JP6061995B1 - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To protect a surface used for various applications requiring good adhesive properties and handleability, for example, for preventing scratches and preventing adhesion of dirt during transport, storage and processing of resin plates, metal plates, etc. Provided is a laminated film that can be suitably used for applications such as a film. SOLUTION: One surface of a non-polyolefin film has an adhesive layer having an adhesive strength with a polymethyl methacrylate plate in the range of 1 to 1000 mN / cm, and the non-polyolefin film surface on the opposite side of the adhesive layer. And a layer containing particles, and multiplying the average particle diameter (nm) of the particles in the layer by the cube of the average particle diameter (nm) and the particle content (wt%) in the layer, nm), and a value obtained by dividing (nm) is 50,000 or more. [Selection figure] None

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 and handleability.

  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 tension during various processing such as bonding to an adherend. However, since polyolefin films generally have poor mechanical strength, they have the disadvantage of being unsuitable for high-tension processing due to increasing the processing speed in order to emphasize 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 it is used for various surface protection films and the like, has few fish eyes, is excellent in mechanical strength and heat resistance, and has good adhesive properties and handling. It is providing the laminated film which has property.

  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 has an adhesive layer with a film thickness of 10 nm to 1 μm on one surface of the non-polyolefin film, the adhesive strength with the polymethyl methacrylate plate is in the range of 1 to 1000 mN / cm, It has a layer containing particles on the non-polyolefin film side opposite to the adhesive layer, the cube of the average particle diameter (nm) of the particles in the layer, and the particle content (wt%) in the layer ) And dividing the film thickness (nm) of the layer to 50,000 or more, a laminated film characterized by having a polymethyl An adhesive layer having an adhesive strength with a methacrylate plate in the range of 1 to 1000 mN / cm is provided, and a layer containing particles is applied to the surface of the non-polyolefin film opposite to the adhesive layer by an in-line coating method. And obtained by multiplying the cube of the average particle size (nm) of the particles in the layer by the particle content (% by weight) in the layer and dividing the film thickness (nm) of the layer. The present invention resides in a method for producing a laminated film, wherein the value is 50,000 or more.

  According to the laminated film of the present invention, as various surface protective films, it is possible to provide a film having few fish eyes, excellent mechanical strength and heat resistance, and having good adhesive properties and handleability, and its industrial value. Is expensive.

  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, it is preferable to be superior in heat resistance and mechanical properties in order to develop into various applications, and polyester films, polycarbonate films, fluororesin films, and polyimide films are preferably used. In consideration of moldability and versatility, polyester films 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 mechanical strength and heat resistance (dimensional stability by heating) are high, and for that purpose, it is sometimes preferable that the amount of the copolyester 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 size exceeds 10 μm, there may be a concern about problems such as particle dropping off.

  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 such as dropping off of particles. When there are no particles or when there are few particles, the slipperiness may be insufficient. Therefore, it may be necessary to devise measures such as improving the slipperiness by putting particles in the adhesive layer.

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% can be mentioned. In the above-described stretching, a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges. 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. Considering the ease of forming the adhesive layer, it is preferable to form it 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 offline coating, thin film coating 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, the adhesive strength with the polymethylmethacrylate plate is in the range of 1 to 1000 mN / cm, the non-polyolefin film surface on the opposite side of the adhesive layer has a particle-containing layer, In the particle-containing layer, the value obtained by multiplying the cube of the average particle diameter (nm) by the particle content (% by weight) in the particle-containing layer and dividing the film thickness (nm) of the particle-containing layer is It is an essential requirement to be 50,000 or more.

  By setting the adhesive strength with the polymethylmethacrylate plate to be in the range of 1 to 1000 mN / cm, it is possible to achieve both adhesive performance and peeling performance for peeling after bonding, and various processes for performing an adhesion-peeling operation. It becomes possible to make an optimal film for use.

