WO2018230122A1 - エステル樹脂、反可塑化剤、セルロースエステル樹脂組成物、光学フィルム及び液晶表示装置 - Google Patents
エステル樹脂、反可塑化剤、セルロースエステル樹脂組成物、光学フィルム及び液晶表示装置 Download PDFInfo
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- WO2018230122A1 WO2018230122A1 PCT/JP2018/015022 JP2018015022W WO2018230122A1 WO 2018230122 A1 WO2018230122 A1 WO 2018230122A1 JP 2018015022 W JP2018015022 W JP 2018015022W WO 2018230122 A1 WO2018230122 A1 WO 2018230122A1
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- ester resin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to an ester resin suitable as an antiplasticizer for a resin for optical materials, a cellulose ester resin containing the ester resin, an optical film obtained using the resin composition, and a liquid crystal display device using the same.
- TAC triacetyl cellulose resin
- TAC is hard and brittle, there is a problem that when it is formed into a film, the strength is insufficient and breakage easily occurs. Moreover, since TAC has high moisture permeability and dimensional change due to moisture absorption is likely to occur, it is necessary to suppress moisture absorption by additives, and various additives have been provided (see, for example, Patent Document 1).
- the problem to be solved by the present invention is particularly suitable as an antiplasticizer for optical resins, which can increase the strength at the time of processing into a film and improve the moisture permeability. It is an object to provide an ester resin that can be used in the present invention, a resin composition containing the ester resin, an optical film obtained using the resin composition, and a liquid crystal display device using the same.
- the present invention provides the following general formula (1) B- (GA) n -GB (1)
- B is an aryl monocarboxylic acid residue or an aliphatic monocarboxylic acid residue
- G is an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue
- A is an alkylene dicarboxylic acid residue.
- Residue (A1) or aryl dicarboxylic acid residue (A2) which is the sum of alkylene dicarboxylic acid residue (A1) and aryl dicarboxylic acid residue (A2) (A1 + A2) of aryl dicarboxylic acid residue (A2)
- the content is 70 to 100 mol%
- n is the number of repetitions
- G and A may be the same or different for each repetition
- a plurality of B and G may be the same or different.
- an ester resin that has an excellent balance between strength and moisture permeability when processed into a film and can be suitably used as an antiplasticizer for optical resins.
- the specific ester resin particularly in an optical film containing a cellulose ester resin, it is possible to achieve both improvement in elastic modulus and suppression of moisture permeation, and it can be suitably used as an optical film used in a liquid crystal display device. it can.
- FIG. 1 is a GPC chart of the ester resin (1-1) obtained in Example 1.
- the ester resin of the present invention has the following general formula (1) B- (GA) n -GB (1) [In the formula (1), B is an aryl monocarboxylic acid residue or an aliphatic monocarboxylic acid residue, G is an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue, and A is an alkylene dicarboxylic acid residue.
- Residue (A1) or aryl dicarboxylic acid residue (A2) which is the sum of alkylene dicarboxylic acid residue (A1) and aryl dicarboxylic acid residue (A2) (A1 + A2) of aryl dicarboxylic acid residue (A2)
- the content is 70 to 100 mol%
- n is the number of repetitions
- G and A may be the same or different for each repetition
- a plurality of B and G may be the same or different.
- B in the general formula (1) is an aryl monocarboxylic acid residue or an aliphatic monocarboxylic acid residue.
- the “carboxylic acid residue” refers to a group other than —OH in the carboxy group.
- the aryl monocarboxylic acid residue is an aryl monocarboxylic acid residue having 6 to 12 carbon atoms, which is easy to obtain raw materials, easy to esterify, and mixed with a cellulose ester resin described later.
- benzoic acid dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cumin
- examples thereof include acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, ethoxybenzoic acid, propoxybenzoic acid, anisic acid, naphthoic acid and the like, and they may be used alone or in combination of two or more.
- a residue of benzoic acid, p-toluic acid, or dimethylbenzoic acid is preferable, and a residue of benzoic acid is more preferable.
- the number of carbon atoms does not include the carbon atom in the carboxy group. Further, it may be a residue such as nicotinic acid or furoic acid having an aromaticity, which may have a substituent.
- the aliphatic monocarboxylic acid residue is an aliphatic monocarboxylic acid residue having 1 to 8 carbon atoms, which is mixed with raw material availability, ease of esterification reaction, and cellulose ester resin described later. At this time, it is preferable from the viewpoint of easy balance between moisture permeability and improvement in elastic modulus, and examples thereof include residues such as acetic acid, propionic acid, butanoic acid, hexanoic acid, octanoic acid, octylic acid, and the like. The above may be included, and acetic acid is particularly preferable.
- the number of carbon atoms does not include the carbon atom in the carboxy group.
- G in the general formula (1) is an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue.
- the glycol residue refers to a group after removing a hydrogen atom from a hydroxyl group.
- the alkylene glycol residue is preferably an alkylene glycol residue having 2 to 12 carbon atoms from the viewpoint of more easily exhibiting the effects of the present invention.
- ethylene glycol, 1,2-propylene glycol, 1 3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl 1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propane Diol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2, , 4-trimethyl 1,3-pent
- those having 3 or less carbon atoms that do not include a branch between OH groups are preferable, among which ethylene glycol, It is preferably a residue of 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, ethylene glycol, More preferred is a residue of 1,2-propylene glycol.
- the oxyalkylene glycol residue is preferably an oxyalkylene glycol residue having 4 to 12 carbon atoms from the viewpoint of more easily expressing the effects of the present invention.
- diethylene glycol, triethylene glycol, tetraethylene glycol And residues such as dipropylene glycol and tripropylene glycol may be used alone or in combination of two or more.
- the aryl glycol residue is preferably an aryl glycol residue having 6 to 18 carbon atoms from the viewpoint of more easily exhibiting the effects of the present invention.
- hydroquinone, resorcin, bisphenol A, alkylene oxide of bisphenol A examples include residues such as adducts, bisphenol F, alkylene oxide adducts of bisphenol F, biphenols, alkylene oxide adducts of biphenols, etc., which may be used alone or in combination of two or more.
- a in the general formula (1) is an alkylene dicarboxylic acid residue (A1) or an aryl dicarboxylic acid residue (A2).
