0, more preferably 1.2~3.0, particularly preferably 1.3~2.0, most preferably 1.3~1.7.Mw and molecular weight distribution (Mw/Mn) in the range when, the formability of methacrylic resin composition becomes well, to be easy to get mechanical strength (impact resistance and toughness etc.) excellent formed body.

The melt of methacrylic resin composition of the invention measured under conditions of 230 DEG C and 3.8kg load Flow rate (MFR) is preferably 0.1~30g/10 minutes, and more preferably 0.5~20g/10 minutes, particularly preferably 1.0~ 15g/10 minutes.

The mist degree when film for being processed into 3.2mm thickness of methacrylic resin composition of the invention is preferably 3.0% hereinafter, more preferably 2.0% hereinafter, particularly preferably 1.5% or less.

(manufacturing method of methacrylic resin composition)

It as the manufacturing method of methacrylic resin composition of the invention, can enumerate: by methacrylic The method that resin (M1), (M2) and other polymers as needed carry out melting mixing.Melting mixing can be used kneading and squeeze The melting mixings such as machine, extruder, mixing mill and banbury mixers device carries out out.Melting temperature can be according to metering system The softening temperature of acid resin (M1), (M2) and other polymers used as needed is suitably adjusted, usually 150 DEG C~ Temperature in the range of 300 DEG C.Shear velocity when mixing can be at 10~5000 seconds^-1In the range of be adjusted.

As other manufacturing methods of methacrylic resin composition of the invention, there are as below methods: in methyl-prop In the presence of one of olefin(e) acid resinoid (M1), (M2) methacrylic resin and other polymers used as needed It polymerize another methacrylic resin.The manufacturing method is applied to metering system compared with above-mentioned manufacturing method The thermal history of acid resin shortens, and therefore, methacrylic resin thermally decomposes to yield inhibition, is easy to get coloring and foreign matter Few methacrylic resin composition.

In order to improve convenience when preservation, carrying or forming, methacrylic resin composition of the invention can be with Form the forms such as pellet.

" formed body "

Formed body of the invention is obtained from the methacrylic resin composition of aforementioned present invention is formed. It as forming process, can enumerate: T-die method (laminating method and coetrusion etc.), inflation method (coetrusion etc.), compression molding Method, blow-moulding process, calendaring molding method, vacuum forming process, injection molding method (inserts method, two color methods, pressing, move back core method and Sandwich method etc.) etc. melt-shaping method；Solution casting method etc..Wherein, consider from the viewpoints such as productivity and cost, preferably T-shaped mould Head method, inflation method and injection molding method etc..

" film "

The form of formed body be it is any, film etc. can be enumerated.Film of the invention is the methacrylic acid by aforementioned present invention The film that based resin composition is constituted.It should be noted that being usually mainly classified into a thickness of 5~250 μm of planar formed body " film ", the planar formed body than 250 μ m-thicks are mainly classified into " piece ", but in the present specification, they are referred to as " film ".

As film method, melted masking method and solution film-forming method, from the viewpoint of productivity, preferred molten can be enumerated Film method.As melted masking method, inflation method, T-die method, rolling process and cutting method etc. can be enumerated.Wherein, preferred T-type Die head method.As melted masking device, the extrusion pressing type melting extrusion with extrusion screw rod of single screw rod or twin-screw can be enumerated Device etc..Melting extrusion temperature is preferably 150~350 DEG C, and more preferably 200~300 DEG C.Using melt extrusion apparatus come into In the case where row melting mixing, from the viewpoint of inhibiting from coloring, preferably carry out under reduced pressure or under the torpescence atmosphere such as nitrogen Melting mixing.In melt extrusion apparatus, it is preferably provided for the polymer filter of foreign matter removing and for improving thickness and precision Gear pump.

In extrusion molding method, from the viewpoint for the film for obtaining good surface smoothness, good bright luster and low haze Consider, preferably methacrylic resin composition is squeezed out with molten condition from T-die and make its with it is more than one cold But mirror roller or mirror surface band contacts or is clamped it to carry out cooling method.Mirror roller or mirror surface band preferably at least mirror Face is chrome-plated metal system.

From mechanical strength, film uniformity and it is windability from the viewpoint of, pass through the above method be film-made methacrylic The thickness of resin film (unstretching film) is preferably 10~500 μm, and more preferably 20~200 μm.Thickness distribution is relative to average value Within preferably ± 10%, within more preferably ± 5%, within particularly preferably ± 3%.When thickness distribution is greater than ± 10%, It is uneven there may be stretching when carrying out stretch processing.

Stretch processing can be implemented to the methacrylic resin film (unstretching film) being film-made by the above method.Pass through Stretch processing, available mechanical strength (impact resistance and toughness etc.) and hot physical property improve, are not likely to produce the film in crack.It stretches Processing includes stretching process, heat fixation process and relaxation process.As drawing process, biaxial stretching process, same can be enumerated gradually When biaxial stretching process and tubular pull method etc..

In the case where gradually biaxial stretching process, for any draw direction, tensile speed is preferably 1~8000%/ Minute, more preferably 100~6000%/minute.It should be noted that tensile speed in two directions can it is identical can also be with It is different.At the same time in the case where biaxial stretching process, tensile speed is preferably 1~8000%/minute, more preferably 50~ 6000%/minute.In either method, when tensile speed is too small, productivity is all deteriorated, and when tensile speed is excessive, may all produce Filming fracture.

