KR20060121223A - Ink and laminated sheet - Google Patents

Abstract

The present invention is a binder resin containing at least one metal thin film having an average thickness of 0.01 to 0.1 µm and an average particle diameter of 5 to 25 µm, and at least one selected from the group consisting of carboxyl groups, phosphoric acid groups, sulfonic acid groups, metal salts thereof, and amino groups. It provides an ink containing. In addition, the present invention has a decorative layer having a mirror-like metallic luster at any one laminated interface of at least two molding synthetic resin films laminated, the decorative layer is an ink film made of the ink, The laminated sheet which has a film thickness of 0.05-2.0 micrometers is provided.

Description

Ink and Laminated Sheets {INK AND LAMINATE SHEET}

The present invention relates to inks and laminated sheets.

Conventionally, after a molded member is generally molded by injection molding or the like, coating is performed by spray coating for designability, surface protection and the like and crosslinking by firing. However, no solvent has been attempted, such as the use of powder paints to protect the working environment and the external environment from the discharge of volatile organic solvents. At the same time, a method of integrating and molding a colored sheet with a moldable resin has been introduced.

In particular, as a laminated sheet having a high gloss mirror-like metallic luster, a laminated sheet obtained by dry laminating an aluminum vapor-deposited polyethylene terephthalate film, a polypropylene film, or the like is known. Japanese Laid-Open Patent Publication No. 5-111991 discloses a laminated sheet having a dry cured coating layer of an acrylate emulsion containing aluminum particles having a flaky shape or a smooth surface.

These sheets are initially flat and have a high gloss mirror-like metallic luster. However, since the elongation property is not enough in a vapor deposition surface, and an ink layer is used as a surface layer, when shaping | molding processes, such as vacuum shaping | molding or in-mold molding, are performed, the glossiness | dyeness generate | occur | produces after shaping | molding, glossiness falls, etc. There was not enough mirror polished metal luster with processing.

In addition, Japanese Laid-Open Patent Publication No. 2002-46230 proposes to use a laminated sheet having an ink film obtained by dispersing thin metal thin films in a binder resin varnish. According to this method, stretchability and gloss unevenness can be improved to some extent. However, the laminated sheet maintains its apparent gloss with respect to the molding process, but the binder resin in the high-volatile ink used has no functional groups such as carboxyl groups. Therefore, since the adhesion between the thin metal fragments in the form of fairly thin flakes and the binder resin is not sufficient, peeling easily occurs at the interface between the binder resin and the metal thin film fragments, and as a result, the ink layer tends to be cohesive peeled.

For this reason, generally, in order to improve the adhesiveness of a binder resin and a pigment surface, the pigment surface has been silane-coupled, or the adhesive improvement agent which consists of low molecular materials containing polar functional groups, such as a carboxylic acid and an amino group, was mix | blended with ink, but it is not enough. Did.

The 1st subject of this invention is providing the high volatile ink which has the high glossiness of the mirror surface metal luster, and high adhesiveness between metal thin film fragments and a binder resin. The 2nd subject of this invention is providing the laminated sheet which has the said high volatile ink film layer, has the high gloss mirror-like metallic gloss, and has favorable workability (extension) with little gloss fall by molding process. will be.

The present invention comprises a metal thin film fragment having an average thickness of 0.01 to 0.1 µm and an average particle diameter of 5 to 25 µm, and at least one binder resin selected from the group consisting of carboxyl groups, phosphoric acid groups, sulfonic acid groups, metal salts thereof, and amino groups. Ink.

The present invention has a decorative layer having a mirror-like metallic luster at any one laminated interface of two or more laminated synthetic resin films for molding, wherein the decorative layer has an average thickness of 0.01 to 0.1 µm and an average particle diameter. It consists of an ink film made of a metal thin film having a thickness of 5 to 25 µm, and an ink containing at least one binder resin selected from the group consisting of carboxyl groups, phosphoric acid groups, sulfonic acid groups, metal salts thereof, and amino groups, and the thickness of the coating film. Is 0.05 to 2.0 µm.

According to the present invention, a printing sheet is provided with a high brightness mirror metal gloss in the form of a mirror, and a highly volatile ink having high adhesion between the thin metal thin film and the binder resin, and a laminated sheet having stretchability necessary for molding.

Best Mode for Carrying Out the Invention

The present invention relates to a laminated sheet having a high volatile ink that gives a high brightness of the mirror surface metallic luster to the printing surface and a laminated sheet having a high brightness of the mirror surface metallic luster using the ink, in particular automobile-related members, building materials, home appliances, etc. The present invention relates to a laminated sheet used for molding that does not require painting.

