JP2019081330A - Graphic film for license plate, and method of manufacturing license plate using the graphic film - Google Patents

Abstract

To provide a graphic film for a license plate, having chemical resistance necessary for use as for a license plate, and having a surface protective layer excellent in printing adaptability with a printing layer such as a registration number.SOLUTION: The graphic film for a license plate includes a surface protective layer to which a printing layer is applied, has a cyclohexanone absorption amount of 0.0017 g/cmand 0.0025 g/cmwhen cyclohexanone is applied to a surface of the surface protective layer and a cyclohexanone absorption amount of 0.0010 g/cmwhen cyclohexanone is applied to the surface of the surface protective layer after a heat treatment at 150°C for 10 min.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a graphic film for a license plate and a method of manufacturing a license plate using the graphic film.

  In recent years, a technique for applying a decoration to a license plate (also referred to as a "license plate", and the same applies in the present disclosure) has been proposed. As a means for providing a decoration, a means etc. which employ | adopt paint or a graphic film are used.

  In the column of the prior art of Patent Document 1 (Japanese Patent Application Laid-Open No. 05-155976), as a method of decorating molded articles such as body side moldings of automobiles, "the film for the interior and exterior with an adhesive on the base after molding A method of sticking and a method of spray-coating a paint and clear using a two-component polyurethane consisting of an acrylic polyol / hexamethylene diisocyanate-based polyisocyanate combination as a binder on a substrate after molding are described.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2016-210286) forms an embossed portion which becomes a character portion after bonding a graphic film for a license plate having an adhesive layer, a substrate and a print image to a base plate of the license plate. A method for producing a license plate is described in which a printing layer such as a registration number is applied by roll coating to the embossed portion and then a clear coat is applied to the entire surface.

Unexamined-Japanese-Patent No. 05-155976 JP, 2016-210286, A

  The conventional coating method is prone to defects based on foreign matter or coating spots, etc., and requires a highly clean working environment and skilled coating technology. Therefore, a simpler means of decoration has been desired.

  A graphic film provided with an adhesive layer, a decorative layer, and a resin layer or the like made of a flexible resin such as polyvinyl chloride to which a registration number or the like is applied is easier to decorate than a method by painting. However, flexible resins such as polyvinyl chloride are insufficient in chemical resistance and gasoline resistance and may deteriorate the decorative layer and the like located on the lower side from the outermost layer side. After printing, it has been recommended to further apply a protective coating such as urethane to the outermost surface. On the other hand, a graphic film which can obtain sufficient chemical resistance and gasoline resistance which does not require a protective coating after printing a registration number or the like has been desired. In this case, a graphic film which is excellent in both solvent resistance such as chemical resistance and printing compatibility is desired for the resin layer to be the base of the printing layer such as the registration number.

  In view of the above problems, it is an object of the present disclosure to provide a license having a surface protection layer that has chemical resistance necessary for use for a license plate and that is excellent in printing compatibility with a printing layer such as a registration number. It is providing a graphic film for a plate.

According to one embodiment of the present disclosure, the surface protection layer to which the print layer is applied, and when cyclohexanone is applied to the surface of the surface protection layer, the absorbed amount of cyclohexanone is about 0.0017 g / cm ² or more and about 0 .0025g / cm ² or less, 0.99 ° C., cyclohexanone absorption when applying cyclohexanone the surface protective layer surface after heat treatment at 10 minutes, approximately 0.0010 g / cm ² or less, a graphic license plate A film is provided.

  According to another embodiment of the present disclosure, there is provided a graphic film laminated plate comprising the graphic film for a license plate and a base plate.

According to still another embodiment of the present disclosure, there is provided a step of preparing a graphic film precursor for a license plate including a surface protective layer, and the amount of absorbed cyclohexanone when cyclohexanone is applied to the surface protective layer surface of such precursor. about 0.0017 g / cm ² or more and to be about 0.0025 g / cm ² or less, and a step of curing the surface protective layer to form a license plate for graphic film, the manufacturing of the license plate for graphic film A method is provided.

According to yet another embodiment of the present disclosure, providing a base plate, applying the graphic film for a license plate on or above the base plate to form a graphic film laminate plate, and a graphic film A process of embossing or debossing the laminate plate, a process of applying a printing layer to the projections or depressions of the embossed or debossed graphic film laminate plate, and a surface protection layer surface of the graphic film for a license plate Curing the surface protective layer to form a license plate such that the amount of absorbed cyclohexanone when applied is about 0.0010 g / cm ² or less, and a method of manufacturing a license plate is provided.

  According to the present disclosure, the surface protection layer is made of the intermediate resin cured product, and when printing such as the registration number is applied, it exhibits good absorption characteristics of the printing ink and exhibits excellent printing compatibility, as well as printing application Later, by performing additional heat curing, it is possible to provide a graphic film for a license plate capable of adding durability performance such as chemical resistance required for use for a license plate.

  The above description should not be taken as disclosing all embodiments of the invention and all advantages associated with the invention.

FIG. 1 is a cross-sectional view of a graphic film for a license plate according to an embodiment of the present disclosure. FIG. 7 is a cross-sectional view of a graphic film for a license plate according to another embodiment of the present disclosure. FIG. 7 is a cross-sectional view of a graphic film for a license plate according to another embodiment of the present disclosure. FIG. 1 is a cross-sectional view of a retroreflective graphic film for a license plate according to an embodiment of the present disclosure. FIG. 7 is a cross-sectional view of a retroreflective graphic film for a license plate according to another embodiment of the present disclosure. The preparation procedure of the license plate of one embodiment of this indication is shown in a sectional view. The preparation procedure of the license plate of one embodiment of this indication is shown in a sectional view. The preparation procedure of the license plate of one embodiment of this indication is shown in a sectional view. The preparation procedure of the license plate of one embodiment of this indication is shown in a sectional view. The preparation procedure of the license plate of one embodiment of this indication is shown in a sectional view. It is a figure which shows the hardening site | part and hardening condition of resin used by the surface protective layer of one embodiment of this indication. It is a graph of the infrared spectroscopy regarding the peak of the silanol group of resin used in the surface protective layer of one embodiment of this indication. (A) is a simplified view of a printing layer which exhibits an end white part accompanying ink dripping, and (b) is a simplified drawing of a printing layer which does not accompany ink dripping. (A) is a photograph of the printing layer which exhibits an end white spot due to ink dripping, and (b) is a photograph of the printing layer without ink dripping.

The graphic film for a license plate in the first embodiment includes a surface protection layer to which the printing layer is applied, and the amount of cyclohexanone absorbed when cyclohexanone is applied to the surface protection layer surface is about 0.0017 g / cm ² or more. and it is about 0.0025 g / cm ² or less, 0.99 ° C., cyclohexanone absorption when applying cyclohexanone the surface protective layer surface after heat treatment at 10 minutes is about 0.0010 g / cm ² or less. That is, in the graphic film of this embodiment, the surface protective layer is an intermediate resin cured product having a cured state in which the amount of absorbed cyclohexane becomes a predetermined amount, and when performing roll ink such as registration number, the ink is suitably used. Since the ink can be absorbed and the repelling of the ink can be suppressed, the printing compatibility is excellent, and by applying the heat treatment, it is possible to obtain the chemical resistance necessary for use as a license plate.

  In the graphic film for a license plate in the first embodiment, the surface protective layer is crosslinked with at least one selected from a resin containing a carboxyl group and a silanol group, and a mixture of a resin containing a carboxyl group and a resin containing a silanol group. And may have an unreacted silanol group. The graphic film for a license plate having the surface protective layer of such a constitution can satisfy the above-mentioned cyclohexanone absorption amount.

  The crosslinking agent in the surface protection layer of the graphic film for a license plate in the first embodiment may be at least one selected from an epoxy crosslinking agent and a carbodiimide crosslinking agent. The crosslinking agent is excellent in the reactivity with the carboxyl group.

  The graphic film for a license plate in the first embodiment may further include a support layer having a breaking elongation of about 50% or more below or below the surface protective layer. The graphic film provided with such a support layer can improve impact resistance.

  The graphic film for a license plate in the first embodiment can be applied to a base plate for a license plate to obtain a graphic film laminated plate. The laminated plate of such a configuration can be used as an intermediate of the license plate.

The method for producing a graphic film for a license plate according to the first embodiment includes the steps of preparing a graphic film precursor for a license plate including a surface protection layer, and cyclohexanone when cyclohexanone is applied to the surface of the surface protection layer of the precursor. absorption amount, to be about 0.0017 g / cm ² or more and about 0.0025 g / cm ² or less, and a step of curing the surface protective layer to form a license plate for graphic film, the.

A method of manufacturing a license plate using a graphic film for a license plate in the first embodiment comprises the steps of providing a base plate, and applying the graphic film for a license plate described above on or above the base plate Forming a graphic film laminate plate, embossing or debossing the graphic film laminate plate, applying a printing layer to the projections or depressions of the embossed or debossed graphic film laminate plate, and graphic film for a license plate Curing the surface protective layer to form a license plate such that the amount of absorbed cyclohexanone when applying cyclohexanone to the surface protective layer of the above is about 0.0010 g / cm ² or less. Well.

  These production methods can produce graphic films and license plates that have the chemical resistance necessary for use for license plates and that are excellent in printing compatibility with ink layers such as registration numbers.

  The present invention will hereinafter be described in more detail with reference to the drawings for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments. Like-numbered elements in different drawings indicate corresponding or corresponding elements in the drawings.

  In the present disclosure, "film" also includes an item called "sheet".

  In the present disclosure, “(meth) acrylic” means acrylic or methacrylic, and “(meth) acrylate” means acrylate or methacrylate.

  In the present disclosure, the “intermediate resin cured product” refers to one in which curing is at an intermediate stage under the conditions for curing the resin. That is, it refers to a resin in a state where the cured state can be further advanced by a higher curing temperature or a longer curing time.

The graphic film for license plate according to one embodiment of the present disclosure (hereinafter, may be simply referred to as "graphic film") includes a surface protection layer to which a print layer is applied, and cyclohexanone is applied to the surface protection layer surface. cyclohexanone absorption in the case of the approximately 0.0017 g / cm ² or more and is about 0.0025 g / cm ² or less, 0.99 ° C., cyclohexanone when applying cyclohexanone the surface protective layer surface after heat treatment at 10 minutes The absorbed amount is about 0.0010 g / cm ² or less.