About draft temperature, using the Tg of methacrylic resin composition of the invention as benchmark, gradually/simultaneously Tg~(Tg+30 DEG C), more preferably (Tg+5 DEG C)~(Tg+25 DEG C) are preferably either in biaxial stretching process in method.? When within the scope of this, uneven thickness is inhibited.When draft temperature is too low, it is possible to create film fracture, when excessively high, stretch processing institute band The improvement effect of the mechanical strength and hot physical property come may become inadequate.

Stretched film is preferably 1.01~12.25 times relative to the area multiplying power of unstretching film, and more preferably 1.10~9 times. When stretching ratio is less than 1.01 times, the improvement effect of the mechanical strength of film is become inadequate, when being greater than 12.25 times, mechanical strength It may be decreased.In the case where biaxial stretch-formed, the stretching ratio of each axis direction is preferably 1.01~3.5 times.

Film of the invention is suitable for the surface of polaroid protective film, phase difference film, liquid crystal protective film, portable data assistance Material, light guiding film, on surface is coated with the transparent of silver nanoparticle silk or carbon nanotube at the display window protective film of portable data assistance Film etc. before conductive film and various displays, particularly suitable for polaroid protective film etc..

In addition to this, film of the invention is suitable for IR (infrared) cut film, crime prevention film, anti-disperse film, decorating film, gold Belong to decorating film, the tergite of solar battery, flexible solar battery anter, shrink film, in-mold labels film and gas barrier film etc..

Film of the invention is also suitable for the optical film of organic electroluminescent (EL) lighting device.

" stacked film "

Film (unstretching film or stretched film) of the invention can be formed in the stacking that other layers are laminated at least one face The form of film.Stacked film of the invention has the layer being made of the film (unstretching film or stretched film) of aforementioned present invention.

As other layers, various functions layers can be enumerated.As functional layer, hard conating, anti-dazzle photosphere, counnter attack can be enumerated Penetrate layer, antiblocking layers, diffusing layer, antiglare layer, antistatic layer, stain-proofing layer and easy slip layer containing particle etc. etc..

Other layers can be the polarizing film being made of the polyvinyl alcohol film doped with iodine.One as stacked film of the invention The polarizer of a mode has above-mentioned polarizing film and to be layered in being made of the film of aforementioned present invention for its at least one surface inclined Shake piece protective film.It is laminated in the mode of film of the invention on a surface of polarizing film, on another surface of polarizing film On can according to need the arbitrary optical film being laminated other than film of the invention.As arbitrary optical film, this hair can be enumerated Polaroid protective film, both view angle adjustment film, phase difference film and brightness enhancement film other than bright film etc..Stacking can according to need across glue Adhesive layer carries out.

The polarizer of aforesaid way can be used for image display device.It as image display device, can enumerate: (organic) Electroluminescent display (ELD), plasma display (PD) and Field Emission Display (FED:Field Emission The self-luminous display devices such as Display)；Liquid crystal display device (LCD) etc..LCD has liquid crystal cell and configures at least single at it The polarizer of side.

Other layers can be the layer being made of metal and/or metal oxide.As metal, can enumerate for example aluminium, silicon, Magnesium, palladium, zinc, tin, nickel, silver, copper, gold, indium, stainless steel, chromium and titanium etc..As metal oxide, can enumerate such as aluminium oxide, Zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silica, cobalt oxide, zirconium oxide, Tin oxide, titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesia, manganese oxide, molybdenum oxide, Vanadium oxide and barium monoxide etc..One or more can be used in these metals and metal oxide.Wherein, the gloss of indium is excellent It is good, therefore there is excellent design, even if to the stacked film for being laminated with metal layer on film of the invention using vapor deposition etc. It carries out also being not easy to tarnish when deep-draw forming, thus it is preferred that.In addition, the gloss of aluminium is excellent, therefore has excellent design, And industrially also can cheap low acquisition, it is therefore, especially preferred on the way in the use for not needing deep-draw forming.As formation By the method for the layer that metal and/or metal oxide are constituted, usually using vacuum vapour deposition, but ion plating also can be used, splash The methods of penetrate with CVD (Chemical Vapor Deposition: chemical gaseous phase accumulation).It is being formed by metal and/or metal oxygen Before the layer that compound is constituted, the surface treatment such as sided corona treatment can be implemented to film of the invention in advance.By metal and/or metal oxygen The thickness for the layer that compound is constituted is typically about 5nm~about 100nm, in the case where carrying out deep-draw forming after layer formation, preferably 5 ~250nm.

Other layers can be the layer being made of other thermoplastic resins.As be suitable for stacking other thermoplastic resins, Polycarbonate resin, pet resin, polyamide, polyvinyl resin, polypropylene tree can be enumerated Rouge, polystyrene resin, Corvic, other (methyl) acrylic resins, ABS (acrylonitrile-butadiene-styrene (ABS) Copolymerization) resin, ethylene vinyl alcohol, polyvinyl butyral resin, polyvinyl acetal resin, polystyrene thermoplasticity Elastomer, olefin series thermoplastic elastomer and acrylic acid series thermoplastic elastomer (TPE) etc..The layer being made of these thermoplastic resins Thickness is suitably designed depending on the application, is not particularly limited, from the viewpoint of secondary workability, preferably 500 μm or less.