As a result of extensive studies to solve the above problems, in the highly volatile ink having the metal thin film fragment and the binder resin, by using the binder resin having a specific functional group together with the metal thin film fragment of the specific shape, the metal thin film fragment and the binder resin The adhesiveness between them improved significantly. In addition, by discovering that the laminated sheet having the coating layer of the high volatile ink has excellent elongation with the high gloss mirror metal gloss, the above problems are solved and the present invention has been completed.

1. Ink

The ink of the present invention is a highly volatile ink in which metallic thin films of high brightness are obtained by dispersing thin metal thin films in a binder resin varnish. It is preferable that it is the range of 10-60 mass%, and, as for content with respect to a non volatile component in the ink of three thin metal films, it is more preferable that it is 20-45 mass%. Metallic powders are usually used for metallic inks, but when thin metal thin films are used, the thin metal thin films are oriented parallel to the surface of the workpiece when the ink is printed or applied. A metallic luster in the form of a mirror can be obtained.

(Metal thin film fragments)

As metal for thin metal fragments used in the high volatile ink of the present invention, aluminum, gold, silver, copper, brass, titanium, chromium, nickel, nickel chromium, stainless steel, and the like can be used. As a method of thinning the metal, vapor deposition is performed on metals having a low melting point such as aluminum, and rolling is performed when the properties of gold, silver, copper, etc. are high, and sputtering is performed on metals having a high melting point and no conductivity. I can do it. Among these, the thin metal thin film obtained from the vapor deposition metal thin film is preferable. The thickness of the metal thin film is in the range of 0.01 to 0.1 µm, preferably 0.02 to 0.08 µm, and more preferably 0.02 to 0.045 µm. The average particle diameter of the three thin metal films to be dispersed in the ink is in the range of 5 to 25 µm, and preferably 10 to 15 µm. If the average particle diameter is less than 5 µm, the gloss of the coating film is not sufficient, and if it exceeds 25 µm, the thin metal thin film becomes difficult to be oriented and the gloss is lowered. In addition, when the ink is printed or applied by a gravure method or a screen printing method, it causes clogging of the plate.

Hereinafter, the manufacturing method of a thin metal thin film is demonstrated using the especially preferable vapor deposition method as an example. As a support film which deposits a metal, a polyolefin film, a polyester film, etc. can be used. First, after forming a peeling layer by application | coating on a support film, metal is deposited on a peeling layer so that it may become a predetermined thickness. An overcoat layer is applied to the deposited film surface to prevent oxidation. The same coating agent for forming a release layer and an overcoat layer can be used.

Resin used for a peeling layer or an overcoat layer is not specifically limited. Specific examples include cellulose derivatives, acrylic resins, vinyl resins, polyamides, polyesters, EVA resins, chlorinated polypropylenes, chlorinated EVA resins, petroleum resins, and the like. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, esters such as ethyl acetate and propyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol and acetone Ketones such as methyl ethyl ketone, alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, and the like can be used.

The said metal vapor deposition film is dipped and stirred in the solvent which melt | dissolves a peeling layer and an overcoat layer, and peels a metal vapor deposition film from a support film. Subsequently, the mixture is further stirred to have an average particle diameter of the thin metal vapor deposition thin film being about 5 to 25 µm, preferably 10 to 15 µm, followed by filtration, separation, and drying. The solvent is not particularly limited as long as it can dissolve the resin used in the release layer or the overcoat layer.

It is preferable to surface-treat the metal vapor deposition thin film in order to improve the dispersibility in ink. Examples of the surface treatment agent include cellulose derivatives such as organic fatty acids such as stearic acid, oleic acid and palmitic acid, methylsilyl isocyanate, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate and ethyl cellulose.

(Binder resin)