  Cross-sectional views of a graphic film for a license plate according to an embodiment of the present disclosure are shown in FIGS.

<< Surface protection layer >>
<Cyclohexanone absorbed amount>
The graphic film for a license plate of the present disclosure has a surface protection layer to which a printing layer on which character information such as at least a registration number is printed is applied. Cyclohexanone absorption when applying cyclohexanone the surface protective layer surface of the, about 0.0017 g / cm ² or more and is about 0.0025 g / cm ² or less, and, 0.99 ° C., the surface after heat treatment at 10 minutes The amount of absorbed cyclohexanone when cyclohexanone is applied to the surface of the protective layer is about 0.0010 g / cm ² or less, so before heat treatment at 150 ° C. or higher, the roll coat ink etc. used for printing layers such as registration numbers etc. While it is excellent in print compatibility and ink dripping, that is, white spots on the end of the printing layer can be prevented, durability performance such as chemical resistance can be improved after such heat treatment. Surface protective layer of the graphic film cyclohexanone absorption amount is about 0.0017 g / cm ² or more and about 0.0025 g / cm ² or less is excellent in printing suitability is not limited to the printing layer, applying a decorative layer It can also be done. The cyclohexanone absorption amount is more preferably about 0.0018 g / cm ² or more from the viewpoint of printing compatibility. When the amount of absorption increases, the printing compatibility with roll coat ink etc. improves, but when the amount of absorption becomes too large, problems such as surface roughening and generation of wrinkles may occur due to the roll coat ink. Therefore, the absorption amount, for example, from about 0.0024 g / cm ² or less, or more preferably about 0.0023 g / cm ² or less. The amount of cyclohexanone absorbed when cyclohexanone is applied to the surface of the surface protective layer of the graphic film after heat treatment at 150 ° C. for 10 minutes is about 0.0008 g / cm ² or less, or about 0. ² from the viewpoint of chemical resistance. It is more preferable to be 0007 g / cm ² or less. The surface protection layer of the graphic film of the present disclosure which satisfies the above-mentioned cyclohexanone absorption amount can achieve both solvent resistance and print compatibility which have been in a trade-off relationship. Although absorption of cyclohexanone mainly occurs in the surface protective layer, cyclohexanone may penetrate into other layers adjacent to the surface protective layer and may be absorbed there, not only in the case where it is absorbed only by the surface protective layer.

<Thickness of surface protective layer>
The thickness of the surface protective layer may vary, and is not limited to the following, but may be about 1 μm or more, about 2 μm or more, or about 3 μm or more, about 100 μm or less, about 70 μm or less or about 50 μm or less. When the surface protective layer is applied on the support layer described below, the thickness of the surface protective layer is about 1 μm or more, about 2 μm or more, about 3 μm or more, about 20 μm or less, about 15 μm or less or about 10 μm It can be

<Material of surface protective layer>
As the surface protective layer of the present disclosure, any material can be used as long as the graphic film can satisfy the above-mentioned cyclohexanone absorption, and is not limited to the following, for example, a resin containing a carboxyl group and a silanol group And materials containing at least one selected from a mixture of resins containing carboxyl groups and resins containing silanol groups, and a crosslinker. By including at least two crosslinkable functional groups of a carboxyl group and a silanol group, for example, as shown in FIG. 7, different crosslinking (curing) sites are formed under the temperature conditions of heat treatment, 150 ° C., 10 minutes The crosslink density can be made different before and after the heat treatment in In such a material, unreacted silanol groups remain at least before heat treatment at 150 ° C. for 10 minutes, and the presence of unreacted silanol groups is, for example, infrared spectroscopy as shown in FIG. It can be confirmed from the graph of. The surface protection layer concerned has a low crosslink density and a high cyclohexanone absorption amount before heat treatment at 150 ° C. for 10 minutes, that is, it is inferior in solvent resistance such as chemical resistance and gasoline resistance, but following to embossing etc. And ink absorption of printed layer etc., after heat treatment at 150 ° C for 10 minutes, crosslink density is high and cyclohexanone absorption is low, ie ink absorption is poor but solvent resistance such as chemical resistance etc. And can exhibit excellent performance such as hardness. In the present disclosure, crosslinking and curing may be used synonymously.

(Resin containing carboxyl group and silanol group)
As a resin containing a carboxyl group and a silanol group, for example, a polysiloxane of a composite resin (AB) formed by chemically bonding a polymer segment (A) having a neutralized carboxyl group and a polysiloxane segment (B) Composite resin in which the segment (B) and the polysiloxane segment (C) derived from the condensation product (c) of alkyltrialkoxysilane having 1 to 3 carbon atoms of alkyl group are bonded via a silicon-oxygen bond (ABC) etc. can be used. More specifically, for example, a composite resin having a graft structure in which a polysiloxane segment (B) is chemically bonded to a side chain of a polymer segment (A) having a neutralized carboxyl group; a polymer segment (A) A condensation product of a polysiloxane segment (B) of a composite resin having a block structure in which a polysiloxane segment (B) is chemically bonded to the end of) and an alkyltrialkoxysilane having 1 to 3 carbon atoms of an alkyl group Composite resin etc. which have a structure which the polysiloxane segment (C) derived from c) chemically-bonded via a silicon-oxygen bond are mentioned. The composite resin which concerns can be used individually or in combination of 2 or more types, and modification processes, such as urethane, etc. may be optionally applied.

  There is no particular limitation on the chemical bond between the polymer segment (A) and the polysiloxane segment (B), which the composite resin (ABC) has, for example, the following structural formula (S-1) or structural formula Among these, from the viewpoint of weatherability, it is preferable to use a composite resin having a bonding mode of the structural formula (S-1). However, the carbon atom in the structural formula (S-1) constitutes a part of the polymer segment (A), and the silicon atom and the oxygen atom constitute a part of the polysiloxane segment (B). The carbon atom in Formula (S-2) constitutes a part of polymer segment (A), and the silicon atom constitutes a part of polysiloxane segment (B).

  The polymer segment (A) constituting the composite resin (ABC) is a polymer segment having a neutralized carboxyl group in order to disperse or dissolve the composite resin (ABC) in an aqueous medium. Among them, the polysiloxane segment (B) or the hydroxyl group bonded to the silicon atom of the synthetic raw material or the hydrolyzable group bonded to the silicon atom is easily hydrolyzed and condensed to form the chemical formula in the bonding mode of the structural formula (S-1) As it combines, it is abbreviated as a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom together with a neutralized carboxyl group (hereinafter referred to as “a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom”) It is preferable that it is a polymer segment derived from the polymer (a) which has. The type of the polymer (a) is, for example, (meth) acrylic polymer, fluoroolefin polymer, vinyl ester polymer, aromatic vinyl polymer, vinyl polymer such as polyolefin polymer, polyurethane polymer, Polyester polymers, polyether polymers and the like can be mentioned. Among them, vinyl polymers and polyurethane polymers are preferable, and (meth) acrylic polymers are more preferable.

  Examples of the basic compound to be used for neutralizing the carboxyl group include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, organic amines such as 2-aminoethanol and 2-dimethylaminoethanol; ammonia, Inorganic basic compounds such as sodium hydroxide and potassium hydroxide; quaternary ammonium hydroxide of tetramethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide and the like can be used. Among them, organic amines and ammonia (may be ammonia water) are preferably used.

  The neutralized carboxyl group in the polymer (a) is a composite resin from the viewpoint of maintaining good storage stability of an aqueous dispersion or an aqueous solution in which the composite resin (ABC) is dispersed or dissolved in an aqueous medium. Preferably, it is present in a proportion of about 0.1 mass% or more, about 0.2 mass% or more, about 20 mass% or less, or about 10 mass% or less with respect to 100 mass% of (ABC).

  The hydrolyzable group bonded to the silicon atom in the polymer (a) may be a functional group capable of generating a hydroxyl group (silanol group) bonded to the silicon atom by hydrolysis, for example, A halogen atom bonded to a silicon atom, an alkoxy group bonded to a silicon atom, an acyloxy group bonded to a silicon atom, a phenoxy group bonded to a silicon atom, a mercapto group bonded to a silicon atom, an amino group bonded to a silicon atom, silicon Examples thereof include an amido group bonded to an atom, an aminooxy group bonded to a silicon atom, an iminooxy group bonded to a silicon atom, and an alkenyloxy group bonded to a silicon atom. Among them, an alkoxy group bonded to a silicon atom is preferable because the hydrolysis reaction can easily proceed and the by-products after the reaction can be easily removed.

  The polymer segment (A) may have other functional groups other than the neutralized carboxyl group, the silicon atom-bonded hydroxyl group, and / or the hydrolysable group, as long as the effects of the present invention are not impaired. . As other functional groups concerned, for example, non-neutralized carboxyl group, blocked carboxyl group, carboxylic acid anhydride group, hydroxyl group, blocked hydroxyl group, cyclocarbonate group, epoxy group, carbonyl group, primary amide group , A secondary amide group, a carbamate group, a polyethylene glycol group, a polypropylene glycol group, a group represented by the following structural formula (S-3), and the like.

  As a polysiloxane segment (B) which comprises a composite resin (ABC), the segment derived from the polysiloxane which has a hydroxyl group and / or a hydrolysable group of a silicon atom bond is mentioned, for example. Examples of the hydrolyzable group bonded to the silicon atom include the same hydrolyzable groups bonded to the silicon atom described in the polymer segment (A).

  Among them, as the polysiloxane segment (B), one having a structure represented by the following general formula (S-4) or (S-5) is preferable. The polysiloxane segment having a structure represented by the following general formulas (S-4) and (S-5) has a three-dimensional network-like polysiloxane structure, so that a sufficiently cured coating is resistant to solvents. Excellent in performance such as resistance and weatherability.