The preparation method of stacked film with the layer being made of other thermoplastic resins is not particularly limited.For example, can enumerate: (1) method for being continuously laminated the film of the invention prepared respectively and other thermoplastic resin films between a pair of of heating roller； (2) method for being thermally compressed the film of the invention prepared respectively and other thermoplastic resin films using hot press；(3) respectively Prepare film and other thermoplastic resin films of the invention, it is laminated while carrying out by a film and pressing empty forming or vacuum forming The method of his film；(4) side for being laminated the film of the invention prepared respectively and other thermoplastic resin films via adhesive layer Method (wet type laminating method)；(5) other thermoplastic resins from T-die melting extrusion are laminated on pre-prepd film of the invention The method of rouge；(6) methacrylic resin composition and other thermoplastic resins of the invention are subjected to coextrusion forming Method；Deng.

" being laminated into body "

The body that is laminated into of the invention is that above-mentioned film of the invention or above-mentioned layer of the invention are laminated on substrate The formed body of folded film.As substrate, be not particularly limited, can enumerate other thermoplastic resin substrates, thermosetting resin substrate, Wood substrate and non-wood substrate etc..Other thermoplastic resins used in substrate illustrate and as composition stacked film The example that the material of other layers illustrates is identical.As other thermosetting resins used in substrate, epoxy resin, benzene can be enumerated Phenol resin and melamine resin etc..

The preparation method for being laminated into body is not particularly limited.For example, incite somebody to action this via adhesive layer as needed on above-mentioned substrate (stacking) film of invention carries out vacuum forming, the empty forming of pressure or compression molding etc. under heating, thus, it is possible to be laminated into Body.

As other preparation methods, it is also preferred that following injection moulding is bonded method simultaneously: (stacking) film of the invention is inserted into note It penetrates between forming male and female mold, the thermoplastic resin melted in the mold to a surface side injection of (stacking) film, by This, while carrying out the formation of injection-molded body and being bonded for injection-molded body and (stacking) film.The present invention used in this method (stacking) film can be planar film, be also possible to carry out preform using vacuum forming and the empty forming of pressure etc. and figuration is any Concaveconvex shape film.It should be noted that the preform of (stacking) film of the invention can be bonded method in injection moulding simultaneously Used in injection machine mold in carry out, also can be used other molding equipment progress.After preform (stacking) film Insert part forming method is also referred to as to the method for its single side injecting molten resin.

Of the invention is laminated into body, preferably using the layer comprising film of the invention as most surface layer.Stacking of the invention Surface smoothness, surface hardness and the lustrous surface of formed body etc. are excellent.There is the case where printing layer in stacked film of the invention Under, pattern etc. can be made brightly to be shown.In addition, in the feelings using the stacked film with the layer comprising metal or metal oxide Under condition, the available bright luster being equal to metal.

As discussed above, in accordance with the invention it is possible to which providing can be obtained hot forming well and have to heat There is the methacrylic resin composition of the formed body of high-dimensional stability.Methacrylic resin composition of the invention If exposed to than it is previous it is high at a temperature of, there is for example, about 280 DEG C of thermal history when for example passing through polymer filter etc., Also there is good formability, thus, it is also possible to cope with the complication etc. of the shape of formed body.In addition, obtained formed body There can be high-dimensional stability to about 130 DEG C hot.

In accordance with the invention it is possible to provide hot forming good and the transparency can be obtained, to the dimensional stability of heat and The methacrylic resin composition of the excellent formed body of mechanical strength (impact resistance and toughness etc.).

Embodiment

Hereinafter, being illustrated to examples and comparative examples of the present invention.

[assessment item and evaluation method]

Assessment item and evaluation method is as follows described.

(polymerisation conversion)

The connection GLSciencesInc. manufacture on the gas chromatograph GC-14A of company, Shimadzu Seisakusho Ltd. manufacture InertCAP1 (df=0.4 μm, I.D.=0.25mm, length=60m) is used as chromatographic column.Injection temperature is set as 180 DEG C, It will test device temperature and be set as 180 DEG C.Column temperature is set as following temperature model: keeping at 60 DEG C after five minutes, from 60 DEG C 200 DEG C are warming up to 10 DEG C/min of heating rate, is kept for 10 minutes at 200 DEG C.It is measured under these conditions, base Polymerisation conversion is calculated in obtained result.

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

It is dissolved in measure object resin 4mg in tetrahydrofuran (THF) 5ml, is filtered with 0.1 μm of the filter in aperture, it will Gains are as sample solution.As GPC device, the Tosoh strain formula meeting for having differential refraction rate detector (RI detector) is used " HLC-8320 " of society's manufacture.As column, " TSKgelSuperMultiporeHZM-M " for manufacturing TOSOH Co., Ltd is used Two connect with " SuperHZ4000 " obtained from column.As eluant, eluent, use tetrahydrofuran (THF).By the temperature of column oven It is set as 40 DEG C, with 0.35ml/ minutes elution flow quantities, 20 μ l of sample solution is injected into device, measures chromatogram.Color Spectrogram is will to make from sample solution and the value of electrical signals (intensity Y) of the refringence referring to solution to retention time X Scheme obtained from figure.

