JP6278085B2 - Manufacturing method of optical member - Google Patents

Description

The present invention relates to a method for producing an optical member using an optical member surface protective film that suppresses electrification due to peeling and friction, has good adhesive properties, reduces sticking of adhesive due to cutting, and has few defects. In particular, the present invention relates to a method for producing an optical member using an optical member surface protective film that can be used for protecting the surface of an optical member such as a polarizing plate, a retardation plate, and a viewing angle expansion.

  Liquid crystal displays such as TVs, personal computers and mobile phones are used in various places. In an optical member such as a polarizing plate used for a liquid crystal display, an adhesive or the like is usually applied to a transparent film such as a polyethylene film, a polypropylene film or a polyester film to protect the surface, and as a surface protective film. Can be pasted. Thereafter, after the assembly of the optical member is completed, the surface protective film is peeled and removed. However, there is a problem that peeling electrification occurs at the time of peeling, and surrounding dust or the like adheres due to static electricity. Due to the adhesion of dust or the like, there is a problem that, for example, it becomes difficult to distinguish a defect of a liquid crystal member from dust during product inspection, which hinders inspection.

  In order to solve these problems, proposals have been made to provide an antistatic layer on the opposite side of the base film from the adhesive layer (Patent Documents 1 and 2).

  However, particularly in the case of a polarizing plate, a surface protective film is attached and may be subjected to a process such as cutting in a laminated state. In that case, the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer protrudes from the cut surface, and there is a problem that the pressure-sensitive adhesive adheres to the back side of the surface protective film when the polarizing plates are overlapped. As a countermeasure, Patent Document 2 proposes to provide an antifouling layer. However, in order to solve the original problem, a film that is devised so that the adhesive does not protrude is required.

  In addition, the adhesive layer is formed by a method in which coating is performed in a process separate from film production (off-line coating), or an adhesive layer is formed on a release layer of a release film having a release layer, and then bonded. The method is common. Since these methods involve many processes, there are more opportunities for defects such as scratches and foreign objects on the film, and it may not be possible to meet the quality requirements with fewer defects around liquid crystal displays in recent years. Improvements are also required. Furthermore, since price competition is also a severe field, cost reduction technology is also regarded as important.

Japanese Patent Laid-Open No. 7-26223 JP 11-256115 A

The present invention has been made in view of the above circumstances, and the problem to be solved is due to peeling or friction that can be used for protecting the surface of an optical member such as a polarizing plate, a retardation plate, and a viewing angle expansion. An object of the present invention is to provide a method for producing an optical member using an optical member surface protective film that suppresses electrification, has good adhesive properties, reduces the protrusion of an adhesive due to cutting, and has few defects.

  As a result of intensive studies in view of the above circumstances, the present inventor has found that the above-described problems can be easily solved by using a film having a specific configuration, and has completed the present invention.

That is, the gist of the present invention is that a pressure-sensitive adhesive layer containing a resin having a glass transition point of 0 ° C. or lower is formed on one surface of a polyester film, and an antistatic layer is formed on the opposite surface. A method for producing an optical member in which an optical member is bonded to the optical member , wherein the adhesive layer is formed on the polyester film by in-line coating, and then formed through a heat treatment step in the range of 180 to 270 ° C. It exists in the manufacturing method of a member.

According to the production method of the present invention, it is possible to provide an optical member using an optical member surface protective film that suppresses electrification due to peeling or friction, has good adhesive properties, and has few defects, and its industrial value. Is expensive.

  The polyester film serving as the substrate constituting the optical member surface protective film in the present invention may have a single layer structure or a multilayer structure, and may have a structure other than the two-layer or three-layer structure as long as the gist of the present invention is not exceeded. There may be four or more layers, and there is no particular limitation. It is preferable to have a multi-layer structure of two or more layers and to give each layer a characteristic so as to achieve multiple functions.

  The polyester used in the present invention may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Typical polyester includes polyethylene terephthalate and the like. On the other hand, the dicarboxylic acid component of the copolyester includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxybenzoic acid, etc.), etc. 1 type or 2 types or more are mentioned, As a glycol component, 1 type or 2 types or more, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexane dimethanol, neopentyl glycol, is mentioned.

  From the viewpoint of forming a film that can withstand various processing conditions, it is preferable that the mechanical strength and heat resistance (dimensional stability by heating) are high, and for that purpose, it is preferable that the copolymer polyester component is small. Specifically, the proportion of the monomer forming the copolyester in the polyester film is preferably in the range of 10 mol% or less, more preferably 5 mol% or less, and more preferably produced as a by-product during homopolyester polymerization. It is a grade which contains the diether component of 3 mol% or less which is a grade which will carry out. In view of mechanical strength and heat resistance, a more preferable form of polyester is more preferably a film formed from polyethylene terephthalate or polyethylene naphthalate, which is polymerized from terephthalic acid and ethylene glycol, among the above compounds. In consideration of ease of handling and handling properties as a surface protective film, a film formed from polyethylene terephthalate is more preferable.

  There is no restriction | limiting in particular as a polymerization catalyst of polyester, A conventionally well-known compound can be used, For example, an antimony compound, a titanium compound, a germanium compound, a manganese compound, an aluminum compound, a magnesium compound, a calcium compound etc. are mentioned. Among these, antimony compounds are preferable because they are inexpensive, and titanium compounds and germanium compounds have high catalytic activity, can be polymerized in a small amount, and the amount of metal remaining in the film is small. Since transparency of this becomes high, it is preferable. Furthermore, since a germanium compound is expensive, it is more preferable to use a titanium compound.

  In the case of polyester using a titanium compound, the titanium element content is preferably 50 ppm or less, more preferably 1 to 20 ppm, and still more preferably 2 to 10 ppm. If the content of the titanium compound is too high, the polyester may be deteriorated in the process of melt-extruding the polyester, resulting in a strong yellowish film. If the content is too low, the polymerization efficiency is poor and the cost is low. In some cases, a film having a sufficient strength or a sufficient strength cannot be obtained. Moreover, when using the polyester by a titanium compound, it is preferable to use a phosphorus compound in order to reduce the activity of a titanium compound for the purpose of suppressing deterioration in the step of melt extrusion. As the phosphorus compound, orthophosphoric acid is preferable in view of the productivity and thermal stability of the polyester. The phosphorus element content is preferably in the range of 1 to 300 ppm, more preferably 3 to 200 ppm, and still more preferably 5 to 100 ppm with respect to the amount of polyester to be melt-extruded. If the content of the phosphorus compound is too large, it may cause gelation or foreign matter. If the content is too small, the activity of the titanium compound cannot be lowered sufficiently, and the yellowish It may be a film.

  In the polyester layer of the film of the present invention, particles can be blended for the purpose of imparting slipperiness, preventing scratches in each step, and improving anti-blocking properties. When the particles are blended, the kind of the particles to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness, and specific examples thereof include, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, sulfuric acid. Examples thereof include inorganic particles such as calcium, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin. Furthermore, precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used. Of these, silica particles and calcium carbonate particles are preferable because they are particularly effective in a small amount.

  The average particle diameter of the particles is preferably 10 μm or less, more preferably in the range of 0.01 to 5.0 μm. When the average particle diameter exceeds 10 μm, there may be a concern about problems due to dropout of particles or reduction in transparency of the film.

  Further, the particle content in the polyester layer cannot be generally described because it has a balance with the average particle diameter of the particles, but is preferably 5% by weight or less, more preferably in the range of 0.0003 to 3% by weight, Preferably it is 0.0005 to 1 weight% of range. When the particle content exceeds 5% by weight, there may be a concern about problems due to dropout of particles or reduction in transparency of the film.

  If there are no or few particles, the transparency of the film will be high and a good film will be obtained, but the slipperiness may be insufficient, so by putting particles in the adhesive layer or antistatic layer In some cases, it is necessary to improve the slipping property.

  The shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction | limiting in particular also about the hardness, specific gravity, a color, etc. These series of particles may be used in combination of two or more as required.

  The method for adding particles to the polyester layer is not particularly limited, and a conventionally known method can be adopted. For example, it can be added at any stage for producing the polyester constituting each layer, but it is preferably added after completion of esterification or transesterification.

  In the polyester film of the present invention, conventionally known ultraviolet absorbers, antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, and the like can be added as necessary in addition to the above-described particles. .

  The thickness of the polyester film in the present invention is not particularly limited as long as it can be formed as a film, but is preferably 2 to 350 μm, more preferably 5 to 200 μm, and still more preferably 10 to 75 μm. is there.

  As a film forming method of the film of the present invention, a generally known film forming method can be adopted, and there is no particular limitation. For example, when producing a biaxially stretched polyester film, the polyester raw material described above is first melt-extruded from a die using an extruder, and the molten sheet is cooled and solidified with a cooling roll to obtain an unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method or a liquid application adhesion method is preferably employed. Next, the obtained unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine. The stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Next, the film is stretched in the direction perpendicular to the first-stage stretching direction at usually 70 to 170 ° C. and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Subsequently, a method of obtaining a biaxially oriented film by performing heat treatment at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% can be mentioned. In the above-described stretching, a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.

