TWI461291B - Production process of multi layer and the multi layer produced by such process - Google Patents

Description

Manufacturing method of laminated body and laminated body produced by the same

The present invention relates to a method for producing a laminate of an active energy ray-curable coating film having excellent hardness, abrasion resistance and adhesion, and a laminate produced by the method.

In order to protect the surface by imparting various properties such as hardness, scratch resistance, abrasion resistance, and chemical resistance to the surface of a substrate such as paper, wood, plastic, metal, or glass, it is coated.

As the coating agent, an active energy ray hardening composition is mainly used. This is because it has superior surface scratch resistance and abrasion resistance than in the case of using a thermoplastic resin or a thermosetting resin.

When the active energy ray-hardening composition is directly applied to various substrates or substrates to form a pattern layer, the volume of the active energy ray-curable composition is reduced during shrinkage, and the adhesion between the layers is lowered to cause adhesion failure.

In order to solve the problem of the above-mentioned adhesion failure, there is a case where a primer layer is provided to an intermediate layer called a fixed layer to obtain an adhesion between layers. Although these thermosetting resins and thermoplastic resins are used as a primer and fixed, they are not used as the outermost layer for physical properties such as hardness, scratch resistance, abrasion resistance, and chemical resistance.

In the field of decorative sheets, it is known to become non-adhesive by heat drying, and heat or electron beams are used to completely harden the fixing agent. However, since only the thermosetting type or the electron beam curing type fixing agent is insufficient in hardness or scratch resistance, for example, a top coat layer made of an electronic hardening type resin containing a matting agent is provided in total. However, the composition of a suitable fixative is not specific. (Refer to Patent Document 1).

In the same field, an active energy ray-curable aqueous resin composition containing an aqueous emulsion resin as a first protective layer and an active energy ray hardening without an aqueous emulsified resin as a second protective layer are known. A surface-reinforced paper composed of a water-based resin composition. Although the first protective layer is an active energy ray-curable composition, in the case of using an aqueous emulsified system, the hardness which can be used as the outermost layer is not sufficient, so a second protective layer is provided to improve surface hardness and durability (refer to Patent Document 2).

Further, for example, it is known to use a heat-drying type ionizing radiation-curing resin for an intermediate layer. These resins are aqueous emulsions containing ionizing radiation-reactive double bonds or water-soluble or solvent-soluble resins containing electron-radioactive double bonds, and the resin has a Tg of 40 ° C or higher, preferably 60 ° C or higher. Even if the intermediate layer is an active energy ray-curable composition, since it has an aqueous emulsification system, it does not have the hardness which can be used as the outermost layer. Therefore, the top coat layer is provided to improve the surface hardness (see Patent Document 3).

As an example of use as a top coater for transfer formation, a transfer sheet in which a pattern layer is formed before electron beam irradiation after forming an acrylic ionizing radiation-curable resin protective layer is known. However, in order to exhibit non-adhesiveness before electron irradiation, it is necessary to be a non-crosslinked thermoplastic acrylic resin with respect to ionizing radiation, but sufficient hardness cannot be obtained (see Patent Document 4).

As an example of use of a top coat agent for transfer formation, it is known that after forming a urethane-based curable resin protective layer, ultraviolet rays are applied to cure the coating film to form an ultraviolet absorber layer to an adhesive. The method of the layer (refer to Patent Document 5).

However, the laminate having the active energy ray-curable coating film cannot obtain complete satisfaction with surface hardness, scratch resistance, and adhesion.

[Patent Document 1] Japanese Patent Publication No. 8-281896

[Patent Document 2] Japanese Patent Publication No. 9-290487

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-119226

[Patent Document 4] Japanese Patent Publication No. 7-314995

[Patent Document 5] JP-A-2008-6708

An object of the present invention is to provide a method for producing a laminate having a coating film having excellent hardness, abrasion resistance and adhesion, and a laminate obtained by the production method.

In order to sufficiently exhibit the curability of the coating film and to obtain the interlayer adhesion during repeated application, the above-mentioned material is obtained by including a non-adhesive urethane resin in the active energy ray-curable composition. The present invention has been completed by the subject matter. That is, first, the present invention provides a method for producing a laminate, which is characterized by the following steps: (1) coating on a substrate containing (a) having a urethane bond in the main skeleton, (b) a step of softening point of 40 to 150 ° C, (c) an active energy ray-curable composition of an active energy ray-curable resin having a weight average molecular weight of 5,000 to 1,000,000, and (d) soluble in an organic solvent; a drying step that is not accompanied by irradiation with an active energy ray; (3) one or more selected from the group consisting of a thermoplastic composition, a thermosetting composition, and an active energy ray-curable composition, in a total or partial repeated application. a step of the composition; (4) a hardening step of irradiating the active energy ray.

