TW201332800A - Hair line tone decorative molded article having specific tactile of hairline processing and having function of anti-fingerprint property - Google Patents

Abstract

The present invention provides a decorative molded article that not only can get the unique rugged design tactile hairline when touched with fingers but also difficult to adhere fingerprint even when touched by fingers, easy to take fingerprints even if adheres fingerprints. The decorative molded article is formed by having molding, adhesion layer and protective layer. The molding has a plurality of convex portions on one surface. The height of said convex portion is 1-10 &mgr; m. The distance between adjacent vertices of said convex portions is 1-100 &mgr; m. The adhesion layer is formed on surface formed by said convex portions of said molding. The protective layer is formed on said adhesion layer and has fine convex portions on surface opposite to surface contacting with said adhesion layer. The height of said fine convex portion is 0.1-1 &mgr; m. The distance between adjacent vertices of said fine convex portions is 0.1-100 &mgr; m.

Description

Thin line style decorative moldings that combine the special touch and fingerprint resistance of fine lines

The present invention relates to a fine line style decorative molded article having a fine line style design, and more particularly to a fine line style decorative molded article having a fingerprint resistance function.

A method of protecting or affixing the surface of an article of a plastic part or an exterior article using a transfer sheet has been known from the past. For example, Patent Document 1 discloses a transfer sheet in which a transfer layer is formed on a surface of a base sheet of a support, and a transfer sheet is inserted into an injection molding die, and in-mold injection molding is performed. A decorative injection molded body is obtained.

The transfer sheet is composed of a structure in which a transfer layer is provided on a base sheet of a support, and the transfer layer is transferred onto the surface of the molded article. The transfer layer resin or the laminate in which the pattern is layered on the surface of the molded article is formed on the surface of the molded article to form a protective coating or a decorative coating.

Compared with the prior art, the protection function of the molded article has been taken seriously. When the protective function is taken into consideration, it is provided with a protective layer on the outermost side of the transfer sheet. Further, depending on the application, the protective layer is designed to have a thin line. At this time, a fine line layer is provided between the base sheet and the protective layer. The surface layer shape of the fine line layer is a concave-convex shape, and is printed on the protective layer by the uneven shape, and the protective layer is designed to have fine lines.

Referring to Fig. 5, the decorative molded article 500 obtained by using the transfer sheet is a protective layer 512 from the surface of the molded article 510 and the protective molded article 510, and an adhesive layer 511 in which the protective layer 512 is adhered to the molded article 510. The protective layer 512 has a convex portion 513 and a concave portion on the surface thereof. 514. Further, the difference in height between the convex portion 513 and the concave portion 514 is a fine-line processed product peculiar to the decorative molded article 500, so that it has a rough touch and is as large as possible.

However, when the height difference between the convex portion 513 and the concave portion 514 is increased, when the decorative molded article 500 is brought into contact with the finger 600, the oil component of the finger (hereinafter referred to as a fingerprint) is likely to adhere to the concave portion 514 of the protective layer 512, and if Once attached, there is a problem that the protective layer 512 is wiped with cloth or paper and is difficult to erase.

Prior technical literature Patent literature

Patent Document 1 Japanese Special Kaiping 10-58895

Patent Document 2 Japanese Special Open 2003-103673

The present invention provides a decorative molded article which solves the above-mentioned problems and which has a rough touch feeling due to the special fine-line processed product and which is difficult to adhere to the fingerprint by finger contact, and which can easily erase the fingerprint even if the fingerprint is attached.

The decorative molded article of the present invention comprises a molded article having a plurality of convex portions on one surface, a height of the convex portion of 1 to 10 μm, and a distance between adjacent vertices of the convex portion of 1 to 100 μm; An adhesive layer is formed on a surface of the product on which the convex portion is formed; and a surface formed on the adhesive layer and opposite to the contact surface of the adhesive layer includes a fine convex portion, and the height of the fine convex portion is 0.1~ 1 μm, a protective layer having a distance between adjacent vertices of the above-mentioned fine convex portions of 0.1 to 100 μm.

In one embodiment, the arithmetic mean roughness (Ra2) of the surface of the protective layer is smaller than the arithmetic mean roughness (Ra1) between the molded article and the adhesive layer.