  The material for forming the adhesive layer is not particularly limited as a result of various studies, but by using a resin having a glass transition point of 0 ° C. or lower, an adhesive having a range of the above adhesive strength can be applied to a non-polyolefin film. We found that it is easy to impart characteristics. 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. An acrylic resin and a urethane resin are preferable, and a polyester resin and an acrylic resin are more preferable due to the strength of the adhesive property. 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 consideration of suitability for in-line coating, it is preferable to use an aqueous system, and for that purpose, a hydrophilic functional group, sulfonic acid, sulfonic acid metal salt, carboxylic acid, or carboxylic acid metal salt is contained in the polyester resin. preferable. 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 the polycarbonate-based 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, dicyclohexylmethane diamine, isoproterenol Piride emissions cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexa Alicyclic diamines, etc. and the like.

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

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

For example, dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid and the like are copolymerized with a diol used for polymerization of a urethane resin. Can do. The carboxyl group is preferably in the form of a salt neutralized with ammonia, amine, alkali metal, inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
In such a urethane resin, the carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by another crosslinking agent. Thereby, it is possible to further improve the durability, solvent resistance, water resistance, blocking resistance and the like of the obtained 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. As the crosslinking agent, conventionally known materials can be used, and examples thereof include epoxy compounds, melamine compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. 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 the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as α, α, α ′, α′-tetramethylxylylene diisocyanate. Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate Ne Alicyclic isocyanates such as bets are exemplified. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.

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

  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 order not to reduce the adhesive strength so much, it is preferable that the average particle size of the particles used is 3 times or less the thickness of the adhesive layer, more preferably 1.5 times or less, and even more preferably 1.0 times or less. Particularly preferably, the range is 0.8 times or less. In particular, when it is desired to exhibit the adhesive performance of the resin of the adhesive layer as it is, it may be preferable not to contain particles in the adhesive layer.

  In the present invention, the film surface opposite to the adhesive layer has a layer containing particles, and the average particle diameter (nm) of the particles in the particle-containing layer is the cube of the particle-containing layer. Value obtained by multiplying the content (% by weight) and dividing the film thickness (nm) of the particle-containing layer (that is, (the average particle diameter to the third power) × (particle content) / (particle-containing layer) Film thickness))) is 50,000 or more.

  As a result of various studies by the present inventors, it has been found that when the above-mentioned adhesive layer is formed and the film is held in a stacked state, blocking may occur depending on the adhesive force. When the solution was examined, the effect of reducing blocking was confirmed by providing the particle-containing layer. Furthermore, it has been found that the improvement effect is greater as the average particle size of the particles is larger, and the improvement effect is greater as the content of the particles in the layer is larger. From the results, it is considered that there is a relationship with the volume of the particles protruding from the particle-containing layer, and the value calculated by the above calculation formula has a correlation with the effect of blocking improvement, and is effective when it is more than 50,000. I found out that it would be improved. Furthermore, when the value of the above formula was 50,000 or more, not only blocking but also slipperiness could be improved, and a film having good handleability could be obtained. In the following, the above formula may be abbreviated as a particle volume formula.

  The value of the particle volume calculation formula must be 50,000 or more, preferably 100,000 or more, more preferably 500,000 or more, still more preferably 1,000,000 or more, and particularly preferably 5,000,000 or more. Is 100 million. When the value is too large, there is a concern that the particles may fall off, and thus the use in the above range is optimal.

  Conventionally known various particles can be used as the particles, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide. And inorganic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin. Among them, inorganic particles are preferable in that hardness can be imparted, and silica particles are more preferable in consideration of stability in the state of the coating liquid.

  The average particle size of the particles used in the particle-containing layer is preferably 10 to 2000 nm, more preferably 50 to 1000 nm, still more preferably 100 to 700 nm, and particularly preferably 200 to 500 nm. If the average particle size is too large, dropout of the particles is a concern. Conversely, if the average particle size is too small, the slipping property may not be sufficient when blocking cannot be reduced. By using in the said range, blocking with an adhesion layer can be reduced, Furthermore, slipperiness can improve and it can be set as a film which is easy to handle.

  In the present invention, it is preferable to contain a polymer in the particle-containing layer. The role of the polymer is mainly to keep the particles described above in the layer.

  A conventionally well-known polymer can be used as a polymer. Specific examples of the polymer include acrylic resin, polyester resin, urethane resin, polyvinyl (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches and the like. . Among these, from the viewpoint of improving the appearance, it is preferable to use a polyester resin, an acrylic resin, or a urethane resin. In view of compatibility with the polyester film of the base material, a polyester resin is more preferable. From the viewpoint that the light transmittance is increased and defect inspection by various defect inspection machines can be facilitated, acrylic resin and urethane resin are used. preferable.

