WO2019142615A1 - 易接着性ポリエステルフィルム - Google Patents
易接着性ポリエステルフィルム Download PDFInfo
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- WO2019142615A1 WO2019142615A1 PCT/JP2018/047553 JP2018047553W WO2019142615A1 WO 2019142615 A1 WO2019142615 A1 WO 2019142615A1 JP 2018047553 W JP2018047553 W JP 2018047553W WO 2019142615 A1 WO2019142615 A1 WO 2019142615A1
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- film
- mass
- resin
- polyester
- polyvinyl alcohol
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to an easily adhesive polyester film which is free from blocking even when dew condensation water adheres, is excellent in adhesion to a polarizer and a functional layer, and is also excellent in environmental suitability.
- the easily-adhesive polyester film of the present invention is suitable as a base film of an optical member such as a display, and is particularly suitable as a polarizer protective film.
- the polarizing plate has a structure in which a polarizer protective film is attached to both sides of a polarizer made of a polyvinyl alcohol film and a dichroic material such as iodine via a hydrophilic adhesive such as polyvinyl alcohol resin.
- a protective film used to protect a polarizer a triacetyl cellulose film has conventionally been used in terms of optical properties and transparency.
- triacetyl cellulose is not sufficiently durable.
- a polarizing plate using a triacetyl cellulose film as a polarizer protective film is used under high temperature or high humidity, the performance of the polarizing plate such as the degree of polarization and hue decreases. There is a case.
- the reduction in thickness of the polarizing plate is required, but there is a limit to the reduction in thickness of the triacetyl cellulose film from the viewpoint of maintaining the moisture barrier properties.
- using a polyester film is proposed as a polarizer protective film which has endurance and moisture barrier property (for example, refer to patent documents 1).
- the triacetyl-cellulose film used as a polarizer protective film has very high affinity with a hydrophilic adhesive. Therefore, the protective film which consists of a triacetyl-cellulose film has very high adhesiveness with the polarizer by which the hydrophilic adhesive was apply
- the polyester film has insufficient adhesion to a hydrophilic adhesive, and in particular, in the case of a polyester film having orientation upon stretching, the tendency is more pronounced. Therefore, in order to improve the adhesion with the polarizer or the hydrophilic adhesive applied to the polarizer, the polyester film is coated with a highly hydrophilic material such as the easy adhesion layer disclosed in Patent Document 1 Has been done.
- Polyester films have a low affinity to water, and polyester films having an aromatic dicarboxylic acid as a dicarboxylic acid component are particularly remarkable in this tendency. Moreover, the polyester film which has crystal orientation by extending
- a polarizer and an adhesive applied on a polarizer generally have a polyvinyl alcohol-based resin as a main component, and have high hydrophilicity. From such a difference in properties, the easy-adhesion layer disclosed in Patent Document 1 is a means for firmly bonding a polyester film and a polarizer or a polyvinyl alcohol-based resin layer such as an adhesive applied on a polarizer. Materials have been used that are more hydrophilic as used.
- an organotin catalyst is often used as a raw material in order to accelerate the crosslinking reaction of the easily bonding layer (curing of the easily bonding layer).
- coating solutions containing conventional polyvinyl alcohols, polyesters and isocyanate crosslinking agents there are many cases which do not mention the inclusion of a crosslinking / curing catalyst, but they have usually been used without description. is there.
- organotin is highly toxic, and even small amounts are known to affect organisms, and the use of organotin compounds has recently been limited.
- the problem of the present invention is that the composition for forming the easily adhesive layer does not substantially contain an organotin compound as a crosslinking / curing catalyst, such as a polyester film, a polarizer, an adhesive layer, etc.
- An object of the present invention is to provide an easily adhesive polyester film which is excellent in adhesion to a functional layer and does not cause blocking in the presence of condensation water.
- the present invention has the following constitution.
- a polyester film having an easy-adhesion layer on at least one side, wherein the easy-adhesion layer is cured by a composition containing a polyester resin, a polyvinyl alcohol resin and an active methylene block isocyanate crosslinking agent, in the easy-adhesion layer An easily adhesive polyester film substantially free of organotin as a curing catalyst for the composition and having a peeling force of 2 N / cm or less after water adhesion. 2.
- the polyester film used as a substrate in the present invention is a film mainly composed of a polyester resin.
- a film mainly composed of a polyester resin means that it is a film formed from a resin composition containing 50% by mass or more of a polyester resin.
- the polyester resin contains 50% by mass or more, and when copolymerized with another monomer, it means that the polyester structural unit is contained 50% by mole or more.
- the polyester film contains 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass of the polyester resin.
- the material of the polyester resin is not particularly limited, but a copolymer formed by polycondensation of a dicarboxylic acid component and a diol component, or a blend resin thereof can be used.
- the dicarboxylic acid component include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyl Carboxylic acid, diphenoxy ethane dicarboxylic acid, diphenyl sulfone carboxylic acid, anthracene dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, hexahydroterephthalic acid, hexahydro Is
- diol component constituting the polyester resin examples include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, 1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexadiol, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone and the like can be mentioned.
- the dicarboxylic acid component and the diol component constituting the polyester resin may be used alone or in combination of two or more. Further, other acid components such as trimellitic acid and other hydroxyl components such as trimethylolpropane may be added as appropriate.
- polyester resin examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polyethylene naphthalate.
- polyethylene terephthalate is preferable in terms of the balance between physical properties and cost.
- the copolymerization component etc. which have diethylene glycol and norbornene in a side chain can be mentioned.
- the polyester film of the present invention preferably has high transparency when used as a polarizer protective film.
- the total light transmittance of the film of the present invention is preferably 85% or more, more preferably 87% or more, still more preferably 88% or more, still more preferably 89% or more, and 90% or more. Particularly preferred.
- the haze is preferably 3% or less, more preferably 2.5% or less, still more preferably 2% or less, and particularly preferably 1.5% or less.
- inert particles may be contained in the film, but in order to maintain high transparency, the inert particles in the film
- the content is preferably as small as possible. Therefore, a multilayer structure in which the particles are contained only in the surface layer of the film, or the particles are not contained substantially in the film, and the particles are contained only in the covering layer laminated on at least one side of the polyester film. Is preferred.
- substantially free of particles means 50 ppm or less, preferably 10 ppm or less, most preferably detection when quantitative analysis of an element derived from the particles is performed by fluorescent X-ray analysis. It means the content to be below the limit. This is unavoidable even if particles are not positively added to the base film, contamination components derived from extraneous foreign matter, and dirt adhering to lines and devices in the manufacturing process of the raw material resin or film are exfoliated in the film. It is because it may be mixed in.
- 2 types and 3 layer structure which does not contain an inert particle in an inner layer substantially, and contains an inactive particle only in outermost layer makes transparency and processability compatible. Is possible and preferred.
- the thickness of the substrate film is not particularly limited in the present invention, but when the thickness of the polarizing plate is reduced to thin the display, the thickness of the film is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less . On the other hand, from the viewpoint of maintaining the mechanical strength as the protective film, the thickness of the film is preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more, and still more preferably 20 ⁇ m or more.
- the polyester film as the base material may be a single layer or a laminate of two or more layers.
- various additives can be contained in the film as needed, as long as the effects of the present invention can be achieved.
- the additive include an antioxidant, a light resistant agent, an antigelling agent, an organic wetting agent, an antistatic agent, an ultraviolet light absorber, a surfactant and the like.
- the film has a laminated structure, it is also preferable to include an additive according to the function of each layer as needed. For example, in order to prevent light deterioration of the polarizer, it is also a preferable embodiment to add an ultraviolet absorber or the like to the inner layer.
- a polyester film can be manufactured according to a conventional method. For example, it can be obtained by a method of melt extruding the above-mentioned polyester resin in the form of a film, and cooling and solidifying it with a casting drum to form a film.
- the polyester film in the present invention any of a non-oriented film and a stretched film can be used, but a stretched film is preferable from the viewpoint of durability such as mechanical strength and chemical resistance.
- the stretching method is not particularly limited, and a longitudinal uniaxial stretching method, a transverse uniaxial stretching method, a longitudinal and lateral sequential biaxial stretching method, a longitudinal and transverse simultaneous biaxial stretching method, and the like can be adopted.
- the stretching may be performed before laminating the easy adhesion layer described later, or may be performed after laminating the easy adhesion layer. It is also possible to uniaxially stretch in the longitudinal or transverse direction before laminating the easy adhesion layer, and to stretch in the other direction after laminating the covering layer.
