Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes

Definitions

• the present invention relates to a coated film, and particularly to a coated film having excellent adhesion to a functional layer laminated on the coated film.
• films are widely used due to their excellent properties, they have the drawback of poor adhesion depending on the application.
• printing ink (cellophane printing ink, chlorinated PP ink, UV curable ink, magnetic ink, etc.), thermal transfer ink, magnetic paint, adhesive (lamination adhesive, wood bonding adhesive, etc.), vapor deposited Adhesion to metals and inorganic substances (aluminum, silver, gold, ITO, silicon oxide, aluminum oxide, etc.), mold release agent, ink image-receiving layer, gelatin, polyvinyl alcohol, polyvinyl acetal, cellulose acetate, cellulose butylacetate, methylcellulose, carboxymethylcellulose, etc. Inferior.
• Patent Documents 1 and 2 As a method for improving the adhesiveness of the film, there are a method of treating the film with a solvent, a method of corona discharge treatment and plasma treatment, etc. (Patent Documents 1 and 2). The effect of improving the adhesion with the functional layer is insufficient, and a method of laminating an adhesive coating layer on the film by coating treatment has also been proposed, but still in the type of functional layer provided on the coating layer The case where adhesiveness was inadequate was seen (patent document 3).
• the present invention has been made in view of the above circumstances, and the problem to be solved is to provide a coated film having excellent adhesion to a functional layer laminated on the coated film.
• the gist of the present invention is a coating film characterized by having a coating layer formed from a coating solution containing a composite resin composed of a resin containing a (meth) acryloyl group and a urethane resin on at least one side of the film.
• the coating film excellent in adhesiveness can be provided with respect to various functional layers, such as an ink layer containing an active energy ray hardening-type compound etc., and the industrial value is high. .
• polyester film, polycarbonate film, fluororesin film, polyimide film, triacetyl cellulose film, polyolefin film, polyacrylate film examples thereof include polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, ethylene vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, and nylon film.
• polyester film, polycarbonate film, fluororesin film, and polyimide film are preferably used, and polyester is further considered in view of transparency, moldability, and versatility. A film is used more suitably.
• the film constituting the coated film of 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.
• the polyester used as the polyester film may be a homopolyester or a copolyester.
• a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
• the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
• examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
• Typical polyester includes polyethylene terephthalate and the like.
• examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (for example, p-oxybenzoic acid).
• examples of the glycol component include one or more types such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like.
• the polymerization catalyst for polyester is not particularly limited, and conventionally known compounds can be used. Examples thereof include antimony compounds, titanium compounds, germanium compounds, manganese compounds, aluminum compounds, magnesium compounds, calcium compounds and the like. Among these, titanium compounds and germanium compounds are preferable because they have high catalytic activity, can be polymerized in a small amount, and the amount of metal remaining in the film is small, so that the brightness of the film becomes high. Furthermore, since a germanium compound is expensive, it is more preferable to use a titanium compound.
• the titanium element content is preferably 50 ppm or less, more preferably 1 to 20 ppm, 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.
• the phosphorus element content is preferably in the range of 1 to 300 ppm, more preferably 3 to 200 ppm, still more preferably 5 to 100 ppm, based on the amount of polyester to be melt-extruded. If the content of the phosphorus compound is too 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.
• polycarbonate film a conventionally known polycarbonate can be used, but a type containing a bisphenol A structure is particularly preferable.
• fluororesin film a conventionally known fluororesin can be used.
• fluororesin film a conventionally known fluororesin can be used.
• an ultraviolet absorber can be contained in order to improve the weather resistance of the film and prevent deterioration of the liquid crystal.
• the ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays and can withstand the heat applied in the film production process.
• an organic ultraviolet absorber there are an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency.
• an organic type ultraviolet absorber For example, a cyclic imino ester type, a benzotriazole type, a benzophenone type etc. are mentioned. From the viewpoint of durability, a cyclic imino ester type and a benzotriazole type are more preferable. It is also possible to use two or more ultraviolet absorbers in combination.
• particles can be blended mainly for the purpose of imparting slipperiness and preventing scratches in each process.
• the kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness.
• Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid.
• examples include inorganic particles such as magnesium, kaolin, aluminum oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin.
• precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed during the film production process.
• 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
• the average particle diameter of the particles is preferably 5 ⁇ m or less, more preferably in the range of 0.01 to 3 ⁇ m.
• the particle content in the film is preferably less than 5% by weight, more preferably in the range of 0.0003 to 3% by weight.
• the transparency of the film becomes high and the film becomes a good film, but the slipperiness may be insufficient. There are cases where improvement is required.
