JP6168106B2 - Laminated film - Google Patents

Description

  The present invention relates to a laminated film, for example, as a surface protection film for preventing scratches and preventing dirt adhesion during transport, storage and processing of resin plates, metal plates, etc. The present invention relates to a laminated film having excellent mechanical strength and heat resistance and having good adhesive properties.

  Conventionally, when transporting, storing and processing resin plates, metal plates, glass plates, etc., preventing scratches and dirt, and scratching when processing components used in electronic fields such as liquid crystal panels and polarizing plates Wide range of surface protection films for applications such as prevention of dust and dirt, prevention of dirt and dirt during transportation and storage of automobiles, protection of automobile coating from acid rain, and protection during plating and etching of flexible printed circuit boards It is used.

  These surface protective films have an appropriate adhesive force to the adherend during transport, storage, processing, etc. of various adherends such as resin plates, metal plates and glass plates, It is required that the surface of the adherend be protected by adhering to the surface of the adherend 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 defects caused by gel-like materials and deteriorated products, which are generally called fisheye, For example, when inspecting an adherend in a state where the surface protective film is bonded, there is a problem that it becomes an obstacle such as detecting a defect of the surface protective film.

  In addition, as a base material for the surface protection film, a film having a certain degree of mechanical strength is required so that the base material is not stretched due to various processing tensions such as bonding to an adherend. However, since polyolefin films generally have poor mechanical strength, there is a drawback that they are unsuitable for high-tension processing due to an increase in processing speed in order to place importance on productivity.

  Furthermore, even when the processing temperature is increased to improve the processing speed and various characteristics, the polyolefin-based film is not excellent in shrinkage stability due to heat, so that the dimensional stability is poor. Therefore, there is a demand for a film that has little thermal deformation even when processed at high temperature and has excellent dimensional stability.

JP-A-5-98219 JP 2007-270005 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is that there are few fish eyes used for various surface protection films, etc., excellent mechanical strength and heat resistance, and good adhesive properties. It is to provide a laminated film.

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

That is, the gist of the present invention is that the film thickness is 1 to 4 on at least one side of the polyester film.
The range is 00 nm, and the adhesive strength with the polymethyl methacrylate plate is 1-1000 mN / c.
It has the adhesion layer which is the range of m, and it exists in the manufacturing method of the laminated | multilayer film characterized by being formed by extending | stretching with the polyester film after the said adhesion layer was provided on the polyester film.

  According to the laminated film of the present invention, as various surface protective films, a film having few fish eyes, excellent mechanical strength and heat resistance, and having good adhesive properties can be provided, and its industrial value is high.

  In order to reduce fish eyes, improve mechanical strength, and improve heat resistance, the fundamental material of the base film needs to be changed significantly. It has been found that this can be achieved by using a system material. Examples thereof include a polyester film, a polycarbonate film, a fluororesin film, a polyimide film, a triacetyl cellulose film, a polyacrylate film, a polystyrene film, a polyvinyl chloride film, a polyvinyl alcohol film, and a nylon film. In particular, in order to develop into various applications, it is preferable to be superior in heat resistance and mechanical properties, and polyester film, polycarbonate film, fluororesin film, and polyimide film are preferably used, and further, transparency, moldability, and versatility are improved. In consideration, a polyester film is more preferably used.

  However, by greatly changing the material system of the base film to a non-polyolefin material, the adhesive properties are greatly reduced, and cannot be achieved with general non-polyolefin films as described above. . Therefore, improvement was achieved by providing an adhesive layer on the substrate film, and the present invention was achieved. Hereinafter, the details of the present invention will be described.

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

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

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

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

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

  As the polycarbonate film that can be used as the film of the present invention, a conventionally known polycarbonate can be used, but a type containing a bisphenol A structure is particularly preferable.

  As the fluororesin film that can be used as the film of the present invention, a conventionally known fluororesin can be used. For example, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoro Examples include ethylene-perfluoroalkyl vinyl ether copolymers.