  For the production of the polyester film, a simultaneous biaxial stretching method can also be employed. The simultaneous biaxial stretching method is a method in which the above-mentioned unstretched sheet is usually stretched and oriented in the machine direction and the width direction at a temperature controlled normally at 70 to 120 ° C., preferably 80 to 110 ° C. Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a stretched oriented film. With respect to the simultaneous biaxial stretching apparatus that employs the above-described stretching method, a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.

  Next, formation of the adhesive layer in the present invention will be described. The adhesive layer is formed directly on the polyester film by in-line coating.

  In-line coating is a method of coating within the process of manufacturing a polyester film, and specifically, a method of coating at any stage from melt extrusion of a polyester to heat setting after stretching and winding up. Usually, it is preferable to coat on either an unstretched sheet obtained by melting and quenching, or a stretched uniaxially stretched film.

  Although not limited to the following, for example, in sequential biaxial stretching, a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, film formation and formation of the adhesive layer can be performed at the same time, which is advantageous in terms of manufacturing cost. In addition, in order to perform stretching after coating, the thickness of the adhesive layer can be changed by the stretching ratio. In addition, thin film coating can be performed more easily than off-line coating.

  Moreover, by providing the adhesive layer on the film before stretching, the adhesive layer can be stretched together with the base film, whereby the adhesive layer can be firmly adhered to the base film. Furthermore, in the production of a biaxially stretched polyester film, the film can be restrained in the longitudinal and lateral directions by stretching while gripping the film end with a clip, etc. High temperature can be applied while maintaining the properties. Therefore, since the heat treatment performed after the formation of the adhesive layer can be performed at a high temperature that cannot be achieved by other methods, the film forming property of the adhesive layer is improved, and the adhesive layer and the base film are adhered more firmly. In addition, a strong adhesive layer can be obtained. Therefore, the effect of suppressing the component of the adhesive layer from protruding during cutting in a state of being bonded to the polarizing plate is also improved.

  According to the above-mentioned process by in-line coating, the film size does not change greatly depending on whether or not the adhesive layer is formed, and the risk of scratches and adhesion of foreign substances does not change greatly depending on whether or not the adhesive layer is formed. This is a great advantage over offline coating or the like in which one or more extra steps of coating and bonding are performed. Furthermore, as a result of various studies, it has been found that in-line coating has an advantage that adhesive residue on the adherend can be reduced. This can be heat-treated at a high temperature that cannot be obtained by off-line coating, and is considered to be a result of the adhesive layer and the base film being more firmly adhered to each other.

  In the present invention, it is an essential requirement to have an adhesive layer formed by in-line coating and to have an antistatic layer on the side of the polyester film opposite to the adhesive layer.

  As a material for forming the adhesive layer, as a result of various studies, it has been found that an appropriate adhesive property can be imparted to the polyester film, particularly by using a resin having a glass transition point of 0 ° C. or less. Conventionally known resins can be used as the resin having a glass transition point of 0 ° C. or lower. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.) and the like. Acrylic resin and urethane resin are preferred. Furthermore, when considering stronger adhesive properties and reusability of the film, a polyester resin or an acrylic resin is preferable, and adhesion to the polyester film as a base material and a small amount of adhesive residue on the adherend are required. A polyester resin is the best when considered, and an acrylic resin is preferred when blocking properties with the back surface side are considered.

  The polyester resin includes, for example, those composed of the following polyvalent carboxylic acid and polyvalent hydroxy compound as main constituent components. That is, as the polyvalent carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutar Acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, trimellitic acid monopotassium salt and ester-forming derivatives thereof can be used. As the polyvalent hydroxy compound, ethylene Recall, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol , Neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol Polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like can be used. One or more compounds may be appropriately selected from these compounds, and a polyester resin may be synthesized by a conventional polycondensation reaction.

  Among them, it is preferable to contain an aliphatic polyvalent carboxylic acid or an aliphatic polyvalent hydroxy compound as a constituent component in order to lower the glass transition point to 0 ° C. or lower. In general, since a polyester resin is composed of an aromatic polyvalent carboxylic acid and a polyvalent hydroxy compound including an aliphatic group, in order to lower the glass transition point than a general polyester resin, an aliphatic polyvalent compound is used. It is effective to contain a carboxylic acid. From the viewpoint of lowering the glass transition point, the aliphatic polyvalent carboxylic acid should have a long carbon number, preferably 6 or more (adipic acid), more preferably 8 or more, and still more preferably 10 or more. The upper limit of the preferred range is 20.

  Further, from the viewpoint of improving adhesive properties, the content of the aliphatic polyvalent carboxylic acid in the acid component in the polyester resin is preferably 2 mol% or more, more preferably 4 mol% or more, and even more preferably 6 mol%. As mentioned above, it is 10 mol% or more especially preferably, and the upper limit of a preferable range is 50 mol%.

  In the aliphatic polyvalent hydroxy compound, in order to lower the glass transition point, the number of carbon atoms is preferably 4 or more (butanediol), and the content of the hydroxy component in the polyester resin is preferably 10 mol. % Or more, more preferably in the range of 30 mol% or more.

  In view of suitability for in-line coating, it is preferable to use an aqueous system. For this reason, it is preferable that a sulfonic acid, a sulfonic acid metal salt, a carboxylic acid, and a carboxylic acid metal salt are contained in the polyester resin. In view of good dispersibility in water, sulfonic acid and sulfonic acid metal salt are preferable, and sulfonic acid metal salt is particularly preferable.

  When using the sulfonic acid, sulfonic acid metal salt, carboxylic acid, or carboxylic acid metal salt, the content in the polyester resin is preferably 0.1 to 10 mol%, more preferably 0.2 to 8 mol%. Range. By using in the above range, water dispersibility is good.

  Considering the appearance of the pressure-sensitive adhesive layer in in-line coating, adhesion and blocking to the polyester film, and reduction of adhesive residue on the adherend, some aromatic polyvalent carboxylic acid is used as the acid component in the polyester resin. It is preferable to contain. Among aromatic polycarboxylic acids, a benzene ring structure such as terephthalic acid or isophthalic acid is preferable to a naphthalene ring structure from the viewpoint of adhesive properties. In order to further improve the adhesive properties, it is more preferable to use two or more kinds of aromatic polyvalent carboxylic acids in combination.

  The glass transition point of the polyester resin for improving the adhesive property is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, particularly preferably −20 ° C. or lower, and the lower limit of the preferable range is −60. ° C. It becomes easy to set it as the film which has the optimal adhesion characteristic by using in the said range.

  The acrylic resin is a polymer composed of a polymerizable monomer including acrylic and methacrylic monomers (hereinafter, acrylic and methacryl may be abbreviated as (meth) acryl). These may be either homopolymers or copolymers, and copolymers with polymerizable monomers other than acrylic and methacrylic monomers.

  Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer.

  Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion is also included. Similarly, a polymer obtained by polymerizing a polymerizable monomer in a polyurethane solution or a polyurethane dispersion (sometimes a mixture of polymers) is also included. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in another polymer solution or dispersion is also included.

  The polymerizable monomer is not particularly limited, but particularly representative compounds include, for example, various carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid. Monomers, and salts thereof; such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate Various hydroxyl group-containing monomers; various such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate No (meta) acrylic Acid esters; various nitrogen-containing compounds such as (meth) acrylamide, diacetone acrylamide, N-methylolacrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene Various vinyl esters such as vinyl propionate and vinyl acetate; various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane; phosphorus-containing vinyl monomers; Examples include various vinyl halides such as vinyl and biliden chloride; and various conjugated dienes such as butadiene.

  In order to lower the glass transition point to 0 ° C. or lower, it is necessary to use a (meth) acrylic system having a glass transition point of the homopolymer of 0 ° C. or lower. For example, ethyl acrylate (glass transition point: −22 ° C.), n-propyl acrylate (glass transition point: −37 ° C.), isopropyl acrylate (glass transition point: −5 ° C.), normal butyl acrylate (glass transition point: −55 ° C.), n-hexyl acrylate (glass transition point: − 57 ° C), 2-ethylhexyl acrylate (glass transition point: -70 ° C), isononyl acrylate (glass transition point: -82 ° C), lauryl methacrylate (glass transition point: -65 ° C), 2-hydroxyethyl Examples include acrylate (glass transition point: −15 ° C.).

  From the viewpoint of adhesive properties, the content of the monomer having a homopolymer glass transition point of 0 ° C. or less as the monomer constituting the acrylic resin is preferably 30% by weight or more, more preferably 45%, as a proportion of the entire acrylic resin. % By weight or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more. The upper limit of the preferred range is 99% by weight. It is easy to obtain good adhesive properties by using in this range.

  Moreover, as a glass transition point of the monomer whose homopolymer has a glass transition point of 0 ° C. or lower for improving the adhesive property, it is preferably −20 ° C. or lower, more preferably −30 ° C. or lower, and further preferably −40 ° C. or lower. Especially preferably, it is -50 degrees C or less, and the minimum of a preferable range is -100 degreeC. By using it in the said range, it becomes easy to set it as the film which has moderate adhesive characteristics.