- the dicarboxylic acid residue refers to a group excluding —OH in the carboxy group.
- the alkylene dicarboxylic acid residue (A1) is preferably an alkylene dicarboxylic acid residue having 2 to 12 carbon atoms from the viewpoint of more easily exhibiting the effects of the present invention.
- oxalic acid, malonic acid, Residues such as succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, 1,2-dicarboxycyclohexane, 1,2-dicarboxycyclohexene and the like can be mentioned. Also good.
- a residue of succinic acid, adipic acid, and 1,2-dicarboxycyclohexane is preferable, and an adipic acid residue is most preferable because an optical film having more excellent moisture resistance can be obtained.
- Examples of the aryl dicarboxylic acid residue (A2) include phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7 -Residues such as naphthalenedicarboxylic acid and 1,8-naphthalenedicarboxylic acid are mentioned, and they may be used alone or in combination of two or more.
- a residue of phthalic acid, terephthalic acid, and isophthalic acid is preferable because an optical film having higher strength can be obtained, and a residue of phthalic acid is most preferable.
- the content of the aryldicarboxylic acid residue (A2) in the total number of moles (A1 + A2) of the alkylenedicarboxylic acid residue (A1) and the aryldicarboxylic acid residue (A2) in A in the general formula (1) is determined according to the present invention.
- the content is 70 to 100 mol%, and the range is preferably 75 to 100 mol%.
- the ester resin represented by the general formula (1) wherein B, G, and A are the same, and n, that is, a mixture of compounds that differ only in the number of repetitions, or It may be a mixture of compounds in which B, G, A and n in the general formula (1) are different.
- an alkylene dicarboxylic acid in the general formula (1) is used in order to combine improvement in moisture permeability and elastic modulus.
- the content of the aryldicarboxylic acid residue (A2) in the sum (A1 + A2) of the residue (A1) and the aryldicarboxylic acid residue (A2) is 70 to 100 mol%, and the area ratio in GPC measurement is the above general formula.
- n 0 component, so-called diester compound, to a specific content, it is suitably placed in the gap between the resin for optical materials, particularly the cellulose ester resin, and as a result, the effect of suppressing moisture permeability is manifested.
- the content of components having n of 3 or more compatibility with the optical material resin can be ensured, and transparency that can be used as an optical film can be maintained.
- the GPC measurement in the present invention was performed under the following conditions.
- [GPC measurement conditions] Measuring device: Tosoh Corporation high-speed GPC device "HLC-8320GPC” Column: “TSK GARDCOLUMN SuperHZ-L” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation "TSK gel SuperHZ-2000” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: “EcoSEC Data Analysis version 1.07” manufactured by Tosoh Corporation Column temperature: 40 ° C Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min Sample to be measured: A sample obtained by dissolving 7.5 mg of a sample in 10 ml of tetrahydrofuran and filtering the obtained solution through a microfilter
- B is a residue of benzoic acid and acetic acid
- G is ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, , 2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol residue
- A1 is succinic acid, adipic acid, 1,2-dicarboxycyclohexane residue
- A2 is phthalic acid , Isophthalic acid, terephthalic acid residue, particularly B is benzoic acid residue
- G is ethylene glycol, 1,2-propylene glycol residue
- A1 is adipic acid residue
- A2 is a residue of phthalic acid.
- the number average molecular weight of the ester resin of the present invention is preferably in the range of 350 to 800, particularly preferably in the range of 350 to 600, from the viewpoint of achieving both compatibility and film properties. Further, the average value of the repeating number n in the general formula (1) is preferably in the range of 0.2 to 3 from the viewpoint of achieving both compatibility and film physical properties. The number average molecular weight and the average value of n are also values measured by the GPC measurement.
- the acid value of the ester resin of the present invention is preferably 5 or less, more preferably 1 or less, from the viewpoint of better compatibility with the resin for optical materials.
- the hydroxyl value of the ester resin is preferably 50 or less, and more preferably 20 or less.
- the ester resin of the present invention is produced, for example, by subjecting the above raw materials to an esterification reaction in the presence of an esterification catalyst as necessary, for example, within a temperature range of 180 to 250 ° C. for 10 to 25 hours. be able to.
- an esterification catalyst as necessary, for example, within a temperature range of 180 to 250 ° C. for 10 to 25 hours. be able to.
- conditions, such as temperature of esterification reaction and time are not specifically limited, You may set suitably.
- the monocarboxylic acid and dicarboxylic acid the acid itself may be used as a raw material, or an esterified product, an acid chloride, an anhydride of dicarboxylic acid, or the like may be used as a raw material.
- esterification catalyst examples include titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin catalysts such as dibutyltin oxide; and organic sulfonic acid catalysts such as p-toluenesulfonic acid.
- the amount of the esterification catalyst used may be set as appropriate, but usually it is preferably used in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of raw materials.
- the properties of the ester resin of the present invention vary depending on factors such as the number average molecular weight and the combination of raw materials, but are usually liquid, solid, paste, etc. at room temperature.
- an ester resin there is a method of reacting a monocarboxylic acid with a compound having a hydroxyl group at the terminal obtained by using the above-mentioned alkylene glycol, oxyalkylene glycol or aryl glycol and dicarboxylic acid.
- the alkylene glycol, oxyalkylene glycol or aryl glycol, dicarboxylic acid and monocarboxylic acid may be charged into the reaction system in a lump and reacted with each other, or alkylene glycol, oxyalkylene glycol or aryl glycol and dicarboxylic acid may be reacted.
- a sequential reaction in which a monocarboxylic acid is further charged into the reaction system may be used.
- the ester resin obtained above may be used as the ester resin of the present invention as long as the composition defined by the present invention is obtained by determining the composition for each repetition of n by the GPC measurement, or
- the raw material used for the ester resin and the raw material of the diester compound prepared separately may be the same or different.
- B2-G2-B2 (2) (In the formula, B2 is an aryl monocarboxylic acid residue or an aliphatic monocarboxylic acid residue, G2 is an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue, and a plurality of B2 are the same or different. May be.)
- B2 in the general formula (2) is an aryl monocarboxylic acid residue or an aliphatic monocarboxylic acid residue.
- the “carboxylic acid residue” refers to a group other than —OH in the carboxy group.