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

  The average particle diameter of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, and still more preferably 0.01 to 3 μm. When the average particle diameter exceeds 10 μm, there may be a concern about problems due to dropout of particles or reduction in transparency of the film.

  Further, the content of the particles in the film is unclear because there is a balance with the average particle size of the particles, but is preferably 5% by weight or less, more preferably in the range of 0.0003 to 3% by weight, and still more preferably. The range is 0.0005 to 1% by weight. When the particle content exceeds 5% by weight, there may be a concern about problems due to dropout of particles or reduction in transparency of the film. When there are no or few particles, the transparency of the film will be high and a good film will be obtained, but the slipperiness may be insufficient. There are cases where improvement is required.

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

  The method for adding particles to the film is not particularly limited, and a conventionally known method can be adopted. For example, it can be contained at any stage of producing the resin forming the film constituting each layer, or the resin can be contained after production.

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

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

  Next, although the manufacture example of the film in this invention is demonstrated concretely, it is not limited to the following manufacture examples at all. In general, the resin is melted, formed into a sheet, and stretched for the purpose of increasing the strength and the film is formed. As an example, the case where the polyester film mentioned above is manufactured is introduced. 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 with a cooling roll to obtain an unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method or a liquid application adhesion method is preferably employed. Next, the obtained unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine. The stretching temperature is preferably 70 to 120 ° C, more preferably 80 to 110 ° C, and the stretching ratio is preferably 2.5 to 7 times, more preferably 3.0 to 6 times. Next, the film is stretched in the direction orthogonal to the first-stage stretching direction, preferably at 70 to 170 ° C., and the stretching ratio is preferably 2.5 to 7 times, more preferably 3.0 to 6 times. Subsequently, a method of obtaining a biaxially oriented film by performing heat treatment at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% is mentioned. In the above-described stretching, a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges. In addition, the simultaneous biaxial stretching method can be used for stretching.

  Next, formation of the adhesion layer which comprises the laminated | multilayer film in this invention is demonstrated. Examples of the method for forming the adhesive layer include methods such as coating, transfer, and lamination. In consideration of the ease of forming the adhesive layer and the control of the film thickness in the range of 1 to 3000 nm, it is preferably formed by coating.

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

  Specifically, the in-line coating is a method in which coating is performed at an arbitrary stage from melt extrusion of a resin forming a film to heat setting after stretching and winding. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding. Although not limited to the following, for example, in sequential biaxial stretching, a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, since film formation and adhesion 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 adhesion layer can be changed by the stretching ratio. Compared to off-line coating, thin film coating in the range of 1 to 3000 nm can be performed more easily.

  Moreover, by providing the adhesive layer on the film before stretching, the adhesive layer can be stretched together with the base film, whereby the adhesive layer can be firmly adhered to the base film. Furthermore, in the manufacture of biaxially stretched films, the film can be restrained in the vertical and horizontal directions by stretching while gripping the film edges with clips, etc., and flatness is not generated in the heat setting process. High temperature can be applied while maintaining

  Therefore, since the heat treatment performed after coating can be performed at a high temperature that cannot be achieved by other methods, the film forming property of the adhesive layer can be improved, and the adhesive layer and the base film can be more firmly adhered to each other. In addition, a strong adhesive layer can be obtained.

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

  In the present invention, it is an essential requirement to have an adhesive layer having a thickness of 1 to 3000 nm and an adhesive strength with a polymethyl methacrylate plate of 1 to 1000 mN / cm.

  In general, the adhesive layer has a thickness of several tens of μm, but in the present invention, the adhesive layer has a thickness in the range of 1 to 3000 nm, for example, when used for manufacturing a polarizing plate. When the film of the present invention is bonded to an adherend such as a polarizing plate and cut, the protrusion of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer can be minimized. Moreover, since the absolute amount of the adhesive layer present on the film is small, it is effective in reducing adhesive residue, in which components of the adhesive layer migrate to the adherend. Regarding the adhesive strength, by setting the adhesive strength to the polymethyl methacrylate plate in the range of 1 to 1000 mN / cm, it is possible to achieve both the adhesive performance and the peeling performance to be peeled after bonding. It is possible to obtain an optimum film for various processes.

