WO2011158626A1 - Hard-coating base film - Google Patents

Hard-coating base film Download PDF

Info

Publication number
WO2011158626A1
WO2011158626A1 PCT/JP2011/062079 JP2011062079W WO2011158626A1 WO 2011158626 A1 WO2011158626 A1 WO 2011158626A1 JP 2011062079 W JP2011062079 W JP 2011062079W WO 2011158626 A1 WO2011158626 A1 WO 2011158626A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
hard coat
group
compound
base film
Prior art date
Application number
PCT/JP2011/062079
Other languages
French (fr)
Japanese (ja)
Inventor
崇 南條
村上　隆
Original Assignee
コニカミノルタオプト株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタオプト株式会社 filed Critical コニカミノルタオプト株式会社
Priority to JP2012520353A priority Critical patent/JP5617922B2/en
Publication of WO2011158626A1 publication Critical patent/WO2011158626A1/en

Links

Images

Classifications

    • 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
    • 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
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • 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
    • G02B1/105—

Definitions

  • the present invention relates to a base film for hard coat excellent in surface processing suitability (hardness and adhesion) while maintaining appropriate optical performance.
  • LCD liquid crystal display devices
  • TAC triacetyl cellulose
  • the hardness is improved by stretching, but the haze is increased by performing the stretching, so it is difficult to improve the hardness and the haze at the same time.
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is a hard coat that is excellent in surface processing suitability (adhesion with a polarizer and a hard coat layer) and has little deterioration in hardness and haze. It is to provide a substrate film for use.
  • a stretched base film for hard coat characterized in that the total acyl group substitution degree is in the range of 2.80 to 2.95, and contains a cellulose ester containing the following two types of compounds: Base film for hard coat.
  • Compound (1) A copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 and not more than 250,000.
  • Compound (2) A polymer of acrylic monomer C having no hydroxy group in the molecule and having a weight average molecular weight in the range of 300 to 3,000.
  • the maximum value tan ⁇ max of dynamic viscoelastic loss tangent obtained when the dynamic viscoelasticity in the width direction of the base film for hard coat is measured at 1 Hz in the range of 25 to 200 ° C. is 0.85 to 1 2.
  • the flow sheet which shows the manufacturing method of the base film for hard-coats of this invention Schematic diagram showing a state in which glycerin is dropped on a slide glass Schematic diagram showing the state of a sample film placed on glycerin Schematic diagram showing the state in which glycerin is dropped on the sample film Schematic diagram showing a state where a cover glass is placed on glycerin
  • the base film for hard coat of the present invention is a stretched base film for hard coat having a total acyl group substitution degree in the range of 2.80 to 2.95, and the two kinds of compounds ( It contains a cellulose ester containing the compound (1) and the compound (2)).
  • This feature is a technical feature common to the inventions according to claims 1 to 4.
  • An embodiment of the present invention is obtained when the dynamic viscoelasticity in the width direction of the base film for hard coat is measured at 1 Hz in the range of 25 to 200 ° C. from the viewpoint of manifesting the effects of the present invention.
  • the maximum value tan ⁇ max of the dynamic viscoelastic loss tangent is preferably in the range of 0.85 to 1.00.
  • the molar ratio of the acrylic monomer A and the acrylic monomer B constituting the compound (1) is in the range of 85:15.
  • the base film for hard coats of the present invention contains a polyester having an aromatic group at the terminal.
  • the base film for hard coat of the present invention is a stretched base film for hard coat having a total acyl group substitution degree in the range of 2.80 to 2.95, and the following two kinds of compounds: It contains a cellulose ester containing.
  • Compound (1) A copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 and not more than 250,000. A preferable weight average molecular weight is more than 40,000 and not more than 230,000.
  • Compound (2) A polymer of acrylic monomer C having no hydroxy group in the molecule and having a weight average molecular weight in the range of 300 to 3,000.
  • the base film for hard coat of the present invention has the above characteristics, and thus exhibits excellent surface processing suitability (hardness, adhesion) while maintaining appropriate optical performance.
  • the excellent surface processing suitability can be expressed by improving the compatibility between molecules and the orientation of molecules by stretching. That is, the acrylic resin alone has a drawback that it is highly transparent but brittle, and the brittleness is improved by mixing with the cellulose ester. In addition, it is considered that the hydroxy group of the compound (1) interacts with the cellulose ester at the time of stretching to properly align the molecules, and the low molecular weight compound (2) maintains compatibility to suppress an increase in haze. It is done.
  • the dynamic viscoelastic loss tangent tan ⁇ ( loss) obtained when the dynamic viscoelasticity in the width direction of the base film for hard coat of the present invention is measured in the range of 25 to 200 ° C. at 1 Hz.
  • the maximum value tan ⁇ max of the elastic modulus / storage elastic modulus is preferably adjusted so as to be in the range of 0.85 to 1.00.
  • a method of controlling the tan ⁇ max within a predetermined range it can be performed by adjusting the content ratio and the stretching ratio of the compound (1) and the compound (2).
  • dynamic viscoelasticity was measured under the following conditions.
  • the sample used what was humidity-controlled for 24 hours in 23 degreeC55% RH atmosphere beforehand, and measured it, raising humidity on 55% RH and the following conditions.
  • Measuring device RSA III manufactured by TI Instruments Sample: width 5 mm, length 50 mm (gap set to 20 mm) Measurement conditions: Tensile mode Measurement temperature: 25-200 ° C Temperature rising condition: 5 ° C / min Frequency: 1Hz
  • the stretching conditions are preferably a stretching temperature of 150 to 170 ° C. and a stretching ratio of 1.2 to 1.5 times.
  • the base film for hard coat of the present invention is characterized by containing a cellulose ester having a total acyl group substitution degree in the range of 2.80 to 2.95.
  • the cellulose ester used in the present invention preferably has a number average molecular weight in the range of 125000 to 155000.
  • the measuring method of the substitution degree of an acyl group can be measured according to ASTM-D817-96.
  • the cellulose ester according to the present invention preferably has a degree of acetyl group substitution in the range of 2.80 to 2.95, and more preferably in the range of 2.84 to 2.94.
  • the number average molecular weight (Mn) is 125000 to 155000, preferably 129000 to 152000.
  • the weight average molecular weight (Mw) is preferably in the range of 265,000 to 310000.
  • Mw / Mn is preferably 1.9 to 2.1.
  • the average molecular weight (Mn, Mw) and molecular weight distribution of the cellulose ester according to the present invention can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the cellulose ester according to the present invention can be synthesized with reference to the methods described in JP-A-10-45804 and JP-A-2005-281645.
  • the trace metal component in the cellulose ester is preferably 1 ppm or less with respect to the iron (Fe) component.
  • the calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm.
  • the magnesium (Mg) component is preferably 0 to 70 ppm, particularly preferably 0 to 20 ppm.
  • Metal components such as iron (Fe) content, calcium (Ca) content, magnesium (Mg) content, etc. are pre-processed by completely digesting cellulose ester with micro digest wet cracking equipment (sulfuric acid decomposition) and alkali melting. After being performed, it can be analyzed using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer).
  • the cellulose ester according to the present invention may be mixed with, for example, a cellulose ester such as cellulose acetate propionate within a range that does not hinder the performance of the present invention (10% by mass or less).
  • cellulose obtained by graft polymerization of substituents is mixed in the total cellulose ester, or cellulose diacetate is mixed so that the average degree of substitution of all vinegared cotton is 2.75 to 2.85. This is preferable in terms of increasing retardation and preventing brittle deterioration of the stretched film.
  • the cellulose graft-polymerized with a substituent is preferably a cellulose ester having a repeating unit represented by the following general formula (1) or (2).
  • the cellulose ester having a repeating unit represented by the general formula (1) or (2) in the present invention is a cellulose having an unsubstituted hydroxy group (hydroxyl group), an acetyl group, a propionyl group, a butyryl group, a phthalyl group, or the like.
  • An esterification reaction of a polybasic acid or an anhydride thereof with a polyhydric alcohol in the presence of a cellulose ester in which a part of the hydroxy group (hydroxyl group) has already been substituted with an acyl group of L-lactide or D-lactide Can be obtained by ring-opening polymerization of L-lactic acid and self-condensation of L-lactic acid and D-lactic acid.
  • polybasic acid anhydride used in the esterification reaction examples include, but are not limited to, maleic anhydride, phthalic anhydride, and fumaric anhydride.
  • polyhydric alcohol examples include glycerin, ethylene glycol, and propylene glycol, but are not particularly limited.
  • the esterification reaction can be performed without a catalyst, but a known Lewis acid catalyst or the like can be used.
  • catalysts that can be used include metals such as tin, zinc, titanium, bismuth, zirconium, germanium, antimony, sodium, potassium, and aluminum, and derivatives thereof.
  • the derivatives include metal organic compounds, carbonates, oxides, halides. Is preferred. Specific examples include octyl tin, tin chloride, zinc chloride, titanium chloride, alkoxy titanium, germanium oxide, zirconium oxide, antimony trioxide, and alkyl aluminum.
  • an acid catalyst typified by p-toluenesulfonic acid can also be used as the catalyst.
  • stimulate the dehydration reaction of carboxylic acid and alcohol you may add well-known compounds, such as carbodiimide and dimethylaminopyridine.
  • Such a reaction may be a reaction in an organic solvent capable of dissolving cellulose ester and other compounds to be reacted, or a reaction using a batch kneader capable of heating and stirring while adding a shearing force. It may be by reaction using a uniaxial or biaxial extruder.
  • the repeating unit can be appropriately contained in the range of 0.5 to 190% by mass with respect to the cellulose in the part.
  • the degree of substitution of the cellulose ester can be selected as appropriate, but is preferably 2.2 to 2.95 from the viewpoint of thermoplasticity and thermal processability.
  • the hydrogen atom of the hydroxy group (hydroxyl group) part of cellulose is a fatty acid ester with an aliphatic acyl group
  • the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetyl Propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, lauroyl, stearoyl and the like.
  • the repeating unit has a number average molecular weight of 300 to 10000, preferably 500 to 8000, from the viewpoint of thermal workability.
  • the number average molecular weight of only the repeating unit of the cellulose ester is GPC data obtained by polystyrene conversion of the cellulose ester before the esterification reaction and the cellulose ester after the reaction, or 1 H-NMR (JNM-EX- manufactured by JEOL Ltd.). 270: solvent: methylene dichloride).
  • an oligomer or polyester having a repeating unit represented by formula (1) or (2) may be produced as a side reaction, but these compounds act as a plasticizer. However, it is not always necessary to completely remove the cellulose ester by purification. If content is 30 mass% or less with respect to a cellulose ester, there will be little change in the property of a cellulose ester. From the viewpoint of plasticity, it is preferably 0.5 to 20% by mass.
  • oligomers and polyesters have a number average molecular weight of 300 to 10,000, preferably 500 to 8,000 from the viewpoint of plasticity.
  • the cellulose ester used in the present invention is characterized by containing the following two types of compounds.
  • Compound (1) A copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 and not more than 250,000.
  • Compound (2) A polymer of acrylic monomer C having no hydroxy group in the molecule and having a weight average molecular weight in the range of 300 to 3,000.
  • Acrylic monomers A or C having no hydroxy group (hydroxyl group) in the molecule include, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s -, T-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i -), Nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid ( ⁇ -caprolactone), etc.
  • the acrylic monomers A and C may be different or the same, but are preferably different.
  • the acrylic monomer B is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxy group (hydroxyl group).
  • the polymer X according to the present invention includes an acrylic monomer A that does not have an aromatic ring and a hydroxy group (hydroxyl group) in the molecule, an acrylic monomer B that does not have an aromatic ring in the molecule and has a hydroxy group (hydroxyl group), and an acrylic monomer.
  • the compound (1) according to the present invention is a copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 to 250,000. It is as follows.
  • acrylic monomer A is an acrylic or methacrylic monomer having no aromatic ring and hydroxy group (hydroxyl group) in the molecule
  • acrylic monomer B is an acrylic or methacrylic monomer having no aromatic ring in the molecule and having a hydroxy group (hydroxyl group). It is.
  • Preferred compound (1) according to the present invention is represented by the following general formula (1).
  • R 1 and R 3 each represent a hydrogen atom or a methyl group.
  • R2 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group.
  • R 4 represents —CH 2 —, —C 2 H 4 —, or C 3 H 6 —.
  • the hydroxy group (hydroxyl group) includes not only the hydroxy group (hydroxyl group) but also a group having an ethylene oxide chain.
  • the molar composition ratio m: n of acrylic monomer A and acrylic monomer B is preferably in the range of 97: 3 to 85:15, more preferably in the range of 95: 5 to 90:10.
  • the molar composition ratio of the acrylic monomer B exceeds the above range, haze tends to occur during film formation. Moreover, when there is no acrylic monomer B or when there is little, brittleness deteriorates remarkably.
  • the molecular weight of the compound (1) is a weight average molecular weight of more than 30,000 and 250,000 or less. Note that the hardness is low outside this range.
  • the compound (2) according to the present invention is a polymer of acrylic monomer C having no hydroxy group in the molecule and has a weight average molecular weight in the range of 300 to 3,000. Outside this range, there is a tendency for haze to appear during film formation.
  • the weight average molecular weights of the compound (1) and the compound (2) according to the present invention can be adjusted by a known molecular weight adjusting method.
  • a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.
  • the polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 ° C. to 100 ° C., but this temperature or the polymerization reaction time can be adjusted.
  • the measuring method of the weight average molecular weight can be obtained by the following method.
  • the weight average molecular weight Mw and the number average molecular weight Mn were measured using gel permeation chromatography (GPC).
  • the measurement conditions are as follows.
  • Examples of such a polymerization method include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than usual polymerization, and a mercapto compound in addition to the polymerization initiator. And a method using a chain transfer agent such as carbon tetrachloride, a method using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further disclosed in JP 2000-128911 or 2000-344823.
  • a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide
  • a method using a polymerization initiator in a larger amount than usual polymerization and a mercapto compound in addition to the polymerization initiator.
  • a chain transfer agent such as carbon tetrachloride
  • Examples include a compound having one thiol group and a secondary hydroxy group (hydroxyl group), or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination. It is preferably used in the present invention.
  • the hydroxy group (hydroxyl group) value of the compound (1) is preferably 30 to 150 [mgKOH / g].
  • hydroxy (hydroxyl group) value is based on JIS K 0070 (1992). This hydroxy group (hydroxyl group) value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxy group (hydroxyl group) when 1 g of a sample is acetylated.
  • sample Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml) is accurately added thereto. Attach an air cooling tube to the mouth of the flask and heat in a glycerin bath at 95-100 ° C. After 1 hour and 30 minutes, the mixture is cooled, 1 ml of purified water is added from an air condenser, and acetic anhydride is decomposed into acetic acid.
  • an acetylating reagent a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml
  • titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is set as the end point.
  • hydroxy group (hydroxyl group) value is calculated by the following formula.
  • Hydroxy (hydroxyl group) value ⁇ (BC) ⁇ f ⁇ 28.05 / X ⁇ + D
  • B is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test
  • C is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for titration
  • f is a factor of a 0.5 mol / L potassium hydroxide ethanol solution
  • D is an acid value
  • 28.05 is 1/2 of 1 mol amount 56.11 of potassium hydroxide.
  • All of the above-mentioned compounds (1) are excellent in compatibility with cellulose ester, excellent in productivity without evaporation and volatilization, good retention as a protective film for polarizing plates, low moisture permeability, and excellent in dimensional stability. ing.
  • the content of the compound (1) in the cellulose ester film is preferably in a range satisfying the following formula (i).
  • a preferable range of (X + Y) in the formula (i) is 2 to 10% by mass.
  • Compound (1) and Compound (2) can be directly added and dissolved as a material constituting the dope solution described later, or can be added to the dope solution after being previously dissolved in an organic solvent for dissolving the cellulose ester.
  • the base film for hard coat of the present invention preferably contains a plasticizer as necessary.
  • the plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, a polyhydric alcohol ester plasticizer, or a polyester plasticizer. Agent, acrylic plasticizer and the like.
  • At least one is preferably a polyhydric alcohol ester plasticizer.
  • the polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
  • the polyhydric alcohol preferably used in the present invention is represented by the following general formula (Pa).
  • R 1 represents an n-valent organic group
  • n represents a positive integer of 2 or more
  • an OH group represents an alcoholic and / or phenolic hydroxyl group.
  • Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these.
  • triethylene glycol triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited to this.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used.
  • the number of carbon atoms is more preferably 1-20, and particularly preferably 1-10.
  • acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.
  • the carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • citrate plasticizer examples include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
  • fatty acid ester plasticizers examples include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
  • the polyvalent carboxylic acid ester compound is composed of an ester of a divalent or higher, preferably a divalent to 20valent polyvalent carboxylic acid and an alcohol.
  • the aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or alicyclic polyvalent carboxylic acid, it is preferably trivalent to 20-valent.
  • the polyvalent carboxylic acid is represented by the following general formula (Pb).
  • R 2 (COOH) m (OH) n (Wherein R 2 is an (m + n) -valent organic group, m is a positive integer of 2 or more, n is an integer of 0 or more, a COOH group is a carboxy group, and an OH group is an alcoholic or phenolic hydroxyl group)
  • R 2 is an (m + n) -valent organic group, m is a positive integer of 2 or more, n is an integer of 0 or more, a COOH group is a carboxy group, and an OH group is an alcoholic or phenolic hydroxyl group
  • Examples of preferred polyvalent carboxylic acids include the following, but the present invention is not limited to these.
  • Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal
  • An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used.
  • the alcohol used in the polyvalent carboxylic acid ester compound that can be used in the present invention is not particularly limited, and known alcohols and phenols can be used.
  • an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof
  • aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can be preferably used.
  • the alcoholic or phenolic hydroxyl group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid.
  • monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a straight-chain or side-chain fatty acid having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid.
  • the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750.
  • the larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.
  • the alcohol used for the polyvalent carboxylic acid ester that can be used in the present invention may be one kind or a mixture of two or more kinds.
  • the acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of retardation is also suppressed.
  • the acid value refers to the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present in the sample) contained in 1 g of the sample.
  • the acid value is measured according to JIS K0070.
  • tributyl trimellitic acid and tetrabutyl pyromellitic acid.
  • the polyester plasticizer is not particularly limited, and a polyester plasticizer having an aromatic ring or a cycloalkyl ring in the molecule can be used.
  • the polyester plasticizer is not particularly limited.
  • an ester having an aromatic group represented by the following general formula (Pc) at the end also referred to as “aromatic terminal ester” can be used as the plasticizer.
  • benzene monocarboxylic acid component of the polyester plasticizer used in the present invention examples include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, and normalpropyl.
  • benzoic acid aminobenzoic acid, acetoxybenzoic acid, etc., and these can be used as 1 type, or 2 or more types of mixtures, respectively.
  • alkylene glycol component having 2 to 12 carbon atoms of the polyester plasticizer examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1, 3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neo Pentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane) 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-pen Diol, 2-
  • alkylene glycols having 2 to 12 carbon atoms are particularly preferable because of excellent compatibility with cellulose esters.
  • Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like. Or it can be used as a mixture of two or more.
  • alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds.
  • arylene dicarboxylic acid component having 6 to 12 carbon atoms examples include phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.
  • the number average molecular weight of the polyester plasticizer used in the present invention is preferably in the range of 300 to 1500, more preferably 400 to 1000.
  • the acid value is 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.
  • Example No. 1 (Aromatic terminal ester sample)> A reaction vessel was charged with 410 parts of phthalic acid, 610 parts of benzoic acid, 737 parts of dipropylene glycol, and 0.40 part of tetraisopropyl titanate as a catalyst. While the monohydric alcohol was refluxed, heating was continued at 130 to 250 ° C. until the acid value became 2 or less, and water produced was continuously removed. Next, the distillate is removed at 200 to 230 ° C. under reduced pressure of 1.33 ⁇ 10 4 Pa to finally 4 ⁇ 10 2 Pa or less, and then filtered to remove an aromatic terminal ester plastic having the following properties: An agent was obtained.
  • Viscosity 25 ° C., mPa ⁇ s); 43400 Acid value: 0.2
  • this invention is not limited to this.
  • the plasticizer it is preferable to contain a polyester having an aromatic group at the terminal as the plasticizer.
  • the base film for hard coat of the present invention preferably contains an ultraviolet absorber.
  • the ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less.
  • the transmittance at a wavelength of 370 nm is preferably 10% or less, and more preferably 5% or less. is there.
  • the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
  • the amount of UV absorber used is not uniform depending on the type of UV absorber, the operating conditions, etc., but if the dry film thickness of the hard coat substrate film is 30 to 200 ⁇ m, 0.5 to 10% by mass is preferable, and 0.6 to 4% by mass is more preferable.
  • the base film for hard coat of the present invention preferably contains fine particles from the viewpoint of slipperiness and storage stability.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
  • Silicon dioxide that has been subjected to a hydrophobization treatment is preferable for achieving both slipperiness and haze.
  • silanol groups those in which two or more are substituted with a hydrophobic substituent are preferred, and those in which three or more are substituted are more preferred.
  • the hydrophobic substituent is preferably a methyl group.
  • the primary particle diameter of silicon dioxide is preferably 20 nm or less, and more preferably 10 nm or less.
  • Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferable because they have a large effect of reducing the friction coefficient while keeping the haze of the hard coat base film low, and Aerosil R812 is most preferably used in the present invention.
  • the dynamic friction coefficient of at least one surface is preferably 0.2 to 1.0.
  • a dye may be added to the base film for hard coat of the present invention for adjusting the color.
  • a blue dye may be added to suppress the yellowness of the film.
  • Preferred examples of the dye include anthraquinone dyes.
  • the base film for hard coat of the present invention can be produced by any of the usual solution casting method and melt casting method.
  • Production of the base film for hard coat of the present invention by the solution casting method is a step of preparing a dope by dissolving the cellulose ester and the above-mentioned additive in a solvent, and flowing on an endless metal support that allows the dope to move indefinitely.
  • the step of extending, the step of drying the cast dope as a web, the step of peeling from the metal support, the step of stretching or maintaining the width, the step of further drying, and the step of winding up the finished film are performed.
  • the concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • Solvents used in dope may be used alone or in combination of two or more. It is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester from the viewpoint of production efficiency.
  • the good solvent is particularly preferably methylene chloride or methyl acetate.
  • Examples of the poor solvent include methanol, ethanol, n- Butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope contains 0.01 to 2% by mass of water.
  • a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
  • the cellulose ester solution is filtered using an appropriate filter medium such as filter paper.
  • a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is more preferable.
  • the filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene and Teflon (registered trademark) and a metal filter medium such as stainless steel are preferable because they do not drop off fibers. .
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
  • the increase in the difference (referred to as differential pressure) is small, and the preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 45 to 55 ° C.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 to 4 m.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to a temperature lower than the boiling point of the solvent, and the preferable support temperature is 0 to 40 ° C., more preferably 5 to 30 ° C.
  • the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to It is 130% by mass, particularly preferably 20 to 30% by mass or 70 to 120% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is peeled from the metal support and further dried to make the residual solvent amount 1% by mass or less, more preferably 0.1% by mass or less. Particularly preferably, it is 0 to 0.01% by mass or less.
  • a roll drying method (a method in which a plurality of rolls arranged at the top and bottom are alternately passed through the web for drying) or a tenter method for drying while transporting the web is employed.
  • the web is stretched in the longitudinal direction (MD direction) where there is a large amount of residual solvent of the web immediately after peeling from the metal support, and both ends of the web are clipped. It is preferable to perform stretching in the width direction (TD direction) by a tenter system that grips with the like.
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air in terms of simplicity.
  • the drying temperature in the web drying step is preferably 90 ° C. to 200 ° C., more preferably 110 ° C. to 190 ° C.
  • the drying temperature is preferably increased stepwise.
  • the preferred drying time depends on the drying temperature, but is preferably 5 minutes to 60 minutes, more preferably 10 minutes to 30 minutes.
  • the film thickness of the base film for hard coat is not particularly limited, but 10 to 200 ⁇ m is used.
  • the film thickness is particularly preferably 10 to 100 ⁇ m. More preferably, it is 20 to 60 ⁇ m.
  • the base film for hard coat of the present invention has a width of 1 to 4 m. From the viewpoint of productivity, those having a width of 1.6 to 4 m are preferably used, and particularly preferably 1.8 to 3.6 m. If it exceeds 4 m, conveyance becomes difficult.
  • the stretching operation can be performed sequentially or simultaneously with respect to the longitudinal direction (MD direction) and the width direction (TD direction) of the film.
  • the draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 1.0 to 2.0 times in the MD direction and 1.07 to 2.0 times in the TD direction, respectively. It is preferably performed in the range of 1.0 to 1.5 times and 1.07 to 2.0 times in the TD direction.
  • a method of stretching in the MD direction a method of stretching in the transverse direction and stretching in the TD direction, a method of stretching in the MD / TD direction simultaneously and stretching in both the MD / TD directions, and the like.
  • a tenter it may be a pin tenter or a clip tenter.
  • the film transport tension in the film forming process such as in the tenter depends on the temperature, but is preferably 120 N / m to 200 N / m, and more preferably 140 N / m to 200 N / m. 140 N / m to 160 N / m is most preferable.
  • the glass transition temperature of the film of the present invention is Tg (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C., and more preferably (Tg-5) to (Tg + 20) ° C.
  • Tg of the base film for hard coat can be controlled by the material type constituting the film and the ratio of the constituting materials.
  • the Tg when the film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher.
  • the glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower.
  • the Tg of the film can be determined by the method described in JIS K7121.
  • the temperature during stretching is 150 ° C. or more and the stretching ratio is 1.15 times or more because the surface is appropriately roughened.
  • Roughening the film surface is preferable because it improves not only the slipperiness but also the surface processability, particularly the adhesion of the clear hard coat.
  • the average surface roughness Ra is preferably 2.0 nm to 4.0 nm, more preferably 2.5 nm to 3.5 nm.
  • the film preferably contains the above-mentioned hydrophobized silicon dioxide fine particles, and R972V and R812 are particularly preferred for improving haze stability.
  • the base film for hard coat is preferably heat-set after stretching, but the heat setting is usually higher than the final TD direction stretching temperature and usually within 0.5 to 300 ° C. within a temperature range of Tg-20 ° C. or less. It is preferable to fix. At this time, it is preferable to perform heat fixing while sequentially raising the temperature in a range where the temperature difference is 1 to 100 ° C. in the region divided into two or more.
  • the heat-fixed film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound. At this time, it is preferable to perform a relaxation treatment of 0.1 to 10% in the TD direction and / or MD direction within a temperature range not higher than the final heat setting temperature and not lower than Tg.
  • the cooling is preferably performed by gradually cooling from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second.
  • Means for cooling and relaxation treatment are not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to carry out these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film.
  • the cooling rate is a value obtained by (T1-Tg) / t, where T1 is the final heat setting temperature and t is the time until the film reaches Tg from the final heat setting temperature.
  • More optimal conditions of these heat setting conditions, cooling, and relaxation treatment conditions vary depending on the type of additives such as cellulose ester and plasticizer constituting the film, so the physical properties of the obtained biaxially stretched film are measured and preferable characteristics are obtained. What is necessary is just to determine by adjusting suitably so that it may have.
  • the slow axis or fast axis of the base film for hard coat of the present invention exists in the film plane, and ⁇ 1 is preferably ⁇ 1 ° or more and + 1 ° or less when the angle formed with the film forming direction is ⁇ 1. More preferably, the angle is ⁇ 0.5 ° or more and + 0.5 ° or less.
  • This ⁇ 1 can be defined as an orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • KOBRA-21ADH Oji Scientific Instruments
  • the moisture permeability of the base film for hard coat of the present invention is preferably 10 to 1200 g / m 2 ⁇ 24 h at 40 ° C. and 90% RH, more preferably 20 to 1000 g / m 2 ⁇ 24 h, and 20 to 850 g / m 2. -24h is particularly preferred.
  • the moisture permeability can be measured according to the method described in JIS Z 0208.
  • the base film for hard coat of the present invention has a storage modulus at 30 ° C. of 3.2 to 4.7 GPa in the MD direction and 4.7 to 7.0 GPa in the TD direction. Being preferred.
  • the storage elastic modulus can be obtained by the same measurement as tan ⁇ .
  • the base film for hard coat of the present invention preferably has a tear strength that is a brittleness index of 35 mN or more, more preferably 50 mN or more.
  • the breaking elongation of the base film for hard coat of the present invention is preferably 5 to 80%, more preferably 8 to 50%.
  • the visible light transmittance of the base film for hard coat of the present invention is preferably 90% or more, and more preferably 93% or more.
  • the haze of the base film for hard coat of the present invention is preferably less than 1%, particularly preferably 0 to 0.4%.
  • the substrate film for hard coat of the present invention preferably has a retardation value Ro represented by the following formula of 0 to 150 nm and Rt of ⁇ 100 to 300 nm, particularly preferably Ro of 0 to 10 nm and Rt of 0. ⁇ 100 nm.
  • Rt ⁇ 0.85 nm / film thickness 1 ⁇ m.
  • the film is a thin film and has a certain Rt or more. For example, if it is 30 to 50 ⁇ m, Rt is 26 to 200 nm, and if it is 50 to 70 ⁇ m, Rt is 43 to 200 nm. It is preferable.
  • Rt relative to the unit film thickness is more preferably 0.9 to 5.0 nm / film thickness 1 ⁇ m, and further preferably 1.0 to 5.0 nm / film thickness 1 ⁇ m.
  • the hard coat substrate film of the present invention can be provided with a hard coat layer.
  • the film thickness (dry film thickness) of the hard coat layer is 3 to 30 ⁇ m, preferably 5 to 15 ⁇ m.
  • High hardness is desired because it is less likely to be scratched during use on the surface of a display device such as an LCD or in the polarizing plate forming process, and the high hardness in the present invention means that the pencil hardness, which is an index of hardness, is 3H or more. More preferably, it is 4H or more.
  • the pencil hardness is defined by JIS K 5400 using a test pencil specified by JIS S 6006 after the prepared hard coat film is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more. It is the value measured according to the evaluation method.
  • Or Martens hardness of Dokoto is, 400 N / mm 2 or more, and preferably 800 N / mm 2 or less.
  • Martens hardness is a microhardness meter using a Vickers indenter and a triangular pyramid indenter whose angle between ridges is 115 degrees.
  • the hard coat surface of the film is approximately 1 / th of the film thickness of the hard coat layer.
  • Fmax maximum load test force
  • an active energy ray curable resin As the resin binder for forming the hard coat layer, an active energy ray curable resin is preferable.
  • the active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.
  • the active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed.
  • the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin.
  • the ultraviolet curable resin is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable.
  • polyfunctional acrylate is preferable.
  • the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
  • the polyfunctional acrylate is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule. These compounds are used alone or in combination of two or more.
  • the amount of the energy active ray curable resin added is preferably 15% by mass or more and less than 70% by mass in the solid content.
  • the docoat layer preferably contains a photopolymerization initiator in order to accelerate the curing of the energy active ray curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
  • a binder such as a thermoplastic resin, a thermosetting resin, or a hydrophilic resin such as gelatin can also be used.
  • the docoat layer may contain particles of an inorganic compound or an organic compound in order to adjust slipperiness and refractive index.
  • the average particle size of these fine particle powders is preferably 0.01 to 5 ⁇ m, more preferably 0.1 to 5.0 ⁇ m, and particularly preferably 0.1 to 4.0 ⁇ m. Moreover, it is preferable to contain 2 or more types of microparticles
  • the hard coat layer preferably contains reactive silica particles (Xa) surface-treated with an organic compound having a polymerizable unsaturated group.
  • reactive silica particles (Xa) surface-treated with an organic compound having a polymerizable unsaturated group will be described.
  • silica particles can be used. Further, the shape may be spherical or irregular, and is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core / shell particles, or the like.
  • the number average particle diameter of the silica particles determined by the dynamic light scattering method is preferably 30 nm or more, more preferably 30 to 200 nm, and particularly preferably 40 to 80 nm.
  • Examples of commercially available products include MEK-ST-L, IPA-ST-L, and IPA-ST-ZL manufactured by Nissan Chemical Industries, Ltd. as colloidal silica.
  • the reactive silica particles (Xa) are obtained by surface treatment with an organic compound having a polymerizable unsaturated group (hereinafter referred to as “organic compound (X)”).
  • organic compound (X) used for the production of the reactive silica particles (Xa) is a compound having a polymerizable unsaturated group, preferably an ethylenically unsaturated group, and further has a group represented by the following general formula (a). It is preferable that it is an organic compound to contain.
  • the organic compound is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
  • This ethylenically unsaturated group is a structural unit that undergoes addition polymerization with active radical species.
  • the group [—UC ( ⁇ V) —NH—] represented by the formula (a) contained in the organic compound is specifically represented by [—O—C ( ⁇ O) —NH—], [—O—C ( ⁇ S) —NH—], [—S—C ( ⁇ O) —NH—], [—NH—C ( ⁇ O) —NH—] , [—NH—C ( ⁇ S) —NH—], and [—S—C ( ⁇ S) —NH—].
  • These groups can be used individually by 1 type or in combination of 2 or more types.
  • the group [—UC ( ⁇ V) —NH—] represented by the formula (a) generates an appropriate cohesive force due to hydrogen bonds between molecules, and has excellent mechanical strength and group when cured. Excellent adhesion to materials and adjacent layers.
  • Silanol groups or compounds that generate silanol groups by hydrolysis examples include compounds in which an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, or the like is bonded to a silicon atom.
  • a compound in which an alkoxy group or an aryloxy group is bonded to a silicon atom that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
  • R 21 and R 22 may be the same or different and each represents a hydrogen atom or an alkyl or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl , Phenyl, xylyl group and the like.
  • j is an integer of 1 to 3.
  • Examples of the group represented by [(R 21 O) j R 22 3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
  • R 23 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
  • R 24 is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
  • divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
  • Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products.
  • These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
  • R 25 is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
  • Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species.
  • K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.
  • Specific examples of the compound represented by the general formula (b) include compounds represented by the following (b-1) or the following (b-2).
  • ⁇ (Xa) reactive silica particles The organic compound (X) is mixed with silica particles, hydrolyzed, and bonded together.
  • the binding amount of the organic compound (X) to the silica particles is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the reactive silica particles (Xa). Especially preferably, it is 1 mass% or more. Within the above range, the dispersibility is excellent, and the mechanical strength of the obtained cured product is also excellent.
  • the blending ratio of the silica particles in the raw material during the production of the reactive silica particles (Xa) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass.
  • the content of the silica particles constituting the reactive silica particles (Xa) is preferably 65 to 95% by mass.
  • the content of the reactive silica particles (Xa) in the coating composition for the hard coat layer is preferably 5 to 80% by mass when the total solid content in the composition is 100% by mass, and preferably 10 to 80% by mass. % Is more preferable. By using it in the ratio of this range, it exists stably in a composition and it is easy to exhibit the target effect of this invention.
  • an antioxidant that does not inhibit the photocuring reaction can be selected and used.
  • examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like.
  • the hard coat layer forming composition may contain a solvent, or may be appropriately contained and diluted as necessary.
  • the hard coat layer has a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 ⁇ m, or a fine hard particle, Ra is adjusted to 0.1 to 1 ⁇ m.
  • Ra center line average roughness
  • An antiglare hard coat layer may also be used.
  • the center line average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.
  • the hard coat layer may contain a fluorine compound or a silicone compound. Moreover, you may contain the surfactant shown below.
  • the hard coat layer further has a vinyl group and a carboxy group in the side chain of the polyurethane resin as a curing aid, has a weight average molecular weight of 10,000 to 30,000, and a double bond equivalent of 500 to 2,000.
  • Commercially available products include Showa Denko Co., Ltd., trade name Karenz MT series, and the like.
  • a fluorine-acrylic copolymer resin may be contained.
  • fluorine-acrylic copolymer resins include Nippon Oil & Fats Co., Ltd., Modiper F-200, Modiper F-600, Modiper F-2020, and the like.
  • the refractive index of the coated layer is preferably adjusted to a range of 1.4 to 2.2 by measuring the refractive index at 23 ° C. and a wavelength of 550 nm.
  • the means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like.
  • Metal oxide The metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.
  • the kind of metal oxide fine particles is at least one metal oxide fine particle selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate. It is particularly preferable to use as the main component. In particular, it is preferable to contain zinc antimonate particles.
  • the average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and is particularly preferably 10 to 150 nm.
  • the average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like.
  • the metal oxide fine particles may be surface-treated with an organic compound.
  • the hard coat layer according to the present invention for example, a clear hard coat layer, can be applied by the following known method.
  • solvent for coating the clear hard coat layer for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, other solvents can be appropriately selected, or these can be mixed and used. .
  • propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether or propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass or more.
  • the containing solvent is used.
  • any light source that generates ultraviolet rays can be used.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • the irradiation conditions vary depending on individual lamps, but the amount of light irradiated may if 20 ⁇ 10000mJ / cm 2 degrees, preferably 50 ⁇ 2000mJ / cm 2.
  • the near ultraviolet region to the visible light region it can be used by using a sensitizer having an absorption maximum in that region.
  • the UV curable resin composition is coated and dried and then irradiated with UV light from a light source.
  • the irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 due to the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.
  • the base film for hard coat of the present invention can be used for a polarizing plate.
  • the polarizing plate can be produced by a general method.
  • the polarizer side of the base film for hard coat of the present invention is subjected to alkali saponification treatment, and is bonded to at least one surface of a polarizer prepared by immersion and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Is preferred.
  • the hard coat base film of the present invention may be used, or another hard coat base film may be used.
  • Commercially available cellulose ester films for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC8UY-HA, KC8UTA-HA, KC8UX Opt Co., Ltd.
  • cellulose ester films for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC8UY-HA, KC8UTA-HA, KC8UX Opt Co., Ltd.
  • the base film for hard coat of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), and IPS. Particularly preferred are VA (MVA, PVA) type and IPS type liquid crystal display devices.
  • the measurement conditions are as follows.
  • Aerosil R812 manufactured by Nippon Aerosil Co., Ltd. 10 parts by mass (average diameter of primary particles 7 nm) 90 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution. The mixture was filtered with a fine particle dispersion dilution filter (Advantech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
  • a fine particle dispersion dilution filter Advancedtech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
  • the belt was cast evenly on a stainless steel band support using a belt casting apparatus.
  • the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off.
  • the web of cellulose ester film was evaporated at 35 ° C., slit to 1.65 m width, and dried at a drying temperature of 160 ° C.
  • the amount of residual solvent when drying was started was 20%. Thereafter, the film is dried for 15 minutes while being transported in a drying apparatus at 120 ° C. by a number of rolls, then subjected to knurling with a width of 15 mm and a height of 10 ⁇ m at both ends of the film, wound on a core, and a base film for hard coating 101 was obtained.
  • the residual solvent amount of the base film for hard coat was 0.2%, the film thickness was 40 ⁇ m, and the winding number was 6000 m.
  • the average surface roughness Ra of the base film 101 for hard coat is 2.2 nm
  • the storage elastic modulus at 30 ° C. is 5.0 GPa in the MD direction
  • 4.5 GPa in the TD direction
  • the draw ratio in the MD direction (conveyance direction) calculated from the operating speed was 1.10 times.
  • a hard coat layer coating solution is prepared by filtering the following hard coat layer coating composition 1 on the hard coat base film 101 through a polypropylene filter having a pore size of 0.4 ⁇ m, applying the solution by a die coater, and drying at 70 ° C. Then, while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, using an ultraviolet lamp, the illuminance of the irradiated part is 300 mW / cm 2 and the irradiation amount is 0.3 J / cm 2 to cure the coating layer. Further, in the heat treatment zone, heat treatment was performed at 130 ° C. for 5 minutes at a conveyance tension of 300 N / m to form a hard coat layer having a dry film thickness of 7 ⁇ m, and the hard coat film 101 was produced and wound.
  • Hard coat layer composition The following materials were stirred and mixed to obtain hard coat layer coating composition 1.
  • Curing agent Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.) (Synthesis of radical polymerizable fluororesin (A))
  • a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet was added to cefal coat CF-803 (1554 parts by mass), xy
  • the weight average molecular weight was determined by GPC. Further, the mass% of the fluorine-siloxane graft polymer I was determined by HPLC (liquid chromatography).
  • ⁇ Preparation of Hard Coat Base Film 102> In preparation of 101, after slitting to a width of 1.65 m, the film was dried at a drying temperature of 160 ° C. while being stretched 1.3 times in the TD direction (the width direction of the film) with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C. with many rolls, slitting to 2.2 m width, applying a knurling process with a width of 15 mm and a height of 10 ⁇ m at both ends of the film, and winding it around the core The hard coat substrate film 102 was obtained. The residual solvent amount of the base film for hard coat was 0.2%, the film thickness was 40 ⁇ m, and the winding number was 6000 m.
  • the average surface roughness Ra is 3.0 nm
  • the storage elastic modulus at 30 ° C. is 4.1 GPa in the MD direction
  • the MD direction is calculated from the rotational speed of the 5.5 GPa stainless band support in the TD direction and the operating speed of the tenter.
  • the draw ratio of was 1.01 times.
  • Cellulose esters and compounds (1) and (2) were changed as shown in Tables 1 and 2, and various hard coat substrate films (103 to 115) were prepared in the same manner as the hard coat substrate film 102. . Further, a clear hard coat layer was provided on these hard coat base films.
  • the dynamic viscoelasticity tan ⁇ max of the base film for hard coat was measured under the following conditions.
  • the sample used was conditioned at 23 ° C. and 55% RH for 24 hours in advance, and the measurement was performed while the temperature was increased at a humidity of 55% RH and the following conditions.
  • Measuring device RSA III manufactured by TI Instruments Sample: width 5 mm, length 50 mm (gap set to 20 mm) Measurement conditions: Tensile mode Measurement temperature: 25-210 ° C Temperature rising condition: 5 ° C / min Frequency: 1Hz ⁇ Measurement of pencil hardness> A hard coat film sample conditioned at 23 ° C. and 55% RH for 24 hours in accordance with the pencil hardness evaluation method specified by JISK5400 under the same conditions, using a 1 kg weight on the surface of the clear hard coat layer with a pencil of each hardness. Scratching was repeated 5 times, and the hardness of up to one scratch was measured. The higher the number, the higher the hardness.
  • the blank haze 1 of a measuring instrument other than a film is measured.
  • the haze 2 including the sample is measured by the following procedure. 4).
  • 0.05 ml of glycerin is dropped on a slide glass (see FIG. 2). 5.
  • a sample film to be measured is placed thereon so that air bubbles do not enter (see FIG. 3).
  • 0.05 ml of glycerin is dropped on the sample film (see FIG. 4). 7).
  • a cover glass is placed thereon (see FIG. 5). 8).
  • the laminate prepared as described above from above, cover glass / glycerin / sample film / glycerin / slide glass) is set on a haze meter and haze 2 is measured. 9.
  • (Haze 2) ⁇ (Haze 1) (Internal haze of the cellulose ester film of the present invention) is calculated.
  • the glass and glycerin used in the above measurement are as follows.
  • the dynamic viscoelasticity tan ⁇ max of the example according to the present invention is within an appropriate range, and is high in hardness and has a low internal haze value, as compared with the comparative example. I understand.
  • the means of the present invention can provide a base film for hard coat excellent in surface processing suitability (hardness and adhesion) while maintaining appropriate optical performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polarising Elements (AREA)

