JP2006198938A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which can be used appropriately in an assembly such as a clear case or a clear box and has adhesive properties (especially after a long time), scratch resistance, transparency, etc. <P>SOLUTION: The laminate comprises a coating film of 0.005-0.3 g/m<SP>2</SP>laminated on a thermoplastic resin substrate. The coating film contains 100 pts.mass of a binder resin (A) and 100-10,000 pts.mass of a tin oxide compound (B) as components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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. Further, the antistatic performance is insufficient only by corona discharge treatment, and there is a problem that dust and dust adhere.

  In order to solve the above problems in the corona discharge treatment of films and sheets, a method of laminating on the surface using a coating agent having excellent adhesion as a primer has been studied. The present applicants disclose a laminate in which an antistatic coating agent is coated on the surface of a thermoplastic resin film in Patent Documents 1 and 2.

JP 2002-265860 A JP 2003-268164 A

  As in Patent Documents 1 and 2, the laminate obtained by applying the coating agent solves the above-mentioned long-term printability, and also has good anti-blocking properties after coating, In comparison with corona-treated surfaces of films and sheets, there are problems such as inferior in transparency, adhesion (particularly long-term performance), and scratch resistance (property to scratch the surface).

As a result of intensive studies, the present inventors have dramatically improved the scratch resistance of the coating and the adhesiveness due to the adhesive by providing a specific composition and a specific amount of coating on the thermoplastic substrate. We have found an unexpected effect of improving the performance, and found that the above problems can be solved all at once.
That is, the gist of the present invention is as follows.
(1) A laminate in which a coating film of 0.005 to 0.3 g / m ² is laminated on a thermoplastic resin substrate, and a binder resin (A) and a tin oxide compound (B) as constituent components of the coating film And (B) 100 to 10,000 parts by mass with respect to (A) 100 parts by mass.
(2) The laminate according to (1), further comprising a cross-linking agent component (C), wherein (C) is 100 parts by mass or less with respect to 100 parts by mass.
(3) The laminate according to (1) or (2), wherein the binder resin (A) is at least one selected from polyolefin resins, polyester resins, polyurethane resins, acrylic resins, and vinyl resins.
(4) The laminate according to any one of (1) to (3), wherein the crosslinking agent component (C) is an oxazoline group-containing compound.
(5) The laminate according to any one of (1) to (4), further comprising at least one selected from waxes, silicone compounds, fatty acid amide compounds, and fatty acid metal salt compounds.
(6) The laminate according to any one of (1) to (5), wherein the thermoplastic resin base material is a thermoplastic resin film or sheet, and the haze of the laminate is 10% or less.
(7) The laminate according to any one of (1) to (6), wherein the thermoplastic resin base material is a polyolefin resin film or sheet, and the binder resin (A) is a polyolefin resin. body.
(8) The laminate according to any one of (1) to (6), wherein the thermoplastic resin substrate is a polyester resin film or sheet, and the binder resin (A) is a polyester resin. body.
(9) An assembly formed from the laminate according to any one of (1) to (8).
(10) A clear case or a clear box formed from the laminate according to any one of (1) to (8).

  The laminate of the present invention is excellent in adhesion (particularly adhesion after a long period of time) and scratch resistance, and also has improved transparency as compared with conventional laminates. For this reason, it can adhere | attach and it can use suitably for assemblies, such as a clear case and a clear box, and since it is hard to be damaged, the fall of aesthetics is small and there is little damage to a commercial value.

  In addition, the adhesion of the coating film to the base material, anti-blocking property between the coated surfaces, slipperiness, and antistatic performance are maintained, so it can be rolled up and stored on a roll, and the adhesion of dust and dust is also suppressed. Can do.

  Furthermore, since both the adhesive property and the printing property last for a long time, it can be used well after long-term storage or after export by sea mail.

  The present invention will be described in detail below.

In the present invention, the coating amount of the coating film is required to be 0.005~0.3g / ^{m 2,} preferably 0.008~0.2g / ^{m 2,} 0.008~0.1g / ^{m 2} is more preferable, 0.01 to 0.08 g / m ² is more preferable, and 0.015 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. When the stacking amount is less than 0.005 g / m ² , it is difficult to stack uniformly and the antistatic performance deteriorates. The antistatic performance can be evaluated by a surface specific resistance value, and from the viewpoint of suppressing adhesion of dust, dust and the like, it is practically preferable if this value is less than 10 ¹⁴ Ω / □.

