JP4836524B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate having a thermoplastic resin as a base material.

  Since films and sheets such as polypropylene and polyethylene terephthalate have high transparency, they are suitably used in clear cases and clear boxes by assembling them and adhering them appropriately. Since these films and sheets have a high hydrophobicity on the surface of the substrate as it is and poor in adhesion and printability, the surface is usually treated with corona discharge to make it hydrophilic and improve wettability. Improves sex.

  Corona discharge treatment is a very effective surface treatment method because the surface can be modified without impairing the properties of the substrate, but the effect of treatment gradually disappears over time, and the surface state changes. It was necessary to pay attention to problems such as difficulty in printing and the need to select an adhesive and printing ink suitable for the surface condition at that time.

  On the other hand, the present applicants apply anti-fogging properties to the film surface by applying a coating solution containing a polyolefin resin and a silica-based inorganic colloid to the surface of the thermoplastic resin film, and also provide long-term printability and coating properties. Improved blocking resistance after work (Patent Document 1).

JP 2003-286472 A

  However, in the method described in Patent Document 1, there are problems that transparency, adhesiveness (particularly long-term performance), and scratch resistance (property to scratch the surface) are insufficient compared to corona treatment. there were.

  The present invention is intended to solve the above-described problems, and to provide a laminate having excellent transparency in which the scratch resistance of a coating film and the adhesiveness due to an adhesive are dramatically improved.

As a result of intensive studies, the present inventors have found that all the above problems can be solved by providing a thermoplastic substrate with a specific composition and a specific amount of a coating film.
That is, the gist of the present invention is as follows.
(1) A laminate in which a coating film of 0.001 to 0.3 g / m ² is laminated on a thermoplastic resin substrate, and as a constituent component of the coating film , a polyolefin resin or a mixture of a polyolefin resin and a polyurethane resin 100 parts by mass of the binder resin (A) made of any of the resins, 100 to 10,000 parts by mass of silica-based fine particles (B) having a number average particle diameter of 50 nm or less , and 100 parts by mass or less of the oxazoline group-containing compound (C) A laminate characterized by the following.
( 2 ) The laminate as described above, wherein the coating film further contains at least one selected from the group consisting of a wax, a silicone compound, a fatty acid amide compound, and a fatty acid metal salt compound.
( 3 ) An assembly formed from the laminate.
( 4 ) A clear case or clear box formed from the laminate.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in adhesiveness (especially adhesiveness after a long period of time) and scratch resistance, the laminated body which transparency improved compared with the conventional laminated body is obtained. This laminated body can be suitably used for an assembly such as a clear case or a clear box by bonding, and since it is difficult to be scratched, the product value and aesthetic appearance of the assembly are small.

  In addition, since the substrate adhesion of the coating film, the blocking resistance between the coated surfaces, and the slipperiness are maintained, the film can be wound and loaded with a roll.

  In addition, both adhesive and printability properties last for a long period of time, so it can be used for long-term storage and shipping.

  The present invention will be described in detail below.

In the present invention, the coating amount of the coating film is required to be 0.001~0.3g / ^{m 2,} preferably 0.003~0.2g / ^{m 2,} 0.005~0.1g / ^{m 2} is more preferable, 0.005 to 0.08 g / m ² is further preferable, and 0.005 to 0.06 g / m ² is particularly preferable. When the amount of lamination exceeds 0.3 g / m ² , the scratch resistance of the coating film is deteriorated, and transparency, substrate adhesion, and blocking resistance are lowered. If the stacking amount is less than 0.001 g / m ² , it is difficult to stack uniformly.

  Examples of the binder resin (A) used in the present invention include polyolefin resins, polyester resins, polyurethane resins, acrylic resins, vinyl resins, and the like, and one or more of these can be used. These binder resins can also be mixed and used. It is preferable from the viewpoint of adhesiveness that the binder resin is mainly composed of the same type of resin as the thermoplastic resin substrate described later. For example, when the substrate is a polyolefin resin such as polypropylene, a polyolefin resin is preferably used as the binder resin, and when the substrate is a polyester resin such as polyethylene terephthalate, a polyester resin is preferably used as the binder resin. Furthermore, from the viewpoint of improving slipperiness, a mixed system of polyolefin resin and polyurethane resin and a mixed system of polyester resin and polyurethane resin are more preferable.