As binder resin, resin which has any 1 or more types of groups of a carboxy group, a phosphoric acid group, a sulfonic acid group, these metal salts, and an amino group can be used. It is preferable to have about 50-500 mmol / kg, and more preferably 50-250 mmol / kg of these groups in resin. Specifically, for example, polymerization systems such as acrylic resins for paints, vinyl chloride resins, vinylidene chloride resins, vinyl chloride-vinyl acetate resins, ethylene-vinyl acetate resins, polyolefin resins, chlorinated olefin resins, ethylene-acrylic resins, and the like. (Meth) acrylic acid, maleic anhydride, fumaric acid and / or its salt, (meth) acryloyloxyethylsulfonyl sodium salt, dimethylaminopropyl (meth) acrylic acid ester, etc. are used as a copolymerization component at the time of superposition | polymerization of resin. ; Or as a condensation component at the time of condensation of the condensed resin such as a polyurethane resin for coating (amide modified, urea modified, epoxy modified), polyester resin (amide modified, urea modified, epoxy modified). 2,2-dimethylolpropionic acid, phthalic acid having a sulfonic acid group, diethanolamide ethyl phosphoric acid, salts thereof, and the like, as part of the polyol component and polycarboxylic acid component; It is preferable to use petroleum-based resins, epoxy resins, cellulose derivative resins and the like modified with acetic acid chloride, bromic acetic acid, concentrated sulfuric acid and the like. Among these, urethane resins having a carboxyl group or sulfonic acid group, vinyl chloride-vinyl acetate resins having a carboxyl group or sulfonic acid group, acrylic resins having a carboxyl group or sulfonic acid group, and the like are particularly preferable. Moreover, in order to fully extend a decorative layer in a shaping | molding process, resin which has a softening point lower than the softening point of the synthetic resin film for shaping | molding as a binder resin is preferable, and it is more preferable that the difference becomes 20 degreeC or more. By using these binder resins, the decorative layer in a laminated sheet can be prevented from being easily cohesive peeled.

(Acid anhydride)

An acid anhydride can be added to the high volatile ink of this invention in order to improve storage stability. The high volatile ink of the present invention may increase the viscosity of the ink or cause gelation when stored for a long time, but can be prevented by addition of an acid anhydride. As the acid anhydride, monobasic acid anhydrides such as acetic anhydride; Dibasic acid anhydrides such as succinic anhydride, phthalic anhydride, tetrahydro phthalic anhydride; Tribasic acid anhydrides such as trimellitic anhydride; Tetrabasic anhydrides such as pyromellitic dianhydride and substituted compounds thereof. Especially, dibasic acid anhydride is preferable. The content of these acid anhydrides is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 1.0 to 15% by mass, based on the metal thin film fragments in the high volatile ink. It is more preferable to contain. If it is less than 0.01%, there is no ink stabilization effect, and if it exceeds 30%, stability may worsen rather than it. Here, the anhydride group part of an acid anhydride refers to -C (= O) OC (= O) -group (molecular weight 72).

(additive)

In the high-volatile ink of the present invention, if necessary, conventional gravure ink, flexo ink, for the purpose of antifoaming, sedimentation prevention, pigment dispersion, fluidity modification, blocking prevention, antistatic, oxidation prevention, ultraviolet absorption, internal crosslinking, and the like. Various additives used for screen inks, paints, and the like can be used. Examples of such additives include coloring pigments, dyes, waxes, plasticizers, leveling agents, surfactants, dispersants, antifoaming agents, chelating agents, and polyisocyanates.

(solvent)

The high volatile ink of the present invention is a solvent-based ink, and the solvent used herein may be a known and common solvent used in conventional gravure ink, flexo ink, screen ink or paint. Specifically, aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, esters such as ethyl acetate and propyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, acetone, Ketones, such as methyl ethyl ketone and methyl isobutyl ketone, alkylene glycol monoalkyl ethers, such as ethylene glycol monoethyl ether and propylene glycol monoethyl ether, and their acetic acid ester, etc. are mentioned.

(Production method of ink)

The metal-deposited thin film fragments blended to express the metallic luster in the mirror form in the highly volatile ink of the present invention have a thickness of 0.01 to 0.1 µm, an average particle diameter of 5 to 25 µm, preferably a thickness of 0.02 to 0.45 µm and an average particle diameter of 10 to 15 micrometers. In the case of the kneading, the metal-deposited thin film fragments are made into fine particles, and the metallic luster in the mirror surface form is extremely reduced. Therefore, in the high volatile ink of the present invention, kneading is not carried out, but a blending raw material consisting of the above binder resin, thin metal deposited thin film fragments and a solvent is mixed with a mixer to produce a high volatile ink.

2. Laminated Sheet

The laminated sheet of the present invention is a laminated sheet having a decorative layer having a high gloss mirror-like metallic luster by the high volatile ink of the present invention at any one laminated interface of at least two synthetic resin films for molding. .

(Synthetic resin film for molding)

As the synthetic resin film for molding to be used in the present invention, a film having stretchability can be used as a single layer or a multilayer film containing a transparent, translucent or coloring agent. In addition, transparent or translucent shall also include the case of transparent or semitransparent colored clear. It is preferable that the synthetic resin film for molding of at least one of the decorative layers is transparent or semitransparent.