Using the 10 points of progress GPC measurements of standard polystyren for the range that molecular weight is 400~5000000, expression is made The standard curve of retention time and the relationship of molecular weight.Based on the standard curve, the Mw and Mw/Mn of measure object resin are determined. It should be noted that the baseline of chromatogram is set as one from retention time morning by the slope at the peak of the high molecular weight side of GPC figure The slope of point and the peak of low molecular weight side that side observation becomes positive value from zero becomes from the unilateral observation of retention time morning from negative value Line obtained from zero point connection.In the case where chromatogram shows multiple peaks, by the slope at the peak of highest weight side from zero Become the point of positive value and point that the slope at the peak of lowest molecular weight side becomes zero from negative value connect obtained from line as baseline.

(degree of syndiotacticity (rr) in terms of three unit groups)

For measure object resin, implement¹H-NMR measurement.As measurement device, nuclear magnetic resonance device (Bruker is used " ULTRASHIELD400PLUS " of company's manufacture).For sample 10mg, use deuterated chloroform 1mL as deuterated solvent.Measurement Temperature is set as room temperature (20~25 DEG C), and cumulative number is set as 64 times.0.6 when measurement makes primary standard substance (TMS) to be 0ppm The area (Y) in the region of the area (X) and 0.6~1.35ppm in the region of~0.95ppm, utilizes formula: (X/Y) × 100 is counted It calculates, using resulting value as the degree of syndiotacticity (rr) (%) in terms of three unit groups.

(Measurement of Dynamic Viscoelasticity)

The strip test film that width is 5mm is cut from the hot forming film of thickness 1mm, implements dynamic viscoelastic survey It is fixed.As measurement device, using forced vibration type measurement of dynamic viscoelasticity device, (ユービーエム company, Co., Ltd. is manufactured " Rheogel-E4000 ").Test film is set in device with collet spacing 20mm.In basic frequency: 1Hz, measurement mould Formula: stretch mode, strain controlling: 5 μm, strain waveform: sine wave, dead load control: under the conditions of automatically, with 3 from 50 DEG C DEG C/min heating rate be warming up to 230 DEG C, carry out the measurement of temperature dependency.To storage modulus (E '), loss modulus (E ") It maps with tan δ, the peak for the tan δ that 100 DEG C to 180 DEG C are occurred is as α relaxation peak.The summit temperature of the α relaxation is made For α relaxation temperature.

(melt flow rate (MFR) (MFR))

According to JISK7210, the MFR of measure object resin is surveyed in 230 DEG C, 3.8kg load, 10 minutes conditions It is fixed.

(melt viscosity η)

By measure object resin at 80 DEG C after dry 12 hours, " the キャピ that is manufactured using Toyo Seiki Co., Ltd. ログラ Off 1D ", at 260 DEG C, shear velocity 122 seconds^-1Under conditions of measure melt viscosity η.

(hot forming (thermogravimetric conservation rate))

As measurement device, use thermogravimetric measurement device (" TGA-50 " of Shimadzu Seisakusho Ltd.'s manufacture).In air atmosphere, It is kept after being warming up to 290 DEG C from 50 DEG C with 20 DEG C/min of heating rate, at 290 DEG C under 20 minutes temperature models, The thermogravimetric reduction of measure object resin is measured.Weight at the time of using 50 DEG C is found out as benchmark (conservation rate 100%) Weight retention rate after twenty minutes is kept at 290 DEG C, and hot forming (resistance to pyrolytic) is commented by following benchmark Valence.It should be noted that thermogravimetric conservation rate is higher, then resistance to pyrolytic is higher, and it is more excellent to can be hot forming.

< determinating reference >

A (good): thermogravimetric conservation rate is 80% or more,

B (bad): thermogravimetric conservation rate is less than 80%.

(mist degree)

The mist of biaxially-stretched film is measured using haze meter (color research institute manufactures in village, HM-150) according to JISK7136 Degree.

(total light transmittance)

Biaxially-stretched film is measured using haze meter (color research institute manufactures in village, HM-150) according to JISK7361-1 Total light transmittance.

(dimensional stability (thermal linear expansion coefficient))

Width 4mm × length 20mm × 40 μm of thickness test film is cut from biaxially-stretched film.As measurement device, use Thermo-mechanical analysis TMA (" Q400EM " of the manufacture of TA instrument company).Under conditions of collet spacing 8mm, load 0.01N, from 25 It DEG C rises and with 10 DEG C/min of heating rate to be warming up to 130 DEG C, the size changing amount of measurement test piece.According to 50~90 DEG C of temperature The slope for spending the size changing amount in range calculates thermal linear expansion coefficient.

(impact resistance (impact resistance value))

40 μm of 80mm × 80mm × thickness of test film is cut from biaxially-stretched film.Use film shock machine (peace field The manufacture of Jing Ji company), impact resistance value when rupturing test film using the sphere of 12.7 ± 0.2mm of diameter φ is measured.

(phase difference (Rth) of film thickness direction)

The test film of 40mm × 30mm is cut from obtained biaxially-stretched film.The test film is set to automatic two-fold It penetrates in meter (" KOBRA-WR " that prince measures Co., Ltd.'s manufacture).In 23 ± 2 DEG C of temperature, humidity 50 ± 5%, the wave for measuring light The phase difference of 40 ° of inclined directions is measured under conditions of long 590nm.Refractive index n is calculated by the value and mean refractive index n_x、n_y、n_z, Calculate phase difference the Rth (=((n of thickness direction_x+n_y)/2-n_z)×d).It should be noted that n_xFor phase axis direction slow in face Refractive index, n_yFor the refractive index of phase axis orthogonal direction slow in face, n_zFor the refractive index of thickness direction, d is the thickness of test film [nm].The thickness d [nm] of test film uses digital display dial gauge (デジマティッ Network イ Application ジケータ) (Mitutoyo Corp's system Make) it measures.Mean refractive index n uses digital precision the refractometer (" KPR- of カ Le ニュー optics industry Co., Ltd. manufacture 20 ") it measures.