- the aryl monocarboxylic acid residue is an aryl monocarboxylic acid residue having 6 to 12 carbon atoms, which is easy to obtain raw materials, easy to esterify, and mixed with a cellulose ester resin described later.
- benzoic acid dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cumin
- examples thereof include acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, ethoxybenzoic acid, propoxybenzoic acid, anisic acid, naphthoic acid and the like, and they may be used alone or in combination of two or more.
- a residue of benzoic acid, p-toluic acid, or dimethylbenzoic acid is preferable, and a residue of benzoic acid is more preferable.
- the number of carbon atoms does not include the carbon atom in the carboxy group. Further, it may be a residue such as nicotinic acid or furoic acid having an aromaticity, which may have a substituent.
- the aliphatic monocarboxylic acid residue is an aliphatic monocarboxylic acid residue having 1 to 8 carbon atoms, which is mixed with raw material availability, ease of esterification reaction, and cellulose ester resin described later.
- residues such as acetic acid, propionic acid, butanoic acid, hexanoic acid, octanoic acid, octylic acid, and the like. It may have both of the above, and is particularly preferably a residue of acetic acid.
- the number of carbon atoms does not include the carbon atom in the carboxy group.
- G in the general formula (1) is an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue.
- the glycol residue refers to a group after removing a hydrogen atom from a hydroxyl group.
- the alkylene glycol residue is preferably an alkylene glycol residue having 2 to 12 carbon atoms from the viewpoint of more easily exhibiting the effects of the present invention.
- ethylene glycol, 1,2-propylene glycol, 1 3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl 1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propane Diol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2, , 4-trimethyl 1,3-pent
- 1,2-propylene glycol 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propane It is preferably a residue of diol or 1,5-pentanediol.
- the oxyalkylene glycol residue is preferably an oxyalkylene glycol residue having 4 to 12 carbon atoms from the viewpoint of more easily expressing the effects of the present invention.
- diethylene glycol, triethylene glycol, tetraethylene glycol And residues such as dipropylene glycol and tripropylene glycol may be used alone or in combination of two or more.
- the aryl glycol residue is preferably an aryl glycol residue having 6 to 18 carbon atoms from the viewpoint of more easily exhibiting the effects of the present invention.
- hydroquinone, resorcin, bisphenol A, alkylene oxide of bisphenol A examples include residues such as adducts, bisphenol F, alkylene oxide adducts of bisphenol F, biphenols, alkylene oxide adducts of biphenols, etc., which may be used alone or in combination of two or more.
- B2 is a residue of benzoic acid or acetic acid
- G is 1,2-propylene glycol, 1,3-propanediol
- 1,2- The residue is preferably a residue of butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, diethylene glycol or dipropylene glycol.
- the diester compound (II) may be synthesized or commercially available.
- diester compound (II) you may use the several thing which consists of a different raw material.
- the ester resin of the present invention obtained by such a method or the like can be made to have an excellent balance between moisture permeability and elastic modulus of the resulting film by blending it with the resin for optical materials. It can be used as an antiplasticizer, and can be particularly suitably used as an optical film.
- the resin for optical material is not particularly limited as long as it is highly transparent and can be processed into a film shape.
- the range is from 1 to 50 parts by mass, preferably from 1 to 30 parts by mass, and more preferably from 5 to 20 parts by mass.
- cellulose ester resin examples include those obtained by esterifying part or all of the hydroxyl groups of cellulose obtained from cotton linter, wood pulp, kenaf and the like.
- cellulose ester resin examples include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate.
- cellulose acetate is used. Is preferable because a film having excellent mechanical properties and transparency can be obtained.
- These cellulose ester resins may be used alone or in combination of two or more.
- the cellulose acetate preferably has a polymerization degree in the range of 250 to 400, and an acetylation degree in the range of 54.0 to 62.5% by mass, preferably 58.0 to 62.5. More preferably, it is in the range of mass%. If the cellulose acetate has a polymerization degree and an acetylation degree within a range, a film having excellent mechanical properties can be obtained. In the present invention, it is more preferable to use so-called cellulose triacetate.
- the acetylation degree said by this invention is the mass ratio of the acetic acid produced
- the number average molecular weight of the cellulose acetate is preferably in the range of 70,000 to 300,000, and more preferably in the range of 80,000 to 200,000. When the number average molecular weight of the cellulose acetate is within this range, a film having excellent mechanical properties can be easily obtained.
- the optical film in the present invention uses the cellulose ester resin composition containing the ester resin of the present invention and the cellulose ester resin, and uses a resin composition containing other various additives as necessary. Also good.
- an unstretched optical film can be extruded using an extruder equipped with a T die, a circular die, or the like.
- a resin composition obtained by melting and kneading the ester resin, cellulose ester resin, and other additives in advance can be used. However, it can be extruded as it is.
- additives examples include other modifiers other than the ester resin of the present invention, thermoplastic resins, ultraviolet absorbers, matting agents, deterioration inhibitors (for example, antioxidants, peroxide decomposers, radical prohibitions). Agents, metal deactivators, acid scavengers, etc.) and dyes.
- ester resins other than the ester resins defined in the present invention examples include ester resins other than the ester resins defined in the present invention, phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate, and cresyl diphenyl phosphate, dimethyl phthalate, diethyl phthalate, Phthalic acid esters such as dibutyl phthalate and di-2-ethylhexyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, trimethylol propane tribenzoate, pentaerythritol tetraacetate, tributyl acetylcitrate, etc. It can be used as long as the effect is not impaired.
- phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate, and cresyl diphenyl phosphate
- dimethyl phthalate
- thermoplastic resin is not particularly limited, and examples thereof include polyester resins other than the ester resin of the present invention, polyester ether resins, polyurethane resins, epoxy resins, and toluenesulfonamide resins.
- the ultraviolet absorber is not particularly limited, and examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like.
- the ultraviolet absorber is preferably used in the range of 0.01 to 2 parts by mass with respect to 100 parts by mass of the cellulose ester resin.
- Examples of the matting agent include silicon oxide, titanium oxide, aluminum oxide, calcium carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, kaolin, and talc.
- the matting agent is preferably used in the range of 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the cellulose ester resin.
- the type and amount of the dye are not particularly limited as long as they do not impair the object of the present invention.