  Examples of the polyolefin resin used as the binder resin (A) include alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, and the like. It can also be used. Among these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, and ethylene and propylene are particularly preferable. The content of the olefin component is preferably 50% by mass or more, and more preferably 70% by mass or more from the viewpoints of substrate adhesion and water resistance.

  Moreover, it is preferable that the polyolefin resin contains 0.1-25 mass% of unsaturated carboxylic acid components from the point of the water resistance of a coating film, or adhesiveness with a base material, and 0.5-15 mass% More preferably, 1-8 mass% is further more preferable, and 1-5 mass% is especially preferable. This component is introduced by unsaturated carboxylic acid or its anhydride. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc. And half esters and half amides of unsaturated dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. Moreover, the unsaturated carboxylic acid component should just be copolymerized in polyolefin resin, The form is not limited, For example, random copolymerization, block copolymerization, graft copolymerization etc. are mentioned.

  The polyolefin resin preferably contains a (meth) acrylic acid ester component from the viewpoint of improving adhesion to a substrate, particularly a polyolefin substrate such as polypropylene. The content of this component is preferably 0.5 to 40% by mass, and more preferably 10 to 25% by mass in order to have good adhesion to various thermoplastic resin film substrates. preferable.

  In the present invention, a polyolefin resin having a melt flow rate of 190 to 5000 g / 10 minutes, preferably 1 to 500 g / 10 minutes at 190 ° C. and a load of 2160 g, which is a measure of molecular weight, can be used.

  The method for synthesizing the polyolefin resin is not particularly limited, and is generally obtained by high-pressure radical copolymerization of a monomer constituting the polyolefin resin in the presence of a radical generator. Furthermore, the polyolefin resin may be chlorinated in the range of 5 to 40% by mass.

  The polyester resin as the binder resin (A) is composed of an acid component and an alcohol component. The polymerization method is not particularly limited, and may be appropriately performed by a conventional method.

  The acid component of the polyester resin includes terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, oxalic acid, succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hydrogenated Dimer acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, dimer acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2- Examples include cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-norbornene dicarboxylic acid and its anhydride, tetrahydrophthalic acid and its anhydride, etc. Among them, terephthalic acid and isophthalic acid are preferable. .

  A tribasic or higher polybasic acid may be used as the acid component, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, Examples include trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), 1,2,3,4-butanetetracarboxylic acid and the like.

  Examples of the alcohol component of the polyester resin include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, Neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol Examples thereof include ethylene glycol and dipropylene glycol. Further, glycols obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols (for example, 2,2-bis (4-hydroxyethoxyphenyl) propane), Furthermore, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can also be used as the alcohol component. Among these, 1,2-propanediol, neopentyl glycol, and ethylene glycol are preferable in terms of cost and ease of polymerization.

  As the alcohol component, a trifunctional or higher polyhydric alcohol may be used, and examples thereof include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

  Polyester resins include fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and ester-forming derivatives thereof, benzoic acid, and p-tert-butylbenzoic acid as necessary. , Cyclocarboxylic acid, 4-hydroxyphenyl stearic acid, etc., high boiling point monocarboxylic acid, stearyl alcohol, 2-phenoxyethanol, etc., high boiling point monoalcohol, ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxybenzoic acid, etc. The hydroxycarboxylic acid may be copolymerized.

  The weight average molecular weight of the polyester resin is preferably 4000 or more, more preferably 6000 or more, and particularly preferably 9000 or more. When the weight average molecular weight is less than 4000, the water resistance of the resin coating film and the adhesion to the substrate tend to be insufficient.

  The polyurethane resin as the binder resin (A) is a polymer containing a urethane bond in the main chain, and is obtained, for example, by a reaction between a polyol compound and a polyisocyanate compound.

  The polyol component constituting the polyurethane resin is not particularly limited. For example, water, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1 , 3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,3-hexane Low molecular weight glycols such as diol, diethylene glycol, triethylene glycol, and dipropylene glycol; low molecular weight polyols such as trimethylolpropane, glycerin, and pentaerythritol; and polyols having ethylene oxide and propylene oxide units. Le compounds, polyether diols, high molecular weight diols such as polyester diols, bisphenols such as bisphenol A, bisphenol F, dimer diol, and the like to the carboxyl group of the dimer acid was converted to hydroxyl groups.