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

It will be replaced in the autoclave for being equipped with stirring blade and three-way cock with nitrogen.It puts into thereto at room temperature Bis- (the 2,6- di-t-butyl -4- methylenedioxy phenoxies of isobutyl group of toluene 1600kg, 1,2- dimethoxy-ethane 80kg, concentration 0.45M Base) aluminium toluene solution 73.3kg (42.3mol) and concentration 1.3M s-butyl lithium solution (solvent: 95 mass % of hexamethylene/ 5 mass % of n-hexane) 8.44kg (14.1mmol).While agitating, distillation essence was added dropwise thereto with 30 minutes at 15 DEG C The MMA550kg of system.After completion of dropwise addition, stirred 90 minutes at 15 DEG C.The color of solution becomes colorless from yellow.The moment The polymerisation conversion of MMA is 100%.Toluene 1500kg is added in obtained solution to be diluted.Then, dilution is infused Enter into a large amount of methanol, obtains sediment.Obtained sediment is 24 hours dry at 80 DEG C, 140Pa, obtain methyl Acrylic resin (M1-1).

The Mw of methacrylic resin (M1-1) is 70000, melt viscosity η be 1200Pas, Mw/Mn 1.06, Same steric regularity (rr) is 75%, α relaxation temperature is 142 DEG C, the content of MMA monomeric unit is 100 mass % (poly- methyl-props E pioic acid methyl ester (PMMA)).The physical property of methacrylic resin (M1-1) is shown in Table 1.

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

It will be replaced in the autoclave for being equipped with stirring blade and three-way cock with nitrogen.It puts into thereto at room temperature Bis- (the 2,6- di-t-butyl -4- methylenedioxy phenoxies of isobutyl group of toluene 1600kg, 1,2- dimethoxy-ethane 60kg, concentration 0.45M Base) aluminium toluene solution 73.3kg (42.3mol) and concentration 1.3M s-butyl lithium solution (solvent: 95 mass % of hexamethylene/ 5 mass % of n-hexane) 4.22kg (7.1mmol).While agitating, distillation purification was added dropwise thereto with 30 minutes at 15 DEG C MMA550kg.After completion of dropwise addition, stirred 90 minutes at 15 DEG C.The color of solution becomes colorless from yellow.The MMA at the moment Polymerisation conversion be 100%.Toluene 1500kg is added in obtained solution to be diluted.Then, dilution is injected Into a large amount of methanol, sediment is obtained.Obtained sediment is 24 hours dry at 80 DEG C, 140Pa, obtain methyl-prop Olefin(e) acid resinoid (M1-2).

The Mw of methacrylic resin (M1-2) is 36000, melt viscosity η be 400Pas, Mw/Mn 1.07, Same steric regularity (rr) is 75%, α relaxation temperature is 138 DEG C, the content of MMA monomeric unit is 100 mass % (poly- methyl-props E pioic acid methyl ester (PMMA)).The physical property of methacrylic resin (M1-2) is shown in Table 1.

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

It will be replaced in the autoclave for being equipped with blender and collection tube with nitrogen.In the MMA100 for being wherein packed into purification Bis- (2- methyl propionitrile (hydrogen-taking capacity: 1%, 1 hour half life temperature: 83 DEG C) 0.0054 mass parts of mass parts, 2,2 '-azos With 0.200 mass parts of n octylmercaptan, it is stirred, obtains material liquid.It is sent into nitrogen into the material liquid, it will be in material liquid Dissolved oxygen removes.

Above-mentioned raw materials liquid is packed into the tank reactor connecting by piping with autoclave until the 2/3 of capacity.? In the state that temperature is maintained at 140 DEG C, polymerization reaction is first started with intermittent mode.Reach 55 mass % in polymerisation conversion When, material liquid is supplied from autoclave with the flow that mean residence time is 150 minutes in the state of being maintained at 140 DEG C of temperature Into tank reactor, while to extract reaction solution from tank reactor out with the comparable flow of the supply flow rate of material liquid, Be converted to the polymerization reaction of continuous flow mode.After conversion, the polymerisation conversion under stable state is 48 mass %.

The reaction solution extracted out from the tank reactor for reach stable state is supplied with the flow that mean residence time is 2 minutes It is heated in the multi tube heat exchanger for being 230 DEG C to interior temperature.Then, the reaction solution after heating is imported into flash vessel, It will make volatile ingredient as main component with unreacted monomer to remove, and obtain molten resin.By the melting after removing volatile ingredient In the double screw extruder that it is 260 DEG C to interior temperature that resin, which is supplied, with strands shape discharge, is cut with pelletizer, obtain pellet The methacrylic resin (M2-1) of shape.

The Mw of methacrylic resin (M2-1) is 112000, melt viscosity η be 1000Pas, Mw/Mn 1.86, Degree of syndiotacticity (rr) is 52%, α relaxation temperature is 129 DEG C, the content of MMA monomeric unit is 100 mass % (poly- methyl Methyl acrylate (PMMA)).The physical property of methacrylic resin (M2-1) is shown in Table 1.

