WO2015107954A1 - 共重合体および成形体 - Google Patents
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- WO2015107954A1 WO2015107954A1 PCT/JP2015/050241 JP2015050241W WO2015107954A1 WO 2015107954 A1 WO2015107954 A1 WO 2015107954A1 JP 2015050241 W JP2015050241 W JP 2015050241W WO 2015107954 A1 WO2015107954 A1 WO 2015107954A1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/005—Polyesters prepared from ketenes
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0065—Manufacturing aspects; Material aspects
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
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- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- 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
- C08J2333/00—Characterised by the use 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; Derivatives of such polymers
- C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
Definitions
- the present invention relates to a copolymer which is excellent in transparency and heat resistance, has a high tensile breaking strain without containing rubber, and a molded article containing such a copolymer.
- methacrylic resin is excellent in optical properties such as transparency and weather resistance, so conventionally, display members used for lighting fixtures, signboards, etc., optical members used for display devices, interior members, building members, electronic / electrical members It is used in various applications including medical parts. In these applications, in addition to optical properties and weather resistance, mechanical properties such as flexibility, flex resistance, impact resistance, and flexibility are often required.
- a methacrylic resin composition in which various other resins are added to a methacrylic resin has been proposed.
- a method of blending methacrylic resin with multilayer structure acrylic rubber particles produced by an emulsion polymerization method is mentioned (Patent Document 1).
- a methacrylic resin composition comprising a methacrylic resin and a block copolymer having a methacrylic ester polymer block and an acrylic ester polymer block is known (Patent Documents 2 and 3).
- An object of the present invention is to provide a copolymer that is excellent in transparency and heat resistance, has a high tensile breaking strain without containing other resins, and a molded body containing such a copolymer. .
- the present inventors have made various studies in order to achieve the above object. As a result, by introducing an ester structural unit derived from a cyclic ketene acetal monomer into a structural unit derived from a methacrylic acid ester monomer, the high transparency and rigidity originally possessed by the methacrylic resin are greatly increased. It was found that it can be made difficult to break without lowering.
- the present invention provides the following aspects.
- a copolymer comprising a structural unit derived from 80% by mass to 98% by mass of a methacrylic acid ester monomer and an ester structural unit derived from 2 to 10% by mass of a cyclic ketene acetal monomer. And a copolymer having a weight average molecular weight of 80,000 or more and a molecular weight distribution of 1.75 or more and 3.80 or less.
- the copolymer of the present invention is excellent in transparency and heat resistance, and can be obtained as a non-crackable copolymer having a large tensile breaking strain without containing other resins. Moreover, the molded object with few external appearance defects containing this copolymer can be provided.
- FIG. 4 is an enlarged view of a strain 0 to 4% portion of a strain-stress curve in Examples 1 and 2 and Comparative Examples 1 and 2.
- the copolymer of the present invention contains a structural unit derived from a methacrylic acid ester monomer and an ester structural unit derived from a cyclic ketene acetal monomer.
- the copolymer of the present invention contains 80% by mass to 98% by mass of structural units derived from methacrylic acid esters with respect to the mass of the copolymer.
- the content of the structural unit is more preferably 85% by mass to 97% by mass, and particularly preferably 90% by mass to 96% by mass.
- methacrylic acid ester examples include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; methacrylic acid aryl esters such as phenyl methacrylate; cyclohexyl methacrylate, 2-isobornyl methacrylate, and methacrylic acid 8 Methacrylic acid cycloalkyl esters such as tricyclo [5.2.1.0 2,6 ] decanyl, 2-norbornyl methacrylate and 2-adamantyl methacrylate; alkyl methacrylates are preferred, and methyl methacrylate is preferred. Most preferred.
- the copolymer of the present invention contains 2 to 10% by mass of an ester structural unit derived from a cyclic ketene acetal monomer with respect to the mass of the copolymer.
- the content of the structural unit is more preferably 3% by mass to 9% by mass, and particularly preferably 4% by mass to 8% by mass.
- the ester structural unit derived from the cyclic ketene acetal monomer is formed by the ring-opening polymerization of the cyclic ketene acetal monomer. That is, the structural unit derived from the cyclic ketene acetal monomer and having an ester bond by ring-opening polymerization is 2 to 10% by mass with respect to the mass of the copolymer.
- the ring opening rate of the structure derived from the cyclic ketene acetal monomer in the copolymer is preferably 50% or more, more preferably 70% or more, most Preferably it is 100%.
- the copolymer of the present invention has a structure derived from a radical polymerizable monomer other than a methacrylic acid ester monomer and a cyclic ketene acetal monomer (hereinafter sometimes referred to as a radical polymerizable monomer (A)). You may have a unit.
- the radical polymerizable monomer (A) include vinyl aromatic hydrocarbons such as styrene, ⁇ -methylstyrene, p-methylstyrene, and m-methylstyrene; vinylcyclohexane, vinylcyclopentane, vinylcyclohexene, vinylcycloheptane.
- Vinyl cycloaliphatic hydrocarbons such as vinylcycloheptene and vinyl norbornene; ethylenically unsaturated carboxylic acids such as maleic anhydride, maleic acid and itaconic acid; ethylene, propylene, 1-butene, isobutylene, 1-octene and the like Olefin; Conjugated dienes such as butadiene, isoprene, myrcene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride; methyl acrylate, acrylic acid N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl
- the amount of the structural unit derived from the radical polymerizable monomer (A) contained in the copolymer of the present invention is preferably relative to the mass of the copolymer from the balance of ductility performance, heat resistance, and water absorption. Is 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
- the copolymer of the present invention has a ductile performance because an ester structural unit that easily entangles the molecular chain between the copolymers is introduced into the main chain. It is expressed. Therefore, it is important that the weight average molecular weight, which is a factor affecting the ease of entanglement between the molecular chains of the copolymer, is large to some extent.
- the weight average molecular weight is 80,000 or more, preferably 80,000 to 2,000,000, more preferably 90,000 to 1,000,000, still more preferably 100,000 to 700,000, and particularly preferably 120,000 to 500,000. When the weight average molecular weight is too low, the entanglement between the copolymers is reduced, and it becomes difficult to exhibit ductility performance. If the weight average molecular weight is too high, molding becomes difficult.
