JP5109094B2 - Easy-adhesive polyester film for polarizer protection - Google Patents

Abstract

Provided is a highly adhesive polyester film for protecting polarizers, which has excellent adhesion to polarizers. A highly adhesive polyester film for protecting polarizers, which has a highly adhesive layer on at least one surface thereof, wherein the highly adhesive layer comprises a polyester resin (A), a polyvinyl alcohol resin (B) and a cross-linking agent (C), the polyester resin (A) has an acid value of 20 KOHmg/g or less, and the polyvinyl alcohol resin (B) has a degree of saponification of 60-85 mol%.

Description

  The present invention relates to an easily adhesive polyester film for protecting a polarizer used for protecting a polarizer. In detail, it is related with the easily-adhesive polyester film for polarizer protection excellent in adhesiveness with a polarizer.

  In the liquid crystal display device, polarizing plates are arranged on both sides of a glass substrate that forms the surface of the liquid crystal panel due to the image forming method. The polarizing plate generally has a configuration in which a polarizer protective film is bonded to both surfaces of a polarizer made of a dichroic material such as a polyvinyl alcohol film and iodine via a hydrophilic adhesive such as a polyvinyl alcohol resin. have. As a protective film used for protecting a polarizer, a triacetyl cellulose film has been conventionally used from the viewpoint of optical properties and transparency.

  However, triacetyl cellulose is not sufficiently durable, and when a polarizing plate using a triacetyl cellulose film as a polarizer protective film is used at high temperature or high humidity, the performance of the polarizing plate such as the degree of polarization and hue deteriorates. There is a case. In recent years, there has been a demand for thinning the polarizing plate in order to cope with the thinning of the display. However, from the viewpoint of maintaining moisture barrier properties, there has been a limit to thinning the triacetyl cellulose film. Therefore, it has been proposed to use a polyester film as a polarizer protective film having durability and moisture barrier properties (see Patent Documents 1 to 5).

  The triacetyl cellulose film used as a polarizer protective film is subjected to alkali treatment or the like on its surface, and has an extremely high affinity with a hydrophilic adhesive. Therefore, the protective film made of a triacetyl cellulose film has extremely high adhesiveness with a polarizer coated with a hydrophilic adhesive. However, the polyester film has insufficient adhesion to the hydrophilic adhesive, and this tendency becomes more prominent particularly in the case of a polyester film having orientation by a stretching treatment. Therefore, Patent Documents 1 to 3 and 5 propose providing a polyester film with an easy-adhesion layer in order to improve the adhesion to the polarizer or the hydrophilic adhesive applied to the polarizer.

JP-A-8-271733 JP-A-8-271734 JP 2009-157361 A JP 2010-277028 A JP 2011-8170 A

  A polyester film has a low affinity for water, and this tendency is particularly remarkable in a polyester film having an aromatic dicarboxylic acid as a dicarboxylic acid component. Moreover, the polyester film which has crystal orientation by extending | stretching has a low affinity with water further. On the other hand, the polarizer and the adhesive applied on the polarizer are mainly composed of a polyvinyl alcohol-based resin and have high hydrophilicity. Due to the difference in properties, the polyester film, the polarizer, and the adhesive have low affinity, and it is difficult to firmly bond the two. Therefore, even if it is a polyester film which has an easily bonding layer disclosed by patent documents 1-3 and 5, compared with a triacetyl cellulose film, sufficient adhesiveness is not yet acquired. Therefore, when a polarizing plate using a conventional polyester film as a protective film is used as a display member for a long time, floating or peeling occurs between the protective film and the polarizer, and the polarization characteristics deteriorate due to a change in the amount of moisture in the polarizer. Visibility such as white spots may deteriorate.

  Under such circumstances, an object of the present invention is to provide a polyester film provided with means for firmly bonding the polyester film and a polarizer or a polyvinyl alcohol-based resin layer such as an adhesive applied on the polarizer. For the purpose.

  The inventors of the present invention have made extensive studies and examinations to solve the above problems, and have a polyester resin having a high affinity with a polyester film and a polyvinyl alcohol resin having a high affinity with a polyvinyl alcohol resin layer and a crosslinking agent. It came to the idea of providing the layer to contain between a polyester film and a polyvinyl alcohol-type resin layer. However, the present inventors have found that the function of closely adhering the polyester film and the polyvinyl alcohol-based resin layer due to each component cannot be sufficiently exhibited by simply combining these components. Therefore, as a result of repeated researches day and night, the present inventors adopted a polyester resin having a certain acid value as the polyester resin in the above concept, and further, polyvinyl alcohol having a certain degree of saponification as the polyvinyl alcohol resin. It has been found that by using a system resin, it is possible to effectively exert the adhesive action of each component with a resin layer having high affinity.

  As a result of further research based on the above findings, the present inventors have adopted a cross-linking agent having high reactivity with a hydroxyl group, so that a polyester film and a polyvinyl alcohol resin layer such as a polarizer and an adhesive are used. It has been found that it is possible to adhere to each other more firmly. Based on these findings, the present inventors have made further investigations and improvements and invented the present invention.

  Below, the typical example of this invention is shown.

  1st invention is a polyester film which has an easily bonding layer on at least one surface, The said easily bonding layer contains a polyester-type resin (A), a polyvinyl alcohol-type resin (B), and a crosslinking agent (C), The polyester resin (A) has an acid value of 20 KOH mg / g or less, and the polyvinyl alcohol resin (B) has a saponification degree of 60 to 85 mol%.

  2nd invention is the said easily adhesive polyester film for polarizer protection in which the said polyester resin (A) contains 1-15 mol% of 5-sulfoisophthalic acid components in a dicarboxylic acid component.

  3rd invention is the said easily adhesive polyester film for polarizer protection whose said crosslinking agent (C) is an isocyanate compound or a melamine compound.