Abstract

The disclosed hard-coating base film exhibits excellent surface workability (hardness and adhesiveness) while still exhibiting appropriate optical performance. Said hard-coating base film, a stretched hard-coating base film, is characterized by containing a cellulose ester that has a total acyl-group substitution degree between 2.80 and 2.95 and contains the following two compounds: compound (1), which is a copolymer of an acrylic monomer (A) that contains no hydroxy groups and an acrylic monomer (B) that does contain hydroxy groups; and compound (2), which is a polymer of an acrylic monomer (C) that contains no hydroxy groups. Compound (1) has a weight-average molecular weight greater than 30,000 and no greater than 250,000, and compound (2) has a weight-average molecular weight between 300 and 3000.

Description

ハードコート用基材フィルムBase film for hard coat
　本発明は、適切な光学性能を維持しながら、表面加工適性（硬度、密着性）に優れたハードコート用基材フィルムに関する。 The present invention relates to a base film for hard coat excellent in surface processing suitability (hardness and adhesion) while maintaining appropriate optical performance.
　昨今、自動車搭載用の液晶ディスプレイ、大型液晶テレビのディスプレイ、携帯電話、ノートパソコン等の普及から液晶表示装置（以下「ＬＣＤ」ともいう。）の需要が旺盛である。このようなＬＣＤには、偏光フィルムや位相差フィルムなどの基材フィルムが使用されている。 Recently, the demand for liquid crystal display devices (hereinafter also referred to as “LCD”) is strong due to the widespread use of liquid crystal displays mounted on automobiles, large liquid crystal television displays, mobile phones, notebook computers, and the like. Such LCDs use base films such as polarizing films and retardation films.
　ＬＣＤの需要が増加し、これに合わせ使用される偏光板についても薄膜化、軽量化、高生産化が要望されている。さらに、ＬＣＤの大画面化に伴い、部材としての偏光板保護フィルム、位相差フィルム等の基材フィルムも薄膜化、広面積化が求められている。 Demand for LCDs has increased, and there is a demand for polarizing plates used to meet this demand for thinner, lighter and higher production. Furthermore, with the increase in the screen size of LCDs, substrate films such as polarizing plate protective films and retardation films as members are also required to be thinner and have a larger area.
　偏光板保護フィルムとしては、表面の硬度向上及び低コスト化のため総アシル基置換度が２．８０～２．９５である所謂トリアセチルセルロース（ＴＡＣ）フィルムが使用されることが多い。しかしながら、薄膜化したＴＡＣの偏光板保護フィルムを液晶表示装置の最表面に使用した場合、ハードコート層を設けた後、経時でハードコート層の膜剥がれを生じやすいという問題があった。 As the polarizing plate protective film, a so-called triacetyl cellulose (TAC) film having a total acyl group substitution degree of 2.80 to 2.95 is often used for improving the surface hardness and reducing the cost. However, when a thin TAC polarizing plate protective film is used on the outermost surface of the liquid crystal display device, there is a problem that the hard coat layer is likely to peel off over time after the hard coat layer is provided.
　このような問題を解決する手段として、エチレン性不飽和ポリマーや芳香族末端ポリマーによりハードコート用基材フィルムを改質する技術が提案されている（例えば特許文献１参照。）しかしながら、このようなポリマーを添加した場合には解決手段としては、必ずしも十分ではなく、偏光子との密着性は良いが、ハードコート層との密着性改良が不十分であったり、硬度が低下するという問題があり、更なる改良が望まれている。 As a means for solving such a problem, a technique for modifying a base film for hard coat with an ethylenically unsaturated polymer or an aromatic terminal polymer has been proposed (for example, see Patent Document 1). When a polymer is added, the solution is not always sufficient, and the adhesion to the polarizer is good, but there is a problem that the adhesion improvement with the hard coat layer is insufficient or the hardness decreases. Further improvements are desired.
　また、硬度については、延伸する事により向上するが、延伸を行うことによりヘイズも上昇するため、硬度とヘイズを同時に改良することは困難であった。 Further, the hardness is improved by stretching, but the haze is increased by performing the stretching, so it is difficult to improve the hardness and the haze at the same time.
特開２００７－３９１８号公報Japanese Patent Laid-Open No. 2007-3918
　本発明は、上記問題・状況にかんがみてなされたものであり、その解決課題は、表面加工適性（偏光子及びハードコート層との密着性）に優れ、かつ硬度やヘイズの劣化が少ないハードコート用基材フィルムを提供することである。 The present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is a hard coat that is excellent in surface processing suitability (adhesion with a polarizer and a hard coat layer) and has little deterioration in hardness and haze. It is to provide a substrate film for use.
　本発明に係る上記課題は、以下の手段により解決される。 The above-mentioned problem according to the present invention is solved by the following means.
　１．延伸されたハードコート用基材フィルムであって、総アシル基置換度が２．８０～２．９５の範囲であり、かつ下記の二種類の化合物を含むセルロースエステルを含有することを特徴とするハードコート用基材フィルム。
化合物（１）：分子内にヒドロキシ基を有さないアクリルモノマーＡとヒドロキシ基を有するアクリルモノマーＢとの共重合体であり、その重量平均分子量が３０，０００超２５０，０００以下である。
化合物（２）：分子内にヒドロキシ基を有さないアクリルモノマーＣの重合体であり、重量平均分子量が３００～３０００の範囲内である。 1. A stretched base film for hard coat, characterized in that the total acyl group substitution degree is in the range of 2.80 to 2.95, and contains a cellulose ester containing the following two types of compounds: Base film for hard coat.
Compound (1): A copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 and not more than 250,000.
Compound (2): A polymer of acrylic monomer C having no hydroxy group in the molecule and having a weight average molecular weight in the range of 300 to 3,000.
　２．前記ハードコート用基材フィルムの幅手方向の動的粘弾性を２５～２００℃の範囲で１Ｈｚにて測定したときに得られる動的粘弾性損失正接の最大値ｔａｎδｍａｘが、０．８５～１．００の範囲内であることを特徴とする前記第１項に記載のハードコート用基材フィルム。 2. The maximum value tan δmax of dynamic viscoelastic loss tangent obtained when the dynamic viscoelasticity in the width direction of the base film for hard coat is measured at 1 Hz in the range of 25 to 200 ° C. is 0.85 to 1 2. The base film for hard coat as set forth in claim 1, which is within a range of 0.00.
　３．前記化合物（１）を構成するアクリルモノマーＡとアクリルモノマーＢとのモル比が、９７：３～８５：１５の範囲内であることを特徴とする前記第１項又は第２項に記載のハードコート用基材フィルム。 3. 3. The hardware according to item 1 or item 2, wherein the molar ratio of acrylic monomer A and acrylic monomer B constituting the compound (1) is in the range of 97: 3 to 85:15. Base film for coating.
　４．芳香族基を末端に有するポリエステルを含有していることを特徴とする前記第１項から第３項までのいずれか一項に記載のハードコート用基材フィルム。 4. The base film for hard coat according to any one of items 1 to 3, wherein the polyester has an aromatic group-terminated polyester.
　本発明の上記手段により、適切な光学性能を維持しながら、表面加工適性（硬度、密着性）に優れたハードコート用基材フィルムを提供することができる。 By the above means of the present invention, it is possible to provide a base film for hard coat excellent in surface processing suitability (hardness and adhesion) while maintaining appropriate optical performance.
本発明のハードコート用基材フィルムの製造方法を示すフローシートThe flow sheet which shows the manufacturing method of the base film for hard-coats of this invention スライドガラス上にグリセリンを滴下した状態を示す模式図Schematic diagram showing a state in which glycerin is dropped on a slide glass グリセリン上に試料フィルムを置いた状態を示す模式図Schematic diagram showing the state of a sample film placed on glycerin 試料フィルム上にグリセリンを滴下した状態を示す模式図Schematic diagram showing the state in which glycerin is dropped on the sample film グリセリン上にカバーガラスを置いた状態を示す模式図Schematic diagram showing a state where a cover glass is placed on glycerin
　本発明のハードコート用基材フィルムは、延伸されたハードコート用基材フィルムであって、総アシル基置換度が２．８０～２．９５の範囲であり、かつ前記の二種類の化合物（化合物（１）及び化合物（２））を含むセルロースエステルを含有することを特徴とする。この特徴は、請求項１から請求項４までの請求項に係る発明に共通する技術的特徴である。 The base film for hard coat of the present invention is a stretched base film for hard coat having a total acyl group substitution degree in the range of 2.80 to 2.95, and the two kinds of compounds ( It contains a cellulose ester containing the compound (1) and the compound (2)). This feature is a technical feature common to the inventions according to claims 1 to 4.
　本発明の実施態様としては、本発明の効果発現の観点から、前記ハードコート用基材フィルムの幅手方向の動的粘弾性を２５～２００℃の範囲で１Ｈｚにて測定したときに得られる動的粘弾性損失正接の最大値ｔａｎδｍａｘが、０．８５～１．００の範囲内であることが好ましい。また、前記化合物（１）を構成するアクリルモノマーＡとアクリルモノマーＢとのモル比が、８５：１５の範囲内であることが好ましい。さらに、本発明のハードコート用基材フィルム芳香族基を末端に有するポリエステルを含有していることが好ましい。 An embodiment of the present invention is obtained when the dynamic viscoelasticity in the width direction of the base film for hard coat is measured at 1 Hz in the range of 25 to 200 ° C. from the viewpoint of manifesting the effects of the present invention. The maximum value tan δmax of the dynamic viscoelastic loss tangent is preferably in the range of 0.85 to 1.00. Moreover, it is preferable that the molar ratio of the acrylic monomer A and the acrylic monomer B constituting the compound (1) is in the range of 85:15. Furthermore, it is preferable that the base film for hard coats of the present invention contains a polyester having an aromatic group at the terminal.
　以下、本発明とその構成要素、及び本発明を実施するための形態について詳細な説明をする。 Hereinafter, the present invention, its components, and modes for carrying out the present invention will be described in detail.
　（本発明のハードコート用基材フィルムの概要）
　本発明のハードコート用基材フィルムは、延伸されたハードコート用基材フィルムであって、総アシル基置換度が２．８０～２．９５の範囲であり、かつ下記の二種類の化合物を含むセルロースエステルを含有することを特徴とする。
化合物（１）：分子内にヒドロキシ基を有さないアクリルモノマーＡとヒドロキシ基を有するアクリルモノマーＢとの共重合体であり、その重量平均分子量が３０，０００超２５０，０００以下である。好ましい重量平均分子量は、４０，０００超２３０，０００以下である。
化合物（２）：分子内にヒドロキシ基を有さないアクリルモノマーＣの重合体であり、重量平均分子量が３００～３０００の範囲内である。 (Outline of base film for hard coat of the present invention)
The base film for hard coat of the present invention is a stretched base film for hard coat having a total acyl group substitution degree in the range of 2.80 to 2.95, and the following two kinds of compounds: It contains a cellulose ester containing.
Compound (1): A copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 and not more than 250,000. A preferable weight average molecular weight is more than 40,000 and not more than 230,000.
Compound (2): A polymer of acrylic monomer C having no hydroxy group in the molecule and having a weight average molecular weight in the range of 300 to 3,000.
　本発明のハードコート用基材フィルムは、上記特徴を有することにより、適切な光学性能を維持しながら、優れた表面加工適性（硬度、密着性）を発現する。 The base film for hard coat of the present invention has the above characteristics, and thus exhibits excellent surface processing suitability (hardness, adhesion) while maintaining appropriate optical performance.
　当該優れた表面加工適性は、延伸により分子同士の相溶性と分子の配向性が改善されることで発現できると考えられる。すなわち、アクリル樹脂単独では、透明性が高いが脆いという欠点があるところ、セルロースエステルと混合することで脆性は改善される。また、化合物（１）のヒドロキシ基が延伸時にセルロースエステルと相互作用することにより分子同士が適切に配向し、低分子量の化合物（２）が相溶性を保つことによりヘイズ上昇を抑えていると考えられる。 The excellent surface processing suitability can be expressed by improving the compatibility between molecules and the orientation of molecules by stretching. That is, the acrylic resin alone has a drawback that it is highly transparent but brittle, and the brittleness is improved by mixing with the cellulose ester. In addition, it is considered that the hydroxy group of the compound (1) interacts with the cellulose ester at the time of stretching to properly align the molecules, and the low molecular weight compound (2) maintains compatibility to suppress an increase in haze. It is done.
　本発明においては、本発明のハードコート用基材フィルムの幅手方向の動的粘弾性を２５～２００℃の範囲で１Ｈｚにて測定したときに得られる動的粘弾性損失正接ｔａｎδ（＝損失弾性率／貯蔵弾性率）の最大値ｔａｎδｍａｘが、０．８５～１．００の範囲内であるように調整されていることが好ましい。 In the present invention, the dynamic viscoelastic loss tangent tan δ (= loss) obtained when the dynamic viscoelasticity in the width direction of the base film for hard coat of the present invention is measured in the range of 25 to 200 ° C. at 1 Hz. The maximum value tan δmax of the elastic modulus / storage elastic modulus is preferably adjusted so as to be in the range of 0.85 to 1.00.
　当該ｔａｎδｍａｘを所定の範囲内に制御する方法としては、前記化合物（１）と化合物（２）の含有率及び延伸率を調整することで行うことができる。 As a method of controlling the tan δmax within a predetermined range, it can be performed by adjusting the content ratio and the stretching ratio of the compound (1) and the compound (2).
　なお、本発明においては、下記条件で動的粘弾性を測定した。なお、試料はあらかじめ２３℃５５％ＲＨの雰囲気下２４時間調湿したものを使用し、湿度５５％ＲＨ、下記条件で昇温させながら測定した。 In the present invention, dynamic viscoelasticity was measured under the following conditions. In addition, the sample used what was humidity-controlled for 24 hours in 23 degreeC55% RH atmosphere beforehand, and measured it, raising humidity on 55% RH and the following conditions.
　測定装置：ティーエイインスツルメント社製　ＲＳＡIII
　試料：幅５ｍｍ、長さ５０ｍｍ（ギャップ２０ｍｍに設定）
　測定条件：引張モード
　測定温度：２５～２００℃
　昇温条件：５℃／ｍｉｎ
　周波数：１Ｈｚ
　本発明において、延伸の条件としては、延伸温度は１５０～１７０℃、延伸倍率は１．２～１．５倍であることが好ましい。 Measuring device: RSA III manufactured by TI Instruments
Sample: width 5 mm, length 50 mm (gap set to 20 mm)
Measurement conditions: Tensile mode Measurement temperature: 25-200 ° C
Temperature rising condition: 5 ° C / min
Frequency: 1Hz
In the present invention, the stretching conditions are preferably a stretching temperature of 150 to 170 ° C. and a stretching ratio of 1.2 to 1.5 times.
　＜セルロースエステル＞
　本発明のハードコート用基材フィルムは、総アシル基置換度が２．８０～２．９５の範囲であるセルロースエステルを含有することを特徴とする。 <Cellulose ester>
The base film for hard coat of the present invention is characterized by containing a cellulose ester having a total acyl group substitution degree in the range of 2.80 to 2.95.
　本発明に用いるセルロースエステルは、数平均分子量が、１２５０００～１５５０００の範囲内であることが好ましい。 The cellulose ester used in the present invention preferably has a number average molecular weight in the range of 125000 to 155000.
　なお、アシル基の置換度の測定方法はＡＳＴＭ－Ｄ８１７－９６に準じて測定することができる。 In addition, the measuring method of the substitution degree of an acyl group can be measured according to ASTM-D817-96.
　本発明に係るセルロースエステルは、アセチル基置換度が２．８０～２．９５の範囲内であることが好ましく、さらに、２．８４～２．９４の範囲内であることが好ましい。 The cellulose ester according to the present invention preferably has a degree of acetyl group substitution in the range of 2.80 to 2.95, and more preferably in the range of 2.84 to 2.94.
　数平均分子量（Ｍｎ）は、１２５０００～１５５０００であり、１２９０００～１５２０００であることが好ましい。 The number average molecular weight (Mn) is 125000 to 155000, preferably 129000 to 152000.
　さらに、重量平均分子量（Ｍｗ）は、２６５０００～３１００００の範囲内であることが好ましい。また、Ｍｗ／Ｍｎは、１．９～２．１であることが好ましい。 Furthermore, the weight average molecular weight (Mw) is preferably in the range of 265,000 to 310000. Mw / Mn is preferably 1.9 to 2.1.
　本発明に係るセルロースエステルの平均分子量（Ｍｎ、Ｍｗ）及び分子量分布は、ゲルパーミエーションクロマトグラフィーにより測定することができる。測定条件は以下の通りである。 The average molecular weight (Mn, Mw) and molecular weight distribution of the cellulose ester according to the present invention can be measured by gel permeation chromatography. The measurement conditions are as follows.
　溶媒：　　　メチレンクロライド
　カラム：　　Ｓｈｏｄｅｘ　Ｋ８０６、Ｋ８０５、Ｋ８０３Ｇ（昭和電工（株）製を３本接続して使用した）
　カラム温度：２５℃
　試料濃度：　０．１質量％
　検出器：　　ＲＩ　Ｍｏｄｅｌ　５０４（ＧＬサイエンス社製）
　ポンプ：　　Ｌ６０００（日立製作所（株）製）
　流量：　　　１．０ｍｌ／ｍｉｎ
　校正曲線：　標準ポリスチレンＳＴＫ　ｓｔａｎｄａｒｄ　ポリスチレン（東ソー（株）製）Ｍｗ＝２，８００，０００～５００迄の１３サンプルによる校正曲線を使用した。１３サンプルは、ほぼ等間隔に用いることが好ましい。 Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 2,800,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.
　本発明に係るセルロースエステルは、特開平１０－４５８０４号、特開２００５－２８１６４５号公報に記載の方法を参考にして合成することができる。 The cellulose ester according to the present invention can be synthesized with reference to the methods described in JP-A-10-45804 and JP-A-2005-281645.
　また、セルロースエステルは、セルロースエステル中の微量金属成分は、鉄（Ｆｅ）成分については、１ｐｐｍ以下であることが好ましい。カルシウム（Ｃａ）成分は６０ｐｐｍ以下、好ましくは０～３０ｐｐｍである。マグネシウム（Ｍｇ）成分については、０～７０ｐｐｍであることが好ましく、特に０～２０ｐｐｍであることが好ましい。鉄（Ｆｅ）分の含量、カルシウム（Ｃａ）分含量、マグネシウム（Ｍｇ）分含量等の金属成分は、絶乾したセルロースエステルをマイクロダイジェスト湿式分解装置（硫硝酸分解）、アルカリ溶融で前処理を行った後、ＩＣＰ－ＡＥＳ（誘導結合プラズマ発光分光分析装置）を用いて分析することができる。 Further, in the cellulose ester, the trace metal component in the cellulose ester is preferably 1 ppm or less with respect to the iron (Fe) component. The calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm. The magnesium (Mg) component is preferably 0 to 70 ppm, particularly preferably 0 to 20 ppm. Metal components such as iron (Fe) content, calcium (Ca) content, magnesium (Mg) content, etc. are pre-processed by completely digesting cellulose ester with micro digest wet cracking equipment (sulfuric acid decomposition) and alkali melting. After being performed, it can be analyzed using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer).
　本発明に係るセルロースエステルには、本発明の性能を妨げない範囲（１０質量％以下）で、例えば、セルロースアセテートプロピオネート等のセルロースエステルを混合してもよい。 The cellulose ester according to the present invention may be mixed with, for example, a cellulose ester such as cellulose acetate propionate within a range that does not hinder the performance of the present invention (10% by mass or less).
　更に、置換基をグラフト重合させたセルロースを全セルロースエステル中に２％～２０％混合、もしくは、全酢綿の平均置換度が２．７５～２．８５となるようにセルロースジアセテートを混合することは、高リターデーション化及び、延伸後のフィルムの脆性劣化を防ぐ上で、好ましい。 Furthermore, 2% to 20% of cellulose obtained by graft polymerization of substituents is mixed in the total cellulose ester, or cellulose diacetate is mixed so that the average degree of substitution of all vinegared cotton is 2.75 to 2.85. This is preferable in terms of increasing retardation and preventing brittle deterioration of the stretched film.
　置換基をグラフト重合させたセルロースとしては、下記一般式（１）又は（２）で表される繰り返し単位を有するセルロースエステルであることが好ましい。 The cellulose graft-polymerized with a substituent is preferably a cellulose ester having a repeating unit represented by the following general formula (1) or (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　以下にＡの具体例を挙げる。
Ａ－１　－ＣＨ２ＣＨ２－
Ａ－２　－ＣＨ２ＣＨ２ＣＨ２－
Ａ－３　－ＣＨ＝ＣＨ－
Ａ－４ Specific examples of A are given below.
A-1 —CH 2 CH 2 —
A-2 —CH 2 CH 2 CH 2 —
A-3 -CH = CH-
A-4
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Ａ－５ A-5
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Ａ－６　－ＣＨ２Ｃ（ＣＨ３）２－
　以下Ｂの具体例を挙げる。
Ｂ－１　－ＣＨ２ＣＨ２－
Ｂ－２　－ＣＨ２ＣＨ２ＣＨ２ＣＨ２－
Ｂ－３ A-6 —CH 2 C (CH 3 ) 2 —
Specific examples of B are given below.
B-1 —CH 2 CH 2 —
B-2 —CH 2 CH 2 CH 2 CH 2 —
B-3
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Ｂ－４ B-4
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　本発明における前記一般式（１）又は（２）で表される繰り返し単位を有するセルロースエステルは、未置換のヒドロキシ基（水酸基）を有するセルロース、又はアセチル基、プロピオニル基、ブチリル基、フタリル基等のアシル基によってすでに一部のヒドロキシ基（水酸基）が置換されているセルロースエステルの存在下で、多塩基酸又はその無水物と多価アルコールとのエステル化反応、又はＬ－ラクチド、Ｄ－ラクチドの開環重合、Ｌ－乳酸、Ｄ－乳酸の自己縮合を行わせることによって得ることができる。 The cellulose ester having a repeating unit represented by the general formula (1) or (2) in the present invention is a cellulose having an unsubstituted hydroxy group (hydroxyl group), an acetyl group, a propionyl group, a butyryl group, a phthalyl group, or the like. An esterification reaction of a polybasic acid or an anhydride thereof with a polyhydric alcohol in the presence of a cellulose ester in which a part of the hydroxy group (hydroxyl group) has already been substituted with an acyl group of L-lactide or D-lactide Can be obtained by ring-opening polymerization of L-lactic acid and self-condensation of L-lactic acid and D-lactic acid.
　エステル化反応に用いる多塩基酸無水物として、無水マレイン酸、無水フタル酸、無水フマル酸が挙げられるが特に限定されない。 Examples of the polybasic acid anhydride used in the esterification reaction include, but are not limited to, maleic anhydride, phthalic anhydride, and fumaric anhydride.
　エステル化反応に用いることができる多価アルコールとして、グリセリン、エチレングリコール、プロピレングリコールなどが挙げられるが特に限定されない。 Examples of the polyhydric alcohol that can be used for the esterification reaction include glycerin, ethylene glycol, and propylene glycol, but are not particularly limited.
　エステル化反応は、無触媒で反応をすることもできるが、公知のルイス酸触媒などを用いることができる。使用できる触媒としてはスズ、亜鉛、チタン、ビスマス、ジルコニウム、ゲルマニウム、アンチモン、ナトリウム、カリウム、アルミニウムなどの金属及びその誘導体が挙げられ、特に誘導体については金属有機化合物、炭酸塩、酸化物、ハロゲン化物が好ましい。具体的にはオクチルスズ、塩化スズ、塩化亜鉛、塩化チタン、アルコキシチタン、酸化ゲルマニウム、酸化ジルコニウム、三酸化アンチモン、アルキルアルミニウムなどを例示することができる。また、触媒としてパラトルエンスルホン酸に代表される酸触媒を用いることもできる。また、カルボン酸とアルコールとの脱水反応を促進するためにカルボジイミド、ジメチルアミノピリジンなど公知の化合物を添加してもよい。 The esterification reaction can be performed without a catalyst, but a known Lewis acid catalyst or the like can be used. Examples of catalysts that can be used include metals such as tin, zinc, titanium, bismuth, zirconium, germanium, antimony, sodium, potassium, and aluminum, and derivatives thereof. Particularly, the derivatives include metal organic compounds, carbonates, oxides, halides. Is preferred. Specific examples include octyl tin, tin chloride, zinc chloride, titanium chloride, alkoxy titanium, germanium oxide, zirconium oxide, antimony trioxide, and alkyl aluminum. Moreover, an acid catalyst typified by p-toluenesulfonic acid can also be used as the catalyst. Moreover, in order to accelerate | stimulate the dehydration reaction of carboxylic acid and alcohol, you may add well-known compounds, such as carbodiimide and dimethylaminopyridine.
　係る反応は、セルロースエステル及びその他の反応させる化合物を溶解させることが可能な有機溶媒中における反応によってもよいし、剪断力を付加しながら加熱攪拌が可能なバッチ式ニーダーを用いた反応によるものであってもよいし、一軸或いは二軸のエクストルーダーを用いた反応によるものであってもよい。 Such a reaction may be a reaction in an organic solvent capable of dissolving cellulose ester and other compounds to be reacted, or a reaction using a batch kneader capable of heating and stirring while adding a shearing force. It may be by reaction using a uniaxial or biaxial extruder.
　繰り返し単位は、当該部分のセルロースに対して０．５～１９０質量％の範囲で適宜含有させることができる。 The repeating unit can be appropriately contained in the range of 0.5 to 190% by mass with respect to the cellulose in the part.
　セルロースエステルの置換度は、適宜選択することができるが、２．２～２．９５であることが熱可塑性、熱加工性の点から好ましい。 The degree of substitution of the cellulose ester can be selected as appropriate, but is preferably 2.2 to 2.95 from the viewpoint of thermoplasticity and thermal processability.
　本発明に係るセルロースエステルにおいて、セルロースのヒドロキシ基（水酸基）部分の水素原子が脂肪族アシル基との脂肪酸エステルであるとき、脂肪族アシル基は炭素原子数が２～２０で具体的にはアセチル、プロピオニル、ブチリル、イソブチリル、バレリル、ピバロイル、ヘキサノイル、オクタノイル、ラウロイル、ステアロイル等が挙げられる。 In the cellulose ester according to the present invention, when the hydrogen atom of the hydroxy group (hydroxyl group) part of cellulose is a fatty acid ester with an aliphatic acyl group, the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetyl Propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, lauroyl, stearoyl and the like.
　繰り返し単位は、当該部分のセルロースに対しての数平均分子量として３００～１００００であり、５００～８０００であることが熱加工性の点から好ましい。なお、当該セルロースエステルが有する繰り返し単位のみの数平均分子量は、エステル化反応する前のセルロースエステルと反応後のセルロースエステルをポリスチレン換算したＧＰＣデータ又は、１Ｈ－ＮＭＲ（日本電子製ＪＮＭ－ＥＸ－２７０：溶媒：重塩化メチレン）により比較して求めた。 The repeating unit has a number average molecular weight of 300 to 10000, preferably 500 to 8000, from the viewpoint of thermal workability. Note that the number average molecular weight of only the repeating unit of the cellulose ester is GPC data obtained by polystyrene conversion of the cellulose ester before the esterification reaction and the cellulose ester after the reaction, or 1 H-NMR (JNM-EX- manufactured by JEOL Ltd.). 270: solvent: methylene dichloride).
　繰り返し単位をセルロースに導入する際に副反応として、一般式（１）又は（２）で表される繰り返し単位を有するオリゴマー、ポリエステルが生成することあるが、これらの化合物は可塑剤として作用することから精製により必ずしも完全に除去する必要はなくセルロースエステルに含んでもよい。含有量としてはセルロースエステルに対して３０質量％以下であればセルロースエステルの性質を大きく変化させることは少ない。可塑性の点から、好ましくは０．５～２０質量％である。 When a repeating unit is introduced into cellulose, an oligomer or polyester having a repeating unit represented by formula (1) or (2) may be produced as a side reaction, but these compounds act as a plasticizer. However, it is not always necessary to completely remove the cellulose ester by purification. If content is 30 mass% or less with respect to a cellulose ester, there will be little change in the property of a cellulose ester. From the viewpoint of plasticity, it is preferably 0.5 to 20% by mass.