- the weight average molecular weight can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent in the polymerization reaction during copolymer synthesis.
- the copolymer of the present invention has a weight average molecular weight / number average molecular weight ratio (hereinafter, this ratio is referred to as “molecular weight distribution”), preferably 1.75 to 3.80, more preferably 1. 80 to 3.50, more preferably 1.90 to 3.20. If the molecular weight distribution is too narrow, the ratio between the high molecular weight substance and the low molecular weight substance generally decreases.However, if the ratio of the high molecular weight substance decreases, the ductility performance is remarkably lowered, and if the ratio of the low molecular weight substance decreases, molding is performed. The nature will decline.
- the weight average molecular weight and molecular weight distribution are values in terms of standard polystyrene measured by GPC (gel permeation chromatography).
- Such weight average molecular weight and molecular weight distribution can be controlled by adjusting the type and amount of the polymerization initiator and chain transfer agent during the polymerization reaction. Further, a purification method such as reprecipitation that removes low molecular weight substances is not preferable because the molecular weight distribution is smaller than 1.80.
- GPC measurement is performed as follows. Tetrahydrofuran is used as the eluent, and TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 are connected in series as the column.
- HLC-8320 product number
- RI detector differential refractive index detector
- As a sample a solution in which 4 mg of methacrylic resin was dissolved in 5 ml of tetrahydrofuran was used.
- the column oven temperature was set to 40 ° C., 20 ⁇ l of sample solution was injected at an eluent flow rate of 0.35 ml / min, and the chromatogram was measured.
- Standard polystyrene having a molecular weight in the range of 5000000 to 400 was measured, and a calibration curve showing the relationship between retention time and molecular weight was prepared.
- the baseline connecting the point where the slope on the high molecular weight side of the chromatogram changes from zero to positive and the point where the slope of the peak on the low molecular weight side changes from negative to zero was taken as the baseline. If the chromatogram shows multiple peaks, connect the line connecting the point where the slope of the highest molecular weight peak changes from zero to positive and the point where the slope of the lowest molecular weight peak changes from negative to zero. Baseline.
- the copolymer of the present invention has a glass transition temperature of preferably 70 to 180 ° C, more preferably 80 to 180 ° C, still more preferably 80 to 120 ° C, and still more preferably 85 to 120 ° C. If the glass transition temperature is too low, the heat resistance of the copolymer is insufficient, and the usable applications are limited. If the glass transition temperature is too high, the copolymer is brittle and easily cracked, and the effects of the present invention are hardly exhibited.
- the glass transition temperature is a value measured in accordance with JIS K7121.
- the copolymer of the present invention was heated once to 230 ° C., then cooled to room temperature, and then DSC curve was measured by differential scanning calorimetry under the condition that the temperature was raised from room temperature to 230 ° C. at 10 ° C./min. And the midpoint glass transition temperature obtained from the DSC curve measured at the second temperature rise was defined as the glass transition temperature of the present invention.
- the ester structural unit introduced into the main chain of the copolymer of the present invention can be cleaved by methanolysis.
- the molar ratio of the ester structural unit introduced into the main chain of the copolymer of the present invention can be determined from the number average molecular weight of the polymer obtained after the decomposition with methanol. Further, by measuring the molecular weight distribution of the polymer obtained after the decomposition with methanol, it can be seen how uniformly the ester structural unit is introduced into the main chain of the copolymer.
- the polymer obtained after methanol decomposition is a polymer or copolymer obtained by methanol decomposition.
- the polymer which consists only of methacrylic acid ester corresponds.
- a structural unit derived from the radically polymerizable monomer (A) is present in the copolymer before being decomposed
- what is obtained by methanol decomposition is a structure derived from a methacrylic acid ester monomer. It becomes a copolymer comprising a unit and a structural unit derived from the radical polymerizable monomer (A).
- Such a copolymer is also referred to as a polymer obtained after methanol decomposition. It can be seen that the narrower the molecular weight distribution of the polymer obtained after methanol decomposition, the more uniformly the cyclic ketene acetal monomer was copolymerized.
- the molecular weight distribution of the polymer obtained after the decomposition with methanol is narrow, that is, the ester structure unit is uniformly introduced into the copolymer main chain, the entanglement between the copolymers increases, and the higher ductility.
- the molecular weight distribution of the polymer obtained after methanol decomposition is preferably 2.0 or less, more preferably 1.90 or less, and most preferably 1.75 or less.
- the method for producing the copolymer of the present invention There is no particular limitation on the method for producing the copolymer of the present invention. Usually, from the viewpoint of productivity, a radical polymerization method is employed to produce a copolymer by adjusting the polymerization temperature, polymerization time, type and amount of chain transfer agent, type and amount of polymerization initiator, etc. The method is preferred.
- the radical polymerization method is preferably performed in the absence of a solvent or in a solvent, and is preferably performed in the absence of a solvent from the viewpoint of obtaining a copolymer having a low impurity concentration. From the viewpoint of suppressing the occurrence of silver and coloring in the molded body, the polymerization reaction is preferably performed with a low dissolved oxygen content.
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.
- the polymerization initiator used in the radical polymerization method for producing the copolymer of the present invention is not particularly limited as long as it generates a reactive radical.
- t-hexyl peroxyisopropyl monocarbonate t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate T-hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 , 1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2′-azobis (2-methylpropionitrile), 2, 2
- t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2'-azobis (2-methylpropionate) are preferable.
- the 1-hour half-life temperature of such a polymerization initiator is preferably 60 to 140 ° C, more preferably 80 to 120 ° C.
- the polymerization initiator used for the production of the copolymer preferably has a hydrogen abstraction ability of 20% or less, more preferably 10% or less, and even more preferably 5% or less.
- Such polymerization initiators can be used alone or in combination of two or more.
- the amount of the polymerization initiator used is preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.01 parts by mass, and still more preferably 100 parts by mass of the monomer subjected to the polymerization reaction. Is 0.005 to 0.007 parts by mass.