According to a fourth aspect of the present invention, in the easy-adhesive layer, the mass ratio of the polyester resin (A), the polyvinyl alcohol resin (B) and the cross-linking agent (C) satisfies the following formula: It is a polyester film.
0.8 ≦ (A) / (B) ≦ 5
2 ≦ ((A) + (B)) / (C) ≦ 50

  5th invention is a polarizing plate which has a polarizer protective film on both surfaces of a polarizer, Comprising: The polarizing plate whose polarizer protective film of at least one surface is the said easily-adhesive polyester film for polarizer protection It is.

  The easily protective polyester film for protecting a polarizer of the present invention is excellent in adhesiveness with a polarizer or a polyvinyl alcohol-based resin layer typified by an adhesive applied thereon. Therefore, the polyester film of the present invention can be suitably used as a protective film for a polarizer. By using such a polyester film of the present invention as a protective film for a polarizer, it is possible to produce a polarizing plate having superior durability and water barrier properties at a lower cost than before. Moreover, since the polarizing plate of the present invention is excellent in durability, it can be made thinner than before. Therefore, it is possible to further reduce the thickness of the liquid crystal display by using the polarizing plate of the present invention.

(Polyester film)
The polyester film used as a substrate in the present invention is a film mainly composed of a polyester resin. Here, “a film mainly composed of a polyester resin” is a film formed from a resin composition containing 50% by mass or more of a polyester resin. When blended with another polymer, the polyester resin is 50% by mass. % When it is copolymerized with other monomers, it means that 50 mol% or more of the polyester structural unit is contained. Preferably, the polyester film contains a polyester resin in an amount of 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass.

  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. Examples of 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, and diphenyl. Carboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfonecarboxylic acid, anthracene dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydro Isophthalic acid, malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid The die Over acid, sebacic acid, suberic acid, dodecamethylene dicarboxylic acid and the like.

  Examples of the diol component constituting the polyester resin include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, 1,3- Examples include propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexadiol, 2,2-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) sulfone.

  Each of 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 appropriately added.

  Specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Among these, polyethylene terephthalate is preferable from the balance of physical properties and cost. Moreover, in order to control optical characteristics, such as polarization, it is also a preferable aspect that other copolymer components or other polymers are included. Preferred copolymer components from the viewpoint of controlling the optical properties of the polyester film include diethylene glycol and copolymer components having norbornene in the side chain.

  Since the polyester film of the present invention is used as a protective film for a polarizer, it preferably has high transparency. The transparency of the polyester film for protecting a polarizer of the present invention is preferably such that the total light transmittance is 85% or more, more preferably 87% or more, still more preferably 88% or more, and even more preferably 89% or more. 90% or more is particularly preferable. The haze is preferably 3% or less, more preferably 2.5% or less, further preferably 2% or less, and particularly preferably 1.5% or less. The total light transmittance of a polyester film can be measured according to the method described in the Example mentioned later, for example.

  In order to improve handling properties such as slipperiness and rollability of the polyester film, inert particles may be included in the film. However, in order to maintain high transparency, the inert particles in the film may be included. The content is preferably as low as possible. Therefore, a multilayer structure in which particles are included only in the surface layer of the film, or particles are substantially not included in the film, and particles are included only in the easy-adhesion layer laminated on at least one side of the polyester film. It is preferable.

  “Substantially no particles” means, for example, in the case of inorganic particles, when the element derived from the particles is quantitatively analyzed by fluorescent X-ray analysis, 50 ppm or less, preferably 10 ppm or less, most preferably detected The content is below the limit. This means that even if particles are not actively added to the base film, contaminants derived from foreign substances and raw material resin or dirt adhering to the line or equipment in the film manufacturing process will be peeled off and mixed into the film. It is because there is a case to do.

  In addition, when the base film has a multi-layer structure, the two-layer / three-layer structure that does not substantially contain inert particles in the inner layer and contains inert particles only in the outermost layer achieves both transparency and workability. It is possible and preferable.

  In the present invention, the thickness of the film is not particularly limited, but when the thickness of the polarizing plate is reduced in order to make the display thinner, the thickness of the film is preferably 200 μm or less, and more preferably 100 μm or less. On the other hand, in order to maintain the mechanical strength as the protective film, the thickness of the film is preferably 10 μm or more, more preferably 12 μm or more, and further preferably 20 μm or more.

  The polyester film used as the substrate may be a single layer or a laminate of two or more layers. Moreover, as long as it exists in the range with the effect of this invention, various additives can be contained in a film as needed. Examples of the additive include an antioxidant, a light resistance agent, an antigelling agent, an organic wetting agent, an antistatic agent, an ultraviolet absorber, and a surfactant. When a film has a laminated structure, it is also preferable to contain an additive according to the function of each layer as needed. For example, in order to prevent photodegradation of the polarizer, it is also a preferred embodiment to add an ultraviolet absorber or the like to the inner layer.

  The polyester film is obtained by, for example, a method of forming the film by melt-extruding the above-described polyester resin into a film and cooling and solidifying with a casting drum. As the polyester film of the present invention, either a non-stretched film or a stretched film can be used, but a stretched film is preferable from the viewpoint of durability such as mechanical strength and chemical resistance. When the polyester film is a stretched film, the stretching method is not particularly limited, and a longitudinal uniaxial stretching method, a transverse uniaxial stretching method, a longitudinal and transverse sequential biaxial stretching method, a longitudinal and transverse simultaneous biaxial stretching method, and the like can be employed.

(Easily adhesive layer)
The polyester film of the present invention has an acid value of 20 KOHmg / g or less on at least one surface thereof in order to improve the adhesion between the polarizer and a polyvinyl alcohol resin layer such as a water-based adhesive provided on one surface or both surfaces thereof. A polyester resin (A), a polyvinyl alcohol resin (B) having a saponification degree of 60 to 85 mol%, and an easy adhesion layer formed from a resin composition containing a crosslinking agent (C) are laminated. Yes. The easy adhesion layer may be provided on both sides of the polyester film, may be provided only on one side of the polyester film, and a different type of resin coating layer may be provided on the other side.