When the molding process by heat, such as vacuum molding, is needed, the film containing a thermoplastic resin as a main body is preferable. For example, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, acrylic resin, silicone-acrylic resin, polystyrene, polyurethane, nylon, polyvinyl alcohol, ethylene-vinyl alcohol, polyvinyl chloride, polyvinylidene It is preferable to use thermoplastic resins such as chloride, polyvinyl fluorate and polyvinylidene fluorate. Among these, preferably a film having a softening point in the range of 60 to 300 ° C, more preferably a film in the range of 70 to 220 ° C, still more preferably a film in the range of 80 to 90 ° C.

(Decorative floor)

The decorative layer used for the laminated sheet of the present invention is located at any one laminated interface of at least two synthetic resin films for molding, and contains a film made of the high volatile ink of the present invention, and the film thickness is It is a layer having a high gloss specular metal gloss, which is 0.05 to 2.0 µm, preferably 0.5 to 2.0 µm, and more preferably 1.0 to 2.0 µm. When setting film thickness below 1 micrometer, it is preferable to make metal thin film fragment content in a film into 20-60 mass%.

(Printing or coating method)

The printing or coating method of the laminated sheet decorative layer of the present invention is a printing method such as gravure printing, flexographic printing, screen printing, gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, air knife Coating methods such as a coater, a kiss touch coater, a kiss touch reverse coater and a comma coater, a comma reverse coater, and a microgravure coater can be used.

(Stacked)

On the printed or coated decorative layer, a synthetic resin film for molding selected from the above various synthetic resin films is further laminated. Such lamination may or may not interpose an adhesive at the interface between the decorative layer and the synthetic resin film for molding. As the adhesive, it is preferable to use a dry laminate adhesive, a wet laminate adhesive, a heat seal adhesive, a hot melt adhesive, or the like. As mentioned above, although it may have an adhesive bond layer in the interface of the molding synthetic resin film and a decorative layer, the thermal lamination which does not use a special adhesive bond layer is also possible. In this case, resin which has adhesiveness can be used for binding resin of a decorative layer at normal temperature-about 60 degreeC.

It is also possible to laminate | stack the coating film of a coloring agent containing ink on the decorative layer which has a high volatile ink film containing a metal thin film fragment and a binder resin, and has a high gloss mirror-like metallic luster. In addition, a transparent varnish layer may be formed between the decorative layer and the colorant-containing ink film. In addition, an ink film similar to the decorative layer may be laminated on the decorative layer via the transparent varnish layer. Examples of the binder resin for varnish used in the colorant-containing ink include acrylic resins, polyurethane resins, polyamide resins, urea resins, epoxy resins, polyester resins, vinyl resins, vinylidene resins, ethylene-vinyl acetate resins, polyolefin resins, and chlorinations. It is preferable to use thermoplastic resins such as oleine resin, ethylene-acrylic resin, petroleum resin and cellulose derivative resin. Moreover, in order to fully extend the decorative layer which has an ink film, resin which has a softening point lower than the softening point of resin contained in the synthetic resin film for shaping | molding is preferable.

About 0.05-100 micrometers is preferable, as for the dry film thickness of the coloring agent containing ink film which can be laminated | stacked further on a decorative layer, about 0.5-30 micrometers is more preferable, and about 0.5-15 micrometers is still more preferable. In the case of having a colorant-containing ink coating, the surface layer can pass through the high-volatile ink coating, and the design of the colored high gloss mirror surface metallic luster can be obtained. In this case, it is preferable that the film thickness of the decorative layer which has the high volatile ink film of this invention is about 1.0 micrometer or less, and, as for a permeability, it is more preferable that it is 0.05 or more and about 0.7 micrometer or less.

In addition, in the case where the colorant-containing ink film further laminated on the decorative layer is an ink of the same color series as the decorative layer having the high gloss mirror-like metallic luster, concealability is prevented by the colorant-containing ink film. You can give it.

(glue)

A decorative layer can be made into the some layer in which the synthetic resin film for shaping | molding was interposed. In the case of adhering the adhesive layer to the interface between the decorative layer and the molding synthetic resin film, it is preferable to use a dry laminate adhesive, a wet laminate adhesive, a wet thread adhesive, a hot melt adhesive, or the like as the adhesive.

(adhesive)

In the laminated sheet of this invention, an adhesive layer can be further formed in one molding synthetic resin film. As an adhesive, it is preferable to use an acryl type, rubber type, polyalkyl silicone type, urethane type, polyester type, etc.

(Protective layer)

In the laminated sheet of the present invention, an overcoat layer of transparent, translucent or colored clear is prepared in order to give performances such as designability, friction resistance, scratch resistance, weather resistance, stain resistance, water resistance, chemical resistance and heat resistance to the surface layer side during molding. It can form more than a layer. As an overcoat agent, it is preferable to use the crosslinking type, UV crosslinking type, or EB crosslinking type by lacquer type, an isocyanate, an epoxy, etc. within the range which does not inhibit the stretchability of a laminated sheet.