In one embodiment, the arithmetic mean roughness (Ra1) between the molded article and the adhesive layer is 0.1 to 10 μm.

In one embodiment, the arithmetic mean roughness (Ra2) of the surface of the protective layer is 0.01 to 1 μm.

In one aspect, the pattern layer including at least one of a polyvinyl chloride resin, an acrylic resin, a polyurethane resin, a cellulose ester resin, and a polyvinyl acetal resin is provided between the protective layer and the adhesive layer. And the above-mentioned molded article is a metal plate, and the above-mentioned adhesive layer is obtained by reacting a polyester having a carboxyl group at both terminals with a bisphenol-type epoxy resin at a weight ratio of 75/25 to 90/10 to obtain a glass transition temperature of 30~ The epoxy modified polyester resin having a molecular weight of 100 ° C and a molecular weight of 20,000 to 30,000 is 5 to 10 μm.

In one embodiment, the adhesive layer contains a citric acid gel in an amount of 0.05 to 0.1 by weight based on the epoxy-modified polyester.

In one embodiment, the adhesive layer comprises a blocked isocyanate as a curing agent.

The decorative molded article of the present invention comprises a molded article having a plurality of convex portions on one surface, a height of the convex portion of 1 to 10 μm, and a distance between adjacent vertices of the convex portion of 1 to 100 μm; An adhesive layer is formed on a surface of the product on which the convex portion is formed; and a surface formed on the adhesive layer and opposite to a surface connected to the adhesive layer has a fine convex portion, and the height of the fine convex portion is 0.1. ~1μm, the above fine convex The protective layer between the apex of the part is 0.1~100μm. As a result, it is possible to provide a decorative molded article in which a rough touch is obtained by a special thin line design when a finger is touched, and it is difficult to attach a fingerprint with a finger contact, and a fingerprint can be easily erased even if a fingerprint is attached.

[Formation of the Invention]

Embodiments of the present invention will be described in further detail based on the drawings below. Furthermore, the size, material, shape, relative position, and the like of the portion or portion described in the embodiments of the present invention are not limited to the specific description, and the scope of the invention is not limited to the purpose of the invention. And only for illustrative purposes.

Finished molding

Fig. 1 is a view showing the decorative molded article 100 of the present invention. Figure 2 is an enlarged view of the alpha region of Figure 1. Figure 3 is an enlarged view of the beta region of Figure 1. Referring to Fig. 1, in the decorative molded article 100 of the present invention, the adhesive layer 2, the pattern layer 3, and the protective layer 4 are sequentially formed on the molded article 1.

Molded product

The molded article is a decorative article applied by a pattern or color formed by the pattern layer. Examples of the material of the molded article include various synthetic resins, metals, glass, wood, paper members, and the like. When the molded article is made of a metal, the material constituting the molded article may, for example, be a metal such as iron, tinplate, stainless steel, titanium, copper or aluminum, or glass. Further, a surface treatment such as an easy-to-continue treatment or the like may be applied to the surface formed on the adhesive layer or the like of the molded article, or various primers or the like may be formed.

Referring to Fig. 1 and Fig. 2, the surface of the molded article 1 on the side where the adhesive layer 2 or the like is formed has an uneven shape, and the uneven shape is composed of a plurality of convex portions 5 and concave portions 6. Further, the height H of the convex portion 5 and the distance A between the apexes of the adjacent convex portions 5 are preferably 1 μm to 10 μm and 1 to 100 μm, respectively. More preferably, they are 1 μm to 4 μm and 1 μm to 10 μm. When the height H of the convex portion 5 and the distance A between the apexes of the adjacent convex portions 5 are in the above range, the design of the fine lines can be expressed by the uneven shape of the convex portion 5, and the decorative article can be decorated by fingers. The molded article is specially processed with fine lines to obtain a rough touch.

In addition, when the height H of the convex portion 5 is less than 1 μm, the difference in the height of the uneven shape is too small to cause a problem that the original pattern of the fine-line processed product cannot be expressed. On the other hand, if it exceeds 10 μm, the fingerprint or the like adheres to the protective layer. It is difficult to remove such a fingerprint or the like.