  The material for forming the adhesive layer is not particularly limited as a result of various studies. By using a resin having a glass transition point of 0 ° C. or lower, the above-mentioned film thickness and adhesive strength can be applied to a non-polyolefin film. We found that it was easy to give a range of adhesive properties. Conventionally known resins can be used as the resin having a glass transition point of 0 ° C. or lower. Specific examples of the resin include a polyester resin, an acrylic resin, a urethane resin, a polyvinyl resin (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.) and the like. Acrylic resin and urethane resin are preferred. Furthermore, when considering the reusability of the film, a polyester resin or an acrylic resin is preferable, and when the base material is a polyester film, the adhesiveness with the base material and the small amount of adhesive residue on the adherend are considered. In this case, a polyester resin is most preferable, and an acrylic resin is most preferable in consideration of little change with time.

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

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

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

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

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

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

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

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

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

  Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion is also included. Similarly, a polymer obtained by polymerizing a polymerizable monomer in a polyurethane solution or a polyurethane dispersion (sometimes a mixture of polymers) is also included. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in another polymer solution or dispersion is also included.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  When using a cross-linking agent other than an epoxy compound, if the content in the adhesive layer increases too much, the adhesive properties may deteriorate too much. Therefore, when using a crosslinking agent other than an epoxy compound, it is necessary to pay attention to the content in the adhesive layer.

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

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

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

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

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

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

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

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

  A carbodiimide-based compound is a compound having a carbodiimide structure, and is used for improving the wet heat resistance of the adhesive layer. The carbodiimide compound is a compound having one or more carbodiimide or carbodiimide derivative structures in the molecule, but a polycarbodiimide compound having two or more in the molecule is more preferable for better adhesion and the like.

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

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

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

  In forming the adhesive layer, it is also possible to use particles in combination for blocking, improving slipperiness and adjusting adhesive properties. However, care should be taken because the adhesive strength may decrease depending on the type of particles used. In particular, when the adhesive performance of the resin of the adhesive layer is desired to be exhibited as it is, it is preferable not to contain particles in the adhesive layer.

  In the present invention, a functional layer may be provided on the surface opposite to the adhesive layer of the film for providing 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 in order to prevent defects due to adhesion of dust around the film due to film peeling or frictional charging, an antistatic layer is provided. Providing is also a preferred form. The functional layer may be provided by coating, may be provided by in-line coating, or may employ offline coating. In-line coating is preferably used from the viewpoint of stabilization of production cost, release performance by in-line heat treatment, antistatic performance, and the like.

  For example, when a release functional layer is provided on the surface opposite to the adhesive layer of the film, the release agent contained in the functional layer is not particularly limited, and conventionally known release agents can be used. Yes, for example, long-chain alkyl group-containing compounds, fluorine compounds, silicone compounds, waxes and the like. Among these, a long-chain alkyl compound and a fluorine compound are preferable from the viewpoint of low contamination and excellent blocking reduction, and a silicone compound is preferable when it is particularly important to reduce blocking. Also, wax is effective for improving the surface decontamination property. These release agents may be used alone or in combination.

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

The polymer compound having a long-chain alkyl group in the side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride.
Examples of the compound having such a reactive group include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, and a reactive group-containing poly (meth) acrylic resin. Among these, polyvinyl alcohol is preferable in view of releasability and ease of handling.

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

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

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

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

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

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

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

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

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

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

  The polyether group content of the polyether group-containing silicone is preferably in the range of 0.001 to 0.30, more preferably 0.01 to 0.20 in terms of a molar ratio, where the siloxane bond of the silicone is 1. %, More preferably 0.03 to 0.15%, particularly preferably 0.05 to 0.12%. By using within this range, it is possible to maintain the dispersibility in water, the durability of the functional layer, and the good releasability.