(Colored clear layer)

In order to provide designability and / or improve adhesiveness, a transparent or semitransparent colored clear layer can be formed between the transparent or semitransparent molding synthetic resin film and the decorative layer.

(Usage)

The laminated sheet of the present invention can be used as a surface layer in various molding methods. For example, a transparent or translucent molding synthetic resin film is disposed on the surface side, and is formed into a preform having a three-dimensional shape by thermoforming, and then inserted into an injection molding mold and integrated with the injection resin by an insert injection molding method. It can be molded. Moreover, it can insert in a sheet form in an injection molding metal mold | die, and can shape | mold by the in-mold injection molding method which integrates with injection resin in a metal mold | die. Since the laminated sheet of the present invention is excellent in stretchability, it is possible to maintain the designability, that is, the high gloss shape metal gloss accordingly.

(Extensible)

Elongation is defined as follows using the rate of change of surface glossiness. After molding at a temperature higher than the softening point of the material constituting the laminated sheet, the thickness of the laminated sheet is measured, and the portion having the same thickness as before the molding process (non-stretched portion) and the portion having a thickness of 1/2 before the molding process ( Surface gloss to 200% stretched part) is measured under conditions of 60 ° / 60 ° on the transparent or translucent molding synthetic resin film side using a glossmeter: micro-TRI-gloss (by BYK Gardner). The rate of change of the surface glossiness is defined as (the glossiness of the non-stretched portion-200% glossiness of the stretched portion) ÷ (the glossiness of the non-stretched portion) x 100 (%).

The stretchability of the laminated sheet of the present invention is based on the rate of change of the surface glossiness on the side of the synthetic resin film for molding that is transparent or translucent at the time of 200% stretching, but is preferably 20% or less, particularly preferably 10% or less.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. The part and% in an Example represent a mass part and mass%.

High Volatility Ink Examples

(Production of Example and Comparative Example Ink)

The aluminum thin film fragment and the aluminum thin film slurry were prepared under the following conditions.

(Aluminum thin film fragment)

Nitrocellulose (HIG7) was dissolved in a mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4 to obtain a 6% solution. This solution was applied onto a polyester film with a gravure plate having a screen line of 175 lines / inch and a cell depth of 25 µm to form a release layer. After drying sufficiently, aluminum was deposited on the release layer so as to have a thickness of 0.04 mu m. The same nitrocellulose solution used for the peeling layer was applied to this vapor deposition film surface on the same conditions as the peeling layer, and the overcoat layer was formed.

The vapor deposition film was immersed in a mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4 to exfoliate the aluminum vapor deposition film from the polyester film. Thereafter, the aluminum thin film was pulverized with a stirrer to have a size of about 150 μm, thereby preparing thin aluminum thin films.

(Aluminum Thin Film Slurry Slurry)

10 parts of the aluminum thin film fragments

35 parts ethyl acetate

Methyl ethyl ketone 30 parts

Isopropyl Alcohol 30 parts

5 parts of nitrocellulose solutions of the following composition were added, mixing and stirring the said component.

Nitrocellulose (HIG1 / 4) 25%

Ethyl acetate: isopropyl alcohol = 6: 4 mixed solvent 75%

While maintaining the temperature of the mixture at 35 ° C. or less, the mixture was stirred until the average particle diameter of the aluminum thin film pieces was 5 to 25 μm using a turbo mixer to prepare an aluminum thin film slurry (10% nonvolatile component).

1 ink 1

30 parts of the aluminum thin film slurry (10% nonvolatile component)

Binder resin carboxyl group-containing vinyl chloride-vinyl acetate resin 3 parts

("Vinylite VMCH" manufactured by UCC Corporation, Carboxyl group concentration 204mmo1 / kg)

Urethane resin

(32% of non-volatile components of Nether Chemicals "Polyurethane 2593") 8 parts

23 parts ethyl acetate

Methyl ethyl ketone 26 parts

Isopropanol 10 parts

The said component was mixed and the ink 1 which is 35 mass% of aluminum thin film fragment concentration in a non volatile component was produced.

(2) Ink 1-A

Example 1 Ink containing 100 parts of Epikron B-4400 manufactured by Nippon Ink Chemical Co., Ltd. (55% anhydrous part content, 18.3% of the aluminum thin film in the ink) and containing an acid anhydride 1-A was prepared.