Further, when the inter-vertex distance A is less than 1 μm, the adjacent convex portion is too close to cause a problem that the three-dimensional shape of the thin line originally provided by the fine-line processed product cannot be expressed; on the contrary, if it exceeds 100 μm, the adjacent convex portion is interposed. If the distance is too far and too much clearance occurs, there is a problem that the three-dimensional shape of the processed product of the thin line cannot be expressed.

Further, the arithmetic mean surface roughness (Ra1) of the uneven shape of the molded article 1 is preferably from 0.1 μm to 10 μm, more preferably from 0.1 μm to 1.0 μm. When the arithmetic mean surface roughness (Ra1) is in the above range, the touch feeling caused by the three-dimensional shape of the original fine-line processed product can be obtained, and a thin line design with fingerprint resistance can be realized.

In addition, when the arithmetic mean surface roughness (Ra1) is less than 0.1 μm, the difference in height of the uneven shape is too small, and there is a problem that the touch feeling caused by the three-dimensional shape of the original fine-line processed product cannot be obtained; on the contrary, if it exceeds 10 μm Then, the difference in height between the concave and convex shapes is too large, and there is a problem that the touch feeling caused by the three-dimensional shape of the original fine-line processed product cannot be obtained.

Next layer

Next, a layer is a layer for bonding a molded article to a layer such as a pattern layer, and is formed between the molded article and the pattern layer. For the material used for the adhesive layer, a resin suitable for the heat sensitivity or pressure resistance of the type of the molded article is selected.

In particular, when the molded article is composed of a metal, an epoxy modified polyester obtained by reacting a polyester having a carboxyl group at both ends with a bisphenol epoxy resin can be used as the constituent material of the adhesive layer. Resin.

A polyester having a carboxyl group at both ends is obtained by subjecting a dibasic acid and a polyhydric alcohol to a condensation reaction.

Examples of the dibasic acid include aromatic dibasic acids such as phthalic acid, isophthalic acid, and terephthalic acid, bisphenol acids, and anhydrides of the aromatic dibasic acids. a saturated aliphatic dibasic acid such as hydride, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane dioic acid, or the like, and a dimer derived from an unsaturated fatty acid An acid or the like; these dibasic acids may be used singly or in combination of two or more. Among these dibasic acids, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, diacid acid, bisphenolic acid, etc. are excellent for human body safety, and are particularly suitable. use.

The polyhydric alcohol may, for example, be ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, 2,3- Butylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-dialkyl-1,3-propanediol, butanediol, a linear diol such as 1,6-hexanediol; a glycol having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol or hydrogenated bisphenol A; and ethylene oxide of bisphenol A A diol such as an adduct or an adduct of propylene oxide of bisphenol A. Among these polyols, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and butylene glycol are excellent in human safety and are particularly suitable for use.

The ratio of the above dibasic acid to the above polyol is usually adjusted so that the equivalent ratio of the hydroxyl group of the dibasic acid to the hydroxyl group of the polyhydric alcohol is 1.01/1 to 2/1. When the equivalent ratio is less than 1.01/1, the molecular weight of the obtained polyester becomes large and the viscosity becomes too large, and the reactivity with the epoxy resin becomes insufficient; and if it exceeds 2/1, the unreacted two The acid remains and the adhesion of the formed subsequent layer decreases.

The number average molecular weight (hereinafter referred to as Mn) of the polyester having a carboxyl group at both ends is determined according to the blending ratio of the dibasic acid and the above polyol, and is usually 300 to 10,000, preferably 500 to 8,000. When Mn is less than 300, the adhesion of the formed adhesive layer is lowered. When the Mn is more than 10,000, the viscosity of the epoxy-modified polyester described below is increased, so that the fluidity is deteriorated and the unevenness of the molded article 1 is obtained. It is difficult to form an epoxy-modified polyester without a gap.

The polyester-based glass having a carboxyl group at both ends has a transition temperature (Tg) of 5 to 60 ° C, preferably 15 to 45 ° C, more preferably 25 to 30 ° C. If the Tg is less than At 5 ° C, the hardness of the decorative coating decreases; if it exceeds 60 ° C, the adhesion of the subsequent layer decreases.