  Although not limited by theory, it is crosslinked with a specific polyester resin (A) having a saponification degree of 20 KOH mg / g or less and a specific polyvinyl alcohol resin (B) having a saponification degree of 60 to 85 mol%. By combining the agent (C), it is considered that the polyester-based resin and the polyvinyl alcohol-based resin form separate domain units in the easy-adhesion layer, and form a phase separation structure generally called a sea-island structure. By adopting such a domain unit separation structure, the adhesiveness to the polyester film by the domain constituted by the polyester resin and the adhesiveness to the polyvinyl alcohol resin layer by the domain constituted by the polyvinyl alcohol resin are two. It is considered that the two functions are preferably compatible with each other without being impaired. The crosslinking agent (C) is considered to promote and maintain the formation of the domain structure by crosslinking and aggregating the polyvinyl alcohol resin (B).

Hereinafter, each composition of an easily bonding layer is explained in full detail.
(Polyester resin (A))
The polyester resin (A) used in the easy-adhesion layer of the present invention is a copolymer obtained by polycondensation of a dicarboxylic acid component and a diol component, and the dicarboxylic acid component and the diol component are polyesters as the above-mentioned base material. Film materials can be used. From the viewpoint of improving the adhesion to the polyester film substrate, a dicarboxylic acid component having the same or similar structure and properties as the dicarboxylic acid component in the polyester film as the substrate is used as the dicarboxylic acid component of the polyester resin (A). It is preferable to use it. Therefore, for example, when an aromatic dicarboxylic acid is 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 (A). As such an aromatic dicarboxylic acid component, terephthalic acid and isophthalic acid are most preferred. Other aromatic dicarboxylic acids may be added and copolymerized within a range of 10 mol% or less with respect to the total dicarboxylic acid component.

  Moreover, as a glycol component of a polyester-type resin (A), it is preferable to make ethylene glycol and the branched glycol into a structural component. By having a branched structure, it is considered that it contributes to stress relaxation in the easy-adhesion layer, and it is possible to suitably exhibit adhesion. Examples of the branched glycol component include 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, and 2-methyl-2-butyl-1,3. -Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2-n-hexyl-1,3-propanediol 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl-1,3-propanediol, 2, Such as 2-di-n-butyl-1,3-propanediol, 2-n-butyl-2-propyl-1,3-propanediol, and 2,2-di-n-hexyl-1,3-propanediol. And the like.

  The molar ratio of the branched glycol component is preferably 10 mol%, particularly preferably 20 mol%, based on the total glycol component. On the other hand, the upper limit is preferably 80 mol%, more preferably 70 mol%, and particularly preferably 60 mol%. If necessary, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol or the like may be used in combination.

  The polyester resin (A) used in the present invention is preferably a water-soluble or water-dispersible resin from the viewpoint of compatibility with the polyvinyl alcohol resin (B). In order to make the polyester resin water-soluble or water-dispersed, it is preferable to copolymerize a compound containing a hydrophilic group such as a sulfonate group or a carboxylate group. Among these, a dicarboxylic acid component having a sulfonate group is preferable from the viewpoint of imparting hydrophilicity while keeping the acid value of the polyester-based resin (A) low and controlling the reactivity with the crosslinking agent. Examples of the dicarboxylic acid component having a sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthaleneisophthalic acid-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid or an alkali thereof. Examples of the metal salt include 5-sulfoisophthalic acid. 1-15 mol% is preferable in the dicarboxylic acid component of a polyester resin (A), the dicarboxylic acid component which has a sulfonate group has more preferable 1.5-12 mol%, and 2-10 mol% is further more preferable. When the dicarboxylic acid component having a sulfonate group is at least the above lower limit, it is suitable for 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 (A) preferably has fewer carboxylic acid groups which are reactive groups with the crosslinking agent (C). By reducing the number of carboxyl groups that are reactive with the cross-linking agent, the reactivity with the cross-linking agent is reduced. As a result, the cross-linking polyvinyl alcohol-based resin does not completely mix with the polyvinyl alcohol-based resin. It is considered possible to maintain the domain structure that is formed. From such a viewpoint, the acid value of the polyester resin (A) is 20 KOHmg / g or less, preferably 15 KOHmg / g or less, more preferably 10 KOHmg / g or less, further preferably 8 KOHmg / g or less, and still more preferably 5 KOHmg. / G or less. The acid value of the polyester resin (A) can be theoretically determined from the result of component analysis by titration method described later or NMR.

  In order to control the acid value of the polyester resin (A) within the above range, the introduction amount of the carboxylic acid base for water solubilization or water dispersion is reduced, or hydrophilic groups other than the carboxylic acid base are employed. Or lowering the carboxylic acid terminal concentration of the polyester resin. As a method for lowering the carboxylic acid terminal concentration of the polyester resin, it is preferable to employ a polyester resin in which the carboxylic acid terminal group is modified, or a polyester resin having a large number average molecular weight of the polyester resin. For this reason, the number average molecular weight of the polyester resin (A) is preferably 5000 or more, more preferably 6000 or more, and further preferably 10,000 or more. Moreover, it is preferable to make low content of the acid component which has a polyester-type resin (A) as a structural component and has three or more carboxyl groups.

  Although the glass transition temperature of a polyester-type resin (A) is not specifically limited, It is preferable that it is 20-90 degreeC, and it is more preferable that it is 30-80 degreeC. When the glass transition temperature is not less than the above lower limit, it is suitable for blocking resistance, and when the glass transition temperature is not more than the above upper limit, it is suitable for adhesiveness to a polyester film substrate.

  40 mass% or more and 90 mass% or less are preferable, as for content of the polyester-type resin (A) in an easily bonding layer, 45 mass% or more and 85 mass% or less are more preferable, and 50 mass% or more and 80 mass% or less are more preferable. . When the content of the polyester resin (A) is not less than the above lower limit, it is suitable for adhesion to the polyester film substrate, and if it is not more than the above upper limit, it is with the polyvinyl alcohol resin such as a polarizer and a hydrophilic adhesive. Suitable for adhesiveness.