  The monomer used for improving the adhesive properties is preferably an alkyl (meth) in which the alkyl group has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms. Acrylate. Acrylic resins containing normal butyl acrylate and 2-ethylhexyl acrylate are optimal from the viewpoint of mass production industrially and handling and supply stability.

  As a more optimal form of the acrylic resin for improving the adhesive properties, the total content of normal butyl acrylate and 2-ethylhexyl acrylate in the acrylic resin is preferably 30% by weight or more, more preferably 40% by weight. % Or more, more preferably 50% by weight or more, and the upper limit of the preferred range is 99% by weight.

  The glass transition point of the acrylic resin for improving the adhesive properties is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, more preferably −20 ° C. or lower, particularly preferably −30 ° C. or lower. The lower limit of the preferred range is −80 ° C. It becomes easy to set it as the film which has the optimal adhesion characteristic by using in the said range.

  The urethane resin is a polymer compound having a urethane bond in the molecule, and is usually produced by a reaction between a polyol and an isocyanate. Examples of the polyol include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.

  Polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction. Examples of the polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane and the like can be mentioned. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Examples of polycarbonate polyols obtained from these reactions include poly (1,6-hexylene) carbonate, poly (3- And methyl-1,5-pentylene) carbonate.

  From the viewpoint of improving adhesive properties, the chain alkyl chain is a polycarbonate polyol composed of a diol component preferably in the range of 4 to 30, more preferably 4 to 20, and even more preferably 6 to 12. In terms of industrial mass production and good handling and supply stability, 1,6-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol It is optimal that it is a copolymerized polycarbonate polyol containing at least two diols selected from among them.

  Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like.

  From the viewpoint of improving the adhesive properties, the monomer forming the polyether is an aliphatic diol, particularly a straight chain fat, preferably having 2 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms. It is a polyether polyol containing a group diol.

  Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides. Product and polyhydric alcohol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 2-methyl-2-propyl-1 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexane Diol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyl dialkanolamine, lactone diol, etc.) and those having derivative units of lactone compounds such as polycaprolactone.

  Considering the adhesive properties, among the polyols, polycarbonate polyols and polyether polyols are more preferably used, and polycarbonate polyols are particularly preferable.

  Examples of the polyisocyanate compound used for obtaining the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, α, α, α ′, α ′. -Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate, aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Methanzi Cyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination.

  A chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Alternatively, a chain extender having two amino groups can be mainly used.

  Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. And glycols such as glycols. Examples of the chain extender having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprobilitincyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexa And alicyclic diamines such as

  The urethane resin in the present invention may use a solvent as a medium, but preferably uses water as a medium. In order to disperse or dissolve the urethane resin in water, there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, and a water-soluble type. In particular, a self-emulsification type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance and transparency of the resulting adhesive layer.

  Examples of the ionic group to be introduced include various groups such as a carboxyl group, sulfonic acid, phosphoric acid, phosphonic acid, and quaternary ammonium salt, and a carboxyl group is preferred. As a method for introducing a carboxyl group into a urethane resin, various methods can be taken in each stage of the polymerization reaction. For example, there are a method of using a carboxyl group-containing resin as a copolymer component during prepolymer synthesis, and a method of using a component having a carboxyl group as one component such as polyol, polyisocyanate, and chain extender. In particular, a method in which a desired amount of carboxyl groups is introduced using a carboxyl group-containing diol depending on the amount of this component charged is preferred.

For example, dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid and the like are copolymerized with a diol used for polymerization of a urethane resin. Can do. The carboxyl group is preferably in the form of a salt neutralized with ammonia, amine, alkali metal, inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
In such a urethane resin, the carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by another crosslinking agent. Thereby, it is possible to further improve the durability, solvent resistance, water resistance, blocking resistance, and the like of the obtained coating layer, as well as excellent stability in a liquid state before coating.

  The glass transition point of the urethane resin for improving the adhesive properties is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, more preferably −20 ° C. or lower, particularly preferably −30 ° C. or lower. The lower limit of the preferred range is −80 ° C. It becomes easy to set it as the film which has the optimal adhesion characteristic by using in the said range.

  Moreover, it is also possible to use a crosslinking agent in combination for adjusting the strength and adhesive properties of the adhesive layer. A conventionally well-known material can be used with a crosslinking agent, For example, an epoxy compound, a melamine compound, an oxazoline compound, an isocyanate type compound, a carbodiimide type compound, a silane coupling compound, a hydrazide compound, an aziridine compound etc. are mentioned. From the viewpoint of the strength of the coating layer and the adjustment of the adhesive property, an epoxy compound, a melamine compound, an oxazoline compound, an isocyanate compound, a carbodiimide compound, and a silane coupling compound are preferable, and an epoxy compound is particularly preferable.

  When a crosslinking agent other than an epoxy compound is used, if the content in the coating layer is too large, the adhesive properties may be deteriorated too much. Therefore, when using a crosslinking agent other than an epoxy compound, it is necessary to pay attention to the content in the adhesive layer.

  The epoxy compound is a compound having an epoxy group in the molecule, and examples thereof include condensates of epichlorohydrin with ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and the like hydroxyl groups and amino groups, There are polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane. Examples of the polyglycidyl ether and diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, poly Examples of tetramethylene glycol diglycidyl ether and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N′-tetraglycidyl-m-xylyl. Examples include range amine and 1,3-bis (N, N-diglycidylamino) cyclohexane.

  Of the above, polyether epoxy compounds are preferable from the viewpoint of good adhesive properties. The amount of the epoxy group is preferably a polyepoxy compound that is trifunctional or more polyfunctional than bifunctional.

  The melamine compound is a compound having a melamine skeleton in the compound. For example, an alkylolized melamine derivative, a compound partially or completely etherified by reacting an alcohol with an alkylolated melamine derivative, and these Mixtures can be used. As alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used. Moreover, as a melamine compound, either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used. In view of reactivity with various compounds, it is preferable that the melamine compound contains a hydroxyl group. Further, a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.

  The oxazoline compound is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer. Addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be mentioned, and one or a mixture of two or more thereof can be used. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer. For example, alkyl (meth) acrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alkyl ( (Meth) acrylamide, N, N-dialkyl (meth) acrylamide, As the alkyl group, unsaturated amides such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group and cyclohexyl group); vinyl acetate , Vinyl esters such as vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride And α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene, and the like, and one or more of these monomers can be used.

  The amount of the oxazoline group of the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, still more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. By using in the said range, durability of a coating film improves and it becomes easy to adjust an adhesive characteristic.

  The isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate. Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as α, α, α ′, α′-tetramethylxylylene diisocyanate. Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate Ne Alicyclic isocyanates such as bets are exemplified. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.

  When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol. Compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, mercaptan compounds such as butyl mercaptan, dodecyl mercaptan, ε-caprolactam, δ-valerolactam, etc. Lactam compounds, amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, Examples include oxime compounds such as maldehyde, acetoald oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more. Among these, from the viewpoint of good heat resistance, a blocked isocyanate compound with active methylene is preferable.

  In addition, the isocyanate compound in the present invention may be used alone, or may be used as a mixture or bond with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

  A carbodiimide-based compound is a compound having a carbodiimide structure, and is used to improve adhesion with various surface functional layers that can be formed on a coating layer and to improve the heat and humidity resistance of the coating layer. is there. The carbodiimide compound is a compound having one or more carbodiimide or carbodiimide derivative structures in the molecule, but a polycarbodiimide compound having two or more in the molecule is more preferable for better adhesion and the like.

  The carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used. The diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa Examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.

  Furthermore, in order not to lose the effect of the present invention, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound, adding a surfactant, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, You may add and use hydrophilic monomers, such as a hydroxyalkyl sulfonate.

  These cross-linking agents are used in a design for improving the performance of the adhesive layer by reacting in the drying process or the film forming process. It can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or a mixture thereof exist in the resulting adhesive layer.

  In forming the adhesive layer, it is also possible to use particles in combination for blocking, improving slipperiness and adjusting adhesive properties.

  The antistatic layer in the present invention is mainly provided for imparting antistatic performance and reducing adhesion of surrounding dust and the like due to peeling charging and frictional charging. Regarding the antistatic layer, it may be provided by in-line coating, or offline coating may be employed. In-line coating is preferably used from the viewpoint of stabilization of the antistatic performance by the manufacturing cost and in-line heat treatment.

  The antistatic agent contained in the antistatic layer is not particularly limited, and a conventionally known antistatic agent can be used. However, since it has good heat resistance and moist heat resistance, the polymer type charging agent can be used. An inhibitor is preferred. Examples of the polymer type antistatic agent include a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, and a conductive polymer.

  The compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include aliphatic amines, alicyclic amines, and ammonium compounds of aromatic amines. The compound having an ammonium group is preferably a compound having a polymer type ammonium group, and the ammonium group has a structure incorporated in the main chain or side chain of the polymer, not as a counter ion. It is preferable. For example, a polymer obtained by polymerizing a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine is used as a polymer compound having an ammonium group, which is preferably used. As the polymer, a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine may be polymerized alone, or it may be a copolymer of a monomer containing these and another monomer. May be.