- the optical film is obtained by casting a resin solution obtained by dissolving the cellulose ester resin composition in an organic solvent on a metal support, and then the organic solvent. It can also be obtained by forming by a so-called solution casting method (solvent casting method) by distilling off and drying.
- solution casting method solvent casting method
- the resulting film can exhibit substantially optical isotropy.
- the film showing optical isotropy can be used for an optical material such as a liquid crystal display, and is particularly useful as a protective film for a polarizing plate.
- the film obtained by the said method cannot form an unevenness
- the solution casting method generally includes a first step in which the cellulose ester resin composition is dissolved in an organic solvent, and the resulting resin solution is cast on a metal support, and in the cast resin solution.
- Examples of the metal support used in the first step include endless belt-shaped or drum-shaped metal supports, for example, stainless steel with a mirror-finished surface can be used. .
- the drying method in the second step is not particularly limited.
- it is included in the cast resin solution by applying air in a temperature range of 30 to 50 ° C. to the upper surface and / or the lower surface of the metal support.
- Examples thereof include a method of evaporating 50 to 80% by mass of an organic solvent to form a film on the metal support.
- the third step is a step in which the film formed in the second step is peeled off from the metal support and is heated and dried under a temperature condition higher than that in the second step.
- a heat drying method for example, a method in which the temperature is raised stepwise under a temperature condition of 100 to 160 ° C. is preferable because good dimensional stability can be obtained.
- the organic solvent remaining in the film after the second step can be almost completely removed by heating and drying under the temperature condition.
- the organic solvent can be recovered and reused.
- the organic solvent that can be used when the resin composition is mixed and dissolved in an organic solvent is not particularly limited as long as it can dissolve them.
- organic halogen compounds such as methylene chloride and dioxolanes are preferably used.
- a poor solvent such as methanol, ethanol, 2-propanol, n-butanol, cyclohexane, cyclohexanone together with the good solvent in order to improve the production efficiency of the film.
- the concentration of the cellulose ester resin in the resin solution is preferably 10 to 50% by mass, more preferably 15 to 35% by mass.
- the unstretched optical film obtained by the above-described method is stretched by uniaxially stretching in the mechanical flow direction and transversely uniaxially stretching in the direction orthogonal to the mechanical flow direction, as necessary.
- the obtained optical film can be obtained.
- the stretched film biaxially stretched can be obtained by stretching by a sequential biaxial stretching method of roll stretching and tenter stretching, a simultaneous biaxial stretching method by tenter stretching, a biaxial stretching method by tubular stretching, or the like.
- the draw ratio is preferably 0.1% or more and 1000% or less in at least one direction, more preferably 0.2% or more and 600% or less, and more preferably 0.3% or more and 300% or less. Especially preferred. By designing in this range, a stretched optical film preferable in terms of birefringence, heat resistance and strength can be obtained.
- the optical film of the present invention is excellent in moisture permeation resistance, transparency and elastic modulus, and can be used, for example, as an optical film for liquid crystal display devices.
- the optical film of the liquid crystal display device include a protective film for a polarizing plate, a retardation film, a reflective film, a viewing angle improving film, an antiglare film, an antireflective film, an antistatic film, and a color filter.
- a protective film for polarizing plates preferably as a protective film for polarizing plates.
- the film thickness of the optical film is preferably in the range of 20 to 120 ⁇ m, more preferably in the range of 25 to 100 ⁇ m, and particularly preferably in the range of 25 to 80 ⁇ m.
- a film thickness in the range of 25 to 80 ⁇ m is suitable for reducing the thickness of the liquid crystal display device, and has sufficient film strength and Rth stability. Excellent performance such as moisture permeability resistance can be maintained.
- the optical film of the present invention is characterized in that the elastic modulus is higher than when no ester resin is blended.
- a polyester resin blended for the purpose of enhancing the processability of cellulose ester resin is sometimes referred to as “plasticizer”, but the ester resin of the present invention is more optical than plasticizing effect. From the viewpoint of improving the strength of the resin for materials, it has a performance different from the conventional one in that it is used as an antiplasticizer.
- the polarizing plate protective film can be adjusted to a desired Rth without causing bleed under high temperature and high humidity, so that it can be used widely in various liquid crystal display systems depending on the application. Can do.
- liquid crystal display method examples include IPS (In-Plane Switching), TN (Twisted Nematic), VA (Vertically Aligned), and OCB (Optical Compensatory Bend).
- IPS In-Plane Switching
- TN Transmission Nematic
- VA Very Aligned
- OCB Optical Compensatory Bend
- An example is Optically Compensatory Bend).
- the optical film according to the present invention includes, as an optical material, a polarizing plate protective film used for a display such as a liquid crystal display device, a plasma display, an organic EL display, a field emission display, a rear projection television, a quarter wavelength plate, and a half. It can be suitably used for a retardation film such as a wave plate, a viewing angle control film, a liquid crystal optical compensation film, a display front plate and the like.
- the resin composition of the present invention is also used in the fields of optical communication systems, optical switching systems, and optical measurement systems, such as waveguides, lenses, optical fibers, optical fiber substrates, coating materials, LED lenses, and lens covers. It can also be used.
- Synthesis example 1 405 g of 1,2-propylene glycol (PG) as the glycol component, 79 g of adipic acid (AA) as the dicarboxylic acid, 240 g of phthalic anhydride (PA), 586 g of benzoic acid (BzA) as the monocarboxylic acid, and tetraisopropyl titanate as the esterification catalyst (TIPT) 0.08 g was charged into a two-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser, and the temperature was raised stepwise to 230 ° C. while stirring under a nitrogen stream. The reaction was continued at 230 ° C.
- PG 1,2-propylene glycol
- AA adipic acid
- PA phthalic anhydride
- BzA benzoic acid
- TIPT tetraisopropyl titanate
- FIG. 1 shows a chart obtained by GPC measurement.
- Synthesis example 2 The ester resin (1-2) was obtained by synthesizing in the same manner as in Synthesis Example 1 using PG 405 g as the glycol component, 320 g PA as the dicarboxylic acid component, and 586 g BzA and 0.08 g TIPT as the monocarboxylic acid component. The properties are also shown in Table 1.
- Synthesis example 3 The ester resin (1-3) was synthesized by synthesizing in the same manner as in Synthesis Example 1 using 330 g of ethylene glycol (EG) as the glycol component, AA 79 g, PA 240 g as the dicarboxylic acid component, and BzA 586 g and TIPT 0.08 g as the monocarboxylic acid component. Obtained. The properties are also shown in Table 1.