　これらのオリゴマー、ポリエステルの数平均分子量は、３００～１００００であり、可塑性の点から好ましくは５００～８０００である。 These oligomers and polyesters have a number average molecular weight of 300 to 10,000, preferably 500 to 8,000 from the viewpoint of plasticity.
　《アクリルモノマーと（共）重合体》
　本発明において用いるセルロースエステルは、下記の二種類の化合物を含有することを特徴とする。 << Acrylic monomer and (co) polymer >>
The cellulose ester used in the present invention is characterized by containing the following two types of compounds.
　化合物（１）：分子内にヒドロキシ基を有さないアクリルモノマーＡとヒドロキシ基を有するアクリルモノマーＢとの共重合体であり、その重量平均分子量が３０，０００超２５０，０００以下である。 Compound (1): A copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 and not more than 250,000.
　化合物（２）：分子内にヒドロキシ基を有さないアクリルモノマーＣの重合体であり、重量平均分子量が３００～３０００の範囲内である。 Compound (2): A polymer of acrylic monomer C having no hydroxy group in the molecule and having a weight average molecular weight in the range of 300 to 3,000.
　分子内にヒドロキシ基（水酸基）を有しないアクリルモノマーＡ又はＣは、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル（ｉ－、ｎ－）、アクリル酸ブチル（ｎ－、ｉ－、ｓ－、ｔ－）、アクリル酸ペンチル（ｎ－、ｉ－、ｓ－）、アクリル酸ヘキシル（ｎ－、ｉ－）、アクリル酸ヘプチル（ｎ－、ｉ－）、アクリル酸オクチル（ｎ－、ｉ－）、アクリル酸ノニル（ｎ－、ｉ－）、アクリル酸ミリスチル（ｎ－、ｉ－）、アクリル酸（２－エチルヘキシル）、アクリル酸（ε－カプロラクトン）、等、又は上記アクリル酸エステルをメタクリル酸エステルに変えたものを挙げることができる。中でも、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル（ｉ－、ｎ－）であることが好ましい。 Acrylic monomers A or C having no hydroxy group (hydroxyl group) in the molecule include, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s -, T-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i -), Nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), etc. The thing changed into acid ester can be mentioned. Of these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-) are preferable.
　なお、アクリルモノマーＡとＣは、異なっていても同一であってもよいが、異なっていることが好ましい。 The acrylic monomers A and C may be different or the same, but are preferably different.
　アクリルモノマーＢは、ヒドロキシ基（水酸基）を有するモノマー単位として、アクリル酸又はメタクリル酸エステルが好ましく、例えば、アクリル酸（２－ヒドロキシエチル）、アクリル酸（２－ヒドロキシプロピル）、アクリル酸（３－ヒドロキシプロピル）、アクリル酸（４－ヒドロキシブチル）、アクリル酸（２－ヒドロキシブチル）、又はこれらアクリル酸をメタクリル酸に置き換えたものを挙げることが出来、好ましくは、アクリル酸（２－ヒドロキシエチル）及びメタクリル酸（２－ヒドロキシエチル）、アクリル酸（２－ヒドロキシプロピル）、アクリル酸（３－ヒドロキシプロピル）である。 The acrylic monomer B is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxy group (hydroxyl group). For example, acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3- Hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), or those obtained by replacing these acrylic acids with methacrylic acid, preferably acrylic acid (2-hydroxyethyl) And methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid (3-hydroxypropyl).
　本発明に係る重合体Ｘは、分子内に芳香環とヒドロキシ基（水酸基）を有しないアクリルモノマーＡと分子内に芳香環を有せず、ヒドロキシ基（水酸基）を有するアクリルモノマーＢとアクリルモノマーＡとを共重合して得られた重量平均分子量２０００以上、３００００以下の重合体である。 The polymer X according to the present invention includes an acrylic monomer A that does not have an aromatic ring and a hydroxy group (hydroxyl group) in the molecule, an acrylic monomer B that does not have an aromatic ring in the molecule and has a hydroxy group (hydroxyl group), and an acrylic monomer. A polymer having a weight average molecular weight of 2000 or more and 30000 or less obtained by copolymerizing with A.
　〈化合物（１）：共重合体〉
　本発明に係る化合物（１）は、分子内にヒドロキシ基を有さないアクリルモノマーＡとヒドロキシ基を有するアクリルモノマーＢとの共重合体であり、その重量平均分子量が３０，０００超２５０，０００以下である。 <Compound (1): Copolymer>
The compound (1) according to the present invention is a copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 to 250,000. It is as follows.
　好ましくは、アクリルモノマーＡは分子内に芳香環とヒドロキシ基（水酸基）を有しないアクリル又はメタクリルモノマー、アクリルモノマーＢは分子内に芳香環を有せずヒドロキシ基（水酸基）を有するアクリル又はメタクリルモノマーである。 Preferably, acrylic monomer A is an acrylic or methacrylic monomer having no aromatic ring and hydroxy group (hydroxyl group) in the molecule, and acrylic monomer B is an acrylic or methacrylic monomer having no aromatic ring in the molecule and having a hydroxy group (hydroxyl group). It is.
　本発明に係る好ましい化合物（１）は、下記一般式（１）で表される。 Preferred compound (1) according to the present invention is represented by the following general formula (1).
　一般式（１）
　　－［ＣＨ２－Ｃ（－Ｒ１）（－ＣＯ２Ｒ２）］ｍ－［ＣＨ２－Ｃ（－Ｒ３）（－ＣＯ２Ｒ４－ＯＨ）－］ｎ
　上記一般式（１）において、Ｒ１、Ｒ３は、それぞれ水素原子又はメチル基を表す。Ｒ２は炭素数１～１２のアルキル基又はシクロアルキル基を表す。Ｒ４は－ＣＨ２－、－Ｃ２Ｈ４－又はＣ３Ｈ６－を表す。ｍ、及びｎは、モル組成比を表す。ただしｍ≠０、ｎ≠０、ｍ＋ｎ＝１００である。 General formula (1)
— [CH 2 —C (—R 1 ) (— CO 2 R 2 )] m — [CH 2 —C (—R 3 ) (— CO 2 R 4 —OH) —] n
In the general formula (1), R 1 and R 3 each represent a hydrogen atom or a methyl group. R2 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. R 4 represents —CH 2 —, —C 2 H 4 —, or C 3 H 6 —. m and n represent molar composition ratios. However, m ≠ 0, n ≠ 0, and m + n = 100.
　化合物（１）を構成するモノマー単位において、ヒドロキシ基（水酸基）とは、ヒドロキシ基（水酸基）のみならずエチレンオキシド連鎖を有する基を含む。 In the monomer unit constituting the compound (1), the hydroxy group (hydroxyl group) includes not only the hydroxy group (hydroxyl group) but also a group having an ethylene oxide chain.
　アクリルモノマーＡ及びアクリルモノマーＢのモル組成比ｍ：ｎは９７：３～８５：１５の範囲内が好ましく、更に好ましくは９５：５～９０：１０の範囲である。 The molar composition ratio m: n of acrylic monomer A and acrylic monomer B is preferably in the range of 97: 3 to 85:15, more preferably in the range of 95: 5 to 90:10.
　また、アクリルモノマーＢのモル組成比が上記範囲を超えると製膜時にヘイズが出る傾向がある。また、アクリルモノマーＢが無い場合、又は少ない場合には脆性が著しく劣化する。 Also, if the molar composition ratio of the acrylic monomer B exceeds the above range, haze tends to occur during film formation. Moreover, when there is no acrylic monomer B or when there is little, brittleness deteriorates remarkably.
　化合物（１）の分子量は、重量平均分子量が３０，０００超２５０，０００以下である。なお、当該範囲外では硬度が低くなる。 The molecular weight of the compound (1) is a weight average molecular weight of more than 30,000 and 250,000 or less. Note that the hardness is low outside this range.
　〈化合物（２）：重合体〉
　本発明に係る化合物（２）は、分子内にヒドロキシ基を有さないアクリルモノマーＣの重合体であり、重量平均分子量が３００～３０００の範囲内である。なお、当該範囲外では製膜時にヘイズが出る傾向がある。 <Compound (2): Polymer>
The compound (2) according to the present invention is a polymer of acrylic monomer C having no hydroxy group in the molecule and has a weight average molecular weight in the range of 300 to 3,000. Outside this range, there is a tendency for haze to appear during film formation.
　本発明に係る化合物（１）及び化合物（２）の重量平均分子量は、公知の分子量調節方法で調整することができる。そのような分子量調節方法としては、例えば、四塩化炭素、ラウリルメルカプタン、チオグリコール酸オクチル等の連鎖移動剤を添加する方法等が挙げられる。 The weight average molecular weights of the compound (1) and the compound (2) according to the present invention can be adjusted by a known molecular weight adjusting method. Examples of such a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.
　また、重合温度は、通常、室温から１３０℃、好ましくは５０℃から１００℃で行われるが、この温度又は重合反応時間を調整することで可能である。 The polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 ° C. to 100 ° C., but this temperature or the polymerization reaction time can be adjusted.
　重量平均分子量の測定方法は、下記の方法により求めることができる。 The measuring method of the weight average molecular weight can be obtained by the following method.
　（平均分子量測定方法）
　重量平均分子量Ｍｗ、数平均分子量Ｍｎは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定した。 (Average molecular weight measurement method)
The weight average molecular weight Mw and the number average molecular weight Mn were measured using gel permeation chromatography (GPC).
　測定条件は以下の通りである。 The measurement conditions are as follows.
　溶媒：　　　メチレンクロライド
　カラム：　　Ｓｈｏｄｅｘ　Ｋ８０６、Ｋ８０５、Ｋ８０３Ｇ（昭和電工（株）製を３本接続して使用した）
　カラム温度：２５℃
　試料濃度：　０．１質量％
　検出器：　　ＲＩ　Ｍｏｄｅｌ　５０４（ＧＬサイエンス社製）
　ポンプ：　　Ｌ６０００（日立製作所（株）製）
　流量：　　　１．０ｍｌ／ｍｉｎ
　校正曲線：　標準ポリスチレンＳＴＫ　ｓｔａｎｄａｒｄ　ポリスチレン（東ソー（株）製）Ｍｗ＝１００００００～５００の１３サンプルによる校正曲線を使用した。１３サンプルは、ほぼ等間隔に用いる。 Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 1000,000 to 500 13 calibration curves were used. Thirteen samples are used at approximately equal intervals.
　化合物（１）及び化合物（２）を合成するには、通常の重合では分子量のコントロールが難しく、分子量を余り大きくしない方法で、かつできるだけ分子量を揃えることのできる方法を用いることが望ましい。 In order to synthesize the compound (1) and the compound (2), it is difficult to control the molecular weight by ordinary polymerization, and it is desirable to use a method that can adjust the molecular weight as much as possible without increasing the molecular weight.
　かかる重合方法としては、クメンペルオキシドやｔ－ブチルヒドロペルオキシドのような過酸化物重合開始剤を使用する方法、重合開始剤を通常の重合より多量に使用する方法、重合開始剤の他にメルカプト化合物や四塩化炭素等の連鎖移動剤を使用する方法、重合開始剤の他にベンゾキノンやジニトロベンゼンのような重合停止剤を使用する方法、更に特開２０００－１２８９１１号又は同２０００－３４４８２３号公報にあるような一つのチオール基と２級のヒドロキシ基（水酸基）とを有する化合物、或いは、該化合物と有機金属化合物を併用した重合触媒を用いて塊状重合する方法等を挙げることが出来、何れも本発明において好ましく用いられる。 Examples of such a polymerization method include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than usual polymerization, and a mercapto compound in addition to the polymerization initiator. And a method using a chain transfer agent such as carbon tetrachloride, a method using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further disclosed in JP 2000-128911 or 2000-344823. Examples include a compound having one thiol group and a secondary hydroxy group (hydroxyl group), or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination. It is preferably used in the present invention.
　化合物（１）のヒドロキシ基（水酸基）価は、３０～１５０［ｍｇＫＯＨ／ｇ］であることが好ましい。 The hydroxy group (hydroxyl group) value of the compound (1) is preferably 30 to 150 [mgKOH / g].
　（ヒドロキシ（水酸基）価の測定方法）
　ヒドロキシ（水酸基）価の測定は、ＪＩＳ　Ｋ　００７０（１９９２）に準ずる。このヒドロキシ基（水酸基）価は、試料１ｇをアセチル化させたとき、ヒドロキシ基（水酸基）と結合した酢酸を中和するのに必要とする水酸化カリウムのｍｇ数と定義される。 (Method for measuring hydroxy value)
The measurement of hydroxy (hydroxyl group) value is based on JIS K 0070 (1992). This hydroxy group (hydroxyl group) value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxy group (hydroxyl group) when 1 g of a sample is acetylated.
　具体的には試料Ｘｇ（約１ｇ）をフラスコに精秤し、これにアセチル化試薬（無水酢酸２０ｍｌにピリジンを加えて４００ｍｌにしたもの）２０ｍｌを正確に加える。フラスコの口に空気冷却管を装着し、９５～１００℃のグリセリン浴にて加熱する。１時間３０分後、冷却し、空気冷却管から精製水１ｍｌを加え、無水酢酸を酢酸に分解する。 Specifically, sample Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml) is accurately added thereto. Attach an air cooling tube to the mouth of the flask and heat in a glycerin bath at 95-100 ° C. After 1 hour and 30 minutes, the mixture is cooled, 1 ml of purified water is added from an air condenser, and acetic anhydride is decomposed into acetic acid.
　次に電位差滴定装置を用いて０．５ｍｏｌ／Ｌ水酸化カリウムエタノール溶液で滴定を行い、得られた滴定曲線の変曲点を終点とする。 Next, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is set as the end point.
　更に空試験として、試料を入れないで滴定し、滴定曲線の変曲点を求める。ヒドロキシ基（水酸基）価は、次の式によって算出する。 Further, as a blank test, titration is performed without a sample, and the inflection point of the titration curve is obtained. The hydroxy group (hydroxyl group) value is calculated by the following formula.
　　ヒドロキシ（水酸基）価＝｛（Ｂ－Ｃ）×ｆ×２８．０５／Ｘ｝＋Ｄ
　式中、Ｂは空試験に用いた０．５ｍｏｌ／Ｌの水酸化カリウムエタノール溶液の量（ｍｌ）、Ｃは滴定に用いた０．５ｍｏｌ／Ｌの水酸化カリウムエタノール溶液の量（ｍｌ）、ｆは０．５ｍｏｌ／Ｌ水酸化カリウムエタノール溶液のファクター、Ｄは酸価、また、２８．０５は水酸化カリウムの１ｍｏｌ量５６．１１の１／２を表す。 Hydroxy (hydroxyl group) value = {(BC) × f × 28.05 / X} + D
In the formula, B is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, C is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, f is a factor of a 0.5 mol / L potassium hydroxide ethanol solution, D is an acid value, and 28.05 is 1/2 of 1 mol amount 56.11 of potassium hydroxide.
　上述の化合物（１）は何れもセルロースエステルとの相溶性に優れ、蒸発や揮発もなく生産性に優れ、偏光板用保護フィルムとしての保留性がよく、透湿度が小さく、寸法安定性に優れている。 All of the above-mentioned compounds (1) are excellent in compatibility with cellulose ester, excellent in productivity without evaporation and volatilization, good retention as a protective film for polarizing plates, low moisture permeability, and excellent in dimensional stability. ing.
　化合物（１）のセルロースエステルフィルム中での含有量は、下記式（ｉ）を満足する範囲であることが好ましい。化合物（１）の含有量をＸ（質量％＝（化合物（１）の質量／セルロースエステルの質量）×１００）、化合物（２）の含有量をＹ（質量％）とすると、
　式（ｉ）　１≦Ｘ＋Ｙ≦２０（質量％）
　式（ｉ）の（Ｘ＋Ｙ）の好ましい範囲は、２～１０質量％である。 The content of the compound (1) in the cellulose ester film is preferably in a range satisfying the following formula (i). When the content of compound (1) is X (mass% = (mass of compound (1) / mass of cellulose ester) × 100) and the content of compound (2) is Y (mass%),
Formula (i) 1 <= X + Y <= 20 (mass%)
A preferable range of (X + Y) in the formula (i) is 2 to 10% by mass.
　化合物（１）と化合物（２）は、後述するドープ液を構成する素材として直接添加、溶解するか、もしくはセルロースエステルを溶解する有機溶媒に予め溶解した後ドープ液に添加することができる。 Compound (1) and Compound (2) can be directly added and dissolved as a material constituting the dope solution described later, or can be added to the dope solution after being previously dissolved in an organic solvent for dissolving the cellulose ester.
　（可塑剤）
　本発明のハードコート用基材フィルムは、必要に応じて可塑剤を含有することが好ましい。 (Plasticizer)
The base film for hard coat of the present invention preferably contains a plasticizer as necessary.
　可塑剤は特に限定されないが、好ましくは、多価カルボン酸エステル系可塑剤、グリコレート系可塑剤、フタル酸エステル系可塑剤、脂肪酸エステル系可塑剤及び多価アルコールエステル系可塑剤、ポリエステル系可塑剤、アクリル系可塑剤等から選択される。 The plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, a polyhydric alcohol ester plasticizer, or a polyester plasticizer. Agent, acrylic plasticizer and the like.
　そのうち、可塑剤を二種以上用いる場合は、少なくとも一種は多価アルコールエステル系可塑剤であることが好ましい。 Of these, when two or more plasticizers are used, at least one is preferably a polyhydric alcohol ester plasticizer.
　多価アルコールエステル系可塑剤は２価以上の脂肪族多価アルコールとモノカルボン酸のエステルよりなる可塑剤であり、分子内に芳香環又はシクロアルキル環を有することが好ましい。好ましくは２～２０価の脂肪族多価アルコールエステルである。 The polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. A divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
　本発明に好ましく用いられる多価アルコールは次の一般式（Ｐａ）で表される。 The polyhydric alcohol preferably used in the present invention is represented by the following general formula (Pa).
　一般式（Ｐａ）：　　Ｒ１－（ＯＨ）ｎ
　但し、Ｒ１はｎ価の有機基、ｎは２以上の正の整数、ＯＨ基はアルコール性、及び／又はフェノール性水酸基を表す。 Formula (Pa): R 1- (OH) n
However, R 1 represents an n-valent organic group, n represents a positive integer of 2 or more, and an OH group represents an alcoholic and / or phenolic hydroxyl group.
　好ましい多価アルコールの例としては、例えば以下のようなものを挙げることができるが、本発明はこれらに限定されるものではない。 Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these.
　アドニトール、アラビトール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ジブチレングリコール、１，２，４－ブタントリオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ヘキサントリオール、ガラクチトール、マンニトール、３－メチルペンタン－１，３，５－トリオール、ピナコール、ソルビトール、トリメチロールプロパン、トリメチロールエタン、キシリトール等を挙げることができる。 Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol.
　特に、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ソルビトール、トリメチロールプロパン、キシリトールが好ましい。 In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.
　多価アルコールエステルに用いられるモノカルボン酸としては、特に制限はなく、公知の脂肪族モノカルボン酸、脂環族モノカルボン酸、芳香族モノカルボン酸等を用いることができる。脂環族モノカルボン酸、芳香族モノカルボン酸を用いると透湿性、保留性を向上させる点で好ましい。 There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.
　好ましいモノカルボン酸の例としては以下のようなものを挙げることができるが、本発明はこれに限定されるものではない。 Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited to this.
　脂肪族モノカルボン酸としては、炭素数１～３２の直鎖又は側鎖を有する脂肪酸を好ましく用いることができる。炭素数は１～２０であることが更に好ましく、１～１０であることが特に好ましい。酢酸を含有させるとセルロースエステルとの相溶性が増すため好ましく、酢酸と他のモノカルボン酸を混合して用いることも好ましい。 As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
　好ましい脂肪族モノカルボン酸としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、２－エチル－ヘキサン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ラクセル酸等の飽和脂肪酸、ウンデシレン酸、オレイン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸等の不飽和脂肪酸等を挙げることができる。 Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
　好ましい脂環族モノカルボン酸の例としては、シクロペンタンカルボン酸、シクロヘキサンカルボン酸、シクロオクタンカルボン酸、又はそれらの誘導体を挙げることができる。 Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
　好ましい芳香族モノカルボン酸の例としては、安息香酸、トルイル酸等の安息香酸のベンゼン環にアルキル基、メトキシ基或いはエトキシ基などのアルコキシ基を１～３個を導入したもの、ビフェニルカルボン酸、ナフタリンカルボン酸、テトラリンカルボン酸等のベンゼン環を２個以上有する芳香族モノカルボン酸、又はそれらの誘導体を挙げることができる。特に安息香酸が好ましい。 Examples of preferred aromatic monocarboxylic acids include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
　多価アルコールエステルの分子量は特に制限はないが、３００～１５００であることが好ましく、３５０～７５０であることが更に好ましい。分子量が大きい方が揮発し難くなるため好ましく、透湿性、セルロースエステルとの相溶性の点では小さい方が好ましい。 The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.
　多価アルコールエステルに用いられるカルボン酸は一種類でもよいし、二種以上の混合であってもよい。また、多価アルコール中のＯＨ基は、全てエステル化してもよいし、一部をＯＨ基のままで残してもよい。 The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
　以下に、多価アルコールエステルの具体的化合物を例示する。 The following are specific compounds of polyhydric alcohol esters.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　グリコレート系可塑剤は特に限定されないが、アルキルフタリルアルキルグリコレート類が好ましく用いることができる。 The glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
　アルキルフタリルアルキルグリコレート類としては、例えばメチルフタリルメチルグリコレート、エチルフタリルエチルグリコレート、プロピルフタリルプロピルグリコレート、ブチルフタリルブチルグリコレート、オクチルフタリルオクチルグリコレート、メチルフタリルエチルグリコレート、エチルフタリルメチルグリコレート、エチルフタリルプロピルグリコレート、メチルフタリルブチルグリコレート、エチルフタリルブチルグリコレート、ブチルフタリルメチルグリコレート、ブチルフタリルエチルグリコレート、プロピルフタリルブチルグリコレート、ブチルフタリルプロピルグリコレート、メチルフタリルオクチルグリコレート、エチルフタリルオクチルグリコレート、オクチルフタリルメチルグリコレート、オクチルフタリルエチルグリコレート等が挙げられる。 Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.
　フタル酸エステル系可塑剤としては、ジエチルフタレート、ジメトキシエチルフタレート、ジメチルフタレート、ジオクチルフタレート、ジブチルフタレート、ジ－２－エチルヘキシルフタレート、ジオクチルフタレート、ジシクロヘキシルフタレート、ジシクロヘキシルテレフタレート等が挙げられる。 Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
　クエン酸エステル系可塑剤としては、クエン酸アセチルトリメチル、クエン酸アセチルトリエチル、クエン酸アセチルトリブチル等が挙げられる。 Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
　脂肪酸エステル系可塑剤として、オレイン酸ブチル、リシノール酸メチルアセチル、セバシン酸ジブチル等が挙げられる。 Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
　リン酸エステル系可塑剤としては、トリフェニルホスフェート、トリクレジルホスフェート、クレジルジフェニルホスフェート、オクチルジフェニルホスフェート、ジフェニルビフェニルホスフェート、トリオクチルホスフェート、トリブチルホスフェート等が挙げられる。 Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
　多価カルボン酸エステル化合物としては、２価以上、好ましくは２価～２０価の多価カルボン酸とアルコールのエステルよりなる。また、脂肪族多価カルボン酸は２～２０価であることが好ましく、芳香族多価カルボン酸、脂環式多価カルボン酸の場合は３価～２０価であることが好ましい。 The polyvalent carboxylic acid ester compound is composed of an ester of a divalent or higher, preferably a divalent to 20valent polyvalent carboxylic acid and an alcohol. The aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or alicyclic polyvalent carboxylic acid, it is preferably trivalent to 20-valent.
　多価カルボン酸は次の一般式（Ｐｂ）で表される。 The polyvalent carboxylic acid is represented by the following general formula (Pb).
　一般式（Ｐｂ）：　　Ｒ２（ＣＯＯＨ）ｍ（ＯＨ）ｎ
（但し、Ｒ２は（ｍ＋ｎ）価の有機基、ｍは２以上の正の整数、ｎは０以上の整数、ＣＯＯＨ基はカルボキシ基、ＯＨ基はアルコール性又はフェノール性水酸基を表す）
　好ましい多価カルボン酸の例としては、例えば以下のようなものを挙げることができるが、本発明はこれらに限定されるものではない。 Formula (Pb): R 2 (COOH) m (OH) n
(Wherein R 2 is an (m + n) -valent organic group, m is a positive integer of 2 or more, n is an integer of 0 or more, a COOH group is a carboxy group, and an OH group is an alcoholic or phenolic hydroxyl group)
Examples of preferred polyvalent carboxylic acids include the following, but the present invention is not limited to these.
　トリメリット酸、トリメシン酸、ピロメリット酸のような３価以上の芳香族多価カルボン酸又はその誘導体、コハク酸、アジピン酸、アゼライン酸、セバシン酸、シュウ酸、フマル酸、マレイン酸、テトラヒドロフタル酸のような脂肪族多価カルボン酸、酒石酸、タルトロン酸、リンゴ酸、クエン酸のようなオキシ多価カルボン酸などを好ましく用いることができる。特にオキシ多価カルボン酸を用いることが、保留性向上などの点で好ましい。 Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used. In particular, it is preferable to use an oxypolycarboxylic acid from the viewpoint of improving retention.
　本発明に用いることのできる多価カルボン酸エステル化合物に用いられるアルコールとしては特に制限はなく公知のアルコール、フェノール類を用いることができる。 The alcohol used in the polyvalent carboxylic acid ester compound that can be used in the present invention is not particularly limited, and known alcohols and phenols can be used.
　例えば炭素数１～３２の直鎖又は側鎖を持った脂肪族飽和アルコール又は脂肪族不飽和アルコールを好ましく用いることができる。炭素数１～２０であることが更に好ましく、炭素数１～１０であることが特に好ましい。 For example, an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
　また、シクロペンタノール、シクロヘキサノールなどの脂環式アルコール又はその誘導体、ベンジルアルコール、シンナミルアルコールなどの芳香族アルコール又はその誘導体なども好ましく用いることができる。 Also, alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof, aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can be preferably used.
　多価カルボン酸としてオキシ多価カルボン酸を用いる場合は、オキシ多価カルボン酸のアルコール性又はフェノール性の水酸基をモノカルボン酸を用いてエステル化しても良い。好ましいモノカルボン酸の例としては以下のようなものを挙げることができるが、本発明はこれに限定されるものではない。 When an oxypolycarboxylic acid is used as the polycarboxylic acid, the alcoholic or phenolic hydroxyl group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
　脂肪族モノカルボン酸としては炭素数１～３２の直鎖又は側鎖を持った脂肪酸を好ましく用いることができる。炭素数１～２０であることが更に好ましく、炭素数１～１０であることが特に好ましい。 As the aliphatic monocarboxylic acid, a straight-chain or side-chain fatty acid having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
　好ましい脂肪族モノカルボン酸としては酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、２－エチル－ヘキサンカルボン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ラクセル酸などの飽和脂肪酸、ウンデシレン酸、オレイン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸などの不飽和脂肪酸などを挙げることができる。 Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
　好ましい脂環族モノカルボン酸の例としては、シクロペンタンカルボン酸、シクロヘキサンカルボン酸、シクロオクタンカルボン酸、又はそれらの誘導体を挙げることができる。 Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
　好ましい芳香族モノカルボン酸の例としては、安息香酸、トルイル酸などの安息香酸のベンゼン環にアルキル基を導入したもの、ビフェニルカルボン酸、ナフタリンカルボン酸、テトラリンカルボン酸などのベンゼン環を２個以上もつ芳香族モノカルボン酸、又はそれらの誘導体を挙げることができる。特に酢酸、プロピオン酸、安息香酸であることが好ましい。 Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. Aromatic monocarboxylic acids possessed by them, or derivatives thereof. Particularly preferred are acetic acid, propionic acid, and benzoic acid.
　多価カルボン酸エステル化合物の分子量は特に制限はないが、分子量３００～１０００の範囲であることが好ましく、３５０～７５０の範囲であることが更に好ましい。保留性向上の点では大きい方が好ましく、透湿性、セルロースエステルとの相溶性の点では小さい方が好ましい。 The molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.
　本発明に用いることのできる多価カルボン酸エステルに用いられるアルコール類は一種類でも良いし、二種以上の混合であっても良い。 The alcohol used for the polyvalent carboxylic acid ester that can be used in the present invention may be one kind or a mixture of two or more kinds.
　本発明に用いることのできる多価カルボン酸エステル化合物の酸価は１ｍｇＫＯＨ／ｇ以下であることが好ましく、０．２ｍｇＫＯＨ／ｇ以下であることが更に好ましい。酸価を上記範囲にすることによって、レターデーションの環境変動も抑制されるため好ましい。 The acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of retardation is also suppressed.
　なお、酸価とは、試料１ｇ中に含まれる酸（試料中に存在するカルボキシ基）を中和するために必要な水酸化カリウムのミリグラム数をいう。酸価はＪＩＳ　Ｋ００７０に準拠して測定したものである。 The acid value refers to the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present in the sample) contained in 1 g of the sample. The acid value is measured according to JIS K0070.
　特に好ましい多価カルボン酸エステル化合物の例を以下に示すが、本発明はこれに限定されるものではない。 Examples of particularly preferred polyvalent carboxylic acid ester compounds are shown below, but the present invention is not limited thereto.
　例えば、トリエチルシトレート、トリブチルシトレート、アセチルトリエチルシトレート（ＡＴＥＣ）、アセチルトリブチルシトレート（ＡＴＢＣ）、ベンゾイルトリブチルシトレート、アセチルトリフェニルシトレート、アセチルトリベンジルシトレート、酒石酸ジブチル、酒石酸ジアセチルジブチル、トリメリット酸トリブチル、ピロメリット酸テトラブチル等が挙げられる。 For example, triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyl triphenyl citrate, acetyl tribenzyl citrate, dibutyl tartrate, diacetyl dibutyl tartrate, Examples include tributyl trimellitic acid and tetrabutyl pyromellitic acid.
　ポリエステル系可塑剤は特に限定されないが、分子内に芳香環又はシクロアルキル環を有するポリエステル系可塑剤を用いることができる。 The polyester plasticizer is not particularly limited, and a polyester plasticizer having an aromatic ring or a cycloalkyl ring in the molecule can be used.
　ポリエステル系可塑剤としては、特に限定されないが、例えば、下記一般式（Ｐｃ）で表せる芳香族基を末端に有するエステル（「芳香族末端エステル」ともいう。）を可塑剤として用いることができる。 The polyester plasticizer is not particularly limited. For example, an ester having an aromatic group represented by the following general formula (Pc) at the end (also referred to as “aromatic terminal ester”) can be used as the plasticizer.
　一般式（Ｐｃ）：　Ｂ－（Ｇ－Ａ）ｎ－Ｇ－Ｂ
（式中、Ｂはベンゼンモノカルボン酸残基、Ｇは炭素数２～１２のアルキレングリコール残基又は炭素数６～１２のアリールグリコール残基又は炭素数が４～１２のオキシアルキレングリコール残基、Ａは炭素数４～１２のアルキレンジカルボン酸残基又は炭素数６～１２のアリールジカルボン酸残基を表し、またｎは１以上の整数を表す。）