  Further, as the polyisocyanate component, one or a mixture of two or more known aromatic, aliphatic and alicyclic known diisocyanates can be used. Specific examples of the diisocyanates include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, Examples thereof include lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and adducts, biurets, and isocyanurates. As the diisocyanate, trifunctional or higher functional polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate may be used.

  As acrylic resin and vinyl resin, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, styrene, substituted styrene, divinylbenzene, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl formate, acetic acid Examples thereof include resins obtained by radical polymerization of vinyl compounds such as vinyl, vinyl propionate, vinyl pivalate, vinyl versatate, and (meth) acrylonitrile.

  The binder resin preferably has an anionic group of 20 to 700 (equivalent / ton) from the viewpoint of improving the mixing property with the silica-based fine particles. More preferably, it is 70-530 (equivalent / ton). An anionic group is a functional group capable of forming a salt with a basic compound such as a carboxyl group, a sulfonic acid group, a sulfuric acid group, or a phosphoric acid group, preferably a carboxyl group or a sulfonic acid group, Most preferred.

  As the silica-based fine particles (B), colloidal silica is preferable. Colloidal silica is an ultrafine silica sol dispersed in water in a colloidal form. Colloidal silica may be surface-treated with metal ions such as colloidal aluminum phosphate or metaaluminate ion, or may be monodispersed, or the particles may be linked to a pearl necklace by special treatment, It may branch and proliferate, or may become an aggregate. The number average particle diameter of the silica-based fine particles (B) needs to be 50 nm or less. When the number average particle diameter exceeds 50 nm, it is difficult not only to form a thin coating film uniformly, but also the transparency and adhesion to the substrate when used as a coating film are lowered. In order to improve these performances, the number average particle diameter is more preferably 30 nm or less, and further preferably 20 nm or less. The volume average particle diameter is preferably 200 nm or less, more preferably 50 nm or less, and further preferably 20 nm or less.

  As commercially available colloidal silica, “Snowtex” series (Snowtex 20, 30, 40, C, N, O, S, 20L, OL, HS) manufactured by Nissan Chemical Industries, Ltd., “Mizukasil” series manufactured by Mizusawa Chemical, etc. There is.

  The amount of the silica-based fine particles (B) needs to be in the range of 100 to 10000 parts by mass with respect to 100 parts by mass of the binder resin (A), preferably 200 to 5000 parts by mass, and more preferably 400 to 3000 parts by mass. Preferably, 500-2000 mass parts is more preferable. When (B) is less than 100 parts by mass, the blocking resistance, the solvent resistance of the coating film, etc. tend to decrease, and when it exceeds 10,000 parts by mass, the adhesion to the substrate and the adhesiveness of the adhesive tend to decrease. There is.

  In order to further improve various coating film performances such as scratch resistance of the coating film and adhesiveness of the adhesive, it is preferable to add a crosslinking agent (C). The addition amount is preferably 100 parts by mass or less, more preferably 0.1 to 80 parts by mass, further preferably 5 to 80 parts by mass, and 10 to 70 parts by mass with respect to 100 parts by mass of the binder resin (A). Part is particularly preferred. When the addition amount of a crosslinking agent exceeds 100 mass parts, the adhesiveness with a base material and the adhesiveness by an adhesive agent may fall. As the crosslinking agent, there can be used a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal having a polyvalent coordination site, etc., of which an isocyanate compound, Melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. Moreover, you may use combining these crosslinking agents. Among these, an isocyanate compound and an oxazoline group-containing compound are preferable, and an oxazoline group-containing compound is more preferable because the coating film performance can be improved at a relatively low temperature.