The epoxy resin is exemplified by an aliphatic dioxy compound, a bisphenol epoxy resin such as bisphenol A or bisphenol F, and the like. Usually used alone or in combination of two or more. Among these epoxy resins, a polyglycidyl ether of bisphenol A or an epi-bis type epoxy resin is particularly preferable in terms of safety of the human body.

The number of epoxy groups contained in one molecule of the epoxy resin is 1.1 to 2, and particularly preferably 2. When the amount of the above epoxy group is less than 1.1, the reactivity with the polyester becomes insufficient; and in the case of more than two, the reaction system becomes highly viscous when it is condensed with the polyester, and the remarkable case is Gelatinized.

Further, the epoxy resin has an Mn of 340 to 20,000, preferably 350 to 10,000. If Mn is less than 340, the effect caused by the hard segment epoxy resin may not be sufficiently exhibited; if it exceeds 20,000, the viscosity of the epoxy modified polyester described below becomes large, so fluidity It is difficult to form an epoxy-modified polyester without a gap in the uneven portion of the molded article 1.

The epoxy resin has a Tg of 40 to 180 ° C, preferably 70 to 130 ° C, more preferably 95 to 100 ° C. When the Tg is less than 40 ° C, the hardness of the decorative coating is lowered, and when it exceeds 180 ° C, the adhesion of the subsequent layer is lowered.

The blending ratio (weight ratio) of the polyester to the above epoxy resin is 50/50 or more, preferably 60/40 to 95/5, more preferably 75/25 to 90/10. If the ratio is less than 50/50, the adhesion of the layer will decrease, and if it exceeds 95/5, the hardness of the decorative coating will decrease.

The reaction of the above polyester with an epoxy resin can be carried out by a usual solution polymerization method. An example of the solution polymerization method, for example, preparing a desired amount of the polyester and the epoxy resin, and dissolving the same in a solvent, for example, heating at 100 to 200 ° C for 30 minutes in an inert gas atmosphere such as nitrogen. ~6 hours method. The solvent is selected from those which do not cause side reactions, and examples thereof include cyclohexanone and xylene. Further, at the time of the reaction, an alkaline catalyst such as a tertiary amine may be appropriately formulated to promote the reaction.

The epoxide modified polyester thus obtained has an Mn of 10,000 to 20,000, preferably 12,000 to 20,000. When Mn is less than 12,000, the hardness of the protective layer is lowered. When it exceeds 50,000, the printability is lowered, and the peeling of the portion of the transfer layer where the pattern is not present is easily formed.

The layer is preferably a compound containing a thermosetting property such as a blocked isocyanate as a curing agent. In the case where a curing agent such as a thermosetting resin is blended, a resin cured product having a three-dimensional network structure between the epoxy-modified polyesters is formed upon heating.

In the case of blending the above-mentioned curing agent, it is preferably 2 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, based on 100 parts by weight of the epoxy-modified polyester. When the amount of the curing agent is less than the above range, the effect of the curing of the hardening agent at the time of heating and laminating, that is, the tendency of the curing reaction rate is hardly increased; and, when it is larger than the above range, When the curing agent is condensed, the amount of water, ethanol, and the like is increased, and the adhesion of the subsequent layer is lowered.

The layer may also contain inorganic particles. Thereby, the hardness of the decorative covering is further enhanced. In the case where the adhesive layer contains inorganic particles, the particle system is preferably used in an amount of 0.5 or less by weight relative to the epoxy-modified polyester. Amount of 0.05~0.1. When the amount of the inorganic particles is more than 0.5 with respect to the epoxy-modified polyester, the adhesion of the subsequent layer is lowered.

As the inorganic particles, a citric acid gel is preferred. The amount of free sterol groups of the citrate gel particles is 1 to 50 (counts/nm 2 ). If the amount of the free sterol group is in the above range, it is highly reactive and preferable. The citric acid gel particle has a primary particle diameter of usually 1 to 200 nm, preferably 10 to 50 nm. In this range, the foil burr is suppressed, and the protective film does not lose transparency. Further, citric acid gum having a particle diameter of 10 to 20 nm is commercially available and can be easily and inexpensively purchased.

