JP6531715B2 - Laminated polyester film - Google Patents

Description

  The present invention relates to a laminated polyester film, and has few fish eyes, for example, as a surface protection film for preventing damage or adhesion of dirt during transportation, storage or processing of resin plates, metal plates, etc. The present invention relates to a laminated polyester film which is excellent in mechanical strength and heat resistance and has excellent adhesion characteristics and discrimination.

  Conventionally, during transportation of resin plates, metal plates, glass plates, etc., damage and dirt adhesion are prevented during storage or processing, and damage occurs during processing of members used in electronic related fields such as liquid crystal panels and polarizing plates. Surface protection films are widely used in applications such as prevention of dust and dirt, prevention of dirt and adhesion during storage, protection of automobile paint from acid rain during transportation, and plating and etching of flexible printed circuit boards. It is used.

  These surface protection films have appropriate adhesion to the adherend during transportation, storage, processing, etc. of various adherends such as resin plates, metal plates, and glass plates. By adhering to the surface of the adherend, it is required that the surface of the adherend is protected and easily peeled off after the end of the purpose. In order to overcome these problems, proposals have been made to use polyolefin-based films for surface protection (Patent Documents 1 and 2).

  However, since a polyolefin-based film is used as the surface protective film substrate, it is not possible to remove the defects caused by the gel-like material or the degraded material caused by the film substrate material, which is generally called a fish eye. For example, when inspecting a to-be-adhered body in the state which bonded surface protection film, there exists a problem of becoming an obstruction of detecting the defect of a surface protection film, etc.

  Moreover, as a base material of a surface protective film, a film having a certain degree of mechanical strength is required so that the base material is not stretched due to tensions during various processes such as bonding to an adherend. However, polyolefin-based films are generally inferior in mechanical strength, and have the disadvantage of being unsuitable for high-tensile processing, which is caused by, for example, increasing the processing speed in order to emphasize productivity.

  Furthermore, even when the processing temperature is raised to improve the processing speed and various characteristics, etc., the polyolefin-based film is not excellent in the shrinkage stability due to heat, so the dimensional stability is poor. Therefore, there is a demand for a film which is less in thermal deformation even when subjected to high temperature processing and is excellent in dimensional stability.

Japanese Patent Laid-Open No. 5-98219 Japanese Patent Application Publication No. 2007-270005

  The present invention has been made in view of the above situation, and the problem to be solved is that it has few fish eyes, is excellent in mechanical strength and heat resistance, and has good adhesion characteristics and is used for various surface protection films etc. An object of the present invention is to provide a laminated polyester film having properties.

  As a result of intensive investigations in view of the above situation, the present inventor has found that if the laminated polyester film having a specific configuration is used, the above-mentioned problems can be easily solved, and the present invention has been completed.

That is, the gist of the present invention relates to a polyester resin having a glass transition temperature of 0 ° C. or less, an acrylic resin having a glass transition temperature of −20 ° C. or less, and a urethane having a glass transition temperature of 0 ° C. or less A laminated polyester film characterized by having a pressure-sensitive adhesive layer containing at least one selected from resins and a colorant having a maximum absorption wavelength in the range of 570 to 650 nm , and a glass transition point on at least one side of the polyester film Providing an application layer containing at least one selected from a polyester resin having a glass transition temperature of 0 ° C. or less, an acrylic resin having a glass transition temperature of −20 ° C. or less, and a urethane resin having a glass transition temperature of 0 ° C. or less Forming an adhesive layer by stretching the coated layer in at least one direction It consists in the production method of the laminated polyester film according to symptoms.

  According to the laminated polyester film of the present invention, as various surface protective films, films having few fish eyes, excellent in mechanical strength and heat resistance, and having good adhesive properties and discrimination can be provided, and the industrial use thereof Value is high.

  We believe that it is necessary to make major changes to the base material of the base film in order to reduce the fisheye, improve mechanical strength and improve heat resistance, which is the problem, and as a result of various studies, it differs significantly from conventionally used polyolefin materials It has been found that this can be achieved by using polyester based materials. However, by largely changing the material system of the base film, the adhesive properties are greatly reduced, and it has become impossible to achieve with conventional polyester films. Then, improvement was aimed at by providing an adhesion layer on a substrate film, and it came to the present invention.

  In addition, it is desirable that even before or after laminating a laminated polyester film, it is desirable to be able to distinguish the difference in the adhesive strength of the adhesive layer, the difference in the type of adherend, and the like. By incorporating a coloring agent in the adhesive layer, if the color can be classified according to the difference in adhesive strength or the color according to the type of adherend, the discriminability is remarkably improved, and it is considered that working errors and the like can be prevented. The

  The polyester film may have a single layer structure or a multilayer structure. In the case of a multilayer structure, the surface layer and the inner layer, or both surface layers or layers can be different polyester layers according to the purpose, and a multilayer structure of two or more layers, each layer having characteristics, and multifunctionalization Is preferred.

  The polyester used may be homopolyester or copolyester. When it consists of homo polyesters, what is obtained by polycondensing aromatic dicarboxylic acid and aliphatic glycol is 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. A polyethylene terephthalate etc. are illustrated as a typical polyester. On the other hand, as the dicarboxylic acid component of the copolyester, isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-hydroxybenzoic acid etc.), etc. 1 type, or 2 or more types are mentioned, 1 or 2 or more types, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4- cyclohexane dimethanol, neopentyl glycol etc. are mentioned as a glycol component.

  From the viewpoint of forming a film that can withstand various processing conditions, it is preferable that the mechanical strength and the heat resistance (dimensional stability by heating) be high, and for that purpose, it may be preferable that the amount of the copolymerized polyester component be small. Specifically, the proportion of monomers forming the copolyester occupied in the polyester film is usually 10 mol% or less, preferably 5 mol% or less, and more preferably generated as a by-product during homopolyester polymerization In other words, it contains only 3 mol% or less of the diether component. Among the above-mentioned compounds, a film formed of polyethylene terephthalate or polyethylene naphthalate, which is polymerized from terephthalic acid and ethylene glycol, is more preferable, in view of mechanical strength and heat resistance. A film formed of polyethylene terephthalate is more preferable in consideration of ease of handling and handleability as an application such as a surface protective film.

  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 them, 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 because the amount of metal remaining in the film is small, the film Is preferable because the transparency of the Furthermore, it is more preferable to use a titanium compound because the germanium compound is expensive.

  In the case of a polyester using a titanium compound, the titanium element content is usually 50 ppm or less, preferably 1 to 20 ppm, more preferably 2 to 10 ppm. When the content of the titanium compound is too large, deterioration of the polyester may be promoted in the step of melt extruding the polyester, and a film having a strong yellow color may be obtained. When the content is too small, the polymerization efficiency is poor and the cost is low. In some cases, a film having up or sufficient strength can not be obtained. Moreover, when using 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 the deterioration suppression in the process of melt-extrusion. As the phosphorus compound, orthophosphoric acid is preferable in consideration of the productivity and the thermal stability of the polyester. The phosphorus content is usually in the range of 1 to 300 ppm, preferably 3 to 200 ppm, more preferably 5 to 100 ppm, based on the amount of polyester to be melt extruded. If the content of the phosphorus compound is too high, it may cause gelation or foreign matter, and if the content is too low, the activity of the titanium compound can not be sufficiently lowered, and the yellowish It may be a film.

  In the polyester layer, it is also possible to blend particles for the purpose of imparting lubricity, preventing scratching in each step, and improving the blocking resistance. In the case of blending particles, the type of particles to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness, and as specific examples, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, sulfuric acid 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 can be mentioned. Furthermore, precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed can also be used in the polyester production process. Among these, silica particles and calcium carbonate particles are preferable in that they are particularly effective in small amounts.

  The average particle size of the particles is usually in the range of 10 μm or less, preferably 0.01 to 5 μm, more preferably 0.01 to 3 μm. When the average particle size exceeds 10 μm, there may be a concern that the film may be impaired due to the decrease in transparency.

  Furthermore, the content of particles in the polyester layer is generally not more than 5% by weight, preferably in the range of 0.0003 to 3% by weight, and more preferably 0, although it is not general because there is also a balance with the average particle diameter of the particles. It is in the range of .0005 to 1% by weight. When the particle content is more than 5% by weight, problems such as the dropout of the particles and the decrease in the transparency of the film may be concerned. When there are no particles or few particles, the slipperiness may be insufficient. Therefore, some measures such as improvement of the slipperiness may be required by putting the particles in the adhesive layer.

The shape of the particles to be used is not particularly limited, and any of spherical, massive, rod-like, flat 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 needed.

  It does not specifically limit as method to add particle | grains in a polyester layer, A conventionally well-known method can be employ | adopted. For example, although it can be added at any stage of producing the polyester constituting each layer, it is preferably added after completion of the esterification or transesterification reaction.

In addition to the above-mentioned particles, conventionally known ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments and the like can be added to the polyester film, as required.

  The thickness of the polyester film is not particularly limited as long as it can form a film as a film, but is usually 2 to 350 μm, preferably 5 to 200 μm, more preferably 8 to 75 μm.

  Although the production example of a film is concretely demonstrated, it is not limited at all to the following production example, The film forming method generally known can be employ | adopted. Generally, the resin is melted, sheeted, and stretched for the purpose of increasing the strength, etc., to form a film. For example, when producing a biaxially stretched polyester film, first, a polyester raw material is melt extruded from a die using an extruder, and the molten sheet is cooled and solidified by a cooling roll to obtain an unstretched sheet. In this case, in order to improve the planarity of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and the electrostatic application adhesion method or the liquid application adhesion method is preferably employed. Next, the unstretched sheet obtained is stretched in one direction by a roll or 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 at a draw ratio of usually 2.5 to 7 times, preferably 3.0 to 6 times, usually at 70 to 170 ° C., in a direction perpendicular to the first-stage stretching direction. Subsequently, a heat treatment is usually performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially oriented film. In said extending | stretching, the method of performing extending | stretching of one direction in two or more steps is also employable. In that case, it is preferable to carry out so that the draw ratio of two directions finally becomes the said range, respectively.

  Moreover, the simultaneous biaxial stretching method can also be employ | adopted regarding polyester film manufacture which comprises a lamination | stacking polyester film. The simultaneous biaxial stretching method is a method of simultaneously stretching and orienting the above-mentioned unstretched sheet in the machine direction and the width direction in a state where the temperature is usually controlled at 70 to 120 ° C., preferably 80 to 110 ° C. Is usually 4 to 50 times, preferably 7 to 35 times, more preferably 10 to 25 times in area ratio. Then, heat treatment is subsequently performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a stretched and oriented film. With respect to the simultaneous biaxial stretching apparatus adopting the above-described stretching method, conventionally known stretching methods such as a screw method, a pantograph method, and a linear drive method can be adopted.

  Next, formation of the adhesion layer which comprises a lamination | stacking polyester film is demonstrated. Examples of the method for forming the adhesive layer include methods such as coating, transfer, and lamination. It is preferable to form by coating in consideration of the ease of forming the adhesive layer.

  The coating method may be provided by in-line coating performed in the process of film production, or may be provided by off-line coating, which coats the film once produced, outside the system. More preferably, it is formed by in-line coating.

  Specifically, in-line coating is a method in which coating is performed at any stage from melt extrusion of a resin forming a film to stretching after heat setting and winding. Usually, the unstretched sheet obtained by melting and quenching, the stretched uniaxially stretched film, the biaxially stretched film before heat setting, and the film after heat setting and before winding are coated. Although not limited to the following, for example, in the sequential biaxial stretching, a method of stretching in the transverse direction after coating on a uniaxially stretched film stretched particularly in the longitudinal direction (longitudinal direction) is excellent. According to this method, since film formation and adhesive layer formation can be performed simultaneously, there is a merit in manufacturing cost, and in order to perform stretching after coating, the thickness of the adhesive layer can be changed by the stretching ratio. Thin film coating can be performed more easily than offline coating.