Here, R ¹ in the general formulas (S-4) and (S-5) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a silicon atom A methyl group bonded to a hydrogen atom or an ethyl group bonded to a silicon atom. Among them, R ¹ is preferably a hydrocarbon group having 4 to 12 carbon atoms bonded to a silicon atom, and more preferably a phenyl group or an alkyl group having 4 carbon atoms. R ² and R ³ are both preferably a methyl group bonded to a silicon atom or an ethyl group bonded to a silicon atom, and more preferably both are a methyl group bonded to a silicon atom.

  The polysiloxane segment having a structure represented by the general formula (S-4) or (S-5) is, for example, an organoalkoxysilane, preferably an organic group having 4 to 12 carbon atoms bonded to a silicon atom A monoorganotrialkoxysilane having “SiC bonded organic group having 4 to 12 carbon atoms” and / or an ethyl group bonded to a methyl group bonded to a silicon atom and / or a silicon atom A segment derived from a polysiloxane obtained by hydrolytic condensation of two diorganodialkoxysilanes (hereinafter abbreviated as “silicon-bonded methyl and / or ethyl groups bonded to silicon atoms”) may be mentioned. These polysiloxane segments are composed of a silicon-bonded organic group having 4 to 12 carbon atoms, a silicon-bonded hydroxyl and / or hydrolyzable group, and / or a silicon-bonded methyl and / or ethyl group. It has a hydroxyl group and / or a hydrolyzable group bonded to an individual and a silicon atom, and may have any of linear, branched and cyclic structures.

  Examples of the organic group having 4 to 12 carbon atoms bonded to a silicon atom include, for example, an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group each having 4 to 12 carbon atoms bonded to a silicon atom. These organic groups may have a substituent.

  As the organic group having 4 to 12 carbon atoms bonded to a silicon atom, a hydrocarbon group bonded to a silicon atom is preferable. For example, an n-butyl group, an isobutyl group, an n-butyl group bonded to a silicon atom Alkyl groups such as hexyl group, n-octyl group, n-dodecyl group and cyclohexylmethyl group; cycloalkyl groups such as cyclohexyl group and 4-methylcyclohexyl group; aryl groups such as phenyl group and 4-methylphenyl group; benzyl group Etc., and the like. Among them, a phenyl group bonded to a silicon atom or an alkyl group having 4 carbon atoms bonded to a silicon atom is more preferable.

  The polysiloxane segment (C) constituting the composite resin (ABC) is a segment derived from the condensation product (c) of an alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group, and the alkyl group used herein The condensation product (c) of an alkyltrialkoxysilane having 1 to 3 carbon atoms has a hydroxyl group bonded to a silicon atom and / or an alkoxy group bonded to a silicon atom.

As a condensation product (c) of alkyltrialkoxysilane, it is preferable to have a structure shown by the following general formula (S-6). Here, R ⁴ in the general formula (S-6) is an alkyl group having 1 to 3 carbon atoms. The polysiloxane segment derived from the condensation product of an alkyltrialkoxysilane having a structure represented by the general formula (S-6) has a three-dimensional network polysiloxane structure, and thus a sufficiently cured coating is Excellent performance such as solvent resistance and weather resistance.

  Among them, as the composite resin (ABC), a coating film having excellent weatherability can be obtained, and thus a poly derived from the condensation product (c) of the polysiloxane segment (B) and the alkyltrialkoxysilane in the composite resin (ABC) It is more preferable that the total amount (B + C) with the siloxane segment (C) is about 15 parts by mass or more, about 20 parts by mass or more, about 85 parts by mass or less, or about 50 parts by mass or less.

  Among them, as the composite resin (ABC), a coating film having excellent weatherability and crack resistance can be obtained, so that the polysiloxane segment (C) derived from the condensation product (c) of alkyltrialkoxysilane in the composite resin (ABC) More preferably, the amount of) is about 5 parts by weight or more, or about 10 parts by weight or more, about 50 parts by weight or less, or about 30 parts by weight or less.

  Although composite resin (ABC) can be manufactured by various methods, it is preferable to manufacture at the process which consists of following (I), and (II-1) or (II-2) especially.

  As the step (I), a polymer (a ′) in which a carboxyl group and a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom are present together, an organoalkoxysilane (b) and / or a hydrolysis condensate (b A composite resin comprising a polymer segment (A ') derived from a polymer (a') and a polysiloxane segment (B) derived from an organoalkoxysilane (b) chemically bonded by hydrolytic condensation with -1) A step of obtaining (A'B) can be employed.

  As a process (II-1), the condensation product (c) of the composite resin (A'B) obtained at the process (I) and the alkyltrialkoxysilane having 1 to 3 carbon atoms of an alkyl group is hydrolyzed By condensation, the polysiloxane segment (B) of the composite resin (A'B) and the polysiloxane segment (C) derived from the condensation product (c) of an alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group Is a composite resin (A'BC) bonded via a silicon-oxygen bond, and then the carboxyl group in the composite resin (A'BC) is neutralized with a basic compound to obtain a composite resin (ABC). The process of obtaining can be adopted.

  In the step (II-2), after the carboxyl group in the composite resin (A'B) obtained in the step (I) is neutralized with a basic compound to form a composite resin (AB), carbon of an alkyl group is obtained The condensation product (c) of alkyltrialkoxysilane having 1 to 3 atoms is hydrolyzed and condensed to form the polysiloxane segment (B) of the composite resin (AB) and the alkyl having 1 to 3 carbon atoms. A step of obtaining a composite resin (ABC) in which the polysiloxane segment (C) derived from the condensate of trialkoxysilane (c) is bonded via a silicon-oxygen bond can be employed.

(A mixture of a resin containing a carboxyl group and a resin containing a silanol group)
The surface protective layer of the present disclosure is not limited to the above composite resin, and a mixture of a resin containing a carboxyl group and a resin containing a silanol group can also be used. The compounding amount of these resins can be appropriately adjusted so as to obtain desired properties such as printing compatibility, weather resistance, chemical resistance and the like according to the compatibility or the use application and the like.

  The resin having a carboxyl group and the resin containing a silanol group is not particularly limited to the resin type, and specifically, for example, (meth) acrylic resin, polyolefin resin, silicone resin, polyurethane resin, epoxy Examples thereof include system resins, phenol resins, polyester resins, alkyd resins, and polycarbonate resins. These can be used alone or in combination of two or more. These resins may be modified as, for example, urethane-modified acrylic resins, or may be graft-polymerized.

(Crosslinking agent)
In the formation of the surface protective layer of the present disclosure, a crosslinking agent can be used, and in particular, at least one selected from a resin containing a carboxyl group and a silanol group, and a resin containing a carboxyl group and a resin containing a silanol group. When using 1 type, it is preferable to use a crosslinking agent together. The type and blending amount of the crosslinking agent can be appropriately selected and adjusted so as to obtain desired properties such as printing compatibility, weather resistance, chemical resistance and the like according to the compatibility or the use environment and the like.

  As silanol groups are shown in FIG. 7, adjacent silanol groups can be hydrolyzed and crosslinked at a predetermined temperature. Therefore, in the configuration containing a carboxyl group and a silanol group, a compound having a functional group which does not react with a silanol group but reacts with a carboxyl group is used as a crosslinking agent from the viewpoint of obtaining a predetermined cyclohexanone absorption amount. Preferable examples include compounds having functional groups such as epoxy group, cyclocarbonate group, amido group, hydroxyl group, oxazoline group, carbodiimide group and hydrazino group. Among them, an epoxy-based crosslinking agent or a carbodiimide-based crosslinking agent having an epoxy group or a carbodiimide group is preferable. Here, even if it is an agent called a silane coupling agent, if it is a silane coupling agent which has these functional groups, it can also be functioned as a crosslinking agent of this indication.

(Other optional ingredients)
In the formation of the surface protective layer of the present disclosure, as an optional component, a pigment, a dye, a filler, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a dispersant, a plasticizer, a flow improver, a surfactant Conventional materials such as agents, leveling agents, silane coupling agents, catalysts, solvents and the like can be used.

<< Any Layer >>
The graphic film of the present disclosure is selected from the group consisting of a support layer, a decorative ink receiving layer, a decoration layer, an adhesive layer, a bonding layer, a retroreflective layer, and a release liner under or under a surface protective layer. Can further comprise at least one.

<Support layer>
In the graphic film of the present disclosure, a support layer can be applied below or below the surface protective layer. In particular, a support layer having an elongation at break of about 50% or more, about 55% or more, or about 60% or more can improve the impact resistance of the graphic film.

(Thickness of support layer)
The thickness of the support layer may vary, but from the viewpoint of impact resistance, it may be about 10 μm or more, about 15 μm or more, about 50 μm or less, about 40 μm or less, or about 30 μm or less.

(Resin material)
The support layer may be any material as long as it can support the surface protective layer, and is not limited to the following. For example, (meth) acrylic resin, polyolefin resin, silicone resin, polyurethane resin, epoxy Examples thereof include system resins, phenol resins, polyester resins, alkyd resins, and polycarbonate resins. These can be used alone or in combination of two or more. Among them, polyurethane resins are preferable from the viewpoint of impact resistance. The support layer may be a single layer of these materials or a layer of laminated constitution.

(Optional ingredient)
The support layer of the present disclosure includes, as optional components, a crosslinking agent (for example, a carbodiimide crosslinking agent), a filler, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a dispersant, a plasticizer, and a flow improver. Conventional additives such as surfactants, leveling agents, silane coupling agents (e.g. 3-glycidoxypropyltrimethoxysilane) may be included.

<Decorated ink receptive layer>
In the graphic film of the present disclosure, as shown in FIGS. 2 and 3, a decorative ink receiving layer can be applied under or under the surface protective layer. Such a receptive layer is a layer for receiving the ink of the decorative layer described below, and the decorative layer can be applied to one side or both sides of the receptive layer. Similar to the support layer described above, the impact resistance can be improved by setting the breaking elongation of the receiving layer to about 50% or more, about 55% or more, or about 60% or more.

(Thickness of decorative ink receptive layer)
The thickness of the decorative ink receptive layer may vary, but from the viewpoint of ink receptivity and followability during pressing, the thickness is about 5 μm or more, or about 10 μm or more, about 100 μm or less, about 60 μm or less, or It can be about 50 μm or less.