- the hydrogen abstraction ability can be known from the technical data of the polymerization initiator manufacturer (for example, Nippon Oil & Fats Co., Ltd. technical document “Hydrogen abstraction capacity and initiator efficiency of organic peroxide” (created in April 2003)). . Further, it can be measured by a radical trapping method using ⁇ -methylstyrene dimer, that is, ⁇ -methylstyrene dimer trapping method. The measurement is generally performed as follows. First, the polymerization initiator is cleaved in the presence of ⁇ -methylstyrene dimer as a radical trapping agent to generate radical fragments.
- radical fragments having a low hydrogen abstraction ability are added to and trapped by the double bond of ⁇ -methylstyrene dimer.
- a radical fragment having a high hydrogen abstraction capacity abstracts hydrogen from cyclohexane to generate a cyclohexyl radical, and the cyclohexyl radical is added to and trapped by a double bond of ⁇ -methylstyrene dimer to generate a cyclohexane trapping product. Therefore, the ratio (mole fraction) of radical fragments having a high hydrogen abstraction capacity with respect to the theoretical radical fragment generation amount, which is obtained by quantifying cyclohexane or cyclohexane-trapped product, is defined as the hydrogen abstraction capacity.
- the chain transfer agent used in the radical polymerization method for producing the copolymer of the present invention includes n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexane.
- Dithiol ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- ( ⁇ -thiopro)
- alkyl mercaptans such as pentaerythritol tetrakisthiopropionate.
- monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferred.
- These chain transfer agents can be used alone or in combination of two or more.
- the amount of the chain transfer agent used is preferably 0.1 to 1 part by weight, more preferably 0.15 to 0.8 part by weight, and still more preferably 0 to 100 parts by weight of the monomer to be subjected to the polymerization reaction. .2 to 0.6 parts by mass, most preferably 0.2 to 0.5 parts by mass.
- the amount of the chain transfer agent used is preferably 2500 to 10000 parts by mass, more preferably 3000 to 9000 parts by mass, and further preferably 3500 to 6000 parts by mass with respect to 100 parts by mass of the polymerization initiator. When the amount of chain transfer agent used is within the above range, the resulting copolymer tends to have good moldability and high mechanical strength.
- the solvent used in the radical polymerization method for producing the copolymer of the present invention is not limited as long as it can dissolve the monomer and the copolymer, but aromatic hydrocarbons such as benzene, toluene, and ethylbenzene are not limited. preferable. These solvents can be used alone or in combination of two or more.
- the usage-amount of a solvent can be suitably set from a viewpoint of the viscosity and productivity of a reaction liquid.
- the amount of the solvent used is, for example, preferably 100 parts by mass or less, more preferably 90 parts by mass or less with respect to 100 parts by mass of the polymerization reaction raw material.
- the temperature during the polymerization reaction is preferably 100 to 200 ° C., more preferably 110 to 180 ° C.
- productivity tends to be improved due to an improvement in the polymerization rate, a decrease in the viscosity of the polymerization solution, and the like.
- polymerization temperature is 200 degrees C or less, control of a superposition
- the polymerization reaction time is preferably 0.5 to 4 hours, more preferably 1.5 to 3.5 hours, and further preferably 1.5 to 3 hours.
- the polymerization reaction time is an average residence time in the reactor.
- the polymerization conversion rate in the radical polymerization method for producing the copolymer of the present invention is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 35 to 65% by mass.
- the polymerization conversion rate is 20% by mass or more, the remaining unreacted monomer can be easily removed, and the appearance of the molded body made of the copolymer tends to be good.
- the polymerization conversion rate is 70% by mass or less, the viscosity of the polymerization solution is lowered and productivity tends to be improved.
- Radical polymerization may be carried out using a batch reactor, but it is preferred to carry out using a continuous flow reactor from the viewpoint of productivity and the ductility performance of the resulting copolymer.
- a polymerization reaction raw material (monomer (meaning methacrylate ester, cyclic ketene acetal, radical polymerizable monomer (A)), polymerization initiator, chain transfer agent, etc.
- a mixed solution containing the liquid, and is supplied to the reactor at a constant flow rate, and the liquid in the reactor is withdrawn at a flow rate corresponding to the supply amount.
- a tubular reactor that can be in a state close to plug flow and / or a tank reactor that can be in a state close to complete mixing can be used.
- continuous flow polymerization may be performed in one reactor, or continuous flow polymerization may be performed by connecting two or more reactors.
- the amount of liquid in the tank reactor during the polymerization reaction is preferably 1/4 to 3/4, more preferably 1/3 to 2/3 with respect to the volume of the tank reactor.
- the reactor is usually equipped with a stirring device.
- the stirring device include a static stirring device and a dynamic stirring device.
- the dynamic agitation device include a Max blend type agitation device, an agitation device having a grid-like blade rotating around a vertical rotation shaft disposed in the center, a propeller type agitation device, and a screw type agitation device.
- a Max blend type stirring apparatus is preferably used from the point of uniform mixing property.
- the removal method is not particularly limited, but heating devolatilization is preferable.
- the devolatilization method include an equilibrium flash method and an adiabatic flash method.
- the devolatilization temperature by the adiabatic flash method is preferably 200 to 280 ° C, more preferably 220 to 260 ° C.
- the time for heating the resin by the adiabatic flash method is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and further preferably 0.5 to 2 minutes. When devolatilized in such a temperature range and heating time, a copolymer with little coloring is easily obtained.
- the removed unreacted monomer can be recovered and used again for the polymerization reaction. Since the yellow index of the recovered monomer may be high due to heat applied during the recovery operation, etc., the recovered monomer should be purified by an appropriate method to reduce the yellow index. Is preferred.
- another copolymer may be mixed with the copolymer of the present invention within a range not impairing the effects of the present invention.
- examples of such other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, and high impact polystyrene.
- the molded product of the present invention preferably contains 80% by mass or more of the copolymer of the present invention, more preferably 90% by mass or more.
- the manufacturing method of the molded object of this invention is not specifically limited.
- the copolymer of the present invention or a molding material containing the copolymer of the present invention is, for example, a T-die method (lamination method, coextrusion method, etc.), an inflation method (coextrusion method, etc.), a compression molding method, a blow molding.
- a melt molding method such as a method, a calendar molding method, a vacuum molding method, and an injection molding method (insert method, two-color method, press method, core back method, sandwich method, etc.) and a solution casting method.