  Also, 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 the biaxially stretched polyester film, the film can be restrained in the longitudinal and transverse directions by holding the film end with a clip or the like while stretching, and in the heat setting step, no wrinkles or the like occur and the plane is flat. High temperature can be applied while maintaining the sex.

  Therefore, since the heat treatment applied after coating can be at a high temperature which can not be achieved by other methods, the film forming property of the adhesive layer can be improved, and the adhesive layer and the substrate film can be more firmly adhered. Furthermore, it can be made a strong adhesive layer. In particular, it is very effective for reacting a crosslinking agent.

  According to the process by the above-mentioned in-line coating, the film size does not largely change depending on the presence or absence of the adhesive layer, and the risk of scratching or foreign matter adhesion does not significantly change depending on the presence or absence of the adhesive layer. This is a great advantage over one extra offline coating. Furthermore, as a result of various investigations, it was found that in-line coating also has the advantage of being able to reduce adhesive residue, which is the migration of the components of the adhesive layer when the film of the present invention is bonded to an adherend. The It is considered that this can be heat-treated at a high temperature that can not be obtained by off-line coating, and that the adhesion layer and the base film are more firmly adhered.

  In the present invention, it is an essential requirement to have an adhesive layer containing a resin having a glass transition temperature of 0 ° C. or less and a colorant.

  As the resin having a glass transition temperature of 0 ° C. or less, conventionally known resins can be used. 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, and among them, polyester resin, in particular in consideration of adhesive property and coating property. Acrylic resins and urethane resins are preferable, and polyester resins and acrylic resins are more preferable from the viewpoint of strength of adhesive properties, and polyester resins are further preferable because they have high adhesive strength to various adherends. In consideration of the reusability of the film, polyester resins and acrylic resins are preferred, and when the substrate is a polyester film, the polyester resin exhibits little change with time when adhesion to the substrate is considered. Acrylic resins are most preferred when considered. Furthermore, in consideration of the migration of the components of the adhesive layer to the adherend, it was also found that the acrylic resin has less migration and is preferable to the polyester resin.

  With polyester resin, what consists of a polyvalent carboxylic acid and a polyvalent hydroxy compound as follows as a main structural component is mentioned, for example. That is, as polyvalent carboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6 -Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutar Acids, succinic acids, trimellitic acids, trimesic acids, pyromellitic acids, trimellitic anhydrides, phthalic anhydrides, p-hydroxybenzoic acids, trimellitic acid monopotassium salts and their ester-forming derivatives can be used. And ethylene as polyvalent hydroxy compounds Recall, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanedio- , Neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol And polytetramethylene glycol, polytetramethylene oxide glycol, dimethylol propionic acid, glycerin, trimethylol propane, sodium dimethyl ethyl sulfonate, potassium dimethyl propionate and the like can be used. Among these compounds, one or more may be appropriately selected, and a polyester resin may be synthesized by a polycondensation reaction in a conventional manner.

  Among the above, in order to lower the glass transition point to 0 ° C. or lower, it is preferable to contain an aliphatic polyvalent carboxylic acid or an aliphatic polyvalent hydroxy compound as a constituent. Generally, polyester resins are composed of polyvalent hydroxy compounds including aromatic polyvalent carboxylic acids and aliphatics, so in order to lower the glass transition point than common polyester resins, aliphatic polyvalent compounds are used. It is effective to contain a carboxylic acid. From the viewpoint of lowering the glass transition point, among aliphatic polyvalent carboxylic acids, the carbon number is preferably long, and usually, the carbon number is 6 or more (adipic acid), preferably 8 or more, more preferably 10 or more. And the upper limit of the preferred range is 20.

  In addition, the content of the aliphatic polyvalent carboxylic acid in the acid component in the polyester resin is usually 2 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more, from the viewpoint of improving adhesion properties. More preferably, it is 10 mol% or more, and the upper limit of the preferable range is 50 mol%.

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

  In view of the suitability for in-line coating, it is preferable to use an aqueous system, and it is therefore preferable to contain a hydrophilic functional group, sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylic acid salt, in the polyester resin. In particular, sulfonic acids and sulfonates are preferable, and in particular, sulfonates are preferable, in that the dispersibility in water is good. Among the sulfonates, metal sulfonates are more preferred.

  When the above sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylic acid salt is used, the content in the acid component in the polyester resin is usually 0.1 to 10 mol%, preferably 0.2 to 8 mol% Range. By using in the said range, the dispersibility to water becomes favorable.

  As an acid component in the polyester resin, considering the appearance of coating in in-line coating, adhesion and blocking to a film, and reduction of migration (adhesion residue) to an adherend when used as a surface protective film, It is preferable to contain a certain amount of aromatic polyvalent carboxylic acid. The proportion of the aromatic polyvalent carboxylic acid as the proportion in the acid component in the polyester resin is usually 30 mol% or more, preferably 50 mol% or more, more preferably 60 mol% or more, and the upper limit of the preferable range is 98 It is mol%. Among aromatic polyvalent carboxylic acids, benzene ring structures such as terephthalic acid and isophthalic acid are more preferable than naphthalene ring structures from the viewpoint of adhesive properties. Furthermore, in order to further improve the adhesive property, 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 essentially 0 ° C. or less, preferably −10 ° C. or less, more preferably −20 ° C. or less, and the lower limit of the preferred range is − 60 ° C. By using in the said range, it becomes easy to set it as the film which has an optimal adhesion characteristic.

  An acrylic resin is a polymer which consists of a polymerizable monomer containing an acrylic type and a methacrylic type monomer (Hereafter, acrylic and a methacryl may be put together and it may be abbreviated as (meth) acrylic). These may be homopolymers or copolymers, and further copolymers with polymerizable monomers other than acrylic and methacrylic monomers.

  Also included are copolymers of these polymers with other polymers such as polyesters, polyurethanes and the like. For example, a block copolymer and a graft copolymer. Alternatively, it also includes a polyester solution, or a polymer obtained by polymerizing a polymerizable monomer in a polyester dispersion (in some cases, a mixture of polymers). Also included are polyurethane solutions, polymers obtained by polymerizing polymerizable monomers in polyurethane dispersions (in some cases mixtures of polymers). Similarly, other polymer solutions, or polymers obtained by polymerizing polymerizable monomers in dispersion (in some cases, polymer mixtures) are also included. However, in view of adhesive properties and adhesion residue to adherends, it does not contain other polymers such as polyester and polyurethane (polymerizable monomers containing carbon-carbon double bond (both homopolymer and copolymer) (Meth) acrylic resin composed only of (a) is preferable.

  The polymerizable monomer is not particularly limited, but as typical compounds, various carboxyl group-containing compounds such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and citraconic acid are exemplified. 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 kinds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate (Meta) Acry Acid esters; various nitrogen-containing compounds such as (meth) acrylamide, diacetone acrylamide, N-methylol acrylamide 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 and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; And vinyl, various halogenated vinyls such as pyridene chloride; various conjugated dienes such as butadiene.

  In order to lower the glass transition temperature to 0 ° C. or less, it is necessary to use (meth) acrylics having a glass transition temperature of the homopolymer of 0 ° C. or less, for example, ethyl acrylate (glass transition temperature: −22 ° C.), n-propyl acrylate (glass transition temperature: -37 ° C), isopropyl acrylate (glass transition temperature: -5 ° C), normal butyl acrylate (glass transition temperature: -55 ° C), normal hexyl acrylate (glass transition temperature: -57) ° C), 2-ethylhexyl acrylate (glass transition: -70 ° C), normal octyl acrylate (glass transition: -65 ° C), isooctyl acrylate (glass transition: -83 ° C), normal nonyl acrylate (glass) Transition point: -63 ° C), normal nonyl methacrylate (glass transition point: -35 ° C), isono Acrylate (glass transition: -82 ° C), normal decyl acrylate (glass transition: -70 ° C), normal decyl methacrylate (glass transition: -45 ° C), isodecyl acrylate (glass transition: -55 ° C) , Isodecyl methacrylate (glass transition temperature: -41 ° C), lauryl acrylate (glass transition temperature: -30 ° C), lauryl methacrylate (glass transition temperature: -65 ° C), tridecyl acrylate (glass transition temperature: -75 ° C) And tridecyl methacrylate (glass transition temperature: −46 ° C.), isomystyryl acrylate (glass transition temperature: −56 ° C.), 2-hydroxyethyl acrylate (glass transition temperature: −15 ° C.) and the like.

  Among the above, the carbon number of the alkyl group is usually 4 or more, preferably 4 to 30, more preferably 4 to 20, and still more preferably 4 to 14 to improve the adhesion property The alkyl (meth) acrylate which is The (meth) acrylic resin which is mass-produced industrially and contains normal butyl acrylate and 2-ethylhexyl acrylate is optimal from the viewpoint of handleability and supply stability.

  The content of the (meth) acrylate unit having an alkyl group having 4 or more carbon atoms at the ester end in the (meth) acrylic resin is usually 20% by weight or more, preferably 35 to 99% by weight, more preferably 50 to 98 %, More preferably 65 to 95%, particularly preferably 75 to 90% by weight. The larger the content of the (meth) acrylate unit having an alkyl group having 4 or more carbon atoms at the ester end, the stronger the adhesion properties. On the contrary, when the content is too small, the adhesive strength may not be sufficient.

  In the above (meth) acrylic resin, the content of the (meth) acrylate unit having a homopolymer having a glass transition point of 0 ° C. or less and an alkyl group having a carbon number of less than 4 at the ester end is usually 50% by weight or less Preferably it is 40 weight% or less, More preferably, it is 30 weight% or less range. By using in the said range, it becomes a favorable adhesion characteristic.

Further, from the viewpoint of reducing the migration of the adhesive component to the adherend, among the above, a compound having 2 or less carbon atoms at the ester end is preferable, or a compound having a cyclic structure is more preferable. Is a compound having one carbon or an aromatic compound.
Specific examples thereof include methyl methacrylate, acrylonitrile, styrene and cyclohexyl acrylate as preferable compounds.

  The content of the compound unit having 2 or less carbon atoms at the ester end in the (meth) acrylic resin is usually 50% by weight or less, preferably 1 to 40% by weight, more preferably 3 to 30% %, More preferably 5 to 20% by weight. If the content of the unit is small, it is possible to impart an appropriate range of adhesion characteristics without significantly lowering the adhesion characteristics, and conversely, if the content is large, it is to the adherend. It is possible to reduce the migration of the adhesive component. Therefore, if it is the said range, it will become easy to achieve two objectives, an adhesion characteristic and a transition reduction.

  The content of the compound unit having a cyclic structure in the (meth) acrylic resin is usually 50% by weight or less, preferably 1 to 45% by weight, and more preferably 5 to 40% by weight. If the content of the unit is small, it is possible to impart an appropriate range of adhesion characteristics without significantly lowering the adhesion characteristics, and conversely, if the content is large, it is to the adherend. It is possible to reduce the migration of the adhesive component. Therefore, if it is the said range, it will become easy to achieve two objectives, an adhesion characteristic and a transition reduction.

  From the viewpoint of adhesive properties, the content of a monomer having a glass transition point of 0 ° C. or less of a homopolymer as a monomer constituting the (meth) acrylic resin is usually 30% by weight or more as a ratio to the entire (meth) acrylic resin Preferably it is 45 weight% or more, More preferably, it is 60 weight% or more, More preferably, it is 70 weight% or more range. The upper limit of the preferred range is 99% by weight. Favorable adhesion characteristics are easy to be obtained by using in the said range.