(Resin material)
The decorative ink receiving layer may be any material as long as it is a material that receives the ink of the decorative layer, and is not limited to the following, and for example, (meth) acrylic polymers can be used. The monoethylenically unsaturated monomer constituting the (meth) acrylic polymer is generally represented by the formula CH ₂ CRCR ⁱ COOR ⁱⁱ (wherein, R ⁱ is hydrogen or a methyl group, R ⁱⁱ is linear or branched) In addition to those represented by an alkyl group, a phenyl group, an alkoxyalkyl group and a phenoxyalkyl group, aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, and vinyl esters such as vinyl acetate are also included. As such a monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Phenoxyalkyl (meth) acrylates such as isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate and 2-methoxy There are alkoxyalkyl (meth) acrylates such as butyl (meth) acrylate and the like, and in order to obtain desired elongation properties, ink receptivity, etc., one or more kinds can be used according to the purpose.

  The (meth) acrylic polymer may be a carboxyl group-containing (meth) acrylic polymer, and may optionally contain a nitrogen atom-containing (meth) acrylic polymer. The carboxyl group-containing (meth) acrylic polymer can be obtained by copolymerizing the above-mentioned monoethylenically unsaturated monomer and the carboxyl group-containing unsaturated monomer. The nitrogen atom-containing (meth) acrylic polymer is obtained by copolymerizing a monoethylenically unsaturated monomer and a nitrogen atom-containing unsaturated monomer.

  This copolymerization can be carried out by radical polymerization. In this case, known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization can be used. The initiator may, for example, be benzoyl peroxide, lauroyl peroxide, an organic peroxide such as bis (4-tert-butylcyclohexyl) peroxydicarbonate, 2,2'-azobisisobutyronitrile, 2,2 ' -Azobis-2-methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (2-methylpropionic acid) dimethyl, azobis 2,4-dimethylvaleroditolyl (AVN), etc. Azo-based polymerization initiators and the like are used. The initiator can be used in an amount of about 0.01 parts by weight or more and about 5 parts by weight or less per 100 parts by weight of the monomer mixture.

  Examples of unsaturated monomers containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxypolycaprolactone monoacrylate, monohydroxyethyl (meth) acrylate phthalate, β-carboxyethyl acrylate, 2- (2-) Meta) acryloyl oxyethyl succinic acid, 2- (meth) acryloyl oxy ethyl hexahydrophthalic acid, etc. are mentioned.

  The carboxyl group-containing (meth) acrylic polymer contains, as a main component, a monoethylenically unsaturated monomer, specifically about 60 parts by mass or more, about 80 parts by mass or more, about 99.5 parts by mass or less, or about 97 Copolymerized in an amount of at most about 0.5 parts by mass, or at least about 3 parts by mass, at most about 40 parts by mass, or at most about 20 parts by mass of a carboxyl group-containing unsaturated monomer Can be obtained.

  As a nitrogen atom-containing unsaturated monomer, N, N-dimethylaminoethyl acrylate (DMAEA), dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl methacrylate (DMAEMA), N, N-dimethylamino Representative examples are dialkylaminoalkyl (meth) acrylamides such as propyl acrylamide (DMAPAA) and N, N-dimethylaminopropyl methacrylamide, and vinyl monomers having a nitrogen-containing heterocycle such as N, N-dimethyl (meth) acrylamide and vinylimidazole. And the like.

  The nitrogen atom-containing (meth) acrylic polymer contains, as a main component, a monoethylenically unsaturated monomer, specifically about 60 parts by mass or more, about 70 parts by mass or more, about 99.5 parts by mass or less, or about 97 Copolymerized in an amount of at most about 0.5 parts by mass, or at least about 3 parts by mass, at most about 40 parts by mass, or at most about 30 parts by mass of a nitrogen atom-containing unsaturated monomer Can be obtained.

(Crosslinking agent)
The decorative ink receptive layer can contain a crosslinking agent, and the receptive layer forms a network structure by crosslinking, and the performance such as chemical resistance is improved. Specific examples of the crosslinking agent include bisamide crosslinking agents (for example, RD 1054 manufactured by 3M), aziridine crosslinking agents (for example, Chemitite (registered trademark) PZ33 manufactured by Nippon Shokubai, NeoCryl (registered trademark) CX-100 manufactured by Avicia) Carbodiimide-based crosslinking agent (eg, Carbodilite V-03, V-05, V-07, manufactured by Nisshinbo Co., Ltd.), epoxy-based crosslinking agent (eg, E-AX, E-5 XM, E5C, manufactured by Soken Chemical Co., Ltd.), isocyanate-based crosslinking agent (eg, For example, Duranate (registered trademark) TPA-100) manufactured by Asahi Kasei Chemicals Corporation can be used. Although a crosslinking agent can be suitably mix | blended in the range from which a desired performance is obtained, For example, It is about 0.01 mass part or more and about 5 mass parts or less with respect to 100 mass parts of (meth) acrylic-type polymers It can be used.

(Other optional ingredients)
The decorative ink receptive layer of the present disclosure contains, as an optional component, a filler, an antioxidant, a UV absorber, a light stabilizer, a heat stabilizer, a dispersant, a plasticizer, and a flow as long as the ink receptivity is not impaired. Conventional additives such as improvers, surfactants, leveling agents, and silane coupling agents may be included.

<Modified layer>
The decorative layer can be used to impart decorativeness or design to the graphic film. When a graphic film is used for a license plate, a pattern, a pattern or the like may be formed on a background portion other than the characters of the license plate. Examples of the decorative layer include a color layer exhibiting a special color or metal color, a pattern such as wood grain or stone, a pattern layer for applying a logo, a pattern or the like to a structure, and the like. As a material of a color layer or a pattern layer, what colored pigments, such as an inorganic pigment, an organic pigment, and a luster etc., were disperse | distributed to binder resin can be used, for example. In one embodiment, the decorative layer can be formed by an inkjet printer, screen printing, offset printing, and the like.

(Thickness of decoration layer)
The thickness of the decorative layer may vary, and in general, when a solvent-based ink is used, it may be about 1 μm or more, or about 2 μm or more, about 8 μm or less, or about 5 μm or less. When a UV curable ink is used, it can be about 1 μm or more, or about 5 μm or more, about 50 μm or less, or about 30 μm or less.

(Pigment)
The pigments used in the decorative layer can be used singly or in combination of two or more. The amount of the pigment used can be generally about 1 part by mass or more, about 2 parts by mass or more, about 30 parts by mass or less, or about 25 parts by mass or less with respect to 100 parts by mass of the ink composition.

a. Organic pigments Organic pigments conventionally known as pigments can be used. As specific examples of the organic pigment, C.I. I. Pigment White 6, C.I. I. Pigment Black 7, C.I. I. Pigment Red 122, 202, 254, 255, C.I. I. Pigment Orange 43, C.I. I. Pigment Violet 19, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, C.I. I. Pigment Brown 23, 25 and C.I. I. Pigment Yellow 74, 109, 110, 128, and C.I. I. And organic pigments such as Pigment Green 7 and 36.

b. Inorganic Pigments Inorganic pigments conventionally known as pigments can also be used. Specific examples of inorganic pigments include carbon black such as furnace black, channel black, thermal black and acetylene black, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, bitumen blue, cobalt blue, titanium yellow, turquoise, molybdate orange And inorganic pigments such as titanium oxide.

c. Slurry In order to improve the dispersibility of the pigment in the ink composition, a slurry in which the pigment is supported on a resin may be used. As such a slurry, a pigment is carried on a vinyl chloride-vinyl acetate copolymer resin, Microlith (TM) Yellow 2040 K, Red 3630 K, Magenta 4535 K, Blue 7080 K, Green 8750 K, Black 0066 K, White 0022 K (BASF) and the like.

(Binder resin)
Suitable binder resins for use with the aforementioned pigments include, but are not limited to, vinyl chloride-vinyl acetate copolymers containing vinyl chloride units and vinyl acetate units. The vinyl chloride-vinyl acetate copolymer may contain other polymerized units, such as vinyl alcohol units, maleic acid units, hydroxyalkyl acrylic ester units and the like. As specific examples of such binder resin, SOLBIN (registered trademark) C, SOLBIN (registered trademark) CL, SOLBIN (registered trademark) CNL (vinyl chloride-vinyl acetate copolymer resin, Nisshin Chemical Industry Co., Ltd.), SOLBIN (SOLBIN) Registered trademark A, SOLBIN (registered trademark) AL (vinyl chloride-vinyl acetate-vinyl alcohol copolymer resin, Nisshin Chemical Industry Co., Ltd.), UCAR (registered trademark) Solution Vinyl Resin VYHH (vinyl chloride-vinyl acetate copolymer resin) Dow Chemical Japan Ltd.), UCAR (R) Solution Vinyl Resin VAGH (vinyl chloride-vinyl acetate-vinyl alcohol copolymer resin, Dow Chemical Japan Ltd.), UCAR (R) Solution Vinyl Resin VM H (vinyl chloride-vinyl acetate-maleic acid copolymer resin, Dow Chemical Japan Ltd.), UCAR (registered trademark) Solution Vinyl Resin VMCC (vinyl chloride-vinyl acetate-maleic acid copolymer resin, Dow-Chemical Japan Ltd. ), UCAR (registered trademark) Solution Vinyl Resin VMCA (vinyl chloride-vinyl acetate-maleic acid copolymer resin, Dow Chemical Japan Co., Ltd.), UCAR (registered trademark) Solution Vinyl Resin VROH (vinyl chloride-vinyl acetate-hydroxyalkyl) Acrylic ester copolymer resins, Dow Chemical Japan Ltd., VINNOL (registered trademark) E15 / 45 (vinyl chloride-vinyl acetate copolymer resin, Wacker Chemie AG), and the like.

  The binder resin can be used alone or in combination of two or more. The amount of the binder resin used can be generally about 5 parts by mass or more, about 10 parts by mass or more, about 50 parts by mass or less, or about 20 parts by mass or less with respect to 100 parts by mass of the ink composition.

