TW202246061A - Antistatic polyester film - Google Patents

Abstract

The present invention provides an antistatic polyester film which has good adhesion to an antistatic layer, while being excellent in terms of retention of the adhesion at high levels for a long period of time. An antistatic polyester film which is obtained by sequentially superposing a highly adhesive layer and an antistatic layer in this order on at least one surface of a polyester film, wherein the highly adhesive layer is obtained by curing a coating layer that is formed of a composition containing a polyurethane resin that has a carboxyl group and an acid value of 30 to 50 mgKOH/g and a crosslinking agent that has a carboxyl group and an acid value of 30 to 50 mgKOH/g.

Description

Antistatic polyester film and adhesive film

The present invention relates to an antistatic polyester film. More specifically, the present invention relates to an antistatic polyester film laminated with an antistatic layer and an adhesive layer on the antistatic laminated layer, especially to an optical component (such as organic EL (Electroluminescence; electroluminescence) or liquid crystal Constituents of displays) and other protective films.

Thermoplastic resin films, among them, polyester films have excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance, so they are widely used in magnetic recording materials, packaging materials, and solar cells. Optical films such as anti-reflection films, diffusion sheets, and smear sheets used in flat-panel displays, etc., as well as films for label printing, antistatic films, protective films, etc. However, the surface of the polyester film is highly crystalline, so it has the disadvantage of lacking adhesion to various paints, resins, and inks during processing in these applications. Therefore, studies to provide adhesiveness to the surface of a polyester film by various methods have been performed conventionally.

Conventionally, as a method of imparting adhesiveness, for example, surface activation methods such as corona discharge treatment, ultraviolet irradiation treatment, and plasma treatment on the surface of a polyester film used as a base material have been known. However, the adhesion obtained by these treatments Since the effect decreases over time, it is difficult to maintain a high level of adhesion over a long period of time (Patent Document 1). Therefore, the following method is mainly used: coating various resins on the surface of the polyester film, and providing a coating layer with easy adhesion.

Heretofore, there has been known a technique in which a coating solution containing a copolymerized polyester resin or a urethane resin, or a coating solution using these resins and a crosslinking agent in combination is used for the coating layer, and Improves affinity with resin components such as urethane or ester acrylate used in hard coat agents and lens agents, and imparts adhesiveness to them (Patent Document 2, Patent Document 3). However, UV (Ultraviolet) inks (ultraviolet curable inks) used in label printing contain dyes or pigments in addition to resins in order to express color tones. In pigments with relatively good light resistance, the ink composition is 15% by weight to 10% by weight. About 25% by weight is used. Furthermore, in the white ink system where concealment is important, the content of the white pigment is as high as about 50% by weight, so the adhesiveness in the prior art is not sufficient, especially the adhesiveness at a low dosage is difficult.

It is proposed to provide an antistatic layer or an adhesive layer on a polyester film about a protective film (patent document 4). However, in the conventional method, the adhesion of the polyester film to the antistatic layer or the adhesive layer is not sufficient, especially the durability is insufficient when it is stored under high temperature and high humidity, and a decrease in the adhesion is a problem. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 58-27724. [Patent Document 2] Japanese Patent Laid-Open No. 2000-229355. [Patent Document 3] Japanese Patent Laid-Open No. 2009-220376. [Patent Document 4] Japanese Patent Laid-Open No. 2018-172473.

[Problem to be Solved by the Invention]

The present invention is made against the background of this prior art subject. That is, an object of the present invention is to provide an antistatic polyester film which has good adhesiveness between a polyester film and an antistatic layer and excellently maintains a high level of adhesiveness over a long period of time. [Means to solve the problem]

That is, the present invention is constituted by the following configurations. [1] An antistatic polyester film, in which at least one side of the polyester film is sequentially laminated with an easy-adhesive layer and an antistatic layer, and the aforementioned easy-adhesive layer consists of an acid with a carboxyl group having an acid value of 30 mgKOH/g to A layer formed by hardening the composition of a polyurethane resin of 50 mgKOH/g and a cross-linking agent having a carboxyl group with an acid value of 30 mgKOH/g to 50 mgKOH/g. [2] In one aspect, the crosslinking agent is an isocyanate compound. [3] In one aspect, the surface resistivity is 10 ¹⁰ Ω/□ or less. [4] In one aspect, the antistatic layer includes a conductive polymer. [5] In one aspect, the film haze is 3.0% or less. [6] An adhesive film comprising an adhesive layer on at least one side of the above-mentioned antistatic polyester film. [Efficacy of the invention]

The antistatic polyester film of the present invention has excellent adhesion to UV curable resins such as hard coat layers, lens layers, and inks, and is especially excellent in high-level adhesion to UV inks. The antistatic polyester film system of the present invention can provide an antistatic polyester film with excellent blocking resistance, excellent initial adhesion between the antistatic layer and the easy-adhesive layer and the polyester film substrate, and excellent moisture and heat resistance adhesion.

[Polyester film substrate] The polyester resin constituting the polyester film substrate in the present invention is not polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate, polyethylene terephthalate In addition to propylene glycol, a copolymerized polyester resin obtained by substituting a part of the diol component or dicarboxylic acid component of the aforementioned polyester resin with the following copolymerized components, for example, as the copolymerized component, may be List: Diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, polyalkylene glycol and other diol components; or adipic acid, sebacic acid, phthalic acid, isophthalic acid Dicarboxylic acid components such as formic acid, 5-sodium isophthalic acid, and 2,6-naphthalene dicarboxylic acid, etc.

The polyester resin that can suitably be used for the polyester film substrate in the present invention is mainly selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, poly Ethylene 2,6-naphthalene dicarboxylate. Among these polyester resins, polyethylene terephthalate is the best in terms of the balance between physical properties and cost. In addition, the polyester film substrate composed of these polyester resins is preferably a biaxially stretched polyester film, which can improve chemical resistance, heat resistance, mechanical strength, and the like.

The polycondensation catalyst used in the production of polyester resin is not particularly limited, but antimony trioxide is suitable because it is inexpensive and has excellent catalytic activity. In addition, it is also preferable to use a germanium compound or a titanium compound. Examples of more preferable polycondensation catalysts include catalysts containing aluminum and/or its compounds and phenolic compounds, catalysts containing aluminum and/or its compounds and phosphorus compounds, and catalysts containing aluminum salts of phosphorus compounds.

In addition, the layer composition of the polyester film base material in the present invention is not particularly limited, and it may be a single-layer polyester film, or may be composed of two layers with different components, or may have an outer layer and an inner layer. Polyester film substrate composed of at least three layers.

[easy adhesion layer] In order to improve the adhesion to the antistatic layer or the adhesive layer and improve the blocking resistance, the antistatic polyester film of the present invention preferably has an easy-adhesive layer on at least one layer of the polyester film base material. The layer is formed by a polyurethane resin having a carboxyl group with an acid value of 30 mgKOH/g to 50 mgKOH/g, and a crosslinking agent with a carboxyl group with an acid value of 30 mgKOH/g to 50 mgKOH/g. The easy-adhesive layer can be provided on both sides of the polyester film, or only on one side of the polyester film, and a different type of resin coating layer can be provided on the other side.

The easy-adhesive layer in the present invention has excellent adhesion to antistatic layers, hard coat layers, lens layers, inks, and other UV curable resins or thermosetting resins. In addition, since the polyurethane resin and the cross-linking agent have a certain range of carboxyl groups, it is possible to suppress the disadvantages of the monomeric resin having a large number of carboxyl groups, which leads to a decrease in water resistance and heat and humidity resistance, and makes it easy to adhere. The layer itself contains a large number of carboxyl groups.

The polyurethane resin with carboxyl group and the crosslinking agent with carboxyl group are preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, and even more preferably It is in the range of 70/30 to 30/70. When there is little crosslinking agent, durability, such as heat-and-moisture resistance, falls, and when there is little polyurethane resin, adhesiveness falls.

Each composition of the easily-adhesive layer will be described in detail below. [Polyurethane resin having a carboxyl group with an acid value of 30 mgKOH/g to 50 mgKOH/g] The polyurethane resin having a carboxyl group is a urethane resin synthesized from at least a polyol component and a polyisocyanate component, and if necessary, a chain extender, etc., and has a carboxyl group in a molecule or a side chain. The term "in the molecule" mentioned here refers to existing in the main chain or terminal of the aforementioned polyurethane resin. In addition, the so-called side chain refers to the presence of three or more terminal functional groups of any of the above-mentioned raw material components constituting the molecular chain, and is introduced into the molecular chain on the branch after synthesis and polymerization. The polyurethane resin having a carboxyl group in the present invention can be obtained mainly by using a carboxyl group-containing polyol component as a component of urethane.

Examples of the carboxyl group-containing polyol component include the following components. Components with relatively high molecular weight can be used, such as carboxyl-containing polyalkylene glycol, carboxyl-containing acrylic polyol, carboxyl-containing polyolefin polyol, carboxyl-containing polyester polyol, and the like. Alternatively, relatively low molecular weight components such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolbutyric acid, 2,2-dihydroxymethylbutanoic acid, Methylvaleric acid, etc. In the case of carboxyl group introduction, dimethylolpropionic acid and dimethylolbutyric acid are particularly suitably used.

The acid value of the polyurethane resin having carboxyl groups is preferably from 30 mgKOH/g to 50 mgKOH/g, more preferably from 35 mgKOH/g to 45 mgKOH/g. When the acid value is 30 mgKOH/g or more, the adhesiveness with respect to an antistatic layer or an adhesive layer will improve. On the other hand, if the acid value is 50 mgKOH/g or less, the water resistance of the coating layer will be maintained, and the films will not be easily bonded to each other due to moisture absorption, so it is preferable. However, in the polyurethane resin of the present invention, in order to fill up the water solubility or water dispersibility of the polyurethane resin, other hydrophilic groups such as hydroxyl, Ether, sulfonic acid, phosphonic acid, quaternary amine, etc.