  Moreover, as a glass transition point of the monomer which improves the adhesive property and whose glass transition point of the homopolymer is 0 ° C. or less, it is usually −20 ° C. or less, preferably −30 ° C. or less, more preferably −40 ° C. or less Preferably it is -50 degrees C or less, and the minimum of a preferable range is -100 degrees C. By using it in the said range, it becomes easy to set it as the film which has a suitable adhesion characteristic.

  Further, as the form of (meth) acrylic resin for further improving the adhesive property, the total content of normal butyl acrylate and 2-ethylhexyl acrylate in the (meth) acrylic resin is usually 30% by weight or more, The content is preferably 40% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, particularly preferably 70% by weight or more, and the upper limit of the preferable range is 99% by weight. Although it depends on the composition of the (meth) acrylic resin to be used and the composition of the adhesive layer, 2-ethylhexyl is particularly desirable in order to eliminate the migration of the adhesive component to the adherend with a small amount of crosslinking agent. The content of acrylate is usually in the range of 90% by weight or less, preferably 80% by weight or less.

  Moreover, in consideration of application to in-line coating etc., it is also possible to introduce various hydrophilic functional groups in order to obtain a (meth) acrylic resin which can be used as a water system. Preferred examples of the hydrophilic functional group include a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid group and a hydroxyl group. Among these, a carboxylic acid group, a carboxylic acid group and a hydroxyl group are preferable from the viewpoint of water resistance.

  As the introduction of carboxylic acid, copolymerization of various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and citraconic acid can be mentioned. Among the above, acrylic acid and methacrylic acid are preferable because they can be effectively dispersed in water.

  As the introduction of a hydroxyl group, various kinds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate, etc. Copolymerizing a hydroxyl group containing monomer is mentioned. Among the above, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable in consideration of industrial ease of handling.

  In addition, it is possible to include a copolymer of an amino group-containing monomer such as dimethylaminoethyl (meth) acrylate or a copolymer of an epoxy group-containing monomer such as glycidyl (meth) acrylate as a crosslinking reaction group. is there. However, if the content is too high, the adhesive properties will be affected, and therefore the amount should be appropriate.

  The proportion of the hydrophilic functional group-containing monomer in the (meth) acrylic resin is usually in the range of 30% by weight or less, preferably 1 to 20% by weight, more preferably 2 to 15% by weight, still more preferably 3 to 10% by weight It is. By using in the said range, aqueous system development becomes easy.

  The glass transition point of the (meth) acrylic resin for improving the adhesive property is essentially 0 ° C. or less, preferably −10 ° C. or less, more preferably −20 ° C. or less, further preferably It is a range of -30 ° C or less, and the lower limit of the preferred range is -80 ° C. By using in the said range, it becomes easy to set it as the film which has an optimal adhesion characteristic. Moreover, when it is necessary to consider the reduction of migration of the adhesive component to the adherend, it is preferably in the range of -70 ° C or more, more preferably -60 ° C or more, and still more preferably -50 ° C or more.

  The urethane resin is a polymer compound having a urethane bond in the molecule, and is usually prepared by the reaction of 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 of two or more.

  Polycarbonate polyols are obtained from polyhydric alcohols and carbonate compounds by a dealcoholization reaction. As polyhydric alcohols, 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-dimethylolheptane and the like can be mentioned. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like. Polycarbonate polyols obtained from these reactions include, for example, poly (1,6-hexylene) carbonate, poly (3- (3) Methyl-1,5-pentylene) carbonate and the like can be mentioned.

  From the viewpoint of improving adhesion properties, it is a polycarbonate polyol composed of a diol component in which the carbon number of the linear alkyl chain is usually in the range of 4 to 30, preferably 4 to 20, more preferably 6 to 12, Of 1,6-hexanediol, or 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol from the viewpoint of good handling and supply stability. The copolycarbonate polyol containing at least two selected diols is optimum.

  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 adhesion properties, monomers forming polyethers are aliphatic diols having a carbon number of usually 2 to 30, preferably 3 to 20, more preferably 4 to 12, and particularly linear aliphatic diols. Is a polyether polyol containing

  As polyester polyols, polyvalent carboxylic 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 And polyhydric alcohols (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 Those obtained from the reaction of a diol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyl dialkanolamines, lactone diols, etc.), those having a derivative unit of a lactone compound such as polycaprolactone, etc. may be mentioned.

  Among the above-mentioned polyols, polycarbonate polyols and polyether polyols are more preferably used in consideration of the adhesive property, and polycarbonate polyols are particularly preferable.

  As polyisocyanate compounds used to obtain urethane resins, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, α, α, α ′, α ′ Aliphatic diisocyanates having an aromatic ring such as tetramethyl xylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Methane diy Cyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination of two or more.

  When synthesizing a urethane resin, a chain extender may be used, and as the chain extender, there is no particular limitation as long as it has two or more active groups that react with isocyanate groups, generally, hydroxyl groups Alternatively, a chain extender having two amino groups can be mainly used.

  Examples of chain extenders 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 Glycols such as glycol can be mentioned. Moreover, as a chain extender having two amino groups, for example, aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, etc., 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 decanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 3-Bisaminomethylcyclohexa And alicyclic diamines, and the like.

  The urethane resin 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 emulsifying type using an emulsifying agent, a self-emulsifying type or a water-soluble type using a hydrophilic group in the urethane resin, and the like. In particular, a self-emulsification type in which ion groups are introduced into the structure of the urethane resin to make it ionomerized is preferable because it is excellent in the storage stability of the liquid and the water resistance and transparency of the obtained adhesive layer.

  Moreover, as an ionic group to introduce | transduce, although various things, such as a carboxyl group, a sulfonic acid, phosphoric acid, a phosphonic acid, a quaternary ammonium salt, are mentioned, a carboxyl group is preferable. As a method of introducing a carboxyl group into the urethane resin, various methods can be taken in each step of the polymerization reaction. For example, there is a method of using a resin having a carboxyl group as a copolymerization component, or a method of using a component having a carboxyl group as one component such as a polyol, a polyisocyanate, or a chain extender at the time of prepolymer synthesis. In particular, it is preferable to use a carboxyl group-containing diol and introduce a desired amount of carboxyl group depending on the amount of this component charged.

For example, copolymerizing dimethylol propionic acid, dimethylol butanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid, etc. with a diol used for polymerization of urethane resin Can. The carboxyl group is preferably in the form of a salt neutralized with ammonia, an amine, an alkali metal, an inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
Such a urethane resin can use the carboxyl group from which the neutralizing agent was removed in the drying process after application as a crosslinking reaction point by another crosslinking agent. This makes it possible to further improve the durability, solvent resistance, water resistance, blocking resistance and the like of the adhesive layer obtained, as well as having excellent stability in the liquid state before coating.

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

  The above-mentioned resin having a glass transition temperature of 0 ° C. or less may use only one type, or two or more types may be used in combination. As a preferable form in the case of using 2 or more types together, a polyester resin and a urethane resin, a polyester resin and an acrylic resin, and a urethane resin and an acrylic resin are mentioned.

  The colorant is not particularly limited as long as it is a compound having coloring properties such as a pigment, a dye, a pigment and the like. For example, although the compounds described in the Color Index are mainly mentioned, it is also possible to use, for example, azo dyes and various dyes which are not described in the Color Index. Pigments and dyes are preferred because they have good weather resistance, and pigments are particularly preferred.

  Furthermore, in view of weather resistance, blue colorants, purple colorants and green colorants are preferable, and in terms of high discrimination, purple colorants and green colorants are preferable. The absorption wavelength is a colorant having a maximum absorption wavelength (a wavelength at which absorption is most visible in the visible light range) is 500 to 740 nm, preferably 550 to 700 nm, and more preferably 570 to 650 nm.

  Specific examples of blue colorants include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 28, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 61, C.I. I. Pigment Blue 80, a pigment such as Brilliant Blue, C.I. I. Acid Blue 3, C.I. I. Acid Blue 9, C.I. I. Acid Blue 80, C.I. I. Acid Blue 93, C.I. I. Acid Blue 182, C.I. I. Solvent Blue 35, C.I. I. And dyes such as Solvent Blue 45.

  Specific examples of purple colorants include C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 32 or a pigment such as C.I. I. Acid Violet 48, C.I. I. Acid Violet 66, C.I. I. Acid Violet 126, C.I. I. Solvent C. I. Violet 13, C.I. I. And dyes such as Solvent Violet 36.

  Specific examples of the green colorant include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 50, C.I. I. Pigment Green 58, Basic Green 1, C.I. I. Acid Green 3, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Acid Green 26, C.I. I. Acid Green 27, C.I. I. Acid Green 50, C.I. I. And dyes such as Acid Green 108.

  In addition, only one type of these coloring agents may be used, and it is also possible to use many types together.

  Moreover, it is also preferable to use a crosslinking agent in combination from the viewpoint of the strength of the adhesive layer. Although the adhesive layer using a resin having a glass transition point of 0 ° C. or lower was mainly examined, it has been found that the adhesive component is transferred to the adherend under severe conditions. Then, as a result of conducting various examinations, it also discovered that it was a direction which can improve transfer to the adherend of an adhesion layer by using a crosslinking agent together.

  As the crosslinking agent, conventionally known materials can be used, and examples thereof include melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, aziridine compounds and the like. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferable, and further, from the viewpoint of being able to appropriately maintain adhesion and being easy to adjust, melamine compounds, isocyanate compounds A compound and an epoxy compound are more preferable, and in particular, an isocyanate compound and an epoxy compound are preferable because the decrease in adhesion due to the combined use can be suppressed. In particular, from the viewpoint of reducing migration to the adherend, melamine compounds and isocyanate compounds are preferable, and among these, melamine compounds are particularly preferable. Further, from the viewpoint of the strength of the adhesive layer, melamine compounds are particularly preferred. In addition, one type of these crosslinking agents may be used, or two or more types may be used in combination.

  In addition, depending on the configuration of the pressure-sensitive adhesive layer and the type of the crosslinking agent, if the content of the crosslinking agent in the pressure-sensitive adhesive layer is too large, the pressure-sensitive adhesive properties may be excessively lowered. Therefore, it is preferable to pay attention to the content in the adhesive layer.

  The melamine compound is a compound having a melamine skeleton in the compound and, for example, an alkylolated melamine derivative, a compound obtained by reacting an alcohol with an alkylolated melamine derivative to partially or completely etherify, and a compound thereof Mixtures can be used. As alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol etc. are used suitably. Moreover, as a melamine compound, any of a monomer or the multimer more than a dimer may be sufficient, or you may use these mixtures. Considering the reactivity with various compounds, it is preferable that the melamine compound contains a hydroxyl group. Furthermore, a product obtained by co-condensing urea or the like with part of melamine can also be used, and a catalyst can also be used to increase the reactivity of the melamine compound.

  An isocyanate type compound is a compound which has an isocyanate derivative structure represented by isocyanate or block isocyanate. As an isocyanate, for example, aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and aromatic rings such as α, α, α ′, α′-tetramethyl xylylene diisocyanate Aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, aliphatic isocyanate such as hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyldiisocyanate Ne Alicyclic isocyanates such as bets are exemplified. In addition, polymers and derivatives such as burettes, isocyanurates, uretdiones and carbodiimide-modified products of these isocyanates can also be mentioned. These may be used alone or in combination of two or more. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet light.