  As a polyester resin, an acrylic resin, or a urethane resin, the above-described general polymer can be used. From the viewpoint of reducing blocking with the adhesive layer, the glass transition point is preferably higher than 0 ° C.

  In order to strengthen the film, it is preferable to use a crosslinking agent in combination. As the crosslinking agent, it is possible to use the same crosslinking agent as that used in the adhesive layer. Among them, melamine compounds, oxazoline compounds, epoxy compounds, isocyanate compounds, and carbodiimide compounds are preferable from the viewpoint of easily increasing the strength and being easy to use, and in particular, combining the melamine compounds from the viewpoint of increasing the strength. Is preferred. It has been found that the effect is particularly great when the average particle size is 200 nm or more and the particle content exceeds 10% by weight.

  The particle-containing layer may contain a release agent in order to further reduce blocking with the adhesive layer, and prevent defects due to adhesion of surrounding dust or the like due to film peeling or frictional charging. Therefore, it is possible to contain an antistatic agent.

  There is no restriction | limiting in particular as a mold release agent, It is possible to use a conventionally well-known mold release agent, For example, a long chain alkyl group containing compound, a fluorine compound, a silicone compound, wax etc. are mentioned. 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 slipperiness. 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 of the polyether group is usually in the range of 1-30, preferably in the range of 2-20, more preferably 3 from the viewpoint of improving the dispersibility in an aqueous solvent and the durability of the particle-containing layer. The range is -15. 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 particle-containing 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 0.000 in terms of a molar ratio, where the siloxane bond of the silicone is 1. It is in the range of 20%, more preferably in the range of 0.03 to 0.15%, particularly preferably in the range of 0.05 to 0.12%. By using within this range, the dispersibility in water, the durability of the coating layer, and the good performance of the release agent can be maintained.

  The molecular weight of the polyether group-containing silicone is preferably not so large in consideration of dispersibility in an aqueous solvent, and is preferably large in consideration of the durability and release performance of the particle-containing 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 time-dependent change and release performance of the particle-containing layer and the contamination of various processes, it is preferable that the low molecular component (number average molecular weight is 500 or less) of the silicone is as small as possible. The ratio of the whole compound 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 a condensation type silicone, vinyl groups (vinyl silane) bonded to silicon, hydrogen groups (hydrogen silane), if left in the particle-containing layer in an unreacted state, will cause changes in various performances over time, The content of the functional group in the silicone is preferably 0.1 mol% or less, and 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 the formation of the particle-containing layer, anionic dispersants and nonionic dispersants are used. 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. Useful synthetic hydrocarbon, for example, Fischer-Tropsch wax (aka service zone Ruwakkusu) include polyethylene wax, it is a low molecular weight polymer (specifically a polymer a number average molecular weight of 500 20000 to) In addition to this 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.

  The antistatic agent is not particularly limited, and a conventionally known antistatic agent can be used. However, since it has good heat resistance and moist heat resistance, it may be a polymer type antistatic agent. preferable. Examples of the polymer type antistatic agent include a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, 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 one of preferable modes that the particle-containing layer contains both the above-mentioned release agent and antistatic agent and has an antistatic release function.

  The particle-containing layer is preferably provided by coating in consideration of ease of formation, may be provided by in-line coating, or may employ offline coating. In-line coating is preferably used from the viewpoint of improving the coating cost due to the manufacturing cost and in-line heat treatment.

  Further, as long as it does not impair the gist of the present invention, an antifoaming agent, a coating property improving agent, a thickening agent, an organic lubricant, an antistatic agent, and an ultraviolet absorber are optionally formed for forming the adhesive layer and the particle-containing layer. In addition, an antioxidant, a foaming agent, a dye, a pigment, 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.

  As a ratio in the particle-containing layer constituting the laminated film in the present invention, the particles are preferably 5% by weight or more, more preferably 8 to 70% by weight, still more preferably 10 to 50% by weight, and particularly preferably 15 to 40%. It is in the range of wt%. When the content is less than 5% by weight, the reduction of blocking with the adhesive layer may not be sufficient, and the use within the above range facilitates the reduction of blocking with the adhesive layer and the improvement of slipperiness.