- the T die method, the inflation method, or the injection molding method is preferable from the viewpoint of high productivity and cost.
- the copolymer of the present invention can be in the form of pellets or the like in order to enhance convenience during storage, transportation or molding.
- the molding may be performed a plurality of times.
- the pellet-shaped molded body can be further molded to obtain a molded body having a desired shape.
- an antioxidant as required for the copolymer, an antioxidant, a thermal deterioration inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, an antistatic agent, a flame retardant, Various additives such as dyes and pigments, light diffusing agents, organic dyes, matting agents, and phosphors may be added.
- the blending amount of such various additives can be appropriately determined within a range not impairing the effects of the present invention, and the total amount is preferably 7% by mass or less, more preferably 5% by mass. Hereinafter, it is more preferably 4% by mass or less.
- additives may be added to the polymerization reaction solution when the copolymer is produced, may be added to the copolymer produced by the polymerization reaction, or may be added during the production of the molded article. Also good.
- An antioxidant is effective in preventing oxidative degradation of a resin alone in the presence of oxygen.
- examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. These antioxidants may be used alone or in combination of two or more.
- a phosphorus-based antioxidant and a hindered phenol-based antioxidant are preferable, and a combination of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is more preferable.
- the amount of phosphorus antioxidant used is 1: 5 to 2: 1 is preferable, and 1: 2 to 1: 1 is more preferable.
- Examples of phosphorus antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: ADK STAB HP-10), tris (2,4-di-) t-butylphenyl) phosphite (manufactured by BASF; trade name: IRGAFOS168), 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3 , 9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADK STAB PEP-36) and the like.
- pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANOX 1010), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name IRGANOX1076) is preferred.
- the thermal degradation inhibitor is capable of preventing thermal degradation of the resin by capturing polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
- thermal degradation inhibitor examples include 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumitizer GS) preferable.
- the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays, and is mainly said to have a function of converting light energy into heat energy.
- ultraviolet absorbers examples include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. These may be used alone or in combination of two or more.
- Benzotriazoles are preferable as ultraviolet absorbers used when the film of the present invention is applied to optical applications because it has a high effect of suppressing deterioration of optical properties such as coloring due to ultraviolet irradiation.
- benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H- Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2′-methylenebis [6- (2H-benzotriazole-2) -Yl) -4-t-octylphenol] (manufactured by ADEKA; LA-31), 2- (5-octylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4
- an ultraviolet absorber for triazines 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70) Further, hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; TINUVIN477 and TINUVIN460), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5- A triazine etc. can be mentioned.
- the light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light.
- Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
- lubricant examples include stearic acid, behenic acid, stearamide acid, methylene bisstearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hardened oil.
- the release agent examples include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
- higher alcohols and glycerin fatty acid monoester are used in combination, the ratio is not particularly limited, but the amount of higher alcohol used: the amount of glycerin fatty acid monoester is 2.5: 1 to 3. 5: 1 is preferable, and 2.8: 1 to 3.2: 1 is more preferable.
- polymer particles having a particle diameter of 0.05 to 0.5 ⁇ m which can be usually produced by an emulsion polymerization method, are used.
- the polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be.
- particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.
- the polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g. If the intrinsic viscosity is too small, the effect of improving moldability tends to be low. If the intrinsic viscosity is too large, the molding processability of the copolymer tends to be lowered.
- organic dye a compound having a function of converting ultraviolet light into visible light is preferably used.
- Examples of the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate and the like.
- Fluorescent substances include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent brighteners, fluorescent bleaches, and the like.
- a film which is one form of the molded body of the present invention can be produced by a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method, or the like.
- the extrusion molding method is preferred from the viewpoint that a film having excellent transparency, improved toughness, excellent handleability, and excellent balance between toughness, surface hardness and rigidity can be obtained.
- the temperature of the copolymer discharged from the extruder is preferably set to 160 to 270 ° C, more preferably 220 to 260 ° C.
- a film points out the planar molded object of thickness 0.005mm or more and 0.25mm or less.
- the copolymer of the present invention or the molding material containing the copolymer of the present invention is in a molten state.
- a method comprising extruding from a T-die and then forming it by sandwiching it with two or more mirror rolls or mirror belts is preferred.
- the mirror roll or mirror belt is preferably made of metal.
- the linear pressure between the pair of mirror rolls or the mirror belt is preferably 10 N / mm or more, more preferably 30 N / mm or more.
- the surface temperature of the mirror roll or the mirror belt is preferably 130 ° C. or less.
- the pair of mirror rolls or mirror belts preferably have at least one surface temperature of 60 ° C. or higher.
- the copolymer of the present invention discharged from the extruder or the molding material containing the copolymer of the present invention can be cooled at a faster rate than natural cooling, and the surface smoothness can be achieved. It is easy to produce a film having excellent properties and low haze.
- the thickness of the unstretched film obtained by extrusion molding is preferably 10 to 300 ⁇ m.
- the haze of the film is preferably 0.5% or less, more preferably 0.3% or less at a thickness of 100 ⁇ m.
- a stretch treatment may be applied to the molded product of the present invention formed into a film.
- the stretching process increases the mechanical strength, and a film that is difficult to crack can be obtained.
- the stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tuber stretching method. From the viewpoint that a film having high strength that can be stretched uniformly is obtained, the lower limit of the temperature during stretching is 10 ° C. higher than the glass transition temperature of the copolymer, and the upper limit of the temperature during stretching is the glass transition of the copolymer. The temperature is 40 ° C. higher than the temperature. Stretching is usually performed at 100 to 5000% / min. A film with less heat shrinkage can be obtained by heat setting after stretching.
- the thickness of the stretched film is preferably 10 to 200 ⁇ m.
- the copolymer and molded product of the present invention are difficult to break due to ductility, and have high transparency and heat resistance. Therefore, the copolymer and the molded product are suitable for optical applications.
- Polarizer protective film, liquid crystal protective plate, surface of portable information terminal It is particularly suitable for use as a material, a display window protection film for a portable information terminal, a light guide film, and front plates for various displays.
- a building material such as a decorative film, vehicle interior, furniture, door material, and baseboard.
- a sample solution was prepared by dissolving 4 mg of the polymer, copolymer or polymer composition to be measured in 5 ml of tetrahydrofuran.