  When used in the form of blocked isocyanate, examples of the blocking agent include bisulfite, phenol, phenolic compounds such as cresol and ethylphenol, propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, alcohol such as methanol and ethanol Active methyl methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, ε-caprolactam, δ-valerolactam, etc. Lactam compounds, amine compounds such as diphenylaniline, aniline and ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, Oxime compounds such as mualdehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime and the like may be mentioned, and these may be used alone or in combination of two or more. Among the above, from the viewpoint of being particularly effective in reducing the migration of the adhesive layer to the adherend, an isocyanate compound blocked by an active methylene compound is preferable.

  In addition, the isocyanate compound may be used alone, or may be used as a mixture or a bond with various polymers. In order to improve the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a binder with a polyester resin or a urethane resin.

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

  Among these, polyether-based epoxy compounds are preferable from the viewpoint of good adhesion properties. Moreover, as an amount of an epoxy group, a polyepoxy compound which is a trifunctional or higher polyfunctional than a bifunctional one is preferable.

  The oxazoline compound is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and it 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, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like, and a mixture of one or more of these can be used. Among these, 2-isopropenyl-2-oxazoline is industrially easily available and suitable. The other monomer is not particularly limited as long as it is a monomer copolymerizable with the addition polymerizable oxazoline group-containing monomer. For example, alkyl (meth) acrylate (as alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, (Meth) acrylic esters such as n-butyl, isobutyl, t-butyl, 2-ethylhexyl and cyclohexyl); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salt (sodium salt, potassium salt, ammonium salt, tertiary amine salt etc.) unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl ( Meta) 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, cyclohexyl group etc .; 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 oxazoline group of the oxazoline compound is usually in the range of 0.5 to 10 mmol / g, preferably 1 to 9 mmol / g, more preferably 3 to 8 mmol / g, and still more preferably 4 to 6 mmol / g. By using in the said range, durability improves and it becomes easy to adjust the adhesion characteristic.

  A carbodiimide type compound is a compound which has a carbodiimide or one or more carbodiimide derivative structures in a molecule | numerator. The polycarbodiimide type compound which has 2 or more in a molecule | numerator is more preferable for the strength etc. of a more favorable adhesive layer.

  The carbodiimide type 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, hexadiisocyanate can be used. Methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and the like can be mentioned.

  Furthermore, in order to improve the water solubility and the water dispersibility of the polycarbodiimide compound within the range not to lose the effect of the present invention, adding a surfactant, or quaternary ammonium salt of polyalkylene oxide or dialkylamino alcohol And hydrophilic monomers such as hydroxyalkyl sulfonates may be used.

  The content of the carbodiimide group contained in the carbodiimide compound is usually 100 to 1000, preferably 250 to 800, more preferably 300 in terms of carbodiimide equivalent (weight [g] of the carbodiimide compound to give 1 mol of carbodiimide group). It is preferably in the range of -700, more preferably 350-650. Use within the above range is preferable because the strength of the adhesive layer is improved.

  The silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule. For example, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-) Epoxy-containing compounds such as epoxycyclohexyl) ethyltrimethoxysilane, vinyl-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, styryl-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane 3- (Meth) acryloxypropyltrimethoxysilane, 3- (Meth) acryloxypropyltriethoxysilane, 3- (Meth) acryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, etc. (Meth) acrylic group-containing compound, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N Amino group-containing compounds such as-(1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, tris (trimethoxysilylpropyl) Isocyanurate, tris (triethoxysilylpropyl) i Isocyanurate group-containing compounds such as cyanurate, mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, etc. Be

  Among the above compounds, an epoxy group-containing silane coupling compound, a double bond-containing silane coupling compound such as a vinyl group and a (meth) acrylic group, and an amino group-containing silane coupling from the viewpoint of retention of strength and adhesion of the adhesive layer. Compounds are more preferred.

  In addition, these crosslinking agents are used by the design which makes it react in a drying process or a film forming process, and improves the performance of the adhesion layer. It can be inferred that in the resulting adhesive layer, unreacted products of these crosslinking agents, compounds after reaction, or mixtures thereof (compounds derived from crosslinking agents) are present.

  In addition, the glass transition point is 0 ° C. from the viewpoints of the appearance of the adhesive layer, adjustment of adhesive strength, reinforcement of the adhesive layer, adhesion to the base film, blocking resistance, and prevention of migration of adhesive components to adherends. It is also possible to use a resin in excess of As the resin having a glass transition temperature exceeding 0 ° C., it is possible to use a conventionally known material. Among them, polyester resins, acrylic resins, urethane resins and polyvinyls (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.) are preferable, and polyester resins, acrylic resins and urethanes in consideration of the appearance and adhesion of the adhesive layer. Resins selected from resins are preferred. However, depending on the method of use, there is a concern that the adhesive strength may be greatly reduced, and caution is required.

  Resins with a glass transition temperature exceeding 0 ° C are used to adjust the appearance of the adhesive layer, adjust the adhesive strength, strengthen the adhesive layer, adhere to the substrate film, improve the blocking resistance, etc., depending on the method of use. It is necessary to be careful because there is a concern that adhesion will be greatly reduced.

  As a polyester resin as resin whose glass transition point exceeds 0 degreeC, the polyester resin containing an aromatic compound is preferable. Further, as the aromatic compound, an aromatic polyvalent carboxylic acid is preferable to an aromatic polyvalent hydroxy compound from the viewpoint of adjustment of adhesive strength and the like. The content of the aromatic polyvalent carboxylic acid is usually 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight, as a proportion of the acid component in the polyester resin. %, And it is preferable from the viewpoint of adhesion control, blocking resistance and the like that it does not contain an aliphatic polyvalent carboxylic acid, particularly an aliphatic polyvalent carboxylic acid having 6 or more carbon atoms.

  Various urethanes can be used as the urethane resin as a resin having a glass transition temperature exceeding 0 ° C. Among them, urethanes by polyester polyols from the viewpoints of adjustment of adhesive strength, slipperiness, and blocking resistance. Resin is more preferred. The polyester polyols preferably contain an aromatic compound, and an aromatic polyvalent carboxylic acid is more preferable than an aromatic polyvalent hydroxy compound from the viewpoint of adjustment of adhesive strength and the like. The content of the aromatic polyvalent carboxylic acid as a proportion in the urethane resin is usually 5 to 80% by weight, preferably 15 to 65% by weight, and more preferably 20 to 50% by weight. By using it in the said range, it becomes easy to adjust the adhesive force and to improve the performance of blocking resistance.

  The glass transition temperature of the resin having a glass transition temperature exceeding 0 ° C. is usually in the range of 10 ° C. or more, preferably 20 ° C. or more, more preferably 30 ° C. or more, and the upper limit of the preferable range is 150 ° C. By setting it as the said range, it can adjust without dropping adhesive force too much, and it becomes easy to improve performance, such as slipperiness and blocking resistance.

  In addition, for the formation of the adhesive layer, it is also possible to use particles in combination for the purpose of blocking and slipperiness improvement, and adjustment of adhesive properties. However, depending on the type of particles used, adhesion may be reduced, so care must be taken. In order not to reduce the adhesive strength so much, the average particle diameter of the particles to be used is preferably 3 times or less of the thickness of the adhesive layer, more preferably 1.5 times or less, still more preferably 1.0 times or less And particularly preferably in the range of 0.8 times or less. In particular, when it is desired to exhibit the adhesive performance of the resin of the adhesive layer as it is, it may be preferable not to contain particles in the adhesive layer.

  A functional layer may be provided on the surface of the film opposite to the pressure-sensitive adhesive layer in order to impart various functions. For example, it is preferable to provide a release layer in order to reduce blocking of the film by the adhesive layer, and to prevent defects due to adhesion of dust around the film due to peeling charging of the film or frictional charging, etc. Providing is also a preferred form. The functional layer may be provided by coating, may be provided by in-line coating, or may adopt off-line coating. In-line coating is preferably used from the viewpoint of stabilization such as manufacturing cost and mold release performance and antistatic performance by in-line heat treatment.

  For example, when a release functional layer is provided on the side opposite to the adhesive layer of the film, the release agent contained in the functional layer is not particularly limited, and it is possible to use conventionally known release agents. For example, long-chain alkyl group-containing compounds, fluorine compounds, silicone compounds, waxes and the like can be mentioned. Among them, long-chain alkyl compounds and fluorine compounds are preferable from the viewpoint of low contamination and excellent blocking reduction, and silicone compounds are particularly preferable when importance is given to reducing blocking. In addition, a wax is effective to improve the surface stain removability. These release agents may be used alone or in combination of two or more.

  The long chain alkyl group-containing compound is a compound having a linear or branched alkyl group having a carbon number of usually 6 or more, preferably 8 or more, more preferably 12 or more. 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, long-chain alkyl group-containing quaternary ammonium salts and the like. . In view of heat resistance and contamination, a polymer compound is preferable. In addition, from the viewpoint of obtaining mold releasability effectively, a polymer compound having a long chain alkyl group in a 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. As said reactive group, a hydroxyl group, an amino group, a carboxyl group, an acid anhydride etc. are mentioned, for example.
As a compound which has these reactive groups, polyvinyl alcohol, polyethylene imine, polyethylene amine, reactive group containing polyester resin, reactive group containing poly (meth) acrylic resin etc. are mentioned, for example. Among these, polyvinyl alcohol is preferable in consideration of releasability and handling.

  The compound having an alkyl group capable of reacting with the above-mentioned reactive group is, for example, a long chain alkyl group-containing isocyanate such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, behenyl isocyanate, hexyl chloride, octyl chloride And long-chain alkyl group-containing acid chlorides such as decyl chloride, lauryl chloride, octadecyl chloride and behenyl chloride, long-chain alkyl group-containing amines, long-chain alkyl group-containing alcohols and the like. Among these, long-chain alkyl group-containing isocyanates are preferable in consideration of releasability and handling ease, and octadecyl isocyanate is particularly preferable.

  In addition, a polymer compound having a long chain alkyl group as a side chain can also be obtained by polymerization of long chain alkyl (meth) acrylate or copolymerization of long chain alkyl (meth) acrylate with other vinyl group-containing monomer . Examples of long-chain alkyl (meth) acrylates include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, behenyl (meth) acrylate and the like. Be

  The fluorine compound is a compound containing a fluorine atom in the compound. Organic fluorine compounds are suitably used in view of coating appearance by in-line coating, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing a fluorine atom, and aromatic fluorine compounds such as fluorobenzene. . It is preferable that it is a compound which has a perfluoroalkyl group from a viewpoint of mold release property. Furthermore, as the fluorine compound, a compound containing a long chain alkyl compound as described later can also be used.

  The compound having a perfluoroalkyl group is, for example, perfluoroalkyl (meth) acrylate, perfluoroalkylmethyl (meth) acrylate, 2-perfluoroalkylethyl (meth) acrylate, 3-perfluoroalkylpropyl (meth) acrylate Perfluoroalkyl group-containing (meth) acrylates such as 3-perfluoroalkyl-1-methylpropyl (meth) acrylate and 3-perfluoroalkyl-2-propenyl (meth) acrylate or polymers thereof, perfluoroalkylmethyl vinyl ethers , 2-perfluoroalkylethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenylbi 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 alone or a polymer of a plurality of compounds. The perfluoroalkyl group preferably has 3 to 11 carbon atoms from the viewpoint of releasability. Furthermore, 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, methyl phenyl silicones and the like. As the silicone, those having various functional groups can be used, and examples thereof include ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various kinds. Examples thereof include hydrocarbon groups such as aromatic groups. As other functional groups, silicones having a vinyl group and hydrogen silicones in which a hydrogen atom is directly bonded to a silicon atom are also generally used, and both of them are used together to form addition type (type by addition reaction of vinyl group and hydrogen silane) It is also possible to use as.