The thickness of the layer is then 15 μm or less, preferably 5 to 10 μm. When the thickness of the adhesive layer is 15 μm or more, the hardness of the protective layer is lowered.

Pattern layer

The pattern layer is applied to a layer of a decorative article or the like, and is formed on the protective layer as needed. The material of the pattern layer is a polyethylene resin, a polyamide resin, a polyacryl resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, A resin such as a cellulose ester resin or an alkyd resin is used as a binder, and a pigment ink containing a pigment or a dye of a suitable color as a colorant can be used, and in the case of coloring a metal, aluminum or titanium can also be used. Metal particles such as bronze or pearl pigment coated with titanium oxide on mica. Further, the pattern layer may be transmissive or light-shielding.

The protective layer

The protective layer is disposed on a layer of the surface of the article, and protects the molded article or the like disposed under the protective layer from the layer from physical or chemical trauma.

Referring to Fig. 3, the protective layer 4 is provided with a fine uneven shape on its surface, and its uneven shape is composed of a plurality of fine convex portions 7 and fine concave portions 8. Further, the height h of the fine convex portion 7 and the distance a between the apexes of the adjacent fine convex portions 7 are preferably 0.1 μm to 1.0 μm and 0.1 μm to 99 μm, respectively. More preferably, it is 0.1 μm to 0.5 μm and 0.1 μm to 1.0 μm.

When the height a of the fine convex portion 7 and the distance a between the apexes of the adjacent fine convex portions 7 are in the above range, when the decorative article is touched by a finger, the connection area between the finger and the protective layer 4 is reduced, so that the molded article is decorated. The proportion of additive fingerprints becomes smaller.

Further, when the height a of the fine convex portion 7 and the distance a between the apexes of the adjacent fine convex portions 7 are in the above range, even if the protective layer 4 is touched by a finger, it is difficult for the fingerprint to penetrate into the fine concave portion 8. As a result, the fingerprint attached to the protective layer 4 can be easily erased by using paper or the like.

In addition, when the height of the fine convex portion 7 is less than 0.1 μm, problems such as a function of failing to exhibit fingerprint resistance are caused by the adhesion of the fingerprint, and conversely, if it exceeds 1.0 μm, it is difficult to remove the attached fingerprint or the like. problem.

Further, when the distance a between the apexes of the adjacent fine convex portions 7 is less than 0.1 μm, problems such as a function of failing to exhibit fingerprint resistance due to the adhesion of the fingerprint are caused, and conversely, if it exceeds 99 μm, it is difficult to remove the adhesion. Fingerprint and other issues.

Further, the arithmetic mean surface roughness (Ra2) of the fine uneven shape of the protective layer 4 is preferably from 0.01 to 1 μm, more preferably from 0.01 to 0.50 μm. When the arithmetic mean surface roughness (Ra2) is in the above range, generation of Newton's rings on the protective layer 4 can be suppressed.

Further, the arithmetic mean surface roughness (Ra2) of the fine uneven shape of the protective layer 4 is preferably smaller than the arithmetic mean surface roughness (Ra1) of the uneven shape of the molded article 1. If it is the above, the protective layer 4 forms a fractal structure and can exhibit fingerprint resistance.

The film thickness of the protective layer 4 is preferably in the range of 1 μm to 20 μm. When the film thickness of the protective layer 4 is less than 1 μm, it is too thin to sufficiently exhibit the protective function. Conversely, when the film thickness of the protective layer 4 exceeds 20 μm, cracking occurs in the protective layer 4 during molding, which is not preferable.

In terms of the material of the protective layer 4, a separate copolymer of acrylic acid or methacrylic acid monomer other than polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, or the like, or the like In addition to the acrylic resin of the monomer copolymer, a melamine resin, an acrylic resin, a urethane resin, an epoxy resin resin or the like can be used.