  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 these may be used in combination. 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.

  The polyolefin resin as the binder resin (A) preferably contains 0.1 to 25% by mass of the unsaturated carboxylic acid component (A1) from the viewpoint of the water resistance of the coating film and the adhesion to the substrate. 0.5-15 mass% is more preferable, 1-8 mass% is further more preferable, and 1-5 mass% is especially preferable. The component (A1) is introduced with an unsaturated carboxylic acid or its anhydride. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc. Besides these, unsaturated dicarboxylic acid half esters, half amides and the like can be mentioned. 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 (A1) should just be copolymerized in polyolefin resin, the form is not limited, For example, random copolymerization, block copolymerization, graft copolymerization etc. are mentioned.

  Examples of the olefin component (A2) of the polyolefin resin include alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, and 1-hexene, and a mixture thereof 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 is particularly preferable. The content of the olefin component is preferably 50% by mass or more, and more preferably 70% by mass or more. When the content of the olefin component is less than 50% by mass, properties derived from the polyolefin resin such as adhesion to the base material and water resistance are lost.

  The polyolefin resin preferably contains a (meth) acrylic acid ester component (A3) from the viewpoint of improving adhesion to a substrate, particularly a polyolefin substrate such as polypropylene. The content of the component (A3) is preferably 0.5 to 40% by mass, and this range is 1 to 35% by mass in order to give good adhesiveness to various thermoplastic resin film substrates. It is more preferable that it is 3-30 mass%, it is especially preferable that it is 5-25 mass%, and it is most preferable that it is 10-25 mass%. When the ratio of the component (A3) is less than 1% by mass, the adhesion with the base film may be lowered. On the other hand, even if the content of the component (A3) exceeds 40% by mass, the properties of the olefin-derived resin are lost, and the adhesion to the substrate may be reduced. Examples of the (meth) acrylic acid ester (A3) component include esterified products of (meth) acrylic acid and alcohols having 1 to 30 carbon atoms. Among these, (meth) acrylic acid and An esterified product with an alcohol having 1 to 20 carbon atoms is preferred. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Among these, from the viewpoint of adhesiveness with the substrate film, methyl (meth) acrylate (ethyl) (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, octyl acrylate are more preferable, ethyl acrylate, More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. ("(Meth) acrylic acid" means "acrylic acid or methacrylic acid".)

  Moreover, you may contain other components other than the said component about 10 mass% or less of the whole polyolefin resin. Other components include alkenes and dienes having more than 6 carbon atoms such as 1-octene and norbornenes, maleates such as dimethyl maleate, diethyl maleate and dibutyl maleate, (meth) acrylic amides Obtained by saponifying vinyl esters such as methyl vinyl ether and alkyl vinyl ethers such as vinyl vinyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and vinyl esters with basic compounds. Examples include vinyl alcohol, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide, and the like, and a mixture thereof can also be used.

  Specific examples of the polyolefin resin include ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid-maleic anhydride copolymer, acid-modified polyethylene, acid-modified polypropylene, acid-modified ethylene-propylene resin, acid Examples thereof include a modified ethylene-butene resin, an acid-modified propylene-butene resin, an acid-modified ethylene-propylene-butene resin, or a resin obtained by further modifying these acid-modified resins with an acrylic ester or the like. In addition, acid modification is modified (specifically, graft modification) with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid or the like. The form of the copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like. Among these, an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer is preferable.

  In the present invention, the polyolefin resin has a melt flow rate at 190 ° C. and a load of 2160 g, which is a measure of molecular weight, usually from 0.01 to 5000 g / 10 minutes, preferably from 0.1 to 1000 g / 10 minutes, more preferably from 1 to 1 g. 500 g / 10 min, more preferably 2 to 300 g / 10 min, particularly preferably 2 to 200 g / 10 min can be used. When the melt flow rate of the polyolefin resin (A) is less than 0.01 g / 10 minutes, the adhesion to the substrate is lowered. On the other hand, when the melt flow rate of the polyolefin resin exceeds 5000 g / 10 minutes, the coating film becomes hard and brittle, and the water resistance and adhesion to the substrate film are lowered.