(Polyvinyl alcohol resin (B))
The polyvinyl alcohol-based resin is not particularly limited. For example, polyvinyl alcohol obtained by saponifying polyvinyl acetate; a derivative thereof; and a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability; And modified polyvinyl alcohol obtained by converting polyvinyl alcohol into acetalized, urethanized, etherified, grafted, phosphoric acid ester or the like. Examples of the monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; α-olefins such as ethylene and propylene, (meth) Examples include allyl sulfonic acid (soda), sulfonic acid soda (monoalkyl malate), disulfonic acid soda alkyl maleate, N-methylol acrylamide, acrylamide alkyl sulfonic acid alkali salt, N-vinyl pyrrolidone, N-vinyl pyrrolidone derivatives, and the like. . These polyvinyl alcohol resins may be used alone or in combination of two or more.

  Examples of the polyvinyl alcohol resin (B) used in the present invention include vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-vinyl butyral copolymer, and ethylene-vinyl alcohol copolymer. Among these, vinyl alcohol-vinyl acetate A copolymer and an ethylene-vinyl alcohol copolymer are preferred. The polymerization degree of the polyvinyl alcohol-based resin (B) is not particularly limited, but the polymerization degree is preferably 3000 or less from the viewpoint of the coating solution viscosity.

  The copolymerization ratio of vinyl alcohol is represented by the degree of saponification. The saponification degree of the polyvinyl alcohol resin (B) of the present invention is preferably 60 mol% or more and 85 mol% or less, more preferably 65 mol% or more and 83 mol% or less, further preferably 68 mol% or more and 80 mol% or less, and 70 More preferably, it is more than mol% and less than 80 mol%, still more preferably 71 mol% or more and 78 mol% or less, and particularly preferably 73 mol% or more and 75 mol% or less. When the degree of saponification of the polyvinyl alcohol resin (B) is not less than the above lower limit, a crosslinked structure can be more suitably formed with the crosslinking agent (C). Further, when the degree of saponification of the polyvinyl alcohol-based resin (B) is not more than the above upper limit (or less), compatibility with the polyester-based resin (A) can be more suitably achieved. The degree of saponification of the vinyl alcohol-based resin can be determined by the amount of alkali consumption required for hydrolysis of copolymer units such as vinyl acetate or the composition analysis by NMR.

  The content of the polyvinyl alcohol resin (B) is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 55% by mass or less, and more preferably 20% by mass or more and 50% by mass or less in the easy-adhesion layer. Further preferred. When the content of the polyvinyl alcohol resin (B) is not less than the above lower limit, it is suitable for adhesiveness with a polyvinyl alcohol resin layer such as a polarizer and an adhesive, and when the content is not more than the above upper limit, Suitable for adhesiveness.

(Crosslinking agent (C))
The crosslinking agent (C) is not particularly limited as long as it has crosslinkability with a hydroxyl group, and examples thereof include melamine-based, isocyanate-based, carbodiimide-based, oxazoline-based, and epoxy-based compounds. Melamine-based, isocyanate-based, carbodiimide-based, and oxazoline-based compounds are preferable from the viewpoint of the temporal stability of the coating solution. Furthermore, the crosslinking agent is preferably a melamine compound or an isocyanate compound that suitably cross-links with the hydroxyl group of the polyvinyl alcohol resin (B). This is because a carbodiimide-based cross-linking agent reacts with a carboxyl group, whereas a melamine-based compound or an isocyanate-based compound reacts with a hydroxyl group, and therefore, a polyvinyl alcohol resin (B) having a hydroxyl group as a functional group is more preferably a crosslinked structure. This is thought to be because of Especially, it is especially preferable to use an isocyanate type compound from a viewpoint that it forms a crosslinking reaction suitably with the hydroxyl group of polyvinyl alcohol-type resin, and is excellent in transparency. Moreover, in order to promote a crosslinking reaction, you may use a catalyst etc. suitably as needed.

  As the isocyanate compound, a low-molecular or high-molecular diisocyanate or a trivalent or higher polyisocyanate can be used. For example, as the isocyanate compound, 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, tetramethylxylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane 4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiph Aromatic diisocyanates such as nil-4,4'-diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, etc. Examples thereof include aliphatic diisocyanates such as alicyclic diisocyanates, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, and trimers of these isocyanate compounds. Furthermore, an excess amount of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols, poly Mention may be made of a polymer containing a terminal isocyanate group of a polymer obtained by reacting a polymer active hydrogen compound such as ether polyols and polyamides.

  As the melamine compound, a melamine compound substituted with a substituent — (CH 2) n —O—R (wherein n is an integer of 1 to 3 and R is an alkyl group having 1 to 4 carbon atoms). R in the above formula is preferably methyl. The number of the substituents that one melamine structure has is preferably 3 to 6. Specific examples of melamine compounds include M-3, MK, M-6, M-100, MC, etc. of Sumitomo Chemical Co., Ltd. Sumitex Resin series and methylated melamine resin MW-22, MX manufactured by Sanwa Chemical Co., Ltd. -706, MX-042 and the like.

  As the crosslinking agent (C) used in the present invention, a blocked isocyanate compound is also preferable. By adding the blocked isocyanate compound, it is possible to more suitably improve the temporal stability of the coating solution.

  The blocked isocyanate compound can be prepared by subjecting the isocyanate compound and the blocking agent to an addition reaction by a conventionally known method. Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; thiophenols such as thiophenol and methylthiophenol; oximes such as acetoxime, methyl etiketooxime, and cyclohexanone oxime. Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol ; Lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propyllactam; aromatic amines; imides; acetylacetone, acetoacetate Active methylene compounds such as malonic acid ethyl ester; mercaptans; imines; ureas; diaryl compounds; and sodium bisulfite and the like.