(Optional ingredient)
a. Solvent The ink composition for forming the decorative layer is, for example, methyl ethyl ketone, methyl isobutyl ketone, ketones such as acetylacetone, aromatic hydrocarbons such as toluene, xylene, ethanol, etc. in order to improve workability and coating properties. It may further contain an organic solvent such as an alcohol such as isopropyl alcohol, an ester such as ethyl acetate or butyl acetate, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or an ether such as dipropylene glycol monomethyl ether acetate. It is not limited. Generally, the amount of the organic solvent used can be about 1 part by mass or more, about 5 parts by mass or more, about 90 parts by mass or less, or about 80 parts by mass or less with respect to 100 parts by mass of the ink composition.

b. Other Optional Components The ink composition contains, as other optional components, conventionally used additives such as an ultraviolet light absorber, a light stabilizer, a thermal stabilizer, a dispersant, a plasticizer, a flow improver, and a leveling agent. May be.

<Adhesive layer>
Adhesives that can be used for the adhesive layer include, but are not limited to, for example, based on (meth) acrylic pressure sensitive adhesives, natural rubber, synthetic rubber, polyesters, polyethers, silicones or other polymers Other pressure sensitive adhesives can be used, including additives such as tackifiers, antioxidants, UV absorbers, plasticizers, etc. as required. In the present disclosure, "pressure sensitive adhesive" refers to an adhesive that is permanently tacky at room temperature, adheres to various surfaces with light pressure, and does not exhibit a phase change (liquid to solid). The adhesive may be thermally crosslinked or crosslinked by radiation (eg, electron beam or ultraviolet light) by a crosslinking agent.

(Thickness of adhesive layer)
The thickness of the adhesive layer can vary, and can generally be about 5 μm or more, or about 10 μm or more, about 150 μm or less, or about 50 μm or less.

(Optional component or member)
a. White pigment A white pigment can be blended in the adhesive layer. As a white pigment, especially titanium oxide is excellent in the ability to hide the color of the base plate (base material) to which a graphic film is applied. As titanium oxide, both rutile type and anatase type can be used, and as examples of commercially available products, Typek (registered trademark) R-820, R-830, R-930, A-100, and A-. 220 (Ishihara Sangyo Co., Ltd.), Thai Pure (registered trademark) R-105, R-960 (Dupont Co., Ltd.) and the like.

b. The substrate side of the laminate in which the adhesive layer is laminated on the substrate may be applied to the decorative ink receptive layer directly or via the bonding layer described below. In this case, the white pigment can be blended in the adhesive layer and / or the substrate.

  The material of the substrate is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate (PET), polycarbonates, polyvinyl chloride, polyvinylidene chloride, polystyrene, (meth) acrylic polymers, or Polyamide etc. can be mentioned, and these can be used individually or in combination of 2 or more types, respectively. The substrate may be a single layer of these materials or a layer of laminated construction. The substrate may have the ability to receive a decorative ink, and a retroreflective layer described below can also be used.

  Although the thickness of the substrate may vary, it may be about 5 μm or more, about 10 μm or more, about 500 μm or less, or about 300 μm or less from the viewpoint of handleability and followability during press processing.

<Bonding layer>
The bonding layer is a layer for bonding each layer of the graphic film, and may be disposed between each layer as needed. The bonding layer can be formed of a conventionally known adhesive, and is appropriately selected according to the material of the article to be bonded. As an adhesive for the bonding layer (hereinafter sometimes referred to as "bonding agent"), for example, those based on (meth) acrylic resin, epoxy resin, polyester resin, etc. can be used, and The same material can also be used. In the case where a decorative layer, a retroreflective layer, and the like are included below the bonding layer, the transparent layer is preferably transparent to visible light so as not to affect the visibility.

(Thickness of bonding layer)
The thickness of the bonding layer is not particularly limited, but may generally be about 5 μm or more, or about 10 μm or more, about 150 μm or less, or about 50 μm or less.

Retroreflective Graphic Film of First Embodiment
The first embodiment of the retroreflective graphic film 300 illustrated in FIG. 4 has a retroreflective layer 310 having a generally flat major surface 316 and a structured surface 314 on the opposite side of the major surface. Structured surface 314 includes a plurality of cube corner elements 312. Adhesive layer 330 is disposed adjacent to retroreflective layer 310. The adhesive layer 330 includes an adhesive 332, and one or more barrier layers 334, and further has a release liner 336 such as a PET film, a polyethylene film, a laminated paper or the like, which is release-treated with a silicone resin or the like described below. It is also good.

(Recursive reflection layer)
The retroreflective layer 310 can include any suitable cube corner element 312 configured to reflect incident light back towards the light source. The cube corner element 312 may have any suitable structure as long as it exhibits a retroreflective function. For example, cube corner elements may be complete cubes (sometimes referred to as full cubes or geometry cubes), truncated cubes, cube corner triangular pyramids, cube corner cavities, etc. For example, a cube-corner element includes a three-sided structure having three sides substantially orthogonal to one another. In use, the retroreflective graphic film 300 is usually placed with its display surface facing the intended viewer and light source. Light incident on the display surface is reflected by each of the three sides of cube-corner element 312 such that it enters retroreflective graphic film 300 and exits the display surface in a direction substantially toward the light source. In some implementations, cube corner elements 312 are angled relative to one another to improve retroreflective properties at a wider range of incident ray angles. Exemplary embodiments of retroreflective sheeting based on cube corners are described in U.S. Patent Nos. 5,138,488 (Szczech), 5,387,458 (Pavelka), and 5,450,235 ( Smith), U.S. Pat. Nos. 5,605,761 (Burns), 5,614,286 (Bacon), 5,691,846 (Benson, Jr.), and 7,422,334. No. (Smith).

a. Material of Retroreflective Layer As a resin suitably used for the retroreflective layer 310, for example, polycarbonate, polymethyl (meth) acrylate, polyethylene terephthalate, aliphatic polyurethane, and ethylene copolymer, and their ionomers, the above-mentioned decoration Materials used for the ink receiving layer may, for example, be mentioned. The cube corner elements 312 included in the retroreflective layer 310 may be formed by direct casting on a resin film as described, for example, in US Pat. No. 5,691,846 (Benson, Jr.) it can. When the retroreflective layer is formed by radiation curing, a cured product of a radiation curable composition containing, for example, polyfunctional (meth) acrylate, epoxy (meth) acrylate, (meth) acrylated urethane and the like is mentioned as a suitable resin. Be The above-mentioned resin is advantageous for any one or more of, for example, heat stability, environmental stability, transparency, excellent releasability from a tool or a mold, and adhesion with other layers, transparency, Cured products of polycarbonate and epoxy (meth) acrylate are particularly advantageous in terms of heat stability and the like.

b. Thickness of Retroreflective Layer The thickness of the retroreflective layer may vary, and is generally about 40 μm or more, about 50 μm or more, or about 55 μm or more, about 150 μm or less, about 100 μm or less, or about 60 μm or less be able to. The thickness of the retroreflective layer refers to the distance between the major surface of the retroreflective layer and the top of the structured surface. The height of the cube-corner elements can vary, and can generally be about 50 μm or more, about 70 μm or more, or about 80 μm or more, about 150 μm or less, about 120 μm or less, or about 100 μm or less. The height of the cube-corner element means the length in the direction perpendicular to the surface of the retroreflective graphic film of the area effective for retroreflection of the side surface constituting the cube-corner element.

(Barrier layer)
The barrier layer 334 has sufficient structural integrity to prevent the adhesive 332 from flowing into the low index layer 338 formed between the structured surface 314 and the barrier layer 334. The barrier layer 334 may be in direct contact with the tip of the cube corner element 312, may be spaced apart from the tip of the cube corner element 312, and may be slightly pushed into the tip of the cube corner element 312 . The dimensions and spacing of the barrier layers may vary. In one embodiment, the barrier layer may form a pattern of grids, stripes, dots, characters, etc. on the retroreflective graphic film.

  The barrier layer 334 provides a physical "barrier" between the adhesive 332 and the cube corner element 312, enabling the formation of a low index layer 338. The presence of the barrier layer 334 allows retroreflection of light rays 350 incident on the low index layer 338 and / or the portion of the structured surface 314 adjacent to the barrier layer 334. A portion of the adhesion layer 330 that does not include the barrier layer 334 adheres to the cube corner element 312, thereby efficiently sealing the retroreflective area to form an optically active area or cell. The adhesive 332 also holds the retroreflective structure 320 comprised of the retroreflective layer 310 and the adhesive layer 330 together as a whole, thereby eliminating the need for a separate sealing film and process. Do.

a. Barrier Layer Material Any material can be used as a material for the barrier layer 334 that prevents the adhesive 332 from contacting the cube corner elements 312 or entering into the low index layer 338. Representative materials used in the barrier layer include resins, UV curable polymers, films, inks, dyes, pigments, inorganic materials, particles, beads, and the like.

b. Barrier Layer Thickness The thickness of the barrier layer can vary, and can generally be about 2 μm or more, or about 3 μm or more, about 10 μm or less, about 8 μm or less, or about 4 μm or less.

(Low refractive index layer)
As shown in FIG. 4, light rays 350 incident on cube corner elements 312 adjacent to low index layer 338 are retroreflected. In the present disclosure, the area of retroreflective graphic film 300 that includes low refractive index layer 338 is an optically active area. In contrast, the area of retroreflective graphic film 300 that does not include low refractive index layer 338 is an optically inactive area as it does not substantially retroreflect incident light ray 350 as shown in FIG. .

  The low refractive index layer 338 is a material having a refractive index of about 1.30 or less, about 1.25 or less, about 1.20 or less, about 1.15 or less, about 1.10 or less, or about 1.05 or less Can be included. For example, as a low refractive index material, air and, for example, U.S. patent application no. 61 / 324,249, the entire disclosure of which is incorporated herein by reference.