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

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

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

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

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

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

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

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

  When providing an antistatic functional layer on the surface opposite to the adhesive layer of the film, the antistatic agent contained in the functional layer is not particularly limited, and conventionally known antistatic agents can be used. A polymer type antistatic agent is preferred because of its good heat resistance and moist heat resistance. Examples of the polymer type antistatic agent include a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, and a conductive polymer.

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

  Among the compounds having an ammonium group, compounds having a pyrrolidinium ring are also preferred in that they are excellent in antistatic properties and heat stability.

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

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

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

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

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

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

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

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

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

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

  It is also a preferred embodiment that the functional layer that can be provided on the surface of the film opposite to the adhesive layer contains both the above-mentioned release agent and antistatic agent and has an antistatic release function.

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

  As long as the gist of the present invention is not impaired, particles can be used in combination with the formation of the functional layer in order to improve blocking and slipperiness. However, when the functional layer has mold release performance, it often has sufficient blocking resistance and slipperiness, and therefore it may be preferable not to use particles from the viewpoint of the appearance of the functional layer.

  Furthermore, in the range not impairing the gist of the present invention, an antifoaming agent, a coating property improving agent, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, Antioxidants, foaming agents, dyes, pigments and the like can be used in combination.

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

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

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

  In the laminated film of the present invention, when providing a functional layer having a release performance on the side opposite to the adhesive layer, the ratio of the release agent as the ratio in the functional layer varies depending on the type of the release agent. Although it cannot be generally stated, it is preferably in the range of 3% by weight or more, more preferably 15% by weight or more, and further preferably in the range of 25 to 99% by weight. If it is less than 3% by weight, the blocking reduction may not be sufficient.

  When a long-chain alkyl compound or a fluorine compound is used as the release agent, the proportion in the functional layer is preferably 5% by weight or more, more preferably 15 to 99% by weight, still more preferably 20 to 95% by weight, particularly Preferably it is the range of 25 to 90 weight%. By using it in the above range, blocking reduction is effective. The proportion of the crosslinking agent is preferably 95% by weight or less, more preferably 1 to 80% by weight, further preferably 5 to 70% by weight, and particularly preferably 10 to 50% by weight. Compounds and isocyanate compounds (block isocyanates blocked with active methylene compounds are particularly preferred among them) are preferred, and melamine compounds are particularly preferred 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 preferably 3% by weight or more, more preferably 5 to 97% by weight, still more preferably 8 to 95% by weight, and particularly preferably. It is in the range of 10 to 90% by weight. By using it in the above range, blocking reduction is effective. The ratio of the crosslinking agent is preferably 97% by weight or less, more preferably 3 to 95% by weight, further preferably 5 to 92% by weight, and particularly preferably 10 to 90% by weight. 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 preferably 5% by weight or more, more preferably 25% by weight or more, further preferably 50% by weight or more, and particularly preferably 70% by weight. % Or more. The upper limit of the preferable range is 99% by weight, and the more preferable upper limit is 90% by weight. By using in the said range, blocking reduction becomes effective and the external appearance of a functional layer also becomes favorable.

  When wax is used as the release agent, the ratio in the functional layer is preferably 10% by weight or more, more preferably 20 to 90% by weight, and further preferably 25 to 70% by weight. By using it in the above range, blocking can be easily reduced. However, when wax is used for the purpose of decontamination of the surface, the above ratio can be reduced, preferably 1% by weight or more, more preferably 2 to 50% by weight, and further preferably 3 to 30% by weight. % Range. The proportion of the crosslinking agent is preferably 90% by weight or less, more preferably 10 to 70% by weight, and still 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 performance is provided on the side opposite to the adhesive layer, the proportion of the antistatic agent as the proportion in the functional layer cannot be generally described because the appropriate amount varies depending on the type of the antistatic agent. Is preferably in the range of 0.5% by weight or more, more preferably in the range of 3 to 90% by weight, still more preferably in the range of 5 to 70% by weight, and particularly preferably in the range of 8 to 60% by weight. If it is less than 0.5% by weight, the antistatic effect is not sufficient, and the effect of preventing the adhesion of surrounding dust and the like may not be sufficient.