Carboxyl groups in polyurethane resins can also be neutralized by basic compounds. Examples of the basic compound used for neutralization include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, and organic amine compounds. Among these, an organic amine compound that is easily dissociated from a carboxyl group by heating is preferred. Examples of organic amine compounds include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, 2-ethylhexylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, and diisopropylamine. , dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, ethylenediamine and other straight-chain or branched primary, secondary or tertiary amines with 1 to 20 carbon atoms; morpholine , N-alkylmorpholine, pyridine and other cyclic amines; monoisopropanolamine, methylethanolamine, methylisopropanolamine, dimethylethanolamine, diisopropanolamine, diethanolamine, triethanolamine, diethyl Hydroxyl-containing amines such as base ethanolamine and triethanolamine.

Among the other polyol components used in the synthesis and polymerization of the urethane resin in the present invention, polycarbonate polyols can be preferably used, especially those containing aliphatic polyols with excellent heat resistance and hydrolysis resistance. carbonate polyols. As aliphatic polycarbonate polyol, aliphatic polycarbonate diol, aliphatic polycarbonate triol, etc. are mentioned, Preferably aliphatic polycarbonate diol can be used. As the aliphatic polycarbonate diol used for synthesizing and polymerizing the urethane resin having a polycarbonate structure in the present invention, for example, ethylene glycol, propylene glycol, 1,3 -Propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1, One or more glycols such as 8-nonanediol, neopentyl glycol, diethylene glycol, and dipropylene glycol are obtained by reacting with carbonates such as dimethyl carbonate, diethyl carbonate, and phosgene Aliphatic polycarbonate diol, etc.

The number average molecular weight of the aforementioned polycarbonate polyol in the present invention is preferably from 300 to 5,000. More preferably 400 to 4000, most preferably 500 to 3000. If it is 300 or more, the adhesiveness with respect to an antistatic layer or an adhesive layer can be improved, and it is preferable. If it is 3000 or less, blocking resistance can be improved and it is preferable.

Examples of the polyisocyanate used in the synthesis and polymerization of the urethane resin in the present invention include: aliphatic diisocyanates having an aromatic ring such as xylene diisocyanate; isophorone diisocyanate and 4,4- Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and 1,3-bis(isocyanatemethyl)cyclohexane; hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate and other aliphatic diisocyanates; or modified polyisocyanates and diisocyanates containing isocyanurate linkages, biuret linkages or allophanate linkages produced from diisocyanates with single or multiple Trimethylolpropane and other pre-added polyisocyanates. When using the above-mentioned aliphatic diisocyanate having an aromatic ring, alicyclic diisocyanate or aliphatic diisocyanate, etc., there is no problem of yellowing and it is preferable.

Examples of chain extenders include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol; glycerin, trimethylolpropane, and Polyols such as pentaerythritol; diamines such as ethylenediamine, hexamethylenediamine, and piperazine; aminoalcohols such as monoethanolamine and diethanolamine; thiodi-glycols such as thiodiethylene glycol; or water. Moreover, if it is a small amount, you may use the polyhydric alcohol, polyamine, etc. of a trifunctional group or more.

The polyurethane resin of the present invention may also have reactive groups such as blocked isocyanate at the terminal or side chain in order to improve rigidity.

[Crosslinking agent] In the present invention, a crosslinking agent having a carboxyl group with an acid value of 30 mgKOH/g to 50 mgKOH/g is used. Moreover, the carboxyl group of a crosslinking agent can also be neutralized with a basic compound similarly to the polyurethane resin mentioned above. The acid value of the crosslinking agent having carboxyl groups is preferably 30 mgKOH/g to 50 mgKOH/g, more preferably 35 mgKOH/g to 45 mgKOH/g. When the acid value is 30 mgKOH/g or more, the adhesion to the antistatic layer or the adhesive layer is improved, which is preferable. On the other hand, if the acid value is 50 mgKOH/g or less, then the water resistance of the coating layer after coating will be maintained, and the films will be easily bonded to each other without moisture absorption, which is preferable. However, other hydrophilic groups such as hydroxyl, ether, sulfonic acid, phosphonic acid, quaternary amine, etc. can also be introduced in order to fill the water solubility or water dispersibility of the crosslinking agent in the present invention within the scope of not deteriorating the performance .

Examples of the crosslinking agent having a carboxyl group include oxazoline compounds, carbodiimide compounds, epoxy compounds, and isocyanate compounds having a carboxyl group introduced into the molecule. In addition, the carboxyl group can also be neutralized in advance with a basic compound so as not to react intramolecularly or intermolecularly with the carboxyl group introduced into the molecule. Among these crosslinking agents, isocyanate compounds that easily introduce carboxyl groups into the molecule are preferred, and blocked isocyanate compounds are particularly preferred.

Examples of the blocking agent include bisulfite-based compounds such as sodium bisulfite; 3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4 -Pyrazole-based compounds such as nitro-3,5-dimethylpyrazole; phenol-based compounds such as phenol and cresol; aliphatic alcohol-based compounds such as methanol and ethanol; active methylene compounds such as dimethyl malonate and acetylacetone Base series; thiol series such as butyl mercaptan and dodecyl mercaptan; acid amide series such as acetaniline and acetate amide; lactam series such as ε-caprolactam and δ-valerolactamide ; Acid imides such as succinic imide and maleic imide; Oxime systems such as acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, etc.; Diphenylaniline, aniline, ethylimine, etc. Blocking agent for amines, etc.

The lower limit of the boiling point of the blocking agent for blocking isocyanate is preferably 150°C, more preferably 160°C, further preferably 180°C, especially preferably 200°C, most preferably 210°C. The higher the boiling point of the blocking agent, the higher the volatilization of the blocking agent can be suppressed even if it is affected by the additional heat in the drying step after coating the coating liquid or in the film forming step in the case of the online coating method. , Inhibit the occurrence of tiny unevenness on the coated surface, and improve the transparency of the film. The upper limit of the boiling point of the end-capping agent is not particularly limited, but about 300° C. is the upper limit in terms of productivity. The boiling point is related to the molecular weight. Therefore, in order to increase the boiling point of the capping agent, it is better to use a capping agent with a large molecular weight. The molecular weight of the capping agent is preferably 50 or more, more preferably 60 or more, and more preferably 80 or more.

The upper limit of the dissociation temperature of the capping agent is preferably 200°C, more preferably 180°C, further preferably 160°C, especially preferably 150°C, most preferably 120°C. The blocking agent is affected by heat added in the drying step after coating of the coating liquid or in the film forming step in the case of an in-line coating method, and the blocking agent is dissociated to generate a regenerated isocyanate group. Therefore, a crosslinking reaction with a urethane resin etc. will progress and adhesiveness will improve. When the dissociation temperature of the blocked isocyanate is below the above-mentioned temperature, the dissociation of the blocking agent proceeds sufficiently, so that the adhesiveness becomes favorable, and especially the heat-and-moisture resistance becomes favorable.

As the blocking agent used in the present invention, the dissociation temperature of the blocked isocyanate is 120° C. or lower and the boiling point of the blocking agent is 150° C. or higher, including the aforementioned sodium bisulfite, 3,5-dimethylpyrazole, 3- Methylpyrazole, dimethyl malonate, diethyl malonate, acetone oxime, methyl ethyl ketone oxime, etc. Among them, pyrazole-based compounds represented by 3,5-dimethylpyrazole and 3-methylpyrazole are preferable in terms of heat and humidity resistance and yellowing.

The aforementioned blocked isocyanate is preferably difunctional or higher, and trifunctional or higher blocked isocyanate is more preferable from the viewpoint of the crosslinkability of the coating film.

The trifunctional or higher polyisocyanate which is the precursor of the blocked isocyanate of the present invention can be obtained suitably by introducing an isocyanate monomer. Examples include biurets and isocyanurates obtained by modifying isocyanate monomers such as aromatic diisocyanate, aliphatic diisocyanate, aromatic aliphatic diisocyanate, or alicyclic diisocyanate having two isocyanate groups. Acid bodies and adducts. The biuret body is a self-condensation product having a biuret bond formed by self-condensing isocyanate monomers, and examples thereof include biuret bodies of hexamethylene diisocyanate and the like. The so-called isocyanurate body is a trimer of isocyanate monomer, for example: trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, trimer of toluene diisocyanate, etc. . The so-called adduct refers to a trifunctional or higher isocyanate compound formed by reacting an isocyanate monomer with a trifunctional or higher low-molecular-weight active hydrogen-containing compound, for example, trimethylolpropane and hexamethylene diisocyanate Compounds formed by the reaction, compounds formed by the reaction of trimethylolpropane and toluene diisocyanate, compounds formed by the reaction of trimethylolpropane and xylene diisocyanate, compounds formed by the reaction of trimethylolpropane Compounds formed by the reaction of isocyanates, etc.

Examples of the isocyanate monomer include: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2 ,2'-Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, phenylene diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenyl ether diisocyanate , 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4, Aromatic diisocyanates such as 4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, xylene diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane; hexamethylene diisocyanate and 2,2,4 - Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate. In terms of transparency, yellowing resistance, adhesiveness, and heat and humidity resistance, aliphatic or alicyclic isocyanate or modified products thereof are preferred.

In the present invention, it can also be used in combination with other resins within the range that does not affect performance. Examples of the resin used in combination include carboxyl-free polyurethane, polyester resin, acrylic resin, cellulose resin, polyolefin resin, polyacetal resin, and the like. Among these resins, polyester resins that improve adhesion to an antistatic layer or an adhesive layer by using in combination are particularly preferable. Moreover, when using polyester resin together, you may contain 1.5 times or more of the total content of a carboxyl group-containing polyurethane resin and a carboxyl group-containing crosslinking agent. Regarding the above-mentioned effect, it is presumed that the reason is that, compared with carboxyl group-containing polyurethane resin or carboxyl group-containing crosslinking agent, polyester resin has a better affinity for polyester resin as a base material, so in the thickness direction It is easy to exist locally on the substrate side, so the adhesion to the substrate interface is improved, and it shows that the carboxyl-containing polyurethane resin and carboxyl-containing cross-linking agent locally present on the surface layer are relatively relative to the antistatic layer or The adhesive resin contained in the adhesive layer has a synergistic effect of improving the adhesion.

[polyester resin] The polyester resin used together in the coating layer in the present invention may be linear, but is more preferably a polyester resin containing dicarboxylic acid and diol (diol) having a branched structure as constituent components. The dicarboxylic acids mentioned here, in addition to the main components of terephthalic acid, isophthalic acid or 2,6-naphthalene dicarboxylic acid, include aliphatic dicarboxylic acids such as adipic acid and sebacic acid; Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalene dicarboxylic acid. In addition, the branched diol is a diol having a branched alkyl group, for example, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1, 3-propanediol, 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, 2,2-di-n-butyl-1,3-propanediol, 2-n-butyl-2-propyl-1,3-propanediol, and 2 , 2-Di-n-hexyl-1,3-propanediol, etc.