(3) ink 2

30 parts of the aluminum thin film slurry (10% nonvolatile component)

12 parts of binder resin carboxyl group-containing urethane resin

(Taphos (registered trademark) product number of Japan Nippon Ink Chemical Co., Ltd. product number: NT-810-45 (45% non-volatile component), carboxyl group concentration 239mmo1 / kg)

28 parts of ethyl acetate

Methyl ethyl ketone 20 parts

Isopropanol 10 parts

The said component was mixed and the ink 2 which is 35 mass% of aluminum thin film fragment concentration in a non volatile component was produced.

(4) ink 2-A

To 100 parts of the ink 2, 0.5 part of trimellitic anhydride (37.5% of anhydrous acid content and 6.3% of the thin aluminum thin film in the ink) was blended to prepare an ink 2-A containing an acid anhydride.

(5) Ink 2-B

Dodecenyl succinic acid (0.04 parts (28% of anhydrous acid content, 0.37% with respect to the aluminum thin film fragment in an ink)) was mix | blended with 100 parts of said ink 2, and ink 2-B containing an acid anhydride was produced.

(6) ink 3

30 parts of the aluminum thin film slurry (non-volatile component 10%) binder resin sulfonic acid-containing urethane resin (product of Takeda Pharmaceutical Co., Ltd.)

30% non-volatile component "E-760", sulfonic acid concentration of 1OOmmo1 / kg)

Part 18

12 parts ethyl acetate

 Methyl ethyl ketone 40 parts

The said component was mixed and the ink 3 which is 35 mass% of aluminum thin film fragment concentration in a non volatile component was produced.

(7) ink 4

30 parts of the aluminum thin film slurry (10% nonvolatile component)

3 parts of binder resin hydroxyl group containing vinyl chloride-vinyl acetate resin

(UCC Corporation "Vinyllite VAGH")

Urethane resin

(32% of non-volatile components of Nether Chemicals "Polyurethane 2593") 8 parts

28 parts of ethyl acetate

Methyl ethyl ketone 21 parts

Isopropanol 10 parts

The above was mixed and the ink 4 which is 35 mass% of aluminum thin film fragment concentration in a non volatile component was produced.

(8) ink 5

25 parts aluminum paste (13% nonvolatile)

(Hiprint TD-200T: Tong Yang Aluminum Co., Ltd.)

20 parts of urethane resin (Nether Chemicals "Polyurethane 2593")

27 parts of ethyl acetate

Methyl ethyl ketone 18 parts

Isopropanol 10 parts

The above was mixed and the ink 5 which is 35 mass% of aluminum paste concentration in a non volatile component was manufactured.

(Adhesive Production Example D-1)

As a main ingredient, 100 parts of aromatic polyether urethane resin (Dick Dry (registered trademark), product number: AS-106A, product of Nippon Ink Chemical Co., Ltd.) and epoxy (LR-100: Nippon Ink Chemical Co., Ltd.) as a curing agent Product) A two-component adhesive (hereinafter referred to as adhesive D-1) consisting of 10 parts was obtained.

As a synthetic resin film for molding for ink evaluation, a rubber-modified PMMA film (hereinafter referred to as film A) having a transparent surface gloss of 150 (60 ° / 60 °) and a thickness of 100 μm (hereinafter, film A) and an ABS film of gray and opaque and 300 μm in thickness (Hereinafter, film C) was used.

(Example 1)

The layer was composed of Film A / Ink 1 / Adhesive D-1 / Film C, Ink 1 was applied once with a gravure coater at a dry film thickness of 2.0 μm, and Adhesive D-1 was applied with a gravure coater at 5.0 g / m ^2. Was applied. After the obtained sheet was aged at 40 ° C. for 3 days, surface glossiness and peel strength were measured. The surface glossiness was measured on the conditions of 60 degrees / 60 degrees using the glossmeter: micro-TRI-gloss (BYK Gardner product). Peeling strength T-peeled film A and film C, and measured peeling strength (N / inch). The results are shown in Table 1.

(Example 2)

The surface glossiness and peel strength were measured in the same manner as in Example 1, except that Ink 1 of Example 1 was changed to Ink 2.

(Example 3)

The surface glossiness and peel strength were measured in the same manner as in Example 1 except that Ink 1 of Example 1 was changed to Ink 3.

(Example 4)

The surface glossiness and peel strength were measured in the same manner as in Example 1 except that Ink 1 of Example 1 was changed to Ink 1-A.

(Example 5)

The surface glossiness and peel strength were measured in the same manner as in Example 1, except that Ink 1 of Example 1 was changed to Ink 2-A.

(Example 6)

The surface glossiness and peeling strength were measured in the same manner as in Example 1 except that Ink 1 of Example 1 was changed to Ink 2-B.