- EG ethylene glycol
- Synthesis example 5 By synthesizing in the same manner as in Synthesis Example 1 using 479 g of 2-methyl-1,3-propanediol (2MPD) as the glycol component, 79 Ag and PA 240 g as the dicarboxylic acid component, 586 g of BzA and 0.08 g of TIPT as the monocarboxylic acid component, An ester resin (1-5) was obtained. The properties are also shown in Table 1.
- 2MPD 2-methyl-1,3-propanediol
- Synthesis Example 6 The ester resin (1-6) was obtained by synthesizing in the same manner as in Synthesis Example 1 using PG 341 g as the glycol component, AA 53 g and PA 160 g as the dicarboxylic acid component, and BzA 586 g and TIPT 0.08 g as the monocarboxylic acid component. The properties are shown in Table 1.
- Synthetic Example 7 Thin Film Distilled Product
- the ester resin (1-1) obtained in Synthetic Example 1 was distilled using a thin film distillation apparatus (thin film molecular distillation apparatus AS-MDA-65FJ-S manufactured by Asahi Seisakusho) Distillation was performed under the conditions of a temperature of 180 ° C., a feed tube temperature of 100 ° C., a condenser temperature of 40 ° C., and a degree of vacuum of 0.012 Pa to obtain an ester resin (1′-1).
- the number average molecular weight (Mn) of the ester resin (1′-1) was 515, and the content of the ester resin having a molecular weight smaller than 350 was 2%.
- Synthesis Example 9 Diester compound (II-2) The ester compound (II-2) was obtained by synthesizing in the same manner as in Synthesis Example 8 using 730 g of 1,3-propanediol, 1954 g of benzoic acid, and 0.2 g of tetraisopropyl titanate.
- Synthesis Example 10 Diester compound (II-3) The ester compound (II-3) was obtained by synthesis in the same manner as in Synthesis Example 8 using 1000 g of 1,5-pentanediol, 1954 g of benzoic acid, and 0.2 g of tetraisopropyl titanate.
- Synthesis Example 11 Diester compound (II-4) The ester compound (II-4) was obtained by synthesizing in the same manner as in Synthesis Example 8 using 572 g of diethylene glycol, 293 g of dipropylene glycol, 1930 g of benzoic acid, and 0.2 g of tetraisopropyl titanate.
- Synthesis Example 12 Diester Compound (II-5) The ester compound (II-5) was obtained by synthesizing in the same manner as in Synthesis Example 8 using PG 648 g, dipropylene glycol 109 g, benzoic acid 1980 g, and tetraisopropyl titanate 0.2 g.
- Synthesis Example 13 The ester resin (1′-2) was obtained by synthesizing in the same manner as in Synthesis Example 1 using PG 405 g as the glycol component, AA 158 g and PA 160 g as the dicarboxylic acid component, and BzA 586 g and TIPT 0.08 g as the monocarboxylic acid component. The properties are also shown in Table 1.
- Synthesis Example 14 The ester resin (1′-3) was obtained by synthesizing in the same manner as in Synthesis Example 1 using PG 405 g as the glycol component, AA 237 g and PA 80 g as the dicarboxylic acid component, and BzA 586 g and TIPT 0.08 g as the monocarboxylic acid component. The properties are also shown in Table 1.
- Synthesis Example 15 The ester resin (1′-4) was obtained by synthesizing in the same manner as in Synthesis Example 1 using PG 405 g as the glycol component, 316 g AA as the dicarboxylic acid component, and BzA 586 g and TIPT 0.08 g as the monocarboxylic acid component. The properties are also shown in Table 1.
- Synthesis Example 16 The ester resin (1′-5) was obtained by synthesizing in the same manner as in Synthesis Example 1 using 730 g of PG as the glycol component, 1954 g of BzA as the monocarboxylic acid component, and 0.2 g of TIPT. The properties are also shown in Table 1.
- Synthesis Example 17 The ester resin (1′-6) was obtained by synthesizing in the same manner as in Synthesis Example 1 using PG 426 g as the glycol component, AA 146 g and PA 444 g as the dicarboxylic acid component, and BzA 195 g and TIPT 0.08 g as the monocarboxylic acid component. The properties are also shown in Table 1.
- Example 1 The ester resin (1′-1) obtained in Synthesis Example 7 and the diester compound (II-1) obtained in Synthesis Example 8 are mixed so that the content of the diester compound (II-1) is 20% by mass. By mixing, an ester resin (1-7) was obtained. The ester resin (1-7) after mixing was measured by GPC. The results are shown in Table 2.
- Example 2 ester resins (1-8) to (1-17) were obtained in the same manner as in Example 1, except that the diester compound used and the content thereof were changed as shown in Table 2. The properties are also shown in Table 2.
- Example 12 (Preparation of cellulose ester resin composition and optical film of the present invention) 100 parts by weight of triacetyl cellulose resin ("LT-35" manufactured by Daicel Corporation) and 10 parts by weight of ester resin (1-1) were added to a mixed solvent consisting of 810 parts by weight of methylene chloride and 90 parts by weight of methanol and dissolved.
- the dope liquid which is the cellulose ester resin composition of the present invention was prepared. This dope solution is cast on a glass plate to a thickness of 0.8 mm and 0.5 mm, dried at room temperature for 16 hours, then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes.
- the optical film of the present invention was obtained. The thickness of the obtained film was 60 ⁇ m and 40 ⁇ m.
- Examples 13 to 28 An optical film was obtained in the same manner as in Example 1 except that ester resins (1-2) to (1-17) were used in place of ester resin (1-1).
- Comparative Example 1 100 parts by mass of a triacetyl cellulose resin (“LT-35” manufactured by Daicel Corporation) was added to a mixed solvent consisting of 810 parts by mass of methylene chloride and 90 parts by mass of methanol to prepare a dope solution.
- This dope solution is cast on a glass plate to a thickness of 0.8 mm and 0.5 mm, dried at room temperature for 16 hours, then dried at 50 ° C. for 30 minutes and further at 120 ° C. for 30 minutes.
- An optical film was obtained. The thickness of the obtained film was 60 ⁇ m and 40 ⁇ m.