• the particle content in the film is preferably less than 5% by weight, more preferably in the range of 0.0003 to 3% by weight.
• the method for adding particles to the film is not particularly limited, and a conventionally known method can be adopted.
• it can be added at an arbitrary stage for producing a film constituting each layer, but it is preferably added after completion of esterification or transesterification.
• antioxidants In addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments and the like can be added to the film as necessary.
• the thickness of the film is not particularly limited as long as it can be formed into a film, but is usually 10 to 350 ⁇ m, more preferably 20 to 300 ⁇ m.
• the production example of the film will be specifically described, but is not limited to the following production example.
• the resin is melted, formed into a sheet, and stretched for the purpose of increasing the strength and the film is formed.
• the polyester film mentioned above is manufactured is introduced.
• a method of obtaining an unstretched film by cooling and solidifying a molten film extruded from a die with a cooling roll using pellets obtained by drying the polyester raw material is preferable.
• it is preferable to improve the adhesion between the film and the rotary cooling drum in order to improve the flatness of the film, it is preferable to improve the adhesion between the film and the rotary cooling drum, and an electrostatic application adhesion method or a liquid application adhesion method is preferably employed.
• the obtained unstretched film is stretched in the biaxial direction.
• the unstretched film is stretched in one direction by a roll or a tenter type stretching machine.
• the stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times.
• the film is stretched in the direction perpendicular to the first stretching direction.
• the stretching temperature is usually 70 to 170 ° C.
• the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. is there.
• heat treatment is performed at a temperature of 180 to 250 ° C. under tension or under relaxation within 30% to obtain a biaxially oriented film.
• 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.
• the simultaneous biaxial stretching method can be adopted for the production of the film.
• the simultaneous biaxial stretching method is a method in which the unstretched sheet is stretched and oriented simultaneously in the machine direction and the width direction in a state of temperature control usually at 70 to 120 ° C., preferably 80 to 110 ° C. Is 4 to 50 times in area magnification, preferably 7 to 35 times, and more preferably 10 to 25 times. Subsequently, heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film.
• a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.
• the coating layer it may be provided by in-line coating, which treats the film surface during the film formation process, or may be applied off-system on a once manufactured film. More preferably, it is formed by in-line coating.
• In-line coating is a method in which coating is performed in the film manufacturing process, and specifically, a method in which coating is performed at any stage from melt extrusion of a resin to heat fixing after stretching and winding up. 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.
• 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.
• a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, film formation and coating layer formation can be performed at the same time, so there is an advantage in manufacturing cost.
• the thickness of the coating layer can be changed by the stretching ratio. Compared to offline coating, thin film coating can be performed more easily. Further, by providing the coating layer on the film before stretching, the coating layer can be stretched together with the base film, whereby the coating 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 coating layer can be improved, and the coating layer and the base film can be more firmly adhered to each other. Furthermore, it can be set as a firm coating layer, and performances such as adhesion to various functional layers that can be formed on the coating layer and wet heat resistance can be improved.
• a coating layer formed from a coating solution containing a composite resin composed of a resin containing a (meth) acryloyl group and a urethane resin on at least one side of the film.
• the coating layer in the present invention is composed of various functional layers, in particular, a curable resin layer by active energy rays, and among them, usually a solventless active energy ray curable paint such as an active energy ray curable ink layer. It is optimal for improving the adhesiveness with the curable resin layer that is generally formed and it is difficult to ensure adhesiveness.
• the present inventors have found that higher adhesiveness can be expressed by using a composite resin composed of a resin containing a (meth) acryloyl group and a urethane resin.
• the presumed mechanism for developing high adhesiveness is that carbon-carbon double bonds due to (meth) acryloyl groups present in the coating layer and carbon-carbon doubles in the compound used for formation as a functional layer on the coating layer. It reacts with a bond to form a covalent bond.
• resins containing (meth) acryloyl groups but also composite resins with urethane resins, not only improved adhesion to functional layers, but also improved adhesion to the film as the substrate. It is speculated that the adhesiveness can be improved as a whole film.
• the resin containing a (meth) acryloyl group is not particularly limited as long as it is a resin containing a (meth) acryloyl group, and examples thereof include conventionally known resins such as an epoxy resin, a polyester resin, and an acrylic resin.
• an epoxy resin is preferable from the viewpoint of easy synthesis and introduction of many (meth) acryloyl groups.
• aromatic-containing epoxy resins are preferable from the viewpoint of excellent durability such as water resistance and solvent resistance, and among them, novolac type epoxy resins and bisphenol type epoxy resins are more preferable. In view of the introduction of acryloyl group, novolac type epoxy resin is more preferable.