Regarding the above-mentioned polyester resin, the branched diol component, which can be said to be the more preferred aspect, is preferably contained in a ratio of 10 mol% or more in the total diol component, and more preferably contained in a ratio of 20 mol% or more. in the total diol component. If it is 10 mol% or more, the crystallinity will not be too high, and it is preferable to maintain the adhesiveness of the coating layer. The upper limit of the diol component in the total diol components is preferably 80 mol% or less, more preferably 70 mol% or less. If it is 80 mol% or less, the concentration of the oligomer as a by-product is unlikely to increase, and it is preferable to maintain the transparency of the coating layer. Ethylene glycol is most preferable as the diol component other than the above compounds. If it is a small amount, diethylene glycol, propylene glycol, butanediol, hexanediol, 1, 4- cyclohexanedimethanol, etc. can also be used.

As for the dicarboxylic acid which is a constituent component of the above-mentioned polyester resin, terephthalic acid or isophthalic acid is most preferable. In addition to the above-mentioned dicarboxylic acids, in order to impart water dispersibility to the copolymerized polyester resin, it is preferable to copolymerize 5-sulfoisophthalic acid or the like in the range of 1 mol % to 10 mol %, for example Examples thereof include sulfonic acid terephthalic acid, 5-sulfonic acid isophthalic acid, 5-sulfonic acid sodium isophthalic acid, and the like.

When the total solid content of the resin and crosslinking agent in the coating solution forming the easy-adhesive layer is taken as 100% by mass, if the polyester resin content is 10% by mass or more, the easily-adhesive layer and the polyester film base The adhesion of the material becomes better and better. The upper limit of the content of the polyester resin is preferably at most 65% by mass, more preferably at most 60% by mass. When the content rate of a polyester resin is 70 mass % or less, heat-and-moisture resistance will become favorable, and it is preferable.

Resins other than the aforementioned polyester resins may also be used in the easy-adhesive layer within the range of not degrading the performance of the present invention. A representative example of the resin other than the aforementioned polyester resin is a polyurethane resin having a carboxyl group, but other resins may be contained, and only the polyurethane resin having a carboxyl group may be used. In this case, if the sum of the solid content of the resin and the crosslinking agent in the coating liquid for forming the easily-adhesive layer is 100% by mass, the content of resins other than the polyester resin is preferably 40% by mass or less. More preferably, it is 30 mass % or less, and especially preferably, it is 20 mass % or less. However, the total content of resins other than the polyester resin and the polyester resin is preferably 70% by mass or less. The content of each of the polyurethane resin and the crosslinking agent in the coating solution for forming the coating layer is preferably 3% by mass or more in terms of the total solid content of the resin and the crosslinking agent. If it is 3 mass % or more, since the effect of the adhesiveness with respect to an antistatic layer or an adhesive layer can be acquired, it is preferable. A more preferable range of the content is 3.5% by mass to 90% by mass, more preferably 7% by mass to 80% by mass, especially preferably 10.5% by mass to 70% by mass.

[additive] In the easy-adhesive layer in the present invention, well-known additives such as surfactants, antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, ultraviolet absorbers, organic slippery Agents, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, etc.

In the present invention, it is also preferable to add particles to the coating layer in order to further improve the blocking resistance of the coating layer. As the particles contained in the coating layer in the present invention, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silicon dioxide, alumina, talc, kaolin, clay, etc. or a mixture of these, and other General inorganic particles such as calcium phosphate, mica, lithium bentonite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, etc.; or styrene, acrylic, melamine, benzoguanamine Organic polymer-based particles such as silicone-based, silicone-based, etc.

The average particle size of the particles in the easy-adhesive layer (the average particle size based on the number obtained by a scanning electron microscope (SEM; Scanning Electron Microscope). The same below) is preferably 0.04 μm to 2.0 μm, more preferably 0.1 μm to 1.0 μm. When the average particle size of the inert particles is 0.04 μm or more, unevenness is easily formed on the surface of the film, so the lubricity and winding properties of the film are improved, and the processability at the time of bonding is good, which is preferable. On the other hand, when the average particle diameter of the inert particles is 2.0 μm or less, it is more difficult for the particles to fall off, which is preferable. The particle concentration in the easily bonding layer is preferably 1% by mass to 20% by mass in the solid content.

The method of measuring the average particle diameter of the particles is measured by the following method: the particles of the cross-section of the laminate of the polyester film substrate and the easy-adhesive layer (hereinafter also referred to as the laminated polyester film) are measured by a scanning electron microscope. Observation was carried out, 30 particles were observed, and the average value of the particles was taken as the average particle diameter.

The shape of the particles is not particularly limited as long as the purpose of the present invention is satisfied, and spherical particles and amorphous non-spherical particles can be used. The particle size of amorphous particles can be calculated by the equivalent diameter of a circle. The circle equivalent diameter is the value obtained by dividing the area of the observed particle by π, calculating the square root and multiplying by 2.

[Manufacture of laminated polyester film] The manufacturing method of the laminated polyester film of this invention is demonstrated using the example which used the polyethylene terephthalate (Polyethylene terephthalate, hereinafter sometimes abbreviated as PET) film base material, However, Of course, it is not limited to this.

After the PET resin is fully vacuum-dried, it is supplied to the extruder, and the molten PET resin at about 280°C is melted and extruded from the T-die in a sheet form to a rotating cooling roll, and cooled and solidified by electrostatic application to obtain an unstretched PET sheet. The aforementioned unstretched PET sheet may be composed of a single layer, or may be composed of multiple layers obtained by co-extrusion.

Crystal alignment was carried out by performing uniaxial stretching or biaxial stretching on the obtained unstretched PET sheet. For example, in the case of biaxial stretching, use a roller heated to 80°C to 120°C to stretch to 2.5 to 5.0 times in the longitudinal direction, and after obtaining a uniaxially stretched PET film, hold the end of the film with a clip (clip) , guided to the hot air zone heated to 80°C to 180°C, and extended to 2.5 to 5.0 times in the width direction. In addition, in the case of uniaxial stretching, it is stretched to 2.5 times to 5.0 times in a tenter. After extension, continue to guide to the heat treatment area, and perform heat treatment to complete the crystal alignment.

The lower limit of the temperature in the heat treatment zone is preferably 170°C, more preferably 180°C. If the temperature in the heat treatment zone is above 170°C, the hardening will become sufficient, and the adhesion will become better in the presence of liquid water, which is better, and there is no need to prolong the drying time. On the other hand, the upper limit of the temperature in the heat treatment zone is preferably 250°C, more preferably 240°C. It is preferable that the temperature of the heat treatment zone is not higher than 240° C., since there is no possibility of a decrease in the physical properties of the film.

The easy-adhesive layer can be provided after film production or during a production step. Especially in terms of productivity, it is preferable to apply the coating solution to at least one side of the PET film at any stage of the film production process (that is, after unstretched or uniaxially stretched), and to stretch at least in the uniaxial direction. , performing heat treatment to form an easy-adhesive layer.

A known arbitrary method can be used for the method for applying this coating liquid to a PET film. For example, reverse roll coating method, gravure coating method, touch coating method, die coating method, roll brush method, spray coating method, air knife coating method, wire bar coating method, tubular doctor blade method, dip coating method, curtain coating method, etc. These methods can be applied alone or in combination.

In the present invention, the thickness of the easy-adhesive layer can be appropriately set in the range of 0.001 μm to 2.00 μm, in order to have both processability and adhesiveness, it is preferably in the range of 0.01 μm to 1.00 μm, more preferably 0.02 μm to 0.80 μm , and more preferably 0.05 μm to 0.50 μm. When the thickness of the easily-adhesive layer is 0.001 μm or more, the adhesiveness is good, which is preferable. If the thickness of the easy-adhesive layer is 2.00 μm or less, it is more difficult to cause blocking, which is preferable.

The upper limit of the haze of the laminated polyester film of the present invention is preferably 2.5%, more preferably 2.0%, still more preferably 1.5%, especially preferably 1.2%. When the haze is 2.5% or less, it is preferable in terms of transparency, and can be suitably used for an optical film requiring transparency. Usually, the smaller the haze, the better, but it may be 0.1% or more, or 0.2% or more.

[Antistatic layer] The antistatic polyester film of the present invention has an antistatic layer on the easy-adhesive layer in the laminated polyester film. The antistatic layer can be laminated on only one side or on both sides. By laminating the antistatic layer, when laminating an adhesive layer and using it as a protective film, it is also possible to suppress detachment electrification from an adherend or to suppress adhesion of foreign matter, which is preferable.

There is no particular limitation on the means of laminating the antistatic layer. Known methods such as coating, vacuum evaporation, and lamination can be used. From the viewpoint of cost, it is preferable to install antistatic The coating solution of the agent.

As an antistatic agent, cationic compounds and other ion-conducting polymers or surfactants, silicon oxide films, conductive metal compounds, π-electron conjugated conductive polymers, etc. can be used for antistatic properties at low humidity. In terms of properties, it is preferable to use a π-electron conjugated conductive polymer. In addition, the π-electron conjugated conductive polymer can maintain antistatic performance at a high level independent of moisture in the air, so it has good antistatic performance in various usage environments of protective films, so it is preferable.

Examples of π-electron conjugated conductive polymers include: aniline-based polymers containing aniline or its derivatives as a constituent unit, pyrrole-based polymers containing pyrrole or its derivatives as a constituent unit, acetylene or its derivatives Acetylene-based polymers as constituent units, thiophene-based polymers containing thiophene or derivatives thereof as constituent units, and the like. If high transparency is to be obtained, it is preferable that the π-electron conjugated conductive polymer does not have a nitrogen atom, and among them, thiophene containing thiophene or its derivatives as a constituent unit is preferable in terms of transparency. It is a polymer, especially suitable for polyalkylene dioxythiophene. Examples of the polyalkylenedioxythiophene include polyethylenedioxythiophene, polypropylenedioxythiophene, poly(ethylene/propylenedioxythiophene), and the like.