  Furthermore, it is preferable to contain at least one selected from the group consisting of a wax, a silicone compound, a fatty acid amide compound, and a fatty acid metal salt compound as a coating film constituent component. By containing these, the slipperiness of a coating film improves and the performance of scratch resistance and slipperiness improves. As waxes, plant waxes such as candelilla wax, carnauba wax, rice wax, and wax, animal waxes such as shellac wax and lanolin wax, mineral waxes such as montan wax and ozokerite, petroleum waxes such as paraffin wax and microcrystalline wax Examples thereof include polyethylene wax and polypropylene wax. The silicone compound is a compound having a silicon-oxygen bond (siloxane bond) in the molecule and an organic group bonded to the side chain of the silicon atom, and examples thereof include an alkylmethoxysilane compound and an alkylethoxysilane compound. . Examples of the fatty acid amide compound include stearic acid amide, bis stearic acid amide, and oleic acid amide. Examples of the fatty acid metal salt compound include zinc stearate and magnesium stearate.

  Non-volatile compounds such as surfactants (cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers or amphoteric emulsifiers) and protective colloid compounds from the viewpoint of water resistance and adhesion to the substrate. Is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably 1 part by mass or less, and most preferably not added. This is because such a compound remains in the coating film even after drying, and may deteriorate the coating film performance such as adhesion over time.

  Examples of the thermoplastic resin used for the base material of the laminate of the present invention include polyolefin resins such as polyethylene, polypropylene, ionomer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 46. Polyamide resins such as polyethylene terephthalate (hereinafter referred to as PET), A-PET, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polylactic acid and other polyester resins, polystyrene resin , Polyimide resin, polycarbonate resin, polyarylate resin, or a mixture thereof. Among these, a thermoplastic resin suitable for use as a clear case is a polyolefin resin or a polyester resin.

  The form of a thermoplastic resin base material is not specifically limited, A molded object, a film, a sheet | seat, a synthetic paper etc. are mentioned. From the viewpoint of sufficiently exerting the coating film performance, it is preferable to use a film or sheet (hereinafter, film or the like) having a haze of 10% or less, more preferably 5% or less, as the thermoplastic resin substrate. The film or the like may be a single substance or a laminate of a plurality of films or the like.

  The thickness of a film etc. is not specifically limited, Usually, it may be in the range of 1 to 10000 μm, and more preferably 10 to 1000 μm. From the viewpoint of improving the coating properties of the coating liquid, the surface of the film or the like is preferably subjected to corona discharge treatment or plasma treatment.

  Moreover, in the laminated body of this invention, the coating film should just be laminated | stacked on the at least single side | surface of the said thermoplastic resin base material.

  Examples of the method of laminating a coating film on a substrate include a method of applying and drying a coating solution obtained by dissolving or dispersing a coating film constituent component in a liquid medium on the substrate. Among these, from the viewpoint of reducing volatile organic compounds (VOC) (environmental aspect) and the stability of the coating liquid, the liquid medium is preferably an aqueous medium. The aqueous medium is water or a mixed solvent of water and a water-soluble organic solvent. As the coating liquid, it is most preferable to use a so-called aqueous dispersion in which a coating film component is dispersed or dissolved in an aqueous medium.

  As an organic solvent used as an aqueous medium, those having a solubility in water at 20 ° C. of 50 g / L or more are preferable, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, cyclohexanone, tetrahydrofuran, ethylene glycol mono Butyl ether is mentioned, and methanol, ethanol, n-propanol, and isopropanol are particularly preferable from the viewpoint of storage stability of the liquid and drying property.

  The organic solvent used as the aqueous medium may be a basic compound. As the basic compound to be used, ammonia or an organic amine compound that volatilizes at the time of coating film formation is preferable from the viewpoint of water resistance of the coating film, and among them, an organic amine compound having a boiling point of 30 to 250 ° C. is preferable, and more preferably 50 to It is an organic amine compound at 200 ° C. When the boiling point is less than 30 ° C., handling becomes difficult. When the boiling point exceeds 250 ° C., it becomes difficult to disperse the organic amine compound from the resin coating film by drying. The anionic group of the binder resin described above is preferably neutralized with these basic compounds. Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, morpholine, N-methylmorpholine and the like.

  The coating liquid can be obtained by mixing an aqueous dispersion of the binder resin (A) and a sol of silica-based fine particles (B) at a predetermined ratio. When the crosslinking agent component (C) is used, a crosslinking agent or an aqueous dispersion thereof is further mixed.

  The number average particle diameter of the binder resin (A) in the aqueous dispersion is preferably 200 nm or less, more preferably 150 nm or less, from the viewpoint that a thin coating film can be uniformly formed and the transparency and adhesion of the coating film are improved. More preferably, it is preferably 100 nm or less. The volume average particle diameter is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less.