  Among the compounds having an ammonium group, a polymer having a structure represented by the following formula (1) is more preferable in that it is excellent in antistatic properties and wet heat resistance. A single polymer or copolymer, or a plurality of other components may be copolymerized.

For example, in the above formula, the substituent R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a hydrocarbon group such as a phenyl group, R ² is —O—, —NH— or —S—, and R ³ is R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkylene group having 1 to 20 carbon atoms or another structure that can form the structure of Formula 1. Or a hydrocarbon group provided with a functional group such as a hydroxyalkyl group, and X ⁻ represents various counter ions.

Among the above, in view of excellent antistatic properties and wet heat resistance, in particular, in the formula (1), the substituent R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ³ is preferably an alkyl group having 1 to 6 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably , R ⁴ , R ⁵ , or R ⁶ is a hydrogen atom, and the other substituent is an alkyl group having 1 to 4 carbon atoms.

  In addition, as the compound having an ammonium group, a compound having a pyrrolidinium ring is also preferable in terms of excellent antistatic properties and heat stability.

The two substituents bonded to the nitrogen atom of the compound having a pyrrolidinium ring are each independently an alkyl group, a phenyl group, and the like. Even if these alkyl groups and phenyl groups are substituted with the groups shown below, Good. Substitutable groups are, for example, hydroxyl group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, and halogen. Moreover, the two substituents bonded to the nitrogen atom may be chemically bonded. For example, — (CH ₂ ) _m — (m = 2 to 5), —CH (CH ₃ ) CH (CH ₃ ) —, —CH═CH—CH═CH—, —CH═CH—CH═N—, —CH═CH—N═C—, —CH ₂ OCH ₂ —, — (CH ₂ ) ₂ O (CH ₂ ) ₂ — and the like.

  In the present invention, the polymer having a pyrrolidinium ring is obtained by cyclopolymerizing a diallylamine derivative using a radical polymerization catalyst. The polymerization is carried out by using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile as a solvent. Although it can implement by a method, it is not limited to these. In the present invention, a compound having a diallylamine derivative and a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component.

  Examples of the anion serving as the counter ion (counter ion) of the ammonium group of the compound having an ammonium group described above include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

  Moreover, the number average molecular weight of the compound which has an ammonium group is 1000-500000, Preferably it is 2000-350,000, More preferably, it is 5000-200000. When the molecular weight is less than 1000, the strength of the coating film may be weakened or the heat stability may be poor. On the other hand, when the molecular weight exceeds 500,000, the viscosity of the coating solution increases, and the handleability and applicability may deteriorate.

  Examples of polyether compounds include polyethylene oxide, polyether ester amide, acrylic resins having polyethylene glycol in the side chain, and the like.

  The compound having a sulfonic acid group is a compound containing a sulfonic acid or a sulfonate in the molecule. For example, a compound having a large amount of sulfonic acid or a sulfonate such as polystyrene sulfonic acid is preferably used. It is done.

  Examples of the conductive polymer include polythiophene-based, polyaniline-based, polypyrrole-based, and polyacetylene-based polymers. Among them, for example, polythiophene-based polymers using poly (3,4-ethylenedioxythiophene) in combination with polystyrene sulfonic acid. Are preferably used. The conductive polymer is preferable to the other antistatic agents described above in that the resistance value is low. However, on the other hand, it is necessary to devise measures such as reducing the amount used in applications where coloring and cost are a concern.

  In the present invention, a release agent may be used for forming the antistatic layer in order to remove contamination on the surface, reduce blocking with the adhesive layer, improve scratch resistance, and the like. As the release agent, conventionally known materials can be used, and examples thereof include a long-chain alkyl group-containing compound, a fluorine compound, a silicone compound, and a wax. Among these, a long-chain alkyl compound and a fluorine compound are preferable from the viewpoint of low contamination and excellent blocking reduction, and a silicone compound is preferable when it is particularly important to reduce blocking. Also, wax is effective for improving the surface decontamination property. These release agents may be used alone or in combination.

  The long-chain alkyl group-containing compound is a compound having a linear or branched alkyl group having usually 6 or more, preferably 8 or more, and more preferably 12 or more carbon atoms. Examples of the alkyl group include hexyl group, octyl group, decyl group, lauryl group, octadecyl group, and behenyl group. Examples of the compound having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. . In view of heat resistance and contamination, a polymer compound is preferable. Further, from the viewpoint that the performance of the release agent can be effectively obtained, a polymer compound having a long-chain alkyl group in the side chain is more preferable.

  The polymer compound having a long-chain alkyl group in the side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride.

  Examples of the compound having such a reactive group include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, and a reactive group-containing poly (meth) acrylic resin. Among these, polyvinyl alcohol is preferable in view of the performance and ease of handling of the release agent.

  Examples of the compound having an alkyl group capable of reacting with the reactive group include, for example, long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate, hexyl chloride, and octyl chloride. Long chain alkyl group-containing acid chlorides such as decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride, long chain alkyl group-containing amines, and long chain alkyl group-containing alcohols. Among these, long chain alkyl group-containing isocyanates are preferable, and octadecyl isocyanate is particularly preferable in consideration of the performance and ease of handling of the release agent.

  In addition, a polymer compound having a long-chain alkyl group in the side chain can also be obtained by copolymerization of a long-chain alkyl (meth) acrylate polymer or a long-chain alkyl (meth) acrylate and another vinyl group-containing monomer. . Examples of the long-chain alkyl (meth) acrylate include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate. It is done.

  The fluorine compound is a compound containing a fluorine atom in the compound. Organic fluorine compounds are preferably used in terms of the appearance of coating by in-line coating, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene. . From the viewpoint of the performance of the release agent, a compound having a perfluoroalkyl group is preferable. Furthermore, the compound containing the long-chain alkyl compound which is mentioned later can also be used for a fluorine compound.

Examples of the compound having a perfluoroalkyl group include perfluoroalkyl (meth) acrylate, perfluoroalkylmethyl (meth) acrylate, 2-perfluoroalkylethyl (meth) acrylate, and 3-perfluoroalkylpropyl (meth) acrylate. Perfluoroalkyl group-containing (meth) acrylates such as 3-perfluoroalkyl-1-methylpropyl (meth) acrylate and 3-perfluoroalkyl-2-propenyl (meth) acrylate, and polymers thereof, and perfluoroalkylmethyl vinyl ether 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl Perfluoroalkyl group-containing vinyl ether and polymers thereof such as ether, and the like. In view of heat resistance and contamination, a polymer is preferable. The polymer may be a single compound or a polymer of multiple compounds. Moreover, it is preferable that a perfluoroalkyl group has 3-11 carbon atoms from a viewpoint of the performance of a mold release agent. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later.
Moreover, it is also preferable that it is a polymer with vinyl chloride from a viewpoint of adhesiveness with a base material.

  The silicone compound is a compound having a silicone structure in the molecule, and examples thereof include alkyl silicones such as dimethyl silicone and diethyl silicone, phenyl silicones having a phenyl group, and methyl phenyl silicone. Silicones having various functional groups can also be used, such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various types. Examples thereof include hydrocarbon groups such as aromatic groups. As other functional groups, silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms are also common, and both are used in combination to form silicones (addition reaction between vinyl groups and hydrogen silane). It can also be used.

  Moreover, it is also possible to use modified silicones such as acrylic graft silicone, silicone graft acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone as the silicone compound. In view of heat resistance and contamination, it is preferable to use a curable silicone resin. As the type of curable type, any of the curing reaction types such as a condensation type, an addition type, and an active energy ray curable type can be used. Among these, a condensation type silicone compound is preferred from the viewpoint that there is little back surface transfer when it is formed into a roll.

  In the case of using a silicone compound, a polyether group-containing silicone compound is preferable from the viewpoint of less back transfer, good dispersibility in an aqueous solvent and high suitability for in-line coating. The polyether group may be present in the side chain or terminal of the silicone or may be present in the main chain. From the viewpoint of dispersibility in an aqueous solvent, it is preferably present in the side chain or terminal.

  A conventionally well-known structure can be used for a polyether group. From the viewpoint of the dispersibility of the aqueous solvent, an aliphatic polyether group is preferable to an aromatic polyether group, and an alkyl polyether group is preferable among the aliphatic polyether groups. Further, from the viewpoint of synthesis due to steric hindrance, a linear alkyl polyether group is preferable to a branched alkyl polyether group, and among them, a polyether group composed of linear alkyl having 8 or less carbon atoms is preferable. Further, when the developing solvent is water, a polyethylene glycol group or a polypropylene glycol group is preferable in consideration of dispersibility in water, and a polyethylene glycol group is particularly optimal.

  The number of ether bonds of the polyether group is usually in the range of 1-30, preferably in the range of 2-20, more preferably 3 in terms of improving the dispersibility in an aqueous solvent and the durability of the coating layer. There are 15 ranges. If there are few ether bonds, dispersibility will worsen, and conversely if too many, the durability and the performance of the release agent will deteriorate.

  When the polyether group has a side chain or a terminal of the silicone, the terminal of the polyether group is not particularly limited, and is a hydroxyl group, an amino group, a thiol group, a hydrocarbon group such as an alkyl group or a phenyl group, a carboxylic acid group, Various functional groups such as a sulfonic acid group, an aldehyde group, and an acetal group can be used. Among these, considering the dispersibility in water and the crosslinkability for improving the strength of the coating layer, a hydroxyl group, an amino group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group is particularly optimal.