- the column oven temperature was set to 40 ° C., 20 ⁇ l of sample solution was injected at an eluent flow rate of 0.35 ml / min, and the chromatogram was measured.
- Ten standard polystyrenes having a molecular weight in the range of 400 to 5000000 were measured by GPC, and a calibration curve showing the relationship between retention time and molecular weight was prepared. Based on this calibration curve, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined, and the molecular weight distribution (Mw / Mn) was determined.
- the DSC curve was measured under the condition of cooling to room temperature and then raising the temperature from room temperature to 230 ° C. at 10 ° C./min.
- the midpoint glass transition temperature obtained from the DSC curve measured at the second temperature rise was defined as the glass transition temperature in the present invention.
- Total light transmittance The polymer, copolymer or polymer composition was hot press molded at 230 ° C. to obtain a test piece (A) of 50 mm ⁇ 50 mm ⁇ thickness 3.2 mm.
- the total light transmittance of the test piece (A) was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) according to JIS K7361-1.
- the haze of the test piece (A) for which the total light transmittance was measured was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) according to JIS K7136.
- Test piece (Tensile modulus / Tensile breaking strain)
- the polymer or copolymer was hot press molded at 230 ° C. to obtain a test piece of 120 mm ⁇ 50 mm ⁇ 0.4 mm thickness.
- the obtained test piece was cut into a size of 90 mm ⁇ 10 mm, and the cross section was polished with No. 1500 sandpaper.
- the cut specimen was set in a tensile tester (manufactured by Shimadzu: Autograph AG-IS 5 kN) set at a distance of 70 mm between the chucks, and a tensile test was performed at a tensile speed of 5 mm / min to measure tensile stress and tensile strain ( Strain-Stress curve). From this measurement, the tensile modulus and tensile breaking strain were calculated.
- the strain at the time of fracture is defined as tensile fracture strain.
- the polymer, copolymer or polymer composition was hot press molded at 230 ° C. to obtain a test piece of 50 mm ⁇ 50 mm ⁇ thickness 3.2 mm.
- the pencil hardness of the obtained test piece was measured according to JIS K5600-5-4 with a 0.75 kg load.
- An emulsion was obtained by maintaining at 70 ° C. for 30 minutes after the completion of the polymerization peak.
- emulsion containing multilayer polymer particles (A) contains 40% multilayer polymer particles (A) (three-stage polymer) having an average particle size of 0.23 ⁇ m. It was.
- the intrinsic viscosity of the (meth) acrylate polymer particles (B) in the resulting emulsion is 0.44 g. / Dl.
- Example 1 The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. The pressure vessel was charged with 19.8 parts by mass of methyl methacrylate and 5 parts by mass of 7MDO obtained in Synthesis Example 2 with respect to 25 parts by mass of toluene.
- the polymerization was stopped by cooling to room temperature. After 25 parts by mass of toluene was added to the obtained solution for dilution, the solution was poured into 2000 parts by mass of methanol to precipitate a solid. The precipitated solid was filtered and sufficiently dried to obtain 12 parts by mass of the copolymer (A1).
- the content of structural units derived from methyl methacrylate was 92% by mass
- the content of structural units derived from 7MDO was 8.0% by mass
- the copolymer (A1) had a weight average molecular weight (Mw) of 272,000 and a molecular weight distribution (Mw / Mn) of 2.23.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- Example 2 The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. The pressure vessel was charged with 21 parts by mass of methyl methacrylate and 4.1 parts by mass of 7MDO obtained in Synthesis Example 2 with respect to 25 parts by mass of toluene.
- the copolymer (A2) had a weight average molecular weight (Mw) of 312,000 and a molecular weight distribution (Mw / Mn) of 2.17.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- Example 3 The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen. The pressure vessel was charged with 21 parts by mass of methyl methacrylate, 4.1 parts by mass of 7MDO obtained in Synthesis Example 2, and 0.100 parts by mass of n-octyl mercaptan with respect to 25 parts by mass of toluene. Was polymerized in the same manner as in Example 1 to obtain 12 parts by mass of the copolymer (A3). When 1 H-NMR of the copolymer (A3) was measured, the content of structural units derived from methyl methacrylate was 94.1% by mass, and the content of structural units derived from 7MDO was 5.9% by mass.
- the copolymer (A3) had a weight average molecular weight (Mw) of 147,000 and a molecular weight distribution (Mw / Mn) of 3.04. The results are shown in Table 1 together with other evaluation results.
- Example 4 The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen.
- the polymer (A4) had a weight average molecular weight (Mw) of 285,200 and a molecular weight distribution (Mw / Mn) of 2.84. The results are shown in Table 1 together with other evaluation results.
- Example 5 The inside of the pressure vessel equipped with a stirrer that was sufficiently dried was purged with nitrogen.
- 7.0 parts by mass of 7MDO obtained in Synthesis Example 2 0.084 parts by mass of n-octyl mercaptan, di-t-butyl peroxide with respect to 62.3 parts by mass of methyl methacrylate.
- Polymerization was carried out in the same manner as in Example 4 except that 0.0018 part by mass (Nippon Yushi Co., Ltd .: Perbutyl D) was charged to obtain 40 parts by mass of copolymer (A5).
- the copolymer (A5) had a weight average molecular weight (Mw) of 695,000 and a molecular weight distribution (Mw / Mn) of 3.25. The results are shown in Table 1 together with other evaluation results.
- the polymer (B1) had a weight average molecular weight (Mw) of 853,000 and a molecular weight distribution (Mw / Mn) of 1.85.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- the copolymer (B2) had a weight average molecular weight (Mw) of 176,000 and a molecular weight distribution (Mw / Mn) of 2.02.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- 7MDO was 100% ring-opening polymerized and had ester structural units in the polymer main chain.
- the copolymer (B3) had a weight average molecular weight (Mw) of 75,000 and a molecular weight distribution (Mw / Mn) of 2.20. The results are shown in Table 1 together with other evaluation results.
- the copolymer (B4) had a weight average molecular weight (Mw) of 200,000 and a molecular weight distribution (Mw / Mn) of 2.12. The results are shown in Table 1 together with other evaluation results.