  The number average particle diameter and volume average particle diameter of the binder resin (A) and the silica-based fine particles (B) are measured by a dynamic light scattering method.

  The method for obtaining the aqueous dispersion of the binder resin (A) is not particularly limited, and a commercially available one may be used, and a method of obtaining the resin and dispersing it or polymerizing the monomer in an aqueous medium. Obtainable.

  Commercially available aqueous dispersions of water-based resins include polyurethane resin, Adeka Bon titer series manufactured by Asahi Denka Kogyo Co., Ltd., Takelac series manufactured by Mitsui Takeda Co., Ltd., Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and polyester resin Unitika's Eritel series (KA, KT series), polyolefin resin, Arrow Base series made by Unitika, Sumixen series made by Sumitomo Seika, Chemipearl series made by Mitsui Chemicals, Toho Chemical Co., Ltd. High-tech series. Examples of the acrylic resin include Almatex series, Bonron series manufactured by Mitsui Chemicals, Neokrill series manufactured by Enomoto Kasei Co., Ltd., and Jurimer series manufactured by Nippon Pure Chemicals.

  Coating methods include, for example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. on the surface of various substrate films, etc. A uniform coating film can be formed in close contact with the surface of various substrate films and the like by subjecting it to uniform coating, setting it near room temperature as required, and subjecting it to a drying treatment. As a heating device at this time, a normal hot air circulation type oven, an infrared heater, or the like may be used. In addition, the heating temperature and the heating time are appropriately selected depending on the properties of the substrate film that is the object to be coated. However, in consideration of economy, the heating temperature is 10 ° C. to (such as a film). (Melting point of resin) is preferable, 20 ° C to (melting point of resin such as film) is more preferable, 30 ° C to (melting point of resin such as film) is particularly preferable, and heating time is preferably 1 second to 20 minutes, 5 seconds to 15 minutes are more preferable, and 10 seconds to 10 minutes are particularly preferable.

  The laminated body thus obtained is used for applications such as assemblies such as clear cases and clear boxes; packaging materials; magnetic recording materials such as magnetic tapes and magnetic disks; electronic materials; graphic films; It is particularly suitable for assemblies such as clear cases and clear boxes. As a method for forming an assembly, for example, a laminated body in the form of a film or sheet is creased into a box shape and formed into a box shape using a cyanoacrylate or hot melt adhesive. Since the laminate of the present invention is highly transparent, the contents can be seen through when a product or the like is placed in a box. Note that printing can also be performed on a part of the laminate.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. As the base film, P P film (thickness 300 [mu] m, Idemitsu Unitech Co. Super Pure Ray) (hereinafter, SP) was used. Various evaluations were carried out after being applied to the film and then allowed to stand for 1 day in an atmosphere at a temperature of 23 ° C. and a humidity of 65%.

(1) Coating amount (coating amount)
A predetermined amount of the coating solution was applied to a substrate whose area and mass were measured in advance, and dried at 60 ° C. for 2 minutes. The mass of the obtained laminate was measured, and the coating amount was determined by subtracting the mass of the base material before coating. The coating amount per unit area (g / m ² ) was calculated from the coating amount and the coating area.

(2) Haze Based on JIS-K7361-1, the haze measurement of the coating film (laminated body) was performed using the turbidimeter (Nippon Denshoku Industries Co., Ltd. make, NDH2000). However, this evaluation value is, the turbidity of the base film used in Examples: contains (S P 3.1%).

(3) Solvent resistance The coating film surface of the coating film was rubbed 10 times with a cloth soaked with n-heptane, and the state of the coating film surface was evaluated as follows.
○: No change △: Slight whitening ×: Whitening

(4) Adhesiveness Adhesiveness between the base film and the coating film was evaluated by tape peeling (cross cut test) by the cross-cut method described in JIS K5400. The coating layer was cut into 100 sections by cross-cutting, and the number of sections of the coating film remaining after the tape peeling was evaluated according to the following criteria.

○: Residual for 100 sections Δ: Residual for 90 to 100 sections ×: Residual for 0 to 90 sections (5) Scratch resistance Coating with pencil B (manufactured by Mitsubishi Uni) according to the pencil hardness measurement method described in JIS K5400. The membrane was scratched 5 times and evaluated as follows.