  The polyether group content of the polyether group-containing silicone is preferably in the range of 0.001 to 0.30, more preferably 0.01 to 0.20 in terms of a molar ratio, where the siloxane bond of the silicone is 1. %, More preferably 0.03 to 0.15%, particularly preferably 0.05 to 0.12%. By using within this range, the dispersibility in water, the durability of the coating layer, and the good performance of the release agent can be maintained.

  The molecular weight of the polyether group-containing silicone is preferably not so large in consideration of dispersibility in an aqueous solvent, and is preferably large in consideration of the durability of the coating layer and the performance of the release agent. It is required to balance these characteristics, and the number average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 3000 to 30000, and still more preferably in the range of 5000 to 10,000.

  In addition, considering the change over time of the coating layer, the performance of the release agent, and the contamination of various processes, it is preferable that the silicone low molecular component (number average molecular weight of 500 or less) is as small as possible. The ratio of the entire silicone compound is preferably 15% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less. In addition, when using condensation type silicone, vinyl groups (vinyl silane) and hydrogen groups (hydrogen silane) bonded to silicon may cause changes in performance over time if left unreacted in the coating layer. The content of the functional group is preferably 0.1 mol% or less, more preferably not contained.

  Since polyether group-containing silicone is difficult to apply alone, it is preferable to use it dispersed in water. Various conventionally known dispersants can be used for dispersion, and examples thereof include anionic dispersants, nonionic dispersants, cationic dispersants, and amphoteric dispersants. Among these, when considering the dispersibility of the polyether group-containing silicone and the compatibility with a polymer other than the polyether group-containing silicone that can be used for forming the coating layer, an anionic dispersant and a nonionic dispersant are preferable. . Moreover, it is also possible to use a fluorine compound for these dispersing agents.

  Anionic dispersants include sodium dodecylbenzenesulfonate, sodium alkylsulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyalkylene alkenyl. Sulfonates such as ether ammonium sulfate, sulfate esters, carboxylates such as sodium laurate and potassium oleate, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates Examples thereof include phosphates such as salts. Among these, a sulfonate system is preferable from the viewpoint of good dispersibility.

  Nonionic dispersants include, for example, ether type compounds in which alkylene oxides such as ethylene oxide and propylene oxide are added to compounds having hydroxyl groups such as higher alcohols and alkylphenols, and polyhydric alcohols such as glycerin and saccharides and ester bonds. Examples include an ester type, an ester / ether type in which an alkylene oxide is added to a fatty acid or a polyhydric alcohol fatty acid ester, and an amide type in which a hydrophobic group and a hydrophilic group are connected via an amide bond. Among these, an ether type is preferable in consideration of solubility in water and stability, and a type to which ethylene oxide is added is more preferable in consideration of handleability.

  Although it depends on the molecular weight and structure of the polyether group-containing silicone to be used and depends on the type of the dispersant to be used, it cannot be said unconditionally. As a weight ratio, it is preferably 0.01 to 0.5, more preferably 0.05 to 0.4, and still more preferably 0.1 to 0.3.

  The wax is a wax selected from natural waxes, synthetic waxes, and blended waxes thereof. Natural waxes are plant waxes, animal waxes, mineral waxes, and petroleum waxes. Examples of plant waxes include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil and the like. Animal waxes include beeswax, lanolin, whale wax and the like. Examples of the mineral wax include montan wax, ozokerite, and ceresin. Examples of petroleum wax include paraffin wax, microcrystalline wax, and petrolatum. Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters, ketones, and the like. Synthetic hydrocarbons include, for example, Fischer-Tropsch wax (also known as sazoir wax) and polyethylene wax, and also low molecular weight polymers (specifically, polymers having a number average molecular weight of 500 to 20000). The following polymers are also exemplified: polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol block or graft conjugate, and the like. Examples of the modified wax include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives. The derivative herein is a compound obtained by any of purification, oxidation, esterification, saponification treatment, or a combination thereof. Hydrogenated waxes include hardened castor oil and hardened castor oil derivatives.

  Among these, synthetic waxes are preferable from the viewpoint of stable characteristics, among which polyethylene wax is more preferable, and oxidized polyethylene wax is more preferable. The number average molecular weight of the synthetic wax is preferably in the range of 500 to 30000, more preferably 1000 to 15000, and still more preferably 2000 to 8000, from the viewpoints of stability of properties such as blocking and handleability.

  In addition, in the formation of the antistatic layer, in order to improve the appearance and further reduce the surface resistance, for example, a polyalkylene oxide, glycerin, polyglycerin, glycerin or a polyol compound such as an alkylene oxide addition product to polyglycerin or It is also possible to use a polyether compound in combination.

  Preferred as the polyalkylene oxide or derivative thereof is a compound having an ethylene oxide or propylene oxide structure. If the alkyl group in the alkylene oxide structure is too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution tends to deteriorate, and the antistatic property tends to deteriorate. Particularly preferred is polyethylene oxide. Moreover, the thing of 200-2000 is more preferable in a weight average molecular weight.

  Polyglycerol is a compound in which two or more glycerols are polymerized, and the degree of polymerization is preferably in the range of 2-20. When glycerin is used, transparency may be slightly inferior.

  Further, the alkylene oxide adduct to glycerin or polyglycerin has a structure in which alkylene oxide or a derivative thereof is added to the hydroxyl group of glycerin or polyglycerin.

  Here, the structure of the alkylene oxide added or its derivative may differ for every hydroxyl group of a glycerol or polyglycerol structure. Moreover, it is sufficient that it is added to at least one hydroxyl group in the molecule, and alkylene oxide or a derivative thereof need not be added to all hydroxyl groups.

  Moreover, what is preferable as an alkylene oxide or its derivative added to glycerol or polyglycerol is a compound which has ethylene oxide or a propylene oxide structure. If the alkyl chain in the alkylene oxide structure becomes too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution tends to deteriorate, and the antistatic property and transparency tend to deteriorate. Particularly preferred is ethylene oxide. The number of additions is preferably in the range of 250 to 2000 in terms of the number average molecular weight as the final compound, and more preferably in the range of 300 to 1000.

  For the formation of antistatic layer, various polymers such as polyester resin, acrylic resin, urethane resin and cross-linking agent that can be used for the formation of adhesive layer are used in combination to improve coating appearance and transparency and control slipperiness. It is also possible to do. In particular, in terms of strengthening the antistatic layer and reducing blocking, it is preferable to use a melamine compound, an oxazoline compound, an isocyanate compound, and an epoxy compound, and among them, a melamine compound is particularly preferable.

  As long as the gist of the present invention is not impaired, particles can be used in combination for forming an antistatic layer or for improving blocking or slipperiness.

  Further, as long as it does not impair the gist of the present invention, an antifoaming agent, a coating property improving agent, a thickening agent, an organic lubricant, an ultraviolet absorber, and an antioxidant are necessary for forming the adhesive layer and the antistatic layer. It is also possible to use a foaming agent, a dye, a pigment and the like in combination.

  As a ratio in the adhesive layer constituting the film in the present invention, the resin having a glass transition point of 0 ° C. or less is preferably 30% by weight or more, more preferably 50% by weight or more, further preferably 65% by weight or more, particularly The range is preferably 75% by weight or more, most preferably 85% by weight or more, and the upper limit of the preferred range is 99% by weight. By using in the above range, sufficient adhesive properties can be easily obtained.

  As a ratio in the pressure-sensitive adhesive layer constituting the film in the present invention, the ratio of the epoxy compound is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. When used in the above range, good coating strength and adhesive properties can be easily obtained.

  As a ratio in the pressure-sensitive adhesive layer constituting the film in the present invention, the ratio of the crosslinking agent other than the epoxy compound is 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. It is easy to obtain good coating strength and adjusted adhesive properties by using in the above range, but depending on the material and composition used in the coating layer, it is preferable not to use it because of the concern that the adhesive properties will be too low. In some cases.

  As a proportion in the antistatic layer constituting the film in the present invention, the proportion of the antistatic agent cannot be generally specified because the appropriate amount varies depending on the type of the antistatic agent, but is usually in the range of 0.5% by weight or more, preferably Is in the range of 3 to 90% by weight, more preferably in the range of 5 to 70% by weight, still more preferably in the range of 8 to 60% by weight. If it is less than 0.5% by weight, the antistatic effect is not sufficient, and the effect of preventing the adhesion of surrounding dust and the like may not be sufficient.

  When an antistatic agent other than a conductive polymer is used as the antistatic agent, the proportion in the antistatic layer is usually 5% by weight or more, preferably 10 to 90% by weight, more preferably 20 to 70% by weight, More preferably, it is the range of 25-60 weight%. If it is less than 5% by weight, the antistatic effect is not sufficient, and the effect of preventing the adhesion of surrounding dust and the like may not be sufficient.