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

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

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

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

  Regarding the laminated film in the present invention, the thickness of the pressure-sensitive adhesive layer provided on the film is essential to be 1 to 3000 nm, preferably 10 to 2000 nm, more preferably 15 to 1000 nm, still more preferably 20 to 700 nm, Especially preferably, it is the range of 30-500 nm, Most preferably, it is the range of 30-400 nm. By using the film thickness of the adhesive layer within the above range, it becomes easy to maintain appropriate adhesive properties and blocking properties. In addition, it is possible to reduce the protrusion of the component of the adhesive layer when cutting by bonding with various plastic materials. The thinner the film thickness, the weaker the adhesive force, but the smaller the film thickness, the less the sticking layer sticks out and the adhesive residue on the adherend. Therefore, it is important to control the film thickness according to the application. Furthermore, when forming by in-line coating, the one where a film thickness is thin is preferable from a viewpoint of the ease of manufacture.

  Although the film thickness of the functional layer depends on the function to be provided, it cannot be said unconditionally. For example, the functional layer for imparting release performance or antistatic performance is preferably 1 to 3000 nm, more preferably The range is 10 to 1000 nm, more preferably 20 to 500 nm, and particularly preferably 20 to 200 nm. By using the film thickness of the functional layer within the above range, it becomes easy to improve the blocking characteristics, improve the antistatic performance, or obtain a good appearance.

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

  In the present invention, 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, the drying of a solvent such as water used in the coating solution is not limited. The range is preferably 70 to 150 ° C, more preferably 80 to 130 ° C, and still more preferably 90 to 120 ° C. The drying time is generally 3 to 200 seconds, preferably 5 to 120 seconds. Moreover, in order to improve the intensity | strength of an adhesion layer, in a film manufacturing process, Preferably it is 180-270 degreeC, More preferably, it is 200-250 degreeC, More preferably, it is passing through the heat processing process of the range of 210-240 degreeC. The time for the heat treatment step is generally 3 to 200 seconds, preferably 5 to 120 seconds.

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

  As the adhesive strength of the adhesive layer of the present invention, it is essential to be 1 to 1000 mN / cm, preferably 3 to 800 mN / cm or more, more preferably 5 to 500 mN / cm, with respect to the polymethyl methacrylate plate. More preferably, it is 7-300 mN / cm, Most preferably, it is the range of 10-100 mN / cm. When it is out of the above range, depending on the adherend, there is a case where there is no adhesive force, a case where the adhesive force is too strong to be easily peeled off, or film blocking becomes remarkable.

As the blocking property of the laminated film of the present invention, the peeling load after the laminated films are stacked and pressed under the conditions of 40 ° C., 80% RH, 10 kg / cm ² , 20 hours, is preferably 100 g / cm or less, More preferably, it is 30 g / cm or less, More preferably, it is 20 g / cm or less, Especially preferably, it is 10 g / cm or less, Most preferably, it is the range of 8 g / cm or less. By setting it as the said range, it becomes easy to avoid the risk of blocking and it can be set as a more practical film.

  Moreover, roughening the film surface on the side opposite to the adhesive layer of the film of the present invention may be one of the means for improving the blocking property with the adhesive layer side. Since it depends on the type of adhesive layer and adhesive strength, it cannot be generally stated, but when there is a purpose to improve the blocking characteristics by surface roughness, the arithmetic average roughness of the film surface on the side opposite to the adhesive layer is used. The thickness (Sa) is preferably in the range of 5 nm or more, more preferably 10 nm or more, and even more preferably 30 nm or more. The upper limit is not particularly limited, but is 300 nm from the viewpoint of transparency as the upper limit of the preferred range.