  Moreover, it is also possible to use modified silicones, such as acrylic graft silicone, silicone graft acrylics, amino modified silicone, perfluoroalkyl modified silicone etc., as a silicone compound. In view of heat resistance and stain resistance, it is preferable to use a curable silicone resin, and as a curing type, any curing reaction type such as condensation type, addition type, active energy ray curing type can be used. Among these, a condensation type silicone compound is preferable from the viewpoint that there is little back surface transfer particularly when it is in the form of a roll.

  As a preferable form in the case of using a silicone compound, a polyether group-containing silicone compound is preferable from the viewpoint of low back surface transfer, good dispersibility in an aqueous solvent and high suitability for in-line coating. The polyether group may be present on the side chain or end of the silicone or on the main chain. From the viewpoint of dispersibility in an aqueous solvent, it is preferable to have at the side chain or at the end.

  The polyether group can use a conventionally known structure. From the viewpoint of the dispersibility of the aqueous solvent, an aliphatic polyether group is preferable to an aromatic polyether group, and among the aliphatic polyether groups, an alkyl polyether group is preferable. In addition, from the viewpoint of synthesis due to steric hindrance, linear alkyl polyether groups are preferable to branched alkyl polyether groups, and among these, polyether groups consisting of linear alkyl having 8 or less carbon atoms are preferable. Furthermore, when the solvent to be developed is water, in consideration of the dispersibility in water, polyethylene glycol group or polypropylene glycol group is preferable, and particularly optimum is polyethylene glycol group.

  The number of ether bonds of the polyether group is usually in the range of 1 to 30, preferably 2 to 20, and more preferably 3 to 3, from the viewpoint of improving the dispersibility in the aqueous solvent and the durability of the functional layer. The range is 15 pieces. When the number of ether bonds is small, the dispersibility is deteriorated, and when the number is too large, the durability and the mold release performance are deteriorated.

  When the polyether group is on the side chain or end of the silicone, the end of the polyether group is not particularly limited, and 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 sulfonic acid group, aldehyde group and acetal group can be used. Among them, in consideration of the dispersibility in water and the crosslinkability for improving the strength of the functional layer, a hydroxyl group, an amino group, a carboxylic acid group and a sulfonic acid group are preferable, and a hydroxyl group is particularly preferable.

  The polyether group content of the polyether group-containing silicone is usually in the range of 0.001 to 0.30%, preferably 0.01 to 0.20% in molar ratio, where the siloxane bond of the silicone is 1. Is more preferably in the range of 0.03 to 0.15%, and still more preferably in the range of 0.05 to 0.12%. By using in this range, the dispersibility to water, the durability of the functional layer, and the good releasability can be maintained.

  The molecular weight of the polyether group-containing silicone is preferably not so large in consideration of the dispersibility in the aqueous solvent, and is preferably large in consideration of the durability and the mold release performance of the functional layer. It is required to balance these two properties, and the number average molecular weight is usually in the range of 1000 to 100000, preferably in the range of 3000 to 30000, and more preferably in the range of 5000 to 10000.

  In addition, considering the time-dependent change and release performance of the functional layer and the contamination of various processes, it is preferable that the low molecular weight component of the silicone (500 or less in number average molecular weight) be as small as possible. The total proportion is usually 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less. When condensation type silicone is used, silicon-bonded vinyl groups (vinylsilanes) and hydrogen groups (hydrogensilanes) may cause various changes in performance over time if they remain unreacted in the functional layer, so silicones are used. The content of the amount of functional groups in the inside is preferably 0.1 mol% or less, and more preferably not contained.

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

  As an anionic dispersant, sodium dodecylbenzene sulfonate, sodium alkyl sulfonate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyalkylene alkenyl Sulfonates such as ammonium ether sulfate salts and sulfuric acid ester salts, carboxylates such as sodium laurate and potassium oleate, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphoric acid Examples include phosphates such as salts. Among these, sulfonates are preferred from the viewpoint of good dispersibility.

  As the nonionic dispersant, for example, an ether type obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a compound having a hydroxyl group such as a higher alcohol or alkylphenol, or a polyhydric alcohol such as glycerin or saccharide and an fatty acid ester bond An ester type, an ester / ether type obtained by adding an alkylene oxide to a fatty acid or polyhydric alcohol fatty acid ester, an amide type having a hydrophobic group and a hydrophilic group via an amide bond, and the like can be mentioned. Among them, the ether type is preferable in consideration of the solubility in water and the stability, and the type in which ethylene oxide is added is more preferable in consideration of the handleability.

  Although it depends on the molecular weight and structure of the polyether group-containing silicone used and on the type of the dispersant used, it can not be generally defined, but as a standard, the amount of the dispersant is polyether-containing silicone 1 As a weight ratio, it is usually in the range of 0.01 to 0.5, preferably 0.05 to 0.4, more preferably 0.1 to 0.3.

  The wax is a wax selected from natural waxes, synthetic waxes and waxes blended with them. Natural waxes are plant waxes, animal waxes, mineral waxes and petroleum waxes. Examples of vegetable waxes include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil and the like. As animal-based waxes, there are beeswax, lanolin, spermaceti and the like. Examples of mineral waxes include montan wax, ozokerite and ceresin. The petroleum wax includes paraffin wax, microcrystalline wax, petrolatum and the like. Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters, ketones and the like. Examples of synthetic hydrocarbons include Fischer-Tropsch wax (also known as Sazole wax), polyethylene wax, and low-molecular-weight polymers (specifically, polymers having a number-average molecular weight of 500 to 20,000). The following polymers may also be mentioned: polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, block or graft conjugate of polyethylene glycol and polypropylene glycol, 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 purification, oxidation, esterification, saponification, or a combination thereof. Hydrogenated waxes include hydrogenated castor oil and hydrogenated castor oil derivatives.

  Among them, synthetic waxes are preferred from the viewpoint of stabilizing the characteristics, among which polyethylene wax is more preferred, and oxidized polyethylene wax is even more preferred. The number average molecular weight of the synthetic wax is usually in the range of 500 to 30,000, preferably 1,000 to 15,000, and more preferably 2,000 to 8,000, from the viewpoint of stability of properties such as blocking and handleability.

  When the antistatic functional layer is provided on the side opposite to the adhesive layer of the film, the antistatic agent contained in the functional layer is not particularly limited, and it is possible to use conventionally known antistatic agents. From the viewpoint of good heat resistance and moisture and heat resistance, a polymer type antistatic agent is preferable. 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, a conductive polymer and the like.

  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 is not a counter ion but a structure incorporated into the main chain or side chain of the polymer. Is preferred. 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 may be used as a polymer compound having an ammonium group, and it is preferably used. As the polymer, a monomer containing a precursor of an ammonium group such as an addition polymerizable ammonium group or an amine may be polymerized alone, or a copolymer of a monomer containing these and another monomer is used. May be

  Among the compounds having an ammonium group, compounds having a pyrrolidinium ring are also preferable in that they have 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, and these alkyl groups and phenyl groups may be substituted by the groups shown below Good. The substitutable group is, for example, a hydroxyl group, an amido group, an ester group, an alkoxy group, a phenoxy group, a naphthoxy group, a thioalkoxy, a thiophenoxy group, a cycloalkyl group, a trialkylammonium alkyl group, a cyano group, a halogen. Also, the two substituents bonded to the nitrogen atom may be chemically bonded, for example,-(CH ₂ ) _m- (m is an integer of 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.

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

  Moreover, it is also preferable that it is a polymer which has a structure of following formula (1) at the point that it is excellent in antistatic property and moisture-heat-resistant stability. A single polymer or copolymer, and further, may be copolymerized with a plurality of other components.

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—, R ³ is Each of R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group. hydrocarbon group or a hydrocarbon group which functional groups are applied, such as hydroxyalkyl groups, etc., X ^- is a variety of counter ions.

Among the above, from the viewpoint of particularly excellent antistatic property and moisture and heat resistance stability, in the formula (1), the substituent R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ³ is preferably an alkyl group having 1 to 6 carbon atoms, and each of R ⁴ , R ⁵ , and R ⁶ is preferably independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably And any one of R ⁴ , R ⁵ and R ⁶ is a hydrogen atom, and the other substituent is an alkyl group having 1 to 4 carbon atoms.

  As an anion used as a counter ion (counter ion) of the ammonium group of the compound which has the ammonium group mentioned above, ions, such as a halogen ion, a sulfonate, a phosphate, nitrate, an alkyl sulfonate, a carboxylate, are mentioned, for example.

  The number average molecular weight of the compound having an ammonium group is usually 1,000 to 500,000, preferably 2,000 to 350,000, and more preferably 5,000 to 200,000. When the molecular weight is less than 1000, the strength of the coating may be weak or the heat stability may be poor. Moreover, when molecular weight exceeds 500000, the viscosity of a coating liquid may become high and a handleability or coating property may deteriorate.

  Examples of the polyether compound include polyethylene oxide, polyether ester amide, and an acrylic resin having polyethylene glycol in its side chain.

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

  Examples of the conductive polymer include polythiophenes, polyanilines, polypyrroles, polyacetylenes, etc. Among them, polythiophenes such as using poly (3,4-ethylenedioxythiophene) in combination with polystyrene sulfonic acid Is preferably used. Conducting polymers are preferred over the other antistatic agents described above in that they have lower resistance. However, on the other hand, in applications where coloration and cost are concerned, it is necessary to devise measures such as reducing the amount used.

  The functional layer which may be provided on the side opposite to the adhesive layer of the film contains both the above-mentioned release agent and antistatic agent, and it is also a preferable embodiment to have an antistatic release function.

  In forming the functional layer, various polymers such as polyester resin, acrylic resin, urethane resin and the like, and a crosslinking agent which can be used for forming the adhesive layer are used in combination for the improvement of coating appearance and transparency and control of slipperiness. It is also possible. In particular, from the viewpoint of strengthening the functional layer and reducing blocking, it is preferable to use a melamine compound, an oxazoline compound, an isocyanate compound, an epoxy compound and a carbodiimide compound in combination, and among these, a melamine compound is particularly preferable.

  In addition, these crosslinking agents are used by the design which is made to react in a drying process and a film forming process, and to improve the performance of a functional layer. It can be inferred that unreacted components of these crosslinking agents, compounds after reaction, or mixtures thereof (compounds derived from crosslinking agents) are present in the finished functional layer.

  To the extent that the gist of the present invention is not impaired, it is also possible to use particles in combination with the formation of the functional layer in order to improve blocking and slip. However, when the functional layer has mold release performance, it often has sufficient blocking resistance and slip resistance, so it may be preferable not to use particles in combination from the viewpoint of the appearance of the functional layer.

  Furthermore, in the range which does not impair the main point of the present invention, an antifoamer, a coatability improvement agent, a thickener, an organic system lubricant, an antistatic agent, an ultraviolet absorber as needed in formation of an adhesion layer and a functional layer. It is also possible to use an antioxidant, a foaming agent, etc. in combination.

The resin having a glass transition temperature of 0 ° C. or less is usually 5% by weight or more, preferably 10 to 99.3% by weight, more preferably 30 to 98% by weight, as a ratio in the adhesive layer constituting the laminated polyester film. More preferably, it is in the range of 45 to 96% by weight, particularly preferably 55 to 93% by weight, and most preferably 70 to 90% by weight. By using in the said range, sufficient adhesive force is easy to be obtained, and it is easy to adjust adhesive force. If the content is too small, the adhesive strength may be reduced, and a device such as increasing the thickness of the adhesive layer may be required.
However, in order to increase the film thickness, in some cases the productivity may be adversely affected, for example, by lowering the line speed.

