CN109563328A - Methacrylic resin composition and its manufacturing method, film, stacked film, are laminated into body at formed body - Google Patents
Methacrylic resin composition and its manufacturing method, film, stacked film, are laminated into body at formed body Download PDFInfo
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- CN109563328A CN109563328A CN201780046768.4A CN201780046768A CN109563328A CN 109563328 A CN109563328 A CN 109563328A CN 201780046768 A CN201780046768 A CN 201780046768A CN 109563328 A CN109563328 A CN 109563328A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08L21/00—Compositions of unspecified rubbers
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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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, 1Hzα1For 137 DEG C or more of methacrylic resins (M1) and the α relaxation temperature T at stretch mode, 1Hz when progress Measurement of Dynamic Viscoelasticityα2For 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
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 Tα1It 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 measurementα2For 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 Tα1It is 137 DEG C or more, methacrylic resin (M2) carries out Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz
When α relaxation temperature Tα2For 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 (Tα) ", " 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 Tα1It 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 measurementα2For 132 DEG C of methacrylic resins (M2) below.
In the present specification, " α relaxation temperature (Tα) " refer to relaxation (α relaxation caused by the sub-chain motion because of main polymer chain
Henan) summit temperature.α relaxation temperature (Tα) 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 curveα)
Between it is related, but in the present invention, replace α relaxation temperature (T without using Tgα) 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 Tα1It 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 (Tα) 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 [5.2.1.02,6] 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.
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.
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 [5.2.1.02,6] 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
(Tα) 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 Tα2It 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 (Tα) heat resistance of resin combination can be improved in high, resistance to pyrolytic is low methacrylic resin (M1).But α relaxes
Henan temperature (Tα) 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 (Tα) 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 (Tα) 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 enumeratedmaxFor 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 agentmaxIt 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 agentUV) and the maximum value (A of absorbance that is measuredmax)
The maximum value ε of molar absorption coefficient is calculated using following formulamax。
εmax=[Amax/(10×10-3)]×MUV
< 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 nx、ny、nz,
Calculate phase difference the Rth (=((n of thickness directionx+ny)/2-nz)×d).It should be noted that nxFor phase axis direction slow in face
Refractive index, nyFor the refractive index of phase axis orthogonal direction slow in face, nzFor 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 (15)
1. a kind of methacrylic resin composition is α when carrying out Measurement of Dynamic Viscoelasticity at stretch mode, 1Hz
Relaxation temperature Tα1For 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 timingα2For 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 Tα1It is 137 DEG C or more, the methacrylic resin (M2) carries out dynamic viscoelastic at stretch mode, 1Hz
α relaxation temperature T when measurementα2For 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.
Applications Claiming Priority (3)
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JP2016-150205 | 2016-07-29 | ||
JP2016150205 | 2016-07-29 | ||
PCT/JP2017/027148 WO2018021449A1 (en) | 2016-07-29 | 2017-07-27 | Methacrylate resin composition, method for producing same, molded body, film, laminated film, and laminated molded body |
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CN113710452A (en) * | 2019-04-23 | 2021-11-26 | 住友化学株式会社 | Laminate and method for producing laminate |
CN115348979A (en) * | 2020-03-24 | 2022-11-15 | 株式会社可乐丽 | Methacrylic copolymer, composition, molded body, method for producing film or sheet, and laminate |
CN115427227A (en) * | 2020-04-22 | 2022-12-02 | 株式会社可乐丽 | Laminated body |
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JP7177776B2 (en) * | 2017-08-24 | 2022-11-24 | 株式会社クラレ | Laminate and its manufacturing method |
WO2020218447A1 (en) * | 2019-04-24 | 2020-10-29 | 株式会社クラレ | Laminated film |
JPWO2021020426A1 (en) * | 2019-07-30 | 2021-02-04 | ||
JP7341827B2 (en) * | 2019-09-30 | 2023-09-11 | 株式会社クラレ | Thermoplastic resin compositions with excellent long-term weather resistance, molded products and laminates thereof |
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JP2010024337A (en) * | 2008-07-18 | 2010-02-04 | Toray Ind Inc | Resin composition and molded article composed therefrom |
CN105209541A (en) * | 2013-05-16 | 2015-12-30 | 株式会社可乐丽 | Methacrylic resin composition and molded body thereof |
WO2016002750A1 (en) * | 2014-06-30 | 2016-01-07 | 株式会社クラレ | Methacrylic resin or methacrylic resin composition |
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JPS6414216A (en) * | 1987-07-07 | 1989-01-18 | Daicel Chem | Water-resistant material |
JP2882674B2 (en) | 1990-02-14 | 1999-04-12 | 昭和電工株式会社 | Process for producing polymethacrylate and polyacrylate |
JP2002327012A (en) | 2001-05-01 | 2002-11-15 | Kuraray Co Ltd | Syndiotactic methacrylic ester polymer and polymer composition |
JP2008024861A (en) * | 2006-07-24 | 2008-02-07 | Tokyo Institute Of Technology | Method for producing crystalline methacrylic resin |
JP2016094537A (en) * | 2014-11-14 | 2016-05-26 | 株式会社クラレ | Thermoplastic resin composition and manufacturing method therefor, molded body and thermoplastic resin film |
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Patent Citations (3)
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JP2010024337A (en) * | 2008-07-18 | 2010-02-04 | Toray Ind Inc | Resin composition and molded article composed therefrom |
CN105209541A (en) * | 2013-05-16 | 2015-12-30 | 株式会社可乐丽 | Methacrylic resin composition and molded body thereof |
WO2016002750A1 (en) * | 2014-06-30 | 2016-01-07 | 株式会社クラレ | Methacrylic resin or methacrylic resin composition |
Cited By (3)
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CN113710452A (en) * | 2019-04-23 | 2021-11-26 | 住友化学株式会社 | Laminate and method for producing laminate |
CN115348979A (en) * | 2020-03-24 | 2022-11-15 | 株式会社可乐丽 | Methacrylic copolymer, composition, molded body, method for producing film or sheet, and laminate |
CN115427227A (en) * | 2020-04-22 | 2022-12-02 | 株式会社可乐丽 | Laminated body |
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