Further, secondly, the present invention provides a laminate obtained by the aforementioned production method.

The laminated system manufactured by the manufacturing method of the present invention is used as having The decorative sheet structure of the undercoat layer function, wherein the (1) content on the substrate is (a) having a urethane bond in the main skeleton, (b) a softening point of 40 to 150 ° C, and (c) weight A hardened layer of an active energy ray-curable composition having an average molecular weight of 5,000 to 1,000,000 and (d) an active energy ray-curable resin which is soluble in an organic solvent, has sufficient hardness as a substrate and ensures adhesion of the upper layer Sex. Further, even if a transfer sheet having a function as an overcoat layer is used, it has sufficient adhesion, and in particular, it is possible to ensure better surface hardness and scratch resistance by constituting the surface of the same hardened layer.

The present invention provides a method for producing a laminate, characterized in that it has the following steps in sequence: (1) coating on a substrate contains (a) having a urethane bond in the main skeleton, and (b) a softening point of 40 -150 ° C, (c) an active energy ray-curable composition of an active energy ray-curable resin having a weight average molecular weight of 5,000 to 1,000,000 and (d) soluble in an organic solvent (hereinafter, a non-adhesive amine group) a step of an active energy ray-hardening composition of the acid ester resin; (2) a drying step without irradiation with an active energy ray; (3) a coating comprising a thermoplastic composition, a thermosetting composition, and an active energy ray-curable composition a step of selecting one or more components from the group consisting of; (4) a step of hardening the active energy ray.

The structure of the layered body obtained by the production method of the present invention may, for example, be a transfer sheet structure or a decorative sheet structure.

In the case of the transfer sheet structure, the demolded PET original sheet or the like is subjected to the following steps: (1) coating an active energy ray hardening composition containing the above non-adhesive urethane resin as a top coat. a step of layering; (2) a drying step not accompanied by active energy ray irradiation; (3) coating a composition comprising at least one selected from the group consisting of a thermoplastic composition, a thermosetting composition, and an active energy ray-curable composition a step of fixing the layer; in addition, a drying step that is not accompanied by active energy ray irradiation, and a step of applying a subsequent layer to form a transfer sheet, using the transfer sheet, and (4) a transfer and forming step; 5) A hardening step of irradiating the active energy ray to form a molded article.

In the case of the decorative sheet structure, the original sheet of a thin paper, a plastic sheet or the like is subjected to the following steps: (1) applying an active energy ray-curable composition containing the aforementioned non-adhesive urethane resin as a fixed layer. a step; (2) a drying step not accompanied by active energy ray irradiation; (3) a step of coating a composition containing active energy rays as a top coat; (4) forming a decoration by a hardening step of irradiating an active energy ray sheet.

In the case of the transfer sheet structure and the decorative sheet structure, the active energy ray-curing composition containing the non-adhesive urethane resin is dried, and after drying, the coating film is dried by heat or air to evaporate the solvent component. And form a non-adhesive coating film. Therefore, it is not necessary to use an active energy ray to harden the same layer, and the layer of the next step can be coated thereon. This is particularly the case of coating by gravure printing, which is advantageous for the case where the active energy ray irradiation device is not provided for each coating unit, and coating or the like can be repeated. Further, the term "non-adhesive" means that the surface of the coating film that is in contact with the finger is not dry to the extent that it is sticky.

The active energy ray-curable composition used in the present invention is an active energy ray-curable composition containing a non-adhesive urethane resin. The non-adhesive urethane resin has a softening point of 40 to 150 ° C and a weight average molecular weight of 5,000 to 1,000,000, and the urethane resin is soluble in an organic solvent. The softening point is preferably from 60 ° C to 150 ° C, more preferably from 70 ° C to 150 ° C. The weight average molecular weight is preferably from 10,000 to 600,000, more preferably from 50,000 to 600,000. As the organic solvent, an alcohol solvent such as methanol, ethanol, isopropanol or butanol, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, ethyl acetate or butyl acetate may be used. An ester solvent, an ether solvent such as methacetin or ethixos, a hydrocarbon solvent such as toluene, hexane or cyclohexane; an organic solvent such as tetrahydrofuran or a mixed solvent thereof, in consideration of dissolution of a thermoplastic organic compound; The case is preferably a ketone solvent or an ester solvent.