- Comparative Examples 2-7 An optical film was obtained in the same manner as in Example 12 except that ester resins (1′-1) to (1′-6) were used in place of the ester resin (1-1).
- the elastic modulus, moisture permeability, and HAZE of the optical film obtained above were evaluated by the following methods.
- a film with a film thickness of 40 ⁇ m was used, and for the other evaluations, a film with a film thickness of 60 ⁇ m was used.
- the obtained results are shown in Table 3.
- Measurement was performed according to the method described in JIS Z 0208.
- the measurement conditions were a temperature of 40 ° C. and a relative humidity of 90%. It represents that it is excellent in moisture permeability resistance, so that the value obtained is small.
- ⁇ Moist heat test> The film was exposed to an environment of 85 ° C. and a relative humidity of 90% (in a moist heat environment) for 120 hours.
- HAZE> The HAZE value was measured according to JIS K 7105 using a turbidimeter (“NDH 5000” manufactured by Nippon Denshoku Industries Co., Ltd.). The closer the value obtained is to 0%, the more transparent it is.
- HAZE value is less than 0.6%.
- HAZE value is 0.6% or more and less than 0.7.
- X HAZE value is 0.7% or more.
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Abstract
Description
B-(G-A)n-G-B (1)
〔式(1)中、Bはアリールモノカルボン酸残基又は脂肪族モノカルボン酸残基であり、Gはアルキレングリコール残基、オキシアルキレングリコール残基又はアリールグリコール残基であり、Aはアルキレンジカルボン残基(A1)又はアリールジカルボン酸残基(A2)であって、アルキレンジカルボン酸残基(A1)とアリールジカルボン酸残基(A2)の合計(A1+A2)におけるアリールジカルボン酸残基(A2)の含有率が70~100モル%であり、nは繰り返し数であり、繰り返しごとにG、Aは同一でも異なっていてもよく、また複数あるB、Gは同一でも異なっていてもよい。〕
で表されるエステル樹脂であり、
ゲルパーミエーションクロマトグラフィー(GPC)測定における面積比率で前記一般式(1)中のn=0成分が10~70%であり、且つnが3以上の成分の面積%とn=0成分の面積%との比(n≧3)/(n=0)が3以下であることを特徴とするエステル樹脂とこれを含む樹脂組成物、並びに該組成物を用いて得られる光学用フィルム、及び当該光学用フィルムを用いた液晶表示装置を提供するものである。
B-(G-A)n-G-B (1)
〔式(1)中、Bはアリールモノカルボン酸残基又は脂肪族モノカルボン酸残基であり、Gはアルキレングリコール残基、オキシアルキレングリコール残基又はアリールグリコール残基であり、Aはアルキレンジカルボン残基(A1)又はアリールジカルボン酸残基(A2)であって、アルキレンジカルボン酸残基(A1)とアリールジカルボン酸残基(A2)の合計(A1+A2)におけるアリールジカルボン酸残基(A2)の含有率が70~100モル%であり、nは繰り返し数であり、繰り返しごとにG、Aは同一でも異なっていてもよく、また複数あるB、Gは同一でも異なっていてもよい。〕
で表されるエステル樹脂であり、
GPC測定における面積比率で前記一般式(1)中のn=0成分が10~70%であり、且つnが3以上の成分の面積%とn=0成分の面積%との比(n≧3)/(n=0)が3以下であることを特徴とする。
[GPC測定条件]
測定装置:東ソー株式会社製高速GPC装置「HLC-8320GPC」
カラム:東ソー株式会社製「TSK GURDCOLUMN SuperHZ-L」+東ソー株式会社製「TSK gel SuperHZM-M」+東ソー株式会社製「TSK gel SuperHZM-M」+東ソー株式会社製「TSK gel SuperHZ-2000」+東ソー株式会社製「TSK gel SuperHZ-2000」
検出器:RI(示差屈折計)
データ処理:東ソー株式会社製「EcoSEC Data Analysis バージョン1.07」
カラム温度:40℃
展開溶媒:テトラヒドロフラン
流速:0.35mL/分
測定試料:試料7.5mgを10mlのテトラヒドロフランに溶解し、得られた溶液をマイクロフィルターでろ過したものを測定試料とした。
試料注入量:20μl
標準試料:前記「HLC-8320GPC」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
東ソー株式会社製「A-300」
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
東ソー株式会社製「F-288」
本発明のエステル樹脂におけるn=0成分とnが3以上の成分の面積%は、次のようにして算出することができる。エステル樹脂のGPC測定を行って、検出されたピークに対応する各成分のポリスチレン換算分子量を求め、検出されたピーク面積の比から検出されたピークに対応する各成分の含有割合(面積分率)を算出した。
B2-G2-B2 (2)
(式中、B2はアリールモノカルボン酸残基または脂肪族モノカルボン酸残基であり、G2はアルキレングリコール残基、オキシアルキレングリコール残基又はアリールグリコール残基であり、複数あるB2は同一でも異なっていてもよい。)