　一般式（Ｐｃ）中、Ｂで示されるベンゼンモノカルボン酸残基とＧで示されるアルキレングリコール残基又は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、Ａで示されるアルキレンジカルボン酸残基又はアリールジカルボン酸残基とから構成されるものであり、通常のポリエステル系可塑剤と同様の反応により得られる。 Formula (Pc): B- (GA) nGB
(Wherein B is a benzene monocarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
In the general formula (Pc), a benzene monocarboxylic acid residue represented by B and an alkylene glycol residue, oxyalkylene glycol residue or aryl glycol residue represented by G, an alkylene dicarboxylic acid residue or aryl dicarboxylic group represented by A It is composed of an acid residue and can be obtained by a reaction similar to that of a normal polyester plasticizer.
　本発明で使用されるポリエステル系可塑剤のベンゼンモノカルボン酸成分としては、例えば、安息香酸、パラターシャリブチル安息香酸、オルソトルイル酸、メタトルイル酸、パラトルイル酸、ジメチル安息香酸、エチル安息香酸、ノルマルプロピル安息香酸、アミノ安息香酸、アセトキシ安息香酸等があり、これらはそれぞれ一種又は二種以上の混合物として使用することができる。 Examples of the benzene monocarboxylic acid component of the polyester plasticizer used in the present invention include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, and normalpropyl. There exist benzoic acid, aminobenzoic acid, acetoxybenzoic acid, etc., and these can be used as 1 type, or 2 or more types of mixtures, respectively.
　本発明に用いることのできるポリエステル系可塑剤の炭素数２～１２のアルキレングリコール成分としては、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，２－プロパンジオール、２－メチル１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、２，２－ジメチル－１，３－プロパンジオール（ネオペンチルグリコール）、２，２－ジエチル－１，３－プロパンジオール（３，３－ジメチロールペンタン）、２－ｎ－ブチル－２－エチル－１，３プロパンジオール（３，３－ジメチロールヘプタン）、３－メチル－１，５－ペンタンジオール１，６－ヘキサンジオール、２，２，４－トリメチル１，３－ペンタンジオール、２－エチル１，３－ヘキサンジオール、２－メチル１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１２－オクタデカンジオール等があり、これらのグリコールは、一種又は二種以上の混合物として使用される。 Examples of the alkylene glycol component having 2 to 12 carbon atoms of the polyester plasticizer that can be used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1, 3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neo Pentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane) 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-pen Diol, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, etc., and these glycols are , One or a mixture of two or more.
　特に炭素数２～１２のアルキレングリコールがセルロースエステルとの相溶性に優れているため、特に好ましい。 Particularly, alkylene glycols having 2 to 12 carbon atoms are particularly preferable because of excellent compatibility with cellulose esters.
　また、上記芳香族末端エステルの炭素数４～１２のオキシアルキレングリコール成分としては、例えば、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール等があり、これらのグリコールは、一種又は二種以上の混合物として使用できる。 Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like. Or it can be used as a mixture of two or more.
　芳香族末端エステルの炭素数４～１２のアルキレンジカルボン酸成分としては、例えば、コハク酸、マレイン酸、フマール酸、グルタール酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸等があり、これらは、それぞれ一種又は二種以上の混合物として使用される。炭素数６～１２のアリーレンジカルボン酸成分としては、フタル酸、テレフタル酸、イソフタル酸、１，５ナフタレンジカルボン酸、１，４ナフタレンジカルボン酸等がある。 Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds. Examples of the arylene dicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.
　本発明で使用されるポリエステル系可塑剤は、数平均分子量が、好ましくは３００～１５００、より好ましくは４００～１０００の範囲が好適である。また、その酸価は、０．５ｍｇＫＯＨ／ｇ以下、水酸基価は２５ｍｇＫＯＨ／ｇ以下、より好ましくは酸価０．３ｍｇＫＯＨ／ｇ以下、水酸基価は１５ｍｇＫＯＨ／ｇ以下のものである。 The number average molecular weight of the polyester plasticizer used in the present invention is preferably in the range of 300 to 1500, more preferably 400 to 1000. The acid value is 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.
　以下、本発明に用いることのできる芳香族末端エステル系可塑剤の合成例を示す。 Hereinafter, synthesis examples of aromatic terminal ester plasticizers that can be used in the present invention will be shown.
　〈サンプルＮｏ．１（芳香族末端エステルサンプル）〉
　反応容器にフタル酸４１０部、安息香酸６１０部、ジプロピレングリコール７３７部、及び触媒としてテトライソプロピルチタネート０．４０部を一括して仕込み窒素気流中で攪拌下、還流凝縮器を付して過剰の１価アルコールを還流させながら、酸価が２以下になるまで１３０～２５０℃で加熱を続け生成する水を連続的に除去した。次いで２００～２３０℃で１．３３×１０４Ｐａ～最終的に４×１０２Ｐａ以下の減圧下、留出分を除去し、この後濾過して次の性状を有する芳香族末端エステル系可塑剤を得た。 <Sample No. 1 (Aromatic terminal ester sample)>
A reaction vessel was charged with 410 parts of phthalic acid, 610 parts of benzoic acid, 737 parts of dipropylene glycol, and 0.40 part of tetraisopropyl titanate as a catalyst. While the monohydric alcohol was refluxed, heating was continued at 130 to 250 ° C. until the acid value became 2 or less, and water produced was continuously removed. Next, the distillate is removed at 200 to 230 ° C. under reduced pressure of 1.33 × 10 4 Pa to finally 4 × 10 2 Pa or less, and then filtered to remove an aromatic terminal ester plastic having the following properties: An agent was obtained.
　粘度（２５℃、ｍＰａ・ｓ）；４３４００
　酸価　　　　　　　　　　　；０．２
　以下に、本発明に用いることのできる芳香族末端エステル系可塑剤の具体的化合物を示すが、本発明はこれに限定されない。 Viscosity (25 ° C., mPa · s); 43400
Acid value: 0.2
Although the specific compound of the aromatic terminal ester plasticizer which can be used for this invention below is shown, this invention is not limited to this.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　本発明においては、可塑剤として、特に当該芳香族基を末端に有するポリエステルを含有させることが好ましい。 In the present invention, it is preferable to contain a polyester having an aromatic group at the terminal as the plasticizer.
　（紫外線吸収剤）
　本発明のハードコート用基材フィルムは、紫外線吸収剤を含有することが好ましい。紫外線吸収剤は４００ｎｍ以下の紫外線を吸収することで、耐久性を向上させることを目的としており、特に波長３７０ｎｍでの透過率が１０％以下であることが好ましく、よりさらに好ましくは５％以下である。 (UV absorber)
The base film for hard coat of the present invention preferably contains an ultraviolet absorber. The ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less. In particular, the transmittance at a wavelength of 370 nm is preferably 10% or less, and more preferably 5% or less. is there.
　本発明に用いられる紫外線吸収剤は特に限定されないが、例えばオキシベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフェノン系化合物、シアノアクリレート系化合物、トリアジン系化合物、ニッケル錯塩系化合物、無機粉体等が挙げられる。 Although the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
　紫外線吸収剤の使用量は、紫外線吸収剤の種類、使用条件等により一様ではないが、ハードコート用基材フィルムの乾燥膜厚が３０～２００μｍの場合は、ハードコート用基材フィルムに対して０．５～１０質量％が好ましく、０．６～４質量％がさらに好ましい。 The amount of UV absorber used is not uniform depending on the type of UV absorber, the operating conditions, etc., but if the dry film thickness of the hard coat substrate film is 30 to 200 μm, 0.5 to 10% by mass is preferable, and 0.6 to 4% by mass is more preferable.
　（微粒子）
　本発明のハードコート用基材フィルムは、微粒子を含有することが滑り性、保管安定性の観点で好ましい。 (Fine particles)
The base film for hard coat of the present invention preferably contains fine particles from the viewpoint of slipperiness and storage stability.
　微粒子としては、無機化合物の例として、二酸化珪素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、炭酸カルシウム、タルク、クレイ、焼成カオリン、焼成ケイ酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム及びリン酸カルシウム等を挙げることができる。微粒子は珪素を含むものが、濁度が低くなる点で好ましく、特に二酸化珪素が好ましい。 As fine particles, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
　二酸化珪素については疎水化処理をされたものが滑り性とヘイズを両立する上で好ましい。４個のシラノール基のうち、２個以上が疎水性の置換基で置換わったものが好ましく、３個以上が置換わったものがより好ましい。疎水性の置換基はメチル基であることが好ましい。 Silicon dioxide that has been subjected to a hydrophobization treatment is preferable for achieving both slipperiness and haze. Of the four silanol groups, those in which two or more are substituted with a hydrophobic substituent are preferred, and those in which three or more are substituted are more preferred. The hydrophobic substituent is preferably a methyl group.
　二酸化珪素の一次粒径は２０ｎｍ以下が好ましく、１０ｎｍ以下がより好ましい。 The primary particle diameter of silicon dioxide is preferably 20 nm or less, and more preferably 10 nm or less.
　二酸化珪素の微粒子は、例えば、アエロジルＲ９７２、Ｒ９７２Ｖ、Ｒ９７４、Ｒ８１２、２００、２００Ｖ、３００、Ｒ２０２、ＯＸ５０、ＴＴ６００（以上日本アエロジル（株）製）の商品名で市販されており、使用することができる。 Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
　酸化ジルコニウムの微粒子は、例えば、アエロジルＲ９７６及びＲ８１１（以上日本アエロジル（株）製）の商品名で市販されており、使用することができる。 Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
　ポリマーの例として、シリコーン樹脂、フッ素樹脂及びアクリル樹脂を挙げることができる。シリコーン樹脂が好ましく、特に三次元の網状構造を有するものが好ましく、例えば、トスパール１０３、同１０５、同１０８、同１２０、同１４５、同３１２０及び同２４０（以上東芝シリコーン（株）製）の商品名で市販されており、使用することができる。 Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
　これらの中でもアエロジル２００Ｖ、アエロジルＲ９７２Ｖがハードコート用基材フィルムのヘイズを低く保ちながら、摩擦係数を下げる効果が大きいため特に好ましく、本発明に於いてはアエロジルＲ８１２が最も好ましく用いられる。本発明のハードコート用基材フィルムにおいては、少なくとも一方の面の動摩擦係数が０．２～１．０であることが好ましい。 Among these, Aerosil 200V and Aerosil R972V are particularly preferable because they have a large effect of reducing the friction coefficient while keeping the haze of the hard coat base film low, and Aerosil R812 is most preferably used in the present invention. In the base film for hard coat of the present invention, the dynamic friction coefficient of at least one surface is preferably 0.2 to 1.0.
　（染料）
　本発明のハードコート用基材フィルムには、色味調整のため染料を添加することもできる。例えば、フィルムの黄色味を抑えるために青色染料を添加してもよい。好ましい染料としてはアンスラキノン系染料が挙げられる。 (dye)
A dye may be added to the base film for hard coat of the present invention for adjusting the color. For example, a blue dye may be added to suppress the yellowness of the film. Preferred examples of the dye include anthraquinone dyes.
　＜ハードコート用基材フィルムの製造方法＞
　本発明のハードコート用基材フィルムは通常の溶液流延法、溶融流延法のいずれの方法でも製造することができる。 <Method for producing base film for hard coat>
The base film for hard coat of the present invention can be produced by any of the usual solution casting method and melt casting method.
　本発明のハードコート用基材フィルムの溶液流延法による製造は、セルロースエステル及び前記添加剤を溶剤に溶解させてドープを調製する工程、ドープを無限に移行する無端の金属支持体上に流延する工程、流延したドープをウェブとして乾燥する工程、金属支持体から剥離する工程、延伸又は幅保持する工程、さらに乾燥する工程、仕上がったフィルムを巻取る工程により行われる。 Production of the base film for hard coat of the present invention by the solution casting method is a step of preparing a dope by dissolving the cellulose ester and the above-mentioned additive in a solvent, and flowing on an endless metal support that allows the dope to move indefinitely. The step of extending, the step of drying the cast dope as a web, the step of peeling from the metal support, the step of stretching or maintaining the width, the step of further drying, and the step of winding up the finished film are performed.
　ドープを調製する工程について述べる。ドープ中のセルロースエステルの濃度は、濃い方が金属支持体に流延した後の乾燥負荷が低減できて好ましいが、セルロースエステルの濃度が濃過ぎると濾過時の負荷が増えて、濾過精度が悪くなる。これらを両立する濃度としては、１０～３５質量％が好ましく、さらに好ましくは、１５～２５質量％である。 The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become. The concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
　ドープで用いられる溶剤は、単独で用いても二種以上を併用してもよい。セルロースエステルの良溶剤と貧溶剤を混合して使用することが生産効率の点で好ましく、良溶剤として特に好ましくはメチレンクロライド又は酢酸メチルが挙げられ、貧溶剤として、例えば、メタノール、エタノール、ｎ－ブタノール、シクロヘキサン、シクロヘキサノン等が好ましく用いられる。 Solvents used in dope may be used alone or in combination of two or more. It is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester from the viewpoint of production efficiency. The good solvent is particularly preferably methylene chloride or methyl acetate. Examples of the poor solvent include methanol, ethanol, n- Butanol, cyclohexane, cyclohexanone and the like are preferably used.
　また、ドープ中には水が０．０１～２質量％含有していることが好ましい。また、セルロースエステルの溶解に用いられる溶媒は、フィルム製膜工程で乾燥によりフィルムから除去された溶媒を回収し、これを再利用して用いられる。 Further, it is preferable that the dope contains 0.01 to 2% by mass of water. Moreover, the solvent used for melt | dissolution of a cellulose ester collect | recovers the solvent removed from the film by drying at the film-forming process, and uses this again.
　上記記載のドープを調製する時の、セルロースエステルの溶解方法としては、一般的な方法を用いることができる。加熱と加圧を組み合わせると常圧における沸点以上に加熱できる。 As a method for dissolving the cellulose ester when preparing the dope described above, a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
　次に、このセルロースエステル溶液を濾紙等の適当な濾過材を用いて濾過する。濾過材としては、絶対濾過精度０．００８ｍｍ以下の濾材が好ましく、０．００１～０．００８ｍｍの濾材がより好ましく、０．００３～０．００６ｍｍの濾材がさらに好ましい。 Next, the cellulose ester solution is filtered using an appropriate filter medium such as filter paper. As the filter medium, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is more preferable.
　濾材さらには特に制限はなく、通常の濾材を使用することができるが、ポリプロピレン、テフロン（登録商標）等のプラスチック製の濾材や、ステンレススティール等の金属製の濾材が繊維の脱落等がなく好ましい。 The filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene and Teflon (registered trademark) and a metal filter medium such as stainless steel are preferable because they do not drop off fibers. .
　ドープの濾過は通常の方法で行うことができるが、溶剤の常圧での沸点以上で、且つ加圧下で溶剤が沸騰しない範囲の温度で加熱しながら濾過する方法が、濾過前後の濾圧の差（差圧という）の上昇が小さく、好ましい温度は４５～１２０℃であり、４５～７０℃がより好ましく、４５～５５℃であることがさらに好ましい。 The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small, and the preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 45 to 55 ° C.
　濾圧は小さい方が好ましい。濾圧は１．６ＭＰａ以下であることが好ましく、１．２ＭＰａ以下であることがより好ましく、１．０ＭＰａ以下であることがさらに好ましい。 A smaller filtration pressure is preferable. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
　ついで、ドープの流延について説明する。 Next, the dope casting will be explained.
　流延（キャスト）工程における金属支持体は、表面を鏡面仕上げしたものが好ましく、金属支持体としては、ステンレススティールベルトもしくは鋳物で表面をメッキ仕上げしたドラムが好ましく用いられる。キャストの幅は１～４ｍとすることができる。 The metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m.
　流延工程の金属支持体の表面温度は－５０℃～溶剤の沸点未満の温度で、好ましい支持体温度は０～４０℃であり、５～３０℃がさらに好ましい。 The surface temperature of the metal support in the casting step is −50 ° C. to a temperature lower than the boiling point of the solvent, and the preferable support temperature is 0 to 40 ° C., more preferably 5 to 30 ° C.
　ハードコート用基材フィルムが良好な平面性を示すためには、金属支持体からウェブを剥離する際の残留溶媒量は１０～１５０質量％が好ましく、さらに好ましくは２０～４０質量％又は６０～１３０質量％であり、特に好ましくは、２０～３０質量％又は７０～１２０質量％である。 In order for the base film for hard coat to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to It is 130% by mass, particularly preferably 20 to 30% by mass or 70 to 120% by mass.
　本発明においては、残留溶媒量は下記式で定義される。 In the present invention, the amount of residual solvent is defined by the following formula.
　残留溶媒量（質量％）＝｛（Ｍ－Ｎ）／Ｎ｝×１００
　尚、Ｍはウェブ又はフィルムを製造中又は製造後の任意の時点で採取した試料の質量で、ＮはＭを１１５℃で１時間の加熱後の質量である。 Residual solvent amount (% by mass) = {(MN) / N} × 100
M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
　又はドコート用基材フィルムの乾燥工程においては、ウェブを金属支持体より剥離し、さらに乾燥し、残留溶媒量を１質量％以下にすることが好ましく、さらに好ましくは０．１質量％以下であり、特に好ましくは０～０．０１質量％以下である。 Alternatively, in the drying step of the base film for coating, it is preferable that the web is peeled from the metal support and further dried to make the residual solvent amount 1% by mass or less, more preferably 0.1% by mass or less. Particularly preferably, it is 0 to 0.01% by mass or less.
　フィルム乾燥工程では一般にロール乾燥方式（上下に配置した多数のロールをウェブを交互に通し乾燥させる方式）やテンター方式でウェブを搬送させながら乾燥する方式が採られる。 In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged at the top and bottom are alternately passed through the web for drying) or a tenter method for drying while transporting the web is employed.
　本発明のハードコート用基材フィルムを作製するためには、金属支持体より剥離した直後のウェブの残留溶剤量の多いところで多いところで長手方向（ＭＤ方向）に延伸し、さらにウェブの両端をクリップ等で把持するテンター方式で幅手方向（ＴＤ方向）に延伸を行うことが好ましい。 In order to produce the base film for hard coat of the present invention, the web is stretched in the longitudinal direction (MD direction) where there is a large amount of residual solvent of the web immediately after peeling from the metal support, and both ends of the web are clipped. It is preferable to perform stretching in the width direction (TD direction) by a tenter system that grips with the like.
　ウェブを乾燥させる手段は特に制限なく、一般的に熱風、赤外線、加熱ロール、マイクロ波等で行うことができるが、簡便さの点で熱風で行うことが好ましい。 The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air in terms of simplicity.
　ウェブの乾燥工程における乾燥温度は９０℃～２００℃が好ましく、より好ましくは１１０℃～１９０℃である。乾燥温度は段階的に高くしていくことが好ましい。 The drying temperature in the web drying step is preferably 90 ° C. to 200 ° C., more preferably 110 ° C. to 190 ° C. The drying temperature is preferably increased stepwise.
　好ましい乾燥時間は、乾燥温度にもよるが、５分～６０分が好ましく、１０分～３０分がより好ましい。 The preferred drying time depends on the drying temperature, but is preferably 5 minutes to 60 minutes, more preferably 10 minutes to 30 minutes.
　ハードコート用基材フィルムの膜厚は、特に限定はされないが１０～２００μｍが用いられる。特に膜厚は１０～１００μｍであることが特に好ましい。さらに好ましくは２０～６０μｍである。 The film thickness of the base film for hard coat is not particularly limited, but 10 to 200 μm is used. In particular, the film thickness is particularly preferably 10 to 100 μm. More preferably, it is 20 to 60 μm.
　本発明のハードコート用基材フィルムは、幅１～４ｍのものが用いられる。生産性の観点から幅１．６～４ｍのものが好ましく用いられ、特に好ましくは１．８～３．６ｍである。４ｍを超えると搬送が困難となる。 The base film for hard coat of the present invention has a width of 1 to 4 m. From the viewpoint of productivity, those having a width of 1.6 to 4 m are preferably used, and particularly preferably 1.8 to 3.6 m. If it exceeds 4 m, conveyance becomes difficult.
　（延伸操作）
　延伸操作は、フィルムの長手方向（ＭＤ方向）、及び幅手方向（ＴＤ方向）に対して、逐次又は同時に延伸することができる。互いに直交する２軸方向の延伸倍率は、それぞれ最終的にはＭＤ方向に１．０～２．０倍、ＴＤ方向に１．０７～２．０倍の範囲とすることが好ましく、ＭＤ方向に１．０～１．５倍、ＴＤ方向に１．０７～２．０倍の範囲で行うことが好ましい。 (Stretching operation)
The stretching operation can be performed sequentially or simultaneously with respect to the longitudinal direction (MD direction) and the width direction (TD direction) of the film. The draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 1.0 to 2.0 times in the MD direction and 1.07 to 2.0 times in the TD direction, respectively. It is preferably performed in the range of 1.0 to 1.5 times and 1.07 to 2.0 times in the TD direction.
　例えば、複数のロールに周速差をつけ、その間でロール周速差を利用してＭＤ方向に延伸する方法、ウェブの両端をクリップやピンで固定し、クリップやピンの間隔を進行方向に広げてＭＤ方向に延伸する方法、同様に横方向に広げてＴＤ方向に延伸する方法、或いはＭＤ／ＴＤ方向同時に広げてＭＤ／ＴＤ両方向に延伸する方法などが挙げられる。 For example, a method in which peripheral speed differences are applied to a plurality of rolls and a roll peripheral speed difference is used to stretch in the MD direction, both ends of the web are fixed with clips and pins, and the distance between the clips and pins is increased in the traveling direction. And a method of stretching in the MD direction, a method of stretching in the transverse direction and stretching in the TD direction, a method of stretching in the MD / TD direction simultaneously and stretching in both the MD / TD directions, and the like.
　製膜工程のこれらの幅保持或いは幅手方向の延伸はテンターによって行うことが好ましく、ピンテンターでもクリップテンターでもよい。 It is preferable to perform the width maintenance or the stretching in the width direction in the film forming process by a tenter, and it may be a pin tenter or a clip tenter.
　テンター内などの製膜工程でのフィルム搬送張力は温度にもよるが、１２０Ｎ／ｍ～２００Ｎ／ｍが好ましく、１４０Ｎ／ｍ～２００Ｎ／ｍがさらに好ましい。１４０Ｎ／ｍ～１６０Ｎ／ｍが最も好ましい。 The film transport tension in the film forming process such as in the tenter depends on the temperature, but is preferably 120 N / m to 200 N / m, and more preferably 140 N / m to 200 N / m. 140 N / m to 160 N / m is most preferable.
　延伸する際は、本発明のフィルムのガラス転移温度をＴｇとすると（Ｔｇ－３０）～（Ｔｇ＋１００）℃、より好ましくは（Ｔｇ－２０）～（Ｔｇ＋８０）℃、さらに好ましく（Ｔｇ－５）～（Ｔｇ＋２０）℃である。 When stretching, the glass transition temperature of the film of the present invention is Tg (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C., and more preferably (Tg-5) to (Tg + 20) ° C.
　ハードコート用基材フィルムのＴｇは、フィルムを構成する材料種及び構成する材料の比率によって制御することができる。本発明の用途においてはフィルムの乾燥時のＴｇは１１０℃以上が好ましく、さらに１２０℃以上が好ましい。 Tg of the base film for hard coat can be controlled by the material type constituting the film and the ratio of the constituting materials. In the application of the present invention, the Tg when the film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher.
　従ってガラス転移温度は１９０℃以下、より好ましくは１７０℃以下であることが好ましい。このとき、フィルムのＴｇはＪＩＳ　Ｋ７１２１に記載の方法などによって求めることができる。 Therefore, the glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower. At this time, the Tg of the film can be determined by the method described in JIS K7121.
　本発明では、延伸する際の温度は１５０℃以上、延伸倍率は１．１５倍以上にすると、表面が適度に粗れるため好ましい。フィルム表面を粗らすことは、滑り性を向上させるのみでなく、表面加工性、特にクリアーハードコートの密着性が向上するため好ましい。平均表面粗さＲａは、好ましくは２．０ｎｍ～４．０ｎｍ、より好ましくは２．５ｎｍ～３．５ｎｍである。その際、フィルム中には先に述べた疎水化処理された二酸化珪素微粒子を含有していることが好ましく、特にＲ９７２Ｖ及びＲ８１２がヘイズ安定性向上のために好ましい。 In the present invention, it is preferable that the temperature during stretching is 150 ° C. or more and the stretching ratio is 1.15 times or more because the surface is appropriately roughened. Roughening the film surface is preferable because it improves not only the slipperiness but also the surface processability, particularly the adhesion of the clear hard coat. The average surface roughness Ra is preferably 2.0 nm to 4.0 nm, more preferably 2.5 nm to 3.5 nm. At that time, the film preferably contains the above-mentioned hydrophobized silicon dioxide fine particles, and R972V and R812 are particularly preferred for improving haze stability.
　ハードコート用基材フィルムは延伸後、熱固定されることが好ましいが、熱固定はその最終ＴＤ方向延伸温度より高温で、Ｔｇ－２０℃以下の温度範囲内で通常０．５～３００秒間熱固定することが好ましい。この際、２つ以上に分割された領域で温度差が１～１００℃となる範囲で順次昇温しながら熱固定することが好ましい。 The base film for hard coat is preferably heat-set after stretching, but the heat setting is usually higher than the final TD direction stretching temperature and usually within 0.5 to 300 ° C. within a temperature range of Tg-20 ° C. or less. It is preferable to fix. At this time, it is preferable to perform heat fixing while sequentially raising the temperature in a range where the temperature difference is 1 to 100 ° C. in the region divided into two or more.
　熱固定されたフィルムは通常Ｔｇ以下まで冷却され、フィルム両端のクリップ把持部分をカットし巻き取られる。この際、最終熱固定温度以下、Ｔｇ以上の温度範囲内で、ＴＤ方向及び／又はＭＤ方向に０．１～１０％弛緩処理することが好ましい。 The heat-fixed film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound. At this time, it is preferable to perform a relaxation treatment of 0.1 to 10% in the TD direction and / or MD direction within a temperature range not higher than the final heat setting temperature and not lower than Tg.
　また冷却は、最終熱固定温度からＴｇまでを、毎秒１００℃以下の冷却速度で徐冷することが好ましい。冷却、弛緩処理する手段は特に限定はなく、従来公知の手段で行えるが、特に複数の温度領域で順次冷却しながらこれらの処理を行うことがフィルムの寸法安定性向上の点で好ましい。 Further, the cooling is preferably performed by gradually cooling from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. Means for cooling and relaxation treatment are not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to carry out these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film.
　尚、冷却速度は、最終熱固定温度をＴ１、フィルムが最終熱固定温度からＴｇに達するまでの時間をｔとした時、（Ｔ１－Ｔｇ）／ｔで求めた値である。 The cooling rate is a value obtained by (T1-Tg) / t, where T1 is the final heat setting temperature and t is the time until the film reaches Tg from the final heat setting temperature.
　これら熱固定条件、冷却、弛緩処理条件のより最適な条件は、フィルムを構成するセルロースエステルや可塑剤等の添加剤種により異なるので、得られた二軸延伸フィルムの物性を測定し、好ましい特性を有するように適宜調整することにより決定すればよい。 More optimal conditions of these heat setting conditions, cooling, and relaxation treatment conditions vary depending on the type of additives such as cellulose ester and plasticizer constituting the film, so the physical properties of the obtained biaxially stretched film are measured and preferable characteristics are obtained. What is necessary is just to determine by adjusting suitably so that it may have.
　本発明のハードコート用基材フィルムの遅相軸又は進相軸がフィルム面内に存在し、製膜方向とのなす角をθ１とするとθ１は－１°以上＋１°以下であることが好ましく、－０．５°以上＋０．５°以下であることがより好ましい。 The slow axis or fast axis of the base film for hard coat of the present invention exists in the film plane, and θ1 is preferably −1 ° or more and + 1 ° or less when the angle formed with the film forming direction is θ1. More preferably, the angle is −0.5 ° or more and + 0.5 ° or less.
　このθ１は配向角として定義でき、θ１の測定は、自動複屈折計ＫＯＢＲＡ－２１ＡＤＨ（王子計測機器）を用いて行うことができる。θ１が各々上記関係を満たすことは、表示画像において高い輝度を得ること、光漏れを抑制又は防止することに寄与し、カラー液晶表示装置においては忠実な色再現を得ることに寄与できる。 This θ1 can be defined as an orientation angle, and θ1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments). Each of θ1 satisfying the above relationship contributes to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to obtaining faithful color reproduction in a color liquid crystal display device.