• Examples of the novolak type epoxy resin include a cresol novolak type and a phenol novolak type
• examples of the bisphenol type epoxy resin include a bisphenol A type, a bisphenol F type, and a bisphenol S type.
• cresol novolac type epoxy resins and bisphenol A type epoxy resins are more preferable in consideration of versatility and resin flexibility.
• epoxy resin may be used by a single kind or may be used together with multiple types.
• a conventionally known urethane resin can be used as the resin containing the (meth) acryloyl group and the urethane resin for forming the composite resin.
• urethane resin is prepared by reaction of polyol and isocyanate.
• the polyol include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.
• polyester polyols are more preferable.
• polycarbonate polyols are more preferable.
• Polyester polyols include polycarboxylic acids (terephthalic acid, isophthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, etc.) or their acid anhydrides.
• polycarboxylic acids terephthalic acid, isophthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, etc.
• 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- , 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexane Diol, 1,9-nonanediol
• the polyvalent carboxylic acid is preferably an aromatic carboxylic acid, among them, considering the coating appearance and adhesiveness with the film substrate, Terephthalic acid and isophthalic acid are more preferable.
• Terephthalic acid and isophthalic acid are more preferable.
• those having a certain degree of flexibility are preferable, and it is optimal to use terephthalic acid and isophthalic acid in combination.
• the molar ratio of terephthalic acid: isophthalic acid used in combination is preferably 1 to 10: 1 to 10, more preferably 1 to 5: 1 to 5, further preferably 1 to 3: 1 to 3, particularly The range is preferably 1-2: 1-2.
• polyhydric alcohol those having a short molecular chain such as ethylene glycol, diethylene glycol and propylene glycol are preferable in order to increase the aromatic ratio of the carboxylic acid component, and further, considering the flexibility of the resin, diethylene glycol is contained. Those are preferred. In view of durability, coating appearance, and flexibility, it is more preferable to use ethylene glycol and diethylene glycol in combination.
• the molar ratio of ethylene glycol: diethylene glycol used in combination is preferably 1 to 10: 1 to 10, more preferably 1 to 5: 1 to 5, further preferably 1 to 3: 1 to 3, particularly preferably. Is in the range of 1-2: 1-2.
• Polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction.
• 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 Examples thereof include diol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane.
• 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.
• polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
• polyisocyanate compound used for obtaining the urethane resin examples include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′.
• aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′.
• -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 Isocyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination. Among these, in consideration of yellowing, it is preferable not to be an aromatic isocyanate.
• 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.
• chain extender having two hydroxyl groups examples 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.
• chain extender having two amino groups examples include aromatic diamines such as tolylenediamine, xylylenediamine, 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 decanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1, 3-Bisaminomethylcyclohexane Alicyclic diamines, and the like of.
• aromatic diamines
• Urethane resin may use a solvent as a medium, but preferably uses water as a medium.
• a forced emulsification type using an emulsifier 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.
• a self-emulsification type in which an ionic group is introduced into the structure of a urethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance, transparency, and adhesiveness of the resulting coating layer.
• examples of the ionic group to be introduced include various groups such as a carboxyl group, a sulfonic acid, a phosphoric acid, a phosphonic acid, a quaternary ammonium salt, and the carboxyl group is preferable.
• 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.
• 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.
• 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.
• a 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.
• another crosslinking agent it is possible to further improve the durability, solvent resistance, water resistance, blocking resistance, and the like of the obtained coating layer, as well as excellent stability in a liquid state before coating.
• a composite resin of a resin containing a (meth) acryloyl group and a urethane resin for example, it can be produced by mixing and stirring a resin containing a (meth) acryloyl group and a urethane resin in a solvent such as water. is there.
• the urethane resin is a type containing a hydrophilic group
• a resin alone containing a (meth) acryloyl group or It can be synthesized by mixing and stirring a resin containing a (meth) acryloyl group dispersed or dissolved in a solvent.
• the resin containing a (meth) acryloyl group has no or few hydrophilic groups, it becomes hydrophobic and is preferably mixed with a dispersion or solution of a urethane resin in a state of being dispersed or dissolved using an organic solvent.
• the resin containing the hydrophobic (meth) acryloyl group is the core. It becomes possible to obtain a composite resin emulsion having a core-shell structure in which a hydrophilic urethane resin becomes a shell.
• the core-shell structure is more preferable because it provides liquid stabilization and can be stably present even when mixed with other components and can be used widely.