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

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

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

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

(4) Method for measuring film thickness of adhesive layer The surface of the adhesive layer was dyed with RuO ₄ and embedded in an epoxy resin. Thereafter, the section prepared by ultramicrotomy stained with RuO _4, and the adhesive layer cross-section was measured using a TEM (Hitachi High Technologies Corporation H-7650, accelerating voltage 100 V).

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

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

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

(8-1) Adhesive strength evaluation method (adhesive strength 1)
The pressure-sensitive adhesive layer surface of the laminated film of 5 cm width of the present invention is pressure-bonded once with a 2 cm rubber roller of 5 cm width on the surface of a polymethylmethacrylate plate (Kuraray Co., Ltd., Como Glass (registered trademark), thickness 1 mm), The peel strength after standing for 1 hour was measured. For the peeling force, “Ezgraph” manufactured by Shimadzu Corporation was used, and 180 ° peeling was performed under the condition of a tensile speed of 300 mm / min.

(8-2) Adhesive strength evaluation method (adhesive strength 2)
Evaluation was carried out in the same manner as in (8-1) except that the adhesive strength was evaluated using a polycarbonate plate (thickness 1 mm) instead of the polymethyl methacrylate plate of (8-1).

(8-3) Adhesive strength evaluation method (adhesive strength 3)
(8-1) except that the adhesive strength is evaluated using the polyester film surface (thickness: 50 μm) having no adhesive layer obtained in Comparative Example 1 described later instead of the polymethyl methacrylate plate (8-1). ) And the evaluation was performed in the same manner.

(9) Reworkability Evaluation Method for Adhesive Layer Adhesive properties of one A4 size laminated polyester film and the A4 size polyester film without the adhesive layer of Comparative Example 1, which will be described later. Evaluated. 5 points when the film sticks just by lightly pressing it with your finger, and you can hold the attached state even if you have only the film with the adhesive layer. 4 points when you can hold the sticking state even if you have only the film you have, the film sticks by pressing firmly with your finger, and keeps the sticking state even if you have only the film with the adhesive layer Yes, if the film is peeled off within 3 seconds, press the finger firmly. Press the button with your finger. In the case where no adhesive property was observed, 1 point was assigned. When the same operation was performed again at the same location after the film was peeled off, the case where the evaluation results were equivalent was evaluated as ◯, and the case where the adhesive properties were deteriorated was evaluated as ×.

(10) Adhesive residue (transfer properties) evaluation method of adhesive layer In the above evaluation method (9), the adhesive film was observed after peeling off the attached film, and there was no adhesive residue (adhesion layer transfer marks). In the case where there is an adhesive residue, x was given.

(11) Measuring method of blocking property Two polyester films to be measured are prepared, the adhesive layer side and the opposite side (functional layer side) of the adhesive layer are overlapped, and an area of 12 cm × 10 cm is obtained at 40 ° C., 80 Pressing was performed under the conditions of% RH, 10 kg / cm ² , and 20 hours. Thereafter, the films were peeled according to the method specified in ASTM D1893, and the peel load was measured.
A lighter peeling load is more difficult to block, and is preferably 100 g / cm or less, more preferably 30 g / cm or less, still more preferably 20 g / cm or less, and particularly preferably 10 g / cm or less. In this evaluation, those exceeding 300 g / cm, those in which the film was torn during the evaluation, and those in which obvious blocking was generated by the press were not practical. In those cases, the evaluation was x. .

(12) Measuring method of surface resistance Using a high resistance measuring instrument: HP4339B and measuring electrode: HP16008B manufactured by Hewlett-Packard Japan, apply the polyester film after sufficient humidity adjustment in a measurement atmosphere of 23 ° C. and 50% RH. The surface resistance of the antistatic layer after 1 minute at a voltage of 100 V was measured.

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

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

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

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

<Method for producing polyester (D)>
In the production method of polyester (A), polyester (D) is obtained using the same method as the production method of polyester (A) except that 0.6 parts by weight of silica particles having an average particle diameter of 3 μm is added before melt polymerization. It was.