○: No scratches (no scratches)
△: Scratched once ×: Scratched twice or more

(6) Blocking resistance In a state where the coating film surfaces of the coating film are overlapped with each other, a load of 200 g / cm ² is applied, and after leaving in a 40 ° C. atmosphere for 24 hours, peeling is performed. Judging from the state of the coating film surface (whether or not the peeling mark of the other coating film surface remains on one coating film surface), it was determined according to the following criteria.
○: Peel off when touched lightly. No peeling marks remain.
(Triangle | delta): It peels when a film is pulled. No peeling marks remain.
X: The film peels off, but a peeling mark remains.

(7) Sliding property The film was moved up and down in a state where the coating film surfaces of the coating film were overlapped, and the sliding condition was evaluated as follows.
○: No resistance △: Slight resistance ×: Non-slip

(8) Adhesiveness of adhesive A cyanoacrylate adhesive (trade name “Aron Alpha” for plastics, manufactured by Konishi Co., Ltd.) was used as the adhesive. The coating film surface of the coating film was lightly painted with a cotton swab dipped in a primer. Ten minutes later, an adhesive was applied, the coating surfaces were bonded to each other, and peeled by hand after 24 hours in an atmosphere of a temperature of 23 ° C. and a humidity of 65%.
○: The base film was destroyed.
X: The base film did not destroy the material.

(9) Printability (ink wettability)
UV curable ink (manufactured by T & K TOKA, UV STP) is diluted so that the viscosity is 50-60 mPa · S (25 ° C.), and the wettability of ink when gravure printing is performed on the coated film (repellency Degree).
○: No ink repelling ×: Ink repelling

(10) Physical properties after long-term storage The coated film was allowed to stand at 40 ° C. for 1 month, and then subjected to tests (8) and (9).

(11) Particle size The number average particle size and volume average particle size of the binder resin (A) and the silica-based fine particles (B) are dynamically measured using a Nikkiso Microtrac particle size distribution analyzer UPA150 (Model No. 9340). Measured by light scattering method.

<< Aqueous dispersion of binder resin >>

(Polyolefin resin aqueous dispersion)
As the polyolefin resin aqueous dispersion, a commercially available dispersion (manufactured by Unitika, Arrow Base SB-1200) (hereinafter referred to as O-1) was used. The number average particle diameter and the volume average particle diameter were 70 nm and 95 nm, respectively.

(Polyurethane resin aqueous dispersion)
As the polyurethane resin aqueous dispersion, a commercially available dispersion (Mitsui Takeda, Takelac W-6010) (hereinafter referred to as U-1) was used. Both the number average particle diameter and the volume average particle diameter were 100 nm or less.

<Preparation of coating solution>

(Preparation of coating liquid A- 1 )
Colloidal silica ST-O, polyolefin resin aqueous dispersion O-1, oxazoline group-containing compound (Nippon Shokubai Co., Ltd., Epocros K-2030E) (hereinafter referred to as EP) as silica-based fine particles, 100 mass of polyolefin resin in terms of solid content After mixing so as to be 800 parts by mass of silica-based fine particles and 40 parts by mass of EP with respect to parts, water / isopropanol is diluted 10 times with a mixed solvent of 30/70 (mass ratio) to obtain coating liquid A-2 Obtained.

(Preparation of coating liquid A- 2 )
Colloidal silica ST-O, polyolefin resin aqueous dispersion O-1, and EP are mixed as silica-based fine particles so that the amount of silica-based fine particles is 5000 parts by mass and EP is 20 parts by mass with respect to 100 parts by mass of polyolefin resin. Then, it was diluted 10 times with a mixed solvent of water / isopropanol 30/70 (mass ratio) to obtain a coating liquid A-3.

(Preparation of coating liquid A- 3 )
The aqueous polyolefin resin dispersion (O-1) and the aqueous polyurethane resin dispersion (U-1) were mixed so that O-1 and U-1 had a solid content mass ratio of 80/20. Subsequently, after mixing colloidal silica ST-O and EP with the mixture of the said aqueous dispersion so that it may become 800 mass parts of silica-type microparticles and 40 mass parts of EP with respect to 100 mass parts of binder resin in conversion of solid content, / Isopropanol was diluted 10 times with a mixed solvent of 30/70 (mass ratio) to obtain a coating liquid A-4.