  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. In addition, it does not specifically limit about the polymerization method, What is necessary is just to perform suitably 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 cyclohexane dicarboxylic acid, 2,5-norbornene dicarboxylic acid and its anhydride, tetrahydrophthalic acid and its anhydride, and the like. Moreover, a small amount of 5-sodium sulfoisophthalic acid, 5-hydroxyisophthalic acid, etc. can be used as an acid component as long as the water resistance of the coating film is not impaired as required.

  Among the acid components described above, aromatic polybasic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid are preferable, and this ratio is preferably 50 mol% or more of the total acid component, 70 mol% or more is particularly preferable. By increasing the ratio of aromatic polybasic acid, the ratio of aromatic ester bonds, which are harder to hydrolyze than aliphatic and alicyclic ester bonds, to the resin skeleton increases, improving the hardness and water resistance of the coating film. To do.

  Furthermore, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is particularly preferable in that the workability, hardness, water resistance, solvent resistance, weather resistance and the like can be improved while balancing various performances of the resin coating film. preferable.

  Further, as the acid component, a tribasic or higher polybasic acid such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, trimesic acid, Ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), 1,2,3,4-butanetetracarboxylic acid and the like may be contained. At this time, in terms of maintaining good processability of the resin coating film, the ratio of the trifunctional or higher polybasic acid in the acid component of the polyester resin is preferably 10 mol% or less, more preferably 8 mol% or less, 5 mol% or less is particularly preferable.

  Examples of the alcohol component of the polyester resin include aliphatic glycols having preferably 2 to 10 carbon atoms, alicyclic glycols having preferably 6 to 12 carbon atoms, and ether bond-containing glycols. Examples of such aliphatic glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5- Examples include pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, and alicyclic glycols. As an example, 1,4-cyclohexanedimethanol is exemplified, and examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol and the like.

  In addition, since the water resistance and weather resistance of the polyester resin may decrease if the ether structure increases, the amount of the ether bond-containing glycol used should be within a range that does not impair the water resistance and weather resistance of the resin coating film. Is preferred.

  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 the above-described alcohol components, 1,2-propanediol, neopentyl glycol, and ethylene glycol can be particularly preferably used. It is preferable to use “1,2-propanediol and ethylene glycol” or “neopentyl glycol and ethylene glycol” as main components. Moreover, 3 types can also be used together. Ethylene glycol, neopentyl glycol, and 1,2-propanediol are industrially produced in large quantities, so they are inexpensive, and the performance of the resin coating is balanced. In particular, neopentyl glycol and 1,2-propanediol have the advantage of improving the weather resistance of the resin coating.

  The total proportion of 1,2-propanediol, neopentyl glycol and ethylene glycol in the alcohol component of the polyester resin is preferably 50 mol% or more, more preferably 60 mol% or more, and particularly preferably 70 mol% or more. Under the present circumstances, it is preferable that 10-65 mol% of the total amount of the said 3 types of alcohol component is ethylene glycol.

  Moreover, as an alcohol component, trifunctional or more polyhydric alcohols, for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. may be contained. At this time, in terms of maintaining good processability of the resin coating film, the proportion of the trifunctional or higher polyhydric alcohol in the alcohol component of the polyester resin is preferably 10 mol% or less, more preferably 8 mol% or less, 5 mol% or less is particularly preferable.

  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 polyester resin preferably has an anionic group of 20 to 700 (equivalent / ton), more preferably 70 to 530 (equivalent / equivalent / ton) from the viewpoint of improving the mixing property with the tin oxide compound. And particularly preferably 140 to 350 (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.

  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 structure of the polyurethane resin is not particularly limited, but preferably has an anionic group from the viewpoint of improving the mixing property with the tin oxide compound. Examples of the anionic group include a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group. Among these, it is preferable to have a carboxyl group.

  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 include lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, dimerized isocyanate obtained by converting a carboxyl group of dimer acid to 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.

  In order to introduce an anionic group into the polyurethane resin, a polyol component having a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group or the like may be used. Examples of the polyol compound having a carboxyl group include 3, 5 -Dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis ( 4-hydroxyphenyl) acetic acid, 2,2-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxyl-propionamide, etc. Is mentioned.

  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.

  Specific examples of the tin oxide compound (B) in the present invention include tin oxide, antimony-doped tin oxide, indium-doped tin oxide, tin oxide-doped indium, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide- Examples thereof include a composite of tin oxide, a composite of titanium oxide and tin oxide, and solvates and coordination compounds thereof can also be used. Of these, tin oxide, antimony-doped tin oxide, tin oxide-doped indium, and their solvates and coordination compounds, which are excellent in performance such as conductivity and have a good balance between performance and cost, are preferably used.