  As content of a crosslinking agent (C), 2 to 50 mass% is preferable in an easily bonding layer, 5 to 40 mass% is more preferable, 8 to 30 mass% is further more preferable. . When the content of the crosslinking agent (C) is not less than the above lower limit, it is suitable for forming a crosslinked polyvinyl alcohol resin, and when it is not more than the above upper limit, it is suitable for expression of an adhesive effect by the binder resin.

  The blending ratio (A) / (B) of the polyester resin (A) and the polyvinyl alcohol resin (B) is preferably 0.8 to 5, more preferably 1 to 4, more preferably 2 More preferably, it is-4, and it is especially preferable that it is 2.5-3.5. When (A) / (B) is not less than the above lower limit, it is suitable for adhesiveness with a polyester film substrate, and when it is not more than the above upper limit, it is possible to adhere to a polyvinyl alcohol resin layer such as a polarizer or an adhesive. Is preferred.

  The blending ratio ((A) + (B)) / (C) of the polyester resin (A) and the polyvinyl alcohol resin (B) and the crosslinking agent (C) is preferably 2 to 50 in terms of mass ratio. More preferably, it is -40, and it is further more preferable that it is 8-30. When ((A) + (B)) / (C) is not less than the above lower limit, it is suitable for expression of the adhesive effect by the binder resin component, and when it is not more than the above upper limit, it is suitable for the adhesive effect by phase separation. .

  By adopting the above composition, the easy-adhesion layer of the present invention exhibits high adhesiveness equivalent to that of triacetyl cellulose to polarizers and aqueous adhesives, particularly polyvinyl alcohol-based polarizers and aqueous adhesives. Specifically, the remaining area after peeling once is preferably 90% or more, more preferably 95% or more, and further preferably 100% with respect to the water-based adhesive according to the adhesive test described later. The remaining area after is preferably 75% or more, more preferably 85% or more, further preferably 95% or more, and the remaining area after 10 continuous peelings is preferably 50% or more, more preferably 80% or more, Preferably it is 90% or more, More preferably, it is 93% or more, Most preferably, it is 95% or more.

(Additive)
In the easy-adhesion layer of the present invention, known additives such as surfactants, antioxidants, catalysts, heat stabilizers, weathering stabilizers, UV absorbers, organic absorbers, and the like within a range that does not inhibit the effects of the present invention. Lubricants, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, and the like may be added.

  In this invention, in order to improve the blocking resistance of an easily bonding layer, it is also a preferable aspect to add particle | grains to an easily bonding layer. Examples of the particles contained in the easy-adhesion layer in the present invention include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay and the like, or a mixture thereof. Inorganic particles such as calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, etc., and other inorganic particles such as Examples include organic polymer particles.

  The average particle size of the sex particles in the easy-adhesion layer (number-based average particle size by SEM; the same applies hereinafter) is preferably 0.04 to 2.0 μm, more preferably 0.1 to 1.0 μm. If the average particle size of the inert particles is less than 0.04 μm, the formation of irregularities on the film surface becomes insufficient, so that the handling properties such as the slipping property and the winding property of the film are deteriorated and the film is stuck. The workability at the time of alignment may deteriorate. On the other hand, if it exceeds 2.0 μm, the particles are likely to fall off, which is not preferable. The particle concentration in the easy-adhesion layer is preferably 1 to 20% by mass and more preferably 5 to 15% by mass in the solid component.

  In the present invention, the thickness of the easy-adhesion layer can be appropriately set in the range of 0.001 to 2.00 μm, but in the range of 0.01 to 1.00 μm to achieve both workability and adhesiveness. More preferably, it is 0.02-0.80 micrometer, More preferably, it is 0.05-0.50 micrometer. Adhesiveness will become inadequate that the thickness of an easily bonding layer is less than 0.01 micrometer. When the thickness of the easy-adhesion layer exceeds 2.00 μm, blocking may occur.

(Manufacture of easy-adhesive polyester film for protecting polarizers)
The method for producing an easily-adhesive polyester film for protecting a polarizer of the present invention will be described by taking a polyethylene terephthalate (hereinafter abbreviated as PET) film as an example, but is not limited thereto.

  After sufficiently drying the PET resin in a vacuum, it is fed to an extruder, and melted PET resin at about 280 ° C. is melt-extruded in a sheet form on a rotating cooling roll from a T-die, cooled and solidified by an electrostatic application method, and unstretched PET Get a sheet. The unstretched PET sheet may have a single layer structure or a multilayer structure by a coextrusion method.

  The obtained unstretched PET sheet is crystallized by uniaxial stretching or biaxial stretching. For example, in the case of biaxial stretching, 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 held with a clip And it guide | induces to the hot air zone heated at 80-180 degreeC, and extends | stretches 2.5 to 5.0 time in the width direction. In the case of uniaxial stretching, the film is stretched 2.5 to 5.0 times in the tenter. After stretching, the film is led to a heat treatment zone at 140 to 240 ° C., and heat treatment is performed for 1 to 60 seconds to complete crystal orientation.

  The easy adhesion layer can be provided after the production of the film or in the production process. In particular, from the viewpoint of productivity, it is preferable to apply the coating liquid to at least one side of the PET film after unstretched or uniaxial stretching to form an easy-adhesion layer.

  Any known method can be used as a method for applying the coating solution to the PET film. For example, reverse roll coating method, gravure coating method, kiss coating method, die coater method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, impregnation coating method, curtain coating method, etc. It is done. These methods can be applied alone or in combination.

In this invention, it is preferable that the thickness of the easily bonding layer finally obtained is 0.03-0.20 g / m < ² >. If it is less than 0.03 g / m < ² >, adhesiveness will fall, and if it is thicker than 0.20 g / m < ² >, since blocking property and slipperiness will fall, it is unpreferable.

(Polarizer)
The polarizing plate of the present invention is a polarizing plate having a polarizer protective film on both sides of a polarizer, and the polarizer protective film on at least one surface is the above-mentioned easily adhesive polyester film for protecting a polarizer. Is preferred. The other polarizer protective film may be an easily adhesive polyester film for protecting a polarizer of the present invention, or a film having no birefringence such as a triacetyl cellulose film, an acrylic film, or a norbornene-based film. It is also preferable to use it.