  The coloring agent is not unique because it depends on the thickness of the adhesive layer as a proportion in the adhesive layer constituting the laminated polyester film, but it is usually 0.1 to 50% by weight, preferably 0.3 to 30% by weight More preferably, it is in the range of 0.5 to 20% by weight, still more preferably 1 to 15% by weight, and particularly preferably 1.5 to 10% by weight. When the content is too small, the coloring amount may be small and discrimination may be poor, and when the content is too large, the adhesive strength may be reduced.

  The proportion of the crosslinking agent in the pressure-sensitive adhesive layer constituting the laminated polyester film is usually 80% by weight or less, preferably 0.5 to 75% by weight, more preferably 1 to 65% by weight, still more preferably 3 to 50% by weight Particularly preferably, it is in the range of 5 to 40% by weight, and most preferably 8 to 25% by weight. By using in the said range, while improvement of the intensity | strength of an adhesive layer and transfer to the to-be-adhered body of an adhesive layer can be reduced, adjustment of adhesive force is also easy. If the content is too small, the transition to the adherend will increase, and if the content is too large, the adhesive strength may decrease, so it is necessary to take measures such as increasing the thickness of the adhesive layer. May be However, in order to increase the film thickness, in some cases the productivity may be adversely affected, for example, by lowering the line speed.

  The proportion of the particles in the adhesive layer constituting the laminated polyester film is usually 80% by weight or less, preferably 70% by weight or less, more preferably 0.1 to 50% by weight, and still more preferably 0.5 to 30% by weight And particularly preferably in the range of 1 to 20% by weight. By using in the said range, sufficient adhesion characteristic, blocking resistance property, and slipperiness are easy to be obtained.

  As a ratio in the adhesive layer constituting the laminated polyester film, the resin having a glass transition point exceeding 0 ° C. is usually 80% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less. By using in the said range, the external appearance of an adhesion layer, adjustment of adhesive force, reinforcement of an adhesion layer, adhesiveness with a base film, and the improvement of blocking resistance can be anticipated. If the content is too large, the adhesive strength may be reduced, and it may be necessary to make a film thickness of the adhesive layer thicker.

  When a functional layer having mold release performance is provided on the side opposite to the adhesive layer in the laminated polyester film, the ratio of the mold release agent as the proportion in the functional layer varies depending on the type of the mold release agent, so Although it can not be said, it is usually in the range of 3% by weight or more, preferably 15% by weight or more, and more preferably in the range of 25 to 99% by weight. If it is less than 3% by weight, blocking may not be sufficiently reduced.

  When a long chain alkyl compound or a fluorine compound is used as a mold release agent, the proportion in the functional layer is usually 5% by weight or more, preferably 15 to 99% by weight, more preferably 20 to 95% by weight, still more preferably It is in the range of 25 to 90% by weight. By using in the said range, blocking reduction becomes an effective thing. The proportion of the crosslinking agent is usually 95% by weight or less, preferably 1 to 80% by weight, more preferably 5 to 70% by weight, and still more preferably 10 to 50% by weight. Of these, isocyanate compounds (in particular, blocked isocyanates blocked with active methylene compounds are preferable), and in particular, melamine compounds are preferable from the viewpoint of reducing blocking.

  When a condensation type silicone compound is used as a release agent, the proportion in the functional layer is usually 3% by weight or more, preferably 5 to 97% by weight, more preferably 8 to 95% by weight, and still more preferably 10 to 10%. It is in the range of 90% by weight. By using in the said range, blocking reduction becomes an effective thing. The proportion of the crosslinking agent is usually 97 wt% or less, preferably 3 to 95 wt%, more preferably 5 to 92 wt%, and still more preferably 10 to 90 wt%. Moreover, as a crosslinking agent, a melamine compound is preferable from a viewpoint of blocking reduction.

  When an addition type silicone compound is used as a release agent, the proportion in the functional layer is usually 5% by weight or more, preferably 25% by weight or more, more preferably 50% by weight or more, and still more preferably 70% by weight or more Range. The upper limit of the preferred range is 99% by weight, and the more preferred upper limit is 90% by weight. By using in the said range, blocking reduction becomes an effective thing, and the external appearance of a functional layer also becomes favorable.

  When a wax is used as a mold release agent, the proportion in the functional layer is usually 10% by weight or more, preferably 20 to 90% by weight, more preferably 25 to 70% by weight. By using it in the above-mentioned range, it becomes easy to do blocking reduction. However, in the case where a wax is used for the purpose of removing surface stains, the above ratio can be reduced, usually 1% by weight or more, preferably 2 to 50% by weight, more preferably 3 to 30% by weight It is a range. The proportion of the crosslinking agent is usually 90% by weight or less, preferably 10 to 70% by weight, more preferably 20 to 50% by weight. Moreover, as a crosslinking agent, a melamine compound is preferable from a viewpoint of blocking reduction.

  On the other hand, when a functional layer having antistatic properties is provided on the side opposite to the adhesive layer, the proportion of the antistatic agent as a proportion in the functional layer can not be generally determined because the amount varies depending on the type of antistatic agent. However, it is usually in the range of 0.5% by weight or more, preferably in the range of 3 to 90% by weight, more preferably in the range of 5 to 70% by weight, and still more preferably in the range of 8 to 60% by weight. If the amount is less than 0.5% by weight, the antistatic effect may not be sufficient, and the effect of preventing adhesion of 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 in the range of 25 to 60% by weight. If it is less than 5% by weight, the antistatic effect may not be sufficient, and the effect of preventing adhesion of 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 8%. It is in the range of 30% by weight. If the amount is less than 0.5% by weight, the antistatic effect may not be sufficient, and the effect of preventing adhesion of dust and the like may not be sufficient.

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

  With respect to the formation of the adhesive layer and the functional layer, a solution or solution dispersion of the above-mentioned series of compounds and a solution having a solid content concentration adjusted to about 0.1 to 80% by weight is coated on a film It is preferred to produce a laminated polyester film. In particular, in the case of providing by in-line coating, an aqueous solution or aqueous dispersion is more preferable. The coating solution may contain a small amount of an organic solvent for the purpose of improving the dispersibility in water, the film forming property, and the like. The organic solvent may be used alone or in combination of two or more.

  Although the thickness of the adhesive layer depends on the material used for the adhesive layer, it can not be generally defined, but for the purpose of more suitably adjusting the adhesive strength or improving the appearance of the adhesive layer, etc. The thickness is 10 μm or less, preferably 1 nm to 4 μm, more preferably 10 nm to 1 μm, still more preferably 20 to 700 nm, and particularly preferably 30 to 400 nm.

  A typical adhesive layer has a thick film thickness of several tens of μm. In such a case, for example, when used for manufacturing a polarizing plate, the adhesive film is a polarizing plate, a retardation plate, a viewing angle widening plate, etc. When pasting with the adherend of this invention, or when carrying out a shaping | molding process or cutting etc., the protrusion of the adhesive in an adhesive layer may generate | occur | produce notably.

  However, by adjusting the film thickness to the above-mentioned range, the protrusion can be minimized. This effect is better as the thickness of the adhesive layer is smaller. In addition, as the thickness of the adhesive layer is thinner, the absolute amount of the adhesive layer present on the film may be smaller, which is also effective in reducing adhesive residue in which the components of the adhesive layer migrate to the adherend. Furthermore, it is also understood that by setting the film thickness in the above-mentioned range, it is possible to achieve not only too strong adhesive strength but, for example, coexistence of adhesive performance and peeling performance to be peeled off after laminating. When it is used in an application that needs to be achieved, the operation of adhesion-peeling can be easily performed, and an optimum film can be obtained.

  The thinner the film thickness is, the more effective it is for blocking properties, and it is easy to manufacture when the adhesive layer is formed by in-line coating, but it is preferable if the film thickness is too thin. Since it may disappear, the use in the above-mentioned preferred range is preferred according to a use.

  The film thickness of the functional layer is not unique because it depends on the function to be provided. For example, as a functional layer for imparting mold release performance and antistatic performance, it is usually 1 nm to 3 μm, preferably 10 nm to 1 μm, The range is more preferably 20 to 500 nm, still more preferably 20 to 200 nm. By using the film thickness of the functional layer in the above-mentioned range, it becomes easy to improve the blocking property, to improve the antistatic performance, and to have a good appearance.

  The adhesive layer and the functional layer can be formed, for example, by gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation Conventionally known coating methods such as coat, kiss coat, spray coat, calender coat, and extrusion coat can be used.

  The drying and curing conditions for forming the adhesive layer on the film are not particularly limited, but in the case of the method by coating, it is usually 70 to about drying of the solvent such as water used in the coating liquid. The temperature is 150 ° C., preferably 80 to 130 ° C., more preferably 90 to 120 ° C. The drying time is, as a standard, 3 to 200 seconds, preferably 5 to 120 seconds. Moreover, in order to improve the strength of the adhesive layer, in the film manufacturing process, a heat treatment process in the range of usually 180 to 270 ° C., preferably 200 to 250 ° C., more preferably 210 to 240 ° C. is performed. The time of the heat treatment step is, as a standard, in the range of 3 to 200 seconds, preferably 5 to 120 seconds.

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

  The adhesion of the adhesive layer to the polymethyl methacrylate plate is usually 1 to 5000 mN / cm, preferably 3 to 1000 mN / cm, more preferably 5 to 500 mN / cm, as measured by the measurement method described later. More preferably, it is in the range of 7 to 300 mN / cm, particularly preferably 10 to 100 mN / cm. By setting it as the said range, coexistence of adhesion performance and the peeling performance to peel after bonding can be aimed at, and it becomes possible to set it as the optimal laminated body for various processes which perform operation of adhesion-peeling. . In addition, the blocking property of the film can be easily improved.

  The arithmetic mean roughness (Sa) of the adhesive layer surface is usually 50 nm or less, preferably 30 nm or less, more preferably 20 nm or less, still more preferably 15 nm or less, particularly preferably 10 nm or less. When Sa is too high, sufficient adhesion may not be exhibited. In addition, when Sa is too high, it may be necessary to adjust the film thickness of the adhesive layer to be thick in order to express the adhesive force, and adjustment of the adhesive force and reduction of migration of the adhesive component to the adherend are It can be difficult. The lower limit is not particularly limited, but the lower limit of the preferable range is 1 nm.

  The Sa on the surface of the adhesive layer can be adjusted by the design of the adhesive layer or the design of the polyester film layer on the side in contact with the adhesive layer. If Sa is to be adjusted by the design of the adhesive layer, it is necessary to increase the thickness of the adhesive layer, which raises the hurdle of the adhesive design, so it is preferable to cope with the design of the polyester film layer.

  As the design of the polyester film layer on the adhesive layer side, mainly, the average particle diameter of the contained particles, the content of the particles, and the thickness of the polyester film layer are mentioned as factors affecting Sa. Since the value of Sa is mainly determined by the correlation of these factors, it is not possible to determine the value of Sa considering only one factor, but as a standard for adjustment, the average particle size of the particles is usually 5 μm or less, preferably Is in the range of 3.5 μm or less. It becomes easy to make Sa low by using in the said range.

  The amount of particles contained in the polyester film layer on the adhesive layer side is usually less than 0.30% by weight, preferably 0.15% by weight or less, more preferably 0.10% by weight or less, still more preferably 0.08% by weight It is the following range. It becomes easy to make Sa low by using in the said range.

  The layer thickness of the polyester film layer on the adhesive layer side is usually in the range of 0.5 to 10 μm, preferably 1 to 8 μm, and more preferably 2 to 6 μm. By using in the said range, adjustment of content of particle | grains becomes easy, and adjustment of Sa also becomes easy.