- Example 7 A copolymer was synthesized in the same manner as in Example 8 of JP-A-11-228633. That is, the inside of the pressure vessel equipped with a stirrer sufficiently dried was purged with nitrogen. 25 parts by mass of 7MDO obtained in Synthesis Example 2 with respect to 25 parts by mass of methyl methacrylate in the pressure vessel, 0 of dimethyl 2,2-azobisisobutyrate (Wako Pure Chemicals: V-601) 0.058 part by mass was charged.
- copolymer (B7) After sufficiently replacing the pressure vessel with nitrogen gas, the temperature was raised to 60 ° C. with stirring. The polymerization was carried out at 60 ° C. for 1 hour with stirring, and then cooled to room temperature to stop the polymerization. The obtained solution was poured into 2000 parts by mass of methanol to precipitate a solid. The precipitated solid was filtered and sufficiently dried to obtain 2.5 parts by mass of copolymer (B7).
- 1 H-NMR of the copolymer (B7) was measured, the content of the structural unit derived from methyl methacrylate was 95.5% by mass, and the content of the structural unit derived from 7MDO was 4.5% by mass. 7MDO was 100% ring-opening polymerized and had ester structural units in the polymer main chain.
- the polymer (B7) had a weight average molecular weight (Mw) of 533,000 and a molecular weight distribution (Mw / Mn) of 1.68. The results are shown in Table 1 together with other evaluation results.
- the copolymer of the example has 2 to 10% by mass of an ester structural unit derived from a cyclic ketene acetal monomer, and the structural unit contains an ester structure generated by ring-opening polymerization, Since the average molecular weight is not less than 80,000 and the molecular weight distribution is not less than 1.80 and not more than 3.80, they all have high tensile fracture strain and exhibit high ductility performance without cracking when bent. It can also be seen that the total light transmittance is high, the haze is low, and the transparency is high.
- the copolymer or polymer of Comparative Examples 1 and 2 has high transparency, it does not have an ester structural unit derived from 2 to 10% by mass of a cyclic ketene acetal monomer, so that the tensile strain at break is small. It does not show ductility performance (see FIGS. 1 and 2) and breaks when bent. Further, a copolymer having a weight average molecular weight of less than 80,000 (Comparative Example 3) and a copolymer having less than 2% by mass of an ester structural unit derived from a cyclic ketene acetal monomer (Comparative Example 4) are also subjected to tensile breaking strain. Is small and does not exhibit ductility.
- ester structural unit derived from the cyclic ketene acetal monomer is more than 10% by mass as in the copolymer of Comparative Example 6, the ductility performance is high, but the soft material has a low glass transition temperature and a low tensile elastic modulus. turn into.
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Abstract
Description
これら様々な他の樹脂を添加する場合、分散不良により透明性が低下したり、フィルムやシートの場合、ブツ欠点の原因となったりして外観不良を発生させる。これら課題を根本的に解決するためには、他の樹脂を添加することなく、可撓性、耐屈曲性、耐衝撃性、柔軟性などの機械物性を向上させる究極の手法が必要である。
(重量平均分子量、数平均分子量、分子量分布)
溶離液としてテトラヒドロフラン、カラムとして東ソー株式会社製のTSKgel SuperMultipore HZM-Mの2本とSuperHZ4000を直列に繋いだものを用いた。GPC装置として、示差屈折率検出器(RI検出器)を備えた東ソー株式会社製のHLC-8320(品番)を使用した。測定対象である重合体または共重合体または重合体組成物4mgをテトラヒドロフラン5mlに溶解させて試料溶液を作製した。カラムオーブンの温度を40℃に設定し、溶離液流量0.35ml/分で、試料溶液20μlを注入して、クロマトグラムを測定した。分子量が400~5000000の範囲内にある標準ポリスチレン10点をGPCで測定し、保持時間と分子量との関係を示す検量線を作成した。この検量線に基づいて重量平均分子量(Mw)および数平均分子量(Mn)を決定し、また分子量分布(Mw/Mn)を求めた。