Furthermore, in the thiophene-based polymer containing thiophene or a derivative thereof as a constituent unit, 0.1 to 500 parts by mass of A dopant for better antistatic properties. When the amount of dopant is small, electron migration becomes difficult, so there is a problem that the antistatic performance is lowered. Conversely, when the amount of dopant is large, there is a problem that the dispersibility to the solvent is lowered. Examples of the dopant include: LiCl, R _1-30 COOLi (R _1-30 : a saturated hydrocarbon group with a carbon number of 1 to 30), R _1-30 SO ₃ Li, R _1-30 COONa, R _1‐30 SO ₃ Na, R _1‐30 COOK, R _1‐30 SO ₃ K, Tetraethylammonium, I ₂ , BF ₃ Na, BF ₄ Na, HClO ₄ , CF ₃ SO ₃ H, FeCl ₃ , Tetra Cyanoquinoline (TCNQ), Na ₂ B ₁₀ Cl ₁₀ , Phthalocyanine, Porphyrin, Glutamic Acid, Alkyl Sulfonate, Polystyrene Sulfonate Na(K, Li) Salt, Styrene-Styrene Sulfonate Acid Na(K, Li) salt copolymer, polystyrene sulfonate anion, styrene sulfonic acid-styrene sulfonate anion copolymer, etc.

The antistatic agent contained in the antistatic layer in the present invention is preferably contained at least 1% by mass, more preferably at least 10% by mass, based on 100 parts by mass of the solid content of the antistatic layer. Furthermore, when using a π-electron conjugated conductive polymer as an antistatic agent, in the case of using the aforementioned dopant, the amount of the π-electron conjugated conductive polymer specified in this case in the antistatic layer The content is the total amount of the conductive polymer and the aforementioned dopant. For example, the antistatic agent may be 80 mass % or less, and may be 50 mass % or less.

In the antistatic layer of the present invention, it is preferable to contain a binder resin. The binder resin is not particularly limited, and specific examples of polymers include polyester resins, acrylic resins, urethane resins, polyolefin resins, polyethylene resins (polyvinyl alcohol, etc.), Polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches, etc. Among these, it is preferable to use a polyester resin, an acrylic resin, and a urethane resin from the viewpoint of the adhesiveness with respect to a polyester film. From the viewpoint of the ease of molecular design or molecular weight design, it is more preferable to use an acrylic resin.

Among the binder resins, more reactive functional groups are preferred. Although not particularly limited, it is preferably a hydroxyl group, a carboxyl group, an amino group, an acrylate group, an epoxy group, etc., and it is more preferable to have a hydroxyl group or a carboxyl group.

The above-mentioned binder resin may have a silicone component or a long-chain alkyl group that can express mold release properties. In the case where an adhesive layer is laminated, by providing an antistatic layer with mold release properties on the surface of the laminated film opposite to the adhesive layer, it is possible to prevent blocking, etc. even when it is wound up into a roll state. better.

[Crosslinking agent] In the present invention, in order to form a crosslinked structure in the antistatic layer, the antistatic layer may also be formed by containing a crosslinking agent. By containing a crosslinking agent, the adhesiveness with an easily-adhesive layer improves, or durability improves, and also suppresses the fall of the antistatic performance in the case of processing under high-temperature high-humidity conditions, and it is preferable. Specific examples of crosslinking agents include urea-based, epoxy-based, melamine-based, isocyanate-based, oxazoline-based, carbodiimide-based, aziridine-based, and the like. Especially preferred are melamine-based, oxazoline-based, carbodiimide-based, and aziridine-based. Moreover, in order to promote a crosslinking reaction, a catalyst etc. can be used suitably as needed.

The crosslinking agent contained in the antistatic layer of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, based on 100 parts by mass of the solid content of the antistatic layer. If it is 5 mass % or more, since the heat-and-moisture resistance of an antistatic layer etc. can be improved, it is preferable. In addition, as long as it is a crosslinking agent capable of self-crosslinking, the binder resin may not be present. For example, the crosslinking agent may be 90% by mass or less, or may be 80% by mass or less.

In the antistatic layer in the present invention, a surfactant may also be used to improve the appearance. As the surfactant, for example, nonionic surfactants such as polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan fatty acid ester; Fluoroalkyl carboxylic acid, perfluoroalkylbenzene sulfonic acid, perfluoroalkyl quaternary ammonium, perfluoroalkyl polyoxyethylene alcohol and other fluorine-based surfactants; or silicone-based surfactants.

In the antistatic layer, in addition to the above, a slip agent, a pigment, an ultraviolet absorber, a silane coupling agent, etc. may be mixed as needed within the scope not to impair the object of the present invention.

The film thickness of the antistatic layer of the present invention is preferably not less than 0.005 μm and not more than 1 μm. More preferably, it is not less than 0.01 μm and not more than 0.5 μm, and still more preferably not less than 0.01 μm and not more than 0.2 μm. If the film thickness of the antistatic layer is not less than 0.005 μm, an antistatic effect can be obtained, which is preferable. On the other hand, when it is 1 micrometer or less, since there is little coloring and transparency becomes high, it is preferable.

The surface resistivity of the antistatic film of the present invention is preferably 1×10 ¹⁰ Ω/□ or less. More preferably, it is at most 1×10 ⁹ Ω/□, further preferably at most 1×10 ⁷ Ω/□, and most preferably at most 1×10 ⁶ Ω/□. By setting the surface resistivity to 1×10 ¹⁰ Ω/□ or less, it is possible to suppress the adhesion of foreign matter to the laminated polyester, or to suppress the peeling charge when the laminated adhesive layer is peeled off, so it is preferable. In addition, the lower limit of the surface resistivity of the antistatic film is not particularly limited, but it is preferably at least 1×10 ³ Ω/□. In order to make the surface resistance of the antistatic film less than 1×10 ³ Ω/□, the processing cost of the antistatic layer increases, which is not preferable.

The haze of the antistatic film used in the present invention is preferably 3% or less. More preferably, it is 1.5% or less, More preferably, it is 1.0% or less. It is excellent if it is 0.8% or less. If it is 3% or less, visual inspection and the like can be performed with the protective film bonded to the adherend, which is preferable, especially when the member for optical use is the adherend. The haze is preferably lower, and may be substantially 0% (0% or more), for example, 0.1% or more.

The area average surface roughness (Sa) of the surface of the antistatic film used in the present invention is preferably in the range of 1 nm to 40 nm, more preferably 1 nm to 30 nm. More preferably, it is 1 nm to 10 nm. The maximum protrusion height (P) of the surface of the antistatic film used in the present invention is preferably 2 μm or less, more preferably 1.5 μm or less. More preferably, it is 0.8 μm or less. When Sa is 40 nm or less and P is 2 μm or less, it is preferable that there is no possibility of roughening the adhesive surface when the adhesive layer is laminated and wound up into a roll shape.

As a method of coating a laminated antistatic layer on the surface of a substrate film, there are gravure roll coating, reverse roll coating, knife coating, dip coating, rod coating, and spin coating. There is no particular limitation on the coating method suitable for the conductive composition. In addition, it can be provided by an in-line coating system in which a coating layer is provided in a film production step, or an off-line coating system in which a coating layer is provided after film production.

Regarding the antistatic layer, the drying temperature for forming the antistatic layer by the aforementioned method is usually 60°C to 150°C, preferably 90°C to 140°C. If the temperature is 60° C. or higher, it is sufficient to perform short-time treatment, which is preferable from the viewpoint of improving productivity. Moreover, when a crosslinking agent is contained, a crosslinking reaction fully progresses, and it is preferable. On the other hand, when the temperature is 150° C. or lower, the planarity of the film is maintained, which is preferable.

On the antistatic film of the present invention, an adhesive layer can also be laminated by applying an adhesive and curing it. The adhesive can be used without particular limitation, and the obtained laminated film is used as a protective film. The side of the laminated adhesive layer can be either side of the antistatic film. When using an antistatic film having an antistatic layer on only one side, it is preferable to have an antistatic layer on the side of the antistatic film opposite to the side on which the adhesive layer is laminated. [Example]

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

(1) Haze The haze of the obtained antistatic polyester film was measured in accordance with JIS (Japanese Industrial Standards; Japanese Industrial Standards) K 7136:2000 using a turbidity meter (manufactured by Nippon Denshoku, NDH5000).

(2) acid value The acid values of the resin and the crosslinking agent were measured by the titration method described in JIS K1557-5:2007. However, in the case of a carboxyl group neutralized with an amine or the like, the amine or the like is removed by high-temperature treatment, or the amine or the like is liberated and removed by treatment with hydrochloric acid or the like beforehand, and then measured. In addition, in the case of a crosslinking agent, the measurement is carried out after reacting reactive groups such as isocyanate with amine or the like in advance. In the case where the measured resin has poor solubility to isopropanol as a solvent, N-methylpyrrolidone was used instead. In any one of the above treatments, the measurement for comparison is sufficiently performed.

(3) Anti-adhesion Two film samples were stacked so that the coating layers faced each other, a load of 98 kPa was applied, and the two film samples were left to adhere to each other in an atmosphere of 50° C. for 24 hours. Then, the film was peeled off, and the peeled state of the film was judged according to the following criteria. ◯: The coating layer can be peeled lightly without transferring the coating layer. △: The coating layer was maintained, but the surface layer of the coating layer was partially transferred to the target surface. ×: The two films were fixed and could not be peeled off, or the film substrate was torn although peelable.

(4) Adhesion to the antistatic layer For the antistatic layer laminated on the easy-to-adhesive layer of the laminated polyester film, use a cutter guide with a gap interval of 2mm to cut out 100 grids that penetrate the antistatic layer and reach the film substrate on the antistatic layer shaped incision. Next, cellophane tape (manufactured by Nichiban, No. 405; 24 mm width) was attached to the grid-shaped incision surface so that the cellophane tape was firmly attached. Then, the cellophane tape was peeled vertically from the antistatic layer of the laminated film. After a total of 5 tape attachment and peeling operations at the same place, the number of grids peeled off from the antistatic layer of the laminated film was visually counted, and the adhesion between the antistatic layer and the film substrate was obtained from the following formula . In addition, among the grids, the partially peeled grids were also counted as the peeled grids, and the adhesiveness of the antistatic layer was obtained as in the following formula. The adhesion of the antistatic layer (%) = 100 - (the number of grids peeled off). Adhesion of the antistatic layer was judged according to the following criteria. ◎: 100%; ○: 96% to 99%; △: 80% to 95%; ×: less than 80%. As a standard, 0 or more was regarded as a pass.