(Method of manufacturing retroreflective structure of retroreflective graphic film of the first embodiment)
The method of manufacturing the retroreflective structure of the retroreflective graphic film of the first embodiment illustrated in FIG. 4 includes, for example, disposing a barrier layer 334 on the adhesive 332 and then bonding obtained. Laminating the layer 330 to the retroreflective layer 310. Adhesive layer 330 with barrier layer 334 can be formed in a variety of ways, including but not limited to the following exemplary methods. In one exemplary embodiment, the material forming the barrier layer is printed on an adhesive. The printing method may be a non-contact method, such as printing using an inkjet printer, or may be a contact printing method, such as flexographic printing. In another exemplary embodiment, the material forming the barrier layer is printed on a flat release surface, for example using an inkjet or screen printing method, and then transferred from the flat release surface onto the adhesive. In another exemplary embodiment, the material forming the barrier layer is flood coated onto a liner having a microstructured surface, and the barrier layer has a microstructured surface by laminating an adhesive thereon. Transfer from the liner to the adhesive.

Retroreflective Graphic Film of Second Embodiment
The second embodiment of the retroreflective graphic film 400 illustrated in FIG. 5 has a retroreflective layer 410 comprising a structured surface 414 and a reflective layer 435 adjacent to the structured surface 414. Here, a reflective layer 435 is used in place of the low refractive index layer 338 of FIG. The reflective layer 435 may be, for example, an aluminum coating on the structured surface 414. An adhesive layer 430 comprising an adhesive 432 may be provided on the retroreflective graphic film 400 adjacent the reflective layer 435, the adhesive layer 430 further comprising a release liner 436 further described below on the opposite side of the retroreflective layer 410. You may have. Structured surface 414 includes a plurality of cube corner elements 412.

(Reflective layer)
As shown in FIG. 5, the light ray 450 incident on the cube corner element 412 is retroreflected by the combination of the reflective layer 435 and the cube corner element 412. The area of the retroreflective graphic film 400 where the reflective layer 435 is adjacent to the cube corner element 412 is an optically active area.

  The reflective layer 435 desirably has good adhesion to the cube-corner element 412. As the reflective layer 435, for example, a metal film formed by vapor deposition can be used. Aluminum, silver or the like can be used as the vapor deposition metal. The adhesion between the surface of the cube corner element 412 and the deposited metal film may be improved by primer treatment such as titanium sputtering. It is known that the irradiation angle of cube corner element 412 is increased by using a metal film. Instead of a metal film, the reflective layer 435 may comprise a multilayer reflective coating as described, for example, in US Pat. No. 6,243,201 (Fleming), the entire disclosure of which is incorporated herein. The thickness of the reflective layer 435 can generally be about 30 nanometers or more and about 80 nanometers or less.

<Arbitrary component or member in retroreflective graphic film>
(Infrared absorber)
The retroreflective graphic film of the present disclosure may further comprise an infrared absorber. In this case, the infrared absorber is contained in any layer on the track of the light incident upon the retroreflective graphic film and reflected. For example, a retroreflective layer (for example, a retroreflective element, a body layer, a seal film, an adhesive layer, etc.), a surface protective layer, a decorative ink receptive layer, a decorative layer, a bonding layer, an adhesive layer An infrared absorber may be included. An infrared absorbing layer (not shown) containing an infrared absorbing agent and a binder resin may be disposed between the surface protective layer and the retroreflective layer. In one embodiment, an infrared absorber is included in the retroreflective layer. The average transmittance of light having a wavelength of 800 to 1000 nm of the layer containing the infrared absorber can be preferably about 80% or less, about 70% or less, or about 60% or less. The average transmittance of light having a wavelength of 800 to 1000 nm of the layer containing the infrared absorber may be about 0.5% or more, about 1% or more, or about 5% or more.

  When the infrared light is incident on the retroreflective graphic film containing the infrared absorber at an arbitrary incident angle, the infrared light is absorbed by the layer containing the infrared absorber to suppress the retroreflection of the infrared light. Such retroreflective graphic films are particularly useful for license plates which are required to have visibility by the ALPR infrared system.

  As the infrared absorber, a material that absorbs near infrared radiation (for example, a wavelength of about 760 nm to about 1500 nm) can be used. For example, infrared rays such as cyanine compounds, phthalocyanine compounds, dithiol metal complexes, naphthoquinone compounds, diimonium compounds, azo compounds, etc. Absorbent dyes and cesium tungsten oxide (CWO), antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, zinc oxide, indium oxide, tin oxide, cesium oxide And infrared absorbing pigments such as zinc sulfide. It is advantageous that the infrared absorber comprises cesium tungsten oxide because it is particularly excellent in weatherability. Although cesium tungsten oxide exhibits a deep blue color, it is also advantageous in that the necessary infrared absorption can be maintained without adversely affecting the background color (background color) by adjusting the concentration appropriately.

  As the cesium tungsten oxide, one having a general formula CsxWyOz (wherein, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) can be preferably used. More preferably, 0.1 ≦ x / y <1, 2.45 ≦ z / y ≦ 3.0, and particularly preferably x / y = 0.33 and z / y = 3.

  The average particle size of cesium tungsten oxide is preferably about 300 nm or less, or about 100 nm or less, or about 50 nm or less from the viewpoint of dispersibility, visibility of background color (underground color) in visible light region, etc. it can. The average particle size of the cesium tungsten oxide may be about 10 nm or more, or about 20 nm or more.

(Whiteness improving material)
Including an infrared absorber in the retroreflective graphic film may reduce the whiteness of the retroreflective graphic film. This is because many of the commonly used infrared absorbers show some absorption in the visible light range. Thus, to enhance the whiteness of the retroreflective graphic film, optionally, a whiteness enhancing material such as titanium oxide, zinc oxide, or a brightening agent is included in the retroreflective graphic film, or retroreflective It may be applied between layers of graphic film. By using a whiteness enhancing material, the retroreflective graphic film will appear white in sunlight.

  Whiteness enhancing materials can be included in retroreflective graphic films in various patterns, areas, configurations, and shades. In some embodiments, the whiteness enhancing material coats at least a portion of the retroreflective graphic film. Some whiteness enhancing materials may reduce the retroreflective performance of retroreflective graphic films. In that case, retroreflectivity having a desired level of retroreflection characteristics and whiteness by controlling the application area of the whiteness improving material, the size and density of individual elements constituting the application pattern of the whiteness improving material, etc. Graphic films can be obtained.

(Sealing film)
The retroreflective graphic films of the present disclosure may also have seal films applied to the back of cube corner elements, such as those disclosed in US Pat. Nos. 4,025,159 (McGrath) and 5,117,304. (Huang), the entire disclosure of which is incorporated herein by reference. The sealing film can hold an air boundary at the back of the cube that allows total internal reflection at the boundary and blocks the ingress of contaminants such as dirt and / or moisture.

<Retroreflection characteristics of retroreflective graphic film>
Regarding the retroreflection characteristics of the retroreflective graphic film of the present disclosure, the retroreflection coefficient (based on JIS Z 9117) at an observation angle of 0.2 degrees and an incident angle of 5 degrees should be at least about 1 cd / lx / m ² Can. In certain preferred embodiments, the retroreflection coefficient can be about 45 cd / lx / m ² or more, or about 50 cd / lx / m ² or more. For example, about white specified in ISO7591: 1982 is preferably about 45 cd / lx / m ² or more, and about yellow is preferably about 30 cd / lx / m ² or more. In the case of enclosed lens type 1-B-b according to JIS Z 9117, about 35 cd / lx / m ² or more for white, about 25 cd / lx / m ² or more for yellow, and about 10 cd / lx / m ² for red ² or more, for the yellow red about 13cd / lx / m ² or more, about 5cd / lx / m ² or more for the green, it is desirable for the blue is about 3cd / lx / m ² or more.

<Peeling liner>
The graphic film for a license plate of the present disclosure applies a releasable film member such as a release liner to the adhesive layer and / or the surface protective layer for the purpose of transfer of the adhesive layer, protection from scratches and the like. be able to.

  Examples of release liners include paper; plastic materials such as polyethylene, polypropylene, polyester, cellulose acetate and the like; and papers coated with such plastic materials. These release liners may have surfaces that have been release treated with silicone or the like. The thickness of the release liner can generally be about 5 μm or more, about 15 μm or more, or about 25 μm or more, about 300 μm or less, about 200 μm or less, or about 150 μm or less.

<Optional Properties of Graphic Film for License Plate>
(Breaking strength)
The graphic film for a license plate of the present disclosure may have a breaking strength of preferably about 5 N / 25 mm or more, about 10 N / 25 mm or more, or about 20 N / 25 mm or more from the viewpoint of good durability. From the viewpoint of ease, it may preferably have a breaking strength of about 200 N / 25 mm or less, about 175 N / 25 mm or less, or about 150 N / 25 mm or less. In the present disclosure, the breaking strength is a value measured in accordance with JIS Z 0237.

(Growth)
The graphic film for a license plate of the present disclosure is preferably about 30% or more, or about 35% or more, from the viewpoint of preventing the occurrence of cracks during embossing or debossing, and floating from an adherend such as a base plate. It may have an elongation of about 400% or less, or preferably about 400% or less, from the viewpoint of good mechanical strength. In the present disclosure, the elongation is a value measured in accordance with ASTM test method D882-80a.

<Manufacturing method of graphic film for license plate>
Although the method of producing the graphic film for a license plate is exemplarily described with reference to FIGS. 1 to 3, the method of producing the graphic film is not limited thereto.

  As a method for producing the graphic film 50 of FIG. 1 (but excluding the printing layer 45), for example, a coating liquid of the surface protective layer 40 is applied on a release liner, dried, and optionally, the surface protective layer 40 is A decorative ink is applied by an inkjet printer or the like to form a decorative layer 20, and optionally, a coating liquid for a support layer is applied and dried to form a laminate 1. Next, an adhesive is applied on a release liner and dried to form an adhesive layer 10, whereby a laminate 2 is obtained. By pasting the surface protective layer 40 side of the laminate 1 and the adhesive layer 10 side of the laminate 2, it is possible to obtain the graphic film 50 having the configuration of FIG. 1.