グリコール成分として1,2-プロピレングリコール(PG)405g、ジカルボン酸としてアジピン酸(AA)79g、無水フタル酸(PA)240g、モノカルボン酸として安息香酸(BzA)586g及びエステル化触媒としてテトライソプロピルチタネート(TIPT)0.08gを、温度計、攪拌器、還流冷却器を付した内容積2リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら230℃まで段階的に昇温し、その後230℃で反応を継続させ、合計19時間脱水縮合反応させて反応物(酸価0.22、水酸基価16)を得た。この反応物であるエステル樹脂(1-1)の数平均分子量(Mn)は405であった。図1にGPC測定で得られたチャート図を示す。GPCチャートにおいてn=0成分の面積%は31%、nが3以上の成分の面積%は20%であった。
グリコール成分としてPG405g、ジカルボン酸成分としてPA320g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1-2)を得た。その性状についても表1に示した。
グリコール成分としてエチレングリコール(EG)330g、ジカルボン酸成分としてAA79g、PA240g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1-3)を得た。その性状についても表1に示した。
グリコール成分として1,3-プロパンジオール(13PG)405g、ジカルボン酸成分としてAA79g、PA240g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1-4)を得た。その性状についても表1に示した。
グリコール成分として2-メチル-1,3-プロパンジオール(2MPD)479g、ジカルボン酸成分としてAA79g、PA240g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1-5)を得た。その性状についても表1に示した。
グリコール成分としてPG341g、ジカルボン酸成分としてAA53g、PA160g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1-6)を得た。その性状については表1に示した。
合成例1で得られたエステル樹脂(1-1)を薄膜蒸留装置(株式会旭製作所製の薄膜式分子蒸留装置AS-MDA-65FJ-S)を用いて蒸留管温度180℃、フィード管温度100℃、コンデンサ温度40℃、減圧度0.012Paの条件で蒸留し、エステル樹脂(1’-1)を得た。エステル樹脂(1’-1)の数平均分子量(Mn)は515で、分子量が350よりも小さいエステル樹脂の含有率は2%であった。GPCチャートにおいてn=0成分の面積%は5%であり、nが3以上の成分の面積%は28%である。
温度計、攪拌器、及びキシレンを満たした水分離器を備えた内容積3リットルの四つ口フラスコに、PG730g、BzA1954g、及び、TIPT0.2gを仕込み、240℃まで8時間かけて昇温した。その後、240℃で10時間反応させた。反応後、190℃にて未反応原料を減圧除去し、常温液体であるジエステル化合物(II-1)を得た。この化合物(II-1)の酸価は0.1、水酸基価は10、数平均分子量は265であった。GPCチャートにおいてn=0成分の面積%は100%であり、nが3以上の成分の面積%は0%である。
1,3-プロパンジオール730g、安息香酸1954g、及び、テトライソプロピルチタネート0.2gを用いて合成例8と同様にして合成することでエステル化合物(II-2)を得た。
1,5-ペンタンジオール1000g、安息香酸1954g、及び、テトライソプロピルチタネート0.2gを用いて合成例8と同様にして合成することでエステル化合物(II-3)を得た。
ジエチレングリコール572g、ジプロピレングリコール293g、安息香酸1930g、及び、テトライソプロピルチタネート0.2gを用いて合成例8と同様にして合成することでエステル化合物(II-4)を得た。
PG648g、ジプロピレングリコール109g、安息香酸1980g、及び、テトライソプロピルチタネート0.2gを用いて合成例8と同様にして合成することでエステル化合物(II-5)を得た。
グリコール成分としてPG405g、ジカルボン酸成分としてAA158g、PA160g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1’-2)を得た。その性状についても表1に示した。
グリコール成分としてPG405g、ジカルボン酸成分としてAA237g、PA80g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1’-3)を得た。その性状についても表1に示した。
グリコール成分としてPG405g、ジカルボン酸成分としてAA316g、モノカルボン酸成分としてBzA586g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1’-4)を得た。その性状についても表1に示した。
グリコール成分としてPG730g、モノカルボン酸成分としてBzA1954g、及び、TIPT0.2gを用いて合成例1と同様にして合成することでエステル樹脂(1’-5)を得た。その性状についても表1に示した。
グリコール成分としてPG426g、ジカルボン酸成分としてAA146g、PA444g、モノカルボン酸成分としてBzA195g及びTIPT0.08gを用いて合成例1と同様にして合成することでエステル樹脂(1’-6)を得た。その性状についても表1に示した。
BzA:安息香酸
PG:1,2-プロピレングリコール
EG:エチレングリコール
13PG:1,3-プロパンジオール
2MPD:2-メチル-1,3-プロパンジオール
AA:アジピン酸
PA:無水フタル酸
合成例7で得られたエステル樹脂(1’-1)と合成例8で得られたジエステル化合物(II-1)を、ジエステル化合物(II-1)の含有量が20質量%となるように混合し、エステル樹脂(1-7)を得た。混合後のエステル樹脂(1-7)をGPC測定した。結果を表2に示す。
実施例1において、用いるジエステル化合物とその含有量を表2に示すように変更した以外は実施例1と同様にして、エステル樹脂(1-8)~(1-17)を得た。その性状についても表2に示した。
トリアセチルセルロース樹脂(株式会社ダイセル製「LT-35」)100質量部、エステル樹脂(1-1)10質量部を、メチレンクロライド810質量部及びメタノール90質量部からなる混合溶剤に加えて溶解し、本発明のセルロースエステル樹脂組成物であるドープ液を調製した。このドープ液をガラス板上に厚さ0.8mm、0.5mmとなるように流延し、室温で16時間乾燥させた後、50℃で30分、さらに120℃で30分乾燥させることで、本発明の光学フィルムを得た。得られたフィルムの厚みは60μm、40μmであった。
実施例1において、エステル樹脂(1-1)の代わりにエステル樹脂(1-2)~(1-17)を用いる以外は実施例1と同様にして光学フィルムを得た。
トリアセチルセルロース樹脂(株式会社ダイセル製「LT-35」)100質量部を、メチレンクロライド810質量部及びメタノール90質量部からなる混合溶剤に加えて溶解し、ドープ液を調製した。このドープ液をガラス板上に厚さ0.8mm、0.5mmとなるように流延し、室温で16時間乾燥させた後、50℃で30分、さらに120℃で30分乾燥させることで、光学フィルムを得た。得られたフィルムの厚みは60μm、40μmであった。
実施例12において、エステル樹脂(1-1)の代わりにエステル樹脂(1’-1)~(1’-6)を用いる以外は実施例12と同様にして光学フィルムを得た。