(5) Humidity and heat resistance For the antistatic polyester film laminated with an antistatic layer prepared in the same way as in (4) above, under the environment of 80°C and 80%RH, the coated surface is set vertically and other films, etc. do not touch the coated surface The state is placed for 500 hours. After the treatment, it was left to stand for 10 minutes in an environment of 23°C and 65%RH without other films touching the coated surface. Immediately after the passage of time, the adhesiveness of the coated surface was evaluated in the same manner as described above.

(6) Surface resistivity The surface resistivity of the surface of the release film of the present invention is adjusted for 24 hours at a temperature of 23° C. and a humidity of 55%, using a surface resistivity measuring device (manufactured by Simco Japan Co., Ltd., bench test) Machine (Worksurface tester) ST-3) Measure the surface resistance value of the surface of the release layer, and evaluate according to the following criteria. ⊚: The surface resistance value is less than 10 ⁷ Ω/□. ○: The surface resistance value is 10 ⁷ Ω/□ to 10 ⁸ Ω/□. Δ: The surface resistance value is 10 ⁹ Ω/□ to 10 ¹⁰ Ω/□. ×: The surface resistance value is 10 ¹¹ Ω/□ or more.

[Polymerization of Polyurethane Resin A-1] Into a four-neck flask equipped with a stirrer, a Dimroth condenser, a nitrogen introduction tube, a silicone drying tube and a thermometer, put in 82.8 mass of hydrogenated m-xylene diisocyanate 25.0 parts by mass of dimethylol propionic acid, 21.0 parts by mass of 1,6-hexanediol, 150.0 parts by mass of polyester diol with a number average molecular weight of 2000 composed of adipic acid and 1,4-butanediol, And 110 parts by mass of acetone as a solvent, stirred at 75° C. for 3 hours under a nitrogen atmosphere, and confirmed that the reaction liquid reached a predetermined amine equivalent. Then, after cooling this reaction liquid to 40 degreeC, 19.8 mass parts of triethylamines were added, and the polyurethane polymer solution was obtained. Next, 500 g of water was added to a reaction vessel equipped with a homogenizer capable of high-speed stirring, adjusted to 25° C., and the polyurethane polymer solution was added to perform water dispersion while stirring and mixing at 2000 min ⁻¹ . Then, acetone as a solvent was removed under reduced pressure. The solution of solid content 35 mass % containing the polyurethane resin (A-1) whose acid value is 37.5 mgKOH/g was prepared by concentration adjustment with water.

[Polymerization of Polyurethane Resin A-2] Put 63.0 parts by mass of hydrogenated m-xylene diisocyanate, dihydroxy 21.0 parts by mass of methacrylic acid, 147.0 parts by mass of polycarbonate diol (1,6-hexanediol type) with a number average molecular weight of 2000, and 110 parts by mass of acetone as a solvent were stirred at 75° C. for 3 Hours, confirm that the reaction solution reaches the predetermined amine equivalent. Then, after cooling this reaction liquid to 40 degreeC, 16.6 mass parts of triethylamines were added, and the polyurethane polymer solution was obtained. Next, 500 g of water was added to a reaction vessel equipped with a homogenizer capable of high-speed stirring, adjusted to 25° C., and the polyurethane polymer solution was added to perform water dispersion while stirring and mixing at 2000 min ⁻¹ . Then, acetone as a solvent was removed under reduced pressure. The solution of 35 mass % of solid content containing the polyurethane resin (A-2) whose acid value is 36.3 mgKOH/g was prepared by performing concentration adjustment with water.

[Polymerization of Polyurethane Resin A-3] Put 64.5 parts by mass of hydrogenated diphenylmethane diisocyanate, two 21.5 parts by mass of methylolpropionic acid, 11.2 parts by mass of neopentyl glycol, 150.5 parts by mass of polycarbonate diol (1,6-hexanediol type) with a number average molecular weight of 2000, and 110 parts by mass of acetone as a solvent, Stir at 75° C. for 3 hours under a nitrogen atmosphere, and confirm that the reaction solution has reached the predetermined amine equivalent. Then, after cooling this reaction liquid to 40 degreeC, 17.0 mass parts of triethylamines were added, and the polyurethane polymer solution was obtained. Next, 500 g of water was added to a reaction vessel equipped with a homogenizer capable of high-speed stirring, adjusted to 25° C., and the polyurethane polymer solution was added to perform water dispersion while stirring and mixing at 2000 min ⁻¹ . Then, acetone as a solvent was removed under reduced pressure. The solution of solid content 35 mass % containing the polyurethane resin (A-3) whose acid value is 36.0 mgKOH/g was prepared by performing concentration adjustment with water.

[Polymerization of Polyurethane Resin A-4] Put 83.4 parts by mass of hydrogenated m-xylene diisocyanate, dihydroxy 16.9 parts by mass of methacrylic acid, 28.4 parts by mass of 1,6-hexanediol, 151.0 parts by mass of polyester diol with a number average molecular weight of 2000 composed of adipic acid and 1,4-butanediol, and 110 parts by mass of acetone was stirred at 75° C. for 3 hours under a nitrogen atmosphere, and it was confirmed that the reaction liquid reached a predetermined amine equivalent. Then, after cooling this reaction liquid to 40 degreeC, 13.3 mass parts of triethylamines were added, and the polyurethane polymer solution was obtained. Next, 500 g of water was added to a reaction vessel equipped with a homogenizer capable of high-speed stirring, adjusted to 25° C., and the polyurethane polymer solution was added to perform water dispersion while stirring and mixing at 2000 min ⁻¹ . Then, acetone as a solvent was removed under reduced pressure. A polyurethane resin (A-4) solution having a solid content of 35% by mass of a solid content acid value of 25.3 mgKOH/g was prepared by performing concentration adjustment with water. The solid content 35 mass % solution containing the polyurethane resin (A-4) whose acid value is 25.3 mgKOH/g was prepared.

[Polymerization of Polyurethane Resin A-5] Put 104.9 parts by mass of hydrogenated m-xylene diisocyanate, dihydroxy 41.8 parts by mass of methacrylic acid, 19.0 parts by mass of 1,6-hexanediol, 152.0 parts by mass of polyester diol with a number average molecular weight of 2000 composed of adipic acid and 1,4-butanediol, and 110 parts by mass of acetone was stirred at 75° C. for 3 hours under a nitrogen atmosphere, and it was confirmed that the reaction liquid reached a predetermined amine equivalent. Then, after cooling this reaction liquid to 40 degreeC, 33.1 mass parts of triethylamines were added, and the polyurethane polymer solution was obtained. Next, 500 g of water was added to a reaction vessel equipped with a homogenizer capable of high-speed stirring, adjusted to 25° C., and the polyurethane polymer solution was added to perform water dispersion while stirring and mixing at 2000 min ⁻¹ . Then, acetone as a solvent was removed under reduced pressure. A polyurethane resin (A-5) solution having a solid content of 35% by mass of a solid content acid value of 55.0 mgKOH/g was prepared by performing concentration adjustment with water. The solution of 35 mass % of solid content containing the polyurethane resin (A-5) whose acid value is 55.0 mgKOH/g was prepared.

[Polymerization of Polyurethane Resin A-6] Put 45.0 parts by mass of hydrogenated m-xylene diisocyanate, 1, 20.0 parts by mass of 6-hexanediol, 149.0 parts by mass of polyethylene glycol with a number average molecular weight of 2000, and 110 parts by mass of acetone as a solvent, stirred at 75°C for 3 hours under a nitrogen atmosphere, and confirmed that the reaction solution reached the predetermined amine equivalent . Next, after lowering the temperature of the reaction liquid to 40°C, add 500 g of water to a reaction vessel equipped with a homogenizer capable of high-speed stirring, adjust the temperature to 25°C, and add polyurethane polymer while stirring and mixing at 2000 min ^-1 The solution is water dispersed. Then, acetone as a solvent was removed under reduced pressure. The solution of 35 mass % of solid content containing the polyurethane resin (A-6) whose acid value is 0.2 mgKOH/g was prepared by performing concentration adjustment with water.

[Polymerization of Polyurethane Resin A-7] Put 43.8 parts by mass of hydrogenated diphenylmethane diisocyanate, two 12.9 parts by mass of methylolbutyric acid, 153.4 parts by mass of polycarbonate diol (1,6-hexanediol type) with a number average molecular weight of 2000, and 110 parts by mass of acetone as a solvent, stirred at 75°C under a nitrogen atmosphere After 3 hours, confirm that the reaction solution has reached the predetermined amine equivalent. Then, after cooling this reaction liquid to 40 degreeC, 8.8 mass parts of triethylamines were added, and the polyurethane polymer solution was obtained. Next, 500 g of water was added to a reaction vessel equipped with a homogenizer capable of high-speed stirring, adjusted to 25° C., and the polyurethane polymer solution was added to perform water dispersion while stirring and mixing at 2000 min ⁻¹ . Then, acetone as a solvent was removed under reduced pressure. A polyurethane resin (A-7) solution having a solid content of 35% by mass of a solid content acid value of 23.1 mgKOH/g was prepared by performing concentration adjustment with water. The solution of 35 mass % of solid content containing the polyurethane resin (A-7) with an acid value of 23.1 mgKOH/g was prepared.

[Synthesis of Crosslinking Agent B-1] Put 59.5 parts by mass of hexamethylene diisocyanate, 10.7 parts by mass of neopentyl glycol, 11.0 parts by mass of dimethylol butyric acid, and N-methylpyrrolidone as a solvent into a flask equipped with a stirrer, a thermometer, and a reflux condenser 20.0 parts by mass, stirred at 80° C. for 3 hours under a nitrogen atmosphere, and confirmed that the reaction liquid reached the predetermined amine equivalent. Then, 29.9 parts by mass of 2-butanone oxime was added dropwise to the reaction liquid, and it was kept at 80° C. for 1 hour under a nitrogen atmosphere. Then, after measuring the infrared spectrum of the reaction liquid and confirming that the absorption of the isocyanate group disappeared, the temperature of the reaction liquid was lowered to 40° C., and 7.9 parts by mass of triethylamine was added. After stirring for 1 hour as it was, an appropriate amount of water was added to prepare a solution of a blocked isocyanate-based crosslinking agent (B-1) with a solid content of 40% by mass. The acid value corresponding to the solid content of the crosslinking agent B-1 is 37.6 mgKOH/g.