  Although the manufacturing method of said tin oxide type compound (B) is not specifically limited, For example, the method of hydrolyzing or thermally hydrolyzing metallic tin and a tin compound, the method of carrying out the alkaline hydrolysis of the acidic solution containing a tin ion, and a tin ion are included. Any method such as a method of ion exchange of a solution with an ion exchange membrane or an ion exchange resin can be used.

  Also, a commercially available sol of tin oxide compounds can be used. For example, as an aqueous tin oxide dispersion, EPS-6 manufactured by Yamanaka Chemical Industry Co., Ltd., as an antimony-doped tin oxide aqueous dispersion, SN100D manufactured by Ishihara Sangyo Co., Ltd., as tin oxide-doped indium, ITO manufactured by CI Kasei Co., Ltd. is there.

  The amount of the tin oxide compound (B) needs to be 100 to 10000 parts by mass, preferably 200 to 5000 parts by mass, and more preferably 400 to 3000 parts by mass with respect to 100 parts by mass of the binder resin (A). 500 to 2000 parts by mass is more preferable. If (B) is less than 100 parts by mass, the blocking resistance, the solvent resistance of the coating film, the antistatic performance, etc. tend to decrease, and if it exceeds 10000 parts by mass, the adhesion to the substrate and the adhesiveness of the adhesive are increased. Tends to decrease.

  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 with respect to 100 parts by mass of the binder resin (A), the addition amount is more preferably 0.1 to 80 parts by mass, further preferably 5 to 80 parts by mass, 10-70 mass parts is especially preferable. 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, 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 complex having a polyvalent coordination site, etc. can be used. Of these, isocyanate compounds , 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 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 performance, such as scratch resistance, 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 degrade the coating film performance over time.

  The base material used in the present invention is not particularly limited as long as it is a base material made of a thermoplastic resin, and examples thereof include a molded body, a film, a sheet, and synthetic paper made of a thermoplastic resin. From the viewpoint of sufficiently exerting the coating film performance, it is preferable to use a thermoplastic resin film or sheet (hereinafter referred to as a film) having a haze of 10% or less, more preferably 5% or less. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, ionomer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyamide resins such as nylon 6, nylon 66, nylon 46, polyethylene terephthalate (hereinafter, PET), A-PET, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polylactic acid, etc. polyester resin, polystyrene resin, polyimide resin, polycarbonate resin, polyarylate resin Or a mixture thereof. Examples of the film include a single body such as a film made of the resin or a laminate such as a film. Among these, those suitable for the clear case are polyolefin resins or polyester resins. The thickness of the substrate film or the like is not particularly limited, and may usually be in the range of 1 to 10000 μm, and more preferably 10 to 1000 μm. Further, the plastic resin film or the like may be subjected to a surface treatment such as a corona discharge treatment or a plasma treatment, and the surface treatment may be performed from the viewpoint of improving the coating property of a coating liquid described later. preferable.

  Moreover, the coating film of this invention should just be laminated | stacked on at least single side | surfaces, such as the said thermoplastic resin film.

  Examples of the method of forming a coating film on a substrate to form a laminate include a method of applying and drying a coating solution in which a coating film component is dissolved or dispersed in a liquid medium and drying 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, and may contain a basic compound described later. 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. Such a coating liquid can be obtained by mixing an aqueous dispersion of the binder resin (A) and a sol of the tin oxide compound (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, still more 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. When the number average particle diameter of the binder resin (A) exceeds 200 nm or the volume average particle diameter exceeds 500 nm, not only it becomes difficult to form a thin coating film uniformly, but also the transparency of the coating film decreases. And adhesion to the substrate may be reduced.

  The number average particle diameter of the tin oxide compound is preferably 50 nm or less, more preferably 30 nm or less, and still more preferably 20 nm or less. The volume average particle diameter is preferably 200 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. When the number average particle diameter of the tin oxide compound exceeds 50 nm or the volume average particle diameter exceeds 200 nm, not only is it difficult to form a thin coating film uniformly, but the transparency of the coating film is reduced. Adhesion with the substrate may be reduced.