  As a ratio in the particle-containing layer constituting the laminated film in the present invention, the polymer is preferably in the range of 15 to 80% by weight, more preferably 30 to 70% by weight. By using it in the above range, it is effective in preventing a good appearance and particles from falling off.

  As a ratio in the particle | grain content layer which comprises the laminated | multilayer film in this invention, the component derived from a crosslinking agent becomes like this. Preferably it is the range of 5-70 weight%, More preferably, it is the range of 10-50 weight%. By using it in the above range, a good appearance and a strong layer can be obtained. In particular, when it is desired to strengthen the particle-containing layer, it is preferable to use a melamine compound in combination, and a preferable range thereof is 3 to 50% by weight, more preferably 5 to 40% by weight.

  Analysis of components in the adhesive layer and the particle-containing layer can be performed by analysis of TOF-SIMS, ESCA, fluorescent X-ray, IR, and the like.

  Regarding the formation of the adhesive layer and the particle-containing layer, the above-mentioned series of compounds is used as a solution or solvent dispersion, and the solution is adjusted on the film with a solid content of about 0.1 to 80% by weight as a guide. 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 depends on the material used for the pressure-sensitive adhesive layer. In order to improve the appearance of the layer, the range is 10 μm or less, preferably 1 nm to 4 μm, more preferably 10 nm to 1 μm, still more preferably 20 to 500 nm, and particularly preferably 40 to 400 nm. A general adhesive layer has a thickness of several tens of μm, but in such a case, for example, when used for manufacturing a polarizing plate, the adhesive film is used as a polarizing plate, a retardation plate, a viewing angle expansion plate, and the like. When sticking to the adherend and cutting, the sticking out of the pressure-sensitive adhesive layer may occur remarkably. However, the protrusion can be minimized by adjusting the film thickness within the above-mentioned range. This effect becomes better as the adhesive layer is thinner. In addition, the thinner the adhesive layer is, the smaller the absolute amount of the adhesive layer present on the film is, and the more effective the adhesive paste component is transferred to the adherend and the reduction in adhesive residue. Furthermore, it can be seen that by setting the film thickness in the above-mentioned range, it is possible to achieve an appropriate adhesive strength that is not too strong. For example, for polarizing plate manufacturing processes, both adhesive performance and peeling performance that peels after bonding are achieved. When used in applications where it is necessary to achieve this, the adhesive-peeling operation can be easily performed, and an optimum film can be obtained. The thinner the film is, the more effective it is for blocking properties. When forming an adhesive layer by in-line coating, it is preferable because it is easy to manufacture. Since it may disappear, use in the above-mentioned suitable range according to a use is preferable.

  The film thickness of the particle-containing layer depends on the adhesive strength of the pressure-sensitive adhesive layer and cannot be generally specified, but is preferably 1 to 3000 nm, more preferably 10 nm to 1000 nm, still more preferably 20 to 500 nm, particularly preferably. It is in the range of 20 to 200 nm. By using the film thickness of the particle-containing layer within the above range, it becomes easy to improve the blocking characteristics, improve the slipperiness, and obtain a good appearance.

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

  In the present invention, the drying and curing conditions for forming the adhesive layer 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. , Preferably it is 70-150 degreeC, More preferably, it is 80-130 degreeC, More preferably, it is the range of 90-120 degreeC. The drying time is generally 3 to 200 seconds, preferably 5 to 120 seconds. 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 a friction coefficient that serves as an index of the slipperiness of the laminated film of the present invention, the static friction coefficient between the side surface of the pressure-sensitive adhesive layer and the side surface of the particle-containing layer is preferably 1.0 or less, more preferably 0.8 or less, and still more preferably 0.8. It is 6 or less, particularly preferably 0.5 or less, and a preferred lower limit is 0.1. When the coefficient of friction is within the above range, the film has good slipperiness and is effective in handling and preventing scratches.

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

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

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

(3) Method for measuring film thickness of adhesive layer and particle-containing layer The surface of the adhesive layer or particle-containing 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).

(4) 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.

(5) 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.

(6-1) 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), and brought to room temperature. 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.