  As a method of manufacturing the graphic film 100 of FIG. 2, for example, the coating liquid of the surface protective layer 140 is applied on a release liner, dried, and optionally, the coating liquid of the support layer is coated and dried. Next, the coating liquid for the decorative ink receiving layer 130 is applied onto the surface protective layer 140 or the support layer, and dried to form the decorative ink receiving layer 130, and optionally, the ink jet printer is used on the receiving layer 130. The decorative layer 120 is printed to obtain a laminate 1. Next, an adhesive is applied on a release liner and dried to form an adhesive layer 110, whereby a laminate 2 is obtained. By laminating the decorative ink receiving layer 130 side of the laminate 1 and the adhesive layer 110 side of the laminate 2, the graphic film 100 having the configuration of FIG. 2 can be obtained.

  As a method of producing the graphic film 200 of FIG. 3, for example, the coating liquid of the surface protective layer 240 is applied on a release liner, dried, and optionally the coating liquid of the support layer is coated and dried to form a laminate 1. . Next, a bonding agent is applied on a release liner and dried to form a bonding layer 230, and a laminate 2 is obtained. The surface protective layer 240 side of the laminate 1 and the bonding layer 230 side of the laminate 2 are bonded together to obtain a laminate A. Next, the coating liquid of the decorative ink receiving layer 215 is applied on a release liner and dried to form a decorative ink receiving layer 215, and optionally, the decorative layer is printed on the receiving layer 130 with an inkjet printer. The laminate 3 is obtained. Next, an adhesive is applied on a release liner and dried to form an adhesive layer 210, whereby a laminate 4 is obtained. A laminate B is obtained by laminating the decorative ink receiving layer 215 side of the laminate 3 and the adhesive layer 210 side of the laminate 4. Then, the release liner on the decorative ink receiving layer 215 side of the laminate B is removed, and the decorative layer 220 is optionally printed on the receiving layer 130 by an inkjet printer. The graphic film 200 having the configuration of FIG. 3 is obtained by removing the release liner on the bonding layer 230 side of the laminate A and bonding the bonding layer 230 side of the laminate A and the receiving layer 215 side of the laminate B. be able to.

Here, as a method for the preparation above, cyclohexanone absorption when applying cyclohexanone the surface protective layer surface is about 0.0017 g / cm ² or more and about 0.0025 g / cm ² or less, a surface protection It further comprises the step of curing the layer. The curing at this stage may be at least partially cured, and does not have to be fully cured. The curing process of the surface protective layer may be applied at any stage after the surface protective layer is formed, but from the viewpoint of productivity etc., the coating liquid of the surface protective layer is applied onto the release liner, It is preferable to apply at the drying stage. As a curing means, any curing means such as heat curing or radiation curing such as ultraviolet light and electron beam can be adopted, but heat curing is preferable because heat at drying can be used. As the heat treatment temperature for heat curing, cyclohexanone absorption when applying cyclohexanone the surface protective layer surface after curing, of about 0.0017 g / cm ² or more and about 0.0025 g / cm ² or less Although it may be set as appropriate, for example, it can be set to about 100 ° C. or more, about 105 ° C. or more, or about 110 ° C. or more, about 145 ° C. or less, about 140 ° C. or less, or about 135 ° C. or less. In addition, the graphic film before this curing may be called "graphic film precursor for license plate".

  As a coating means in each of the above manufacturing methods, a conventional coater such as a bar coater, a knife coater, a roll coater, a die coater or the like can be used. The decorative ink-receptive layer may be formed into a film by a melt extrusion method or the like, and may be used by bonding it to an adhesive layer.

<License plate>
In one embodiment of the present disclosure, there is provided a license plate comprising the above graphic film.

(Base plate)
In general, a metal plate or a resin plate can be used as the base plate of the license plate. As a metal plate, an aluminum plate, a stainless steel plate, an iron plate etc. are mentioned. A polycarbonate board, a polyester board, a vinyl chloride board etc. are mentioned as a resin board. If necessary, these plate materials may be formed into a shape such as a frame.

(appearance)
The license plate may generally include numbers, letters, graphics, patterns or combinations thereof. In one embodiment, the appearance of the license plate is defined by the government and / or jurisdiction. In another embodiment, the display can be formed by a print layer. In still another embodiment, for example, in the license plate, the display portion can be formed by combining the embossed portion (convex portion) or the debossed portion (concave portion) and the printing layer. The depths of the embossed portion and the debossed portion are generally about 1 mm or more and about 2 mm or less, respectively, but are not limited to this range.

(Printed layer)
The printing layer is generally formed using a solvent-based ink called roll coating ink, and contains the above-described pigment and a binder such as melamine resin, alkyd resin, urethane resin, and a mixed resin thereof. The ink composition can be formed by applying it on a surface protective layer or the like by roll coating or the like and printing it at a predetermined temperature and time. Specifically, as the ink composition, NSP-UP 401K-1 Green (manufactured by Nikkei Bixs Co., Ltd.), MEG screen ink (manufactured by Teikoku Ink Mfg. Co., Ltd.) which is a one-component heat-curable ink, etc. Can.

<Manufacturing method of license plate>
Although the method of manufacturing the license plate of the present disclosure is exemplarily described with reference to FIGS. 6A to 6E, the method of manufacturing the license plate is not limited thereto.

  In the graphic film shown in FIG. 6A, an adhesive layer 520, a decoration layer 542, a decoration ink receiving layer 545, and a surface protection layer 544 are laminated on a release liner 536.

  As shown in FIG. 6B, the graphic film laminated plate is formed by removing the release liner 536 and adhering and laminating the adhesive layer 520 to the aluminum plate 560 which is a base plate.

  Next, as shown in FIG. 6C, using a blank press die 570, the graphic film laminate plate is blank-pressed to a desired size and cut out.

  As shown in FIG. 6D, the cut out graphic film laminate plate is embossed and / or debossed at normal temperature to form a display portion and a rim frame portion of the license plate. In FIG. 6D, the convex portion (embossed portion) is shown as a pedestal of the display portion. The frame portion can impart strength to the license plate to prevent deformation of the license plate.

As shown in FIG. 6E, the print layer 546 is formed by roll coating or the like on the convex portion (embossed portion) of the embossed graphic film laminate plate. Next, the surface protective layer 544 is cured so that the amount of absorbed cyclohexanone when applying cyclohexanone to the surface of the surface protective layer 544 is about 0.0010 g / cm ² or less, and the license plate 500 including the graphic film is obtained. It can be made. The curing at this stage does not need to be complete curing, but is preferably complete curing from the viewpoint of solvent resistance and the like. Here, complete curing means a state in which the curing reaction does not proceed further. As a curing means for the surface protective layer, any curing means such as heat curing or radiation curing such as ultraviolet light and electron beam can be adopted, but heat can be used at the time of forming the printing layer, so heat curing is possible. Is preferred. The heat treatment temperature for heat curing may be appropriately set so that the amount of absorbed cyclohexanone when cyclohexanone is applied to the surface protective layer surface of the graphic film is about 0.0010 g / cm ² or less, but the graphic film The temperature can be set, for example, to about 150 ° C. or more, about 155 ° C. or more, or about 160 ° C. or more, as long as problems such as yellowing do not occur. In the license plate obtained by the method, since the surface protective layer is excellent in solvent resistance, the clear protective layer conventionally applied to the outermost surface can be omitted.

Examples 1 to 3 and Comparative Examples 1 to 6
Although specific embodiments of the present disclosure are illustrated in the following examples, the present invention is not limited thereto. All parts and percentages are by weight unless otherwise stated.

<material>
The materials used in this example are shown in Table 1.

  The materials shown in Table 1 were mixed at the mixing ratio shown in Table 2 to prepare coating solutions for producing a surface protective layer, a support layer, a decorative ink receiving layer, a bonding layer, and an adhesive layer. Here, all the numerical values in Table 2 mean parts by mass.

  With respect to the preparation of various coating solutions, the coating solution for the surface protective layer and the support layer was prepared by mixing each material at one time. The coating liquid of the decorative ink receptive layer is mixed with the Julimer® YN-5 and SK dyne® 1506 BHE so that the solid content ratio is about 50: about 50, and then the mixture is further mixed with E. Made by adding -5XM and ethyl acetate. The coating liquid for the bonding layer was prepared by mixing SK dyne (registered trademark) 1310 and ethyl acetate, and further adding a bisamide crosslinking agent to the mixture. The coating solution for the adhesive layer is formed by adding Ti-Pure® R-960 to Jurimer® YN-5 to form a mixture, and then adding Acreset® 8820 to the mixture, Furthermore, it produced by adding 2-butanone and a bisamide crosslinking agent.

<Preparation of Graphic Film and License Plate for License Plate>
Example 1
A coating solution for the surface protective layer, TL-1 is coated on Lumirror® T-60 (Toray Industries, Inc .: 50 μm thick PET carrier film) using a knife coater, and at 100 ° C. for 10 minutes It dried and produced the lamination film 1 provided with a surface protection layer about 30 micrometers thick. Here, since TL-1 contains a crosslinking agent, Carbodilite (registered trademark) V-02, carboxyl groups of the carboxyl group- and silanol group-containing resin are cured and crosslinked by heat treatment at 100 ° C. for 10 minutes.

  TAL-1 which is a coating liquid for a bonding layer is coated on Purex (registered trademark) A-31 (manufactured by Teijin DuPont Film Co., Ltd .: PET release liner having a thickness of 38 μm) using a knife coater at 100 ° C. After drying for 5 minutes, a laminated film 2 provided with a bonding layer having a thickness of about 20 μm was produced.

  It laminated so that the surface protective layer of the laminated film 1 and the joining layer of the laminated film 2 may overlap, and laminated film A was produced.

  A coating solution for a decorative ink receptive layer, GR-1 is coated on ACW 200 (manufactured by 3M: 55 μm thick PET carrier film) using a knife coater, dried at 100 ° C. for 5 minutes, and about 30 μm. A laminated film 3 provided with a thick decorative ink receiving layer was produced.

  Coat WAL-1, a coating solution for adhesive layer, on Purex (registered trademark) A-55 (manufactured by Teijin DuPont Film Co., Ltd .: PET release liner with a thickness of 38 μm) using a knife coater at 100 ° C. After drying for 5 minutes, laminated film 4 having a white adhesive layer of about 20 μm thickness was produced.

  It laminated so that the decoration ink receptive layer of laminated film 3 and the white adhesion layer of laminated film 4 may overlap, and laminated film B was produced.