- the polyester film in the present invention has an acid value of 20 KOHmg / g or less on at least one side in order to improve adhesion to a polarizer and a polyvinyl alcohol-based resin layer such as an aqueous adhesive provided on one side or both sides thereof. It is preferable that an easily adhesive layer formed of a polyester resin, a polyvinyl alcohol resin having a degree of saponification of 60 to 85 mol%, and a resin composition containing an active methylene block isocyanate crosslinking agent be laminated.
- the easy adhesion layer may be provided on both sides of the polyester film, or may be provided on only one side of the polyester film, and different resin coating layers may be provided on the other side.
- a specific polyester resin having a degree of saponification of 20 KOH mg / g or less a specific polyvinyl alcohol resin having a degree of saponification of 60 to 85 mol%, and an active methylene-blocked isocyanate crosslinking agent
- the polyester resin and the polyvinyl alcohol resin form separate domain units in the easily adhesive layer by combining and forming a phase separation structure generally referred to as a sea-island structure.
- the active methylene block isocyanate crosslinking agent is considered to promote and maintain the formation of the domain structure by crosslinking and aggregating the polyester resin and the polyvinyl alcohol resin.
- the polyester resin used for the easily bonding layer in the present invention is a copolymer formed by polycondensation of a dicarboxylic acid component and a diol component, and the material of the polyester film as the above-mentioned substrate as the dicarboxylic acid component and the diol component Can be used. From the viewpoint of improving the adhesion to the polyester film substrate, using a dicarboxylic acid component having the same or similar structure and properties as the dicarboxylic acid component in the polyester film as the substrate as the dicarboxylic acid component of the polyester resin preferable.
- aromatic dicarboxylic acid when employed as the dicarboxylic acid component of the polyester film, it is preferable to use the aromatic dicarboxylic acid as the dicarboxylic acid component of the polyester resin.
- aromatic dicarboxylic acid component terephthalic acid and isophthalic acid are most preferred.
- Other aromatic dicarboxylic acids may be added and copolymerized in a range of 10 mol% or less based on the total dicarboxylic acid component.
- glycol component of polyester resin it is preferable to use ethylene glycol and branched glycol as a structural component.
- ethylene glycol and branched glycol By having a branched structure, it is considered that it contributes to stress relaxation in the easily bonding layer, and it is possible to preferably exhibit adhesion.
- the branched glycol component include, for example, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-methyl-2-butyl-1,3.
- the lower limit of the molar ratio of the branched glycol component to the total glycol component is preferably 10 mol%, particularly preferably 20 mol%.
- the upper limit is preferably 80 mol%, more preferably 70 mol%, and particularly preferably 60 mol%.
- diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol or the like may be used in combination.
- the polyester resin used in the present invention is preferably a water-soluble or water-dispersible resin in terms of compatibility with the polyvinyl alcohol resin.
- a compound containing a hydrophilic group such as a sulfonate group or a carboxylate group.
- a dicarboxylic acid component having a sulfonate group is preferable from the viewpoint of imparting hydrophilicity while keeping the acid value of the polyester resin (A) low to control the reactivity with the crosslinking agent.
- dicarboxylic acid component having a sulfonate group for example, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthaleneisophthalic acid-2,7-dicarboxylic acid and 5- (4-sulfophenoxy) isophthalic acid or alkali thereof Metal salts can be mentioned, among which 5-sulfoisophthalic acid is preferred.
- the dicarboxylic acid component having a sulfonate group is preferably 1 to 15 mol%, more preferably 1.5 to 12 mol%, and still more preferably 2 to 10 mol% in the dicarboxylic acid component of the polyester resin (A).
- the dicarboxylic acid component having a sulfonate group is at least the above lower limit, it is suitable for the water-solubilization or water-dispersion of the polyester resin. Moreover, when the dicarboxylic acid component which has a sulfonate group is below the said upper limit, it is suitable for adhesiveness with a polyester film base material.
- the polyester resin has a smaller amount of carboxylic acid groups that are reactive groups with the active methylene block isocyanate crosslinking agent.
- carboxylic acid groups that are reactive with the crosslinking agent By reducing the number of carboxyl groups that are reactive with the crosslinking agent, the reactivity with the crosslinking agent is reduced, and as a result, the polyvinyl alcohol resin is not completely mixed with the polyvinyl alcohol resin, and the crosslinked polyvinyl alcohol resin is used. It is believed possible to maintain the domain structure formed.
- the acid value of the polyester resin is 20 KOHmg / g or less, preferably 15 KOHmg / g or less, more preferably 10 KOHmg / g or less, more preferably 8 KOHmg / g or less, still more preferably 5 KOHmg / g or less It is.
- the acid value of the polyester-based resin can be theoretically determined from the result of component analysis by the below-mentioned titration method or NMR.
- the amount of introduction of a carboxylate group for water-solubilizing or water-dispersion may be reduced, or a hydrophilic group other than a carboxylate group may be employed, It is preferable to lower the carboxylic acid terminal concentration of the polyester resin.
- the number average molecular weight of the polyester resin is preferably 5000 or more, more preferably 6000 or more, and still more preferably 10000 or more.
- the glass transition temperature of the polyester resin is not particularly limited, but is preferably 20 to 90 ° C., and more preferably 30 to 80 ° C. It is suitable to blocking resistance that a glass transition temperature is more than the above-mentioned minimum, and it is suitable to adhesiveness with a polyester film base material that a glass transition temperature is below the above-mentioned upper limit.
- the lower limit of the polyester resin content is preferably 30% by mass (the solid content is preferably 100% by mass, when the total of solid components of the polyester resin, polyvinyl alcohol resin and active methylene block isocyanate crosslinking agent in the coating solution is 100% by mass. More preferably, it is 40 mass%, More preferably, it is 50 mass%, Most preferably, it is 60 mass%. If the content of the polyester-based resin is 30% by mass or more, blocking does not easily occur even if water adheres to the film or the easily bonding layer, and there is no possibility that the peel strength is increased.
- the upper limit of the polyester resin content is preferably 99% by mass, more preferably 95% by mass, still more preferably 90% by mass, and particularly preferably 85% by mass.
- Adhesiveness with polyvinyl alcohol-type resin, such as a polarizer and a hydrophilic adhesive, as content rate of polyester-based resin is 99 mass% or less is favorable, and blocking occurs even if water adheres to a film or an easily bonding layer. There is no fear that the peeling strength will increase.
- the polyvinyl alcohol-based resin is not particularly limited.
- polyvinyl alcohol obtained by saponifying polyvinyl acetate; derivatives thereof; saponification of a copolymer with vinyl acetate and a monomer copolymerizable with the vinyl acetate; Modified polyvinyl alcohols obtained by acetalization, urethanization, etherification, grafting, phosphoric acid esterification, etc. of polyvinyl alcohol, and the like can be mentioned.
- Examples of the monomer include unsaturated carboxylic acids such as (anhydride) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; ⁇ -olefins such as ethylene and propylene (meth) Allyl sulfonic acid (soda), sodium sulfonate (monoalkyl malate), sodium alkyl sulfonate disulfonate, N-methylol acrylamide, alkali metal salts of acrylamido alkyl sulfonate, N-vinyl pyrrolidone, N-vinyl pyrrolidone derivatives, etc. . These polyvinyl alcohol resins may be used alone or in combination of two or more.
- unsaturated carboxylic acids such as (anhydride) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof
- polyvinyl alcohol resins used in the present invention include vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-vinyl butyral copolymer, ethylene-vinyl alcohol copolymer, and among these, vinyl alcohol-vinyl acetate copolymer And ethylene-vinyl alcohol copolymers are preferred.
- the degree of polymerization of the polyvinyl alcohol-based resin is not particularly limited, but the degree of polymerization is preferably 3,000 or less from the viewpoint of viscosity of the coating solution.
- the copolymerization ratio of vinyl alcohol is represented by the degree of saponification. 60 mol% or more and 85 mol% or less are preferable, 65 mol% or more and 83 mol% or less are more preferable, 68 mol% or more and 80 mol% or less are more preferable, and 70 mol% or more is more preferable. Less than 80 mol% is more preferable, 71 mol% or more and 78 mol% or less is still more preferable, and 73 mol% or more and 75 mol% or less is particularly preferable.