(6-2) Adhesive strength evaluation method (adhesive strength 2)
Evaluation was performed in the same manner as in (6-1) except that the adhesive strength was evaluated using a polycarbonate plate (thickness 1 mm) instead of the polymethyl methacrylate plate of (6-1).

(6-3) Adhesive strength evaluation method (adhesive strength 3)
(6-1) except that the adhesive strength was evaluated using the polyester film surface (thickness: 38 μm) without an adhesive layer obtained in Comparative Example 1 described later, instead of the polymethyl methacrylate plate (6-1). ) And the evaluation was performed in the same manner.

(7) 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 ×.

(8) Adhesive residue (transfer properties) evaluation method of the adhesive layer In the above evaluation method (7), the adhesive film was observed after peeling off the adhered film, and there was no adhesive residue (adhesion trace of the adhesive layer). In the case where there is an adhesive residue, x was given.

(9) Measuring method of blocking property The adhesive layer side of one A4 size laminated film and the particle-containing layer side of one A4 size laminated film are placed on a desk and blocked with a thumb from above. The (sticking) characteristics were evaluated. 5 points when blocking property is not seen even if pressed firmly with finger, 4 points when blocking property cannot be kept on the film, but 4 points when strongly pressing with finger, but strong with finger By pressing, the film sticks, and even if you have only the film with the adhesive layer, you can keep the stuck state, but if it peels within 3 seconds, the film sticks by pressing firmly with 3 fingers, Even if you have only the film with the adhesive layer, there are two points to keep the state of sticking, the film sticks just by pressing lightly with your finger, and even if you have only the film with the adhesive layer The case where it was able to hold the state and it was judged that blocking was bad was made 1 point. Considering actual use, 5 points are very preferable, 4 points are preferable, 3 points or more are in a range where there is no big trouble in actual use, and 2 points or less are unsuitable for actual use.

(10) Method of measuring coefficient of friction A film is pasted on a smooth glass plate having a width of 10 mm and a length of 100 mm with the particle-containing layer side as the upper surface, and a film cut into a width of 18 mm and a length of 120 mm is formed on the adhesive layer. With the side as the bottom surface, press against a metal pin with a diameter of 8 mm, slide the metal pin in the longitudinal direction of the glass plate at a load of 30 g, 40 mm / min, and measure the frictional force. The friction coefficient was evaluated. The measurement was performed in an atmosphere of room temperature 23 ° C. and humidity 50% RH. Moreover, it was described as "-" when the slipperiness was poor and measurement was not successful.

(11) Method for evaluating strength of particle-containing layer (strength 1)
The surface of the particle-containing layer was rubbed three times with the finger pad around which the ERILE (registered trademark) Pro Wipe Soft Micro Wiper S220 manufactured by Daio Paper Co., Ltd. was observed, and the surface was observed. The case where the scraped area of the layer was less than 10% was evaluated as ◯, the case where it was 10% or more and less than 50% was evaluated as Δ, and the case where it was 50% or more was evaluated as ×.

(12) Strength evaluation method for particle-containing layer (strength 2)
When the surface of the particle-containing layer was rubbed with the finger pad, no peeling of the layer was observed, and x was a peeling of the layer. The evaluation is weaker than the strength 1 of (11), and when peeling is observed in this evaluation, the strength is too weak to be practically suitable.

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.

Examples of compounds constituting the adhesive layer and the particle-containing 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%)

・ 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: (IIIA)
Consisting 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)
-Urethane resin: (IIIB)
Water of polyester urethane resin formed from isophorone diisocyanate unit: terephthalic acid unit: isophthalic acid unit: ethylene glycol unit: diethylene glycol unit: dimethylolpropanoic acid unit = 12: 19: 18: 21: 25: 5 (mol%) Dispersion.

・ 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.)

-Particles: (VA) Silica particles with an average particle size of 25 nm-Particles: (VB) Silica particles with an average particle size of 45 nm-Particles: (VC) Silica particles with an average particle size of 70 nm-Particles: (VD) Silica particles / particles: (VE) Silica particles / particles with an average particle diameter of 150 nm: (VF) Silica particles / particles with an average particle diameter of 200 nm: (VG) Silica particles / particles with an average particle diameter of 300 nm: (VH) Average particle diameter 450nm silica particles

・ 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.