Specifically, a one-liquid hardening property such as melamine, melamine acrylate, epoxy melamine, alkyd, urethane, or acrylic acid, or a resin mixed with the same, or a hardener such as an isocyanate may be used. Liquid curable resin from polyester acrylate, polyester methacrylate, epoxy acrylate, epoxy methacrylate, urethane acrylate, urethane methacrylate, polyether acrylate Ultraviolet, electron beam hardening resin, etc. composed of a monomer or a prepolymer having an ethylenic unsaturated bond such as an ester, a polyether methacrylate, a polyol acrylate, a melamine acrylate or a melamine methacrylate . Further, when an ultraviolet curable resin is used, a photoinitiator is further added.

As the photoinitiator, it can be appropriately selected. For example, benzoin ether, ketal, acetophenone, 9-oxosulfur (thioxanthone) or the like, a radical photopolymerization initiator, a diazonium salt, a diaryliodonium salt, a triarylsulfonium salt or the like, or a complex cationic photopolymerization initiator; one of these may be used or Two or more.

Method for manufacturing decorative molded article

Fig. 4 is a view showing a method of manufacturing a decorative molded article. Referring to Fig. 4, a molded article is obtained by transferring a transfer sheet 20 including a base sheet 10, a protective layer 11, a pattern layer 12, and an adhesive layer 13 to a molded article 30 by a heat roller. The decoration method of the heat roller transfer first considers the position of the pattern layer 12 existing in the transfer sheet 20, and the pattern layer 12 is disposed at a desired position of the molded article 30 to determine the position of the transfer sheet 20. Then, the surface of the inner side of the transfer sheet 20 (on the side of the layer 13) is superposed on the surface of the molded article, and the transfer machine such as a roll transfer machine or an upper and lower transfer machine is used, and the base sheet 10 side of the transfer sheet 20 is used. Apply heat and pressure. Thereby, the transfer sheet 20 is attached to the surface of the molded article 30 to complete the decoration of the surface of the molded article 30.

The material of the base sheet is composed of a PET film or the like. The protective layer, the pattern layer, the adhesive layer, and the molded article are composed of the above materials. Further, the protective layer, the pattern layer, and the adhesive layer are formed on the base sheet by a printing method such as a gravure printing method, a screen printing method, or a lithography method in the above-described order.

The present invention will be specifically described by the following examples, but the present invention is not limited thereto. Incidentally, the amounts expressed by "parts" or "%" in the examples are based on weight unless otherwise specified.

<Example 1> 1. Fabrication of substrates

As the substrate, an aluminum plate (manufactured by Sumitomo Light Metal Co., Ltd., trade name: A5052) having a thickness of 0.8 μm was used. After the substrate is placed in a fine line processing machine, fine line processing is applied to form a concave-convex shape on the surface of the substrate. The uneven shape formed on the substrate was measured by a magnifying glass (manufactured by JEOL Ltd., trade name: Scanning Electron Microscope (SEM)), and the height of the convex portion of the uneven shape was 3.8 μm, and the adjacent convex portion was used. The distance is 9.8 μm. In addition, the surface roughness (Ra) of the uneven shape formed on the substrate was measured by a surface roughness measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., trade name: SURFCOM) to be 0.6 μm.

2. Manufacturing of transfer sheet

A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used as the base sheet. After the base sheet is placed in the fine line processing machine, fine line processing is applied, and a concave-convex shape is formed on the surface of the base sheet. The uneven shape formed on the base sheet was measured by a scanning electron microscope (manufactured by JEOL Ltd., trade name: Scanning Electron Microscope (SEM)), and the height of the convex portion of the uneven shape was 0.47 μm, and the adjacent convex portion was used. The distance is 0.82 μm. In addition, the surface roughness (Ra) of the uneven shape formed on the base sheet was 0.25 μm after measurement by a surface roughness measuring machine (manufactured by Tokyo Seimi Co., Ltd., trade name: SURFCOM). Next, the base sheet was placed on a multicolor gravure rotary press, and an ultraviolet curable material composed of an acrylic resin was used, and a protective layer was formed on the surface on which the unevenness of the base sheet was formed. Finally, an adhesive layer was formed on the protective layer using the adhesive material to obtain a transfer sheet.

Further, the material is a bisphenol type epoxy resin having a glass transition temperature (Tg) of 25 to 30 ° C at both ends and a carboxyl group having a carboxyl group transition temperature (Tg) of 95 to 100 ° C, and ruthenium. Acid gum (Nissan Chemical Industry Co., Ltd., trade name: MEK-ST) was prepared by mixing and stirring in the ratio shown in Table 1. Further, the glass transition temperature (Tg) and weight average molecular weight of the following materials were as shown in Table 1, and then the materials were used in a ratio of 20% by weight based on the total weight.