　＜物性、光学特性＞
　本発明のハードコート用基材フィルムの透湿度は、４０℃、９０％ＲＨで１０～１２００ｇ／ｍ２・２４ｈが好ましく、さらに２０～１０００ｇ／ｍ２・２４ｈが好ましく、２０～８５０ｇ／ｍ２・２４ｈが特に好ましい。透湿度はＪＩＳ　Ｚ　０２０８に記載の方法に従い測定することができる。 <Physical properties and optical properties>
The moisture permeability of the base film for hard coat of the present invention is preferably 10 to 1200 g / m 2 · 24 h at 40 ° C. and 90% RH, more preferably 20 to 1000 g / m 2 · 24 h, and 20 to 850 g / m 2. -24h is particularly preferred. The moisture permeability can be measured according to the method described in JIS Z 0208.
　本発明のハードコート用基材フィルムは、３０℃での貯蔵弾性率が、ＭＤ方向に３．２～４．７ＧＰａ、ＴＤ方向に４．７～７．０ＧＰａであることが、縦ツレが改良されて好ましい。貯蔵弾性率はｔａｎδと同じ測定で求めることができる。 The base film for hard coat of the present invention has a storage modulus at 30 ° C. of 3.2 to 4.7 GPa in the MD direction and 4.7 to 7.0 GPa in the TD direction. Being preferred. The storage elastic modulus can be obtained by the same measurement as tan δ.
　本発明のハードコート用基材フィルムは脆性指標となる引裂き強度が３５ｍＮ以上であることが好ましく、５０ｍＮ以上であることがより好ましい。 The base film for hard coat of the present invention preferably has a tear strength that is a brittleness index of 35 mN or more, more preferably 50 mN or more.
　本発明のハードコート用基材フィルムの破断伸度は５～８０％であることが好ましく８～５０％であることがさらに好ましい。 The breaking elongation of the base film for hard coat of the present invention is preferably 5 to 80%, more preferably 8 to 50%.
　本発明のハードコート用基材フィルムの可視光透過率は９０％以上であることが好ましく、９３％以上であることがさらに好ましい。 The visible light transmittance of the base film for hard coat of the present invention is preferably 90% or more, and more preferably 93% or more.
　本発明のハードコート用基材フィルムのヘイズは１％未満であることが好ましく０～０．４％であることが特に好ましい。 The haze of the base film for hard coat of the present invention is preferably less than 1%, particularly preferably 0 to 0.4%.
　本発明のハードコート用基材フィルムは、下記式で表されるリターデーション値Ｒｏが０～１５０ｎｍ、Ｒｔが－１００～３００ｎｍであることが好ましく、特に好ましくはＲｏが０～１０ｎｍ、Ｒｔが０～１００ｎｍである。 The substrate film for hard coat of the present invention preferably has a retardation value Ro represented by the following formula of 0 to 150 nm and Rt of −100 to 300 nm, particularly preferably Ro of 0 to 10 nm and Rt of 0. ~ 100 nm.
　式（ｉ）　Ｒｏ＝（ｎｘ－ｎｙ）×ｄ
　式（ii）　Ｒｔ＝（（ｎｘ＋ｎｙ）／２－ｎｚ）×ｄ
（式中、Ｒｏはフィルム面内リターデーション値、Ｒｔはフィルム厚さ方向リターデーション値、ｎｘはフィルム面内の遅相軸方向の屈折率、ｎｙはフィルム面内の進相軸方向の屈折率、ｎｚはフィルムの厚さ方向の屈折率、ｄはフィルムの厚さ（ｎｍ）を表す。）
　上記リターデーションは、例えばＫＯＢＲＡ－２１ＡＤＨ（王子計測機器（株））を用いて、２３℃、５５％ＲＨの環境下で、波長が５９０ｎｍで求めることができる。 Formula (i) Ro = (n x −ny) × d
Formula (ii) Rt = ((n x + n y ) / 2−n z ) × d
(Wherein, Ro is within the film plane retardation value, Rt is the film thickness direction retardation value, n x is a refractive index in a slow axis direction in the film plane, n y is the fast axis direction in the film plane (Refractive index, nz is the refractive index in the thickness direction of the film, and d is the thickness (nm) of the film.)
The retardation can be determined at a wavelength of 590 nm under an environment of 23 ° C. and 55% RH using, for example, KOBRA-21ADH (Oji Scientific Instruments).
　本発明においては、Ｒｔ≧０．８５ｎｍ／膜厚１μｍであることが好ましい。コントラストと視野角を確保する為には薄膜で且つ、一定以上のＲｔであることが好ましく、例えば３０～５０μｍであればＲｔは２６～２００ｎｍ、５０～７０μｍであればＲｔは４３～２００ｎｍであることが好ましい。単位膜厚に対するＲｔは、０．９～５．０ｎｍ／膜厚１μｍであることがより好ましく、１．０～５．０ｎｍ／膜厚１μｍであることが更に好ましい。 In the present invention, it is preferable that Rt ≧ 0.85 nm / film thickness 1 μm. In order to ensure the contrast and the viewing angle, it is preferable that the film is a thin film and has a certain Rt or more. For example, if it is 30 to 50 μm, Rt is 26 to 200 nm, and if it is 50 to 70 μm, Rt is 43 to 200 nm. It is preferable. Rt relative to the unit film thickness is more preferably 0.9 to 5.0 nm / film thickness 1 μm, and further preferably 1.0 to 5.0 nm / film thickness 1 μm.
　（ハードコート層）
　本発明のハードコート用基材フィルムには、ハードコート層を設けることができる。 (Hard coat layer)
The hard coat substrate film of the present invention can be provided with a hard coat layer.
　本発明では、高硬度を発揮する点から、ハードコート層の膜厚（ドライ膜厚）は３～３０μｍであり、好ましくは５～１５μｍの範囲内であることが好ましい。 In the present invention, from the viewpoint of exhibiting high hardness, the film thickness (dry film thickness) of the hard coat layer is 3 to 30 μm, preferably 5 to 15 μm.
　高硬度は、ＬＣＤ等の表示装置の表面における使用や偏光板化工程において傷が付きにくいことから望まれおり、本発明でいう高硬度とは、硬度の指標で有る鉛筆硬度が３Ｈ以上であり、より好ましくは４Ｈ以上である。 High hardness is desired because it is less likely to be scratched during use on the surface of a display device such as an LCD or in the polarizing plate forming process, and the high hardness in the present invention means that the pencil hardness, which is an index of hardness, is 3H or more. More preferably, it is 4H or more.
　鉛筆硬度は、作製したハードコートフィルムを温度２３℃、相対湿度５５％の条件で２時間以上調湿した後、ＪＩＳ　Ｓ　６００６が規定する試験用鉛筆を用いて、ＪＩＳ　Ｋ　５４００が規定する鉛筆硬度評価方法に従い測定した値である。 The pencil hardness is defined by JIS K 5400 using a test pencil specified by JIS S 6006 after the prepared hard coat film is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more. It is the value measured according to the evaluation method.
　又はドコートのマルテンス硬さ（ＨＭｓ）が、４００Ｎ／ｍｍ２以上、８００Ｎ／ｍｍ２以下であることが好ましい。 Or Martens hardness of Dokoto (HMS) is, 400 N / mm 2 or more, and preferably 800 N / mm 2 or less.
　マルテンス硬さ（ビッカース硬さ）とは、ビッカース圧子及び稜線同士の角度が１１５度の三角錐圧子を用いた微小硬度計で、フィルムのハードコート表面を、ハードコート層の膜厚の略１／１０の厚さまで圧子を押し込んだ時の負荷試験力－押し込み深さ曲線において、該負荷試験力－押し込み深さ曲線から求められる最大負荷試験力（Ｆｍａｘ）の５０％値から９０％値までの押し込み深さが負荷試験力の平方根に比例する傾き（ｍ）より、下記式で定義される値をいう。 Martens hardness (Vickers hardness) is a microhardness meter using a Vickers indenter and a triangular pyramid indenter whose angle between ridges is 115 degrees. The hard coat surface of the film is approximately 1 / th of the film thickness of the hard coat layer. In the load test force-indentation depth curve when the indenter is pushed down to a thickness of 10 indentation from the 50% value to the 90% value of the maximum load test force (Fmax) obtained from the load test force-indentation depth curve From the slope (m) in which the depth is proportional to the square root of the load test force, it is a value defined by the following equation.
　１ＨＭｓ＝１／（２６．４ｍ２）
　本発明に係るクリアーハードコート層は、公知のものがそのまま使用することができる。 1HMs = 1 / (26.4m 2 )
As the clear hard coat layer according to the present invention, known ones can be used as they are.
　ハードコート層を形成する樹脂バインダーとしては、活性エネルギー線硬化樹脂が好ましい。活性エネルギー線硬化樹脂とは、紫外線や電子線のような活性線照射により架橋反応等を経て硬化する樹脂をいう。 As the resin binder for forming the hard coat layer, an active energy ray curable resin is preferable. The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.
　活性エネルギー線硬化樹脂としては、エチレン性不飽和二重結合を有するモノマーを含む成分が好ましく用いられ、紫外線や電子線のような活性線を照射することによって硬化させて活性エネルギー線硬化樹脂層が形成される。 As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed.
　活性エネルギー線硬化樹脂としては紫外線硬化性樹脂や電子線硬化性樹脂等が代表的なものとして挙げられるが、特に、紫外線硬化樹脂が機械的膜強度（耐擦性、鉛筆硬度）に優れる点から好ましい。 Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin. Particularly, the ultraviolet curable resin is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable.
　紫外線硬化樹脂としては、多官能アクリレートが好ましい。該多官能アクリレートとしては、ペンタエリスリトール多官能アクリレート、ジペンタエリスリトール多官能アクリレート、ペンタエリスリトール多官能メタクリレート、及びジペンタエリスリトール多官能メタクリレートよりなる群から選ばれることが好ましい。 As the UV curable resin, polyfunctional acrylate is preferable. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
　ここで、多官能アクリレートとは、分子中に２個以上のアクリロイルオキシ基及び／又はメタクロイルオキシ基を有する化合物である。これらの化合物は、それぞれ単独又は二種以上を混合して用いられる。 Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule. These compounds are used alone or in combination of two or more.
　また、上記モノマーの２量体、３量体等のオリゴマーであってもよい。エネルギー活性線硬化性樹脂の添加量は、ハードコート層形成組成物中（以下、ハードコート層塗布液とも言う。）では、固形分中の１５質量％以上７０質量％未満であることが好ましい。 Also, oligomers such as dimers and trimers of the above monomers may be used. In the hard coat layer forming composition (hereinafter also referred to as a hard coat layer coating solution), the amount of the energy active ray curable resin added is preferably 15% by mass or more and less than 70% by mass in the solid content.
　又はドコート層にはエネルギー活性線硬化性樹脂の硬化促進のため、光重合開始剤を含有することが好ましい。光重合開始剤量としては、質量比で、光重合開始剤；エネルギー活性線硬化性樹脂＝２０：１００～０．０１：１００で含有することが好ましい。 Alternatively, the docoat layer preferably contains a photopolymerization initiator in order to accelerate the curing of the energy active ray curable resin. The amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator; energy active ray curable resin = 20: 100 to 0.01: 100.
　光重合開始剤としては、具体的には、アセトフェノン、ベンゾフェノン、ヒドロキシベンゾフェノン、ミヒラーケトン、α－アミロキシムエステル、チオキサントン等及びこれらの誘導体を挙げることができるが、特にこれらに限定されるものではない。 Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
　ハードコート層には、熱可塑性樹脂、熱硬化性樹脂又はゼラチン等の親水性樹脂等のバインダーを用いることもできる。又はドコート層には滑り性や屈折率を調整するために無機化合物又は有機化合物の粒子を含んでもよい。 In the hard coat layer, a binder such as a thermoplastic resin, a thermosetting resin, or a hydrophilic resin such as gelatin can also be used. Alternatively, the docoat layer may contain particles of an inorganic compound or an organic compound in order to adjust slipperiness and refractive index.
　これらの微粒子粉末の平均粒径としては、０．０１～５μｍが好ましく０．１～５．０μｍ、さらに、０．１～４．０μｍであることが特に好ましい。また、粒径の異なる二種以上の微粒子を含有することが好ましい。硬化性樹脂組成物と微粒子の割合は、硬化性樹脂組成物１００質量部に対して、０．１～３０質量部となるように配合することが望ましい。 The average particle size of these fine particle powders is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs. It is desirable that the ratio of the curable resin composition to the fine particles is 0.1 to 30 parts by mass with respect to 100 parts by mass of the curable resin composition.
　本発明においては、ハードコート層に重合性不飽和基を有する有機化合物によって表面処理された反応性シリカ粒子（Ｘａ）を含有させることが好ましい。以下、重合性不飽和基を有する有機化合物によって表面処理された反応性シリカ粒子（Ｘａ）について説明する。 In the present invention, the hard coat layer preferably contains reactive silica particles (Xa) surface-treated with an organic compound having a polymerizable unsaturated group. Hereinafter, the reactive silica particles (Xa) surface-treated with an organic compound having a polymerizable unsaturated group will be described.
　〈シリカ粒子〉
　シリカ粒子としては、公知のものを使用することができる。また、その形状は、球状でも不定形のものでもよく、通常のコロイダルシリカに限らず中空粒子、多孔質粒子、コア／シェル型粒子等であっても構わない。 <Silica particles>
Known silica particles can be used. Further, the shape may be spherical or irregular, and is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core / shell particles, or the like.
　また、動的光散乱法で求めたシリカ粒子の数平均粒子径は３０ｎｍ以上が好ましく、さらに好ましくは３０～２００ｎｍであり、特に好ましくは、４０～８０ｎｍである。 Further, the number average particle diameter of the silica particles determined by the dynamic light scattering method is preferably 30 nm or more, more preferably 30 to 200 nm, and particularly preferably 40 to 80 nm.
　市販品としては、例えば、コロイダルシリカとして、日産化学工業（株）製ＭＥＫ－ＳＴ－Ｌ、ＩＰＡ－ＳＴ－Ｌ、ＩＰＡ－ＳＴ－ＺＬ等を挙げることができる。 Examples of commercially available products include MEK-ST-L, IPA-ST-L, and IPA-ST-ZL manufactured by Nissan Chemical Industries, Ltd. as colloidal silica.
　〈重合性不飽和基を有する有機化合物〉
　反応性シリカ粒子（Ｘａ）は、重合性不飽和基を有する有機化合物（以下、「有機化合物（Ｘ）」という）で表面処理することによって得られる。反応性シリカ粒子（Ｘａ）の製造に用いられる有機化合物（Ｘ）は、重合性不飽和基、好ましくはエチレン性不飽和基を有する化合物であり、さらに、下記一般式（ａ）に示す基を含む有機化合物であることが好ましい。 <Organic compound having a polymerizable unsaturated group>
The reactive silica particles (Xa) are obtained by surface treatment with an organic compound having a polymerizable unsaturated group (hereinafter referred to as “organic compound (X)”). The organic compound (X) used for the production of the reactive silica particles (Xa) is a compound having a polymerizable unsaturated group, preferably an ethylenically unsaturated group, and further has a group represented by the following general formula (a). It is preferable that it is an organic compound to contain.
　また、［－Ｏ－Ｃ（＝Ｏ）－ＮＨ－］基を含み、さらに、［－Ｏ－Ｃ（＝Ｓ）－ＮＨ－］基及び［－Ｓ－Ｃ（＝Ｏ）－ＮＨ－］基の少なくとも１つを含むものであることが好ましい。また、この有機化合物は、分子内にシラノール基を有する化合物又は加水分解によってシラノール基を生成する化合物であることが好ましい。 Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least one of these is included. The organic compound is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
［一般式（ａ）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］
　［１］エチレン性不飽和基
　有機化合物（Ｘ）に含まれるエチレン性不飽和基としては特に制限はないが、例えば、アクリロイル基、メタクリロイル基、ビニル基を好適例として挙げることができる。 [In General Formula (a), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
[1] Ethylenically unsaturated group Although there is no restriction | limiting in particular as an ethylenically unsaturated group contained in organic compound (X), For example, an acryloyl group, a methacryloyl group, and a vinyl group can be mentioned as a suitable example.
　このエチレン性不飽和基は、活性ラジカル種により付加重合をする構成単位である。 This ethylenically unsaturated group is a structural unit that undergoes addition polymerization with active radical species.
　［２］前記一般式（ａ）に示す基
　有機化合物に含まれる前記式（ａ）に示す基［－Ｕ－Ｃ（＝Ｖ）－ＮＨ－］は、具体的には、［－Ｏ－Ｃ（＝Ｏ）－ＮＨ－］、［－Ｏ－Ｃ（＝Ｓ）－ＮＨ－］、［－Ｓ－Ｃ（＝Ｏ）－ＮＨ－］、［－ＮＨ－Ｃ（＝Ｏ）－ＮＨ－］、［－ＮＨ－Ｃ（＝Ｓ）－ＮＨ－］、及び［－Ｓ－Ｃ（＝Ｓ）－ＮＨ－］の６種である。これらの基は、一種単独で又は二種以上を組み合わせて用いることができる。 [2] Group represented by the general formula (a) The group [—UC (═V) —NH—] represented by the formula (a) contained in the organic compound is specifically represented by [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—] , [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types.
　中でも、熱安定性の観点から、［－Ｏ－Ｃ（＝Ｏ）－ＮＨ－］基と、［－Ｏ－Ｃ（＝Ｓ）－ＮＨ－］基及び［－Ｓ－Ｃ（＝Ｏ）－ＮＨ－］基の少なくとも１つとを併用することが好ましい。 Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups.
　前記式（ａ）に示す基［－Ｕ－Ｃ（＝Ｖ）－ＮＨ－］は、分子間において水素結合による適度の凝集力を発生させ、硬化物にした場合、優れた機械的強度、基材や隣接層との密着性に優れる。 The group [—UC (═V) —NH—] represented by the formula (a) generates an appropriate cohesive force due to hydrogen bonds between molecules, and has excellent mechanical strength and group when cured. Excellent adhesion to materials and adjacent layers.
　［３］シラノール基又は加水分解によってシラノール基を生成する化合物
　シラノール基を生成する化合物としては、ケイ素原子にアルコキシ基、アリールオキシ基、アセトキシ基、アミノ基、ハロゲン原子等が結合した化合物を挙げることができるが、ケイ素原子にアルコキシ基又はアリールオキシ基が結合した化合物、即ち、アルコキシシリル基含有化合物又はアリールオキシシリル基含有化合物が好ましい。 [3] Silanol groups or compounds that generate silanol groups by hydrolysis Examples of compounds that generate silanol groups include compounds in which an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, or the like is bonded to a silicon atom. However, a compound in which an alkoxy group or an aryloxy group is bonded to a silicon atom, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
　［４］好ましい態様
　好ましい具体例としては、例えば、下記一般式（ｂ）に示す化合物を挙げることができる。 [4] Preferred embodiment As a preferred specific example, for example, a compound represented by the following general formula (b) can be mentioned.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　一般式（ｂ）中、Ｒ２１、Ｒ２２は、同一でも異なっていてもよく、水素原子又は炭素数１～８のアルキル基若しくはアリール基であり、例えば、メチル、エチル、プロピル、ブチル、オクチル、フェニル、キシリル基等を挙げることができる。ここで、ｊは、１～３の整数である。 In the general formula (b), R 21 and R 22 may be the same or different and each represents a hydrogen atom or an alkyl or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl , Phenyl, xylyl group and the like. Here, j is an integer of 1 to 3.
　［（Ｒ２１Ｏ）ｊＲ２２ ３－ｊＳｉ－］で示される基としては、例えば、トリメトキシシリル基、トリエトキシシリル基、トリフェノキシシリル基、メチルジメトキシシリル基、ジメチルメトキシシリル基等を挙げることができる。このような基のうち、トリメトキシシリル基又はトリエトキシシリル基等が好ましい。 Examples of the group represented by [(R 21 O) j R 22 3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
　Ｒ２３は、炭素数１～１２の脂肪族又は芳香族構造を有する２価の有機基であり、鎖状、分岐状又は環状の構造を含んでいてもよい。具体例として、メチレン、エチレン、プロピレン、ブチレン、ヘキサメチレン、シクロヘキシレン、フェニレン、キシリレン、ドデカメチレン等を挙げることができる。 R 23 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
　Ｒ２４は、２価の有機基であり、通常、分子量１４から１万、好ましくは、分子量７６から５００の２価の有機基の中から選ばれる。具体例として、ヘキサメチレン、オクタメチレン、ドデカメチレン等の鎖状ポリアルキレン基；シクロヘキシレン、ノルボルニレン等の脂環式又は多環式の２価の有機基；フェニレン、ナフチレン、ビフェニレン、ポリフェニレン等の２価の芳香族基；及びこれらのアルキル基置換体、アリール基置換体を挙げることができる。 R 24 is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products.
　また、これら２価の有機基は炭素及び水素原子以外の元素を含む原子団を含んでいてもよく、ポリエーテル結合、ポリエステル結合、ポリアミド結合、ポリカーボネート結合を含むこともできる。 These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
　Ｒ２５は、（ｋ＋１）価の有機基であり、好ましくは、鎖状、分岐状又は環状の飽和炭化水素基、不飽和炭化水素基の中から選ばれる。 R 25 is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
　Ｚは、活性ラジカル種の存在下、分子間架橋反応をする重合性不飽和基を分子中に有する１価の有機基を示す。また、ｋは、好ましくは、１～２０の整数であり、さらに好ましくは、１～１０の整数、特に好ましくは、１～５の整数である。 Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.
　一般式（ｂ）で示される化合物の具体例として、下記（ｂ－１）又は下記（ｂ－２）で示される化合物が挙げられる。 Specific examples of the compound represented by the general formula (b) include compounds represented by the following (b-1) or the following (b-2).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
［（ｂ－１）及び（ｂ－２）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。「Ｍｅ」は、メチル基を示す。］
　有機化合物（Ｘ）の合成は、例えば、特開平９－１００１１１号公報に記載された方法を用いることができる。好ましくは、メルカプトプロピルトリメトキシシランとイソホロンジイソシアネートをジブチルスズジラウレート存在下で混合し、６０～７０℃で数時間程度反応させた後に、ペンタエリスリトールトリアクリレートを添加して、さらに６０～７０℃で数時間程度反応させることにより製造される。 [In (b-1) and (b-2), “Acryl” represents an acryloyl group. “Me” represents a methyl group. ]
For the synthesis of the organic compound (X), for example, the method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent.
　〈（Ｘａ）反応性シリカ粒子〉
　有機化合物（Ｘ）をシリカ粒子と混合し、加水分解させ、両者を結合させる。 <(Xa) reactive silica particles>
The organic compound (X) is mixed with silica particles, hydrolyzed, and bonded together.
　シリカ粒子への有機化合物（Ｘ）の結合量は、反応性シリカ粒子（Ｘａ）を１００質量％として、好ましくは、０．０１質量％以上であり、さらに好ましくは、０．１質量％以上、特に好ましくは、１質量％以上である。上記範囲において分散性に優れ、得られる硬化物の機械強度にも優れる。 The binding amount of the organic compound (X) to the silica particles is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the reactive silica particles (Xa). Especially preferably, it is 1 mass% or more. Within the above range, the dispersibility is excellent, and the mechanical strength of the obtained cured product is also excellent.
　また、反応性シリカ粒子（Ｘａ）製造時の原料中のシリカ粒子の配合割合は、好ましくは、５～９９質量％であり、さらに好ましくは、１０～９８質量％である。反応性シリカ粒子（Ｘａ）を構成するシリカ粒子の含有量は、６５～９５質量％であることが好ましい。 In addition, the blending ratio of the silica particles in the raw material during the production of the reactive silica particles (Xa) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass. The content of the silica particles constituting the reactive silica particles (Xa) is preferably 65 to 95% by mass.
　ハードコート層用塗布組成物中の、反応性シリカ粒子（Ｘａ）の含有量は、組成物中の固形分全量を１００質量％としたときに、５～８０質量％が好ましく、１０～８０質量％がより好ましい。該範囲の割合で用いることで、組成物中で安定に存在し、本発明の目的効果も発揮しやすい。 The content of the reactive silica particles (Xa) in the coating composition for the hard coat layer is preferably 5 to 80% by mass when the total solid content in the composition is 100% by mass, and preferably 10 to 80% by mass. % Is more preferable. By using it in the ratio of this range, it exists stably in a composition and it is easy to exhibit the target effect of this invention.
　ハードコート層の耐熱性を高めるために、光硬化反応を抑制しないような酸化防止剤を選んで用いることができる。例えば、ヒンダードフェノール誘導体、チオプロピオン酸誘導体、ホスファイト誘導体等を挙げることができる。 In order to increase the heat resistance of the hard coat layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like.
　ハードコート層形成組成物には、溶媒が含まれていてもよく、必要に応じて適宜含有し、希釈されたものであってもよい。 The hard coat layer forming composition may contain a solvent, or may be appropriately contained and diluted as necessary.
　ハードコート層は、ＪＩＳ　Ｂ　０６０１で規定される中心線平均粗さ（Ｒａ）が０．００１～０．１μｍのクリアーハードコート層、又は微粒子等を添加しＲａが０．１～１μｍに調整された防眩性ハードコート層であってもよい。 The hard coat layer has a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 μm, or a fine hard particle, Ra is adjusted to 0.1 to 1 μm. An antiglare hard coat layer may also be used.
　中心線平均粗さ（Ｒａ）は光干渉式の表面粗さ測定器で測定することが好ましく、例えばＷＹＫＯ社製非接触表面微細形状計測装置ＷＹＫＯ　ＮＴ－２０００を用いて測定することができる。 The center line average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.
　ハードコート層はフッ素系化合物やシリコーン化合物を含有しても良い。また、以下に示す界面活性剤を含有してもよい。 The hard coat layer may contain a fluorine compound or a silicone compound. Moreover, you may contain the surfactant shown below.
　フッ素系化合物、シリコーン化合物及び界面活性剤は、前記エネルギー活性線硬化性樹脂との含有質量比率をフッ素系化合物、シリコーン化合物及び界面活性剤：活性光線硬化樹脂＝０．０５：１００～５．００：１００で用いることがハードコート層形成組成物中及びハードコート層で安定して存在する。 The fluorine-based compound, silicone compound and surfactant have a mass ratio of the fluorine-based compound, silicone compound and surfactant: active light curable resin = 0.05: 100 to 5.00. : 100 is stably present in the hard coat layer forming composition and in the hard coat layer.
　ハードコート層にはさらに、硬化助剤としてポリウレタン樹脂の側鎖にビニル基とカルボキシ基を有し、重量平均分子量が１００００以上３００００以下であり、且つ、二重結合当量が５００以上２０００以下であるポリマーやポリマーの側鎖にビニル基を有し、重量平均分子量（Ｍｗ）が１００００以上１０００００以下であり、二重結合当量が１０００以下、ポリマーＴｇが－５０℃以上１２０℃以下であるアクリルポリマー、他官能チオール化合物等を含有させてもよい。市販品としては昭和電工社製、商品名カレンズＭＴシリーズ等が挙げられる。 The hard coat layer further has a vinyl group and a carboxy group in the side chain of the polyurethane resin as a curing aid, has a weight average molecular weight of 10,000 to 30,000, and a double bond equivalent of 500 to 2,000. An acrylic polymer having a vinyl group in a polymer or a side chain of the polymer, having a weight average molecular weight (Mw) of 10,000 or more and 100,000 or less, a double bond equivalent of 1,000 or less, and a polymer Tg of −50 ° C. or more and 120 ° C. or less, Other functional thiol compounds may be included. Commercially available products include Showa Denko Co., Ltd., trade name Karenz MT series, and the like.
　また、フッ素－アクリル共重合体樹脂を含有しても良い。フッ素－アクリル共重合体樹脂の市販品としては、日本油脂株式会社の商品名、モディパーＦ－２００、モディパーＦ－６００、モディパーＦ－２０２０等が挙げられる。 Further, a fluorine-acrylic copolymer resin may be contained. Examples of commercially available fluorine-acrylic copolymer resins include Nippon Oil & Fats Co., Ltd., Modiper F-200, Modiper F-600, Modiper F-2020, and the like.
　又はドコート層の屈折率は２３℃、波長５５０ｎｍ測定で、屈折率を１．４～２．２の範囲に調整することが好ましい。屈折率を調整する手段は、金属酸化物微粒子等を添加することで達成できる。金属酸化また、用いる金属酸化物微粒子の屈折率は１．８０～２．６０であるものが好ましく、１．８５～２．５０であるものがさらに好ましい。 Alternatively, the refractive index of the coated layer is preferably adjusted to a range of 1.4 to 2.2 by measuring the refractive index at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like. Metal oxide The metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.
　金属酸化物微粒子の種類は、酸化ジルコニウム、酸化アンチモン、酸化錫、酸化亜鉛、酸化インジウム－スズ（ＩＴＯ）、アンチモンドープ酸化スズ（ＡＴＯ）、及びアンチモン酸亜鉛から選ばれる少なくとも一種の金属酸化物微粒子を主成分として用いることが特に好ましい。特にアンチモン酸亜鉛粒子を含有することが好ましい。 The kind of metal oxide fine particles is at least one metal oxide fine particle selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate. It is particularly preferable to use as the main component. In particular, it is preferable to contain zinc antimonate particles.
　これら金属酸化物微粒子の一次粒子の平均粒子径は１０ｎｍ～２００ｎｍの範囲であり、１０～１５０ｎｍであることが特に好ましい。金属酸化物微粒子の平均粒子径は、走査電子顕微鏡（ＳＥＭ）等による電子顕微鏡写真から計測することができる。 The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and is particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like.
　金属酸化物微粒子は有機化合物により表面処理してもよい。 The metal oxide fine particles may be surface-treated with an organic compound.
　（塗工工程）
　本発明に係るハードコート層、例えば、クリアーハードコート層は次のような公知の方法で塗設することができる。 (Coating process)
The hard coat layer according to the present invention, for example, a clear hard coat layer, can be applied by the following known method.
　クリアーハードコート層を塗設する際の溶媒としては、例えば、炭化水素類、アルコール類、ケトン類、エステル類、グリコールエーテル類、その他の溶媒の中から適宜選択し、或いはこれらを混合し利用できる。 As a solvent for coating the clear hard coat layer, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, other solvents can be appropriately selected, or these can be mixed and used. .
　好ましくは、プロピレングリコールモノ（炭素数１～４のアルキル基）アルキルエーテル又はプロピレングリコールモノ（炭素数１～４のアルキル基）アルキルエーテルエステルを５質量％以上、さらに好ましくは５～８０質量％以上含有する溶媒が用いられる。 Preferably, propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether or propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass or more. The containing solvent is used.
　クリアーハードコート層を光硬化反応により硬化皮膜層を形成するための光源としては、紫外線を発生する光源であればいずれでも使用できる。例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ等を用いることができる。 As a light source for forming a cured film layer by photocuring reaction of the clear hard coat layer, any light source that generates ultraviolet rays can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
　照射条件はそれぞれのランプによって異なるが、照射光量は２０～１００００ｍＪ／ｃｍ２程度あればよく、好ましくは、５０～２０００ｍＪ／ｃｍ２である。近紫外線領域～可視光線領域にかけてはその領域に吸収極大のある増感剤を用いることによって使用できる。 The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may if 20 ~ 10000mJ / cm 2 degrees, preferably 50 ~ 2000mJ / cm 2. In the near ultraviolet region to the visible light region, it can be used by using a sensitizer having an absorption maximum in that region.
　紫外線硬化性樹脂組成物は塗布乾燥された後、紫外線を光源より照射するが、照射時間は０．５秒～５分がよく、紫外線硬化性樹脂の硬化効率、作業効率などから３秒～２分がより好ましい。 The UV curable resin composition is coated and dried and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 due to the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.
　（機能性層）
　本発明のハードコート用基材フィルム製造に際し、延伸の前又は後で帯電防止層、バックコート層、易滑性層、接着層、バリアー層、防眩層、反射防止層、光学補償層等の機能性層を塗設してもよい。 (Functional layer)
When producing the base film for hard coat of the present invention, before or after stretching, such as antistatic layer, backcoat layer, slippery layer, adhesive layer, barrier layer, antiglare layer, antireflection layer, optical compensation layer, etc. A functional layer may be applied.
　＜偏光板、液晶表示装置＞
　本発明のハードコート用基材フィルムは、偏光板に用いることができる。 <Polarizing plate, liquid crystal display>
The base film for hard coat of the present invention can be used for a polarizing plate.
　偏光板は一般的な方法で作製することができる。本発明のハードコート用基材フィルムの偏光子側をアルカリ鹸化処理し、沃素溶液中に浸漬延伸して作製した偏光子の少なくとも一方の面に、完全鹸化型ポリビニルアルコール水溶液を用いて貼り合わせることが好ましい。 The polarizing plate can be produced by a general method. The polarizer side of the base film for hard coat of the present invention is subjected to alkali saponification treatment, and is bonded to at least one surface of a polarizer prepared by immersion and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Is preferred.
　もう一方の面には本発明のハードコート用基材フィルムを用いても、また別のハードコート用基材フィルムを用いてもよい。市販のセルロースエステルフィルム（例えば、コニカミノルタタック　ＫＣ８ＵＸ、ＫＣ４ＵＸ、ＫＣ５ＵＸ、ＫＣ８ＵＹ、ＫＣ４ＵＹ、ＫＣ１２ＵＲ、ＫＣ８ＵＣＲ－３、ＫＣ８ＵＣＲ－４、ＫＣ８ＵＣＲ－５、ＫＣ４ＦＲ－１、ＫＣ８ＵＹ－ＨＡ、ＫＣ８ＵＸ－ＲＨＡ、以上コニカミノルタオプト（株）製）も好ましく用いられる。 On the other side, the hard coat base film of the present invention may be used, or another hard coat base film may be used. Commercially available cellulose ester films (for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC8UY-HA, KC8UTA-HA, KC8UX Opt Co., Ltd.) is also preferably used.
　本発明に係る偏光板を液晶表示装置に組み込むことによって、種々の視認性に優れた液晶表示装置を作製することができる。本発明のハードコート用基材フィルムは、ＳＴＮ、ＴＮ、ＯＣＢ、ＨＡＮ、ＶＡ（ＭＶＡ、ＰＶＡ）、ＩＰＳなどの各種駆動方式の液晶表示装置に用いることができる。特に好ましくは、ＶＡ（ＭＶＡ、ＰＶＡ）型、及びＩＰＳ型液晶表示装置である。 By incorporating the polarizing plate according to the present invention into a liquid crystal display device, various liquid crystal display devices with excellent visibility can be produced. The base film for hard coat of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), and IPS. Particularly preferred are VA (MVA, PVA) type and IPS type liquid crystal display devices.
　以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
　＜ハードコート用基材フィルム１０１の作製＞
　化合物（１）の合成：
　攪拌機、２個の滴下ロート、ガス導入管及び温度計の付いたガラスフラスコに、表２記載の種類及び比率のモノマー混合液４０ｇ、連鎖移動剤のメルカプトプロピオン酸３．０ｇ及びトルエン３０ｇを仕込み、９０℃に昇温した。 <Preparation of base film 101 for hard coat>
Synthesis of compound (1):
A glass flask equipped with a stirrer, two dropping funnels, a gas introduction tube and a thermometer was charged with 40 g of a monomer mixture of the types and ratios described in Table 2, 3.0 g of a chain transfer agent, mercaptopropionic acid, and 30 g of toluene. The temperature was raised to 90 ° C.
　その後、一方の滴下ロートから、表２記載の種類及び比率のモノマー混合液６０ｇを３時間かけて滴下すると共に、同時にもう一方のロートからトルエン１４ｇに溶解したアゾビスイソブチロニトリル０．６ｇを３時間かけて滴下した。その後更に、トルエン５６ｇに溶解したアゾビスイソブチロニトリル０．６ｇを２時間かけて滴下した後、更に２時間反応を継続させ化合物（１）を得た。 Thereafter, from one dropping funnel, 60 g of a monomer mixture liquid of the types and ratios described in Table 2 was dropped over 3 hours, and at the same time, 0.6 g of azobisisobutyronitrile dissolved in 14 g of toluene was added from the other funnel. The solution was added dropwise over 3 hours. Thereafter, 0.6 g of azobisisobutyronitrile dissolved in 56 g of toluene was added dropwise over 2 hours, and the reaction was further continued for 2 hours to obtain Compound (1).
　化合物（２）の合成：
　特開２０００－１２８９１１号公報に記載の重合方法により塊状重合を行った。すなわち、攪拌機、窒素ガス導入管、温度計、投入口及び環流冷却管を備えたフラスコにモノマーとして下記メチルアクリレートを投入し、窒素ガスを導入してフラスコ内を窒素ガスで置換した下記チオグリセロールを攪拌下添加した。 Synthesis of compound (2):
Bulk polymerization was carried out by the polymerization method described in JP-A No. 2000-128911. That is, the following methyl acrylate was introduced as a monomer into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, an inlet, and a reflux condenser, and the following thioglycerol was substituted with nitrogen gas by introducing nitrogen gas. Added with stirring.
　チオグリセロール添加後、４時間重合を行い、内容物を室温に戻し、それにベンゾキノン５質量％テトラヒドロフラン溶液を２０質量部添加し、重合を停止させた。内容物をエバポレーターに移し、８０℃で減圧下、テトラヒドロフラン、残存モノマー及び残存チオグリセロールを除去し、化合物（２）を得た。 After the addition of thioglycerol, polymerization was carried out for 4 hours, the contents were returned to room temperature, and 20 parts by mass of a 5% by mass benzoquinone tetrahydrofuran solution was added thereto to terminate the polymerization. The contents were transferred to an evaporator, and tetrahydrofuran, residual monomer and residual thioglycerol were removed under reduced pressure at 80 ° C. to obtain compound (2).
　表２記載の、ＭＡ、ＭＭＡ、ＨＥＭＡ、ＢｚＭＡはそれぞれ以下の化合物の略称である。 In Table 2, MA, MMA, HEMA, and BzMA are abbreviations for the following compounds, respectively.
　ＭＡ：メチルアクリレート
　ＭＭＡ：メチルメタクリレート
　ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
　ＢｚＭＡ：２－ベンジルメタクリレート
　化合物（１）及び（２）の重量平均分子量は下記測定法により測定した。 MA: methyl acrylate MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate BzMA: 2-benzyl methacrylate The weight average molecular weights of the compounds (1) and (2) were measured by the following measuring method.
　＜分子量測定＞
　重量平均分子量の測定は、高速液体クロマトグラフィーを用いて測定した。 <Molecular weight measurement>
The weight average molecular weight was measured using high performance liquid chromatography.
　測定条件は以下の通りである。 The measurement conditions are as follows.
　溶媒：　　　メチレンクロライド
　カラム：　　Ｓｈｏｄｅｘ　Ｋ８０６，Ｋ８０５，Ｋ８０３Ｇ（昭和電工（株）製を３本接続して使用した）
　カラム温度：２５℃
　試料濃度：　０．１質量％
　検出器：　　ＲＩ　Ｍｏｄｅｌ　５０４（ＧＬサイエンス社製）
　ポンプ：　　Ｌ６０００（日立製作所（株）製）
　流量：　　　１．０ｍｌ／ｍｉｎ
　校正曲線：　標準ポリスチレンＳＴＫ　ｓｔａｎｄａｒｄ　ポリスチレン（東ソー（株）製）Ｍｗ＝１００００００～３００迄の１３サンプルによる校正曲線を使用した。１３サンプルは、ほぼ等間隔に用いる。 Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1000,000 to 300 calibration curves with 13 samples were used. Thirteen samples are used at approximately equal intervals.
　（二酸化珪素分散液の調製）
　アエロジルＲ８１２（日本アエロジル（株）製）　　　　　１０質量部
　（一次粒子の平均径７ｎｍ）
　エタノール　　　　　　　　　　　　　　　　　　　　　　９０質量部
　以上をディゾルバーで３０分間撹拌混合した後、マントンゴーリンで分散を行った。二酸化珪素分散液に８８質量部のメチレンクロライドを撹拌しながら投入し、ディゾルバーで３０分間撹拌混合し、二酸化珪素分散希釈液を作製した。微粒子分散希釈液濾過器（アドバンテック東洋（株）：ポリプロピレンワインドカートリッジフィルターＴＣＷ－ＰＰＳ－１Ｎ）で濾過した。 (Preparation of silicon dioxide dispersion)
Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass (average diameter of primary particles 7 nm)
90 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution. The mixture was filtered with a fine particle dispersion dilution filter (Advantech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
　（ドープ組成物の調製）
　セルローストリアセテート　　　　　　　　　　　　　　　９０質量部
（リンター綿から合成されたセルローストリアセテート、アセチル基置換度２．９０、Ｍｎ＝１４００００）
　化合物（１）　　　　　　　　　　　　　　　　　　　　７．５質量部
　化合物（２）　　　　　　　　　　　　　　　　　　　　２．５質量部
　ポリエステル化合物（表２参照）　　　　　　　　　　　２．５質量部
　チヌビン９２８（チバ・ジャパン（株）製）　　　　　　２．５質量部
　二酸化珪素分散希釈液　　　　　　　　　　　　　　　　　　４質量部
　メチレンクロライド　　　　　　　　　　　　　　　　　４３２質量部
　エタノール　　　　　　　　　　　　　　　　　　　　　　３８質量部
　以上を密閉容器に投入し、加熱し、撹拌しながら、完全に溶解し、安積濾紙（株）製の安積濾紙Ｎｏ．２４を使用して濾過し、ドープ液を調製した。 (Preparation of dope composition)
90 parts by mass of cellulose triacetate (cellulose triacetate synthesized from linter cotton, acetyl group substitution degree 2.90, Mn = 14000)
Compound (1) 7.5 parts by mass Compound (2) 2.5 parts by mass Polyester compound (see Table 2) 2.5 parts by mass Tinuvin 928 (manufactured by Ciba Japan Co., Ltd.) 2.5 parts by mass Dispersion dilution of silicon dioxide Liquid 4 parts by mass Methylene chloride 432 parts by mass Ethanol 38 parts by mass The above was put into a sealed container, heated and stirred to completely dissolve, and Azumi Filter Paper No. Azumi Filter Paper No. No. 24 was used for filtration to prepare a dope solution.
　次に、ベルト流延装置を用い、ステンレスバンド支持体に均一に流延した。ステンレスバンド支持体で、残留溶剤量が１００％になるまで溶剤を蒸発させ、ステンレスバンド支持体上から剥離した。セルロースエステルフィルムのウェブを３５℃で溶剤を蒸発させ、１．６５ｍ幅にスリットし、１６０℃の乾燥温度で乾燥させた。 Next, the belt was cast evenly on a stainless steel band support using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off. The web of cellulose ester film was evaporated at 35 ° C., slit to 1.65 m width, and dried at a drying temperature of 160 ° C.
　乾燥を始めたときの残留溶剤量は２０％であった。その後、１２０℃の乾燥装置内を多数のロールで搬送させながら１５分間乾燥させた後、フィルム両端に幅１５ｍｍ、高さ１０μｍのナーリング加工を施し、巻芯に巻き取り、ハードコート用基材フィルム１０１を得た。ハードコート用基材フィルムの残留溶剤量は０．２％であり、膜厚は４０μｍ、巻数は６０００ｍであった。 The amount of residual solvent when drying was started was 20%. Thereafter, the film is dried for 15 minutes while being transported in a drying apparatus at 120 ° C. by a number of rolls, then subjected to knurling with a width of 15 mm and a height of 10 μm at both ends of the film, wound on a core, and a base film for hard coating 101 was obtained. The residual solvent amount of the base film for hard coat was 0.2%, the film thickness was 40 μm, and the winding number was 6000 m.
　なお、ハードコート用基材フィルム１０１の平均表面粗さＲａは２．２ｎｍ、３０℃における貯蔵弾性率はＭＤ方向に５．０ＧＰａ、ＴＤ方向に４．５ＧＰａ、ステンレスバンド支持体の回転速度とテンターの運転速度から算出されるＭＤ方向（搬送方向）の延伸倍率は１．１０倍であった。 The average surface roughness Ra of the base film 101 for hard coat is 2.2 nm, the storage elastic modulus at 30 ° C. is 5.0 GPa in the MD direction, 4.5 GPa in the TD direction, and the rotation speed and tenter of the stainless steel band support. The draw ratio in the MD direction (conveyance direction) calculated from the operating speed was 1.10 times.
　このハードコート用基材フィルム１０１に、下記ハードコート層塗布組成物１を孔径０．４μｍのポリプロピレン製フィルターで濾過してハードコート層塗布液を調製し、ダイコータにより塗布し、７０℃で乾燥後、酸素濃度が１．０体積％以下の雰囲気になるように窒素パージしながら、紫外線ランプを用い照射部の照度が３００ｍＷ／ｃｍ２、照射量を０．３Ｊ／ｃｍ２として塗布層を硬化させ、さらに加熱処理ゾーンにおいて、１３０℃で５分間、搬送張力３００Ｎ／ｍで加熱処理し、ドライ膜厚７μｍのハードコート層を形成し、ハードコートフィルム１０１を作製し、巻き取った。 A hard coat layer coating solution is prepared by filtering the following hard coat layer coating composition 1 on the hard coat base film 101 through a polypropylene filter having a pore size of 0.4 μm, applying the solution by a die coater, and drying at 70 ° C. Then, while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, using an ultraviolet lamp, the illuminance of the irradiated part is 300 mW / cm 2 and the irradiation amount is 0.3 J / cm 2 to cure the coating layer. Further, in the heat treatment zone, heat treatment was performed at 130 ° C. for 5 minutes at a conveyance tension of 300 N / m to form a hard coat layer having a dry film thickness of 7 μm, and the hard coat film 101 was produced and wound.
　（ハードコート層組成物）
　下記材料を攪拌、混合しハードコート層塗布組成物１とした。 (Hard coat layer composition)
The following materials were stirred and mixed to obtain hard coat layer coating composition 1.
　ペンタエリスリトールトリアクリレート　　　　　　　２０．０質量部
　ペンタエリスリトールテトラアクリレート　　　　　　５０．０質量部
　ジペンタエリスリトールヘキサアクリレート　　　　　３０．０質量部
　ジペンタエリスリトールペンタアクリレート　　　　　３０．０質量部
　イルガキュア１８４（チバ・ジャパン社製）　　　　　　５．０質量部
　フッ素－シロキサングラフトポリマーＩ（３５質量％）　５．０質量部
　シーホスターＫＥＰ－５０（粉体のシリカ粒子、平均粒径０．４７～０．６１μｍ、日本触媒株式会社製）　　　　　　　　　　　２４．３質量部
　プロピレングリコールモノメチルエーテル　　　　　　　　２０質量部
　酢酸メチル　　　　　　　　　　　　　　　　　　　　　　４０質量部
　メチルエチルケトン　　　　　　　　　　　　　　　　　　６０質量部
　《フッ素－シロキサングラフトポリマーＩの調製》
　以下、フッ素－シロキサングラフトポリマーＩの調整に用いた素材の市販品名を示す。 Pentaerythritol triacrylate 20.0 parts by mass Pentaerythritol tetraacrylate 50.0 parts by mass Dipentaerythritol hexaacrylate 30.0 parts by mass Dipentaerythritol pentaacrylate 30.0 parts by mass Irgacure 184 (manufactured by Ciba Japan) 5.0 Part by mass Fluorine-siloxane graft polymer I (35% by mass) 5.0 parts by mass Seahoster KEP-50 (powdered silica particles, average particle size 0.47 to 0.61 μm, manufactured by Nippon Shokubai Co., Ltd.) 24.3 parts by mass Parts propylene glycol monomethyl ether 20 parts by weight methyl acetate 40 parts by weight methyl ethyl ketone 60 parts by weight << Preparation of Fluorine-siloxane Graft Polymer I >>
Hereinafter, commercial names of materials used for preparing the fluorine-siloxane graft polymer I are shown.
　ラジカル重合性フッ素樹脂（Ａ）：セフラルコートＣＦ－８０３（水酸基価６０、数平均分子量１５，０００；セントラル硝子（株）製）
　片末端ラジカル重合性ポリシロキサン（Ｂ）：サイラプレーンＦＭ－０７２１（数平均分子量５，０００；チッソ（株）製）
　ラジカル重合開始剤：パーブチルＯ（ｔ－ブチルパーオキシ－２－エチルヘキサノエート；日本油脂（株）製）
　硬化剤：スミジュールＮ３２００（ヘキサメチレンジイソシアネートのビウレット型プレポリマー；住化バイエルウレタン（株）製）
　（ラジカル重合性フッ素樹脂（Ａ）の合成）
　機械式撹拌装置、温度計、コンデンサー及び乾燥窒素ガス導入口を備えたガラス製反応器に、セフラルコートＣＦ－８０３（１５５４質量部）、キシレン（２３３質量部）、及び２－イソシアナトエチルメタクリレート（６．３質量部）を入れ、乾燥窒素雰囲気下で８０℃に加熱した。８０℃で２時間反応し、サンプリング物の赤外吸収スペクトルによりイソシアネートの吸収が消失したことを確認した後、反応混合物を取り出し、ウレタン結合を介して５０質量％のラジカル重合性フッ素樹脂（Ａ）を得た。 Radical polymerizable fluororesin (A): Cephalal coated CF-803 (hydroxyl value 60, number average molecular weight 15,000; manufactured by Central Glass Co., Ltd.)
One-end radically polymerizable polysiloxane (B): Silaplane FM-0721 (number average molecular weight 5,000; manufactured by Chisso Corporation)
Radical polymerization initiator: Perbutyl O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
Curing agent: Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.)
(Synthesis of radical polymerizable fluororesin (A))
A glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet was added to cefal coat CF-803 (1554 parts by mass), xylene (233 parts by mass), and 2-isocyanatoethyl methacrylate (6 3 parts by mass) and heated to 80 ° C. in a dry nitrogen atmosphere. After reacting at 80 ° C. for 2 hours and confirming that the absorption of isocyanate disappeared by the infrared absorption spectrum of the sample, the reaction mixture was taken out and 50% by mass of radically polymerizable fluororesin (A) via a urethane bond. Got.
　（フッ素－シロキサングラフトポリマーＩの調製）
　機械式撹拌装置、温度計、コンデンサー及び乾燥窒素ガス導入口を備えたガラス製反応器に、上記合成したラジカル重合性フッ素樹脂（Ａ）（２６．１質量部）、キシレン（１９．５質量部）、酢酸ｎ－ブチル（１６．３質量部）、メチルメタクリレート（２．４質量部）、ｎ－ブチルメタクリレート（１．８質量部）、ラウリルメタクリレート（１．８質量部）、２－ヒドロキシエチルメタクリレート（１．８質量部）、ＦＭ－０７２１（５．２質量部）、及びパーブチルＯ（０．１質量部）を入れ、窒素雰囲気中で９０℃まで加熱した後、９０℃で２時間保持した。パーブチルＯ（０．１部）を追加し、さらに９０℃で５時間保持することによって、重量平均分子量が１７１，０００である３５質量％フッ素－シロキサングラフトポリマーＩの溶液を得た。 (Preparation of fluorine-siloxane graft polymer I)
In a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet, the synthesized radical polymerizable fluororesin (A) (26.1 parts by mass), xylene (19.5 parts by mass) ), N-butyl acetate (16.3 parts by mass), methyl methacrylate (2.4 parts by mass), n-butyl methacrylate (1.8 parts by mass), lauryl methacrylate (1.8 parts by mass), 2-hydroxyethyl Add methacrylate (1.8 parts by mass), FM-0721 (5.2 parts by mass), and perbutyl O (0.1 parts by mass), heat to 90 ° C. in a nitrogen atmosphere, and hold at 90 ° C. for 2 hours. did. Perbutyl O (0.1 part) was added, and the mixture was further maintained at 90 ° C. for 5 hours to obtain a 35 mass% fluorine-siloxane graft polymer I solution having a weight average molecular weight of 171,000.
　重量平均分子量はＧＰＣにより求めた。また、フッ素－シロキサングラフトポリマーＩの質量％はＨＰＬＣ（液体クロマトグラフィー）により求めた。 The weight average molecular weight was determined by GPC. Further, the mass% of the fluorine-siloxane graft polymer I was determined by HPLC (liquid chromatography).
　＜ハードコート用基材フィルム１０２の作製＞
　１０１の作製において、１．６５ｍ幅にスリットした後、テンターでＴＤ方向（フィルムの幅手方向）に１．３倍に延伸しながら、１６０℃の乾燥温度で乾燥させた。このときテンターで延伸を始めたときの残留溶剤量は２０％であった。その後、１２０℃の乾燥装置内を多数のロールで搬送させながら１５分間乾燥させた後、２．２ｍ幅にスリットし、フィルム両端に幅１５ｍｍ、高さ１０μｍのナーリング加工を施し、巻芯に巻き取り、ハードコート用基材フィルム１０２を得た。ハードコート用基材フィルムの残留溶剤量は０．２％であり、膜厚は４０μｍ、巻数は６０００ｍであった。 <Preparation of Hard Coat Base Film 102>
In preparation of 101, after slitting to a width of 1.65 m, the film was dried at a drying temperature of 160 ° C. while being stretched 1.3 times in the TD direction (the width direction of the film) with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C. with many rolls, slitting to 2.2 m width, applying a knurling process with a width of 15 mm and a height of 10 μm at both ends of the film, and winding it around the core The hard coat substrate film 102 was obtained. The residual solvent amount of the base film for hard coat was 0.2%, the film thickness was 40 μm, and the winding number was 6000 m.
　尚、平均表面粗さＲａは３．０ｎｍ、３０℃における貯蔵弾性率はＭＤ方向に４．１ＧＰａ、ＴＤ方向に５．５ＧＰａステンレスバンド支持体の回転速度とテンターの運転速度から算出されるＭＤ方向の延伸倍率は１．０１倍であった。 The average surface roughness Ra is 3.0 nm, the storage elastic modulus at 30 ° C. is 4.1 GPa in the MD direction, and the MD direction is calculated from the rotational speed of the 5.5 GPa stainless band support in the TD direction and the operating speed of the tenter. The draw ratio of was 1.01 times.
　セルロースエステル、化合物（１）及び（２）を表１及び２に記載のように変更し、ハードコート用基材フィルム１０２と同様にして各種ハードコート用基材フィルム（１０３～１１５）を作製した。また、これらのハードコート用基材フィルムにクリアーハードコート層を設けた。 Cellulose esters and compounds (1) and (2) were changed as shown in Tables 1 and 2, and various hard coat substrate films (103 to 115) were prepared in the same manner as the hard coat substrate film 102. . Further, a clear hard coat layer was provided on these hard coat base films.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　＜ハードコート用基材フィルムの動的粘弾性の測定＞
　下記条件でハードコート用基材フィルムの動的粘弾性ｔａｎδｍａｘを測定した。なお、試料は、あらかじめ２３℃５５％ＲＨの雰囲気下２４時間調湿したものを使用し、湿度５５％ＲＨ、下記条件で昇温させながら測定した。 <Measurement of dynamic viscoelasticity of base film for hard coat>
The dynamic viscoelasticity tan δmax of the base film for hard coat was measured under the following conditions. The sample used was conditioned at 23 ° C. and 55% RH for 24 hours in advance, and the measurement was performed while the temperature was increased at a humidity of 55% RH and the following conditions.
　測定装置：ティーエイインスツルメント社製　ＲＳＡIII
　試料：幅５ｍｍ、長さ５０ｍｍ（ギャップ２０ｍｍに設定）
　測定条件：引張モード
　測定温度：２５～２１０℃
　昇温条件：５℃／ｍｉｎ
　周波数：１Ｈｚ
　＜鉛筆硬度の測定＞
　２３℃５５％ＲＨの雰囲気下２４時間調湿したハードコートフィルム試料を、同条件下ＪＩＳＫ５４００が規定する鉛筆硬度評価法に従い、クリアーハードコート層の面を１ｋｇのおもりを用いて各硬度の鉛筆で引っ掻きを５回繰り返し、傷が１本までの硬度を測定した。数字か高いほど、高硬度を示す。 Measuring device: RSA III manufactured by TI Instruments
Sample: width 5 mm, length 50 mm (gap set to 20 mm)
Measurement conditions: Tensile mode Measurement temperature: 25-210 ° C
Temperature rising condition: 5 ° C / min
Frequency: 1Hz
<Measurement of pencil hardness>
A hard coat film sample conditioned at 23 ° C. and 55% RH for 24 hours in accordance with the pencil hardness evaluation method specified by JISK5400 under the same conditions, using a 1 kg weight on the surface of the clear hard coat layer with a pencil of each hardness. Scratching was repeated 5 times, and the hardness of up to one scratch was measured. The higher the number, the higher the hardness.
　＜内部ヘイズの評価＞
　作製したセルロースエステルフィルムを、２３℃５５％ＲＨの環境にて５時間以上調湿した後、下記方法により内部ヘイズ値を評価した。 <Evaluation of internal haze>
The prepared cellulose ester film was conditioned for 5 hours or more in an environment of 23 ° C. and 55% RH, and then the internal haze value was evaluated by the following method.
　まず、フィルム以外の測定器具のブランクヘイズ１を測定する。
１．きれいにしたスライドガラスの上にグリセリンを一滴（０．０５ｍｌ）たらす。このとき液滴に気泡が入らないように注意する。ガラスは見た目がきれいでも汚れていることがあるので必ず洗剤で洗浄したものを使用する（図２参照）。
２．その上にカバーガラスを乗せる。カバーガラスは押さえなくてもグリセリンは広がる。
３．ヘイズメーターにセットしブランクヘイズ１を測定する。 First, the blank haze 1 of a measuring instrument other than a film is measured.
1. Drip a drop (0.05 ml) of glycerin on a cleaned glass slide. At this time, care is taken so that bubbles do not enter the droplet. Glass must be washed with a detergent (see Fig. 2).
2. Place the cover glass on top of it. Glycerin spreads without pressing the cover glass.
3. Set on a haze meter and measure blank haze 1.
　次いで以下の手順で、試料を含めたヘイズ２を測定する。
４．スライドガラス上にグリセリン０．０５ｍｌを滴下する（図２参照）。
５．その上に測定する試料フィルムを気泡が入らないように乗せる（図３参照）。
６．試料フィルム上にグリセリン０．０５ｍｌを滴下する（図４参照）。
７．その上にカバーガラスを載せる（図５参照）。
８．上記のように作製した積層体（上から、カバーガラス／グリセリン／試料フィルム／グリセリン／スライドガラス）をヘイズメーターにセットしヘイズ２を測定する。
９．（ヘイズ２）－（ヘイズ１）＝（本発明のセルロースエステルフィルムの内部ヘイズ）を算出する。 Next, the haze 2 including the sample is measured by the following procedure.
4). 0.05 ml of glycerin is dropped on a slide glass (see FIG. 2).
5. A sample film to be measured is placed thereon so that air bubbles do not enter (see FIG. 3).
6). 0.05 ml of glycerin is dropped on the sample film (see FIG. 4).
7). A cover glass is placed thereon (see FIG. 5).
8). The laminate prepared as described above (from above, cover glass / glycerin / sample film / glycerin / slide glass) is set on a haze meter and haze 2 is measured.
9. (Haze 2) − (Haze 1) = (Internal haze of the cellulose ester film of the present invention) is calculated.
　上記測定にて使用したガラス、グリセリンを以下の通りである。 The glass and glycerin used in the above measurement are as follows.
　ガラス：ＭＩＣＲＯ　ＳＬＩＤＥ　ＧＬＡＳＳ　Ｓ９２１３　ＭＡＴＳＵＮＡＭＩ
　グリセリン：関東化学製　鹿特級（純度＞９９．０％）　屈折率１．４７
　また、ヘイズ値は、日本電色工業株式会社製ＮＤＨ２０００を用いて測定した。 Glass: MICRO SLIDE GLASS S9213 MATUNAMI
Glycerin: Deer special grade (Purity> 99.0%) manufactured by Kanto Chemical Co., Ltd.
Moreover, the haze value was measured using Nippon Denshoku Industries Co., Ltd. NDH2000.
　測定したヘイズ値によって下記ランク分けを行った。 The following ranking was performed according to the measured haze value.
　Ａ：０．０４未満
　Ｂ：０．０４以上０．０８未満
　Ｃ：０．０８以上０．１２未満
　Ｄ：０．１２以上
　上記評価結果を表３に示す。 A: Less than 0.04 B: 0.04 or more and less than 0.08 C: 0.08 or more and less than 0.12 D: 0.12 or more The evaluation results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　表３に示した結果から明らかなように、比較例と比べ、本発明に係る実施例の動的粘弾性ｔａｎδｍａｘは適切な範囲内にある上に、高硬度で、かつ内部ヘイズ値が低いことが分かる。 As is clear from the results shown in Table 3, the dynamic viscoelasticity tan δmax of the example according to the present invention is within an appropriate range, and is high in hardness and has a low internal haze value, as compared with the comparative example. I understand.
　すなわち、本発明の手段により、適切な光学性能を維持しながら、表面加工適性（硬度、密着性）に優れたハードコート用基材フィルムを提供できることが分かる。 That is, it can be seen that the means of the present invention can provide a base film for hard coat excellent in surface processing suitability (hardness and adhesion) while maintaining appropriate optical performance.
　１　主ドープ仕込み釜
　２　ドープ送液ポンプ
　５　前後巻回ドラム
　７　ステンレスベルト
　８　剥離ロール
　９　ウェブ
　１０Ａ、１０Ｂ　ロール搬送乾燥装置
　１１　温風（乾燥風）
　１２　テンター
　１３　フィルム巻き取り装置
　Ａ　流延ダイ DESCRIPTION OF SYMBOLS 1 Main dope preparation pot 2 Dope liquid feeding pump 5 Front and rear winding drum 7 Stainless steel belt 8 Peeling roll 9 Web 10A, 10B Roll conveyance dryer 11 Hot air (drying air)
12 Tenter 13 Film take-up device A Casting die