- the degree of saponification of the polyvinyl alcohol-based resin is 60 mol% or more, a crosslinked structure can be more suitably formed with the active methylene block isocyanate crosslinking agent, which is preferable. Further, when the degree of saponification of the polyvinyl alcohol-based resin is 85 mol% or less, compatibility with the polyester-based resin can be more suitably exhibited, which is preferable.
- the degree of saponification of the vinyl alcohol resin can be determined by consumption of alkali required for hydrolysis of copolymerized units such as vinyl acetate and composition analysis by NMR.
- the lower limit of the content of the polyvinyl alcohol resin is preferably 1% by mass (solid content), assuming that the total of solid content of polyester resin, polyvinyl alcohol resin and active methylene block isocyanate crosslinking agent in the coating solution is 100% by mass. Medium), more preferably 5% by mass, still more preferably 10% by mass, particularly preferably 15% by mass, and most preferably 20% by mass.
- Adhesiveness with polyvinyl alcohol-type resin, such as a polarizer and a hydrophilic adhesive is favorable in content rate of polyvinyl alcohol-type resin being 1 mass% or more, and even if water adheres to a film, blocking occurs. This is preferable because there is no fear that the peel strength will increase.
- the upper limit of the content of polyvinyl alcohol resin is preferably 60% by mass, more preferably 55% by mass, still more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass %.
- the content of the polyvinyl alcohol-based resin is 60% by mass or less, blocking does not easily occur even if water adheres to the film, and there is no possibility that the peel strength is increased, which is preferable.
- the active methylene block isocyanate crosslinking agent used to form the coating layer is preferably used to strengthen the coating layer and to provide stable adhesion and light releasability upon water adhesion. is there.
- an isocyanate compound which is a precursor of an active methylene block isocyanate crosslinking agent an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound etc. are mentioned, for example.
- isocyanate compound low molecular weight or high molecular weight diisocyanate or trivalent or higher polyisocyanate can be used.
- Specific isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1, 5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, phenylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane -4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-d
- the active methylene block isocyanate crosslinking agent in the film of the present invention can be synthesized by reacting the isocyanate group of the isocyanate compound with the active methylene compound.
- the active methylene compound for example, Meldrum's acid, dialkyl malonate (eg, dimethyl malonate, diethyl malonate, di n-butyl malonate, di-t-butyl malonate, di 2-ethylhexyl malonate, methyl malonate) n-butyl, ethyl n-butyl malonate, s-butyl methyl malonate, s-butyl ethyl malonate, t-butyl methyl malonate, t-butyl ethyl malonate, diethyl methyl malonate, dibenzyl malonate, malonate Diphenyl, benzyl methyl malonate, ethylphenyl malonate, t-butylphenyl malonate, isopropylidene malonate etc., alkyl acetoacetate (eg methyl acetoacetate, ethy
- the above-mentioned active methylene compounds can be used alone or in combination of two or more. it can.
- the active methylene compound to be used in combination dimethyl malonate and diethyl malonate are preferred in this case as being excellent in low-temperature curability also in this case.
- the active methylene block isocyanate crosslinking agent may, if necessary, be an existing blocking agent such as oxime type, pyrazole type, alcohol type, alkylphenol type, phenol type, mercaptan type, acid amide type, acid imide type, imidazole type, Urea-based, amine-based, imine-based, bisulfite blocking agents and the like can be used in combination in the blocking reaction.
- the existing blocking agents used in combination may be used alone or in combination of two or more.
- the compounding ratio of the active methylene block isocyanate crosslinking agent to the block isocyanate using the above-mentioned existing block agent is not limited in the upper limit, but the lower limit is preferably 0.5 or more in solid content ratio. Since the effect of the active methylene block isocyanate crosslinking agent is reduced if the content is less than the above lower limit, adhesion to a polyvinyl alcohol resin such as a polarizer or a hydrophilic adhesive is deteriorated, or water adheres to the film, It is not preferable because blocking occurs and peel strength increases.
- the active methylene block isocyanate crosslinking agent may be an active methylene blocking agent alone which does not use other existing blocking agents.
- the active methylene-blocked isocyanate crosslinking agent used in the film of the present invention preferably contains a hydrophilic site in order to enhance the compounding properties in the water-based paint, and as a method for adding a hydrophilic site to a blocked isocyanate compound, for example
- the method of making the hydrophilic compound which has an isocyanate group and active hydrogen of the isocyanate compound which is a body react is mentioned.
- hydrophilic compound which has active hydrogen used for the active methylene block isocyanate crosslinking agent used with the film of this invention a polyethylene glycol type compound, a carboxylic acid containing compound, a sulfonic acid containing compound, an amine containing compound etc. are mentioned, for example . These hydrophilic compounds may be used alone or in combination of two or more.
- polyethylene glycol compounds include monoalkoxy polyethylene glycol, polyethylene glycol, polyoxypropylene polyoxyethylene copolymer diol, polyoxypropylene polyoxyethylene block polymer diol and the like, among which monomethoxy polyethylene glycol, mono Monoalkoxy polyethylene glycols such as ethoxy polyethylene glycol are preferred.
- carboxylic acid group-containing compound examples include monohydroxycarboxylic acid, dihydroxycarboxylic acid, and derivatives thereof.
- carboxylic acid group-containing compounds monohydroxycarboxylic acid or dihydroxycarboxylic acid is preferable, and monohydroxycarboxylic acid is more preferable.
- carboxylic acid-containing compound examples include, for example, hydroxypipalic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid or polycaprolactone diol or polyether polyol using these as initiators And derivatives thereof, and salts thereof.
- sulfonic acid group-containing compounds include aminoethylsulfonic acid, ethylenediamino-propyl- ⁇ -ethylsulfonic acid, 1,3-propylenediamine- ⁇ -ethylsulfonic acid, and N, N-bis (2-hydroxyethyl) -2 Aminoethanesulfonic acid, and their salts.
- amine containing compound a hydroxyl-containing amino compound is mentioned. Specifically, dimethylethanolamine, diethylethanolamine and the like can be mentioned.
- the active methylene block isocyanate crosslinking agent used in this invention is used by the design which is made to react in a drying process and a film forming process, and to improve the performance of a coating layer. It can be inferred that in the finished coating layer, the unreacted product of the active methylene-blocked isocyanate crosslinking agent, the compound after reaction, or a mixture thereof is present.
- active methylene-blocked isocyanate crosslinking agent in the present invention may be used alone or in combination of two or more.
- the polyester resin, the polyvinyl alcohol resin and the active methylene block isocyanate crosslinking agent are combined, even if the organic tin catalyst is not contained, the adhesion to the polarizer and the functional layer is excellent, and dew condensation water adheres. Even an easily adhesive layer in which blocking does not occur can be generated. Although this reason is not necessarily clear, since transesterification proceeds when using an active methylene block isocyanate crosslinking agent, the cross-linked network structure is densely formed due to the difference in reactivity with the urethanation reaction that occurs with existing block isocyanates. It is guessed that it was because.
- the lower limit of the content of the active methylene block isocyanate crosslinking agent is preferably 0.1 mass when the total of solid content of the polyester resin, polyvinyl alcohol resin and active methylene block isocyanate crosslinking agent in the coating solution is 100% by mass. % (In solid content), more preferably 1% by mass, still more preferably 2% by mass, particularly preferably 3% by mass, and most preferably 4% by mass. If the content of the active methylene block isocyanate crosslinking agent is 0.1% by mass or more, blocking does not occur easily even if water adheres to the film or the easily bonding layer, and there is no possibility that the peel strength is increased.
- the upper limit of the content of the active methylene-blocked isocyanate crosslinking agent is preferably 60% by mass, more preferably 40% by mass, still more preferably 20% by mass, particularly preferably 15% by mass, and most preferably It is 9.4 mass%. Adhesiveness with functional layers, such as an adhesive bond layer, is favorable in the content rate of an active methylene block isocyanate crosslinking agent being 60 mass% or less, and preferable.
- the compounding ratio of the polyester resin to the polyvinyl alcohol resin is preferably 1 to 30 in mass ratio, and more preferably 2 to 6. It is suitable for adhesiveness with a polyester film base material that the said compounding ratio is one or more, and suitable for adhesiveness with polyvinyl alcohol-type resin layers, such as a polarizer and an adhesive agent, as it is 30 or less.
- the sum of the polyester resin and the polyvinyl alcohol resin with respect to the active methylene block isocyanate crosslinking agent is preferably 3 to 20 by mass, and more preferably 8 to 15 by mass.
- the compounding ratio is 3 or more, it is suitable for exhibiting the adhesive effect by the binder resin component, and when it is 20 or less, it is suitable for the adhesive effect by phase separation.
- the easily bonding layer in the present invention exhibits high adhesion equivalent to that of triacetyl cellulose to a polarizer and an aqueous adhesive, particularly a polyvinyl alcohol-based polarizer and an aqueous adhesive.
- the residual area after one-time peeling is preferably 90% or more, more preferably 95% or more, and still more preferably 100% with respect to the water-based adhesive according to the adhesion test described later.
- Organotins in particular tributyltin, are listed in the “List of chemicals suspected to have endocrine disrupting effects” published by the Ministry of the Environment in 2000, and are designated as substances for which risk is to be evaluated in priority, so their use It is, of course, necessary to avoid the use of organic tin which is not described in such a list as much as possible, and to reduce the risk to the human body and the environment as much as possible. It is preferable not to use organotin intentionally as a crosslinking and curing catalyst of an easily bonding layer for the above-mentioned reason. However, it does not deny the content of 100 ppm or less which is present in the easily bonding layer without intentional use.
- substantially free of organotin as a curing catalyst for the composition in the easily adhesive layer means that the amount of organotin is 100 ppm or less based on the total mass of the easily adherent layer solid content. means.
- the above-mentioned active methylene block isocyanate crosslinking agent is contained in the coating solution for forming the easily adhesive layer, whereby the easily adhesive polyester film is produced without crosslinking even when it is non-catalytic, and is rapidly crosslinked and cured.
- zinc compounds such as zinc acetylacetonate, zinc propionate, zinc octanoate, titanium compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, zirconium tetraisopropoxide, zirconium tetra
- zirconium compounds such as -n-butoxide
- bismuth compounds such as bis (acetylacetone) bismuth and bismuth 2-ethylhexanoate
- the measurement of the content of the organotin catalyst in the easily adhesive layer was performed as follows. Wipe off the easy-adhesion layer on the corresponding surface of the film using a solvent such as MEK.
- additives in the easily adhesive layer of the present invention, known additives as long as the effects of the present invention are not impaired, such as surfactants, antioxidants, heat stabilizers, weather stabilizers, ultraviolet light absorbers, organic lubricants, Pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents and the like may be added. However, those with high environmental toxicity are excluded.
- the particles to be contained in the easily adhesive layer in the present invention are, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay and the like, or a mixture thereof, and further, other general Inorganic particles such as calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride etc. in combination with inorganic particles, etc., styrene type, acrylic type, melamine type, benzoguanamine type, silicone type etc. Organic polymer particles and the like can be mentioned.
- the average particle diameter (average particle diameter based on the number according to SEM, hereinafter the same) of the property particles in the easily adhesive layer is preferably 0.04 to 2.0 ⁇ m, more preferably 0.1 to 1.0 ⁇ m.
- the average particle size of the inert particles is 0.04 ⁇ m or more, the formation of asperities on the film surface becomes easy, so that the handling properties such as the slipperiness and the winding property of the film are improved, and the bonding properties are improved. Processability is good and preferable.
- the average particle diameter of the inactive particles is 2.0 ⁇ m or less, it is preferable that the particles do not easily come off.
- the particle concentration in the easily adhesive layer is preferably 1 to 20% by mass in the solid component.
- the thickness of the easy adhesion layer can be appropriately set in the range of 0.001 to 2.00 ⁇ m, but in order to achieve both processability and adhesiveness, the range of 0.01 to 1.00 ⁇ m is preferable. More preferably, it is 0.02 to 0.80 ⁇ m, further preferably 0.05 to 0.50 ⁇ m. Adhesiveness is favorable for the thickness of an easily bonding layer to be 0.001 micrometer or more, and it is preferable. It is hard to produce blocking that the thickness of an easily bonding layer is 2.00 micrometers or less, and is preferable.
- polyester films having an easily adhesive layer containing a polyester resin, a polyvinyl alcohol resin and a crosslinking agent there are many films satisfying the blocking resistance when left in an environment containing ordinary water vapor.
- liquid water may adhere to the surface of the film or the surface of the adhesive layer, and the polyester resin, polyvinyl alcohol resin, and crosslinking agent at that time.
- the polyester film having an easy-adhesion layer containing B had a problem of causing blocking.
- the easily adhesive polyester film of the present invention is not only resistant to blocking when left in an environment containing ordinary water vapor, but also the environmental temperature of the easily adhesive polyester film transported between the room and the outdoors in winter.
- the peeling force after water adhesion by a measurement method described later is 2 N / cm or less. More preferably, it is 1.5 N / cm or less, still more preferably 1 N / cm or less, particularly preferably 0.5 N / cm or less, and most preferably 0.3 N / cm or less. Although it is preferable that the peeling force after water adhesion is small, it may be 0.01 N / cm or more, and may be 0.02 N / cm or more.
- Such a small post-deposition water peeling force is a phenomenon that appears specifically when using an active methylene-blocked isocyanate crosslinking agent, and a similar effect is expected from a blocked isocyanate crosslinking agent that uses only other blocking agents. hard.
- the active methylene block isocyanate crosslinking agent is used, the small peeling force after water adhesion is obtained particularly effectively when the organic tin curing catalyst is not used.
- an easily adhesive layer formed by curing a composition containing a polyester resin, a polyvinyl alcohol resin and an active methylene block isocyanate crosslinking agent may be laminated on at least one side of a polyester film, as a matter of course
- the easily adhesive layer may be laminated on both sides.
- the said easily bonding layer may be laminated
- the easy-adhesion layer formed by curing the composition containing the polyester resin, polyvinyl alcohol resin and active methylene block isocyanate crosslinking agent in the present invention is a polarizer comprising a polyvinyl alcohol film and a dichroic material such as iodine. And adhesion to a hydrophilic adhesive such as polyvinyl alcohol-based resin, but it also has certain adhesion and adhesion to other functional layers such as a hard coat layer. .
- the expression that the easy-adhesion layer is formed by curing a composition containing a polyester resin, a polyvinyl alcohol resin and an active methylene block isocyanate crosslinking agent is used after the crosslinking and curing.
- the adhesive layer it is thought that the hydroxyl group of polyvinyl alcohol mainly reacts with the isocyanate group to crosslink and cure, but it is extremely difficult to accurately express the composition and chemical structure after the crosslinking and cure. It is because it is impossible. Accordingly, many of polyester resins, polyvinyl alcohol resins and active methylene block isocyanate crosslinking agents do not exist in the same chemical structure in the crosslinked and cured easily adhesive layer.
- PET film Polyethylene terephthalate
- the unstretched PET sheet may have a single-layer structure or a multi-layer structure by a co-extrusion method.
- the resulting unstretched PET sheet is uniaxially stretched or biaxially stretched to cause crystal orientation.
- the film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially stretched PET film, and then the end of the film is gripped with a clip Then, it is led to a hot air zone heated to 80 to 180 ° C. and stretched 2.5 to 5.0 times in the width direction.
- uniaxial stretching the film is stretched 2.5 to 5.0 times in a tenter. After drawing, the heat treatment zone is introduced and heat treatment is performed to complete crystal orientation.
- the longitudinal direction or the longitudinal direction of the film indicates the machine flow direction of the manufacturing process.
- the film when the film is described in the lateral direction or width direction, it points in a direction perpendicular to the machine flow direction.
- the lower limit of the temperature of the heat treatment zone is preferably 170 ° C, more preferably 180 ° C.
- the upper limit of the temperature of the heat treatment zone is preferably 230 ° C., more preferably 200 ° C.
- the temperature of the heat treatment zone is 230 ° C. or less, the physical properties of the film are not likely to be reduced, which is preferable. It is more preferable to heat-process at 200 degrees C or less in order to suppress a refractive index fall in the manufacturing process which uses a polarizer protective film as an application.
- the easy adhesion layer can be provided after the production of the film or in the production process.
- coating this coating liquid to a PET film can use arbitrary well-known methods. For example, reverse roll coating method, gravure coating method, kiss coating method, die coating method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, pipe coating method, impregnation coating method, curtain coating method, etc. are mentioned. Be These methods can be applied alone or in combination.
- the easily adhesive polyester film of the present invention can be suitably used as a polarizer protective film.
- a polarizer protective film is disposed on both sides of a polarizer to form a polarizing plate, but the polarizer protective film on at least one side of the polarizer is the above-mentioned easy-adhesive polyester film for polarizer protection.