  The number average particle size and volume average particle size of the binder resin (A) and tin oxide compound (B) described above are measured by a dynamic light scattering method.

  The water-soluble organic solvent used as a component of the aqueous medium preferably has a solubility in water at 20 ° C. of 50 g / L or more. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, and n-butanol. , Methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether. From the viewpoint of liquid stability and low temperature drying properties, methanol, ethanol, n-propanol, and isopropanol are used. Particularly preferred.

  As the basic compound used as the component of the aqueous medium, ammonia or an organic amine compound that volatilizes during the formation of the coating film 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. The organic amine compound is preferably 50 to 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, and the water resistance of the coating film may deteriorate. 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, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like. The addition amount of the basic compound is preferably 0.5 to 3.0 times equivalent to the anionic group in the resin, more preferably 0.8 to 2.5 times equivalent, and 1.01 to 2 A 0.0-fold equivalent is particularly preferred. If it is less than 0.5 times equivalent, the addition effect of a basic compound is not recognized, and if it exceeds 3.0 times equivalent, the drying time at the time of coating film formation will become long.

  The solid content concentration of the coating liquid used in the present invention may be appropriately determined depending on the amount of the coating film to be laminated, and is usually 0.01 to 20% by mass, from the point of forming a transparent and uniform coating film, 0.01 to 10 mass% is preferable and 0.1-5 mass% is more preferable.

  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.

  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 a resin such as a film. To 20 ° C to the melting point of a resin such as a film, more preferably 30 ° C to a resin such as a film, and the heating time is preferably 1 second to 20 minutes, preferably 5 seconds to 15 minutes. More preferred is 10 seconds to 10 minutes.

  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 has high transparency, it is also possible to put a product in a box and display it for use (the product can be confirmed since the inside is visible). Moreover, you may print on a part of laminated body.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, as a base film, A-PET film (Mitsubishi Chemical Corporation make, thickness 200 micrometers) (henceforth AP) or PP film (thickness 300 micrometers, Idemitsu Unitech super pure array) (henceforth, SP) was used. Various evaluations were performed after the coated film was left for 1 day in an atmosphere of a temperature of 23 ° C. and a humidity of 65%.

(1) Coating amount (coating amount)
A predetermined amount of the coating liquid of the present invention 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 includes the turbidity (AP: 0.72%, SP: 3.1%) of the base film used in each example.

(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) Antistatic properties Based on JIS-K6911, the surface resistivity value of the coating film (laminated body) of the coating film (laminated body) is determined by the following 3 using a digital ultra-high resistance / microammeter R83340 manufactured by Advantest Co., Ltd. Each was measured under one condition and evaluated.

(4-a) Standard characteristic evaluation It measured in temperature 23 degreeC and humidity 65% atmosphere.

(4-b) Flow resistance evaluation After the coated film was exposed to running water for 60 seconds, it was measured under the same conditions as 3-a.

(4-c) Warm water resistance evaluation The coating film was immersed in warm water at 40 ° C. for 24 hours, and then measured under the same conditions as 3-a.

(5) 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 coated layer was cut into 100 sections by cross-cutting, and the number of sections of the coated layer remaining after the tape peeling was evaluated according to the following criteria.
○: 100 section remaining △: 90 to 100 section remaining ×: 0 to 90 section remaining

(6) Scratch resistance According to the pencil hardness measuring method described in JIS K5400, the coating film was scratched 5 times using a B pencil (manufactured by Mitsubishi Uni) and evaluated as follows.
○: No scratches (no scratches)
△: Scratched once ×: Scratched twice or more

(7) 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. Judgment was made according to the following criteria from the state of the coating surface (whether or not the peeling mark of the other coating surface remains on one coating surface).
○: 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.

(8) 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

(9) 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.

(10) 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 coating film (repellency Degree).
○: No ink repelling ×: Ink repelling

(11) 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).

(12) Particle size The number average particle size and the volume average particle size of the binder resin (A) and the tin oxide compound (B) are measured using a Microtrack particle size distribution analyzer UPA150 (Model No. 9340) manufactured by Nikkiso Co., Ltd. Measured by dynamic light scattering.