Claims (4)

  1. 　延伸されたハードコート用基材フィルムであって、総アシル基置換度が２．８０～２．９５の範囲であり、かつ下記の二種類の化合物を含むセルロースエステルを含有することを特徴とするハードコート用基材フィルム。
    化合物（１）：分子内にヒドロキシ基を有さないアクリルモノマーＡとヒドロキシ基を有するアクリルモノマーＢとの共重合体であり、その重量平均分子量が３０，０００超２５０，０００以下である。
    化合物（２）：分子内にヒドロキシ基を有さないアクリルモノマーＣの重合体であり、重量平均分子量が３００～３０００の範囲内である。     A stretched base film for hard coat, characterized in that the total acyl group substitution degree is in the range of 2.80 to 2.95, and contains a cellulose ester containing the following two types of compounds: Base film for hard coat.
    Compound (1): A copolymer of an acrylic monomer A having no hydroxy group in the molecule and an acrylic monomer B having a hydroxy group, and the weight average molecular weight is more than 30,000 and not more than 250,000.
    Compound (2): A polymer of acrylic monomer C having no hydroxy group in the molecule and having a weight average molecular weight in the range of 300 to 3,000.
  2. 　前記ハードコート用基材フィルムの幅手方向の動的粘弾性を２５～２００℃の範囲で１Ｈｚにて測定したときに得られる動的粘弾性損失正接の最大値ｔａｎδｍａｘが、０．８５～１．００の範囲内であることを特徴とする請求項１に記載のハードコート用基材フィルム。 The maximum value tan δmax of dynamic viscoelastic loss tangent obtained when the dynamic viscoelasticity in the width direction of the base film for hard coat is measured at 1 Hz in the range of 25 to 200 ° C. is 0.85 to 1 The base film for hard coat according to claim 1, which is within a range of 0.00.
  3. 　前記化合物（１）を構成するアクリルモノマーＡとアクリルモノマーＢとのモル比が、９７：３～８５：１５の範囲内であることを特徴とする請求項１又は請求項２に記載のハードコート用基材フィルム。 3. The hard coat according to claim 1, wherein the molar ratio of the acrylic monomer A and the acrylic monomer B constituting the compound (1) is in the range of 97: 3 to 85:15. Substrate film.
  4. 　芳香族基を末端に有するポリエステルを含有していることを特徴とする請求項１から請求項３までのいずれか一項に記載のハードコート用基材フィルム。 The base film for hard coat according to any one of claims 1 to 3, comprising a polyester having an aromatic group at the terminal.
PCT/JP2011/062079 2010-06-18 2011-05-26 Hard-coating base film WO2011158626A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012520353A JP5617922B2 (en) 2010-06-18 2011-05-26 Base film for hard coat