  As mentioned above, Sa on the surface of the adhesive layer depends on the design of the adhesive layer, so it can not be said in general, but Sa on the polyester surface from which the adhesive layer has been removed (polyester surface without forming the adhesive layer) is usually 50 nm The thickness is preferably 30 nm or less, more preferably 20 nm or less, still more preferably 15 nm or less, and particularly preferably 10 nm or less. By using in the said range, it becomes easier to adjust Sa of the adhesive layer surface.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The measurement method and evaluation method used in the present invention are as follows.

(1) Method of measuring the intrinsic viscosity of polyester Weigh precisely 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed, and add 100 ml of mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) Dissolved and measured at 30.degree.

(2) Measuring method of average particle diameter (d50: μm) Centrifugation type particle size distribution measuring device manufactured by Shimadzu Corporation, value of integration (weight basis) 50% in equivalent spherical distribution measured using SA-CP type 3 As the average particle size.

(3) Measurement Method of Arithmetic Average Roughness (Sa) A CCD camera: SONY HR- using a non-contact surface / layer cross-sectional shape measurement system VertScan (registered trademark) R550GML manufactured by Ryoka Systems Co., Ltd. 50 1/3 ′, objective lens: 20 ×, lens barrel: 1 × Body, zoom lens: No Relay, wavelength filter: 530 white, measurement mode: measured with Wave, and the output by fourth-order polynomial correction was used.

(4) Method of Measuring Film Thickness of Adhesive Layer and Functional Layer The surface of the adhesive layer or the functional layer was stained with RuO ₄ and embedded in an epoxy resin. Thereafter, the sections prepared by the ultra-thin section method were stained with RuO ₄ , and the cross section of the adhesive layer was measured using TEM (H-7650 manufactured by Hitachi High-Technologies Corporation, acceleration voltage 100 kV).

(5) Measuring method of the maximum absorption wavelength The most intense in the wavelength range of 400 to 740 nm when measured by the reflection method using a spectrocolorimeter (CM-3700d D65 light source manufactured by Konica Minolta Sensing Co., Ltd.) The wavelength of the low point (the point where absorption was most observed) was measured.

(6) Glass transition point It measured on the temperature rising conditions of 10 degrees C / min at -100-200 degreeC using the differential scanning calorimeter (DSC) 8500 made from Perkin-Elmer Japan, Inc. product.

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

(8-1) Adhesive force evaluation method (adhesive force 1)
On the surface of a polymethyl methacrylate plate (Kuraray Co., Ltd., Comoglass (registered trademark), 1 mm thick), the adhesive layer side of the 5 cm wide laminated polyester film of the present invention is crimped once for 1 reciprocation with a 5 cm wide 2 kg rubber roller. The peeling force after leaving for 1 hour was measured. Peeling force performed 180 degrees peeling on the conditions of 300 mm / min of tensile speeds using "Ezgraph" by Shimadzu Corp. make.

(8-2) Adhesive force evaluation method (adhesive force 2)
(8-1) except that in place of the polymethyl methacrylate plate of (8-1), the adhesion is evaluated using the polyester film surface (thickness 25 μm) without the adhesive layer obtained in Comparative Example 1 described later. Evaluation was performed in the same manner as in.

(9) Measuring method of blocking property Two polyester films to be measured are prepared, and the adhesive layer side and the opposite side to the adhesive layer (the functional layer side when there is a functional layer) are overlapped, and the area of 12 cm × 10 cm Were pressed under the conditions of 40 ° C., 80% RH, 10 kg / cm ² for 20 hours. Thereafter, the films were peeled off according to the method defined in ASTM D1893, and the peeling load was measured.
The lighter the peeling load, the harder the blocking and the better, preferably 100 g / cm or less, more preferably 30 g / cm or less, still more preferably 20 g / cm or less, particularly preferably 10 g / cm or less, most preferably 8 g / cm It is the following range. In addition, when it can not measure enough, such as exceeding 300 g / cm, or when a film breaks, it described as "-".

(10) Evaluation Method of Discrimination of Coloring The degree of coloring of the laminated polyester film was observed. Place one laminated polyester film on a transparent glass plate, and if it can be discriminated whether it is colored or not A, on a transparent glass plate it is difficult to discriminate, but if it can be easily discriminated on a blank paper B, even on a blank paper The case where it is difficult to distinguish easily but the case where discrimination can be made by staring from an oblique direction is C, and the case where coloration can not be determined is D.

(11) Evaluation method of base material adhesion of adhesive layer The adhesive layer side of one A4 size laminated polyester film and the A4 size film without adhesive layer of Comparative Example 1 described later are overlapped and strongly pressed with a finger. After pasting, the film having the adhesive layer is peeled off, and the film surface without the adhesive layer of Comparative Example 1 is observed, and there is no adhesive residue (adhesion marks of the adhesive layer) (adhesive layer and original substrate The case where the adhesiveness of (A) is good, and the case where there is adhesive residue (the case where the substrate adhesion of the adhesive layer is poor) is B.

(12) Evaluation method of transferability of adhesive layer to adherend Adhesion of a 5 cm wide laminated polyester film of the present invention to the surface of a polymethyl methacrylate plate (Kuraray Co., Ltd., made by Kuraray Co., Ltd., Comoglass (registered trademark), 1 mm thick) The layer surface was pressed twice for reciprocation by a 5 cm wide 2 kg rubber roller, attached and treated at 60 ° C. for 8 days, then the film was peeled off and the surface of the polymethyl methacrylate plate was observed.

  A: when there is no mark on the polymethyl methacrylate plate (no transition of the adhesive layer is seen); B, when a very slight thin mark is observed when staring under fluorescent light for 3 seconds; When C is observed, a clear white mark is partially observed such as the end where the film is stuck (the adhesive layer is transferred) D, when a clear white mark is observed over the entire surface It was E. In addition, when it did not stick to a to-be-adhered body, it described as "-". In applications that care about migration, it is better to avoid D and E, especially in applications where less migration is required, levels of A and B, especially levels of A are preferred.

(13) Measuring method of surface resistance High resistance measuring instrument made by Nippon Hewlett Packard Co., Ltd .: Measuring electrode: HP16008B, after sufficiently controlling humidity of polyester film in measuring atmosphere at 23 ° C., 50% RH, printing The surface resistance of the antistatic layer after one minute at a voltage of 100 V was measured.

(14) Method of evaluating dust adhesion on the functional layer (antistatic layer) side After sufficiently conditioning the polyester film in a measurement atmosphere at 23 ° C. and 50% RH, rub the antistatic layer 10 times with a cotton cloth. Bring this on gently into the top of the shredded cigarette ash, observe the adhesion of the ash, and if the film does not adhere when it comes in contact with the ash A, if the film comes in contact with the ash a little B, C was a case where a large amount of film was attached only by bringing the film close to ash.

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

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

<Method of producing polyester (C)>
A polyester (C) is obtained using the same method as the polyester (A) production method except that 0.3 parts by weight of silica particles having an average particle diameter of 2 μm is added before the melt polymerization in the production method of the polyester (A). The

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

The example of a compound which comprises an adhesion layer and a functional layer is as follows.
(Example of compound)
・ Polyester resin: (IA)
Aqueous dispersion of polyester resin (glass transition temperature: -20 ° C) consisting of the following composition: Monomer composition: (acid component) dodecanedicarboxylic acid / terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene Glycol / 1,4-butanediol = 20/38/38/4 // 40/60 (mol%)

Acrylic resin: (IC)
Aqueous dispersion of acrylic resin (glass transition temperature: -50 ° C) having the following composition: 2-ethylhexyl acrylate / methyl methacrylate / methacrylic acid = 85/12/3 (% by weight)
-Acrylic resin: (ID)
Aqueous dispersion of acrylic resin (glass transition temperature: -55 ° C) consisting of the following composition: 2-ethylhexyl acrylate / normal butyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate = 77/10/5/8 (% by weight)
-Acrylic resin: (IE)
Aqueous dispersion of acrylic resin (glass transition temperature: -25 ° C) consisting of the following composition: Normal butyl acrylate / Styrene / Acrylic acid = 62/35/3 (% by weight)
Acrylic resin: (IF)
Aqueous dispersion of acrylic resin (glass transition temperature: -40 ° C) consisting of the following composition: 2-ethylhexyl acrylate / normal butyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58/20/15/5 2 (weight%)

-Acrylic resin: (IG)
Aqueous dispersion of acrylic resin (glass transition temperature: -40 ° C) having the following composition: Normal butyl acrylate / 2-ethylhexyl acrylate / acrylonitrile / acrylic acid = 82/10/5/3 (% by weight)
-Acrylic resin: (IH)
Aqueous dispersion of acrylic resin (glass transition temperature: -50 ° C.) having the following composition: 2-ethylhexyl acrylate / normal butyl acrylate / ethyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 50/27/15/5 3 (weight%)

・ Blue colorant: (IIA)
C. I. Pigment Blue 15: 3 (Maximum absorption wavelength = 680 nm)
・ Purple-based coloring agent: (IIB)
C. I. Pigment Violet 23 (maximum absorption wavelength = 610 nm)
・ Green colorant: (IIC)
Basic Green 1 (Maximum absorption wavelength = 640 nm)

Melamine compound: (IIIA) hexamethoxymethylolmelamine isocyanate compound: (IIIB)
1000 parts of hexamethylene diisocyanate were stirred at 60 ° C., and 0.1 part of tetramethylammonium caprylate was added as a catalyst. After 4 hours, 0.2 part of phosphoric acid was added to stop the reaction to obtain an isocyanurate type polyisocyanate composition. 100 parts of the obtained isocyanurate type polyisocyanate composition, 42.3 parts of methoxy polyethylene 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 temperature of the reaction solution was maintained at 60 ° C., 35.8 parts of methyl isobutanoyl acetate, 32.2 parts of diethyl malonate, and 0.88 parts of a 28% methanol solution of sodium methoxide were added, and held for 4 hours. 58.9 parts of n-butanol is added, and the reaction solution temperature is maintained at 80 ° C. for 2 hours, and then blocked polyisocyanate by active methylene obtained by adding 0.86 parts of 2-ethylhexyl acid phosphate

・ Polyester resin: (IVA)
Aqueous dispersion of polyester resin (glass transition temperature: 30 ° C.) consisting of 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: (IVB)
Aqueous dispersion of polyester resin (glass transition temperature: 50 ° C.) consisting of the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4 -Butanediol / diethylene glycol = 50/46/4 // 70/20/10 (mol%)

・ Acrylic resin: (IVC)
Aqueous dispersion of acrylic resin (glass transition temperature: 10 ° C.) consisting of the following composition: Normal butyl acrylate / ethyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid = 10/52/30/5/3 (% by weight)
・ Acrylic resin: (IVD)
Aqueous dispersion of acrylic resin (glass transition temperature: 40 ° C.) consisting of the following composition: ethyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 48/45/4/3 (% by weight)

Particles: (V) Silica particles having an average particle diameter of 45 nm

· Release agent (long-chain alkyl group-containing compound): (VIA)
Two hundred parts of xylene and 600 parts of octadecylisocyanate were added to a four-necked flask and heated with stirring. 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 little by little at intervals of 10 minutes for about 2 hours. After the addition of polyvinyl alcohol, the reaction was further refluxed for 2 hours to complete the reaction. The reaction mixture was cooled to about 80 ° C. and then added to methanol, and the reaction product precipitated as a white precipitate, which was separated by filtration, 140 parts of xylene was added, and the solution was completely dissolved by heating. Then, after repeating the operation of adding methanol again to precipitate, the precipitate was washed with methanol and dried and pulverized.