(Preparation of coating liquid A- 4 )
Colloidal silica ST-O, polyolefin resin aqueous dispersion O-1, EP and an aqueous dispersion of fatty acid amide compound (manufactured by Chukyo Yushi Co., Ltd., Himicron L-271, stearamide) (hereinafter referred to as HM) as silica-based fine particles In addition, after mixing so as to be 800 parts by mass of silica-based fine particles, 40 parts by mass of EP, and 5 parts by mass of HM with respect to 100 parts by mass of polyolefin resin in terms of solid content, water / isopropanol is a mixed solvent of 30/70 (mass ratio). It diluted 10 times and obtained coating liquid A-5.

Examples 1 to 4
After coating the coating liquid A-1 on the corona surface of the SP so that the coating amount (coating amount) after drying is 0.05 g / m ² , the laminate is dried at 60 ° C. for 2 minutes. (Coating film) was obtained (Example 1).
Lamination was carried out in the same manner as in Example 1 except that A-2 (Example 2 ), A-3 (Example 3 ) or A-4 (Example 4 ) was used instead of the coating liquid A-1. A body (coated film) was obtained.

Comparative Example 1
SP which does not apply a coating liquid was used.

Comparative Example 2
In the preparation of the coating liquid A- 1 , a coating liquid H- 1 was prepared in the same manner as in A- 1 , except that the addition amount of the silica-based fine particles was 50 parts by mass. A laminate (coated film) was obtained in the same manner as in Example 1 except that H- 1 was used.

Comparative Example 3
In the preparation of the coating liquid A- 1 , a coating liquid H- 2 was prepared in the same manner as in A- 1 , except that the addition amount of the silica-based fine particles was changed to 15000 parts by mass. A laminate (coated film) was obtained in the same manner as in Example 1 except that H- 2 was used.

The results of Examples 1 to 4 and Comparative Examples 1 to 3 are collectively shown in Table 1.

As shown in Examples 1 to 4 , transparency, solvent resistance, adhesion, scratch resistance, blocking resistance, slipperiness, adhesive properties, and the like by laminating a specific amount of the coating film of the present invention on a PP film. Excellent adhesion and printability. Furthermore, the printability and the adhesiveness of the adhesive were maintained after long-term storage . The scratch resistance was improved by adding a crosslinking agent (Examples 1 to 4 ). Sliding property was improved by using a mixed system of polyolefin resin / polyurethane resin (Example 3 ). Moreover, the slipperiness improved by adding a fatty acid amide compound (Example 4 ).

On the other hand, when the coating film of the present invention was not laminated, the effect of corona treatment decreased after long-term storage, and the printability deteriorated (Comparative Example 1 ). When the ratio between the binder resin and the silica-based fine particles is outside the range of the present invention, the adhesion, scratch resistance, and adhesiveness of the adhesive deteriorated (Comparative Examples 2 and 3 ).

Claims (7)

A laminate in which a coating film of 0.001 to 0.3 g / m ² is laminated on a thermoplastic resin substrate, and as a constituent component of the coating film , either a polyolefin resin or a mixed resin of a polyolefin resin and a polyurethane resin It contains 100 parts by mass of the binder resin (A) composed of the above, 100 to 10,000 parts by mass of silica-based fine particles (B) having a number average particle diameter of 50 nm or less , and 100 parts by mass or less of the oxazoline group-containing compound (C). Laminated body. The laminate according to claim 1 , further comprising one or more selected from the group consisting of a wax, a silicone compound, a fatty acid amide compound, and a fatty acid metal salt compound in the coating film. The laminate according to claim 1 or 2 , wherein the thermoplastic resin substrate is a thermoplastic resin film or sheet, and the haze of the laminate is 10% or less. Laminate according to any one of claims 1 to 3, the thermoplastic resin base material is equal to or Ru polyolefin resin film or sheet der. Laminate according to any one of claims 1 to 3, the thermoplastic resin base material is equal to or Ru polyester resin film or sheet der. The assembly formed from the laminated body in any one of Claims 1-5 . The clear case or clear box formed from the laminated body in any one of Claims 1-5 .