[Synthesis of Crosslinking Agent B-2] In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 66.6 parts by mass of a polyisocyanate compound (manufactured by Asahi Kasei Chemicals, Duranate TPA) with an isocyanurate structure using hexamethylene diisocyanate as a raw material, N-methyl 17.5 parts by mass of pyrrolidone was added dropwise to 21.7 parts by mass of 3,5-dimethylpyrazole, and it was maintained at 70° C. for 1 hour under a nitrogen atmosphere. Then, 9.0 parts by mass of dimethylolpropionic acid was added dropwise. The infrared spectrum of the reaction solution was measured, and after confirming that the absorption of the isocyanate group disappeared, 6.3 parts by mass of N,N-dimethylethanolamine was added. After stirring for 1 hour as it was, an appropriate amount of water was added to prepare a solution of a blocked isocyanate-based crosslinking agent (B-2) with a solid content of 40% by mass. The acid value corresponding to the solid content of the crosslinking agent B-2 is 41.2 mgKOH/g.

[Synthesis of Crosslinking Agent B-3] 150.0 parts by mass of water and 250.0 parts by mass of methoxypropyl alcohol were placed in a flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 80° C. under a nitrogen atmosphere. Then, while keeping the inside of the flask at 80° C., a monomer mixture (126.0 parts by mass of methyl methacrylate, 2-isopropenyl-2-oxazole 210.0 parts by mass of morphine and 53.0 parts by mass of triethylamine methacrylate), and a polymerization initiator solution (2,2'-azobis(2-amidinopropane) dihydrochloride as a polymerization initiator 18.0 parts by mass of salt and 170.0 parts by mass of water). After completion of the dropwise addition, it was stirred at 80° C. for 5 hours, and then cooled to room temperature. An appropriate amount of water was added to prepare a solution of an oxazoline-based crosslinking agent (B-3) with a solid content of 40% by mass. The acid value corresponding to the solid content of the crosslinking agent B-3 is 39.8 mgKOH/g.

[Polymerization of Crosslinking Agent B-4] In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 65.0 parts by mass of a polyisocyanate compound (manufactured by Asahi Kasei Chemicals, Duranate TPA) with an isocyanurate structure using hexamethylene diisocyanate as a raw material, N-methyl 17.5 parts by mass of pyrrolidone, 29.2 parts by mass of 3,5-dimethylpyrazole, and 21.9 parts by mass of polyethylene glycol monomethyl ether with a number average molecular weight of 500 were maintained at 70° C. for 2 hours under a nitrogen atmosphere. Then, 4.0 parts by mass of trimethylolpropane was added dropwise. The infrared spectrum of the reaction liquid was measured, and after confirming that the absorption of the isocyanate group disappeared, 280.0 parts by mass of water were added. An appropriate amount of water was added to prepare a solution of a blocked polyisocyanate crosslinking agent (B-4) with a solid content of 40% by mass. The acid value corresponding to the solid content of the crosslinking agent B-4 is 0.0 mgKOH/g.

[Polymerization of Crosslinking Agent B-5] In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 66.04 parts by mass of a polyisocyanate compound having an isocyanurate structure (manufactured by Asahi Kasei Chemicals, Duranate TPA) using hexamethylene diisocyanate as a raw material, N-methyl 17.50 parts by mass of pyrrolidone was added dropwise to 25.19 parts by mass of 3,5-dimethylpyrazole, and it was maintained at 70° C. for 1 hour under a nitrogen atmosphere. Then, 5.27 parts by mass of dimethylolpropionic acid was added dropwise. The infrared spectrum of the reaction solution was measured, and after confirming that the absorption of the isocyanate group disappeared, 5.59 parts by mass of N,N-dimethylethanolamine and 132.5 parts by mass of water were added. An appropriate amount of water was added to prepare a solution of a blocked polyisocyanate crosslinking agent (B-5) with a solid content of 40% by mass. The acid value corresponding to the solid content of the crosslinking agent B-5 is 22.8 mgKOH/g.

[Synthesis of Crosslinking Agent B-6] Put 59.5 parts by mass of hexamethylene diisocyanate, 6.8 parts by mass of neopentyl glycol, 16.6 parts by mass of dimethylol butyric acid, and N-methylpyrrolidone as a solvent into a flask equipped with a stirrer, a thermometer, and a reflux condenser 20.0 parts by mass, stirred at 80° C. for 3 hours under a nitrogen atmosphere, and confirmed that the reaction liquid reached the predetermined amine equivalent. Then, 30.3 parts by mass of 2-butanone oxime was added dropwise to the reaction liquid, and it was kept at 80° C. for 1 hour under a nitrogen atmosphere. Then, after measuring the infrared spectrum of the reaction liquid and confirming that the absorption of the isocyanate group disappeared, the temperature of the reaction liquid was lowered to 40°C, and 11.9 parts by mass of triethylamine was added. After stirring for 1 hour as it was, an appropriate amount of water was added to prepare a solution of a blocked isocyanate-based crosslinking agent (B-6) with a solid content of 40% by mass. The acid value corresponding to the solid content of the crosslinking agent B-6 is 55.4 mgKOH/g.

[Manufacture of polyester resin C-1] 194.2 parts by mass of dimethyl terephthalate, 184.5 parts by mass of dimethyl isophthalate, 5-sodium sulfonate isophthalic acid, and 14.8 parts by mass of dimethyl ester, 233.5 parts by mass of diethylene glycol, 136.6 parts by mass of ethylene glycol, and 0.2 part by mass of tetra-n-butyl titanate were subjected to a transesterification reaction at a temperature of 160° C. to 220° C. for 4 hours. Then, the temperature was raised to 255° C., and the reaction system was gradually depressurized, then reacted under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin (CR-1). The obtained copolymerized polyester resin (CR-1) was pale yellow and transparent. The reduced viscosity of the copolymerized polyester resin (CR-1) was measured, and the result was 0.70dl/g. Furthermore, 15 parts by mass of copolymerized polyester resin (CR-1) and 15 parts by mass of ethylene glycol n-butyl ether were added to a reactor equipped with a stirrer, a thermometer, and a reflux device, and the resin was dissolved by heating and stirring at 110°C. After the resin was completely dissolved, 70 parts by mass of water was gradually added to the polyester solution while stirring, and after the addition, the liquid was cooled to room temperature while stirring. An appropriate amount of water was added to prepare a polyester resin (C-1) solution with a solid content of 30% by mass. The acid value corresponding to the solid content of the polyester resin C-1 is 0.9 mgKOH/g.

[Manufacture of polyester resin C-2] In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 194.2 parts by mass of dimethyl terephthalate, 194.2 parts by mass of dimethyl isophthalate, 233.5 parts by mass of diethylene glycol, and 136.6 parts by mass of diol and 0.2 part by mass of tetra-n-butyl titanate were subjected to a transesterification reaction at a temperature of 160° C. to 220° C. for 4 hours. Then, the temperature was raised to 255° C., and after the reaction system was gradually decompressed, the reaction was carried out under a reduced pressure of 30 Pa for 1 hour. Furthermore, nitrogen gas was introduced into the system to release the reduced pressure, and the inside of the system was cooled to 200°C. 28.0 parts by mass of trimellitic anhydride was added to the system while stirring, and an addition reaction was performed for 2 hours to obtain a copolymerized polyester resin (CR-2). The obtained copolymerized polyester resin (CR-2) was pale yellow and transparent. The reduced viscosity of the copolymerized polyester resin (CR-2) was measured, and the result was 0.35dl/g. Furthermore, 15 parts by mass of copolymerized polyester resin (CR-2) and 15 parts by mass of tetrahydrofuran were added to a reactor equipped with a stirrer, a thermometer, and a reflux device, and the resin was dissolved by heating and stirring at 70°C. After the resin was completely dissolved, 31 parts by mass of triethylamine and 70 parts by mass of water were gradually added to the polyester solution while stirring. After the addition, the pressure in the system was reduced, tetrahydrofuran was removed, and the mixture was cooled to room temperature. An appropriate amount of water was added to prepare a polyester resin (C-2) solution C-2 with a solid content of 30% by mass. The acid value corresponding to the solid content of polyester resin C-2 is 37.4 mgKOH/g.

[Manufacture of Acrylic Resin D-1] Add 40 parts of propylene glycol monomethyl ether to a flask equipped with a stirrer, a thermometer and a reflux condenser, heat to 100°C and keep it, and dropwise add 60.0 parts by mass of n-butyl acrylate, 42.0 parts by mass of methyl methacrylate, methyl A mixture of 2.9 parts by mass of 2-hydroxyethyl acrylate, 5.7 parts by mass of acrylic acid and 5 parts by azobisisobutyronitrile. After the dropwise addition, it was matured at the same temperature for 2 hours. Then, the temperature of this reaction liquid was lowered to 40 degreeC, and 8.4 mass parts of triethylamines and 165 mass parts of water were added, stirring. After stirring for 1 hour as it was, an appropriate amount of water was added to prepare an acrylic resin (D-1) solution with a solid content of 35% by mass. The acid value corresponding to the solid content of the acrylic resin D-1 was 40.1 mgKOH/g.

[Manufacture of acrylic resin D-2] In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 231 parts by mass of methyl methacrylate (MMA), 130 parts by mass of stearyl methacrylate (SMA), hydroxymethacrylate 100 parts by mass of ethyl ester (HEMA), 33 parts by mass of methacrylic acid (MAA), and 1153 parts by mass of isopropyl alcohol (IPA) were heated up to 80° C. while stirring. After stirring for 3 hours while maintaining the inside of the flask at 80° C., 0.5 parts by mass of 2,2-azobis-2-methyl-N-2-hydroxyethylpropionamide was added to the flask. After nitrogen substitution was carried out while heating the inside of the flask to 120°C, the mixture was stirred at 120°C for 2 hours. Then, a 1.5kPa decompression operation was performed at 120° C. to remove unreacted raw materials and solvents to obtain a long-chain alkyl-containing acrylic resin. The inside of the flask was returned to atmospheric pressure and cooled to room temperature, and 1592 parts by mass of an IPA aqueous solution (water content: 50% by mass) was added and mixed. Then, ammonia was added using a dropping funnel while stirring, and the long-chain alkyl-containing acrylic resin was neutralized until the pH of the solution reached a range of 5.5 to 7.5 to obtain a long-chain alkyl-containing resin with a solid content concentration of 20% by mass. Based acrylic resin (D-2) solution. The acid value corresponding to the solid content of the acrylic resin (D-2) was 104 mgKOH/g.