<< Preparation of aqueous dispersion of binder resin (A) >>

(Preparation of aqueous polyolefin resin dispersion)
75.0 g of polyolefin resin [Bondaine HX-8290, manufactured by Arkema Co., Ltd., ethylene-acrylic acid ester (17-18% by mass)- Maleic anhydride copolymer (2 to 3% by mass), melt flow rate 65 g / 10 min)], 60.0 g isopropanol, 5.1 g triethylamine and 159.9 g distilled water were charged into a glass container and stirred. When stirring was performed at a blade rotation speed of 300 rpm, no sedimentation of resin granules was observed at the bottom of the container, confirming that it was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform polyolefin resin aqueous dispersion O-1 was obtained. The number average particle diameter and the volume average particle diameter were 70 nm and 91 nm, respectively.

(Preparation of aqueous polyester resin dispersion)
A mixture consisting of 25.10 kg of terephthalic acid, 10.76 kg of isophthalic acid, 9.38 kg of ethylene glycol and 13.48 kg of neopentyl glycol was heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. Next, 1.57 kg of ethylene glycol solution containing 1% by mass of antimony trioxide as a catalyst was added, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction is continued, and after 2 hours, the system is brought to atmospheric pressure with nitrogen gas. The temperature of the system is lowered, and when it reaches 270 ° C., 817 g of trimellitic acid is added and stirred at 250 ° C. for 1 hour. The depolymerization reaction was performed. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin. The obtained polyester resin had a carboxyl group amount of 251 equivalents / ton and a weight average molecular weight of 31,000. As a result of analyzing the composition of this polyester resin by ¹ H-NMR, terephthalic acid / isophthalic acid / trimellitic acid (molar ratio) was 70.7 / 29.3 / 2, and ethylene glycol / neopentyl glycol (molar ratio) was 45/55.

  300 g of the polyester resin, 180 g of isopropanol, 9.2 g of triethylamine using a stirrer (Toki Robotics, manufactured by Tokushu Kika Kogyo Co., Ltd.) equipped with a jacketed 2 liter glass container that can be sealed. And 510.8 g of distilled water were charged into a glass container and stirred at a rotational speed of a stirring blade (homodisper) of 7,000 rpm. No precipitation of resin particles was observed at the bottom of the container, It was confirmed that Thus, while maintaining this state, hot water was passed through the jacket after 10 minutes. Then, the system temperature was maintained at 73 to 75 ° C., and further stirred for 30 minutes. Thereafter, cold water was poured into the jacket, and the rotational speed was lowered to 4000 rpm, followed by cooling to room temperature (about 25 ° C.) while stirring to obtain a milky white uniform polyester resin aqueous dispersion P-1. The number average particle diameter and the volume average particle diameter were 60 nm and 95 nm, respectively.

(Polyurethane resin aqueous dispersion)
As the polyurethane resin aqueous dispersion, a commercially available dispersion (Adekabon titer HUX-232 manufactured by Asahi Denka Kogyo Co., Ltd.) (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 tin oxide compound (B) >>

(Preparation of tin oxide sol)
Dissolve 28 g (0.1 mol) of stannic chloride pentahydrate in 200 ml of water to make a 0.5 M aqueous solution, and add 28% aqueous ammonia with stirring to add white tin oxide with a pH of 1.5 An ultrafine particle-containing slurry was obtained. The obtained tin oxide ultrafine particle-containing slurry is heated to 70 ° C. and then naturally cooled to around 50 ° C., and then pure water is added to obtain a 1 L tin oxide ultrafine particle-containing slurry, and solid-liquid separation is performed using a centrifuge. went. After adding 800 ml of pure water to this water-containing solid content, stirring and dispersing with a homogenizer, washing was performed by solid-liquid separation using a centrifuge. 75 ml of pure water was added to the water-containing solid content after washing to prepare a tin oxide ultrafine particle-containing slurry.

  To the obtained tin oxide ultrafine particle-containing slurry, 3.0 ml of triethylamine was added and stirred. After the transparency was raised, the temperature was raised to 70 ° C., then the heating was stopped and the solid content was cooled to 10.5 mass. Tin oxide sol Z-1 containing 1% of organic amine as a dispersion stabilizer was obtained. The number average particle diameter and the volume average particle diameter were 8.5 nm and 9.8 nm, respectively.

<Preparation of coating solution>

(Preparation of coating liquid A-1)
After mixing polyolefin resin aqueous dispersion O-1 with tin oxide sol Z-1 so that tin oxide ultrafine particles may be 800 parts by mass with respect to 100 parts by mass of polyolefin resin solids, water / isopropanol is 30/70. It diluted 10 times with the mixed solvent (mass ratio), and obtained coating liquid A-1.