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

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

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

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

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

・ Epoxy compound: (IVA) Polyglycerol polyglycidyl ether which is a polyfunctional polyepoxy compound ・ Melamine compound: (IVB) Hexamethoxymethylolmelamine ・ Oxazoline compound: (IVC)
Acrylic polymer having an oxazoline group and a polyalkylene oxide chain Epocross (Oxazoline group amount = 4.5 mmol / g, manufactured by Nippon Shokubai Co., Ltd.)
・ Isocyanate compounds: (IVD)
1000 parts of hexamethylene diisocyanate was stirred at 60 ° C., and 0.1 part of tetramethylammonium capryate was added as a catalyst. After 4 hours, 0.2 part of phosphoric acid was added to stop the reaction, and an isocyanurate type polyisocyanate composition was obtained. 100 parts of the obtained isocyanurate type polyisocyanate composition, 42.3 parts of methoxypolyethylene glycol having a number average molecular weight of 400, and 29.5 parts of propylene glycol monomethyl ether acetate were charged and maintained at 80 ° C. for 7 hours. Thereafter, the reaction solution temperature was kept at 60 ° C., 35.8 parts of methyl isobutanoyl acetate, 32.2 parts of diethyl malonate, and 0.88 part of 28% methanol solution of sodium methoxide were added and kept for 4 hours. Block polyisocyanate with active methylene obtained by adding 58.9 parts of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 part of 2-ethylhexyl acid phosphate.

-Particles: (V) Silica particles with an average particle size of 0.5 μm

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

・ Releasing agent (fluorine compound): (VIB)
Fluorine compound aqueous dispersion having the following composition: Octadecyl acrylate / perfluorohexyl ethyl methacrylate / vinyl chloride = 66/17/17 (% by weight)

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

・ Additional silicone: (VID)
Addition-type silicone aqueous dispersion mixed with a compound of the following composition: methyl hydrogen polysiloxane containing 80% by weight of methyl vinyl polysiloxane containing 0.6 mol% of vinyl groups and 30 mol% of hydrogen silane groups (hydrogen groups) 5% by weight, 5% by weight of 3-glycidoxypropyltrimethoxysilane, 10% by weight of polyethylene glycol butyl ether, and an aqueous dispersion containing a platinum catalyst.

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

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

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

Example 1:
A mixed raw material in which polyesters (A), (B), and (C) were mixed in proportions of 91%, 3%, and 6%, respectively, was used as a raw material for the outermost layer (surface layer), and polyesters (A) and (B) were each 97 %, 3% of the mixed raw material is used as an intermediate layer raw material, each is supplied to two extruders, melted at 285 ° C., and then on a cooling roll set at 40 ° C. Coextruded and cooled and solidified with a layer structure of layers (surface layer / intermediate layer / surface layer = 3: 44: 3 discharge amount) to obtain an unstretched sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then the coating liquid A1 shown in Table 1 below was applied to the thickness of the adhesive layer (dried) on one side of the film. (After) is applied to 15 nm, and coating liquid B3 shown in the following Table 2 is applied to the opposite surface so that the film thickness (after drying) of the functional layer is 30 nm, and guided to a tenter at 95 ° C. After drying for 10 seconds, the film was stretched 4.3 times in the transverse direction at 120 ° C., heat-treated at 230 ° C. for 10 seconds, relaxed 2% in the transverse direction, 50 μm in thickness, and Sa on the surface on the functional layer side. A 9 nm polyester film was obtained.

  When the finished polyester film was evaluated, the adhesive strength was 6 mN / cm, the adhesive properties were exhibited, and the blocking properties were good. The properties of this film are shown in Tables 3 and 4 below.

Examples 2-57:
In Example 1, except having changed a coating agent composition into the coating agent composition shown to Table 1 and 2, it manufactured like Example 1 and the polyester film was obtained. The completed polyester film had good adhesive force and blocking properties as shown in Tables 3 to 6 below.

Examples 58-73:
In Example 1, except having changed a coating agent composition into the coating agent composition shown to Table 1 and 2, it manufactured like Example 1 and the polyester film was obtained. As shown in Tables 7 and 8 below, the resulting polyester film had good adhesive strength, blocking characteristics and antistatic performance.