[Manufacture of polyester resin E-1 for base material] [Preparation of antimony trioxide solution] Antimony trioxide (manufactured by Sigma-Aldrich Japan Contract Co., Ltd.) and ethylene glycol were put into a flask, stirred at 150° C. for 4 hours to dissolve, and cooled to room temperature to prepare 20 g /l of antimony trioxide in ethylene glycol solution.

[Polymerization of polyester resin E-1 for base material] Put high-purity terephthalic acid and 2 times the molar amount of ethylene glycol in a 2L stainless steel autoclave with a stirrer, add 0.3 mole% triethylamine relative to the acid component, and pressurize at 0.25MPa At 250°C, the esterification reaction was carried out while distilling water out of the system to obtain a mixture of bis(2-hydroxyethyl) terephthalate and oligomers (hereinafter referred to as BHET mixture). The above-mentioned antimony trioxide solution was used as a polycondensation catalyst in the BHET mixture, and it was added so as to be 0.04 mol% in terms of antimony atoms relative to the acid component in the polyester, and then stirred at 250°C under a nitrogen atmosphere at normal pressure 10 minutes. Then, after 60 minutes, the temperature was raised to 280°C while gradually reducing the pressure of the reaction system to 13.3Pa (0.1 Torr), and then the polycondensation reaction was carried out at 280°C and 13.3Pa for 68 minutes to obtain the intrinsic viscosity (IV) (solvent: Phenol/tetrachloroethane=60/40) is 0.61 dl/g, polyester resin E-1 containing substantially no particles.

[Manufacture of polyester resin E-2 for base material] [Preparation example of aluminum compound solution] Ethylene glycol and basic aluminum acetate in the same amount (volume ratio) to a 20 g/l aqueous solution of basic aluminum acetate (aluminum hydroxydiacetate; manufactured by Sigma-Aldrich Japan) were put into the flask together , after stirring at room temperature for 6 hours, under reduced pressure (133 Pa) at 70°C to 90°C for several hours while stirring to remove water from the system to prepare a 20 g/l ethylene glycol solution of the aluminum compound.

[Preparation example of phosphorus compound solution] Put 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester (Irganox 1222 (manufactured by BASF)) as a phosphorus compound into the flask together with ethylene glycol, and replace with nitrogen Next, it was heated at a liquid temperature of 160° C. for 25 hours while stirring to prepare a 50 g/l ethylene glycol solution of a phosphorus compound.

[Preparation of a mixture of a solution of an aluminum compound and a solution of a phosphorus compound] Each of the ethylene glycol solutions obtained in the above-mentioned preparation example of aluminum compound and the above-mentioned preparation example of phosphorus compound was put into a flask, and mixed at room temperature in such a way that the molar ratio of aluminum atoms and phosphorus atoms was 1:2, and stirred 1 day to prepare the catalyst solution.

[Polymerization of polyester resin E-2 for base material] As the polycondensation catalyst, a mixture of the aforementioned aluminum compound solution and phosphorus compound solution was used instead of the antimony trioxide solution, so as to be 0.014 mol % and 0.028 mol % in terms of aluminum atoms and phosphorus atoms, respectively, relative to the acid component in the polyester. %, except that it was polymerized in the same way as polyester resin E-1. Among them, the polymerization time was set to 68 minutes, thereby obtaining polyester resin E-2 having an intrinsic viscosity (IV) of 0.61 dl/g and substantially not containing particles.

[Example 1] (1) Preparation of coating solution Mix the following paints with a mixed solvent of water and isopropanol (80/20 parts by mass ratio) to prepare the solid content of polyurethane resin (A-1) solution/crosslinking agent (B-1) solution The coating liquid for forming an easily-adhesive layer with a mass ratio of 70/30. Mixed solvent (water/isopropanol) 78.26 parts by mass Polyurethane resin (A-1) solution 14.00 parts by mass Crosslinking agent (B-1) solution 5.25 parts by mass Particle I 0.12 parts by mass (Silica sol with an average particle diameter of 100nm and a solid content concentration of 40% by mass) Particle II 1.87 parts by mass (Silica sol with an average particle diameter of 40nm to 50nm, solid content concentration of 30% by mass) Surfactant 0.50 parts by mass (Silicone-based, solid content concentration 10% by mass)

(2) Manufacture of laminated polyester film Resin pellets of polyester resin E-1 as a film raw material polymer were dried at 135° C. for 6 hours under a reduced pressure of 133 Pa. Then, it is supplied to an extruder, melted and extruded in a sheet form 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.

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

Then, the said coating liquid was apply|coated to one side of a PET film so that the coating amount after final (after biaxial stretching) drying might become 0.13 g/m< ² >. After drying the coating solution, it was stretched to 4.0 times in the width direction at 110° C., and heated at 230° C. for 5 seconds in a state where the width direction of the film was fixed. Further, a 3% relaxation treatment in the width direction was performed to obtain a laminated polyester film having an easily-adhesive layer of 100 μm.

3. Production of antistatic polyester film The following coating solution (AS-1) was applied on the easily-adhesive layer of the obtained laminated polyester film so that the coating amount after drying would be 0.08 g/m ² . After coating, use hot air to heat at 140°C for 20 seconds to dry and harden to obtain a laminated polyester film with an antistatic layer (antistatic polyester film). Various physical properties and evaluation results are shown in Table 1 and Table 2. Furthermore, in the table, the abbreviation "AS" means antistatic. (AS-1) 38.9 parts by mass of water 38.9 parts by mass of isopropyl alcohol 3.0 parts by mass of N-methyl-2-pyrrolidone 3.0 parts by mass of acrylic resin (D-1) 1.7 parts by mass of melamine crosslinking agent 0.3 parts by mass (MX-035 Sanwa Chemical Manufactured by the company, solid content concentration 70% by mass) PEDOT/PSS (Poly(3,4-ethylenedioxythiophene)/Poly(styrenesulfonate); poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid)) 16.7 parts by mass of solution (ICP1010, manufactured by Agfa Material, Japan, solid content concentration 1.2 mass %) Surfactant 0.5 parts by mass (silicone-based, solid content concentration 10 mass %)

[Example 2] The polyurethane resin was set to (A-2), and the ratio of the polyurethane resin to the crosslinking agent was changed to 60/40 (mass ratio), in the same manner as in Example 1 Obtain an antistatic polyester film.

[Example 3] The polyurethane resin was set to (A-3), and the ratio of the polyurethane resin to the crosslinking agent was changed to 50/50 (mass ratio), in the same manner as in Example 1 Obtain an antistatic polyester film.

[Example 4] The cross-linking agent was set to (B-2), and the ratio of the polyurethane resin and the cross-linking agent was changed to 60/40 (mass ratio), except that, an antistatic polymer was obtained in the same manner as in Example 1. Ester film.

[Example 5] The cross-linking agent was set to (B-3), and the ratio of the polyurethane resin and the cross-linking agent was changed to 60/40 (mass ratio), except that, an antistatic polymer was obtained in the same manner as in Example 1. Ester film.

[Example 6] In addition to the polyurethane resin (A-1) and the cross-linking agent (B-1), the cross-linking agent (B-4) was used in combination, and the ratio was changed to (A-1)/(B-1)/( Except B-4) = 55/35/10 (mass ratio), it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Example 7] Use polyester resin (C-1) in addition to polyurethane resin (A-1) and crosslinking agent (B-1), and change the ratio to (A-1)/(B-1)/( Except C-1) = 36/24/40 (mass ratio), it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Example 8] Use polyester resin (C-1) in addition to polyurethane resin (A-1) and crosslinking agent (B-1), and change the ratio to (A-1)/(B-1)/( Except C-1) = 24/16/60 (mass ratio), it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Example 9] Except having used the resin pellet of polyester resin E-2 as a film raw material polymer, it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Example 10] Except having changed the coating liquid of the antistatic layer into AS-2, it carried out similarly to Example 1, and obtained the antistatic polyester film. (AS-2) Water 38.3 parts by mass Isopropanol 38.3 parts by mass N-methyl-2-pyrrolidone 3.0 parts by mass Acrylic resin (D-2) 3.0 parts by mass Melamine crosslinking agent 0.3 parts by mass (MX-035, manufactured by Sanwa Chemical Co., Ltd., solid content concentration 70% by mass) PEDOT/PSS solution 16.7 parts by mass (ICP1010, manufactured by Agfa Materials Co., Ltd., Japan, solid content concentration 1.2% by mass) Surfactant 0.5 parts by mass (Silicone-based, solid content concentration 10% by mass)

[Example 11] Except having changed the coating liquid of the antistatic layer into AS-3, it carried out similarly to Example 1, and obtained the antistatic polyester film. (AS-3) Water 38.3 parts by mass Isopropanol 38.3 parts by mass N-methyl-2-pyrrolidone 3.0 parts by mass Melamine crosslinking agent 1.2 parts by mass (MX-035, manufactured by Sanwa Chemical Co., Ltd., solid content concentration 70% by mass) PEDOT/PSS solution 16.7 parts by mass (ICP1010, manufactured by Agfa Materials Co., Ltd., Japan, solid content concentration 1.2% by mass) Surfactant 0.5 parts by mass (Silicone-based, solid content concentration 10% by mass)

[Example 12] Except having changed the coating liquid of the antistatic layer into AS-4, it carried out similarly to Example 1, and obtained the antistatic polyester film. (AS-4) Water 38.3 parts by mass Isopropanol 38.3 parts by mass N-methyl-2-pyrrolidone 3.0 parts by mass Melamine crosslinking agent 0.9 parts by mass (MX-035, manufactured by Sanwa Chemical Co., Ltd., solid content concentration 70% by mass) PEDOT/PSS solution 33.3 parts by mass (ICP1010, manufactured by Agfa Materials Co., Ltd., Japan, solid content concentration 1.2% by mass) Surfactant 0.5 parts by mass (Silicone-based, solid content concentration 10% by mass)

[Comparative example 1] An antistatic polyester film was obtained in the same manner as in Example 1 except that only the polyurethane resin (A-1) was used and the crosslinking agent (B-1) was not used.