(Preparation of coating liquid A-2)
Tin oxide sol Z-1, aqueous polyolefin resin dispersion O-1, oxazoline group-containing compound (manufactured by Nippon Shokubai Co., Ltd., Epocros K-2030E) (hereinafter referred to as EP), based on 100 parts by mass of polyolefin resin in terms of solid content After mixing so that it might become 800 mass parts of tin oxide ultrafine particles, and 40 mass parts of EP, it diluted 10 times with the mixed solvent of water / isopropanol 30/70 (mass ratio), and obtained coating liquid A-2.

(Preparation of coating liquid A-3)
After mixing the tin oxide sol Z-1, the polyolefin resin aqueous dispersion O-1, EP so as to be 5000 parts by mass of tin oxide ultrafine particles and 20 parts by mass of EP with respect to 100 parts by mass of the polyolefin resin in terms of solid content, It diluted 10 times with the mixed solvent of water / isopropanol 30/70 (mass ratio), and obtained coating liquid A-3.

(Preparation of coating liquid A-4)
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 the tin oxide sol Z-1 and EP are mixed with the mixture of the aqueous dispersion so as to be 800 parts by mass of tin oxide ultrafine particles and 40 parts by mass of EP based on 100 parts by mass of the binder resin, It diluted 10 times with the mixed solvent of water / isopropanol 30/70 (mass ratio), and obtained coating liquid A-4.

(Preparation of coating liquid A-5)
Solid oxide conversion of tin oxide sol Z-1, aqueous dispersion of polyolefin resin O-1, EP and aqueous dispersion of fatty acid amide compound (manufactured by Chukyo Yushi Co., Ltd., Himicron L-271, stearamide) (hereinafter referred to as HM) After mixing with 100 parts by mass of polyolefin resin to make 800 parts by mass of ultrafine tin oxide particles, 40 parts by mass of EP, and 5 parts by mass of HM, 10 times with a mixed solvent of 30/70 (mass ratio) of water / isopropanol. Dilution was performed to obtain a coating liquid A-5.

(Preparation of coating liquids B-1 to B-5)
In each of the coating liquids (A-1) to (A-5), a coating liquid was prepared by the same operation except that the aqueous polyester resin dispersion P-1 was used instead of the aqueous polyolefin resin dispersion O-1. (B-1) to (B-5) were obtained.

Example 1
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.

Examples 2 and 3
The laminate (coating) was prepared in the same manner as in Example 1 except that the coating amount (coating amount) was changed to 0.15 g / m ² (Example 2) and 0.01 g / m ² (Example 3). Film).

Examples 4-7
A-2 (Example 4), A-3 (Example 5), A-4 (Example 6) or A-5 (Example 7) was used in place of the coating liquid A-1. A laminate (coating film) was obtained in the same manner as in Example 1.

Comparative Example 1
The same operation as in Example 1 was performed except that the liquid A-1 ^* that was not diluted was used when preparing the coating liquid A-1, and the coating amount (coating amount) was 0.5 g / m ^2. A laminate (coated film) was obtained.

Comparative Example 2
SP which does not apply a coating liquid was used.

Comparative Example 3
In preparing the coating liquid A-2, a coating liquid H-3 was prepared in the same manner as in A-2 except that the addition amount of the tin oxide compound was 50 parts by mass. A laminate (coated film) was obtained in the same manner as in Example 1 except that H-3 was used.

Comparative Example 4
In the preparation of the coating liquid A-2, a coating liquid H-4 was prepared in the same manner as in A-2 except that the addition amount of the tin oxide compound was 15000 parts by mass. A laminate (coated film) was obtained in the same manner as in Example 1 except that H-4 was used.

  Table 1 summarizes the results of Examples 1 to 7 and Comparative Examples 1 to 4.

Example 8
A laminate (coating film) was obtained in the same manner as in Example 1 except that the base material was AP and B-1 was used instead of the coating liquid A-1.

Examples 9, 10
A laminate (coating) was prepared in the same manner as in Example 8, except that the coating amount (coating amount) was changed to 0.15 g / m ² (Example 9) and 0.01 g / m ² (Example 10). Film).