  When a conductive polymer is used as the antistatic agent, the proportion in the antistatic layer is usually 0.5% by weight or more, preferably 3 to 70% by weight, more preferably 5 to 50% by weight, and still more preferably 8 to It is in the range of 30% by weight. If it is less than 0.5% by weight, the antistatic effect is not sufficient, and the effect of preventing the adhesion of surrounding dust and the like may not be sufficient.

  As a ratio in the antistatic layer constituting the film in the present invention, the ratio of the release agent cannot be generally specified because the appropriate amount varies depending on the type of the release agent and the intended performance, but preferably 1 to 80 weights. %, More preferably 3 to 70% by weight, still more preferably 5 to 60% by weight. By using it in the above-mentioned range, it is possible to obtain the effects of surface decontamination, blocking with the adhesive layer, and scratch resistance.

  As a ratio in the antistatic layer constituting the film in the present invention, the ratio of the crosslinking agent is preferably 80% by weight or less, more preferably 5 to 60% by weight, and further preferably 10 to 50% by weight.

  The analysis of the components in the adhesive layer and the antistatic layer can be performed by analysis of TOF-SIMS, ESCA, fluorescent X-ray, IR, etc., for example.

  Regarding the formation of the adhesive layer and the antistatic layer, the above-mentioned series of compounds is applied as a solution or solvent dispersion, and a coating solution adjusted to a solid content concentration of about 0.1 to 80% by weight is applied onto the polyester film. It is preferable to produce a polyester film as described above. In particular, since an adhesive layer is provided by in-line coating, an aqueous solution or a water dispersion is more preferable. A small amount of an organic solvent may be contained in the coating solution for the purpose of improving the dispersibility in water, improving the film forming property, and the like. Moreover, only one type of organic solvent may be used, and two or more types may be used as appropriate.

  Regarding the film in the present invention, the thickness of the pressure-sensitive adhesive layer provided on the polyester film is preferably 0.01 to 10 μm, more preferably 0.03 to 5 μm, still more preferably 0.05 to 3 μm, and particularly preferably 0.00. It is in the range of 08-2 μm, most preferably 0.15-0.90 μm. When the thickness of the pressure-sensitive adhesive layer is large, the components of the pressure-sensitive adhesive layer easily protrude when bonded to the polarizing plate and cut, and conversely, when the film thickness is thin, the pressure-sensitive adhesive characteristics may not be sufficient. By using the film thickness of the adhesive layer in the above range, it becomes easy to maintain an appropriate adhesive property. The film thickness of the antistatic layer is preferably in the range of 0.001 to 1 μm, more preferably 0.01 to 0.5 μm, and still more preferably 0.02 to 0.2 μm. By using the film thickness of the antistatic layer within the above range, it becomes easy to improve the performance of the release agent and to obtain a good coating appearance.

  In the film of the present invention, examples of the method for forming the adhesive layer and the antistatic layer include gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, and transfer. Conventionally known coating methods such as roll coating, squeeze coating, impregnation coating, kiss coating, spray coating, calendar coating, and extrusion coating can be used.

  In the present invention, the drying and curing conditions for forming the adhesive layer and the antistatic layer on the polyester film are not particularly limited, but for the drying of a solvent such as water used in the coating solution, Preferably it is 70-150 degreeC, More preferably, it is 80-130 degreeC, More preferably, it is the range of 90-120 degreeC. The drying time is generally 3 to 200 seconds, preferably 5 to 120 seconds. Further, in order to improve the strength of the adhesive layer or the antistatic layer, it is preferably subjected to a heat treatment step in the range of 180 to 270 ° C., more preferably 200 to 250 ° C., and further preferably 210 to 240 ° C. in the film manufacturing process. It is. The time for the heat treatment step is generally 3 to 200 seconds, preferably 5 to 120 seconds. This high-temperature treatment step is also effective in suppressing the sticking out of the components of the pressure-sensitive adhesive layer when it is bonded to the polarizing plate and cut, similarly to the thickness of the pressure-sensitive adhesive layer.

  Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed. The polyester film constituting the film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

  The adhesive strength of the adhesive layer of the present invention is preferably 3 mN / cm or more, more preferably 10 mN / cm or more, still more preferably 30 mN / cm or more, and the upper limit of the preferable range is 2000 mN with respect to the polarizing plate. / M, and the upper limit of the more preferable range is 500 mN / cm. By setting it in the above range, it has more appropriate adhesive properties and good film handling properties can be obtained.

The surface resistance value of the antistatic layer of the present invention is preferably 1 × 10 ¹² Ω or less, more preferably 1 × 10 ¹¹ Ω or less, and even more preferably 5 × 10 ¹⁰ Ω or less. When it is within the above range, the film has little adhesion of surrounding dust.

  Moreover, roughening the surface of the film on the antistatic layer side of the present invention may be one of the means for improving the blocking property with the adhesive layer side. Since it depends on the kind of the antistatic layer, it cannot be generally stated, but from the viewpoint of blocking characteristics, the arithmetic average roughness (Sa) of the surface on the antistatic layer side is preferably 5 nm or more, more preferably 10 nm. More preferably, the upper limit is 30 nm or more, and the upper limit is not particularly limited. However, the upper limit of the preferable range is 300 nm from the viewpoint of transparency. When the release force of the antistatic layer is good, the influence of Sa is small because the influence of the antistatic layer is dominant. However, when the release force is weak, the influence of Sa may be large.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The measurement method and evaluation method used in the present invention are as follows.

(1) Method for measuring the intrinsic viscosity of polyester 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed are precisely weighed, and 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) is added. And dissolved at 30 ° C.

(2) Measuring method of average particle diameter (d50: μm) Value of 50% of integration (weight basis) in equivalent spherical distribution measured using Shimadzu Corporation, centrifugal sedimentation type particle size distribution measuring device SA-CP3 type Was the average particle size.

(3) Method for Measuring Arithmetic Average Roughness (Sa) Non-contact surface / layer cross-sectional shape measurement system VertScan (registered trademark) manufactured by Ryoka System Co., Ltd. ) Using R550GML, CCD camera: SONY HR-50 1/3 ', objective lens: 20x, lens barrel: 1X Body, zoom lens: No Relay, wavelength filter: 530 white, measurement mode: Wave And the output by the fourth-order polynomial correction was used.

(4) Method for Measuring Film Thickness of Adhesive Layer and Antistatic Layer The surface of the coating layer was dyed with RuO ₄ and embedded in an epoxy resin. Thereafter, the section prepared by ultramicrotomy stained with RuO _4, a coating layer cross-section was measured by using a TEM (Hitachi High Technologies Corporation H-7650, accelerating voltage 100 V). The film thickness was measured at a location not including the particle portion.

(5) Glass transition point Using a differential scanning calorimeter (DSC) 8500, manufactured by PerkinElmer Japan Co., Ltd., measurement was performed at −100 to 200 ° C. under a temperature rising condition of 10 ° C. per minute.

(6) Number average molecular weight measurement method It measured using GPC (HLC-8120GPC by Tosoh Corporation). The number average molecular weight was calculated in terms of polystyrene.

(7) Functional group confirmation of silicone Polyether group-containing silicone was assigned to each peak of ¹ H-NMR using NMR (AVANCE III600 manufactured by Bruker Biospin), and the amount of dimethylsiloxane and polyether group, vinyl silane and hydrogen The presence or absence of silane was confirmed.

(8) Adhesive strength evaluation method The pressure-sensitive adhesive layer surface of the polyester film of the present invention having a width of 5 cm was pressed once on a surface of a polarizing plate made of polyvinyl alcohol resin with a 2 cm rubber roller having a width of 5 cm, and left at room temperature for 1 hour. The subsequent peel force was measured. For the peeling force, “Ezgraph” manufactured by Shimadzu Corporation was used, and 180 ° peeling was performed under the condition of a tensile speed of 300 mm / min.

(9) Bonding characteristic evaluation method of adhesive layer The adhesive layer side of one A4 size polyester film and a polarizing plate made of a 5 cm square polyvinyl alcohol resin were stacked and pressed with a finger to evaluate the bonding characteristics.
5 points when the film can be stuck just by holding it lightly with your finger, and it can be held even if you hold only the polyester film. 4 points when you can hold the attached state, the film sticks by pressing firmly with your finger, you can keep the attached state even if you have only the polyester film, but 3 points when you peel off within 3 seconds, When the film is pressed firmly with a finger, the bonding characteristics are very small on the film. However, 2 points are shown when the film cannot be stuck, and 1 point is when no bonding characteristics are seen even when pressed with a finger. did. In practical use, two or more points are preferable.

(10) Reworkability evaluation method of adhesive layer In the above evaluation method (9), after the film is peeled off, the same operation is performed again at the same location. The case where it worsened was set as x.

(11) Method for evaluating transfer characteristics of adhesive layer to polarizing film In the above evaluation method (9), after the attached film is peeled off, the transfer to the polarizing plate (transfer track of the adhesive layer) is observed. The case where there was no transfer was marked as ◯, and the case where there was transfer to a polarizing film was marked as x.