・ Wax: (VIB)
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.

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: 32: 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. And the coating liquid B1 shown in Table 2 below is applied on the opposite side so that the film thickness (after drying) of the particle-containing layer is 60 nm and guided to a tenter at 95 ° C. After being dried 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, and then relaxed 2% in the transverse direction to obtain a polyester film having a thickness of 38 μm.

  When the completed polyester film was evaluated, the adhesive strength with the polymethylmethacrylate plate was 10 mN / cm, and good adhesive properties were exhibited, and the blocking properties and the coefficient of friction were good. The properties of this film are shown in Tables 3 and 4 below.

Examples 2-125:
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 3 to 10 below, the finished polyester film had good adhesive strength, blocking characteristics and coefficient of friction.

Example 126:
A polyester film was obtained in the same manner as in Example 1 except that the adhesive layer was not provided in Example 1 and the coating composition was changed to the coating composition shown in Table 2. On this polyester film without the adhesive layer (on the side opposite to the particle-containing layer), coating solution A1 shown in Table 1 below was applied so that the thickness (after drying) of the adhesive layer was 100 nm, and 100 ° C. Was dried for 60 seconds to obtain a polyester film laminated with an adhesive layer by off-line coating. As shown in Table 9, the finished polyester film had poor transfer properties but good adhesive strength.

Example 127:
A polyester film was obtained in the same manner as in Example 1 except that the particle-containing layer was not provided. On the polyester film without the particle-containing layer (on the side opposite to the adhesive layer), the coating liquid B3 shown in Table 1 below was applied so that the film thickness (after drying) of the particle-containing layer was 60 nm. Drying was performed at 60 ° C. for 60 seconds to obtain a polyester film on which a particle-containing layer by off-line coating was laminated. As shown in Tables 9 and 10, the finished polyester film had poor particle-containing layer strength but good adhesive strength.

Comparative Example 1:
In Example 1, it manufactured like Example 1 except not having provided an adhesion layer and a particle content layer, and obtained a polyester film. When the completed polyester film was evaluated, as shown in Table 11, it was a film having no adhesive strength.

Comparative Examples 2-6:
In Example 1, except having changed a coating agent composition into the coating agent composition shown to Table 1 and 2, it manufactured like Example 1 and the polyester film was obtained. As shown in Tables 11 and 12, the finished polyester film was found to have no adhesive force or a poor blocking property or friction coefficient.

Comparative Example 7:
On the polyester film without the adhesive layer and particle-containing layer obtained in Comparative Example 1, the coating liquid A1 shown in Table 1 below was applied at 100 ° C. for 120 seconds so that the thickness (after drying) of the adhesive layer was 20 μm. Was dried to obtain a polyester film with an adhesive layer formed by off-line coating. 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. Further, the adhesive strength exceeded 1000 mN / cm, and measurement was not successful. The other characteristics were as shown in Tables 11 and 12.

  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 requiring good adhesive properties and handleability.

Claims (4)

One surface of the non-polyolefin film has an adhesive layer with a film thickness of 10 nm to 1 μm that has an adhesive strength with a polymethyl methacrylate plate of 1 to 1000 mN / cm, and is opposite to the adhesive layer. Having a layer containing particles on the polyolefin film surface, multiplying the cube of the average particle size (nm) of the particles in the layer by the particle content (wt%) in the layer, the layer A film obtained by dividing the film thickness (nm) of the film is 50,000 or more. The laminated film according to claim 1, wherein the adhesive layer contains a polyester resin having a glass transition point of 0 ° C. or less. 2. The laminated film according to claim 1, wherein the adhesive layer contains an acrylic resin in which the content of the monomer having a glass transition point of the homopolymer of 0 ° C. or less is 45% by weight or more with respect to the entire acrylic resin. An adhesive layer having an adhesive strength with a polymethyl methacrylate plate in the range of 1 to 1000 mN / cm is provided on one surface of the non-polyolefin film, and particles are contained on the non-polyolefin film surface opposite to the adhesive layer. A layer to be coated by an in-line coating method, multiplied by the cube of the average particle size (nm) of the particles in the layer and the particle content (% by weight) in the layer, A method for producing a laminated film, wherein a value obtained by dividing the thickness (nm) is 50,000 or more.