- the other polarizer protective film may be the easily adhesive polyester film of the present invention, and it is also preferable to use a film having no birefringence as typified by a triacetyl cellulose film, an acrylic film, and a norbornene film. .
- a polarizer for example, a polyvinyl alcohol-based film containing a dichroic material such as iodine is mentioned.
- the polarizer protective film is laminated to the polarizer directly or through an adhesive layer, but from the viewpoint of improving adhesion, it is preferable to laminate through an adhesive.
- the easily bonding layer of the present invention is preferably disposed on the polarizer surface or the adhesive layer surface.
- a polyvinyl alcohol-based film is dyed and adsorbed with iodine or a dichroic material, uniaxially stretched in a boric acid aqueous solution, and kept in a stretched state
- cleaning and drying is mentioned.
- the stretching ratio of uniaxial stretching is usually about 4 to 8 times.
- Polyvinyl alcohol is preferred as the polyvinyl alcohol-based film, and "Kuraray Vinylon” (manufactured by Kuraray Co., Ltd.), “Toceroviniron” (manufactured by Tohtoro Co., Ltd.), and “Nichigo Vinylon” (Nippon Synthetic Chemical Co., Ltd.) Commercial products, such as] can be utilized.
- the dichroic material may, for example, be iodine, a disazo compound or a polymethine dye.
- the adhesive to be applied to the polarizer is preferably a water-based adhesive, that is, one in which an adhesive component is dissolved in water or one dispersed in water, from the viewpoint of thinning the adhesive layer.
- a composition using a polyvinyl alcohol resin, a urethane resin or the like as the main component, and an isocyanate compound, an epoxy compound or the like as needed can be used to improve the adhesiveness. 10 micrometers or less are preferable, as for the thickness of an adhesive bond layer, 5 micrometers or less are more preferable, and 3 micrometers or less are more preferable.
- polyvinyl alcohol-based resin used as the main component of the adhesive, in addition to partially saponified polyvinyl alcohol and completely saponified polyvinyl alcohol, carboxyl group modified polyvinyl alcohol, acetoacetyl group modified polyvinyl alcohol, methylol group modified polyvinyl alcohol, amino group modified A modified polyvinyl alcohol resin such as polyvinyl alcohol may be used.
- the concentration of the polyvinyl alcohol resin in the adhesive is preferably 1 to 10% by mass, and more preferably 2 to 7% by mass.
- a polyvinyl alcohol aqueous solution (PVA 117 manufactured by Kuraray) adjusted to a solid content concentration of 3% by mass is formed on the surface of the adhesion layer of the easily adhesive polyester film or laminated polyester film described later to a thickness of 200 nm of the polyvinyl alcohol resin layer after drying.
- the solution was applied with a wire bar and dried at 80.degree. C. for 5 minutes.
- the red dye so that determination might become easy was used.
- PVA adhesion On the easily adhesive layer of the easily adhesive polyester film obtained in the example or the resin coating layer of the laminated polyester film, the PVA layer described in the item of formation of the above-mentioned PVA layer was formed. Based on the description of JIS K 5400: 1990, Section 8.5.1, the polyester film for easy adhesion on which PVA is formed is determined for the adhesion between the PVA layer and the base film.
- a coating solution for forming a hard coat layer of the following composition is applied to the easily adhesive layer of the easily adhesive polyester film produced in the examples described later or the resin coating layer of the laminated polyester film using a # 10 wire bar, 70 ° C. Dry for 1 minute to remove the solvent.
- the film coated with the hard coat layer was irradiated with ultraviolet light of 300 mJ / cm 2 using a high pressure mercury lamp to obtain a polarizer protective film having a hard coat layer with a thickness of 5 ⁇ m.
- Hard coat adhesion passes 50 (%) or more.
- Hard coat adhesion (%) ⁇ 1- (number of peeled squares / 100) ⁇ ⁇ 100
- the easily adhesive polyester film manufactured in the examples described later is cut into 10 cm in the width direction and 1.5 cm in the longitudinal direction.
- An optional film of 1.5 cm in the longitudinal direction and 1.5 cm in the width direction is superimposed on the end of the easy adhesion layer side of the cut film.
- the optional film is preferably a general polyester film without a coating layer such as an easy adhesion layer, etc., and may be a release paper, etc.
- Easy adhesion layer side of the opposite end Drop 0.03 g of water drops on top of the After that, the easily adhesive layer surfaces of the film cut into 10 cm in the width direction and 1.5 cm in the longitudinal direction are superposed, and rolled uniformly so that air does not enter from the side where the water drops are dropped to the side where the film is superimposed. The sample is then placed in the oven for 6 hours.
- the removed sample was taken out of the 1.5 cm square film sandwiched between the parts where water was not attached as the handle of the chuck, and at room temperature according to JIS K 6854-3: 1999, a tensile tester [(stock A peel test was conducted at a tensile speed of 0.3 m / min using an autograph manufactured by Shimadzu Corporation, product number AGS-X], and the peel strength (N / cm) was measured 5 times and averaged.
- Each film sample is cut into two 3.5 cm squares (length x width 3.5 cm each), two sheets are stacked so that the adhesion layer side of each sample is in contact, and the film is pressed at a pressure of 0.5 MPa in the direction perpendicular to the surface In an environment of 30 ° C. and 80% for 1 day. Thereafter, the samples were taken out and two samples were peeled off to evaluate the condition of each film.
- copolyester resin (A-1) was pale yellow and transparent.
- the reduced viscosity of the copolyester resin (A-1) was measured to be 0.70 dl / g.
- the glass transition temperature by DSC was 40.degree.
- Copolyester resin (A-2) having another composition was obtained in the same manner.
- the composition (mol% ratio) and other characteristics measured by 1 H-NMR for these copolyester resins are shown in Table 1.
- polyvinyl alcohol resin (B-2) was used instead of polyvinyl alcohol resin (B-1) to prepare an aqueous solution, which was designated as (Bw-2).
- the degree of saponification of the polyvinyl alcohol resin (B-1) (B-2) is shown in Table 2.
- the viscosity of the obtained polyisocyanate at 25 ° C. was 25,000 mPa ⁇ s, the isocyanate group content was 19.9 mass%, the number average molecular weight was 1080, and the average number of isocyanate groups was 5.1. Thereafter, NMR measurement confirmed the presence of a urethane bond, an allophanate bond, and an isocyanurate bond.
- a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blow-in pipe and a dropping funnel is brought into a nitrogen atmosphere, 100 parts by mass of the polyisocyanate obtained above, and a methoxypolyethylene glycol having a number average molecular weight of 400 42. 3 parts and 76.6 parts of dipropylene glycol dimethyl ether were charged and maintained at 80 ° C. for 6 hours.
- reaction temperature is cooled to 60 ° C., and 72 parts by mass of diethyl malonate and 0.88 parts by mass of a 28% methanol solution of sodium methylate are added and maintained for 4 hours, then 0.86 parts by mass of 2-ethylhexyl acid phosphate Was added.
- reaction solution temperature was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketoxime was dropped.
- the infrared spectrum of the reaction solution was measured to confirm that the absorption of the isocyanate group disappeared, and an oxime-blocked isocyanate crosslinking agent (C-2) having a solid content of 75% by mass was obtained.
- the infrared spectrum of the reaction solution was measured, and it was confirmed that the absorption at a wavelength of 2200 to 2300 cm -1 disappeared.
- the mixture was allowed to cool to 60 ° C., and 567 parts by mass of ion exchange water was added to obtain a carbodiimide crosslinking agent (C-3) having a solid content of 40% by mass.
- Epoxy based crosslinking agent As an epoxy-based crosslinking agent, Denacol EX-521 (solid content concentration 100%) manufactured by Nagase ChemteX Corp. was used (epoxy-based crosslinking agent (C-4)).
- Example 1 Preparation of Coating Solution
- the following coating agents are mixed, and the solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1) / active methylene block isocyanate crosslinking agent (C-1) is The coating solution which becomes 92/3/5 was created.
- the aqueous polyester dispersion uses an aqueous dispersion (Aw-1) in which a polyester resin having an acid value of 2 KOH mg / g is dispersed, and an aqueous polyvinyl alcohol solution has an aqueous solution in which polyvinyl alcohol having a degree of saponification of 88 mol% is dissolved. (Bw-1) was used.
- Polyester water dispersion (Aw-1) 33.59% by mass Polyvinyl alcohol aqueous solution (Bw-1) 1.46 mass% Blocked isocyanate crosslinking agent (C-1) 0.40% by mass 0.49 mass% of particles (Silica sol with an average particle size of 450 nm, solid concentration 4% by mass) Particles 1.29% by mass (Silica sol with an average particle size of 40 nm, solid concentration 40% by mass) 0.15 mass% of surfactant (Silicone-based, solid content concentration 10% by mass)
- It dried at 135 degreeC under pressure reduction of 133 Pa for 6 hours. Then, it was supplied to an extruder, and melt extruded into a sheet at about 280 ° C., followed by rapid cooling adhesion solidification on a rotary cooling metal roll kept at a surface temperature of 20 ° C. to obtain an unstretched PET sheet.
- the coating solution was applied to one side of a PET film by roll coating, and then dried at 80 ° C. for 15 seconds.
- the film is stretched 4.0 times in the width direction at 150 ° C. with a tenter, and heated at a heat setting temperature of 180 ° C. for 0.5 seconds, with the length in the width direction of the film fixed.
- the film was subjected to relaxation treatment in the width direction of 3% for 10 seconds to obtain a highly adhesive polyester film having a thickness of 100 ⁇ m.
- the evaluation results are shown in Table 3.
- Table 3 shows the results of evaluating the above-described polyester film for each of the above-described items.
- Example 2 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1) / active methylene block isocyanate crosslinking agent (C-1) becomes 83/5/12 by mixing the following coating agents An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the above was changed.
- Polyester water dispersion (Aw-1) 30.34 mass% Polyvinyl alcohol aqueous solution (Bw-1) 2.67 mass% Blocked isocyanate crosslinking agent (C-1) 0.95% by mass 0.49 mass% of particles (Silica sol with an average particle size of 450 nm, solid concentration 4% by mass) 1.25 mass% of particles (Silica sol with an average particle size of 40 nm, solid concentration 40% by mass) 0.15 mass% of surfactant (Silicone-based, solid content concentration 10% by mass)
- Example 3 An easily adhesive polyester film was obtained in the same manner as in Example 2, except that the polyester resin was changed to (A-2) and the polyester water dispersion was changed to (Aw-2).
- Example 4 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to 55/20/25. In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 5 An easily adhesive polyester film was obtained in the same manner as in Example 4, except that the polyvinyl alcohol resin (B-2) and the polyvinyl alcohol aqueous solution (Bw-2) were changed.
- Example 6 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to 45/15/40. In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 7 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to be 56/37/7. In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 8 Except that the solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to be 80/15/5 In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 9 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to be 65/27/8. In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 10 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed so as to be 71/18/11. In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 11 Except that the solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to 75/16/9 In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 12 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to 45/45/10. In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 13 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed so as to be 40/30/30 In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- Example 14 The solid content ratio of polyester resin (A-1) / polyvinyl alcohol resin (B-1)) / active methylene block isocyanate crosslinking agent (C-1) was changed to 30/5/65. In the same manner as in Example 1, a readily adhesive polyester film was obtained.
- blocking does not occur even when liquid dew condensation water adheres, and the adhesion to a functional layer such as a polarizer or an adhesive layer is excellent, and the organic tin catalyst is not used and the environment is also excellent. It has become possible to provide an easily adhering polyester film that can be suitably used in optical applications, particularly in polarizer protective film applications.
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Abstract
Description
1. 少なくとも片面に易接着層を有するポリエステルフィルムであって、前記易接着層がポリエステル系樹脂、ポリビニルアルコール系樹脂及び活性メチレンブロックイソシアネート架橋剤を含有する組成物が硬化されてなり、易接着層中の組成物の硬化触媒として有機スズを実質的に含まず、水付着後剥離力が2N/cm以下である易接着性ポリエステルフィルム。
2. 偏光子保護フィルムとして使用される上記第1に記載の易接着性ポリエステルフィルム。
本発明で基材として用いるポリエステルフィルムは、主としてポリエステル樹脂より構成されるフィルムである。ここで、「主としてポリエステル樹脂より構成されるフィルム」とは、ポリエステル樹脂を50質量%以上含有する樹脂組成物から形成されるフィルムであることを意味する。他のポリマーとブレンドする場合は、ポリエステル樹脂が50質量%以上含有していることを意味し、他のモノマーと共重合する場合は、ポリエステル構造単位を50モル%以上含有することを意味する。好ましくは、ポリエステルフィルムは、ポリエステル樹脂を90質量%以上、より好ましくは95質量%以上、更に好ましくは100質量%含有する。
本発明におけるポリエステルフィルムは、偏光子及びその片面又は両面に設けられる水系接着剤等のポリビニルアルコール系樹脂層との接着性を向上させるために、その少なくとも片面に、酸価が20KOHmg/g以下であるポリエステル系樹脂、けん化度が60~85モル%であるポリビニルアルコール系樹脂、及び、活性メチレンブロックイソシアネート架橋剤を含有する樹脂組成物から形成される易接着層が積層されていることが好ましい。易接着層はポリエステルフィルムの両面に設けてもよく、ポリエステルフィルムの片面のみに設け、他方の面には異種の樹脂被覆層を設けてもよい。
(ポリエステル系樹脂)
本発明における易接着層に用いるポリエステル系樹脂は、ジカルボン酸成分とジオール成分とが重縮合してなる共重合体であり、ジカルボン酸成分及びジオール成分としては前述の基材としてのポリエステルフィルムの材料を用いることができる。ポリエステルフィルム基材との接着性を向上させる観点から、基材としてのポリエステルフィルム中のジカルボン酸成分と同一又は類似する構造・性質を有するジカルボン酸成分をポリエステル系樹脂のジカルボン酸成分として用いることが好ましい。よって、例えば、ポリエステルフィルムのジカルボン酸成分として芳香族ジカルボン酸が採用される場合は、ポリエステル系樹脂のジカルボン酸成分として芳香族ジカルボン酸を使用することが好ましい。そのような芳香族ジカルボン酸成分としては、テレフタル酸およびイソフタル酸が最も好ましい。全ジカルボン酸成分に対し、10モル%以下の範囲で、他の芳香族ジカルボン酸を加えて共重合させてもよい。
ポリビニルアルコール系樹脂は、特に限定されないが、例えば、ポリ酢酸ビニルをけん化して得られたポリビニルアルコール;その誘導体;更に酢酸ビニルと共重合性を有する単量体との共重合体のけん化物;ポリビニルアルコールをアセタール化、ウレタン化、エーテル化、グラフト化、リン酸エステル化等した変性ポリビニルアルコール;などが挙げられる。前記単量体としては、(無水)マレイン酸、フマール酸、クロトン酸、イタコン酸、(メタ)アクリル酸等の不飽和カルボン酸及びそのエステル類;エチレン、プロピレン等のα-オレフィン、(メタ)アリルスルホン酸(ソーダ)、スルホン酸ソーダ(モノアルキルマレート)、ジスルホン酸ソーダアルキルマレート、N-メチロールアクリルアミド、アクリルアミドアルキルスルホン酸アルカリ塩、N-ビニルピロリドン、N-ビニルピロリドン誘導体等が挙げられる。これらポリビニルアルコール系樹脂は1種のみ用いても良いし2種以上を併用してもよい。
本発明においては、塗布層の形成に使用する活性メチレンブロックイソシアネート架橋剤は、塗布層を強固なものとし、安定した密着性や水付着時の軽剥離性を付与するために好ましく用いられるものである。
有機スズ、中でもトリブチルスズは環境省が2000 年に発表した「内分泌攪乱作用を有すると疑われる化学物質のリスト」に記載され、そのリスクを優先して評価する物質に指定されているので、その使用を避けることは勿論であるが、今後、このようなリストに記載されていない有機スズであっても極力使用を避け、人体や環境に及ぼすリスクを可及的に減少させる必要がある。有機スズは上記理由から易接着層の架橋・硬化触媒として意図的に用いないことが好ましい。ただし、意図的に用いずに易接着層中に存在する100ppm以下の含有を否定するものではない。即ち、本発明において、「易接着層中の組成物の硬化触媒として有機スズを実質的に含まず」とは、易接着層固形分全体の質量に対して有機スズが100ppm以下であることを意味する。本発明においては、易接着層形成用の塗布液に上記の活性メチレンブロックイソシアネート架橋剤を含有していることにより、無触媒でも加熱時に速やかに架橋・硬化し、製造された易接着性ポリエステルフィルムは、液体の水の存在下であってもブロッキングの問題をおこすおそれがないが、必要に応じてスズ以外の環境的に問題のない触媒を使用してもよい。例えば、それらの触媒としては、亜鉛アセチルアセトナート、プロピオン酸亜鉛、オクタン酸亜鉛などの亜鉛系化合物、テトライソプロピルチタネート、テトラ-n-ブチルチタネートなどのチタン系化合物、ジルコニウムテトライソプロポキシド、ジルコニウムテトラ-n-ブトキシドなどのジルコニウム系化合物、ビス(アセチルアセトン)ビスマス、2-エチルヘキサン酸ビスマスなどのビスマス系化合物、アミンなどが挙げられる。易接着層中の有機スズ触媒の含有量の測定は次のように行った。フィルムの該当面の易接着層を拭き取り可能な溶剤、例えばMEKなどを用いて拭き取り、拭き取り完了は該当面の易接着層表面の蛍光X線測定を行い、Siのピーク強度が拭き取り前の100分の1以下になった場合とした。そして、拭き取り前後のA4フィルムの重量を測定し、その差分を該当面の易接着層の乾燥後塗布量とした。該当フィルムの易接着層を溶出しTsuyoshi Kawakami et al,YAKUGAKU ZASSHI 130(2)223-235(2010)に準じた方法で最終的に易接着層中の有機スズ触媒の含有量を算出した。
本発明の易接着層中には、本発明の効果を阻害しない範囲において公知の添加剤、例えば界面活性剤、酸化防止剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、顔料、染料、有機または無機の粒子、帯電防止剤、核剤等を添加しても良い。しかしながら、環境毒性が高いものは除外される。
本発明の偏光子保護用易接着性ポリエステルフィルムの製造方法について、ポリエチレンテレフタレート(以下、PETと略記する)フィルムを例にして説明するが、当然これに限定されるものではない。
本発明の易接着性ポリエステルフィルムは、偏光子保護フィルムとして好適に用いられることができる。一般に、偏光子の両面に偏光子保護フィルムを配して偏光板が形成されるが、偏光子の少なくとも一方の面の偏光子保護フィルムが前記偏光子保護用易接着性ポリエステルフィルムであることが好ましい。他方の偏光子保護フィルムは、本発明の易接着性ポリエステルフィルムであっても良いし、トリアセチルセルロースフィルムやアクリルフィルム、ノルボルネン系フィルムに代表されるような複屈折が無いフィルムを用いることも好ましい。
JIS K7121:2012に準拠し、示差走査熱量計(セイコーインスツルメンツ製、DSC6200)を使用して、樹脂サンプル10mgを25~300℃の温度範囲にわたって20℃/minで昇温させ、DSC曲線から得られた補外ガラス転移開始温度をガラス転移温度とした。
ポリエステル樹脂0.03gをテトラヒドロフラン 10ml に溶かし、GPC-LALLS装置低角度光散乱光度計 LS-8000(東ソー株式会社製、テトラヒドロフラン溶媒、リファレンス:ポリスチレン)を用い、カラム温度30℃、流量1ml/分、カラム(昭和電工社製shodex KF-802、804、806)を用い、数平均分子量を測定した。
ポリエステル樹脂を重クロロホルムに溶解し、ヴァリアン社製核磁気共鳴分析計(NMR)ジェミニ-200を用いて、1H-NMR分析を行ってその積分比より各組成のモル%比を決定した。
1g(固形分)のポリエステル試料を30mlのクロロホルムまたはジメチルホルムアミドに溶解し、フェノールフタレインを指示薬として0.1Nの水酸化カリウムエタノール溶液で滴定して、試料1g当たりのカルボキシル基を中和するのに必要なKOHの量(mg)を求めた。
JIS K6726:1994に準じて水酸化ナトリウムを用いて、ポリビニルアルコール樹脂の残存酢酸基(モル%)を定量し、その値をけん化度(モル%)とした。同サンプルについて3度測定し、その平均値をけん化度(モル%)とした。
後述する易接着性ポリエステルフィルム又は積層ポリエステルフィルムの易接着層表面に、固形分濃度3質量%に調整したポリビニルアルコール水溶液(クラレ製 PVA117)を、乾燥後のポリビニルアルコール樹脂層の厚みが、200nmになるようにワイヤーバーで塗布し、80℃で5分間乾燥した。ポリビニルアルコール水溶液には、判定が容易となるよう赤色染料を加えたものを使用した。
実施例で得られた易接着性ポリエステルフィルムの易接着層上又は積層ポリエステルフィルムの樹脂被覆層に、前述のPVA層の形成の項目で記述したPVA層を形成した。PVAを形成した易接着用ポリエステルフィルムをJIS K5400:1990の8.5.1の記載に準拠し、PVA層と基材フィルムとの密着性を求める。
PVA密着性(%)={1-(剥がれた升目の数/100)}×100
後述する実施例で製造した易接着性ポリエステルフィルムの易接着層上又は積層ポリエステルフィルムの樹脂被覆層に、下記組成のハードコート層形成用塗布液を#10ワイヤーバーを用いて塗布し、70℃で1分間乾燥し、溶剤を除去した。次いで、ハードコート層を塗布したフィルムに高圧水銀灯を用いて300mJ/cm2の紫外線を照射し、厚み5μmのハードコート層を有する偏光子保護フィルムを得た。
・ハードコート層形成用塗布液
メチルエチルケトン 65.00質量%
ジペンタエリスリトールヘキサアクリレート 27.20質量%
(新中村化学製A-DPH)
ポリエチレンジアクリレート 6.80質量%
(新中村化学製A-400)
光重合開始剤 1.00質量%
(チバスペシャリティーケミカルズ社製イルガキュア184)
実施例で得られたポリエステルフィルムの易接着層上に、前述のハードコート層の形成の項目で記述したハードコート層を形成した。ハードコートを形成した易接着用ポリエステルフィルムをJIS K5400:1990の8.5.1の記載に準拠し、ハードコート層と基材フィルムとの密着性を求める。
ハードコート密着性(%)={1-(剥がれたマス目の数/100)}×100
後述する実施例で製造した易接着性ポリエステルフィルムを幅方向に10cm、長手方向に1.5cmにカットする。カットしたフィルムの易接着層面の端部に、幅方向に1.5cm長手方向に1.5cmの任意のフィルムを重ねる。(前記任意のフィルムは、特に易接着層などのコーティング層のない一般的なポリエステルフィルムなどが好適であり、離型紙のようなものであってもよい。)反対側の端部の易接着層面の上に、水滴を0.03g垂らす。その後幅方向に10cm、長手方向に1.5cmにカットしたフィルムの易接着層面同士を重ね合わせ、水滴を落とした側からフィルムを重ねた側へ空気が入らないように均一にロールをかける。その後、サンプルをオーブンに6時間投入する。取り出したサンプルは、間に挟んだ1.5cm角のフィルムを外して水が付着していない部分をチャックの持ち手とし、JIS K 6854-3:1999に準じ室温下で引張試験機〔(株)島津製作所製オートグラフ、品番AGS-X〕を用いて引っ張り速度0.3m/minで剥離試験を行い、剥離力(N/cm)を5回測定し平均をとった。
各フィルムサンプルを3.5cm角(タテ×ヨコそれぞれ3.5cm)に2枚カットし、各サンプルの易接着層面が接するように2枚重ね、フィルムを面に垂直な方向に0.5MPaの圧をかけた状態で、30℃80%の環境下1日放置する。その後サンプルを取り出し2枚のサンプルをはがしそれぞれのフィルムの状態を評価した。実施例比較例で作成した全てのサンプルにおいて、2枚のフィルムが力を加えずにはがれ、接着痕等はまったく見られなかった。
攪拌機、温度計、および部分還流式冷却器を具備するステンレススチール製オートクレーブに、ジメチルテレフタレート194.2質量部、ジメチルイソフタレート184.5質量部、ジメチル-5-ナトリウムスルホイソフタレート14.8質量部、ジエチレングリコール233.5質量部、エチレングリコール136.6質量部、およびテトラ-n-ブチルチタネート0.2質量部を仕込み、160℃から220℃の温度で4時間かけてエステル交換反応を行なった。次いで255℃まで昇温し、反応系を徐々に減圧した後、30Paの減圧下で1時間30分反応させ、共重合ポリエステル樹脂(A-1)を得た。得られた共重合ポリエステル樹脂(A-1)は、淡黄色透明であった。共重合ポリエステル樹脂(A-1)の還元粘度を測定したところ,0.70dl/gであった。DSCによるガラス転移温度は40℃であった。