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

It will be replaced in the autoclave for being equipped with blender and collection tube with nitrogen.In the MMA100 for being wherein packed into purification Bis- (2- methyl propionitrile (hydrogen-taking capacity: 1%, 1 hour half life temperature: 83 DEG C) 0.0065 mass parts of mass parts, 2,2 '-azos With 0.290 mass parts of n octylmercaptan, it is stirred, obtains material liquid.It is sent into nitrogen into the material liquid, dissolved oxygen is removed It goes.

Charging feedstock liquid is until the 2/3 of capacity in the tank reactor being connect by piping with autoclave.Will be warm Degree is maintained in the state of 120 DEG C, first starts polymerization reaction with intermittent mode.When polymerisation conversion reaches 55 mass %, It is maintained in the state of 120 DEG C of temperature and is supplied material liquid to slot from autoclave with the flow that mean residence time is 120 minutes In type reactor, while to extract reaction solution from tank reactor out with the comparable flow of the supply flow rate of material liquid, conversion For the polymerization reaction of continuous flow mode.After conversion, the polymerisation conversion under stable state is 45 mass %.

The reaction solution extracted out from the tank reactor for reach stable state is supplied with the flow that mean residence time is 2 minutes It is heated in the multi tube heat exchanger for being 230 DEG C to interior temperature.Then, the reaction solution after heating is imported into flash vessel, It will make volatile ingredient as main component with unreacted monomer to remove, and obtain molten resin.By the melting after removing volatile ingredient In the double screw extruder that it is 230 DEG C to interior temperature that resin, which is supplied, with strands shape discharge, is cut with pelletizer, obtain pellet The methacrylic resin (M2-2) of shape.

The Mw of methacrylic resin (M2-2) is 83000, melt viscosity η be 700Pas, Mw/Mn 1.87, Same steric regularity (rr) is 55%, α relaxation temperature is 130 DEG C, the content of MMA monomeric unit is 100 mass % (poly- methyl-props E pioic acid methyl ester (PMMA)).The physical property of methacrylic resin (M2-2) is shown in Table 1.

(polycarbonate resin (PC))

Prepare polycarbonate resin below (PC).

(PC-1): the polycarbonate resin of straight chain (firmly changes the " SDPOLYCATR- of Si Tailong polycarbonate company manufacture 2201 ", according to MVR (JISK7210 is measured under conditions of 300 DEG C, load 1.2Kg, 10 minutes)=210cm³/ 10 minutes, Mw=22000, Mw/Mn=2.0).

(Production Example 5) (manufacture of crosslinked rubber particles composition (CD-1))

< Production Example 5-1 >

Ion is put into the reactive tank for being applied with glass lined capacity 100L for having capacitor, thermometer and blender Exchanged water 48kg then puts into odium stearate 416g, sodium lauryl sarcosinate 128g and sodium carbonate 16g, makes it dissolve.Then, MMA11.2kg and allyl methacrylate 110g is put into, is warming up to 70 DEG C while agitating.Then, 2% persulfuric acid is added Aqueous solutions of potassium 560g, starts emulsion polymerization.The fever due to caused by polymerization, internal temperature increase, and then, internal temperature is opened Begin to decline.It after being reduced to 70 DEG C, is stirred 30 minutes at 70 DEG C, carries out emulsion polymerization, obtain the lotion containing seed particles.

2% sodium persulfate aqueous solution 720g is added in the lotion containing seed particles.Then, it was added dropwise with 60 minutes by third The mixture that olefin(e) acid butyl ester 12.4kg, styrene 1.76kg and allyl methacrylate 280g are constituted.After completion of dropwise addition, stirring 60 minutes, emulsion polymerization is carried out, the lotion containing nucleocapsid two layers of particles is obtained.

2% persulfate aqueous solution 320g is added in the lotion containing nucleocapsid two layers of particles, is further added with 30 minutes Add the mixture being made of MMA6.2kg, methyl acrylate 0.2kg and n octylmercaptan 200g.After addition, 60 points are stirred Clock carries out emulsion polymerization, is then cooled to room temperature.By aforesaid operations, obtains the volume reference containing 40 mass % and be averaged grain The lotion of the crosslinked rubber particles (three one polymer particle of acrylic acid series) (CR-1) of 0.23 μm of diameter of nucleocapsid three-decker.

< Production Example 5-2 >

Ion is put into the reactive tank for being applied with glass lined capacity 100L for having capacitor, thermometer and blender Exchanged water 48kg then puts into surfactant (" the ペレッ Network ス SS-H " of Kao Corp's manufacture) 252g, keeps its molten Solution.After reactive tank is warming up to 70 DEG C, add 2% persulfate aqueous solution 160g thereto, then, disposable addition by The mixture that MMA3.04kg, methyl acrylate 0.16kg and n octylmercaptan 15.2g are constituted, starts emulsion polymerization.It is anti-from polymerization Continue stirring 30 minutes from the time of answering caused fever to disappear.

After adding 2% persulfate aqueous solution 160g thereto, continuously it was added dropwise with 2 hours by MMA27.4kg, acrylic acid The mixture that methyl esters 1.44kg and n octylmercaptan 98g is constituted.It after completion of dropwise addition, stirs 60 minutes, carries out emulsion polymerization.By institute Obtained lotion is cooled to room temperature.By aforesaid operations, 0.12 μm of the volume-based average particle size containing 40 mass %, spy are obtained Property viscosity 0.44g/dl acrylic acid series polymeric compounds particle (dispersion auxiliary particle) (DA-1) lotion.