3. Manufacturing of fine line style decorative moldings

The transfer sheet obtained above and the base material were bonded together using a roll transfer machine (manufactured by Navitas Co., Ltd., trade name: RH-300). Finally, the base sheet is peeled off from the bonded molded article to obtain a fine line style decorative molded article.

<Examples 2 to 3, Comparative Examples 1 to 3>

A fine line style decorative molded article was produced in the same manner as in Example 1 except that the width and height of the unevenness formed on the substrate and the width and height of the unevenness formed on the base sheet were changed.

The examples and comparative examples were evaluated based on the following evaluation criteria.

1. Fingerprint resistance (1) Easiness of fingerprint removal

The surface of the hard coat layer in the molded article was decorated, and the fingerprint removal test method according to JIS K2246 was carried out. Further, the judgment as to whether or not the fingerprint was removed was performed by visual observation by a distance of 20 cm from the three-wavelength light source by the appearance of the portion of the test piece to which the artificial fingerprint liquid was attached, and the evaluation was performed as follows. The results are shown in Table 1.

Evaluation basis

○: Less than 5 times, the fingerprint attached to the surface of the decorative molded article can be completely removed.

△: 5 or more times and less than 10 times, the fingerprint attached to the surface of the decorative molded article can be completely removed.

X: It is difficult to completely remove the fingerprint after wiping the surface of the molded article 10 times or more.

(2) difficulty in fingerprint attachment

The surface of the decorative molded article is repeatedly touched back and forth, and how many times the fingerprint is attached to the surface of the decorative molded article. The judgment of whether or not to attach the fingerprint was performed by visual observation by a distance of 20 cm under the three-wavelength light source by the appearance of the portion of the test piece in contact with the finger, and the evaluation was performed as follows. The results are shown in Table 1.

○: Even if the surface of the decorative molded article was touched by a finger 10 times or more, the surface of the decorative molded article did not adhere to the fingerprint.

△: When the surface of the decorative molded article was touched by a finger five times or more and less than 10 times, a fingerprint was attached to the surface of the decorative molded article.

X: When the surface of the molded article was touched with a finger once, a fingerprint was attached to the surface of the decorative molded article.

2. Tactile

The surface of the decorative molded article was wiped with a finger, and it was tested whether or not there was a rough touch due to the special shaped article of the decorative molded article. The evaluation of the contact was carried out by questionnaire survey on the difference in the tactile sensation of the thin-line metal plate (company name: Shimao Steel Co., Ltd., trade name: SUS304HL) and the above-mentioned decorative molded article. In addition, the evaluation criteria of the susceptibility are as follows. The results are shown in Table 1.

Evaluation basis

○: 40 or more of the 50 people answered that there was no difference in the touch between the two.

△: 25 to less than 40 of the 50 people answered that there was no difference in the touch between the two.

×: Less than 25 of the 50 people answered that there was no difference in the touch between the two.

3. Design

The design of the decorative molded article was tested. The design evaluation was conducted by a questionnaire survey of 50 people for the difference in the design of the thin-line metal (Shimao Steel Co., Ltd., trade name: SUS304HL) and the above-mentioned decorative molded articles, respectively, when they were observed at a distance of 30 cm. Conducted the investigation. Furthermore, the evaluation criteria for design are as follows. The results are shown in Table 1.

Evaluation basis

○: 40 or more of the 50 people answered that there is no difference in the beauty of the two.

△: 25 to less than 40 of the 50 people answered that there is no difference in the beauty of the two.

×: Less than 25 of the 50 people answered that there was no difference in the beauty of the two.

4. Surface hardness

The surface hardness of the hard coat layer in the decorative molded article was measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4. Further, the evaluation criteria of the surface hardness are as follows. The results are shown in Table 1.

Evaluation basis

○: The scratch hardness (pencil hardness) is in the range of H to 2H.

△: The scratch hardness (pencil hardness) is in the range of HB to F.