(Comparative Example 1)

The surface glossiness and peel strength were measured in the same manner as in Example 1, except that Ink 1 of Example 1 was changed to Ink 4.

(Comparative Example 2)

The surface glossiness and peel strength were measured in the same manner as in Example 1, except that Ink 1 of Example 1 was changed to Ink 5.

In addition, about each ink of an Example and a comparative example, the residue after apply | coating gravure was sealed, it was stored for 1 week in the 40 degreeC thermostat, and the state of the liquid was observed. Viscosity was measured by room temperature 23 degreeC by the falling number of seconds by Zahn cup No. 3 of the company. The results are shown in Table 1.

TABLE 1

ink Surface glossiness Interlaminar Peeling Strength (N / Ink) Viscosity in Manufacturing Viscosity after 7 days at 40 ℃ Example 1 Ink 1 151 6.0 19 Gelation Example 2 Ink 2 150 7.4 21 106 Example 3 Ink 3 150 6.2 20 96 Example 4 Ink 1-A 150 6.0 19 20 Example 5 Ink 2-A 150 7.4 21 22 Example 6 Ink 2-B 151 8.3 21 24 Comparative Example 1 Ink 4 150 0.4 18 19 Comparative Example 2 Ink 5 90 16.7 17 18

Laminated Sheet Examples

(Manufacture of aluminum vapor deposition film)

An acrylic vapor deposition anchor (MET No. 1850: manufactured by Nippon Ink Chemical Co., Ltd.) was applied to a rubber-modified PMMA film (film A) with a gravure coater at a dry film thickness of 1.0 μm, and aluminum was deposited at a thickness of 0.06 μm.

(Manufacture of transparent varnish)

50 parts of urethane resins (polyurethane 2593: product of sulfur chemical), 30 parts of ethyl acetate, 20 parts of methyl ethyl ketone, and 10 parts of ethyl acetate were mix | blended and the transparent varnish was obtained.

A synthetic resin film for molding, comprising a rubber-modified PMMA film (hereinafter referred to as film A) having a transparent and surface gloss of 150 (60 ° / 60 °) and a thickness of 100 μm in the same manner as the evaluation of ink, and a gray, opaque, and 300 thickness Using a ABS film (hereinafter, referred to as film C) having a thickness, a laminated sheet was produced with the following layer configuration, and the surface glossiness of the non-stretched portion and the 200% stretched portion was measured.

(Example 7)

The layer was composed of Film A / Ink 1 / Adhesive D-1 / Film C, Ink 1 was applied once with a gravure coater at a dry film thickness of 2.0 μm, and Adhesive D-1 was applied with a gravure coater at 5.0 g / m ^2. Was applied. The obtained laminated sheet was aged at 40 ° C. for 3 days, and then molded by vacuum forming. In the molding process, the bottom surface is not stretched and the side surface is stretched 200% by using a trapezoidal test die having a square bottom surface of 5 cm and an opening surface 7 cm of a side surface of 2 cm. Processed as possible.

In addition, the shaping | molding process was performed by the vacuum molding method on the conditions of the sheet temperature of 155 degreeC, and 60-80 degreeC of die temperature.

(Example 8)

Except having changed the ink 1 of Example 7 into the ink 2, the laminated sheet was manufactured and molded by the same method as Example 7.

(Example 9)

A laminated sheet was manufactured and molded in the same manner as in Example 7, except that Ink 1 in Example 7 was changed to Ink 3.

(Example 10)

The layer was composed of film A / ink 1 / varnish / ink 1 / adhesive D-1 / film C, and ink 1 was all applied with a gravure coater at a dry film thickness of 2.0 μm, and the varnish was dried with a gravure coater at a film thickness of 4.0. It applied at micrometer and adhesive D-1 was apply | coated with the dry coating amount 5.Og / m <^2> with the gravure coater. Molding was carried out in the same manner as in Example 7.

(Example 11)

The layer was composed of Film A / Ink 2 / Adhesive D-1 / Film A / Ink 2 / Adhesive D-1 / Film C, and Ink 2 was all coated with a gravure coater with a dry film thickness of 2.0 μm and Adhesive D- 1 was applied with a dry coating amount of 5.0 g / m ² with a gravure coater. Molding was carried out in the same manner as in Example 7.

(Example 12)

A laminated sheet was manufactured and molded in the same manner as in Example 7, except that Ink 1 in Example 7 was changed to Ink 1-A.

(Example 13)

A laminated sheet was produced and molded in the same manner as in Example 7, except that Ink 1 in Example 7 was changed to Ink 2-A.

(Example 14)

A laminated sheet was manufactured and molded in the same manner as in Example 10, except that Ink 1 was changed to Ink 1-A in the layer structure of Example 10.