(12) Method for Measuring Surface Resistance on Antistatic Layer Side The surface resistance of the antistatic layer was measured based on the method (12-1) below. In the method (12-1), since the surface resistivity lower than 1 × 10 ⁸ Ω cannot be measured sufficiently, the method (12-2) was used for the sample that could not be measured in (12-1).
(12-1) High resistance measuring instrument manufactured by Nippon Hewlett-Packard Co., Ltd .: HP4339B and measuring electrode: HP16008B were used, and the polyester film was fully conditioned in a measurement atmosphere of 23 ° C. and 50% RH, and then applied voltage was 100V. The surface resistance of the antistatic layer after 1 minute was measured.
(12-2) Low resistance meter manufactured by Mitsubishi Chemical Co., Ltd .: Loresta GP MCP-T600 was used, the sample was conditioned for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH, and then the surface resistance of the antistatic layer was measured. .

(13) Dust adhesion evaluation method on the antistatic layer side The polyester film is sufficiently conditioned in a measurement atmosphere of 23 ° C. and 50% RH, and then the antistatic layer is rubbed 10 times with a cotton cloth. This was brought close to the finely crushed cigarette ash and the ash adhesion was evaluated according to the following criteria.
○: Even if the film is brought into contact with ash, it does not adhere. Δ: When the film is brought into contact with ash, it adheres a little.

(14) Method of evaluating anti-moisture heat resistance (haze change amount) on the antistatic layer side The haze after the film was treated under conditions of 50 ° C. and 85% RH for 50 hours is a haze meter HM- manufactured by Murakami Color Research Laboratory It was measured by JIS K 7136 using 150. The value obtained by subtracting the haze value before treatment from the haze value after treatment was defined as the amount of change in haze, and the situation was evaluated according to the following criteria.
○: Haze change amount is 0.5% or less △: Haze change amount exceeds 0.5%, 2.0% or less ×: Haze change amount exceeds 2.0%

(15) Measuring method of blocking resistance Two polyester films to be measured are prepared, the adhesive layer side and the antistatic layer side are overlapped, and an area of 12 cm × 10 cm is obtained at 40 ° C., 80% RH, 10 kg / cm. ^2. Pressed for 20 hours. Thereafter, the films were peeled according to the method specified in ASTM D1893, and the peel load was measured. The lighter the peel load, the harder it is to block and the better, and the evaluation was based on the following criteria.
○: Peeling load is 50 g / cm or less. Δ: Peeling load exceeds 50 g / cm and 300 g / cm or less. X: Peeling load exceeds 300 g / cm, film that is torn during evaluation, press Causes obvious blocking

(16) Method for evaluating scratch resistance on the antistatic layer side The surface of the antistatic layer was rubbed with a nail, and the case where there was no nail mark was evaluated as ◯, and the case where a nail mark was generated was evaluated as x.

The polyester used in the examples and comparative examples was prepared as follows.
<Method for producing polyester (A)>
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 30 ppm of ethyl acid phosphate with respect to the resulting polyester, and 100 ppm of magnesium acetate tetrahydrate with respect to the resulting polyester as the catalyst at 260 ° C. in a nitrogen atmosphere at 260 ° C. The reaction was allowed to proceed. Subsequently, 50 ppm of tetrabutyl titanate was added to the resulting polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to 0.3 kPa in absolute pressure, and melt polycondensation was further carried out for 80 minutes. A polyester (A) having 0.63 and an amount of diethylene glycol of 2 mol% was obtained.

<Method for producing polyester (B)>
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and magnesium acetate tetrahydrate as a catalyst were subjected to an esterification reaction at 225 ° C. in a nitrogen atmosphere at 900 ppm with respect to the produced polyester. Subsequently, 3500 ppm of orthophosphoric acid was added to the produced polyester, and 70 ppm of germanium dioxide was added to the produced polyester. The temperature was raised to 280 ° C. over 2 hours and 30 minutes, and the pressure was reduced to an absolute pressure of 0.4 kPa. After 85 minutes of melt polycondensation, polyester (B) having an intrinsic viscosity of 0.64 and a diethylene glycol amount of 2 mol% was obtained.

<Method for producing polyester (C)>
In the production method of the polyester (A), the polyester (C) is produced using the same method as the production method of the polyester (A) except that 0.3 part by weight of silica particles having an average particle diameter of 2.7 μm is added before the melt polymerization. Got.

<Method for producing polyester (D)>
In the production method of the polyester (A), the polyester (D) is produced using the same method as the production method of the polyester (A) except that 0.6 parts by weight of silica particles having an average particle diameter of 3.2 μm is added before the melt polymerization. Got.

Examples of compounds constituting the coating layer are as follows.
(Example compounds)
・ Polyester resin: (IA)
Water dispersion of polyester resin (glass transition point: −20 ° C.) having the following composition: Monomer composition: (acid component) dodecanedicarboxylic acid / terephthalic acid / isophthalic acid / 5-sodiumsulfoisophthalic acid // (diol component) ethylene Glycol / 1,4-butanediol = 20/38/38/4 // 40/60 (mol%)
・ Polyester resin: (IB)
Water dispersion of polyester resin (glass transition point: −30 ° C.) having the following composition: Monomer composition: (acid component) dodecanedicarboxylic acid / terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene Glycol / 1,4-butanediol = 30/33/33/4 // 40/60 (mol%)

・ Polyester resin: (IC)
Water dispersion of polyester resin (glass transition point: 30 ° C.) having the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4 -Butanediol / diethylene glycol = 40/56/4 // 45/25/30 (mol%)
・ Polyester resin: (ID)
Water dispersion of polyester resin having the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56 / 40/4 // 70/20/10 (mol%)

・ Acrylic resin: (IIA)
Aqueous dispersion of acrylic resin (glass transition point: −25 ° C.) having the following composition: normal butyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid = 72/23/3/2 (% by weight)
・ Acrylic resin: (IIB)
Aqueous dispersion of acrylic resin (glass transition point: −40 ° C.) having the following composition: normal butyl acrylate / 2-ethylhexyl acrylate / ethyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 30/30/36/2 / 2 (% by weight)

・ Acrylic resin: (IIC)
Aqueous dispersion of acrylic resin (glass transition point: −50 ° C.) having the following composition: 2-ethylhexyl acrylate / lauryl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid / methacrylic acid = 50/25/15/5/5 (weight%)
・ Acrylic resin: (IID)
Aqueous dispersion of acrylic resin (glass transition point: −55 ° C.) having the following composition 2-ethylhexyl acrylate / vinyl acetate / acrylic acid = 78/20/2 (% by weight)
・ Acrylic resin: (IIE)
Aqueous dispersion of acrylic resin (glass transition point: −15 ° C.) having the following composition: normal butyl acrylate / ethyl acrylate / methyl methacrylate / acrylic acid = 45/23/30/2 (% by weight)
・ Acrylic resin: (IIF)
Aqueous dispersion of acrylic resin (glass transition point: 10 ° C.) having the following composition: ethyl acrylate / normal butyl methacrylate / acrylic acid = 25/73/2 (% by weight)

-Urethane resin: (III)
Consists of 80 parts of polycarbonate polyol having a number average molecular weight of 2000 consisting of 1,6-hexanediol and diethyl carbonate, 4 parts of polyethylene glycol having a number average molecular weight of 400, 12 parts of methylenebis (4-cyclohexylisocyanate), and 4 parts of dimethylolbutanoic acid. Water dispersion obtained by neutralizing urethane resin with triethylamine (glass transition point: -30 ° C)

・ Epoxy compound: (IVA) Polyglycerol polyglycidyl ether which is a polyfunctional polyepoxy compound ・ Melamine compound: (IVB) Hexamethoxymethylolmelamine ・ Oxazoline compound: (IVC)
Acrylic polymer having an oxazoline group and a polyalkylene oxide chain Epocross (Oxazoline group amount = 4.5 mmol / g, manufactured by Nippon Shokubai Co., Ltd.)

・ Isocyanate compounds: (IVD)
1000 parts of hexamethylene diisocyanate was stirred at 60 ° C., and 0.1 part of tetramethylammonium capryate was added as a catalyst. After 4 hours, 0.2 part of phosphoric acid was added to stop the reaction, and an isocyanurate type polyisocyanate composition was obtained. 100 parts of the obtained isocyanurate type polyisocyanate composition, 42.3 parts of methoxypolyethylene glycol having a number average molecular weight of 400, and 29.5 parts of propylene glycol monomethyl ether acetate were charged and maintained at 80 ° C. for 7 hours. Thereafter, the reaction solution temperature was kept at 60 ° C., 35.8 parts of methyl isobutanoyl acetate, 32.2 parts of diethyl malonate, and 0.88 part of 28% methanol solution of sodium methoxide were added and kept for 4 hours. Block polyisocyanate with active methylene obtained by adding 58.9 parts of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 part of 2-ethylhexyl acid phosphate.

-Particles: (V) Silica particles with an average particle size of 0.07 μm

・ Antistatic agent (compound having ammonium group): (VIA)
A polymer compound having a number average molecular weight of 50000, wherein the counter ion is a methanesulfonic acid ion, comprising a structural unit of the following formula 2.

・ Antistatic agent (compound having ammonium group): (VIB)
Polymer polymerized with the following composition having a pyrrolidinium ring in the main chain: Diallyldimethylammonium chloride / dimethylacrylamide / N-methylolacrylamide = 90/5/5 (mol%). Number average molecular weight 30000.