< Production Example 5-3 >

The cream of crosslinked rubber particles (three one polymer particle of acrylic acid series) (CR-1) will be contained obtained in Production Example 5-1 Contain the lotion of acrylic acid series polymeric compounds particle (dispersion auxiliary particle) (DA-1) so that particle obtained in liquid and Production Example 5-2 (CR-1): the mass ratio of particle (DA-1) is that the mode of 2:1 is mixed.The mixed emulsion was frozen at -20 DEG C with 2 hours Knot.Mixed emulsion after freezing is put into 80 DEG C of warm water of its 2 times amounts, makes its defrosting, obtain slurries.The slurries are existed It is kept at 80 DEG C after twenty minutes, dehydration is dried and powdered at 70 DEG C.By aforesaid operations, obtain containing crosslinking rubber granule Sub (CR-1) and the crosslinked rubber particles composition (CD-1) for dispersing auxiliary particle (DA-1).

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

Into the three-necked flask after replacing inside with nitrogen, under room temperature (20~25 DEG C) be added dry toluene 735kg, The toluene of 1,2- dimethoxy-ethane 36.75kg and bis- (2,6- di-t-butyl -4- methylphenoxy) the aluminium 20mol of isobutyl group are molten Liquid 39.4kg.S-butyl lithium 1.17mol is added thereto.MMA39.0kg is further added, reacts 1 hour, obtains at room temperature MMA polymer (methacrylate polymers) (b1-1).The Mw of MMA polymer (b1-1) is 45800.

Then, reaction solution is cooled to -25 DEG C, with 0.5 hour dropwise addition n-butyl acrylate 29.0kg and benzyl acrylate The mixed liquor of 10.0kg continues polymerization reaction from the end of MMA polymer (b1-1).Then, it is added into reaction solution Methanol 4kg, stops polymerization reaction, and reaction solution is injected into a large amount of methanol, and block copolymer (BP-1) is precipitated.Leaching Obtained precipitate, it is 12 hours dry under 80 DEG C, 1 support (about 133Pa).

By aforesaid operations, obtain by MMA polymer blocks (b1-1) and by n-butyl acrylate unit and acrylic acid benzyl The diblock copolymer (BP-1) that the acrylate polymer block (b2-1) that ester units are constituted is constituted.Block copolymer (BP-1) Mw be 92000, Mw/Mn 1.06.The Mw of MMA polymer (b1-1) is 45800, therefore, by acrylate polymer (b2- 1) Mw is determined as 46200.The ratio of benzyl acrylate unit in acrylate polymer (b2-1) is 25.6 mass %. (b1-1)/(b2-1) mass ratio is 50/50.

(ultraviolet absorbing agent (LA))

Prepare ultraviolet absorbing agent below (LA).

(LA-31): 2,2 '-di-2-ethylhexylphosphine oxides [6- (2H- benzotriazole -2- base) -4- tert-octyl phenol] (ADEKA corporation Make),

(LA-F70): 2,4,6- tri- (2- hydroxyl -4- hexyl oxygroup -3- aminomethyl phenyl) -1,3,5- triazine (ADEKA company Manufacture).

(polymer processing aid (PA))

Prepare polymer processing aid below (PA).

(PA-1): Mitsubishi's Li Yang company manufactures " メタ Block レ Application P550A " (average degree of polymerization: 7734, MMA monomeric units Content: 88 mass %, the content of Butyl Acrylate Monomer unit: 12 mass %).

(embodiment 1)

By 20 mass parts of methacrylic resin (M1-1), 80 mass parts of methacrylic resin (M2-1), block 2 matter of 1.0 mass parts of copolymer (BP-1), 0.9 mass parts of ultraviolet absorbing agent (LA-F70) and polymer processing aid (PA-1) Part mixing is measured, using double screw extruder (Co., Ltd. テ Network ノベ Le manufactures " KZW20TW-45MG-NH-600 "), 250 Melting mixing at DEG C squeezes out melting mixing object, manufactures methacrylic resin composition (R11).Implement methacrylic acid The evaluation of physical property of based resin composition (R11).The composition of methacrylic resin composition (R11) and evaluation result are shown in In table 2.

Obtained methacrylic resin composition (R11) is 12 hours dry at 80 DEG C.It is mono- using 20mm φ Screw extruder (manufacture of OCS company), at 260 DEG C of resin temperature, by methacrylic resin composition (R11) from width It squeezes out for the T-die of 150mm, is deflected from using 100 DEG C of roller of surface temperature, obtain width 120mm, 160 μm of thickness Unstretching film.

Obtained unstretching film is cut into 100mm × 100mm.For the film, the biaxial stretch-formed examination of two slot types interval is used It is biaxial stretch-formed to implement to test machine.In the first slot, in Tg+20 DEG C of draft temperature, 860%/minute of tensile speed, stretching ratio 2 Implement simultaneously biaxial drawing under conditions of × 2, then, in the second slot, in Tg-10 DEG C of heat-fixing temperature, 90 seconds conditions Lower implementation heat fixation, is then quenched, and obtains 40 μm of thickness of biaxially-stretched film (F11).By stretching condition and biaxially-stretched film Evaluation result is shown in table in 3.In turn, Corona discharge Treatment is implemented to the single side of obtained biaxially-stretched film (F11), then leads to Vacuum vapour deposition is crossed with the thickness AM aluminum metallization of 30nm.The stacked film obtained in this way is the excellent stacked film of bright luster.