· Releasing agent (fluorine compound): (VIB)
Aqueous dispersion of fluorine compound having the following composition: Octadecyl acrylate / perfluorohexylethyl methacrylate / vinyl chloride = 66/17/17 (% by weight)

・ Polyether group-containing condensation type silicone: (VIC)
Polyether group-containing silicone (silicone siloxane having a number average molecular weight of 7000) containing one polyethylene glycol having 8 ethylene glycol chains (terminal end is hydroxyl group) with respect to dimethylsiloxane 100 in molar ratio in the side chain of dimethyl silicone When the bond is 1, the ether bond of the polyether group is 0.07 at a molar ratio. The low molecular weight component having a number average molecular weight of 500 or less is 3%, and the silicon-bonded vinyl group (vinylsilane) and hydrogen group (hydrogensilane) are not present. The present compound is obtained by mixing and dispersing sodium dodecylbenzene sulfonate at a ratio of 0.25, where the polyether group-containing silicone is 1 by weight ratio.

・ Wax: (VID)
Emulsifying equipment equipped with a stirrer, thermometer, and temperature controller with an internal volume of 1.5 L. Melting point 105 ° C., acid value 16 mg KOH / g, density 0.93 g / mL, polyethylene wax 300 g number average molecular weight 5000, ion exchange water 650 g Add 50g of decaglycerin monooleate surfactant and 10g of 48% potassium hydroxide aqueous solution, replace with nitrogen, seal with sealed, high-speed stirring at 150 ° C for 1 hour, cool to 130 ° C, high pressure homogenizer under 400 atmospheres pressure Wax emulsion passed through and cooled to 40 ° C.

· Antistatic agent (quaternary ammonium salt compound): (VIIA)
Polymer polymerized according to the following composition having a pyrrolidinium ring in the main chain: diaryldimethyl ammonium chloride / dimethyl acrylamide / N-methylol acrylamide = 90/5/5 (mol%). Number average molecular weight 30000.

· Antistatic agent (compound having an ammonium group): (VIIB)
The high molecular compound of the number average molecular weights 50000 whose counter ion is a methanesulfonic acid ion which consists of a structural unit of following formula (2).

Reference Example 1:
A mixed material in which polyesters (A), (B) and (C) are mixed at a ratio of 91%, 3% and 6%, respectively, is used as a material of the outermost layer (surface layer), and polyesters (A) and (B) are each 97 The mixed raw materials mixed at 1% and 3% ratio are used as the raw materials for the middle layer, and each is supplied to two extruders, melted at 285 ° C., and then cooled on a cooling roll set at 40 ° C. The coextrusion was cooled and solidified with a layer configuration of layers (surface layer / middle layer / surface layer = 3: 19: 3 discharge amount) to obtain an unstretched sheet. Next, after stretching 3.3 times in the longitudinal direction at a film temperature of 85 ° C. using the roll peripheral speed difference, the coating liquid A1 shown in Table 1 below is formed on one side of this longitudinally stretched film in a thickness of the adhesive layer (drying Apply the coating solution B1 shown in the following Table 3 on the opposite side so that the film thickness (after drying) of the functional layer is 30 nm, and guide it to a tenter at 90 ° C. After drying for 10 seconds, the film is stretched 4.4 times in the lateral direction at 110 ° C. and heat treated at 230 ° C. for 10 seconds, and then relaxed 2% in the lateral direction to a thickness of 25 μm. A 9 nm polyester film was obtained. In addition, Sa of the polyester surface at the side with the adhesion layer at the time of removing an adhesion layer with ethyl acetate was 9 nm.

  When the obtained polyester film was evaluated, the adhesive force with a polymethyl methacrylate board was 30 mN / cm, the adhesive property was good, and the discrimination by coloring was also good. The properties of this film are shown in Table 4 below.

Reference Examples 2 to 7, 16, 25, 32, 43, 54, 65, 76, 87, 98, 109, 120, Examples 8 to 15, 17 to 24, 26 to 31, 33 to 42, 44 to 53, 55-64, 66-75, 77-86, 88-97, 99-108, 110-119, 121-132 :
A polyester film was obtained in the same manner as in Reference Example 1 except that the coating composition was changed to the coating composition shown in Tables 1 to 3 in Reference Example 1. The obtained polyester film had good adhesion and discrimination as shown in Tables 4 to 8 below.

Reference Example 133:
A mixed material in which polyesters (A), (B) and (D) are mixed at a ratio of 87%, 3% and 10%, respectively, is used as a material of the outermost layer (surface layer), and polyesters (A) and (B) are each 97 The mixed raw materials mixed at 1% and 3% ratio are used as the raw materials for the middle layer, and each is supplied to two extruders, melted at 285 ° C., and then cooled on a cooling roll set at 40 ° C. The coextrusion was cooled and solidified with a layer configuration of layers (surface layer / intermediate layer / surface layer = 6: 13: 6 discharge amount) to obtain an unstretched sheet. Next, after stretching 3.3 times in the longitudinal direction at a film temperature of 85 ° C. using the roll peripheral speed difference, the coating liquid A1 shown in Table 1 below is formed on one side of this longitudinally stretched film in a thickness of the adhesive layer (drying Apply the coating solution B1 shown in the following Table 3 on the opposite side so that the film thickness (after drying) of the functional layer is 30 nm, and guide it to a tenter at 90 ° C. After drying for 10 seconds, the film is stretched 4.4 times in the lateral direction at 110 ° C. and heat treated at 230 ° C. for 10 seconds, and then relaxed 2% in the lateral direction to a thickness of 25 μm. A 15 nm polyester film was obtained. In addition, Sa of the polyester surface at the side with the adhesion layer at the time of removing an adhesion layer with ethyl acetate was 15 nm.

  When the obtained polyester film was evaluated, the adhesive force with a polymethyl methacrylate board was 30 mN / cm, the adhesive property was good, and the discrimination by coloring was also good. The properties of this film are shown in Table 8 below.

Examples 134-143:
A polyester film was obtained in the same manner as in Reference Example 133 except that the coating composition was changed to the coating composition shown in Table 1 or 2 in Reference Example 133. The obtained polyester film had good adhesion and discrimination as shown in Table 8 below.

Example 144:
A polyester film was obtained in the same manner as in Reference Example 1 except that the adhesive layer was not provided in Reference Example 1. Coating solution A18 shown in the following Table 1 is coated on the polyester film without the adhesive layer so that the film thickness (after drying) of the adhesive layer becomes 220 nm, drying is performed at 100 ° C. for 60 seconds, and offline coating is performed. The polyester film in which the adhesion layer was laminated | stacked was obtained. As shown in Table 8, the obtained polyester film had good adhesion and discrimination. However, the adhesion of the adhesive layer to the substrate and the migration to the adherend were not good.

Example 145:
A polyester film was obtained in the same manner as in Example 144 except that the composition of the adhesive layer in Example 144 was changed to the composition shown in Table 2. The obtained polyester film had good adhesion and discrimination as shown in Table 8 below, but the adhesion to substrate and transferability to the adherend of the adhesive layer were not good.

Comparative Example 1:
A polyester film was obtained in the same manner as in Reference Example 1 except that the adhesive layer and the functional layer were not provided in Reference Example 1. When the obtained polyester film was evaluated, as shown in Table 9 below, there was no adhesive force, and the discrimination was poor.

Comparative Examples 2 to 13:
A polyester film was obtained in the same manner as in Reference Example 1 except that the coating composition was changed to the coating composition shown in Table 1 or 2 in Reference Example 1. As shown in Table 9, the obtained polyester film was a film in which the case where there was no adhesive force and the case where the discrimination due to coloring was bad were observed.

Comparative Example 14:
Coating solution C6 shown in the following Table 1 on the polyester film without the adhesive layer and the functional layer obtained in Comparative Example 1 was treated at 100 ° C. for 3 minutes so that the thickness (after drying) of the adhesive layer was 20 μm. It dried and the polyester film in which the adhesion layer was formed by off-line coating was obtained. When the adhesive layer side was pasted together to polyester film and cut, it was seen that the sticking out of the component of the adhesive layer which was not seen in the example was seen, and there was a concern about the contamination by the adhesive component. Also, the adhesion could not be measured well. Other properties are as shown in Table 9.

  The film of the present invention has a small fish eye, for example, in use as a surface protection film used for preventing damage and adhesion of dirt during transportation, storage and processing of resin plates, metal plates, etc. It can be suitably used for applications that are required to have excellent target strength and heat resistance and to have good adhesion properties and discrimination.

Claims (18)

At least one selected from polyester resins having a glass transition temperature of 0 ° C. or less, acrylic resins having a glass transition temperature of −20 ° C. or less, and urethane resins having a glass transition temperature of 0 ° C. or less on at least one surface of the polyester film ; A laminated polyester film comprising an adhesive layer containing a colorant having a maximum absorption wavelength in the range of 570 to 650 nm . At least one surface selected from a polyester resin having a glass transition temperature of 0 ° C. or less, an acrylic resin having a glass transition temperature of −20 ° C. or less, and a urethane resin having a glass transition temperature of 0 ° C. or less on at least one surface of the polyester film A method for producing a laminated polyester film, comprising: providing an application layer containing an agent; and stretching the application layer in at least one direction to form a pressure-sensitive adhesive layer. At least one surface selected from a polyester resin having a glass transition temperature of 0 ° C. or less, an acrylic resin having a glass transition temperature of −20 ° C. or less, and a urethane resin having a glass transition temperature of 0 ° C. or less on at least one surface of the polyester film A method for producing a laminated polyester film, comprising: providing an application layer containing an agent; and heat-treating the application layer in the range of 180 to 270 ° C. to form an adhesive layer. The laminated polyester film according to claim 1, wherein the coloring agent is contained in the adhesive layer in a range of 0.1 to 50% by weight. The laminated polyester film according to claim 1 or 4 , wherein the polyester resin having a glass transition temperature of 0 ° C or less contains an aliphatic polyvalent carboxylic acid or an aliphatic polyvalent hydroxy compound as a component. Polyester resin The glass transition point of 0 ℃ or less, sulfonic acid as a functional group, sulfonate, carboxylic acid or a laminated polyester film according to claim 1, 4, 5 containing carboxylate, . Laminated polyester film according to claim 1, 4-6 wherein the polyester resin glass transition point of 0 ℃ or less, contained in the components of aromatic polycarboxylic acids. The laminated polyester film according to claim 1, wherein the acrylic resin having a glass transition temperature of −20 ° C. or less contains 20% by weight or more of a (meth) acrylate unit having an alkyl group having 4 or more carbon atoms at an ester end. The acrylic resin having a glass transition temperature of −20 ° C. or less contains, as a monomer constituting the acrylic resin, a compound having a carbon number of 2 or less at the ester end or a compound having a cyclic structure. The laminated polyester film as described in 8 . The said acrylic resin whose glass transition point is -20 degrees C or less contains the carboxylic acid group, the carboxylic acid group, the sulfonic acid group, the sulfonic acid group, or the hydroxyl group, The lamination in any one of Claim 1, 8 , 9 Polyester film. The laminated polyester film according to claim 1, wherein the urethane resin having a glass transition temperature of 0 ° C or less has a polycarbonate polyol or a polyether polyol as a polyol component. Laminated polyester film according to claim 1, 4 to 11 wherein the adhesive layer contains a crosslinking agent. The laminated polyester film according to any one of claims 1 and 4 to 12 having a functional layer on the polyester film side opposite to the adhesive layer. The laminated polyester film according to claim 13 , wherein the functional layer contains a release agent. Laminated polyester film according to claim 13 or 14 wherein the functional layer contains an antistatic agent. The laminated polyester film according to any one of claims 13 to 15 , wherein the film thickness of the functional layer is in a range of 1 nm to 3 μm. Laminated polyester film according to any one of the thickness of the adhesive layer, according to claim 1, 4-16 is 10μm or less. Laminated polyester film according to any one of the arithmetic average roughness of the adhesive layer surface (Sa) is, according to claim 1, 4-17 is 50nm or less.