・ Antistatic agent (conductive polymer): (VIC)
An Orgacon ICP1010 manufactured by Agfa Gebalt, made of polyethylene dioxythiophene and polystyrene sulfonic acid.

・ Release agent (long chain alkyl group-containing compound): (VIIA)
To a four-necked flask, 200 parts of xylene and 600 parts of octadecyl isocyanate were added and heated with stirring. From the time when xylene began to reflux, 100 parts of polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of 88 mol% was added in small portions over a period of about 2 hours. After the addition of polyvinyl alcohol, the reaction was completed by further refluxing for 2 hours. When the reaction mixture was cooled to about 80 ° C. and added to methanol, the reaction product was precipitated as a white precipitate. This precipitate was filtered off, added with 140 parts of xylene, and heated to dissolve completely. After repeating the operation of adding methanol again to precipitate several times, the precipitate was washed with methanol and dried and ground.

・ Release agent (polyether group-containing condensed silicone): (VIIB)
Polyether group-containing silicone having a number average molecular weight of 7000 (silicone siloxane) containing 1 polyethylene glycol (terminated with a hydroxyl group) having an ethylene glycol chain of 8 with respect to dimethylsiloxane 100 in the dimethyl silicone side chain in a molar ratio. When the bond is 1, the ether bond of the polyether group is 0.07 at a molar ratio). 3% of low molecular components having a number average molecular weight of 500 or less, no vinyl group (vinyl silane) and hydrogen group (hydrogen silane) bonded to silicon exist. In addition, this compound mix | blends the water which disperse | distributes sodium dodecyl benzenesulfonate in the ratio of 0.25 by making polyether group containing silicone 1 by weight ratio.

・ Release agent (wax): (VIIC)
An emulsification facility with an internal capacity of 1.5 L equipped with a stirrer, thermometer, temperature controller, melting point 105 ° C., acid value 16 mgKOH / g, density 0.93 g / mL, number average molecular weight 5000 polyethylene oxide wax 300 g, ion-exchanged water 650 g After adding 50 g of decaglycerin monooleate surfactant and 10 g of 48% potassium hydroxide aqueous solution and replacing with nitrogen, the mixture was sealed, stirred at 150 ° C. for 1 hour at high speed, cooled to 130 ° C., and a high-pressure homogenizer at 400 atm. A wax emulsion passed through and cooled to 40 ° C.

・ Polyether compounds: (IX)
Polyethylene oxide adduct to diglycerin structure, number average molecular weight 350.

Example 1:
A mixed raw material in which polyesters (A), (B), and (C) are mixed in proportions of 80%, 3%, and 17%, respectively, is used as a raw material for the outermost layer (surface layer), and polyesters (A) and (B) are each 97 %, 3% of the mixed raw material is used as an intermediate layer raw material, each is supplied to two extruders, melted at 285 ° C., and then on a cooling roll set at 40 ° C. Coextruded and cooled and solidified with a layer structure of layers (surface layer / intermediate layer / surface layer = 3: 19: 3 discharge amount) to obtain an unstretched sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then the coating liquid A1 shown in Table 1 below was applied on one side of the longitudinally stretched film to the film thickness (dried) (After) is applied to 0.40 μm (adhesive layer), and coating solution B1 shown in Table 2 below is applied to the opposite side so that the thickness of the coating layer (after drying) is 0.06 μm. (Antistatic layer), guided to a tenter, dried at 95 ° C. for 10 seconds, stretched 4.3 times at 120 ° C. in the transverse direction, heat treated at 230 ° C. for 10 seconds, and then relaxed by 2% in the transverse direction Thus, a polyester film having a thickness of 25 μm and an Sa of the antistatic layer side surface of 12 nm was obtained.

  When the finished polyester film was evaluated, the adhesive properties and dust adhesion were good. The properties of this film are shown in Tables 3 and 4 below.

Examples 2-48:
In Example 1, except having changed a coating agent composition into the coating agent composition shown to Table 1 and 2, it manufactured like Example 1 and the polyester film was obtained. The completed polyester film had good adhesive properties and dust adhesion as shown in Tables 3 to 6 below.

Examples 49-61:
In Example 1, the polyester composition of the surface layer is a mixed raw material in which polyesters (A), (B), and (D) are mixed in proportions of 72%, 3%, and 25%, respectively, and the layer configuration is two types and three layers ( Production is carried out in the same manner as in Example 1 except that the coating composition is coextruded with a layer composition of (surface layer / intermediate layer / surface layer = 3: 19: 3) and the coating composition is changed to the coating composition shown in Tables 1 and 2. A polyester film was obtained. Sa on the surface of the antistatic layer side of the finished polyester film was 30 nm, and the adhesive properties and dust adhesion were good. The properties of this film are shown in Tables 7 and 8 below.

Examples 62-74:
In Example 1, the polyester composition of the surface layer is a mixed raw material in which polyesters (A), (B), and (C) are mixed in proportions of 91%, 3%, and 6%, respectively, and the layer configuration is two types and three layers ( Production is carried out in the same manner as in Example 1, except that coextrusion is carried out with a layer structure of surface layer / intermediate layer / surface layer = 2: 21: 2) and the coating composition is changed to the coating composition shown in Tables 1 and 2. A polyester film was obtained. Sa on the surface of the antistatic layer side of the finished polyester film was 9 nm, and the adhesive properties and dust adhesion were good. The properties of this film are shown in Tables 7 and 8 below.

Comparative Example 1:
In Example 1, it manufactured similarly to Example 1 except having not provided the application layer, and obtained the polyester film. When the completed polyester film was evaluated, as shown in Tables 9 and 10 below, it was a film having no adhesive properties and poor dust adhesion.

Comparative Examples 2-6:
In Example 1, except having changed a coating agent composition into the coating agent composition shown to Table 1 and 2, it manufactured like Example 1 and the polyester film was obtained. As shown in Tables 9 and 10, the finished polyester film was a film that cannot be said to have an adhesive layer, a film with poor adhesive properties, and a film with poor dust adhesion.

Comparative Example 7:
On the polyester film without the coating layer obtained in Comparative Example 1, coating solution A1 shown in Table 1 below was coated so that the coating layer thickness (after drying) was 0.40 μm, and the coating layer was 100 ° C. for 60 seconds. Was dried to obtain a polyester film with an adhesive layer formed by off-line coating. As shown in Table 9, the completed polyester film had good adhesive properties but was poor in adhesive residue.

Comparative Example 8:
In the same manner as in Comparative Example 7, a polyester film having an adhesive layer formed by off-line coating was obtained so that the thickness of the adhesive layer was 20 μm. When the adhesive film side was bonded to the polarizing film and then cut, the adhesive was protruded, and there was a concern about contamination with the adhesive. The other characteristics were as shown in Tables 9 and 10.

The production method of the present invention is a method for producing an optical member using an optical member surface protective film that suppresses charging due to peeling or friction, has good adhesive properties, reduces the sticking out of the adhesive by cutting, and has few defects relates, in particular a polarizing plate, suitably used for optical member such as a larger retardation plate or viewing angle.

Claims (13)

An optical member in which an adhesive layer containing a resin having a glass transition point of 0 ° C. or less is formed on one surface of a polyester film, an antistatic layer is formed on the opposite surface, and the adhesive layer is bonded to an optical member The method for producing an optical member according to claim 1, wherein the adhesive layer is formed on the polyester film by in-line coating and then subjected to a heat treatment step in a range of 180 to 270 ° C. The method for producing an optical member according to claim 1, wherein the optical member is a polarizing plate, a retardation plate, or a viewing angle widening plate. The method for producing an optical member according to claim 2 , wherein the optical member is a polarizing plate made of a polyvinyl alcohol-based resin. The optical member manufacturing method according to any one of claims 1 to 3 film thickness of the adhesive layer is 0.01 to 0.90 [mu] m. The resin glass transition point of 0 ℃ or less, the optical member manufacturing method according to any one of claims 1 to 4, which is a polyester resin. The method for producing an optical member according to claim 5 , wherein the polyester resin includes an aliphatic polyvalent carboxylic acid or an aliphatic polyvalent hydroxy compound as a constituent component. The optical member manufacturing method according to claim 5 or 6 wherein the polyester resin is a water-based. The resin glass transition point of 0 ℃ or less, the optical member manufacturing method according to any one of claims 1 to 4 which is an acrylic resin. The optical component according to claim 8 , wherein a content of a monomer having a glass transition point of 0 ° C or lower in the case of a homopolymer among monomers constituting the acrylic resin is 30% by weight or more as a ratio with respect to the entire acrylic resin. Manufacturing method of member. The method for producing an optical member according to claim 8 or 9 , wherein the acrylic resin is an alkyl (meth) acrylate having an alkyl group having 4 to 30 carbon atoms. Said adhesive layer, the optical member manufacturing method according to any one of claims 8 to 10 you formed using an aqueous dispersion of the acrylic resin. The optical member manufacturing method according to any one of claims 1 to 11, wherein the antistatic layer contains a release agent. The method for producing an optical member according to any one of claims 1 to 12 , wherein the antistatic layer is formed using a crosslinking agent.