装置 :(株)島津製作所製オートグラフAG-IS
試験片 :150mm×10mm短冊形
チャック間:100mm
試験速度 :10mm/min
膜厚 :40μm
×:弾性率が添加剤なし(比較例1)と同等(4.3GPa)以下である。
○:弾性率が添加剤なし(比較例1)よりも高い弾性率(4.4GPa以上)である。
JIS Z 0208に記載の方法に従い、測定した。測定条件は、温度40℃、相対湿度90%で行なった。得られる値が小さい程、耐透湿性に優れることを表す。
○:透湿度が550g/m2×24h未満である。
△:透湿度が550g/m2×24h以上、560g/m2×24h未満である。
×:透湿度が560g/m2×24h以上である。
フィルムを85℃、相対湿度90%の環境下(湿熱環境下)に120時間晒した。
HAZE値は、濁度計(日本電色工業株式会社製「NDH 5000」)を用いて、JIS K 7105に準じて測定した。得られる値が0%に近い程、透明であること表す
○:HAZE値が0.6%未満である。
△:HAZE値が0.6%以上、0.7未満である。
×:HAZE値が0.7%以上である。
Claims (15)
- 下記一般式(1)
B-(G-A)n-G-B (1)
〔式(1)中、Bはアリールモノカルボン酸残基又は脂肪族モノカルボン酸残基であり、Gはアルキレングリコール残基、オキシアルキレングリコール残基又はアリールグリコール残基であり、Aはアルキレンジカルボン残基(A1)又はアリールジカルボン酸残基(A2)であって、アルキレンジカルボン酸残基(A1)とアリールジカルボン酸残基(A2)の合計(A1+A2)におけるアリールジカルボン酸残基(A2)の含有率が70~100モル%であり、nは繰り返し数であり、繰り返しごとにG、Aは同一でも異なっていてもよく、また複数あるB、Gは同一でも異なっていてもよい。〕
で表されるエステル樹脂であり、
GPC測定における面積比率で前記一般式(1)中のn=0成分が10~70%であり、且つnが3以上の成分の面積%とn=0成分の面積%との比(n≧3)/(n=0)が3以下であることを特徴とするエステル樹脂。 - 前記一般式(1)中のBが、炭素原子数6~12のアリールモノカルボン酸残基又は炭素原子数1~8の脂肪族モノカルボン酸残基であり、Gが炭素原子数2~12のアルキレングリコール残基、炭素原子数4~12のオキシアルキレングリコール残基又は炭素数6~18のアリールグリコール残基であり、Aにおけるアルキレンジカルボン酸残基(A1)が炭素原子数2~12のアルキレンジカルボン酸残基であり、Aにおけるアリールジカルボン酸残基(A2)が炭素原子数6~12のアリールジカルボン酸残基であり、nの平均値が0.2~3である請求項1記載のエステル樹脂。
- 前記エステル樹脂の数平均分子量が350~800の範囲である請求項1又は2記載のエステル樹脂。
- 前記一般式(1)中のBが酢酸、安息香酸、パラトルイル酸及びジメチル安息香酸からなる群から選ばれる1種以上の残基であり、Gがエチレングリコール、1,2-プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール及び2-メチルペンチルグリコールからなる群から選ばれる1種以上の残基であり、A1がコハク酸、アジピン酸及びジカルボキシシクロヘキサンからなる群から選ばれる1種以上の残基であり、A2がフタル酸、テレフタル酸及びイソフタル酸からなる群から選ばれる1種以上の残基である請求項1~3の何れか1項記載のエステル樹脂。
- 前記一般式(1)中のAにおけるアルキレンジカルボン酸残基(A1)とアリールジカルボン酸残基(A2)の合計モル数(A1+A2)におけるアリールジカルボン酸残基(A2)の含有率が75~100モル%である請求項1~4の何れか1項記載のエステル樹脂。
- 光学材料用樹脂の反可塑化剤である請求項1~5のいずれか1記載のエステル樹脂。
- 請求項1~5の何れか1項記載のエステル樹脂とセルロースエステル樹脂とを含有することを特徴とするセルロースエステル樹脂組成物。
- 請求項7記載のセルロースエステル樹脂組成物を含有することを特徴とする光学フィルム。
- 偏光板保護用である請求項8記載の光学フィルム。
- 請求項8又は9の光学フィルムを有することを特徴とする液晶表示装置。
- 下記一般式(1)
B-(G-A)n-G-B (1)
〔式(1)中、Bはアリールモノカルボン酸残基又は脂肪族モノカルボン酸残基であり、Gはアルキレングリコール残基、オキシアルキレングリコール残基又はアリールグリコール残基であり、Aはアルキレンジカルボン残基(A1)又はアリールジカルボン酸残基(A2)であって、アルキレンジカルボン酸残基(A1)とアリールジカルボン酸残基(A2)の合計(A1+A2)におけるアリールジカルボン酸残基(A2)の含有率が70~100モル%であり、nは繰り返し数であり、繰り返しごとにG、Aは同一でも異なっていてもよく、また複数あるB、Gは同一でも異なっていてもよい。〕
で表され、GPC測定における面積比率で前記一般式(1)中のn=0成分が10~70%であり、且つnが3以上の成分の面積%とn=0成分の面積%との比(n≧3)/(n=0)が3以下であるエステル樹脂の製造方法であり、
アリールモノカルボン酸又は脂肪族モノカルボン酸と、アルキレングリコール、オキシアルキレングリコール又はアリールグリコールと、アルキレンジカルボン酸、アリールジカルボン酸とを反応させてエステル樹脂(I)を得、薄膜蒸留を行って、前記一般式(1)中のn=0の含有率をGPC測定における面積%で8%以下まで除去した後、ジエステル化合物(II)を添加することを特徴とするエステル樹脂の製造方法。 - 前記ジエステル化合物(II)が、下記一般式(2)
B2-G2-B2 (2)
(式中、B2はアリールモノカルボン酸残基又は脂肪族モノカルボン酸残基であり、G2はアルキレングリコール残基、オキシアルキレングリコール残基又はアリールグリコール残基であり、複数あるB2は同一でも異なっていてもよい。)
で表されるものである請求項11記載の製造方法。 - 前記一般式(2)中のB2が、炭素原子数6~12のアリールモノカルボン酸残基又は炭素原子数1~8の脂肪族モノカルボン酸残基であり、G2が炭素原子数2~12のアルキレングリコール残基、炭素原子数4~12のオキシアルキレングリコール残基又は炭素数6~18のアリールグリコール残基である請求項12記載の製造方法。
- 前記一般式(2)中のB2が酢酸、安息香酸、パラトルイル酸及びジメチル安息香酸からなる群から選ばれる1種以上の残基であり、G2がアルキレングリコール及びオキシアルキレングリコールからなる群から選ばれる1種以上の残基である請求項12又は13記載の製造方法。
- 前記一般式(2)中のB2が安息香酸、パラトルイル酸及びジメチル安息香酸からなる群から選ばれる1種以上の残基であり、G2が1,2-プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,5-ペンタンジオール、2-メチルペンチルグリコール、ジエチレングリコール及びジプロピレングリコールより選ばれる1種以上の残基である請求項12~14の何れか1項記載の製造方法。
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