Examples 74-77:
In Example 1, the polyester composition of the surface layer opposite to the adhesive layer is a mixed raw material in which polyesters (A), (B), and (D) are mixed at a ratio of 72%, 3%, and 25%, respectively. The composition was co-extruded with a layer structure of three types and three layers (surface layer on the adhesive layer side / intermediate layer / surface layer on the opposite side of the adhesive layer = 3: 19: 3 discharge amount), and the coating agent composition was shown in Tables 1 and 2 A polyester film was obtained in the same manner as in Example 1 except that the composition was changed to the coating composition shown in FIG. Sa of the surface on the opposite side to the adhesion layer of the completed polyester film was 30 nm, and the adhesive force and the blocking property were good. The properties of this film are shown in Tables 9 and 10 below.

Examples 78, 79:
In Example 1, except having changed a coating agent composition into the coating agent composition shown to Table 1 and 2, it manufactured like Example 1 and the polyester film was obtained. As shown in Tables 11 and 12 below, the finished polyester film was inferior in blocking properties but had good adhesive strength.

Example 80
In Example 1, it manufactured like Example 1 except not having provided an adhesion layer and a functional layer, and obtained a polyester film. On the polyester film without the adhesive layer and the functional layer, coating solution A1 shown in Table 1 below was applied so that the thickness of the adhesive layer (after drying) was 130 nm, and dried at 100 ° C. for 60 seconds. A polyester film on which an adhesive layer by off-line coating was laminated was obtained. As shown in Tables 11 and 12, the finished polyester film had poor transfer properties and blocking properties, but had good adhesive strength.

Comparative Example 1:
In Example 1, it manufactured like Example 1 except not having provided an adhesion layer and a functional layer, and obtained a polyester film. When the completed polyester film was evaluated, as shown in Table 13 below, it was a film having no adhesive force.

Comparative Examples 2-4:
In Example 1, except having changed a coating agent composition into the coating agent composition shown to Table 1 and 2, it manufactured like Example 1 and the polyester film was obtained. The finished polyester film was a film having no adhesive strength as shown in Table 13.

Comparative Example 5:
On the polyester film without the pressure-sensitive adhesive layer and functional layer obtained in Comparative Example 1, the pressure-sensitive adhesive layer by off-line coating was applied so that the film thickness (after drying) of the coating liquid A1 shown in Table 1 below was 20 μm. A formed polyester film was obtained. When the polyester film was cut after bonding the pressure-sensitive adhesive layer side, the component of the pressure-sensitive adhesive layer that was not seen in the examples was seen to be contaminated by the pressure-sensitive adhesive component. The other characteristics were as shown in Tables 13 and 14.

  The film of the present invention has few fish eyes in applications such as surface protection films used for preventing scratches and preventing dirt adhesion during transportation, storage and processing of resin plates, metal plates, etc. It is excellent in mechanical strength and heat resistance, and can be suitably used for applications that require good adhesive properties.

Claims (6)

At least one surface of the polyester film has a pressure-sensitive adhesive layer having a thickness of 1 to 400 nm and an adhesive strength with a polymethyl methacrylate plate of 1 to 1000 mN / cm, and the pressure-sensitive adhesive layer is on the polyester film. A method for producing a laminated film , wherein the laminated film is formed by being stretched together with a polyester film. The method for producing a laminated film according to claim 1, wherein the adhesive layer is formed by coating. The manufacturing method of the laminated | multilayer film of Claim 1 or 2 which contains resin whose glass transition point is 0 degrees C or less in an adhesion layer. The manufacturing method of the laminated | multilayer film in any one of Claims 1-3 which has a functional layer in the polyester film surface on the opposite side to an adhesion layer. The method for producing a laminated film according to claim 4, wherein the functional layer contains a long-chain alkyl compound or a fluorine compound. The method for producing a laminated film according to claim 4, wherein the functional layer contains a wax.