×: The scratch hardness (pencil hardness) is a range of B or less.

5. Adhesion

The adhesion between the adhesive layer and the substrate in the decorative molded article was measured. The subsequent measurement method was carried out in accordance with the cross cut method described in JIS K5600-5-6. In addition, the evaluation criteria of the adhesion are as follows. The results are shown in Table 1.

Evaluation basis

○: It was completely smooth at the edge of the cutting, and no peeling of the pores of any crystal lattice was observed.

△: It was confirmed that the coating film at the intersection of the cutting had fine peeling, and the peeling occurred between the adhesive layer and the substrate. The spalling system is less than 5% of the cross-cut portion.

×: It was confirmed that the coating film at the intersection of the cutting had fine peeling, and the peeling occurred between the adhesive layer and the substrate. The exfoliation system performs 5% or more of the cross-cut portion.

1‧‧‧Formed goods

2‧‧‧Next layer

3‧‧‧pattern layer

4‧‧‧Protective layer

5‧‧‧ convex

6‧‧‧ recess

7‧‧‧Small convex

8‧‧‧Subtle recesses

10‧‧‧Base film

11‧‧‧Protective layer

12‧‧‧pattern layer

13‧‧‧Next layer

20‧‧‧Transfer film

30‧‧‧Formed products

100‧‧‧Adding molded products

500‧‧‧Adding molded products

510‧‧‧Formed products

511‧‧‧Next layer

512‧‧‧protection layer

513‧‧‧ convex

514‧‧‧ recess

600‧‧‧ fingers

Fig. 1 is a cross-sectional view schematically showing the configuration of a decorative molded article of the present invention.

Figure 2 is an enlarged view of Figure 1.

Figure 3 is an enlarged view of Figure 1.

Fig. 4 is a cross-sectional view schematically showing a method of manufacturing a decorative molded article of the present invention.

Fig. 5 is a cross-sectional view schematically showing the configuration of a prior art decorative article.

1‧‧‧Formed goods

2‧‧‧Next layer

3‧‧‧pattern layer

4‧‧‧Protective layer

100‧‧‧Adding molded products

Claims (7)

A decorative molded article comprising a decorative article having a fine line design, characterized in that it has a plurality of convex portions on one surface, and the height of the convex portion is 1 to 10 μm, and the adjacent vertex of the convex portion a molded article having a distance of 1 to 100 μm; an adhesive layer formed on a surface of the molded article on which the convex portion is formed; and a surface formed on the adhesive layer and having a surface opposite to the adhesive layer in a direction opposite thereto a convex portion having a height of 0.1 to 1 μm and a protective layer having a distance between the adjacent apexes of the fine convex portion of 0.1 to 100 μm. The decorative molded article of claim 1, wherein the arithmetic mean roughness (Ra2) of the surface of the protective layer is smaller than the arithmetic mean roughness (Ra1) between the molded article and the adhesive layer. The decorative molded article according to claim 1 or 2, wherein the arithmetic mean roughness (Ra1) between the molded article and the adhesive layer is 0.1 to 10 μm. The decorative molded article according to any one of claims 1 to 3, wherein the surface of the protective layer has an arithmetic mean roughness (Ra2) of 0.01 to 1 μm. The decorative molded article according to any one of claims 1 to 4, wherein the protective layer and the adhesive layer are provided with a polyvinyl chloride resin, an acrylic resin, a polyurethane resin, and a cellulose. a pattern layer of at least one of an ester resin and a polyvinyl acetal resin, And the molded article is a metal, and the adhesive layer comprises a polyester having a carboxyl group at both ends and a bisphenol epoxy resin reacted at a weight ratio of 75/25 to 90/10 to obtain a glass transition temperature of 30 to 100 ° C. And an epoxy modified polyester resin having a molecular weight of 20,000 to 30,000, and a thickness of 5 to 10 μm. The decorative molded article according to any one of claims 1 to 5, wherein the adhesive layer contains a citric acid gel in an amount of 0.05 to 0.1 by weight relative to the epoxy-modified polyester. The decorative molded article according to any one of claims 1 to 6, wherein the adhesive layer contains a blocked isocyanate as a hardener.