  Examples of the polarizer include a polyvinyl alcohol film containing a dichroic material such as iodine. The polarizer protective film is bonded to the polarizer directly or via an adhesive layer, but it is preferable to bond the polarizer protective film via an adhesive from the viewpoint of improving adhesiveness. In that case, it is preferable to arrange | position the easily bonding layer of this invention to a polarizer surface or an adhesive bond layer surface. As a preferable polarizer for bonding the polyester film of the present invention, for example, iodine or dichroic material is dyed and adsorbed on a polyvinyl alcohol film, uniaxially stretched in a boric acid aqueous solution, and the stretched state is maintained. The polarizer obtained by performing washing | cleaning and drying is mentioned. The draw ratio of uniaxial stretching is usually about 4 to 8 times. Polyvinyl alcohol is suitable as the polyvinyl alcohol film. “Kuraray Vinylon” [manufactured by Kuraray Co., Ltd.], “Tosero Vinylon” [manufactured by Toh Cello Co., Ltd.], “Nichigo Vinylon” [Nippon Synthetic Chemical Co., Ltd.] Commercial products such as “made” can be used. Examples of the dichroic material include iodine, a disazo compound, and a polymethine dye.

  From the viewpoint of thinning the adhesive layer, the adhesive applied to the polarizer is preferably an aqueous one, that is, an adhesive component dissolved in water or dispersed in water. For example, a polyvinyl alcohol resin, a urethane resin, or the like is used as a main component, and a composition containing an isocyanate compound, an epoxy compound, or the like can be used as necessary in order to improve adhesiveness. The thickness of the adhesive layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less.

  When using polyvinyl alcohol resin as the main component of the adhesive, in addition to partially saponified polyvinyl alcohol and fully 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. 1-10 mass% is preferable and, as for the density | concentration of the polyvinyl alcohol-type resin in an adhesive agent, 2-7 mass% is more preferable.

  Next, the present invention will be described in detail using examples, comparative examples, and reference examples, but the present invention is not limited to the following examples. The evaluation method used in the present invention is as follows.

(1) Glass transition temperature In accordance with JIS K7121, using a differential scanning calorimeter (Seiko Instruments, DSC6200), 10 mg of a resin sample was heated at 20 ° C / min over a temperature range of 25 to 300 ° C, and DSC The extrapolated glass transition start temperature obtained from the curve was defined as the glass transition temperature.

(2) Number average molecular weight 0.03 g of resin was dissolved in 10 ml of tetrahydrofuran, and GPC-LALLS apparatus low-angle light scattering photometer LS-8000 (manufactured by Tosoh Corporation, tetrahydrofuran solvent, reference: polystyrene) was used. The number average molecular weight was measured using a flow rate of 1 ml / min and a column (showex KF-802, 804, 806 manufactured by Showa Denko KK).

(3) Resin composition The resin is dissolved in deuterated chloroform, and ¹ H-NMR analysis is performed using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian, and the mol% ratio of each composition is determined from the integral ratio. Were determined.

(4) Acid value 1 g (solid content) of a sample was dissolved in 30 ml of chloroform or dimethylformamide, and titrated with 0.1 N potassium hydroxide ethanol solution using phenolphthalein as an indicator to determine the carboxyl groups per gram of the sample. The amount (mg) of KOH required for neutralization was determined.

(5) Saponification degree Residual acetate groups (mol%) of the polyvinyl alcohol resin were quantified using sodium hydroxide according to JIS-K6726, and the value was defined as the saponification degree (mol%). The sample was measured three times, and the average value was defined as the saponification degree (mol%).

(6) Total light transmittance of polyester film for protecting polarizer The total light transmittance of the polyester film for protecting a polarizer was measured using a turbidimeter (Nippon Denshoku, NDH2000) in accordance with JIS K7105.

(7) Haze of Polyester Film for Protecting Polarizer The haze of the polarizer protective polyester film was measured using a turbidimeter (Nippon Denshoku, NDH2000) in accordance with JIS K7136.

(8) PVA adhesive property The polyvinyl alcohol resin layer after drying the polyvinyl alcohol aqueous solution (Pura117 made from Kuraray) adjusted to solid content concentration 5 mass% on the surface of the easily adhesive layer of the polyester film for protecting a polarizer is 2 μm. Then, it was applied with a wire bar and dried at 70 ° C. for 5 minutes. As the polyvinyl alcohol aqueous solution, a solution in which a red dye was added so as to facilitate the determination was used. The prepared evaluation target film was attached to a glass plate having a thickness of 5 mm to which a double-sided tape was attached, and the opposite surface of the evaluation target laminated film on which the polyvinyl alcohol resin layer was formed was attached to the double-sided tape. Next, 100 grid-like cuts that penetrated through the polyvinyl alcohol resin layer and reached the base film were made using a cutter guide with a gap interval of 2 mm. Then, an adhesive tape (Nichiban Co., Ltd. cello tape (registered trademark) CT-24; 24 mm width) was attached to the grid-shaped cut surface. The air remaining at the interface at the time of pasting was pressed with an eraser to bring it into close contact, and then the work of peeling off the adhesive tape vigorously vertically was performed once, five times and ten times. The number of squares on which the polyvinyl alcohol resin layer was not peeled was counted to determine PVA adhesion. That is, when the PVA layer was not peeled off at all, the PVA adhesion rate was 100, and when all the PVA layer was peeled off, the PVA adhesion rate was 0. In addition, what was partially peeled within one square was also included in the number of peeled.