• the core and the shell since the core and the shell are not bonded, when the emulsion is broken by solvent removal by drying after coating, the core and the shell can move freely separately.
• the (meth) acryloyl group in the portion can also appear on the surface of the coating layer, which can be advantageous for improving the adhesion with various functional layers that can be formed on the coating layer.
• the proportion of (meth) acryloyl groups in the composite resin is usually in the range of 1 to 50% by weight, preferably 3 to 30% by weight, more preferably 5 to 25% by weight, and still more preferably 8 to 20% by weight. By using in the said range, adhesiveness with the various functional layers formed on a coating layer can be improved.
• the weight ratio of (meth) acryloyl group-containing resin: urethane resin is usually in the range of 1 to 5: 1 to 5, preferably 1 to 3: 1 to 3, more preferably 1 to 2: 1 to 2. .
• the adhesiveness with the various functional layers formed on a coating layer and the adhesiveness with the polyester film which is a base material can be improved.
• the use within the above range is preferable from the viewpoint of synthesis.
• various polymers can be used in combination for improving the coating appearance, transparency and adhesion.
• polymer examples include urethane resin, polyester resin, acrylic resin, polyvinyl (polyvinyl alcohol, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, and starches. Etc.
• a crosslinking agent in combination in order to strengthen the coating film of the coating layer and to improve the sufficient adhesiveness and moist heat resistance properties with the active energy ray-curable ink layer or the like.
• crosslinking agent examples include oxazoline compounds, epoxy compounds, carbodiimide compounds, isocyanate compounds, melamine compounds, silane coupling compounds, hydrazide compounds, aziridine compounds, and the like.
• oxazoline compounds, epoxy compounds, carbodiimide compounds, and isocyanate compounds are preferable from the viewpoint of improving adhesiveness.
• the oxazoline compound is a compound having an oxazoline group in the molecule, and is particularly preferably a polymer containing an oxazoline group, 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, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
• the other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer.
• alkyl (meth) acrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, (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-alky
• the content of the oxazoline group contained in the oxazoline compound is usually 0.5 to 10 mmol / g, preferably 1 to 9 mmol / g, more preferably 3 to 8 mmol / g, still more preferably 4 to 6 mmol in terms of the amount of the oxazoline group. / G. Use within the above range is preferable because adhesion to various functional layers is improved.
• 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.
• polyepoxy compound examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
• polyglycidyl ether and diepoxy compound examples 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 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.
• a carbodiimide-based compound is a compound having a carbodiimide structure, and is a compound having one or more carbodiimide structures in the molecule.
• the polycarbodiimide having two or more in the molecule More preferred are system compounds.
• 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.
• 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.
• the isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate.
• isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-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
• Alicyclic isocyanates such as bets are exemplified.
• 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.
• isocyanates aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.
• the blocking agent 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.
• active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ⁇ -caprolactam and ⁇ -valerolactam , Amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, formaldehyde, acetal Examples include oxime compounds such as dooxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.
• the isocyanate compound may be used alone, or may be used as a mixture or a combination 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.
• the melamine compound is a compound having a melamine skeleton in the compound.
• 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.
• alcohol used for etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used.
• a melamine compound either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used.
• 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.
• cross-linking agents are used in a design that improves the performance of the coating layer by reacting in the drying process or film forming process. It can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or mixtures thereof exist in the finished coating layer.
• the average particle diameter of the particles is preferably in the range of 0.001 ⁇ m to 1.0 ⁇ m, more preferably 0.005 ⁇ m to 0.5 ⁇ m, and still more preferably 0.01 ⁇ m to 0.2 ⁇ m, from the viewpoint of film transparency.
• the particles to be used include inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles.
• silica particles are preferred from the viewpoint of dispersibility in the coating layer and transparency of the resulting coating film.
• an antifoaming agent a coating property improver, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, and an antioxidant are formed as necessary for forming the coating layer.
• Foaming agents, dyes, pigments and the like may be used in combination.
• the composite resin composed of a resin containing a (meth) acryloyl group and a urethane resin is usually 5% by weight or more, preferably 35% by weight or more, more preferably It is in the range of 45 to 99% by weight.
• the adhesiveness may not be sufficient depending on the functional layer provided on the coating layer.
• the coated film of the present invention it is also possible to provide a coating layer on the surface opposite to the surface on which the coating layer is provided.
• the opposite surface can be a coating layer according to the application, and conventionally known components can be used as its constituent components. Examples include urethane resins, polyester resins, acrylic resins and other polymers, oxazoline compounds, epoxy compounds, carbodiimide compounds, isocyanate compounds, melamine compounds and other crosslinking agents, and these materials may be used alone. A plurality of types may be used in combination.