攪拌機、温度計と還流装置を備えた反応器に、ポリエステル樹脂(A-1)15質量部、エチレングリコールn-ブチルエーテル15質量部を入れ、110℃で加熱、攪拌し樹脂を溶解した。樹脂が完全に溶解した後、水70質量部をポリエステル溶液に攪拌しつつ徐々に添加した。添加後、液を攪拌しつつ室温まで冷却して、固形分15質量%の乳白色のポリエステル水分散体(Aw-1)を作製した。同様にポリエステル樹脂(A-1)の代わりにポリエステル樹脂(A-2)を使用して、水分散体を作製し、ポリエステル水分散体(Aw-2)とした。
攪拌機と温度計を備えた容器に、水90質量部を入れ、攪拌しながら重合度500のポリビニルアルコール樹脂(クラレ製)(B-1)10質量部を徐々に添加した。添加後、液を攪拌しながら、95℃まで加熱し、樹脂を溶解させた。溶解後、攪拌しながら室温まで冷却して、固形分10質量%のポリビニルアルコール水溶液(Bw-1)を作成した。同様に、ポリビニルアルコール樹脂(B-1)の代わりにポリビニルアルコール樹脂(B-2)を使用し水溶液を作成し、それぞれ(Bw-2)とした。ポリビニルアルコール樹脂(B-1)(B-2)のけん化度を表2に示す。
攪拌器、温度計、還流冷却管、窒素吹き込み管を取り付けた4ツ口フラスコ内を窒素雰囲気にし、HDI 1000質量部、3価アルコールであるトリメチロールプロパン(分子量134)22質量部を仕込み、攪拌下反応器内温度を90℃1時間保持しウレタン化を行った。その後反応液温度を60℃に保持し、イソシアヌレート化触媒トリメチルベンジルアンモニウム・ハイドロオキサイドを加え、転化率が48%になった時点で燐酸を添加し反応を停止した。その後、反応液を濾過した後、未反応のHDIを薄膜蒸留装置により除去した。
攪拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネートを原料としたイソシアヌレート構造を有するポリイソシアネート化合物(旭化成ケミカルズ製、デュラネートTPA)100質量部、プロピレングリコールモノメチルエーテルアセテート55質量部、ポリエチレングリコールモノメチルエーテル(平均分子量750)30質量部を仕込み、窒素雰囲気下、70℃で4時間保持した。その後、反応液温度を50℃に下げ、メチルエチルケトオキシム47質量部を滴下した。反応液の赤外スペクトルを測定し、イソシアネート基の吸収が消失したことを確認し、固形分75質量%のオキシムブロックイソシアネート架橋剤(C-2)を得た。
撹拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネート168質量部とポリエチレングリコールモノメチルエーテル(M400、平均分子量400)220質量部を仕込み、120℃で1時間、撹拌し、更に4,4’-ジシクロヘキシルメタンジイソシアネート26質量部とカルボジイミド化触媒として3-メチル-1-フェニル-2-フォスフォレン-1-オキシド3.8質量部(全イソシイアネートに対し2質量%)を加え、窒素気流下185℃で更に5時間撹拌した。反応液の赤外スペクトルを測定し、波長2200~2300cm-1の吸収が消失したことを確認した。60℃まで放冷し、イオン交換水を567質量部加え、固形分40質量%のカルボジイミド系架橋剤(C-3)を得た。
エポキシ系架橋剤として、ナガセケムテックス社製 デナコールEX-521(固形分濃度100%)を使用した(エポキシ系架橋剤(C-4))。
(1)塗布液の調整
下記の塗剤を混合し、ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1)/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が92/3/5になる塗布液を作成した。ポリエステル水分散体は、酸価が2KOHmg/gであるポリエステル樹脂が分散した水分散体(Aw-1)を使用し、ポリビニルアルコール水溶液は、けん化度が88モル%であるポリビニルアルコールが溶解した水溶液(Bw-1)を使用した。
水 32.62質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 33.59質量%
ポリビニルアルコール水溶液(Bw-1) 1.46質量%
ブロックイソシアネート系架橋剤(C-1) 0.40質量%
粒子 0.49質量%
(平均粒径450nmのシリカゾル、固形分濃度4質量%)
粒子 1.29質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.15質量%
(シリコーン系、固形分濃度10質量%)
フィルム原料ポリマーとして、固有粘度(溶媒:フェノール/テトラクロロエタン=60/40)が0.62dl/gで、かつ粒子を実質上含有していないPET樹脂ペレットを、133Paの減圧下、135℃で6時間乾燥した。その後、押し出し機に供給し、約280℃でシート状に溶融押し出しして、表面温度20℃に保った回転冷却金属ロール上で急冷密着固化させ、未延伸PETシートを得た。
下記の塗剤を混合し、ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1)/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が83/5/12になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 33.75質量%
イソプロパノール 30.40質量%
ポリエステル水分散体(Aw-1) 30.34質量%
ポリビニルアルコール水溶液(Bw-1) 2.67質量%
ブロックイソシアネート系架橋剤(C-1) 0.95質量%
粒子 0.49質量%
(平均粒径450nmのシリカゾル、固形分濃度4質量%)
粒子 1.25質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.15質量%
(シリコーン系、固形分濃度10質量%)
ポリエステル系樹脂を(A-2)、ポリエステル水分散体を(Aw-2)に変更した以外は、実施例2と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が55/20/25になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリビニルアルコール系樹脂(B-2)、ポリビニルアルコール水溶液(Bw-2)になるになるように変更した以外は、実施例4と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が45/15/40になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が56/37/7になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が80/15/5になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が65/27/8になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が71/18/11になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が75/16/9になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が45/45/10になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が40/30/30になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が30/5/65になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が95/0/5になるになるように変更した樹脂被服層を積層した以外は、実施例1と同様にして、積層ポリエステルフィルムを得た。
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が25/65/10になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
塗布液の組成を下記の通り変更した以外は、実施例1と同様にして、易接着性ポリ
エステルフィルムを得た。
水 30.81質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 26.46質量%
ポリビニルアルコール水溶液(Bw-1) 9.69質量%
オキシムブロックイソシアネート架橋剤(C-2) 0.65質量%
粒子 0.49質量%
(平均粒径450nmのシリカゾル、固形分濃度4質量%)
粒子 1.27質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.15質量%
(シリコーン系、固形分濃度10質量%)
触媒
(有機スズ系化合物、固形分濃度10質量%) 0.48質量%
ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/活性メチレンブロックイソシアネート架橋剤(C-1)の固形分比が45/45/10になるになるように変更し、易接着性ポリエステルフィルムの製造で熱固定温度と弛緩処理温度を180℃から160℃に変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ブロックイソシアネート架橋剤をカルボジイミド系架橋剤(C-3)に変更し、ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1))/カルボジイミド系架橋剤(C-3)の固形分比が53/24/23になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
ブロックイソシアネート架橋剤をエポキシ系架橋剤(C-4)に変更し、ポリエステル系樹脂(A-1)/ポリビニルアルコール系樹脂(B-1)/エポキシ系架橋剤(C-4)の固形分比が45/42/13になるになるように変更した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
Claims (2)
- 少なくとも片面に易接着層を有するポリエステルフィルムであって、前記易接着層がポリエステル系樹脂、ポリビニルアルコール系樹脂及び活性メチレンブロックイソシアネート架橋剤を含有する組成物が硬化されてなり、易接着層中の組成物の硬化触媒として有機スズを実質的に含まず、水付着後剥離力が2N/cm以下である易接着性ポリエステルフィルム。
- 偏光子保護フィルムとして使用される請求項1に記載の易接着性ポリエステルフィルム。
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US20230017050A1 (en) * | 2019-12-06 | 2023-01-19 | Kuraray Co., Ltd. | Multilayer Structure, Method for Producing Same, Packaging Material and Product Including Same, and Protective Sheet for Electronic Device |
WO2024014458A1 (ja) * | 2022-07-13 | 2024-01-18 | 大日本印刷株式会社 | 光学フィルム、光学作用フィルム、易接着性フィルム、光学積層体、表面板、画像表示装置および偏光板 |
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