(Polyester resin polymerization)
In a stainless steel autoclave equipped with a stirrer, a thermometer, and a partial reflux condenser, 194.2 parts by weight of dimethyl terephthalate, 184.5 parts by weight of dimethyl isophthalate, 14.8 parts by weight of dimethyl-5-sodium sulfoisophthalate, The mixture was charged with 233.5 parts by mass of diethylene glycol, 136.6 parts by mass of ethylene glycol, and 0.2 parts by mass of tetra-n-butyl titanate, and subjected to a transesterification reaction at a temperature of 160 to 220 ° C. over 4 hours. Next, the temperature was raised to 255 ° C., and the pressure of the reaction system was gradually reduced, followed by reaction for 1 hour 30 minutes under a reduced pressure of 30 Pa to obtain a copolymerized polyester resin (A-1). The obtained copolyester resin (A-1) was light yellow and transparent. It was 0.70 dl / g when the reduced viscosity of copolyester resin (A-1) was measured. The glass transition temperature by DSC was 40 ° C.

In the same manner, copolymer polyester resins (A-2) to (A-5) having different compositions were obtained. Table 1 shows the composition (mole% ratio) and other characteristics measured by ¹ H-NMR for these copolymer polyester resins.

(Adjustment of polyester aqueous dispersion)
30 parts by mass of polyester resin (A-1) and 15 parts by mass of ethylene glycol n-butyl ether were placed in a reactor equipped with a stirrer, a thermometer and a reflux device, and heated and stirred at 110 ° C. to dissolve the resin. After the resin was completely dissolved, 55 parts by mass of water was gradually added to the polyester solution while stirring. After the addition, the solution was cooled to room temperature while stirring to prepare a milky white polyester aqueous dispersion (Aw-1) having a solid content of 30% by mass. Similarly, using the polyester resins (A-2) to (A-5) instead of the polyester resin (A-1), water dispersions are prepared, and the polyester water dispersions (Aw-2) to (Aw) are respectively produced. -5).

(Preparation of aqueous polyvinyl alcohol solution)
In a container equipped with a stirrer and a thermometer, 90 parts by mass of water was added, and 10 parts by mass of polyvinyl alcohol resin (manufactured by Kuraray) (B-1) having a polymerization degree of 500 was gradually added while stirring. After the addition, the solution was heated to 95 ° C. while stirring to dissolve the resin. After dissolution, the mixture was cooled to room temperature with stirring to prepare a polyvinyl alcohol aqueous solution (Bw-1) having a solid content of 10% by mass. Similarly, polyvinyl alcohol resins (B-2) to (B-7) were used instead of the polyvinyl alcohol resin (B-1) to prepare aqueous solutions, which were designated as (Bw-2) to (Bw-7), respectively. . Table 2 shows the degree of saponification of the polyvinyl alcohol resins (B-1) to (B-7).

(Polymerization of block polyisocyanate crosslinking agent)
In a flask equipped with a stirrer, thermometer and reflux condenser, 100 parts by mass of a polyisocyanate compound having an isocyanurate structure using hexamethylene diisocyanate as a raw material (manufactured by Asahi Kasei Chemicals, Duranate TPA), 55 parts by mass of propylene glycol monomethyl ether acetate, polyethylene 30 parts by mass of glycol monomethyl ether (average molecular weight 750) was charged, and kept at 70 ° C. for 4 hours under a nitrogen atmosphere. Thereafter, the reaction solution temperature was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketoxime was added dropwise. The infrared spectrum of the reaction solution was measured to confirm that the absorption of the isocyanate group had disappeared, and a block polyisocyanate aqueous dispersion (C-1) having a solid content of 75% by mass was obtained.

Example 1
(1) Adjustment of coating liquid The following coating agent was mixed and the coating liquid from which the mass ratio of polyester-type resin (A) / polyvinyl alcohol-type resin (B) became 70/30 was created. The polyester aqueous dispersion uses an aqueous dispersion (Aw-1) in which a polyester resin having an acid value of 2 KOH mg / g is dispersed, and the polyvinyl alcohol aqueous solution is an aqueous solution in which polyvinyl alcohol having a saponification degree of 74 mol% is dissolved. (Bw-4) was used.
Water 40.61 mass%
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 11.67 mass%
Polyvinyl alcohol aqueous solution (Bw-4) 15.00 mass%
Block isocyanate-based crosslinking agent (C-1) 0.67% by mass
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Catalyst (Organic tin compound, solid content concentration 14% by mass) 0.3% by mass
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

(2) Manufacture of polarizer protective polyester film PET resin pellet having intrinsic viscosity (solvent: phenol / tetrachloroethane = 60/40) of 0.62 dl / g as a film raw material polymer and containing substantially no particles Was dried at 135 ° C. under reduced pressure of 133 Pa for 6 hours. Thereafter, the sheet was supplied to an extruder, melted and extruded into a sheet at about 280 ° C., and rapidly cooled and solidified on a rotating cooling metal roll maintained at a surface temperature of 20 ° C. to obtain an unstretched PET sheet.

  This unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially stretched PET film.

Subsequently, after apply | coating the said coating liquid to the single side | surface of PET film by the roll coat method, it dried at 80 degreeC for 15 second. The coating amount after drying (after biaxial stretching) was adjusted to 0.12 g / m ² . Subsequently, the film was stretched 4.0 times in the width direction at 150 ° C. with a tenter, and heated at 230 ° C. for 0.5 seconds with the length in the width direction fixed, and further at 230 ° C. for 10 seconds. % Relaxation treatment in the width direction was performed to obtain a polarizer protective polyester film having a thickness of 38 μm. The evaluation results are shown in Table 3.

Example 2
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to an aqueous dispersion (Aw-2) in which a polyester resin having an acid value of 4 KOHmg / g was dispersed.

Example 3
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to an aqueous dispersion (Aw-3) in which a polyester resin having an acid value of 6 KOHmg / g was dispersed.

Example 4
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to a polyvinyl alcohol aqueous solution (Bw-3) in which the saponification degree of polyvinyl alcohol was 79 mol%.

Example 5
A polarizer-protected polyester film was obtained in the same manner as in Example 1, except that the polyvinyl alcohol aqueous solution (Bw-2) had a saponification degree of polyvinyl alcohol of 83 mol%.