重合体または共重合体または重合体組成物の0.5質量部をベンゼンの15質量部に溶解させた。そこに、0.5Nカリウムメトキシドのメタノール溶液を10質量部加えた後、23℃で12時間撹拌した。その溶液をイオン交換水で洗浄後、上澄みを十分乾燥させて、加メタノール分解した重合体を得た。加メタノール分解した重合体の数平均分子量、分子量分布をGPCにて測定した。
(ガラス転移温度)
重合体または共重合体または重合体組成物を、JIS K7121に準拠して、示差走査熱量測定装置(島津製作所製、DSC-50(品番))を用いて、230℃まで一度昇温し、次いで室温まで冷却し、その後、室温から230℃までを10℃/分で昇温させる条件にてDSC曲線を測定した。2回目の昇温時に測定されるDSC曲線から求められる中間点ガラス転移温度を本発明におけるガラス転移温度とした。
重合体または共重合体または重合体組成物を230℃にて熱プレス成形して、50mm×50mm×厚さ3.2mmの試験片(A)を得た。JIS K7361-1に準じて、ヘイズメータ(村上色彩研究所製、HM-150)を用いて試験片(A)の全光線透過率を測定した。
(ヘイズ)
全光線透過率を測定した試験片(A)のヘイズは、JIS K7136に準拠して、ヘイズメータ(村上色彩研究所製、HM-150)を用いて測定した。
(引張弾性率・引張破断ひずみ)
重合体または共重合体を230℃にて熱プレス成形して、120mm×50mm×厚さ0.4mmの試験片を得た。得られた試験片から90mm×10mmのサイズに切り出し、断面を1500番のサンドペーパーで研磨した。切り出した試験片をチャック間70mmにセットした引張り試験機(島津製:オートグラフAG-IS 5kN)にセットし、引張り速度5mm/分にて引張り試験を行い、引張応力および引張ひずみを測定した(Strain-Stressカーブ)。この測定から引張弾性率および引張破断ひずみを算出した。なお、ここでは試験片が降伏する場合、降伏しない場合に関係なく、破断した時点のひずみを引張破断ひずみとした。
後述の合成例で合成した環状ケテンアセタール単量体やその中間体の構造確認、及び、実施例及び比較例の共重合体中の共重合組成、開環率の評価は、1H-NMRにて実施した。1H-NMRスペクトルは、核磁気共鳴装置(Bruker社製 ULTRA SHIELD 400 PLUS)を用いて、分析したい試料10mgに対して重水素化溶媒として重水素化クロロホルムを1mL用い、室温、積算回数64回の条件にて、測定した。
(鉛筆硬度)
重合体または共重合体または重合体組成物を230℃にて熱プレス成形して、50mm×50mm×厚さ3.2mmの試験片を得た。得られた試験片の鉛筆硬度測定は、JIS K5600-5-4に準拠し、0.75Kg荷重で測定した。
2-クロロメチル-1,3-ジオキセパン(i)の合成
1H-NMR(400MHz,CDCl3,ppm,TMS,)δ:1.75(4H,m),3.47(2H,d,J=5.2Hz),3.69(2H,m),3.95(2H,m),4.85(1H,t,J=5.2Hz)
<合成例2>
2-メチレン-1,3-ジオキセパン[7MDO](ii)の合成
1H-NMR(400MHz,CDCl3,ppm,TMS,)δ:1.76(4H,m),3.48(2H,S),3.94(4H,m)
(1) コンデンサー、温度計および撹拌機を備えたグラスライニングを施した反応槽(100リットル)に、イオン交換水48kgを投入し、次いでステアリン酸ナトリウム416g、ラウリルザルコシン酸ナトリウム128gおよび炭酸ナトリウム16gを投入して溶解させた。次いで、メタクリル酸メチル11.2kgおよびメタクリル酸アリル110gを投入し撹拌しながら70℃に昇温した後、2%過硫酸カリウム水溶液560gを添加して重合を開始させた。重合ピーク終了後30分間にわたって70℃に保持してエマルジヨンを得た。
(2) 次いで、上記(1)で得られたエマルジヨンに、2%過硫酸ナトリウム水溶液720gを更に添加した後、アクリル酸ブチル12.4kg、スチレン1.76kgおよびメタクリル酸アリル280gからなる単量体混合物を60分かけて滴下し、その後60分間撹拌を続けてグラフト重合を行った。
(3) 上記(2)で得られたグラフト重合後のエマルジヨンに、2%過硫酸カリウム水溶液320gを添加し、さらにメタクリル酸メチル6.2kg、アクリル酸メチル0.2kgおよびn-オクチルメルカプタン200gからなる単量体混合物を30分間かけて添加し、その後60分間撹拌を続けて重合を完結させた後、冷却して重合体エマルジヨンを得た。それにより得られたエマルジヨン(以下「多層構造重合体粒子(A)を含むエマルジヨン」という)は平均粒径0.23μmの多層構造重合体粒子(A)(3段階重合体)を40%含有していた。
製造例1で用いたのと同様の反応槽を用いて、イオン交換水48kgを投入した後、界面活性剤(花王株式会社製「ペレックスSS-H」)252gを投入して撹拌して溶解させた。70℃に昇温した後、2%過硫酸カリウム水溶液160gを添加し、次いでメタクリル酸メチル3.04kg、アクリル酸メチル0.16kgおよびn-オクチルメルカプタン15.2gからなる混合物を一括添加して重合を開始させた。重合による発熱が終了した時点から30分間撹拌を続けた後、2%過硫酸カリウム水溶液160gを添加し、次いでメタクリル酸メチル27.4kg、アクリル酸メチル1.44kgおよびn-オクチルメルカプタン98gからなる混合物を2時間かけて連続的に滴下して重合を行った。滴下終了後、60分間放置した後冷却して平均粒径0.12μmの(メタ)アクリル酸エステル系重合体粒子(B)を40%含有する重合体エマルジヨンを得た。それにより得られたエマルジヨン(以下「(メタ)アクリル酸エステル系重合体粒子(B)を含むエマルジヨン」という)中の(メタ)アクリル酸エステル系重合体粒子(B)の極限粘度は0.44g/dlであった。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの25質量部に対して、メタクリル酸メチルの19.8質量部、合成例2で得られた7MDOの5質量部を仕込んだ。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの25質量部に対して、メタクリル酸メチルの21質量部、合成例2で得られた7MDOの4.1質量部を仕込んだ。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの25質量部に対して、メタクリル酸メチルの21質量部、合成例2で得られた7MDOの4.1質量部、n-オクチルメルカプタンの0.100質量部を仕込んだ以外は、実施例1と同様に重合して共重合体(A3)12質量部を得た。共重合体(A3)の1H-NMRを測定したところ、メタクリル酸メチルに由来する構造単位の含量は94.1質量%、7MDOに由来する構造単位の含量は5.9質量%であり、7MDOは100%開環重合し、重合体主鎖にエステル構造単位を有していた。共重合体(A3)は、重量平均分子量(Mw)が147,000、分子量分布(Mw/Mn)が3.04であった。その他評価結果と併せて結果を表1に示す。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの17.5質量部に対して、メタクリル酸メチルの48.3質量部、合成例2で得られた7MDOの21質量部、n-オクチルメルカプタンの0.096質量部、ジ-t-ブチルパーオキサイド(日本油脂製:パーブチルD)の0.002質量部を仕込んだ。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にメタクリル酸メチルの62.3質量部に対して、合成例2で得られた7MDOの7.0質量部、n-オクチルメルカプタンの0.084質量部、ジ-t-ブチルパーオキサイド(日本油脂製:パーブチルD)の0.0018質量部を仕込んだ以外は、実施例4と同様に重合して共重合体(A5)40質量部を得た。