As described above, the active energy ray-curable composition containing a non-adhesive urethane resin can be added as described above in order to impart various functions without departing from the object of the present invention. Active energy ray-curable oligomer such as active energy ray-curable monomer, urethane urethane, polyester acrylate or acrylate acrylate, active energy ray-curable polymer such as acryl acrylate, and coloring Agent, extender pigment, polyfluorene oxide, lubricant, plasticizer, defoamer, oxidation inhibitor, ultraviolet absorber, light stabilizer, coupling agent, surfactant, organic solvent and chelating agent, inorganic filler, organic filler, etc. Additives.

In the production method of the present invention, a coating method for a composition for forming a coating film, for example, a stencil printing, an offset printing, a roll coating, a gravure coating, a bar painting machine, or the like.

The active energy ray-curable composition containing the non-adhesive urethane resin used in the production method of the present invention, and the active energy ray-curable composition in the next step are irradiated with an electron beam, ultraviolet rays, or gamma rays. Ionizing radiation, etc. to harden. In the case of curing by ultraviolet rays, a known ultraviolet irradiation device including a high pressure mercury lamp, an excimer lamp, or a metal halide mercury lamp is used. The amount of ultraviolet rays to be cured is preferably from 30 to 1,500 mJ/cm ² . Irradiation dose of less than 30mJ / cm ² is not completely cured, more than 1500mJ / cm ² when yellowing coating, the substrate may be damaged by heat and the like.

In the case of hardening with an electron beam, a known electron beam irradiation device can be used. The electron beam irradiation amount at the time of hardening is preferably 10 to 100 kGy. When the irradiation amount is less than 10 kGy, it is not completely cured, and when it exceeds 100 kGy, damage to the coating film or the substrate may occur.

In the case of curing with ultraviolet rays, the light (polymerization) initiator which generates radicals or the like by irradiation of ultraviolet rays is preferably added in an amount of 0.1 to 20 by mass with respect to 100 parts by mass of the active energy ray-curable compound. About.

As the photopolymerization initiator of the radical generation type, for example, diphenylethylenedione, benzophenone, mischrone, and 2-chlorooxosulfide may be mentioned. 2,4-diethyloxysulfide Light-cleaving type, such as removal of hydrogen form, and benzoin diethyl ether, diethoxyacetophenone, benzyl methyl ketal, hydroxycyclohexyl phenyl ketone, 2-hydroxy-2 methyl phenyl ketone, etc. state. A plurality of them may be used alone or in combination.

In the transfer sheet configuration, the formation of the pinned layer may, for example, be an acrylic resin, a polyester resin, a urethane resin, an epoxy resin, or a melamine resin, which is carried out using a combination of individual or plural substances. Further, various active energy ray-curable compositions, various polyisocyanates, and the like can be used.

In the decorative sheet structure, for example, various active energy ray-curable compositions and the like can be used for the formation of the top coat layer.

Second, the exemplified embodiments are intended to specifically illustrate the invention. Further, in the case where the present specification is not particularly limited in advance, the parts and % are based on the mass. An example of the structure of the transfer sheet is exemplified in Table 1. Table 1 shows the evaluation results of the coating film compositions of the examples and the comparative examples.

In Table 2, an example of the structure of the decorative sheet is exemplified. Table 2 shows the composition of the coating film of Example 3 and Comparative Examples 3 and 4 and the evaluation results.

The materials of Tables 1 and 2 are as follows.

(1) Art resin AH-51M40 Non-adhesive amino acid methyl acrylate manufactured by Gensei Industrial Co., Ltd.

(2) Ultraviolet light UV1700B Synthetic Chemical Co., Ltd. (liquid) urethane acrylate.

(3) DIANAL BR85 Mitsubishi Rayon Co., Ltd. acrylate resin (Tg about 100 ° C).

(4) Dipentaerythritol hexaacrylate manufactured by AROWIXM-402 East Asia Synthetic Co., Ltd.

(5) Acrylic polyol produced by ACRYDIC A-814 DIC Co., Ltd.