Examples 11-14
Implemented except that B-2 (Example 11), B-3 (Example 12), B-4 (Example 13), and B-5 (Example 14) were used instead of the coating liquid B-1. A laminate (coated film) was obtained in the same manner as in Example 8.

Comparative Example 5
The same operation as in Example 8 was performed except that the liquid B-1 ^* which was not diluted was used when preparing the coating liquid B-1, and the coating amount (coating amount) was 0.5 g / m ^2. A laminate (coated film) was obtained.

Comparative Example 6
AP which did not apply a coating liquid was used.

Comparative Example 7
In the preparation of the coating liquid B-2, a coating liquid H-7 was prepared by the same operation as B-2 except that the addition amount of the tin oxide compound was 50 parts by mass. A laminate (coated film) was obtained in the same manner as in Example 8 except that H-7 was used.

Comparative Example 8
In preparing the coating liquid B-2, a coating liquid H-8 was prepared in the same manner as in B-2 except that the addition amount of the tin oxide compound was changed to 15000 parts by mass. A laminate (coated film) was obtained in the same manner as in Example 8 except that H-8 was used.

  Table 2 summarizes the results of Examples 8 to 14 and Comparative Examples 5 to 8.

  As shown in Examples 1 to 7, transparency, solvent resistance, antistatic properties, adhesion, scratch resistance, blocking resistance, slipperiness are obtained by laminating a specific amount of the coating film of the present invention on a PP film. The adhesive was excellent in adhesiveness and printability. Furthermore, the printability and the adhesiveness of the adhesive were maintained after long-term storage. It was confirmed that when the amount of the coating film was increased, the scratch resistance was deteriorated and the antistatic property was improved (Examples 1 to 3). The scratch resistance was improved by adding a crosslinking agent (Examples 4 to 7). Moreover, the slipperiness improved by adding the fatty acid amide compound (Example 7). On the other hand, when the coating amount exceeded the range of the present invention, transparency and adhesiveness of the adhesive deteriorated (Comparative Example 1). 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 2). When the ratio between the binder resin and the tin oxide compound was outside the range of the present invention, the adhesion, scratch resistance and adhesive adhesiveness deteriorated (Comparative Examples 3 and 4).

Moreover, as shown in Examples 8-14, transparency, solvent resistance, antistatic properties, adhesion, scratch resistance, and blocking resistance can be obtained by laminating a specific amount of the coating film of the present invention on an A-PET film. Excellent slipperiness, adhesive adhesion, and printability. On the other hand, when the coating amount exceeded the range of the present invention, transparency and adhesiveness of the adhesive deteriorated (Comparative Example 5). 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 6). When the ratio between the binder resin and the tin oxide-based compound is outside the range of the present invention, the adhesion, scratch resistance, and adhesive adhesion deteriorated (Comparative Examples 7 and 8).

Claims (10)

A laminate in which a coating film of 0.005 to 0.3 g / m ² is laminated on a thermoplastic resin substrate, and contains a binder resin (A) and a tin oxide compound (B) as constituent components of the coating film. (A) The laminated body characterized by being 100-10000 mass parts with respect to 100 mass parts. The laminate according to claim 1, further comprising a cross-linking agent component (C) and being 100 parts by mass or less of (C) with respect to 100 parts by mass of (A). The laminate according to claim 1 or 2, wherein the binder resin (A) is at least one selected from polyolefin resins, polyester resins, polyurethane resins, acrylic resins, and vinyl resins. The layered product according to any one of claims 1 to 3, wherein the crosslinking agent component (C) is an oxazoline group-containing compound. Furthermore, at least 1 sort (s) chosen from a wax, a silicone type compound, a fatty acid amide compound, and a fatty acid metal salt compound is contained, The laminated body in any one of Claims 1-4 characterized by the above-mentioned. The laminate according to any one of claims 1 to 5, wherein the thermoplastic resin substrate is a thermoplastic resin film or sheet, and the haze of the laminate is 10% or less. The laminate according to any one of claims 1 to 6, wherein the thermoplastic resin base material is a polyolefin resin film or sheet, and the binder resin (A) is a polyolefin resin. The laminate according to any one of claims 1 to 6, wherein the thermoplastic resin substrate is a polyester resin film or sheet, and the binder resin (A) is a polyester resin. The assembly formed from the laminated body in any one of Claims 1-8. The clear case or clear box formed from the laminated body in any one of Claims 1-8.