[Comparative example 2] An antistatic polyester film was obtained in the same manner as in Example 1 except that only the crosslinking agent (B-1) was used and no polyurethane resin (A-1) was used.

[Comparative example 3] Except having changed polyurethane resin into (A-4), it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Comparative example 4] The polyurethane resin was set to (A-5), and the ratio of the polyurethane resin to the crosslinking agent was changed to 60/40 (mass ratio), in the same manner as in Example 1 Obtain an antistatic polyester film.

[Comparative Example 5] The polyurethane resin was set to (A-6), and the ratio of the polyurethane resin and the crosslinking agent was changed to 50/50 (mass ratio), in the same manner as in Example 1 Obtain an antistatic polyester film.

[Comparative Example 6] Except having changed the polyurethane resin into (A-7) and the crosslinking agent into (B-5), it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Comparative Example 7] The cross-linking agent was set to (B-5), and the ratio of the polyurethane resin and the cross-linking agent was changed to 75/25 (mass ratio), except that, in the same manner as in Example 1, an antistatic polymer was obtained. Ester film.

[Comparative Example 8] Except having changed the crosslinking agent into (B-6), it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Comparative Example 9] Except having changed polyurethane resin (A-1) into polyester resin (C-2), it carried out similarly to Example 1, and obtained the antistatic polyester film.

[Comparative Example 10] Except having changed polyurethane resin (A-1) into acrylic resin (D-1), it carried out similarly to Example 1, and obtained the antistatic polyester film.

In Table 1 and Table 2, various physical properties and evaluation results of Examples and Comparative Examples were sorted out.

As shown in Table 2, in each example, the haze, blocking resistance, adhesion with respect to the antistatic layer, and heat and humidity resistance can meet the requirements. On the other hand, in Comparative Examples 1 to 10, at least any one of the aforementioned evaluation items could not satisfy the requirements.

[Table 1] Substrate Easy Adhesive Layer Composition for coating layer formation Content rate (mass %) in the composition for coating layer formation Urethane crosslinking agent other Urethane crosslinking agent other resin type Acid value (mgKOH/g) type Acid value (mgKOH/g) type Acid value (mgKOH/g) Example 1 E-1 A-1 37.5 B-1 37.6 - - 70 30 - Example 2 E-1 A-2 36.3 B-1 37.6 - - 60 40 - Example 3 E-1 A-3 36.0 B-1 37.6 - - 50 50 - Example 4 E-1 A-1 37.5 B-2 41.2 - - 60 40 - Example 5 E-1 A-1 37.5 B-3 39.8 - - 60 40 - Example 6 E-1 A-1 37.5 B-1 37.6 B-4 0.0 55 35 10 Example 7 E-1 A-1 37.5 B-1 37.6 C-1 0.9 36 twenty four 40 Example 8 E-1 A-1 37.5 B-1 37.6 C-1 0.9 twenty four 16 60 Example 9 E-2 A-1 37.5 B-1 37.6 - - 70 30 - Example 10 E-1 A-3 36.0 B-1 37.6 - - 50 50 - Example 11 E-1 A-3 36.0 B-1 37.6 - - 50 50 - Example 12 E-1 A-3 36.0 B-1 37.6 - - 50 50 - Comparative example 1 E-1 A-1 37.5 - - - - 100 - - Comparative example 2 E-1 - - B-1 37.6 - - - 100 - Comparative example 3 E-1 A-4 25.3 B-1 37.6 - - 70 30 - Comparative example 4 E-1 A-5 55.0 B-1 37.6 - - 60 40 - Comparative Example 5 E-1 A-6 0.2 B-1 37.6 - - 50 50 - Comparative example 6 E-1 A-7 23.2 B-5 22.8 - - 70 30 - Comparative Example 7 E-1 A-1 37.5 B-5 22.8 - - 75 25 - Comparative Example 8 E-1 A-1 37.5 B-6 53.4 - - 70 30 - Comparative Example 9 E-1 - - B-1 37.6 C-2 37.4 - 30 70 Comparative Example 10 E-1 - - B-1 37.6 D-1 40.1 - 30 70

[Table 2] Antistatic layer Antistatic polyester film evaluation results Composition for coating layer formation Content rate (mass %) in the composition for coating layer formation AS coating solution AS agent Adhesive crosslinking agent AS agent Adhesive crosslinking agent Haze (%) Surface resistivity Anti-blocking AS layer tightness type type type type Ω/□ Evaluation initial Moisture and heat resistance Example 1 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.8 1×10 ⁶ ◎ 〇 ◎ 〇 Example 2 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.7 1×10 ⁶ ◎ 〇 ◎ ◎ Example 3 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.7 1×10 ⁶ ◎ 〇 ◎ ◎ Example 4 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.9 1×10 ⁶ ◎ 〇 ◎ 〇 Example 5 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.7 1×10 ⁶ ◎ 〇 ◎ 〇 Example 6 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.7 1×10 ⁶ ◎ 〇 ◎ 〇 Example 7 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.8 1×10 ⁶ ◎ 〇 ◎ 〇 Example 8 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.6 1×10 ⁶ ◎ 〇 ◎ 〇 Example 9 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.6 1×10 ⁶ ◎ 〇 ◎ 〇 Example 10 AS-2 PEDOT/PSS D-2 Melamine 20 60 20 0.7 3×10 ⁷ 〇 〇 ◎ ◎ Example 11 AS-3 PEDOT/PSS none Melamine 20 - 80 0.5 2×10 ⁵ ◎ 〇 ◎ ◎ Example 12 AS-4 PEDOT/PSS none Melamine 40 - 60 0.6 1×10 ⁴ ◎ 〇 ◎ ◎ Comparative example 1 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.8 1×10 ⁶ ◎ 〇 〇 x Comparative example 2 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.7 1×10 ⁶ ◎ 〇 〇 x Comparative example 3 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.7 1×10 ⁶ ◎ 〇 〇 x Comparative example 4 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 2.2 1×10 ⁶ ◎ 〇 ◎ △ Comparative Example 5 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.8 1×10 ⁶ ◎ x 〇 x Comparative Example 6 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.9 1×10 ⁶ ◎ 〇 〇 x Comparative Example 7 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 1.0 1×10 ⁶ ◎ 〇 〇 x Comparative Example 8 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 2.5 1×10 ⁶ ◎ 〇 ◎ △ Comparative Example 9 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.6 1×10 ⁶ ◎ △ 〇 x Comparative Example 10 AS-1 PEDOT/PSS D-1 Melamine 20 60 20 0.6 1×10 ⁶ ◎ 〇 〇 x

The antistatic polyester film of the present invention has the easy-adhesive layer and the antistatic layer of the present invention in this order. In particular, by having the easy-adhesive layer of the present invention, it is possible to provide an antistatic polyester having excellent blocking resistance, excellent initial adhesion between the antistatic layer and the easy-adhesive layer, and polyester film substrate, and excellent moisture and heat resistance adhesion. membrane.

On the other hand, Comparative Example 1 does not contain the crosslinking agent of the present invention, so it is a result of significantly poor heat and humidity resistance adhesion. Since Comparative Example 2 does not contain the polyurethane resin of the present invention, it is a result of remarkably poor heat-and-moisture adhesiveness. In Comparative Example 3, the acid value of the polyurethane resin was outside the range of the present invention, so it was a result of remarkably poor heat-and-moisture resistance and adhesion. The acid value of the polyurethane resin in Comparative Example 4 is outside the range of the present invention, so it is the result of poor heat and humidity resistance adhesion. Comparative Example 5 is a polyurethane resin that does not substantially have an acid value, so it is a result of significantly inferior blocking resistance and heat-and-moisture resistance adhesion. In Comparative Example 6, the acid values of the polyurethane resin and the cross-linking agent were outside the range of the present invention, and it was the result that the heat-and-moisture resistance was remarkably poor. In Comparative Example 7, the acid value of the crosslinking agent was outside the range of the present invention, and it was the result of significantly poor heat and humidity resistance. In Comparative Example 8, the acid value of the cross-linking agent is outside the range of the present invention, which is the result of poor heat and humidity resistance and adhesion. Comparative example 9 and comparative example 10 are the examples which used polyester resin (comparative example 9) or acrylic resin (comparative example 10) instead of the polyurethane resin of this invention. The range of the acid value of the polyester resin or acrylic resin used is equivalent to that of the polyurethane resin of the present invention. However, in the case of these resins, it is the result that the heat-and-moisture resistance adhesiveness is remarkably inferior. [Industrial availability]

According to the present invention, an antistatic polyester film that can be suitably used in all fields such as optical applications, packaging applications, and label applications can be provided.

Claims (10)

An antistatic polyester film, wherein at least one side of the polyester film is sequentially laminated with an easy-adhesive layer and an antistatic layer, and the aforementioned easy-adhesive layer consists of an acid with a carboxyl group having an acid value of 30 mgKOH/g to 50 mgKOH/g A layer formed by hardening the composition of polyurethane resin and a cross-linking agent having a carboxyl group with an acid value of 30 mgKOH/g to 50 mgKOH/g. The antistatic polyester film as described in claim 1, wherein the crosslinking agent is an isocyanate compound. The antistatic polyester film according to claim 1 or 2, wherein the surface resistivity is 10 ¹⁰ Ω/□ or less. The antistatic polyester film according to claim 1 or 2, wherein the antistatic layer contains a conductive polymer. The antistatic polyester film as described in claim 3, wherein the antistatic layer contains a conductive polymer. The antistatic polyester film as described in claim 1 or 2, wherein the haze of the film is 3.0% or less. The antistatic polyester film as described in Claim 3, wherein the haze of the film is 3.0% or less. The antistatic polyester film as described in Claim 4, wherein the haze of the film is 3.0% or less. The antistatic polyester film as described in claim 5, wherein the haze of the film is 3.0% or less. An adhesive film comprising an adhesive layer on at least one side of the antistatic polyester film as described in any one of Claims 1 to 9.