(Example 15)

The layer was composed of film A / ink 2-B / adhesive D-1 / film A / ink 2-A / adhesive D-1 / film C, and inks 2-B and 2-A were all dried with a gravure coater. It applied at thickness of 2.0 micrometers, and adhesive D-1 was apply | coated with the dry application amount 5.0g / m <^2> with the gravure coater. Molding was carried out in the same manner as in Example 7.

(Comparative Example 3)

A laminated sheet was manufactured and molded in the same manner as in Example 7, except that Ink 1 in Example 7 was changed to Ink 4.

(Comparative Example 4)

A laminated sheet was produced and molded in the same manner as in Example 7, except that Ink 1 in Example 7 was changed to Ink 5.

(Comparative Example 5)

The structure of the layer was made into aluminum vapor deposition film / adhesive D-1 / film C, and adhesive agent D-1 was apply | coated with the dry coating amount 5.Og / m <^2> by the gravure coater. Molding was carried out in the same manner as in Example 7.

After molding, the surface gloss of the portion having the same thickness as the laminated sheet thickness before processing (non-stretched portion) and the portion having half the thickness before processing (200% stretched portion) is measured by the glossmeter: micro-TRI- Using gloss (BYK Gardner), it was measured under the conditions of 60 ° / 60 °. Table 2 shows the evaluation results of the laminated sheet.

TABLE 2

Non-Extended Glossiness 200% elongation gloss % Change Example 7 151 146 3 Example 8 150 145 3 Example 9 150 146 3 Example 10 149 144 3 Example 11 150 145 3 Example 12 150 145 3 Example 13 150 145 3 Example 14 149 144 3 Example 15 151 146 3 Comparative Example 3 150 145 3 Comparative Example 4 90 70 22 Comparative Example 5 300 Not measurable -

In Table 2, "not measurable" means not measurable due to cut of the coating film of the aluminum deposition layer.

ADVANTAGE OF THE INVENTION According to this invention, the high brightness of high-mirror mirror shape can be provided to a printing surface, and high volatile ink with high peeling strength can be provided. In addition, it is possible to provide an excellent laminated sheet having a high gloss mirror-like metallic luster and at the same time having a low gloss change during molding.

Claims (10)

Thin metal thin films having an average thickness of 0.01 to 0.1 µm and an average particle diameter of 5 to 25 µm; And Binder resin containing 1 or more types chosen from the group which consists of a carboxyl group, a phosphoric acid group, a sulfonic acid group, these metal salts, and an amino group. Ink containing. The method of claim 1, An ink containing an acid anhydride. The method of claim 2, The said acid anhydride contains 0.01-30 mass% of anhydride group parts which are -C (= O) OC (= O)-group with respect to the said metal thin film fragment. The method of claim 1, Content of the said metal thin film fragment with respect to the non volatile component in the said ink is 10-60 mass%, and the said binder resin is 50 or more types chosen from the group which consists of a carboxy group, a phosphoric acid group, a sulfonic acid group, these metal salts, and an amino group. Ink containing the ~ 500mmo1 / kg. It has a decorative layer having a mirror-like metallic luster at any one laminated interface of two or more laminated synthetic resin films for molding, Binder which the said decorative layer contains the metal thin film fragment of 0.01-0.1 micrometer of average thickness, 5-25 micrometers of average particle diameters, and 1 or more types chosen from the group which consists of a carboxyl group, a phosphoric acid group, a sulfonic acid group, these metal salts, and an amino group. A laminated sheet comprising an ink film made of an ink containing a resin, wherein the film thickness is 0.05 to 2.0 µm. The method of claim 5, At least one of the said synthetic resin film for shaping | molding of the said decoration layer is a transparent or translucent film, The laminated sheet characterized by the above-mentioned. The method of claim 5, The said synthetic resin film for shaping contains a thermoplastic resin, The laminated sheet characterized by the above-mentioned. The method of claim 5, The said synthetic resin film for shaping | molding contains a thermoplastic resin, The softening point of the binder resin of the said decorative layer is lower than the softening point of the said thermoplastic resin, The laminated sheet characterized by the above-mentioned. The method of claim 5, The laminated sheet characterized by having an adhesive bond layer in the interface of the said synthetic resin film for shaping | molding and the said decorative layer. The method of claim 5, At least one of the said synthetic resin film for shaping | molding of the said decoration layer is a film which is transparent or translucent, The change rate of the surface glossiness of the said synthetic resin film side which is transparent or translucent at 200% elongation is 20% or less, It is characterized by the above-mentioned. Laminated sheet.