• the coating layer (the same coating layer on both surfaces of a film) formed from the coating liquid containing the composite resin which consists of resin containing a (meth) acryloyl group and urethane resin as mentioned above may be sufficient.
• the analysis of the components in the coating layer can be performed, for example, by analysis of TOF-SIMS, ESCA, fluorescent X-rays and the like.
• the coating layer is provided by in-line coating
• the above-mentioned series of compounds is used as an aqueous solution or aqueous dispersion, and the coating solution adjusted to a solid content concentration of about 0.1 to 50% by weight as a guide is applied on the film. It is preferable to produce a coated film.
• a small amount of organic solvents may be contained in the coating liquid for the purpose of improving dispersibility in water, improving film-forming properties, and the like. Only one type of organic solvent may be used, or two or more types may be used as appropriate.
• the thickness of the coating layer is preferably 0.002 to 1.0 ⁇ m, more preferably 0.005 to 0.5 ⁇ m, still more preferably 0.005 to 0.3 ⁇ m, and particularly preferably 0.01 to 0.2 ⁇ m. It is a range. When the film thickness is out of the above range, the adhesiveness, coating appearance, and blocking characteristics may be deteriorated.
• a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating, or the like can be used.
• the drying and curing conditions for forming the coating layer on the film are not particularly limited.
• the coating layer is usually at 80 to 200 ° C. for 3 to 40 seconds, preferably 100.
• Heat treatment is preferably performed at about 180 ° C. for 3 to 40 seconds as a guide.
• the coating layer is provided by in-line coating, it is usually preferable to perform heat treatment at 70 to 280 ° C. for 3 to 200 seconds as a guide.
• heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as necessary.
• the film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
• a functional layer of a non-solvent type solvent content is usually 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, particularly preferably no solvent is contained), and an ink layer is particularly provided.
• solvent content is usually 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, particularly preferably no solvent is contained
• an ink layer is particularly provided.
• the coated film of the present invention is suitable.
• components in the functional layer are not particularly limited. Examples thereof include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
• inorganic or organic fine particles include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers, and leveling agents.
• solvent when the film is dried after film formation in the wet coating method, an arbitrary amount of solvent can be added.
• Adhesive evaluation method On the film surface, FD Carton ACE Indigo (offset printing ink manufactured by Toyo Ink Co., Ltd.), which is an active energy ray-curable ink, is printed with an RI tester, which is an offset printing device, and a metal halide lamp is used with an ultraviolet irradiation device. Ultraviolet rays were irradiated under the effect conditions of an output of 120 W / cm, a line speed of 15 m / min, and a gap between the lamp and the film of 150 mm to cure the resin to obtain a film on which an ink layer having a thickness of 3 ⁇ m was formed.
• a 10 ⁇ 10 cross-cut was made on the ink layer of the obtained film, and a 18 mm wide tape (Cello Tape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was applied on the ink layer.
• the peeled surface after peeling was observed, and if the peeled area was less than 5%, it was A, 5% to less than 20%, B, 20% to less than 50%, C, 50% or more to D (adhesion) Sex 1).
• the adhesiveness of FD Carton ACE Sumiro offset printing ink manufactured by Toyo Ink Co., Ltd.
• Adhesiveness 2 was evaluated (Adhesiveness 2). The evaluation criteria are the same.
• polyester (A) 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. 0.63 polyester (A) was obtained.
• 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 ⁇ m is added before melt polymerization. It was.
• Examples of compounds constituting the coating layer are as follows.
• isophorone diisocyanate terephthalic acid: isophthalic acid: ethylene glycol: diethylene glycol: dimethylol introduced with acryloyl group
• Example 2 In Example 1, except having changed a coating agent composition into the coating agent composition shown in Table 1, it manufactured like Example 1 and obtained the coating film. The obtained coated film was as shown in Table 2 and was an adhesive film.
• Example 1 In Example 1, it manufactured similarly to Example 1 except not providing a coating layer, and obtained the coating film. When the obtained coated film was evaluated, as shown in Table 2, the adhesion of the film was poor.
• Comparative Examples 2 to 5 In Example 1, except having changed a coating agent composition into the coating agent composition shown in Table 1, it manufactured like Example 1 and obtained the coating film. When the obtained coating film was evaluated, it was as shown in Table 2 and was poor in adhesiveness.
• the coated film of the present invention can be suitably used for applications that require various functional layers and good adhesive properties, such as magnetic recording media, packaging materials, building materials, and display applications.

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