(6) Desmodur L-75 Sumitomo Bayer Carbamate Co., Ltd. polyisocyanate.

(7) Paraloid B-72 ROHM & HAAS acrylic resin (Tg about 40 ° C).

(8) IRGACURE 184 Ciba Specialty Chemicals Co., Ltd. photopolymerization initiator.

(9) Sylocene oxide (average particle size of about 5 μm) manufactured by SyLOID 7000 Gemstone Co., Ltd.

The sample formation conditions are as follows.

The original layer was completely coated with the first layer by a bar coater, and dried at 100 ° C for about 60 seconds to volatilize the solvent. The second layer is on the top of the first layer, and the first, second, and comparative examples 1 and 2 are applied in a full-scale manner, and in the case of partial coating of the third embodiment and the comparative examples 4 and 5, at about 100 ° C for about 60 seconds. Drying evaporates the solvent. The coating film was completely cured under the curing conditions described in Tables 1 and 2. The hardening conditions were irradiation of Uv: 1 lamp 120 W/cm high pressure mercury lamp 1 path 10 m/min. The case where the heat hardening was carried out was allowed to stand at 60 ° C for 3 days.

(evaluation method)

The non-adhesive property was evaluated by finger contact after heat drying at 100 ° C for about 60 seconds.

Barrier resistance A PET film (5101, 25 μm manufactured by Toyobo Co., Ltd.) was placed on the coating material, and placed at 100 g/cm ² at 40 ° C for 24 hours to evaluate the state of transfer in the PET film.

Flexibility The coating was bent 180 to evaluate the rupture state of the coating film.

The MEK grinding foamed the cotton wool in the MEK, and evaluated the state of the coating film when the surface of the coating was subjected to 100 times of double-side polishing.

In Examples 1 and 2, the first layer was applied and dried by hot air, and the surface of any coating film was not adhesive (non-adhesive), and the second layer as a fixed layer was smoothly applied. Further, the adhesive applied to the third layer was transferred and dried by irradiation with ultraviolet rays, and exhibited characteristics such as excellent adhesion of the fixed layer and polishing resistance of the surface.

In Example 3, the top coat layer (the second layer) and the pinned layer (the first layer) exhibited good adhesion, and had good solvent resistance and good surface hardness with respect to MEK polishing and polishing resistance.

[Industry Utilization]

In the method for producing a laminate according to the present invention, a method for producing a laminate such as a transfer sheet or a decorative sheet having excellent hardness, solvent resistance, abrasion resistance and adhesion can be applied.

Claims (3)

A method for producing a laminate, which comprises the steps of: (1) coating on a substrate comprising (a) having a urethane bond in the main skeleton, and (b) a softening point of 40 to 150 ° C, (c) a step of a weight average molecular weight of 5,000 to 1,000,000, and (d) an active energy ray-curable resin soluble in an organic solvent and an active energy ray-curable composition of an organic solvent; (2) a non-concomitant active energy ray a step of drying the irradiation; (3) a step of uniformly or partially coating a composition comprising one or more selected from the group consisting of a thermoplastic composition, a thermosetting composition, and an active energy ray-curable composition; 4) A hardening step of irradiating the active energy ray. The method for producing a laminate according to the first aspect of the invention, wherein the (a) has a urethane bond in the main skeleton, (b) has a softening point of 40 to 150 ° C, and (c) has a weight average molecular weight of 5,000. -1,000,000, (d) The active energy ray-curable composition of the active energy ray-curable resin which is soluble in an organic solvent is an inorganic filler having an average particle diameter of 20 μm or less. A laminated body characterized in that a hardened layer having an active energy ray-curing composition on a substrate and one selected from the group consisting of a thermoplastic composition, a thermosetting composition, and an active energy ray-curable composition a hardened layer of the above composition; the laminated system is produced by the following steps: (1) coating on a substrate containing (a) having a urethane bond in the main skeleton and (b) a softening point of 40- 150 ° C, (c) a weight average molecular weight of 5,000 to 1,000,000, (d) an active energy ray-curable resin soluble in an organic solvent and an active energy ray-curable composition of an organic solvent; (2) non-concomitant activity Drying step of energy line irradiation; (3) repeated or partial coating The cloth contains a step of one or more components selected from the group consisting of a thermoplastic composition, a thermosetting composition, and an active energy ray-curable composition, and (4) a curing step of irradiating an active energy ray.