共重合体(A5)の1H-NMRを測定したところ、メタクリル酸メチルに由来する構造単位の含量は95.4質量%、7MDOに由来する構造単位の含量は4.6質量%であり、7MDOは100%開環重合し、重合体主鎖にエステル構造単位を有していた。共重合体(A5)は、重量平均分子量(Mw)が695,000、分子量分布(Mw/Mn)が3.25であった。その他評価結果と併せて結果を表1に示す。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの17.5質量部に対して、メタクリル酸メチルの69.3質量部、ジ-t-ブチルパーオキサイド(日本油脂製:パーブチルD)の0.002質量部を仕込んだ。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にメタクリル酸メチルの69.3質量部に対して、n-オクチルメルカプタンの0.084質量部、ジ-t-ブチルパーオキサイド(日本油脂製:パーブチルD)の0.0018質量部を仕込んだ以外は、比較例1と同様に重合して共重合体(B2)33質量部を得た。共重合体(B2)の1H-NMRを測定したところ、メタクリル酸メチルに由来する構造単位の含量は100質量%であった。共重合体(B2)は、重量平均分子量(Mw)が176,000、分子量分布(Mw/Mn)が2.02であった。その他評価結果と併せて結果を表1、図1および図2に示す。また、230℃にて熱プレス成形して、得られた試験片(120mm×50mm×厚さ0.4mm)を室温(23℃)にて手で180度に折り曲げようとしたところ、割れてしまった。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの25質量部に対して、メタクリル酸メチルの21質量部、合成例2で得られた7MDOの4.1質量部、n-オクチルメルカプタンの0.175質量部を仕込んだ以外は、実施例1と同様に重合して共重合体(B3)12質量部を得た。共重合体(B3)の1H-NMRを測定したところ、メタクリル酸メチルに由来する構造単位の含量は94.1質量%、7MDOに由来する構造単位の含量は5.9質量%であり、7MDOは100%開環重合し、重合体主鎖にエステル構造単位を有していた。共重合体(B3)は、重量平均分子量(Mw)が75,000、分子量分布(Mw/Mn)が2.20であった。その他評価結果と併せて結果を表1に示す。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの17.5質量部に対して、メタクリル酸メチルの65.8質量部、合成例2で得られた7MDOの3.5質量部、n-オクチルメルカプタンの0.105質量部、ジ-t-ブチルパーオキサイド(日本油脂製:パーブチルD)の0.002質量部を仕込んだ以外は、比較例1と同様に重合して共重合体(B4)30質量部を得た。共重合体(B4)の1H-NMRを測定したところ、メタクリル酸メチルに由来する構造単位の含量は98.4質量%、7MDOに由来する構造単位の含量は1.6質量%であり、7MDOは100%開環重合し、重合体主鎖にエステル構造単位を有していた。共重合体(B4)は、重量平均分子量(Mw)が200,000、分子量分布(Mw/Mn)が2.12であった。その他評価結果と併せて結果を表1に示す。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの17.5質量部に対して、メタクリル酸メチルの55.3質量部、合成例2で得られた7MDOの14質量部、n-オクチルメルカプタンの0.105質量部、ジ-t-ブチルパーオキサイド(日本油脂製:パーブチルD)の0.002質量部を仕込んだ以外は、比較例1と同様に重合して共重合体(B5)42質量部を得た。共重合体(B5)の1H-NMRを測定したところ、メタクリル酸メチルに由来する構造単位の含量は93.1質量%、7MDOに由来する構造単位の含量は6.9質量%であり、7MDOは100%開環重合し、重合体主鎖にエステル構造単位を有していた。共重合体(B5)は、重量平均分子量(Mw)が363,000、分子量分布(Mw/Mn)が3.93であった。その他評価結果と併せて結果を表1に示す。
充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にトルエンの17.5質量部に対して、メタクリル酸メチルの34.3質量部、合成例2で得られた7MDOの35.0質量部、n-オクチルメルカプタンの0.096質量部、ジ-t-ブチルパーオキサイド(日本油脂製:パーブチルD)の0.0043質量部を仕込んだ以外は、比較例1と同様に重合して共重合体(B6)21質量部を得た。共重合体(B6)の1H-NMRを測定したところ、メタクリル酸メチルに由来する構造単位の含量は75.1質量%、7MDOに由来する構造単位の含量は24.9質量%であり、7MDOは100%開環重合し、重合体主鎖にエステル構造単位を有していた。共重合体(B6)は、重量平均分子量(Mw)が223,000、分子量分布(Mw/Mn)が2.60であった。その他評価結果と併せて結果を表1に示す。
特開平11-228633号公報の実施例8と同様に共重合体を合成した。すなわち、充分乾燥させた撹拌装置付き耐圧容器内を窒素置換した。該耐圧容器にメタクリル酸メチルの25質量部に対して、合成例2で得られた7MDOの25質量部、ジメチル2,2-アゾビスイソブチレート(和光純薬製:V-601)の0.058質量部を仕込んだ。
(1) 製造例1で得られた多層構造重合体粒子(A)を含むエマルジヨンおよび製造例2で得られた(メタ)アクリル酸エステル系重合体粒子(B)を含むエマルジヨンを、多層構造重合体粒子(A):(メタ)アクリル酸エステル系重合体粒子(B)の重量比が2:1になるようにして混合して混合エマルジヨンをつくり、それを-20℃で2時間かけて凍結した。凍結した混合エマルジヨンをその2倍量の80℃の温水に投入して溶解させてスラリー状にした後、80℃に20分間保持し、次いで脱水し、70℃で乾燥して、粉末状の耐衝撃性改良材を得た。
Claims (7)
- 80質量%~98質量%のメタクリル酸エステル単量体に由来する構造単位と、2~10質量%の環状ケテンアセタール単量体に由来するエステル構造単位よりなる共重合体であって、重量平均分子量8万以上、かつ、分子量分布が1.75以上3.80以下の共重合体。
- 前記共重合体中の前記エステル構造単位を加メタノール分解後に得られる重合体の分子量分布が2.0以下であることを特徴とする請求項1に記載の共重合体。
- 前記メタクリル酸エステル単量体がメタクリル酸メチルである請求項1または2に記載の共重合体。
- 請求項1~3のいずれか一項に記載の共重合体を含有する成形体。
- 請求項4に記載の成型体からなる導光フィルム。
- 請求項4に記載の成型体からなる加飾フィルム。
- 請求項4に記載の成型体からなる偏光子保護フィルム。
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JPWO2015107954A1 (ja) | 2017-03-23 |
EP3095800A1 (en) | 2016-11-23 |
TWI639622B (zh) | 2018-11-01 |
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US10287380B2 (en) | 2019-05-14 |
JP6574138B2 (ja) | 2019-09-11 |
US20160326288A1 (en) | 2016-11-10 |
KR20160108338A (ko) | 2016-09-19 |
TW201531490A (zh) | 2015-08-16 |
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