(embodiment 2~4)

In each example of embodiment 2~4, other than changing composition and stretching condition, operates similarly with example 1, obtain To methacrylic resin composition (R12)~(R14) and biaxially-stretched film (F12)~(F14), and evaluated.By group At, stretching condition and evaluation result is shown in table in 2, table 3.

(comparative example 1~4)

In each example of comparative example 1~4, other than changing composition and stretching condition, operates similarly with example 1, obtain To methacrylic resin composition (R21)~(R24) and biaxially-stretched film (F21)~(F24), and evaluated.By group At, stretching condition and evaluation result is shown in table in 2, table 3.

(result)

In Examples 1 to 4, the methacrylic resin (M1) and α that are 137 DEG C or more containing α relaxation temperature have been manufactured Relaxation temperature is the melt viscosity η of 132 DEG C of methacrylic resins (M2) below, methacrylic resin (M1)₁Greatly In the melt viscosity η of methacrylic resin (M2)₂, methacrylic resin (M1)/methacrylic resin (M2) Mass ratio be 2/98~29/71 methacrylic resin composition (R11)~(R14).Obtained in Examples 1 to 4 Thermogravimetric conservation rate is high, hot forming is good by methacrylic resin composition (R11)~(R14).In Examples 1 to 4 The transparency is high, thermal linear expansion coefficient is small, dimensional stability is good, impact resistance by obtained biaxially-stretched film (F11)~(F14) Property is good.

It is obtained double in using only methacrylic resin (M2) as the comparative example 1 of methacrylic resin The thermal linear expansion coefficient of axis stretched film (F21) is big, and dimensional stability is bad, and impact resistance is also bad.Although being applied in combination Methacrylic resin (M1) and methacrylic resin (M2) are used as methacrylic resin but methacrylic The use level of resin (M1) is in the comparative example 2,3 more than Examples 1 to 3, obtained methacrylic resin composition (R22)~(R23) thermogravimetric conservation rate low and high temperature formability is bad.The melt viscosity η of methacrylic resin (M1)₁It is small In the melt viscosity η of methacrylic resin (M2)₂Comparative example 4 in, linear expansion coefficient is big, therefore, poor dimensional stability, Impact resistance is also poor.

The present invention is not limited to the above embodiments and embodiment, without departing from purport of the invention, then can suitably into Row design alteration.

This application claims preferential based on Japanese publication Patent 2016-150205 proposed by July 29th, 2016 Power, its entire disclosure is incorporated in this specification.

Claims

1. a kind of methacrylic resin composition is α when carrying out Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz Relaxation temperature T_α1For 137 DEG C or more of methacrylic resins (M1) and the progress dynamic viscoelastic survey at stretch mode, 1Hz The α relaxation temperature T of timing_α2For the methacrylic resin composition of 132 DEG C of methacrylic resins (M2) below,

By methacrylic resin (M1) and methacrylic resin (M2) at 260 DEG C, shear velocity 122 seconds^-1Under Melt viscosity is set to η₁And η₂When, η₁> η₂,

Methacrylic resin (M1)/methacrylic resin (M2) mass ratio is 2/98~29/71.

2. methacrylic resin composition as described in claim 1, wherein the molecule of methacrylic resin (M1) Amount is distributed as 1.0~1.4.

3. methacrylic resin composition as claimed in claim 1 or 2, wherein methacrylic resin (M1) Weight average molecular weight is 40000~200000.

4. methacrylic resin composition according to any one of claims 1 to 3, wherein methacrylic tree The content of the methyl methacrylate monomer unit of rouge (M2) is 99 mass % or more.

5. methacrylic resin composition as described in any one of claims 1 to 4, wherein further contain poly- carbon Acid ester resin and/or phenoxy resin.

6. such as methacrylic resin composition according to any one of claims 1 to 5, wherein further containing crosslinking Rubber and/or block copolymer.

7. such as methacrylic resin composition according to any one of claims 1 to 6, wherein further containing ultraviolet Light absorbers.

8. a kind of manufacturing method of methacrylic resin composition, wherein by methacrylic resin (M1) and methyl Acrylic resin (M2) is with methacrylic resin (M1)/methacrylic resin (M2) mass ratio 2/98~29/ 71 carry out melting mixings, when the methacrylic resin (M1) carries out Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz α relaxation temperature T_α1It is 137 DEG C or more, the methacrylic resin (M2) carries out dynamic viscoelastic at stretch mode, 1Hz α relaxation temperature T when measurement_α2For 132 DEG C hereinafter,

By methacrylic resin (M1) and methacrylic resin (M2) at 260 DEG C, shear velocity 122 seconds^-1Under Melt viscosity is set as η₁And η₂When, η₁> η₂。

9. a kind of formed body is made of methacrylic resin composition according to any one of claims 1 to 7.

10. a kind of film is made of methacrylic resin composition according to any one of claims 1 to 7.

11. film as claimed in claim 10 is stretched film.

12. a kind of stacked film, the layer constituted with the film described in claim 10 or 11.

13. stacked film as claimed in claim 12, wherein further have the layer being made of metal and/or metal oxide.

14. stacked film as described in claim 12 or 13, wherein further have adhesive layer.

15. one kind is laminated into body, stacked film described in any one of claim 12~14 is laminated on substrate.