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-139134 2010-06-18
JP2010139134 2010-06-18

Publications (1)

Publication Number Publication Date
WO2011158626A1 true WO2011158626A1 (en) 2011-12-22

Family

ID=45348035

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/062079 WO2011158626A1 (en) 2010-06-18 2011-05-26 Hard-coating base film

Country Status (2)

Country Link
JP (1) JP5617922B2 (en)
WO (1) WO2011158626A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148476A1 (en) * 2013-03-22 2014-09-25 コニカミノルタ株式会社 Polarizing plate, method for manufacturing polarizing plate, and liquid crystal display device
JP5991777B2 (en) * 2014-09-26 2016-09-14 日本製紙株式会社 Hard coat film and method for producing the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007062063A (en) * 2005-08-30 2007-03-15 Konica Minolta Opto Inc Optical film and its manufacturing apparatus
JP2007062200A (en) * 2005-08-31 2007-03-15 Konica Minolta Opto Inc Cellulose ester film, its manufacturing method and liquid-crystal display apparatus using it
JP2007062064A (en) * 2005-08-30 2007-03-15 Konica Minolta Opto Inc Optical film and its manufacturing method
WO2008015911A1 (en) * 2006-07-31 2008-02-07 Konica Minolta Opto, Inc. Polarizing plate protection film, polarizing plate and liquid crystal display
WO2008102647A1 (en) * 2007-02-21 2008-08-28 Konica Minolta Opto, Inc. Cellulose ester film and method for producing the same
JP2009265365A (en) * 2008-04-25 2009-11-12 Konica Minolta Opto Inc Polarizing plate, and liquid crystal display device
JP2010122340A (en) * 2008-11-18 2010-06-03 Konica Minolta Opto Inc Optical film, method for forming the same, polarizing plate using them, and liquid crystal display device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007062063A (en) * 2005-08-30 2007-03-15 Konica Minolta Opto Inc Optical film and its manufacturing apparatus
JP2007062064A (en) * 2005-08-30 2007-03-15 Konica Minolta Opto Inc Optical film and its manufacturing method
JP2007062200A (en) * 2005-08-31 2007-03-15 Konica Minolta Opto Inc Cellulose ester film, its manufacturing method and liquid-crystal display apparatus using it
WO2008015911A1 (en) * 2006-07-31 2008-02-07 Konica Minolta Opto, Inc. Polarizing plate protection film, polarizing plate and liquid crystal display
WO2008102647A1 (en) * 2007-02-21 2008-08-28 Konica Minolta Opto, Inc. Cellulose ester film and method for producing the same
JP2009265365A (en) * 2008-04-25 2009-11-12 Konica Minolta Opto Inc Polarizing plate, and liquid crystal display device
JP2010122340A (en) * 2008-11-18 2010-06-03 Konica Minolta Opto Inc Optical film, method for forming the same, polarizing plate using them, and liquid crystal display device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148476A1 (en) * 2013-03-22 2014-09-25 コニカミノルタ株式会社 Polarizing plate, method for manufacturing polarizing plate, and liquid crystal display device
JP5991777B2 (en) * 2014-09-26 2016-09-14 日本製紙株式会社 Hard coat film and method for producing the same
JPWO2016047796A1 (en) * 2014-09-26 2017-04-27 日本製紙株式会社 Hard coat film and method for producing the same

Also Published As

Publication number Publication date
JPWO2011158626A1 (en) 2013-08-19
JP5617922B2 (en) 2014-11-05

Similar Documents

Publication Publication Date Title
JP5333690B2 (en) Optical film and polarizing plate using the same
JP5262114B2 (en) Cellulose ester film, light diffusion film, polarizing plate, and liquid crystal display device
WO2007026524A1 (en) Polarizing plate and liquid crystal display device manufactured using the same
JP5181862B2 (en) Optical film and polarizing plate
JP5157897B2 (en) Polarizing plate protective film, polarizing plate and liquid crystal display device
WO2008015911A1 (en) Polarizing plate protection film, polarizing plate and liquid crystal display
JP5115500B2 (en) Method for producing optical compensation film
JP2006342227A (en) Cellulose ester film, polarizing plate, and liquid crystal display device
US20120295040A1 (en) Hard coat film, polarizing plate and liquid crystal display device
WO2012035849A1 (en) Antiglare film, antiglare film manufacturing method, polarizing plate and liquid crystal display device
JP5754445B2 (en) Optical film, polarizing plate using the same, and liquid crystal display device
CN106537310A (en) Conductive film, polarizing plate, and touch panel display device
JP2009210777A (en) Optical film and polarizing plate using same
WO2012073692A1 (en) Cellulose ester film, method for producing same, and polarizing plate using same
JP5071257B2 (en) Retardation film, method for producing retardation film, polarizing plate and liquid crystal display device
JP5617922B2 (en) Base film for hard coat
JP2012088479A (en) Polarizing plate
JP5549397B2 (en) Optical film, polarizing plate using the same, and liquid crystal display device
JP2007292917A (en) Polarizing plate
JPWO2018142712A1 (en) Film roll and manufacturing method thereof
JP5673548B2 (en) Optical film, polarizing plate using the same, and liquid crystal display device
JP2007272172A (en) Cellulose ester film, polarizing plate, and liquid crystal display device
US20120207976A1 (en) Polarizing plate and liquid crystal display employing the same
WO2010041514A1 (en) Optical film and polarizing plate using the optical film
JP2012072223A (en) Optical film, and polarizing plate and liquid crystal display device using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11795534

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012520353

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11795534

Country of ref document: EP

Kind code of ref document: A1