Example 6
Polyester for protecting a polarizer in the same manner as in Example 1, except that the following coating agent was mixed and the mass ratio of the polyester resin (A) / polyvinyl alcohol resin (B) was changed to 60/40. A film was obtained.
Water 37.28% by mass
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 10.00 mass%
Polyvinyl alcohol aqueous solution (Bw-4) 20.00 mass%
Block isocyanate-based crosslinking agent (C-1) 0.67% by mass
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Catalyst (Organic tin compound, solid content concentration 14% by mass) 0.3% by mass
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Example 7
A polyester for protecting a polarizer in the same manner as in Example 1, except that the following coating agent was mixed and the mass ratio of the polyester resin (A) / polyvinyl alcohol resin (B) was changed to 80/20. A film was obtained.
43.95% by weight of water
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 13.33 mass%
Polyvinyl alcohol aqueous solution (Bw-4) 10.00 mass%
Block isocyanate-based crosslinking agent (C-1) 0.67% by mass
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Catalyst (Organic tin compound, solid content concentration 14% by mass) 0.3% by mass
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Example 8
A polyester for protecting a polarizer in the same manner as in Example 1 except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 50/50. A film was obtained.
Water 33.95% by mass
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 8.33 mass%
Polyvinyl alcohol aqueous solution (Bw-4) 25.00% by mass
Block isocyanate-based crosslinking agent (C-1) 0.67% by mass
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Catalyst (Organic tin compound, solid content concentration 14% by mass) 0.3% by mass
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Example 9
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the composition of the coating solution was changed as follows.
40.87% by mass of water
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 11.67 mass%
Polyvinyl alcohol aqueous solution (Bw-4) 15.00 mass%
Melamine type crosslinking agent (C-2) 0.71 mass%
(Nikarak MX-042, manufactured by Sanwa Chemical Co., Ltd., solid content concentration 70%)
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Example 10
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was changed to an aqueous solution (Bw-5) in which polyvinyl alcohol having a saponification degree of polyvinyl alcohol of 70 mol% was dissolved. .

Example 11
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was changed to an aqueous solution (Bw-6) in which polyvinyl alcohol having a saponification degree of polyvinyl alcohol of 67 mol% was dissolved. .

Example 12
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the composition of the coating solution was changed as follows.
40.33% by mass of water
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 11.67 mass%
Polyvinyl alcohol aqueous solution (Bw-2) 15.00 mass%
Oxazoline-based crosslinking agent (C-3) 1.25% by mass
(Epocross WS-500, manufactured by Nippon Shokubai, solid concentration 40% by mass)
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Example 13
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to an aqueous dispersion (Aw-5) in which a polyester resin having an acid value of 10 KOHmg / g was dispersed.

Comparative Example 1
Polyester for protecting a polarizer in the same manner as in Example 1, except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 100/0. A film was obtained.
Water 50.62% by mass
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 16.66 mass%
Block isocyanate-based crosslinking agent (C-1) 0.67% by mass
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Catalyst (Organic tin compound, solid content concentration 14% by mass) 0.3% by mass
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Comparative Example 2
A polyester for protecting a polarizer in the same manner as in Example 1 except that the following coating agent was mixed and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 0/100. A film was obtained.
17.28% by mass of water
Isopropanol 30.00% by mass
Polyvinyl alcohol aqueous solution (Bw-4) 50.00 mass%
Block isocyanate-based crosslinking agent (C-1) 0.67% by mass
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Catalyst (Organic tin compound, solid content concentration 14% by mass) 0.3% by mass
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Comparative Example 3
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to an aqueous dispersion (Aw-4) in which a polyester resin having an acid value of 25 KOH mg / g was dispersed.

Comparative Example 4
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to an aqueous solution (Bw-1) in which polyvinyl alcohol having a saponification degree of 88 mol% was dissolved.

Comparative Example 5
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was changed to an aqueous solution (Bw-7) in which polyvinyl alcohol having a saponification degree of 40 mol% was dissolved.

Comparative Example 6
A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the following coating agent was mixed and the crosslinking agent was not mixed.
41.58% by mass of water
Isopropanol 30.00% by mass
Polyester water dispersion (Aw-1) 11.67 mass%
Polyvinyl alcohol aqueous solution (Bw-4) 15.00 mass%
1.25% by mass of particles
(Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
Surfactant 0.5% by mass
(Silicone, solid content concentration 10% by mass)

Reference example 1
The result of having performed the said adhesive test using the TAC film (The Fuji Film Co., Ltd. product, thickness 80micrometer, saponification-processed) is shown as a film for polarizer protection.

  The easy-adhesive polyester film for protecting a polarizer of the present invention has high adhesiveness with a polarizer / water-based adhesive. Therefore, it can be suitably used as a polarizer protective member.

Claims (5)

A polyester film having an easy-adhesion layer on at least one side,
The easy-adhesion layer contains a polyester resin (A), a polyvinyl alcohol resin (B), and a crosslinking agent (C),
The acid value of the polyester resin (A) is 20 KOHmg / g or less,
The easily adhesive polyester film for protecting a polarizer, wherein the saponification degree of the polyvinyl alcohol resin (B) is 60 to 85 mol%.   The easily adhesive polyester film for protecting a polarizer according to claim 1, wherein the polyester resin (A) contains a 5-sulfoisophthalic acid component in an amount of 1 to 15 mol% in the dicarboxylic acid component.   The easily adhesive polyester film for protecting a polarizer according to claim 1 or 2, wherein the crosslinking agent (C) is an isocyanate compound or a melamine compound. The polarizer in any one of Claims 1-3 in which the mass ratio of a polyester-type resin (A), a polyvinyl alcohol-type resin (B), and a crosslinking agent (C) satisfies the following formula | equation in the said easily bonding layer. Easy-adhesive polyester film for protection.
0.8 ≦ (A) / (B) ≦ 5
2 ≦ ((A) + (B)) / (C) ≦ 50 A polarizing plate having a polarizer protective film on both sides of a polarizer,
The polarizing plate whose polarizer protective film of at least one surface is the easily adhesive polyester film for polarizer protection in any one of Claims 1-4.