  After removing ACW200 from laminated | multilayer film B, the decoration layer was printed with the inkjet printer (made by MIMAKI ENGINEERING Co., Ltd .: JV-33-130) on a decoration ink receptive layer. Next, Lumira (registered trademark) T-60 of the laminated film A is replaced with a protective film LD-K-1020 (Hitachi Chemical Co., Ltd.), and then Purex (registered trademark) A-31 is removed, and the laminated film is formed. The bonding layer of A and the decorative ink receiving layer of the laminated film B were laminated to produce a graphic film for a license plate.

  After removing Purex (registered trademark) A-55 from the graphic film concerned, the graphic film is laminated on an aluminum plate (A1050P JIS H4000, 1.0 mm × 165.5 mm × 330.5 mm) which is a base plate. , Graphic film laminated plate was produced.

  The laminated plate was embossed at normal temperature with an embossing machine to form projections of vehicle numbers. After removing the protective film, the print layer is coated with an organic solvent-based color ink for roll coating (NSP-UP 401K-1 Green, manufactured by Hihiro Bixs Co., Ltd.) by the roll coating method only on the protrusions of the vehicle number. It formed. Dry in oven at 150 ° C. for 10 minutes to make a license plate containing graphic film. Here, the silanol group of the carboxyl group- and silanol group-containing resin is cured and crosslinked by heat treatment at 150 ° C. for 10 minutes.

(Example 2)
A coating solution TL-1 for the surface protective layer and a coating solution US1 for the support layer are knifed onto Lumirror® T-60 (made by Toray Industries, Inc .: PET carrier film 50 μm thick). The film was sequentially coated using a coater and dried at 100 ° C. for 10 minutes to produce a laminated film a having a surface protective layer of about 10 μm thickness and a support layer of about 25 μm thickness. A graphic film for a license plate and a license plate were produced in the same manner as in Example 1 except that a laminated film a was used in place of the laminated film 1 in Example 1. Here, as a result of measuring the breaking elongation of only the support layer having a thickness of about 35 μm using Tensilon TC-1325A manufactured by ORIENTIC CO., LTD., The breaking elongation was 90%.

(Example 3)
In the same manner as in Example 1, a laminated film 1 provided with a surface protective layer is prepared, and a decorative layer is formed on the surface protective layer of the laminated film 1 by an inkjet printer (JV-33-130, manufactured by Mimaki Engineering Co., Ltd.). Was printed. Then, in the same manner as in Example 1, a laminated film 4 provided with a white adhesive layer was produced, and the surface protection layer of the laminated film 1 and the white adhesive layer of the laminated film 4 were laminated to produce a graphic film for license plate A license plate was produced in the same manner as in Example 1 except for the above.

(Comparative example 1)
A graphic film and a license plate for a license plate were produced in the same manner as in Example 1 except that the heat treatment in the laminated film 1 was changed from 100 ° C. and 10 minutes to 150 ° C. and 10 minutes.

(Comparative example 2)
A graphic film and a license plate for a license plate were produced in the same manner as in Example 1 except that the heat treatment after forming the printing layer was changed from 150 ° C. and 10 minutes to 100 ° C. and 10 minutes.

(Comparative example 3)
A graphic film and a license plate for a license plate were produced in the same manner as in Example 1 except that the coating liquid for the surface protective layer in the laminated film 1 was changed from TL-1 to TL-2.

(Comparative example 4)
A graphic film and a license plate for a license plate were produced in the same manner as in Comparative Example 3 except that the heat treatment in the laminated film 1 was further changed from 100 ° C. and 10 minutes to 150 ° C. and 10 minutes.

(Comparative example 5)
A graphic film and a license plate for a license plate were produced in the same manner as in Example 1 except that the coating liquid for the surface protective layer in the laminated film 1 was changed from TL-1 to TL-3.

(Comparative example 6)
A graphic film and a license plate for a license plate were produced in the same manner as in Example 1 except that the coating liquid for the surface protective layer in the laminated film 1 was changed from TL-1 to TL-4.

<Evaluation test>
The properties of the graphic film and the license plate containing the film were evaluated using the following test method.

(Cyclohexanone absorption test)
The graphic license plates of Examples 1 to 3 and Comparative Examples 1 to 6 are cut into 4 cm squares, and the license plates are placed on a precision chemical balance under an atmosphere of 25 ° C., and the main solvent of the green ink of the printing layer The cyclohexanone is dropped by a dropper (about 19 to about 21 mg) with a syringe and applied to the surface of the surface protective layer. After 15 seconds, the droplet is absorbed by Bencot (registered trademark) etc., and the mass A (g) of cyclohexanone absorbed and left on the license plate immediately, ie, (the mass of the license plate after droplet absorption (g) )-(Record the value of the mass of the license plate (g) before dropping). The diameter B (cm) of the solvent mark of substantially circular cyclohexanone is measured with a caliper or the like, and the cyclohexanone absorbed amount of the license plate is calculated from the following formula 1.

(Appearance quality test of printed layer)
The appearance change of the printing layer of the produced license plate is visually observed. Those having no change in appearance are regarded as “good”, and those whose appearance is confirmed to change are regarded as “defective”. Here, as a judgment standard of "defect", the edge part of the printing layer is whiteout like FIG. 9 (a) and FIG. 10 (a), and the surface protection layer accompanying the solvent of printing ink It is based on the fact that at least one of those in which surface roughening occurs due to dissolution and / or swelling is generated.

(Chemical resistance test)
Using a lacquer thinner (Sankyo Chemical Co., Ltd .: RA-50) impregnated with a pressure of 500 g, wipe the surface protection layer of the portion of the license plate where the printing layer is not formed for 30 cycles. . Then, the presence or absence of the appearance change of the surface protective layer is visually observed, and the following five-step evaluation is performed. Graphic films of 4 points or more are practically acceptable.
5: no change 4: slight scratches 3: slight surface roughness 2: apparent surface roughness & damage 1: surface dissolution

(Impact resistance test: Dupont impact test)
An impact resistance test according to JIS K-5600-5-3 is performed on the produced license plate, and damage such as cracking and peeling in the coating film is visually observed.

<Result>
The evaluation results of the license plate containing the graphic film obtained in Examples 1 to 3 and Comparative Examples 1 to 6 are shown in Table 3. Here, the “first heat treatment temperature” is the temperature of the heat treatment applied to the laminated film 1 and the laminated film a having the surface protective layer, and the “second heat treatment temperature” is the license plate after the printing layer is applied. Is the temperature of the heat treatment applied to the

  As can be seen from the results in Table 3, the graphic films of the present disclosure in Examples 1 to 3 in which the amount of absorbed cyclohexanone falls within the predetermined range when cyclohexanone is applied to the surface of the surface protective layer are the appearance quality and resistance to printing layers. It has been confirmed that the performance of both of the chemical properties is excellent. In particular, although the surface protective layer of Comparative Examples 1 and 2 uses the same material as the surface protective layer of Example 1, the performance of either the appearance quality or the chemical resistance of the printed layer is insufficient. The result was

  Among Examples 1 to 3, it is confirmed that the graphic film of Example 2 provided with a support layer having a specific elongation at break has excellent impact resistance in addition to the appearance quality and chemical resistance of the printing layer. did it.

  It will be apparent to those skilled in the art that various changes can be made to the embodiments and examples described above without departing from the basic principles of the invention. It will also be apparent to those skilled in the art that various modifications and alterations of the present invention can be implemented without departing from the spirit and scope of the present invention.

50, 100, 200 License plate graphic film 10, 110, 210, 330, 430, 520 Adhesive layer 20, 120, 220, 342, 442, 542 Decorative layer 130, 215, 545 Decorative ink receptive layer 40, 140 240, 348, 448, 544 Surface protection layer 230, 344, 444 Bonding layer 300, 400 Retroreflective graphic film 310, 410 Retroreflective layer 312, 412 Cube corner element 314, 414 Structured surface 316, 416 Main surface 320, 420 retroreflective structure 332, 432 adhesive 334 barrier layer 435 reflective layer 336, 436, 536 release liner 338 low refractive index layer 45, 546 printed layer 350, 450 rays 500 license plate 560 aluminum plate 57 Blank press die

Claims (7)

A graphic film for a license plate, comprising a surface protection layer to which a printing layer is applied,
Cyclohexanone absorption when applying cyclohexanone surface of the surface protective layer has a 0.0017 g / cm ² or more and 0.0025 g / cm ² or less, 0.99 ° C., after heat treatment at 10 minutes, the surface protection A graphic film for a license plate, in which the amount of absorbed cyclohexanone when cyclohexanone is applied to the surface of the layer is 0.0010 g / cm ² or less.   The surface protective layer contains at least one selected from a resin containing a carboxyl group and a silanol group, and a resin containing a carboxyl group and a resin containing a silanol group, and a crosslinking agent, and has an unreacted silanol group. A graphic film for a license plate according to claim 1.   The graphic film for a license plate according to claim 2, wherein the crosslinking agent is at least one selected from an epoxy crosslinking agent and a carbodiimide crosslinking agent.   The graphic film for a license plate according to any one of claims 1 to 3, further comprising a support layer having a breaking elongation of 50% or more under or under the surface protective layer.   A graphic film laminate plate comprising the graphic film for a license plate according to any one of claims 1 to 4 and a base plate. Preparing a graphic film precursor for a license plate including a surface protection layer;
The cyclohexanone absorption when applying the precursor cyclohexanone the surface protective layer surface is, so that the 0.0017 g / cm ² or more and 0.0025 g / cm ² or less, license plate by curing the surface protective layer Forming a graphic film. A method of producing a graphic film for a license plate. Providing a base plate;
Applying a graphic film for a license plate according to any one of claims 1 to 4 on or above the base plate to form a graphic film laminated plate;
Embossing or debossing the graphic film laminate plate;
Applying a printing layer to the projections or depressions of the embossed or debossed graphic film laminate plate;
Curing the surface protective layer to form a license plate such that the amount of absorbed cyclohexanone when applying cyclohexanone to the surface protective layer surface of the graphic film for license plate is 0.0010 g / cm ² or less The method of manufacturing the license plate, including: