WO2013061689A1 - Hairline-like decorative molded article providing sensation unique to hairline processing and providing fingerprint resistance - Google Patents
Hairline-like decorative molded article providing sensation unique to hairline processing and providing fingerprint resistance Download PDFInfo
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- WO2013061689A1 WO2013061689A1 PCT/JP2012/072259 JP2012072259W WO2013061689A1 WO 2013061689 A1 WO2013061689 A1 WO 2013061689A1 JP 2012072259 W JP2012072259 W JP 2012072259W WO 2013061689 A1 WO2013061689 A1 WO 2013061689A1
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- molded product
- adhesive layer
- decorative molded
- hairline
- protective layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
Definitions
- the present invention relates to a hairline-like decorative molded product having a hairline-like design, and more particularly to a hairline-like decorative molded product having a fingerprint resistance function.
- Patent Document 1 A method for protecting or decorating the surface of an article such as a plastic part or an exterior product using a transfer sheet has been conventionally known.
- the transfer sheet has a structure in which a transfer layer is provided on a base sheet as a support, and this transfer layer is transferred to the surface of a molded product.
- the transfer layer transferred to the surface of the molded product is a laminate in which a resin or a pattern is laminated in a layer shape, and forms a protective coating or a decorative coating on the surface of the molded product.
- a protective layer is provided on the outermost side of the transfer sheet. Furthermore, depending on the application, the protective layer is required to have a hairline design. In this case, a hairline layer is provided between the base sheet and the protective layer. The hairline layer has an irregular shape on the surface, and the irregular shape is copied to the protective layer, so that the protective layer has a hairline design.
- a decorative molded product 500 obtained using the transfer sheet includes a molded product 510, a protective layer 512 that protects the surface of the molded product 510 from damage, a protective layer 512, and a molded product 510.
- the protective layer 512 includes a convex portion 513 and a concave portion 514 on the surface thereof.
- the height difference between the convex part 513 and the concave part 514 is configured to be as large as possible so that the decorative molded product 500 has a tactile sensation peculiar to a hairline processed product.
- the present invention solves the above-mentioned conventional problems, and has a bumpy touch peculiar to a hairline processed product, and it is difficult to attach a fingerprint even if it is touched with a finger. Is to provide goods.
- the decorative molded product of the present invention includes a molded product having a plurality of convex portions on one surface, the height of the convex portions is 1 to 10 ⁇ m, and the distance between adjacent vertices of the convex portions is 1 to 100 ⁇ m.
- the arithmetic average roughness (Ra2) on the surface of the protective layer is smaller than the arithmetic average roughness (Ra1) between the molded article and the adhesive layer.
- the arithmetic average roughness (Ra1) between the molded article and the adhesive layer is 0.1 to 10 ⁇ m.
- the arithmetic average roughness (Ra2) on the surface of the protective layer is 0.01 to 1 ⁇ m.
- a pattern layer including at least one of polyvinyl chloride resin, acrylic resin, polyurethane resin, cellulose ester resin and polyvinyl acetal resin is provided between the protective layer and the adhesive layer,
- the molded product is a metal plate
- the adhesive layer is obtained by reacting a polyester having carboxyl groups at both ends with a bisphenol type epoxy resin in a weight ratio of 75/25 to 90/10, and has a glass transition temperature of 30 to 100
- An epoxy-modified polyester resin having a molecular weight of 20000 to 30,000 and a thickness of 5 to 10 ⁇ m is included.
- the adhesive layer contains colloidal silica in an amount of 0.05 to 0.1 with respect to the epoxy-modified polyester.
- the said contact bonding layer contains block isocyanate as a hardening
- the decorative molded product of the present invention comprises a molded product having a plurality of convex portions on one surface, the height of the convex portions being 1 to 10 ⁇ m, and the distance between adjacent vertices of the convex portions being 1 to 100 ⁇ m, An adhesive layer formed on a surface of the molded product on which the convex portions are formed; and a fine convex portion provided on a surface opposite to the surface that is formed on the adhesive layer and is in contact with the adhesive layer.
- a protective layer having a height of 0.1 to 1 ⁇ m and a distance between adjacent vertices of the fine convex portions of 0.1 to 100 ⁇ m.
- FIG. 1 is a diagram showing a decorated molded product 100 of the present invention.
- FIG. 2 is an enlarged view of the ⁇ region in FIG.
- FIG. 3 is an enlarged view of the ⁇ region of FIG.
- an adhesive layer 2 is formed on a molded product 1 in this order.
- a pattern layer 3 is formed on a molded product 1 in this order.
- Molded articles are articles that are decorated with patterns and colors formed on the pattern layer.
- Examples of the material of the molded article include various synthetic resins, metals, glass, wood, paper members, and painted products thereof.
- examples of the material that forms the molded product include metals such as iron, tinplate, stainless steel, titanium, copper, and aluminum, and glass.
- the surface of the molded product on which the adhesive layer or the like is formed may be subjected to surface treatment such as easy adhesion treatment in advance, or various primers may be formed.
- the surface of the molded article 1 on the side where the adhesive layer 2 and the like are formed has a concavo-convex shape, and the concavo-convex shape is formed from a plurality of convex portions 5 and concave portions 6. It is configured.
- the height H of the convex portions 5 and the distance A between the apexes of the adjacent convex portions 5 are preferably 1 ⁇ m to 10 ⁇ m and 1 to 100 ⁇ m, respectively. More preferably, they are 1 ⁇ m to 4 ⁇ m and 1 ⁇ m to 10 ⁇ m, respectively.
- the design of the hairline can be expressed by the concave and convex shape, and the decorative molded product is touched with a finger. This is because it is possible to obtain a bumpy feel peculiar to hairline processing from a decorative molded product.
- the height H of the convex portion 5 is less than 1 ⁇ m, the height difference of the concave and convex shape is too small, and there is a problem that the pattern originally provided in the hairline processed product cannot be expressed. Or the like adheres to the protective layer, there arises a problem that the fingerprint is difficult to remove.
- the arithmetic average surface roughness (Ra1) of the uneven shape of the molded product 1 is preferably 0.1 ⁇ m to 10 ⁇ m. Further, it is preferably 0.1 ⁇ m to 1.0 ⁇ m. This is because, when the arithmetic average surface roughness (Ra1) is within the above range, a hairline design having a tactile sensation inherent to the three-dimensional shape of the hairline processed product and fingerprint resistance can be realized.
- the arithmetic average surface roughness (Ra1) is less than 0.1 ⁇ m, the height of the uneven shape is too small, and a problem arises in that a tactile sensation due to the three-dimensional shape originally provided in the hairline processed product cannot be obtained.
- the thickness exceeds 10 ⁇ m, the height of the uneven shape is too large, and a problem arises that the tactile sensation due to the three-dimensional shape originally provided in the hairline processed product cannot be obtained.
- the adhesive layer adhesive layer is a layer for adhering the molded product to a layer such as a picture layer, and is formed between the molded product and the picture layer.
- a heat-sensitive or pressure-sensitive resin suitable for the type of molded product is selected.
- an epoxy-modified polyester resin obtained by reacting a polyester having a carboxyl group at both ends with a bisphenol-type epoxy resin may be used as a constituent material of the adhesive layer.
- a polyester having carboxyl groups at both ends can be obtained by condensation reaction of a dibasic acid and a polyhydric alcohol.
- dibasic acids examples include aromatic dibasic acids such as phthalic acid, isophthalic acid, and terephthalic acid, diphenolic acids, acid anhydrides and hydrogenated products of these aromatic dibasic acids, succinic acid, adipic acid, and azelaic acid. , Saturated aliphatic dibasic acids such as sebacic acid and dodecanedioic acid and acid anhydrides thereof, and dimer acids derived from unsaturated fatty acids. These dibasic acids are usually used alone or in combination of two or more. Used as a mixture.
- phthalic acid isophthalic acid, terephthalic acid, adipic acid, sebacic acid, dimer acids, diphenolic acid and the like are excellent in safety to the human body and can be used particularly preferably.
- polyhydric alcohol examples include ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2,2 -Linear diols such as dimethyl-1,3-propanediol (neopentyl glycol), 2,2-dialkyl-1,3-propanediol, butylene glycol, 1,6-hexanediol; cyclohexanediol, cyclohexanedi Diols having an alicyclic structure such as methanol and hydrogenated bisphenol A; dihydric alcohols such as an adduct of bisphenol A with ethylene oxide and an adduct of bisphenol A with propylene oxide.
- the mixing ratio of the dibasic acid and the polyhydric alcohol is usually adjusted so that the equivalent ratio of the carboxyl group of the dibasic acid / the hydroxyl group of the polyhydric alcohol is 1.01 / 1 to 2/1.
- the equivalent ratio is less than 1.01 / 1, the molecular weight of the resulting polyester is increased, the viscosity becomes too high, the reactivity with the epoxy resin becomes poor, and when the ratio exceeds 2/1. Unreacted dibasic acid remains, and the adhesiveness of the formed adhesive layer decreases.
- the number average molecular weight (hereinafter referred to as Mn) of the polyester having carboxyl groups at both ends is determined by the blending ratio of the dibasic acid and the polyhydric alcohol, and is generally 300 to 10,000, preferably 500 to 8,000.
- Mn is less than 300, the adhesiveness of the formed adhesive layer is lowered, and when it exceeds 10,000, the viscosity of the epoxy-modified polyester described later increases, resulting in poor fluidity and gaps in the uneven portions of the molded product 1. It becomes difficult to form an epoxy-modified polyester.
- the polyester having carboxyl groups at both ends has a glass transition temperature (Tg) of 5 to 60 ° C., preferably 15 to 45 ° C., more preferably 25 to 30 ° C.
- Tg glass transition temperature
- epoxy resin examples include aliphatic diepoxides and bisphenol-type epoxy resins such as bisphenol A and bisphenol F. These epoxy resins are usually used alone or in combination of two or more. Among these epoxy resins, polyglycidyl ether of bisphenol A, so-called epibis type epoxy resin, is particularly preferable in terms of safety to the human body.
- the average number of epoxy groups contained in one molecule of the epoxy resin is 1.1 to 2, particularly preferably 2.
- the number of the epoxy groups is less than 1.1, the reactivity with the polyester becomes poor, and when the number exceeds 2, the reaction system becomes highly viscous at the time of the condensation reaction with the polyester. It becomes gelled.
- the Mn of the epoxy resin is 340 to 20000, preferably 350 to 10,000.
- the Mn is less than 340, the effect of the epoxy resin as a hard segment is not sufficiently exhibited, and when it exceeds 20000, the viscosity of the epoxy-modified polyester described later increases, resulting in poor fluidity and unevenness of the molded product 1. It becomes difficult to form an epoxy-modified polyester without gaps in the portions.
- the epoxy resin has a Tg of 40 to 180 ° C., preferably 70 to 130 ° C., more preferably 95 to 100 ° C. This is because the hardness of the decorative coating decreases when Tg is less than 40 ° C., and the adhesiveness of the adhesive layer decreases when it exceeds 180 ° C.
- the blending ratio (weight ratio) of the polyester and the epoxy resin is 50/50 or more, preferably 60/40 to 95/5, more preferably 75/25 to 90/10. This is because if the blending ratio is less than 50/50, the adhesiveness of the adhesive layer decreases, and if it exceeds 95/5, the hardness of the decorative coating decreases.
- the reaction between the polyester and the epoxy resin can be performed by an ordinary solution polymerization method.
- a desired amount of polyester and epoxy resin are prepared, dissolved in a solvent, and then in an inert gas atmosphere such as nitrogen gas at 100 to 200 ° C. for 30 minutes to 6 minutes.
- the method of heating for a time is mention
- the solvent those not causing side reactions are selected, and examples thereof include cyclohexanone and xylene.
- a basic catalyst such as a tertiary amine may be appropriately added to promote the reaction.
- the Mn of the epoxy-modified polyester thus obtained is 10000 to 20000, preferably 12000 to 20000.
- Mn is less than 12000, the hardness of the protective layer is lowered, and when it exceeds 50000, printability is lowered, and peeling of a portion of the transfer layer where no pattern is present is likely to occur.
- the adhesive layer preferably contains a compound capable of imparting thermosetting properties such as blocked isocyanate as a curing agent.
- a curing agent such as these thermosetting resins is blended, a cured resin having a so-called three-dimensional network structure is formed with the epoxy-modified polyester during heating.
- the curing agent When the curing agent is blended, it is preferable to blend 2 to 50 parts by weight, particularly 5 to 30 parts by weight of the curing agent with respect to 100 parts by weight of the epoxy-modified polyester.
- the blending amount of the curing agent is less than the above range, the effect of blending the curing agent by heating at the time of heating lamination, that is, the curing reaction rate tends not to be improved so much, and when the blending amount is larger than the above range.
- the amount of water, alcohol, etc. generated during condensation of the curing agent increases, and the adhesiveness of the adhesive layer decreases.
- the inorganic layer may be included in the adhesive layer. By doing so, the hardness of the decorative coating is further improved.
- the particles are used in an amount of 0.5 or less, preferably 0.05 to 0.1 with respect to the epoxy-modified polyester. When the amount of the inorganic particles exceeds 0.5 by weight with respect to the epoxy-modified polyester, the adhesiveness of the adhesive layer is lowered.
- colloidal silica As the inorganic particles, colloidal silica is preferable. Colloidal silica particles have a free silanol group content of 1 to 50 (counts / nm2). It is preferable that the amount of the free silanol group is in the above range since the reactivity is high.
- the colloidal silica particles have a primary particle size of usually 1 to 200 nm, preferably 10 to 50 nm. If it is within this range, the effect of suppressing foil burr will be exhibited, and the protective film will not lose transparency. Colloidal silica having a particle size in the range of 10 to 20 nm is commercially available and can be obtained easily and inexpensively.
- the thickness of the adhesive layer is 15 ⁇ m or less, preferably 5 to 10 ⁇ m. When the thickness of the adhesive layer is 15 ⁇ m or more, the hardness of the protective layer decreases.
- the picture layer is a layer for applying decoration such as a picture to the molded product, and is formed on the protective layer as necessary.
- a resin such as polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin is used as a binder.
- Colored inks containing color pigments or dyes as colorants may be used.
- a pearl pigment in which titanium oxide is coated on metal particles such as aluminum, titanium, bronze, or mica can be used.
- the pattern layer may be transmissive or light-shielding.
- the protective layer is a layer disposed on the surface of the article, and is a layer that protects a molded article or the like disposed under the protective layer from physical or chemical trauma.
- the protective layer 4 has a fine uneven shape on its surface, and the uneven shape is composed of a plurality of fine convex portions 7 and fine concave portions 8.
- the height h of the fine protrusion 7 and the apex distance a of the adjacent fine protrusions 7 are preferably 0.1 ⁇ m to 1.0 ⁇ m and 0.1 ⁇ m to 99 ⁇ m, respectively. Furthermore, it is preferably 0.1 ⁇ m to 0.5 ⁇ m, 0.1 ⁇ m to 1.0 ⁇ m.
- the fingerprint attached to the protective layer 4 can be easily wiped off with paper or the like.
- the height of the fine convex portion 7 is less than 0.1 ⁇ m, a fingerprint is likely to adhere, and thus a problem that the function of fingerprint resistance cannot be exhibited occurs. This causes a problem that it is difficult to remove.
- the arithmetic average surface roughness (Ra2) of the fine irregularities of the protective layer 4 is preferably 0.01 to 1 ⁇ m. Further, it is preferably 0.01 to 0.50 ⁇ m. This is because when the arithmetic average surface roughness (Ra2) is in the above range, the generation of Newton rings on the protective layer 4 can be suppressed.
- the arithmetic average surface roughness (Ra2) of the fine uneven shape of the protective layer 4 is preferably smaller than the arithmetic average surface roughness (Ra1) of the uneven shape of the molded product 1. This is because, as described above, the protective layer 4 forms a fractal structure and thus can exhibit anti-fingerprint performance.
- the thickness of the protective layer 4 is preferably in the range of 1 ⁇ m to 20 ⁇ m. When the thickness of the protective layer 4 is less than 1 ⁇ m, the protective function cannot be sufficiently exhibited because it is too thin. On the other hand, when the thickness of the protective layer 4 exceeds 20 ⁇ m, cracks occur in the protective layer 4 at the time of molding. Absent.
- acrylic or methacrylic monomer homopolymers such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc., or acrylics of copolymers containing these monomers
- resins melamine resins, acrylic resins, urethane resins, epoxy resins, and the like can be used.
- two-component curable resins such as melamine, acrylic melamine, epoxy melamine, alkyd, urethane, acrylic, etc. and a mixture of these, or a combination with a curing agent such as isocyanate, polyester acrylate Polyester methacrylate, epoxy acrylate, epoxy methacrylate, urethane acrylate, urethane methacrylate, polyether acrylate, polyether methacrylate, polyol acrylate, melamine acrylate, melamine methacrylate and other monomers and prepolymers that have ethylenically unsaturated bonds
- Ultraviolet rays, electron beam curable resins, and the like can be used. When an ultraviolet curable resin is used, a photoinitiator is further added.
- the photoinitiator can be selected as appropriate. Examples include radical photopolymerization initiators such as benzoin ether, ketal, acetophenone, and thioxanthone, diazonium salts, diaryliodonium salts, triarylsulfonium salts, and complex cationic photopolymerization initiators. One or more of these can be used. *
- FIG. 4 is a diagram showing a method for producing a decorated molded product.
- the decorative molded product can be obtained by transferring the transfer sheet 20 including the base sheet 10, the protective layer 11, the pattern layer 12, and the adhesive layer 13 to the molded product 30 by hot roll transfer.
- the position of the transfer sheet 20 is set so that the pattern layer 12 is arranged at a desired position of the molded product 30 in consideration of the position of the pattern layer 12 existing on the transfer sheet 20. decide.
- the surface on the inner side (adhesive layer 13 side) of the transfer sheet 20 is superimposed on the surface of the molded product, and heat and heat are transferred from the base sheet 10 side of the transfer sheet 20 using a transfer machine such as a roll transfer machine or an up-down transfer machine. Apply pressure. By doing so, the transfer sheet 20 adheres to the surface of the molded product 30 and the surface of the molded product 30 is decorated.
- the material of the base sheet is composed of PET film or the like.
- the protective layer, the picture layer, the adhesive layer, and the molded product are composed of the above-described materials. Note that the protective layer, the pattern layer, and the adhesive layer are formed on the substrate sheet by a printing method such as a gravure printing method, a screen printing method, and an offset printing method in the above order.
- the adhesive material is made of polyester having carboxyl groups at both ends having a glass transition temperature (Tg) of 25 to 30 ° C., bisphenol type epoxy resin having a glass transition temperature (Tg) of 95 to 100 ° C. and colloidal silica (Nissan Chemical). Kogyo Co., Ltd., trade name: MEK-ST) was formulated and stirred at the ratio shown in Table 1.
- the glass transition temperature (Tg) and the weight average molecular weight of the adhesive material are as shown in Table 1, and the adhesive material having a solid content of 20% with respect to the total weight was used.
- Examples 2 to 3 Comparative Examples 1 to 3> A hairline-like decorative molded product was prepared 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.
- Fingerprint resistance Easiness of fingerprint removal
- the surface of the hard coat layer in the decorative molded product was carried out in accordance with the fingerprint removal test method described in JIS K2246.
- the determination of whether or not the fingerprint was removed was performed by visually observing the appearance of the part of the test piece to which the artificial fingerprint liquid was attached under a three-wavelength light source, and the evaluation was performed according to the following. .
- the results are shown in Table 1.
- the surface of the tactile decorative molded product was traced with a finger to test whether the decorative molded product had a tactile sensation peculiar to hairline processed products.
- the evaluation of the contact property was performed by conducting a questionnaire survey on the difference in tactile sensation felt when 50 people touched the hairline metal plate (company name: Shima Steel Co., Ltd., trade name: SUS304HL) and the decorative molded product.
- the evaluation criteria for tactile sensation are as shown below. The results are shown in Table 1.
- Evaluation criteria ⁇ 40 or more out of 50 responded that there was no difference in the tactile sensation between the two.
- ⁇ Out of 50 people, less than 25 to 40 answered that there was no difference in touch between the two.
- X Less than 25 people out of 50 answered that there was no difference in both tactile sensations.
- the design property of the decorative decorative molded product was tested.
- the evaluation of designability is to conduct a questionnaire survey on the difference in designability that 50 people feel when they observe the hairline metal (Shima Steel Co., Ltd., trade name SUS304 HL) and the above-mentioned decorative molded product from a distance of 30 cm from each other. It went by.
- the evaluation criteria of the designability are as shown below. The results are shown in Table 1.
- the surface hardness of the hard coat layer was measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4.
- the evaluation criteria for the surface hardness are as shown below. The results are shown in Table 1.
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Abstract
Provided is a decorative molded article having a sensation unique to a hairline design and adapted for reducing fingerprint adherence as well as readily removing any adhered fingerprints. The decorative molded article is configured so as to be provided with: a molded article (1) having a plurality of protrusions (5) provided on one surface, the height (H) of the protrusions (5) being 1 to 10 μm and the distance between adjacent apexes (A) of the protrusions (5) being 1 to 100 μm; an adhesive layer (2) formed on the surface of the molded article (1) on which the protrusions (5) are formed; and a protective layer (4) formed above the adhesive layer (2), the protective layer being provided with fine projections (7) on the surface opposite the surface in contact with the adhesive layer (2), the height (h) of the fine projections (7) being 0.1 to 1 μm, and the distance between proximal apexes of the fine projections (a) being 0.1 to 100 μm.
Description
本発明は、ヘアライン調の意匠を備えるヘアライン調加飾成形品に関し、特に、耐指紋性の機能を有するヘアライン調加飾成形品に関する。
The present invention relates to a hairline-like decorative molded product having a hairline-like design, and more particularly to a hairline-like decorative molded product having a fingerprint resistance function.
転写シートを用いて、プラスチック部品や外装品のような物品の表面を保護又は加飾する方法は従来から知られている。例えば、特許文献１には支持体である基体シートの面上に転写層が形成された転写シート、及びその転写シートを射出成形金型内に挿入し、インモールド射出成形して、装飾された射出成形体を得ることが記載されている。
A method for protecting or decorating the surface of an article such as a plastic part or an exterior product using a transfer sheet has been conventionally known. For example, in Patent Document 1, a transfer sheet in which a transfer layer is formed on the surface of a base sheet that is a support, and the transfer sheet is inserted into an injection mold and decorated by in-mold injection molding. It is described that an injection molded body is obtained.
転写シートは、支持体である基体シートの上に転写層が設けられた構成からなり、この転写層が成形品の表面に転写される。成形品の表面に転写された転写層は樹脂や絵柄が層状に積層された積層体であり、成形品表面に保護被覆や装飾被覆を形成する。
The transfer sheet has a structure in which a transfer layer is provided on a base sheet as a support, and this transfer layer is transferred to the surface of a molded product. The transfer layer transferred to the surface of the molded product is a laminate in which a resin or a pattern is laminated in a layer shape, and forms a protective coating or a decorative coating on the surface of the molded product.
従来より、成形品に対する保護機能が重視される場合がある。この保護機能が重視される場合には、転写シートの最外側に保護層が設けられる。更に用途によっては、保護層がヘアラインの意匠を備えることが求められる。この場合、基体シートと保護層との間にヘアライン層が設けられる。ヘアライン層は、表面形状が凹凸形状となっており、この凹凸形状が保護層に写し取られることにより、保護層がヘアラインの意匠を備えるようになっている。
Conventionally, protection functions for molded products may be emphasized. When this protective function is important, a protective layer is provided on the outermost side of the transfer sheet. Furthermore, depending on the application, the protective layer is required to have a hairline design. In this case, a hairline layer is provided between the base sheet and the protective layer. The hairline layer has an irregular shape on the surface, and the irregular shape is copied to the protective layer, so that the protective layer has a hairline design.
図５を参照して、転写シートを使用して得られる加飾成形品５００は、成形品５１０と、成形品５１０の表面を外傷から保護する保護層５１２と、保護層５１２と成形品５１０とを密着させる接着層５１１とから構成され、保護層５１２は、その表面に凸部５１３と凹部５１４を備えている。なお、凸部５１３と凹部５１４の高低差は、加飾成形品５００がヘアライン加工製品に特有のでこぼこした触感を有するよう、できるだけ大きくなるよう構成されている。
Referring to FIG. 5, a decorative molded product 500 obtained using the transfer sheet includes a molded product 510, a protective layer 512 that protects the surface of the molded product 510 from damage, a protective layer 512, and a molded product 510. The protective layer 512 includes a convex portion 513 and a concave portion 514 on the surface thereof. In addition, the height difference between the convex part 513 and the concave part 514 is configured to be as large as possible so that the decorative molded product 500 has a tactile sensation peculiar to a hairline processed product.
しかし、凸部５１３と凹部５１４の高低差が大きくなると、加飾成形品５００を指６００で触ったときに、指の油分（以下、指紋という）が保護層５１２の凹部分５１４に付着しやすくなり、一度付着すると、保護層５１２を布やペーパーなどで拭いても取れないという問題があった。
However, when the height difference between the convex portion 513 and the concave portion 514 becomes large, when the decorative molded product 500 is touched with the finger 600, the oil content of the finger (hereinafter referred to as the fingerprint) easily adheres to the concave portion 514 of the protective layer 512. Thus, once attached, there is a problem that the protective layer 512 cannot be removed even if it is wiped with cloth or paper.
本発明は上記従来の問題を解決するものであり、ヘアライン加工製品特有のでこぼこした触感を有するとともに、指で触っても指紋が付着しにくく、指紋が付着しても指紋が取れやすい加飾成形品を提供することにある。
The present invention solves the above-mentioned conventional problems, and has a bumpy touch peculiar to a hairline processed product, and it is difficult to attach a fingerprint even if it is touched with a finger. Is to provide goods.
本発明の加飾成形品は、複数の凸部を一方の面に備え、前記凸部の高さが１～１０μｍであり、前記凸部の隣接頂点間距離が１～１００μｍである成形品と、前記成形品の前記凸部が形成された面に形成される接着層と、前記接着層の上に形成され、前記接着層と接する面とは反対方向の面に微細凸部を備え、前記微細凸部の高さが０．１～１μｍであり、前記微細凸部の近接頂点間距離が０．１～１００μｍである保護層とを備える。
The decorative molded product of the present invention includes a molded product having a plurality of convex portions on one surface, the height of the convex portions is 1 to 10 μm, and the distance between adjacent vertices of the convex portions is 1 to 100 μm. An adhesive layer formed on the surface of the molded product on which the convex portion is formed, and a fine convex portion on the surface opposite to the surface formed on the adhesive layer and in contact with the adhesive layer, A protective layer in which the height of the fine protrusions is 0.1 to 1 μm, and the distance between adjacent vertices of the fine protrusions is 0.1 to 100 μm.
ある一形態においては、前記保護層の表面における算術平均粗さ（Ｒａ２）が、前記成形品と前記接着層との間における算術平均粗さ（Ｒａ１）より小さい。
In one embodiment, the arithmetic average roughness (Ra2) on the surface of the protective layer is smaller than the arithmetic average roughness (Ra1) between the molded article and the adhesive layer.
ある一形態においては、前記成形品と前記接着層との間における算術平均粗さ（Ｒａ１）が、０．１～１０μmである。
In one embodiment, the arithmetic average roughness (Ra1) between the molded article and the adhesive layer is 0.1 to 10 μm.
ある一形態においては、前記保護層の表面における算術平均粗さ（Ｒａ２）が、０．０１～１μmである。
In one embodiment, the arithmetic average roughness (Ra2) on the surface of the protective layer is 0.01 to 1 μm.
ある一形態においては、前記保護層と前記接着層との間に、ポリ塩化ビニル樹脂、アクリル樹脂、ポリウレタン樹脂、セルロースエステル樹脂及びポリビニルアセタール樹脂のいずれかを少なくとも一種を含む絵柄層を備え、前記成形品が金属板であり、前記接着層が両末端にカルボキシル基を有するポリエステルとビスフェノール型エポキシ樹脂を、７５／２５～９０／１０の重量比で反応させて得られる、ガラス転移温度３０～１００℃及び分子量２００００～３００００のエポキシ変性ポリエステル樹脂を含み、その厚みが５～１０μｍである。
In one embodiment, a pattern layer including at least one of polyvinyl chloride resin, acrylic resin, polyurethane resin, cellulose ester resin and polyvinyl acetal resin is provided between the protective layer and the adhesive layer, The molded product is a metal plate, and the adhesive layer is obtained by reacting a polyester having carboxyl groups at both ends with a bisphenol type epoxy resin in a weight ratio of 75/25 to 90/10, and has a glass transition temperature of 30 to 100 An epoxy-modified polyester resin having a molecular weight of 20000 to 30,000 and a thickness of 5 to 10 μm is included.
ある一形態においては、前記接着層が、前記エポキシ変性ポリエステルに対して、重量比０．０５～０．１の量でコロイダルシリカを含有する。
In one embodiment, the adhesive layer contains colloidal silica in an amount of 0.05 to 0.1 with respect to the epoxy-modified polyester.
ある一形態においては、前記接着層が、硬化剤としてブロックイソシアネートを含有する。
In one certain form, the said contact bonding layer contains block isocyanate as a hardening | curing agent.
本発明の加飾成形品は、複数の凸部を一方の面に備え、前記凸部の高さが１～１０μｍ、前記凸部の隣接頂点間距離が１～１００μｍである成形品と、前記成形品の前記凸部が形成された面に形成される接着層と、前記接着層の上に形成され、前記接着層と接する面とは反対方向の面に微細凸部を備え、前記微細凸部の高さが０．１～１μｍ、前記微細凸部の近接頂点間距離が０．１～１００μｍである保護層とを備える。その結果、指で触ったときにヘアライン意匠特有のでこぼこした触感を得られるとともに、指で触っても指紋が付きにくく、指紋が付着しても指紋が取れやすい加飾成形品を提供できる。
The decorative molded product of the present invention comprises a molded product having a plurality of convex portions on one surface, the height of the convex portions being 1 to 10 μm, and the distance between adjacent vertices of the convex portions being 1 to 100 μm, An adhesive layer formed on a surface of the molded product on which the convex portions are formed; and a fine convex portion provided on a surface opposite to the surface that is formed on the adhesive layer and is in contact with the adhesive layer. A protective layer having a height of 0.1 to 1 μm and a distance between adjacent vertices of the fine convex portions of 0.1 to 100 μm. As a result, it is possible to provide a decorative molded product that can obtain a bumpy tactile sensation peculiar to a hairline design when touched with a finger, is difficult to get a fingerprint even when touched with a finger, and can be easily taken even when a fingerprint is attached.
下記で、本発明に係る実施形態を図面に基づいてさらに詳細に説明する。なお、本発明の実施例に記載した部位や部分の寸法、材質、形状、その相対位置などは、とくに特定的な記載がない限り、この発明の範囲をそれらのみに限定する趣旨のものではなく、単なる説明例にすぎない。
Hereinafter, an embodiment according to the present invention will be described in more detail with reference to the drawings. It should be noted that the dimensions, materials, shapes, relative positions, etc. of the parts and portions described in the embodiments of the present invention are not intended to limit the scope of the present invention only to those unless otherwise specified. This is just an illustrative example.
加飾成形品
図１は、この発明の加飾成形品１００を示した図である。図２は、図１のα領域における拡大図である。図３は、図１のβ領域における拡大図である。図１を参照して、本発明の加飾成形品１００は、成形品１の上に接着層２、絵柄層３、保護層４が、この順番で形成されている。 Decorative Molded Product FIG. 1 is a diagram showing a decorated moldedproduct 100 of the present invention. FIG. 2 is an enlarged view of the α region in FIG. FIG. 3 is an enlarged view of the β region of FIG. Referring to FIG. 1, in a decorative molded product 100 of the present invention, an adhesive layer 2, a pattern layer 3, and a protective layer 4 are formed on a molded product 1 in this order.
図１は、この発明の加飾成形品１００を示した図である。図２は、図１のα領域における拡大図である。図３は、図１のβ領域における拡大図である。図１を参照して、本発明の加飾成形品１００は、成形品１の上に接着層２、絵柄層３、保護層４が、この順番で形成されている。 Decorative Molded Product FIG. 1 is a diagram showing a decorated molded
成形品
成形品は、絵柄層に形成された模様や色彩によって装飾が施される物品である。成形品の材質としては、各種合成樹脂、金属、ガラス、木、紙でなる部材、これらの塗装物などが挙げられる。成形品が、金属から構成される場合、成形品を構成する材料としては、例えば、鉄、ブリキ、ステンレス鋼、チタン、銅、アルミニウム等の金属、及びガラスなどが挙げられる。なお、これらの成形品の接着層などが形成される面にはあらかじめ易接着化処理等の表面処理が施されていてもよく、また各種プライマーなどが形成されていてもよい。 Molded articles Molded articles are articles that are decorated with patterns and colors formed on the pattern layer. Examples of the material of the molded article include various synthetic resins, metals, glass, wood, paper members, and painted products thereof. When the molded product is made of a metal, examples of the material that forms the molded product include metals such as iron, tinplate, stainless steel, titanium, copper, and aluminum, and glass. Note that the surface of the molded product on which the adhesive layer or the like is formed may be subjected to surface treatment such as easy adhesion treatment in advance, or various primers may be formed.
成形品は、絵柄層に形成された模様や色彩によって装飾が施される物品である。成形品の材質としては、各種合成樹脂、金属、ガラス、木、紙でなる部材、これらの塗装物などが挙げられる。成形品が、金属から構成される場合、成形品を構成する材料としては、例えば、鉄、ブリキ、ステンレス鋼、チタン、銅、アルミニウム等の金属、及びガラスなどが挙げられる。なお、これらの成形品の接着層などが形成される面にはあらかじめ易接着化処理等の表面処理が施されていてもよく、また各種プライマーなどが形成されていてもよい。 Molded articles Molded articles are articles that are decorated with patterns and colors formed on the pattern layer. Examples of the material of the molded article include various synthetic resins, metals, glass, wood, paper members, and painted products thereof. When the molded product is made of a metal, examples of the material that forms the molded product include metals such as iron, tinplate, stainless steel, titanium, copper, and aluminum, and glass. Note that the surface of the molded product on which the adhesive layer or the like is formed may be subjected to surface treatment such as easy adhesion treatment in advance, or various primers may be formed.
図１、および図２を参照して、成形品１の接着層２などが形成される側の表面は、凹凸形状を有しており、その凹凸形状は、複数の凸部５と凹部６から構成されている。なお、凸部５の高さＨと、隣接する凸部５の頂点間距離Ａは、それぞれ１μｍ～１０μｍ、１～１００μｍであることが好ましい。さらに、好ましくは、それぞれ１μｍ～４μｍ、１μｍ～１０μｍである。凸部５の高さＨと、隣接する凸部５の頂点間距離Ａが、上記範囲にあると、その凹凸形状でヘアラインの意匠を表現できるとともに、加飾成形品を指で触ったときに、加飾成形品からヘアライン加工特有のでこぼこした触感を得ることができるからである。
With reference to FIG. 1 and FIG. 2, the surface of the molded article 1 on the side where the adhesive layer 2 and the like are formed has a concavo-convex shape, and the concavo-convex shape is formed from a plurality of convex portions 5 and concave portions 6. It is configured. Note that the height H of the convex portions 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, respectively. 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 hairline can be expressed by the concave and convex shape, and the decorative molded product is touched with a finger. This is because it is possible to obtain a bumpy feel peculiar to hairline processing from a decorative molded product.
なお、凸部５の高さＨが１μｍ未満であると凹凸形状の高低差が小さすぎて、ヘアライン加工製品が本来備える模様が表現できないという問題が発生し、反対に１０μmを越えると、一旦指紋などが保護層に付着すると、当該指紋などが除去されにくいという問題が発生する。
In addition, if the height H of the convex portion 5 is less than 1 μm, the height difference of the concave and convex shape is too small, and there is a problem that the pattern originally provided in the hairline processed product cannot be expressed. Or the like adheres to the protective layer, there arises a problem that the fingerprint is difficult to remove.
また、上記頂点間距離Ａが１μｍ未満であると隣り合う凸部が近過ぎて、ヘアライン加工製品が本来備えるヘアラインの立体的形状が表現できないという問題が発生し、反対に、１００μｍを越えると隣接する凸部間の距離が遠すぎて隙間が多く発生するので、ヘアライン加工製品が備える立体的形状が表現できないという問題が発生する。
In addition, when the distance A between the vertices is less than 1 μm, adjacent convex portions are too close, and the problem that the three-dimensional shape of the hairline that the hairline processed product originally has cannot be expressed occurs. Since the distance between the convex parts is too far and many gaps are generated, there arises a problem that the three-dimensional shape of the hairline processed product cannot be expressed.
さらに、成形品１の凹凸形状の算術平均表面粗さ（Ｒａ１）は、０．１μｍ～１０μｍであることが好ましい。さらに、好ましくは０．１μｍ～１．０μｍである。算術平均表面粗さ（Ｒａ１）が上記範囲であると、本来ヘアライン加工製品が備える立体的形状に起因した触感と、耐指紋性を備えたヘアライン意匠が実現できるためである。
Further, the arithmetic average surface roughness (Ra1) of the uneven shape of the molded product 1 is preferably 0.1 μm to 10 μm. Further, it is preferably 0.1 μm to 1.0 μm. This is because, when the arithmetic average surface roughness (Ra1) is within the above range, a hairline design having a tactile sensation inherent to the three-dimensional shape of the hairline processed product and fingerprint resistance can be realized.
なお、算術平均表面粗さ（Ｒａ１）が０．１μｍ未満であると凹凸形状の高低さが小さすぎて、本来ヘアライン加工製品が備える立体的形状に起因した触感が得られないという問題が発生し、反対に、１０μｍを越えると凹凸形状の高低さが大きすぎて、本来ヘアライン加工製品が備える立体的形状に起因した触感が得られないという問題が発生する。
In addition, if the arithmetic average surface roughness (Ra1) is less than 0.1 μm, the height of the uneven shape is too small, and a problem arises in that a tactile sensation due to the three-dimensional shape originally provided in the hairline processed product cannot be obtained. On the other hand, when the thickness exceeds 10 μm, the height of the uneven shape is too large, and a problem arises that the tactile sensation due to the three-dimensional shape originally provided in the hairline processed product cannot be obtained.
接着層
接着層は、成形品を絵柄層などの層と貼着するための層であり、成形品と絵柄層との間に形成される。接着層に用いる材料としては、成形品の種類に適した感熱性又は感圧性のある樹脂が選択される。 The adhesive layer adhesive layer is a layer for adhering the molded product to a layer such as a picture layer, and is formed between the molded product and the picture layer. As the material used for the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the type of molded product is selected.
接着層は、成形品を絵柄層などの層と貼着するための層であり、成形品と絵柄層との間に形成される。接着層に用いる材料としては、成形品の種類に適した感熱性又は感圧性のある樹脂が選択される。 The adhesive layer adhesive layer is a layer for adhering the molded product to a layer such as a picture layer, and is formed between the molded product and the picture layer. As the material used for the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the type of molded product is selected.
特に成形品が、金属から構成される場合、接着層の構成材料としては、両末端にカルボキシル基を有するポリエステルとビスフェノール型エポキシ樹脂を反応させて得られるエポキシ変性ポリエステル樹脂を使用するとよい。
In particular, when the molded product is made of a metal, an epoxy-modified polyester resin obtained by reacting a polyester having a carboxyl group at both ends with a bisphenol-type epoxy resin may be used as a constituent material of the adhesive layer.
両末端にカルボキシル基を有するポリエステルは、二塩基酸および多価アルコールを縮合反応させることにより得られる。
A polyester having carboxyl groups at both ends can be obtained by condensation reaction of a dibasic acid and a polyhydric alcohol.
二塩基酸としては、例えばフタル酸、イソフタル酸、テレフタル酸などの芳香族二塩基酸、ジフェノリック酸、これら芳香族二塩基酸の酸無水物および水添物、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジオイック酸などの飽和脂肪族二塩基酸およびその酸無水物、不飽和脂肪酸から誘導されたダイマー酸類などがあげられ、これらの二塩基酸は通常単独でまたは２種以上を混合して用いられる。これらの二塩基酸のなかでは、フタル酸、イソフタル酸、テレフタル酸、アジピン酸、セバシン酸、ダイマー酸類、ジフェノリック酸などは人体に対する安全性に優れ、特に好適に使用しうる。
Examples of dibasic acids include aromatic dibasic acids such as phthalic acid, isophthalic acid, and terephthalic acid, diphenolic acids, acid anhydrides and hydrogenated products of these aromatic dibasic acids, succinic acid, adipic acid, and azelaic acid. , Saturated aliphatic dibasic acids such as sebacic acid and dodecanedioic acid and acid anhydrides thereof, and dimer acids derived from unsaturated fatty acids. These dibasic acids are usually used alone or in combination of two or more. Used as a mixture. Among these dibasic acids, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, dimer acids, diphenolic acid and the like are excellent in safety to the human body and can be used particularly preferably.
前記多価アルコールとしては、例えばエチレングリコール、ポリエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリプロピレングリコール、１，３－ブタンジオール、２，３－ブタンジオール、１，４－ブタンジオール、２，２－ジメチル－１，３－プロパンジオール（ネオペンチルグリコール）、２，２－ジアルキル－１，３－プロパンジオール、ブチレングリコール、１，６－ヘキサンジオールなどの直鎖状ジオール類；シクロヘキサンジオール、シクロヘキサンジメタノール、水添ビスフェノールＡなどの脂環構造を有するジオール類；ビスフェノールＡのエチレンオキサイドの付加物、ビスフェノールＡのプロピレンオキサイドの付加物などの二価アルコールなどがあげられる。これらの多価アルコールのなかでは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ネオペンチルグリコール、ブチレングリコールなどは、人体に対する安全性に優れ、特に好適に使用しうる。
Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2,2 -Linear diols such as dimethyl-1,3-propanediol (neopentyl glycol), 2,2-dialkyl-1,3-propanediol, butylene glycol, 1,6-hexanediol; cyclohexanediol, cyclohexanedi Diols having an alicyclic structure such as methanol and hydrogenated bisphenol A; dihydric alcohols such as an adduct of bisphenol A with ethylene oxide and an adduct of bisphenol A with propylene oxide. Among these polyhydric alcohols, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, butylene glycol and the like are excellent in safety to the human body and can be particularly preferably used.
前記二塩基酸および前記多価アルコールの配合割合は、通常二塩基酸のカルボキシル基／多価アルコールの水酸基の当量比が１．０１／１～２／１となるように調整される。かかる当量比が１．０１／１よりも小さい場合には、得られるポリエステルの分子量が大きくなって粘度が大きくなりすぎ、エポキシ樹脂との反応性に乏しくなり、また２／１を超える場合には、未反応の二塩基酸が残存し、形成される接着層の接着性が低下する。
The mixing ratio of the dibasic acid and the polyhydric alcohol is usually adjusted so that the equivalent ratio of the carboxyl group of the dibasic acid / 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 resulting polyester is increased, the viscosity becomes too high, the reactivity with the epoxy resin becomes poor, and when the ratio exceeds 2/1. Unreacted dibasic acid remains, and the adhesiveness of the formed adhesive layer decreases.
両末端にカルボキシル基を有するポリエステルの数平均分子量（以下、Ｍｎという）は、前記二塩基酸および前記多価アルコールの配合割合によって決定され、一般に３００～１００００、好ましくは５００～８０００である。Ｍｎが３００未満であると形成される接着層の接着性が低下し、１００００を超えると、後述のエポキシ変性ポリエステルの粘度が大きくなるため、流動性が悪くなり、成形品1の凹凸部分に隙間無くエポキシ変性ポリエステルを形成するのが困難となる。
The number average molecular weight (hereinafter referred to as Mn) of the polyester having carboxyl groups at both ends is determined by the blending ratio of the dibasic acid and the polyhydric alcohol, and is generally 300 to 10,000, preferably 500 to 8,000. When the Mn is less than 300, the adhesiveness of the formed adhesive layer is lowered, and when it exceeds 10,000, the viscosity of the epoxy-modified polyester described later increases, resulting in poor fluidity and gaps in the uneven portions of the molded product 1. It becomes difficult to form an epoxy-modified polyester.
両末端にカルボキシル基を有するポリエステルはガラス転移温度（Ｔｇ）が５～６０℃、好ましくは１５～４５℃、より好ましくは２５～３０℃である。Ｔｇが５℃未満であると装飾被覆の硬度が低下し、６０℃を超えると接着層の接着性が低下する。
The polyester having carboxyl groups at both ends has a glass transition temperature (Tg) of 5 to 60 ° C., preferably 15 to 45 ° C., more preferably 25 to 30 ° C. When Tg is less than 5 ° C., the hardness of the decorative coating decreases, and when it exceeds 60 ° C., the adhesiveness of the adhesive layer decreases.
前記エポキシ樹脂としては、例えば脂肪族系ジエポキシドをはじめ、ビスフェノールＡやビスフェノールＦなどのビスフェノール型エポキシ樹脂などが挙げられ、これらのエポキシ樹脂は通常単独でまたは２種以上を混合して用いられる。これらのエポキシ樹脂のなかでは、ビスフェノールＡのポリグリシジリエーテル、いわゆるエピビス型エポキシ樹脂が人体に対する安全面で特に好ましい。
Examples of the epoxy resin include aliphatic diepoxides and bisphenol-type epoxy resins such as bisphenol A and bisphenol F. These epoxy resins are usually used alone or in combination of two or more. Among these epoxy resins, polyglycidyl ether of bisphenol A, so-called epibis type epoxy resin, is particularly preferable in terms of safety to the human body.
前記エポキシ樹脂１分子中に含まれるエポキシ基の数は平均して１．１～２個、特に好ましくは２個である。前記エポキシ基の数は１．１個よりも少ない場合には、ポリエステルとの反応性に乏しくなり、また２個を超える場合には、ポリエステルとの縮合反応時に反応系が高粘度となり、著しい場合にはゲル化するようになる。
The average number of epoxy groups contained in one molecule of the epoxy resin is 1.1 to 2, particularly preferably 2. When the number of the epoxy groups is less than 1.1, the reactivity with the polyester becomes poor, and when the number exceeds 2, the reaction system becomes highly viscous at the time of the condensation reaction with the polyester. It becomes gelled.
また、前記エポキシ樹脂のＭｎは、３４０～２００００、好ましくは３５０～１００００である。Ｍｎが３４０未満であるとハードセグメントであるエポキシ樹脂による効果が充分に発現されなくなり、２００００を超えると、後述のエポキシ変性ポリエステルの粘度が大きくなるため、流動性が悪くなり、成形品１の凹凸部分に隙間無くエポキシ変性ポリエステルを形成するのが困難となる。
The Mn of the epoxy resin is 340 to 20000, preferably 350 to 10,000. When the Mn is less than 340, the effect of the epoxy resin as a hard segment is not sufficiently exhibited, and when it exceeds 20000, the viscosity of the epoxy-modified polyester described later increases, resulting in poor fluidity and unevenness of the molded product 1. It becomes difficult to form an epoxy-modified polyester without gaps in the portions.
前記エポキシ樹脂はＴｇが４０～１８０℃、好ましくは７０～１３０℃、より好ましくは９５～１００℃である。Ｔｇが４０℃未満であると装飾被覆の硬度が低下し、１８０℃を超えると接着層の接着性が低下するためである。
The epoxy resin has a Tg of 40 to 180 ° C., preferably 70 to 130 ° C., more preferably 95 to 100 ° C. This is because the hardness of the decorative coating decreases when Tg is less than 40 ° C., and the adhesiveness of the adhesive layer decreases when it exceeds 180 ° C.
ポリエステルと前記エポキシ樹脂との配合割合（重量比）は、５０／５０以上、好ましくは６０／４０～９５／５、より好ましくは７５／２５～９０／１０である。この配合割合が５０／５０未満では接着層の接着性が低下し、９５／５を超えると装飾被覆の硬度が低下するためである。
The blending ratio (weight ratio) of the polyester and the epoxy resin is 50/50 or more, preferably 60/40 to 95/5, more preferably 75/25 to 90/10. This is because if the blending ratio is less than 50/50, the adhesiveness of the adhesive layer decreases, and if it exceeds 95/5, the hardness of the decorative coating decreases.
前記ポリエステルとエポキシ樹脂の反応は、通常の溶液重合法によって行なうことができる。かかる溶液重合法の一例をあげれば、例えば所望量のポリエステルとエポキシ樹脂を調整し、これを溶剤に溶解し、例えばチッ素ガスなどの不活性ガス雰囲気中で１００～２００℃で３０分～６時間加熱する方法などがあげられる。前記溶剤としては、副反応をおこさないものが選ばれ、例えばシクロヘキサノン、キシレンなどがあげられる。なお、反応の際には、例えば３級アミンなどの塩基性触媒を適宜配合して反応を促進させてもよい。
The reaction between the polyester and the epoxy resin can be performed by an ordinary solution polymerization method. As an example of such a solution polymerization method, for example, a desired amount of polyester and epoxy resin are prepared, dissolved in a solvent, and then in an inert gas atmosphere such as nitrogen gas at 100 to 200 ° C. for 30 minutes to 6 minutes. The method of heating for a time is mention | raise | lifted. As the solvent, those not causing side reactions are selected, and examples thereof include cyclohexanone and xylene. In the reaction, for example, a basic catalyst such as a tertiary amine may be appropriately added to promote the reaction.
かくして得られるエポキシ変性ポリエステルのＭｎは、１００００～２００００、好ましくは１２０００～２００００である。Ｍｎが１２０００未満であると保護層の硬度が低下し、５００００を超えると印刷適性が低下し、転写層の絵柄が存在しない部分の剥離が生じ易くなる。
The Mn of the epoxy-modified polyester thus obtained is 10000 to 20000, preferably 12000 to 20000. When Mn is less than 12000, the hardness of the protective layer is lowered, and when it exceeds 50000, printability is lowered, and peeling of a portion of the transfer layer where no pattern is present is likely to occur.
接着層は、硬化剤として、ブロックイソシアネートなどの熱硬化性を付与しうる化合物を適宜含有することが好ましい。これらの熱硬化性樹脂などの硬化剤を配合した場合には、加熱時にエポキシ変性ポリエステルとのあいだでいわゆる三次元網目構造を有する樹脂硬化物が形成される。
The adhesive layer preferably contains a compound capable of imparting thermosetting properties such as blocked isocyanate as a curing agent. When a curing agent such as these thermosetting resins is blended, a cured resin having a so-called three-dimensional network structure is formed with the epoxy-modified polyester during heating.
前記硬化剤を配合する場合には、エポキシ変性ポリエステル１００重量部に対して硬化剤を２～５０重量部、特に５～３０重量部配合することが好ましい。かかる硬化剤の配合量が前記範囲よりも少ない場合には、加熱ラミネート時に加熱による硬化剤を配合することによる効果、すなわち硬化反応速度があまり向上しなくなる傾向があり、また前記範囲よりも多い場合には、硬化剤の縮合時に生成した水、アルコールなどの量が多くなり、接着層の接着性が低下する。
When the curing agent is blended, it is preferable to blend 2 to 50 parts by weight, particularly 5 to 30 parts by weight of the curing agent with respect to 100 parts by weight of the epoxy-modified polyester. When the blending amount of the curing agent is less than the above range, the effect of blending the curing agent by heating at the time of heating lamination, that is, the curing reaction rate tends not to be improved so much, and when the blending amount is larger than the above range. However, the amount of water, alcohol, etc. generated during condensation of the curing agent increases, and the adhesiveness of the adhesive layer decreases.
接着層には無機粒子を含有させてもよい。そうすることで、装飾被覆の硬度が更に向上する。接着層に無機粒子を含有させる場合、粒子はエポキシ変性ポリエステルに対して、重量比０．５以下、好ましくは０．０５～０．１になる量で使用される。無機粒子の量がエポキシ変性ポリエステルに対して、重量比０．５を超えると、接着層の接着性が低下する。
The inorganic layer may be included in the adhesive layer. By doing so, the hardness of the decorative coating is further improved. When inorganic particles are contained in the adhesive layer, the particles are used in an amount of 0.5 or less, preferably 0.05 to 0.1 with respect to the epoxy-modified polyester. When the amount of the inorganic particles exceeds 0.5 by weight with respect to the epoxy-modified polyester, the adhesiveness of the adhesive layer is lowered.
無機粒子としては、コロイダルシリカが好ましい。コロイダルシリカ粒子は遊離シラノール基の量が１～５０（ｃｏｕｎｔｓ／ｎｍ２）である。遊離シラノール基の量が上記範囲であると反応性に富み、好ましい。コロイダルシリカ粒子は、一次粒子径が、通常１～２００ｎｍ、好ましくは１０～５０ｎｍである。この範囲にあると、箔バリ抑制の効果が発揮され、保護膜に透明性が失われることがない。また、粒子径が１０～２０ｎｍ範囲のコロイダルシリカが市販されており、容易かつ安価に入手可能である。
As the inorganic particles, colloidal silica is preferable. Colloidal silica particles have a free silanol group content of 1 to 50 (counts / nm2). It is preferable that the amount of the free silanol group is in the above range since the reactivity is high. The colloidal silica particles have a primary particle size of usually 1 to 200 nm, preferably 10 to 50 nm. If it is within this range, the effect of suppressing foil burr will be exhibited, and the protective film will not lose transparency. Colloidal silica having a particle size in the range of 10 to 20 nm is commercially available and can be obtained easily and inexpensively.
接着層の厚みは、１５μｍ以下、好ましくは５～１０μｍである。接着層の厚みが１５μｍ以上であると、保護層の硬度が低下する。
The thickness of the adhesive layer is 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 decreases.
絵柄層
絵柄層は、成形品に絵柄などの装飾を施すための層であり、必要に応じて、保護層の上に形成される。絵柄層の材質としては、ポリビニル系樹脂、ポリアミド系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリビニルアセタール系樹脂、ポリエステルウレタン系樹脂、セルロースエステル系樹脂、アルキッド樹脂などの樹脂をバインダーとし、適切な色の顔料または染料を着色剤として含有する着色インキを用いるとよい。また、金属発色させる場合には、アルミニウム、チタン、ブロンズ等の金属粒子やマイカに酸化チタンをコーティングしたパール顔料を用いることもできる。また、絵柄層は透過性であっても、遮光性であってもよい。 Picture layer The picture layer is a layer for applying decoration such as a picture to the molded product, and is formed on the protective layer as necessary. As the material of the pattern layer, a resin such as polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin is used as a binder. Colored inks containing color pigments or dyes as colorants may be used. In the case of forming a metal color, a pearl pigment in which titanium oxide is coated on metal particles such as aluminum, titanium, bronze, or mica can be used. Further, the pattern layer may be transmissive or light-shielding.
絵柄層は、成形品に絵柄などの装飾を施すための層であり、必要に応じて、保護層の上に形成される。絵柄層の材質としては、ポリビニル系樹脂、ポリアミド系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリビニルアセタール系樹脂、ポリエステルウレタン系樹脂、セルロースエステル系樹脂、アルキッド樹脂などの樹脂をバインダーとし、適切な色の顔料または染料を着色剤として含有する着色インキを用いるとよい。また、金属発色させる場合には、アルミニウム、チタン、ブロンズ等の金属粒子やマイカに酸化チタンをコーティングしたパール顔料を用いることもできる。また、絵柄層は透過性であっても、遮光性であってもよい。 Picture layer The picture layer is a layer for applying decoration such as a picture to the molded product, and is formed on the protective layer as necessary. As the material of the pattern layer, a resin such as polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin is used as a binder. Colored inks containing color pigments or dyes as colorants may be used. In the case of forming a metal color, a pearl pigment in which titanium oxide is coated on metal particles such as aluminum, titanium, bronze, or mica can be used. Further, the pattern layer may be transmissive or light-shielding.
保護層
保護層は、物品の表面に配置される層であり、保護層の下に配置される成形品などを物理的または化学的な外傷から保護する層である。 Protective layer The protective layer is a layer disposed on the surface of the article, and is a layer that protects a molded article or the like disposed under the protective layer from physical or chemical trauma.
保護層は、物品の表面に配置される層であり、保護層の下に配置される成形品などを物理的または化学的な外傷から保護する層である。 Protective layer The protective layer is a layer disposed on the surface of the article, and is a layer that protects a molded article or the like disposed under the protective layer from physical or chemical trauma.
図３を参照して、保護層４は、その表面に微細な凹凸形状を備えており、その凹凸形状は、複数の微細凸部７と、微細凹部８から構成されている。なお、上記微細凸部７の高さｈと、隣接する微細凸部７の頂点間距離ａは、それぞれ０．１μｍ～１．０μｍ、０．１μｍ～９９μｍであることが好ましい。さらに、好ましくは、０．１μｍ～０．５μｍ、０．１μｍ～１．０μｍである。
Referring to FIG. 3, the protective layer 4 has a fine uneven shape on its surface, and the uneven shape is composed of a plurality of fine convex portions 7 and fine concave portions 8. The height h of the fine protrusion 7 and the apex distance a of the adjacent fine protrusions 7 are preferably 0.1 μm to 1.0 μm and 0.1 μm to 99 μm, respectively. Furthermore, it is preferably 0.1 μm to 0.5 μm, 0.1 μm to 1.0 μm.
微細凸部７の高さｈと、隣接する微細凸部７の頂点間距離ａが上記範囲にあると、加飾成形品を指で触ったときに、指と保護層４とが接する面積が小さくなるので、加飾成形加成が指紋に付着する割合が小さくなる。
When the height h 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 molded product is touched with the finger, the area where the finger and the protective layer 4 are in contact with each other Since it becomes small, the ratio by which decorative molding addition adheres to a fingerprint becomes small.
さらに、微細凸部７の高さｈと、隣接する微細凸部７の頂点間距離aが上記範囲にあると、指で保護層４を触っても、指紋が微細凹部８に浸入しづらくなる。その結果、保護層４に付いた指紋はペーパーなどで簡単に拭き取ることができる。
Furthermore, when the height h 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 with a finger, the fingerprint does not easily enter the fine concave portion 8. . As a result, the fingerprint attached to the protective layer 4 can be easily wiped off with paper or the like.
なお、微細凸部７の高さが、０．１μｍ未満であると指紋が付着しやすいため耐指紋性の機能を発現できないという問題が発生し、反対に、１．０μｍを越えると付着した指紋が除去しにくいという問題が発生する。
In addition, if the height of the fine convex portion 7 is less than 0.1 μm, a fingerprint is likely to adhere, and thus a problem that the function of fingerprint resistance cannot be exhibited occurs. This causes a problem that it is difficult to remove.
さらに、隣接する微細凸部７の頂点間距離ａが０．１μｍ未満であると指紋が付着しやすいため耐指紋性の機能を発現できないという問題が発生し、反対に、９９μｍを越えると付着した指紋が除去しにくいという問題が発生する。
Furthermore, when the distance a between the apexes of adjacent fine convex portions 7 is less than 0.1 μm, there is a problem that fingerprints tend to adhere, and thus the function of fingerprint resistance cannot be exhibited. The problem arises that fingerprints are difficult to remove.
さらに、保護層４の微細凹凸形状の算術平均表面粗さ（Ｒａ２）は、０．０１～１μｍであることが好ましい。さらに、好ましくは０．０１～０．５０μｍである。算術平均表面粗さ（Ｒａ２）が上記範囲であると、保護層４上にニュートンリングが発生するのを抑制できるからである。
Furthermore, the arithmetic average surface roughness (Ra2) of the fine irregularities of the protective layer 4 is preferably 0.01 to 1 μm. Further, it is preferably 0.01 to 0.50 μm. This is because when the arithmetic average surface roughness (Ra2) is in the above range, the generation of Newton rings on the protective layer 4 can be suppressed.
さらに、保護層４の微細凹凸形状の算術平均表面粗さ（Ｒａ２）は、成形品１の凹凸形状の算術平均表面粗さ（Ｒａ１）より、小さいことが好ましい。上記のようであると、保護層４がフラクタル構造を形成するため耐指紋性能が発揮できるからである。
Furthermore, the arithmetic average surface roughness (Ra2) of the fine uneven shape of the protective layer 4 is preferably smaller than the arithmetic average surface roughness (Ra1) of the uneven shape of the molded product 1. This is because, as described above, the protective layer 4 forms a fractal structure and thus can exhibit anti-fingerprint performance.
保護層４の膜厚は、１μｍ～２０μｍの範囲であることが好ましい。保護層４の膜厚が１μｍ未満の場合、薄すぎて保護機能を充分に発揮できなくなり、反対に保護層４の膜厚が２０μｍを超えると、成形時に保護層４にクラックが発生するため好ましくない。
The thickness of the protective layer 4 is preferably in the range of 1 μm to 20 μm. When the thickness of the protective layer 4 is less than 1 μm, the protective function cannot be sufficiently exhibited because it is too thin. On the other hand, when the thickness of the protective layer 4 exceeds 20 μm, cracks occur in the protective layer 4 at the time of molding. Absent.
保護層４の材質としては、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸エチル、ポリアクリル酸ブチルなどのアクリルもしくはメタクリルモノマーの単独共重合体もしくはこれらのモノマーを含む共重合体のアクリル系樹脂のほか、メラミン系樹脂、アクリル系樹脂、ウレタン系樹脂、エポキシ系樹脂などを用いることができる。
As the material of the protective layer 4, acrylic or methacrylic monomer homopolymers such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc., or acrylics of copolymers containing these monomers In addition to resins, melamine resins, acrylic resins, urethane resins, epoxy resins, and the like can be used.
具体的には、メラミン、アクリルメラミン、エポキシメラミン、アルキド、ウレタン、アクリルなどの一液硬化性及びこれらを混合した樹脂、またはイソシアネートなどの硬化剤との組み合わせによる二液硬化性の樹脂、ポリエステルアクリレート、ポリエステルメタクリレート、エポキシアクリレート、エポキシメタクリレート、ウレタンアクリレート、ウレタンメタクリレート、ポリエーテルアクリレート、ポリエーテルメタクリレート、ポリオールアクリレート、メラミンアクリレート、メラミンメタクリレートなどのエチレン性不飽和結合を有するモノマーやプレポリマーなどから構成される紫外線、電子線硬化樹脂などが使用できる。なお、紫外線硬化樹脂を用いるときは、光開始剤をさらに添加する。
Specifically, two-component curable resins such as melamine, acrylic melamine, epoxy melamine, alkyd, urethane, acrylic, etc. and a mixture of these, or a combination with a curing agent such as isocyanate, polyester acrylate Polyester methacrylate, epoxy acrylate, epoxy methacrylate, urethane acrylate, urethane methacrylate, polyether acrylate, polyether methacrylate, polyol acrylate, melamine acrylate, melamine methacrylate and other monomers and prepolymers that have ethylenically unsaturated bonds Ultraviolet rays, electron beam curable resins, and the like can be used. When an ultraviolet curable resin is used, a photoinitiator is further added.
光開始剤としては、適宜選択できる。例えば、ベンゾインエーテル系、ケタール系、アセトフェノン系、チオキサントン系等のラジカル型光重合開始剤、ジアゾニウム塩、ジアリールヨードニウム塩、トリアリールスルホニウム塩等や複合系のカチオン型光重合開始剤が挙げられ、これらの１種あるいは２種以上が使用できる。
The photoinitiator can be selected as appropriate. Examples include radical photopolymerization initiators such as benzoin ether, ketal, acetophenone, and thioxanthone, diazonium salts, diaryliodonium salts, triarylsulfonium salts, and complex cationic photopolymerization initiators. One or more of these can be used. *
加飾成形品の製造方法
図４は、加飾成形品の製造方法を示した図である。図４を参照して、加飾成形品は、基体シート１０、保護層１１、絵柄層１２、接着層１３からなる転写シート２０を、成形品３０に熱ロール転写することにより、得ることができる。熱ロール転写における加飾方法は、まず、転写シート２０に存在する絵柄層１２の位置を考慮して、成形品３０の所望の位置に絵柄層１２が配置されるように転写シート２０の位置を決定する。次いで、転写シート２０の内側（接着層１３側）の面を成形品の表面に重ね、ロール転写機、アップダウン転写機などの転写機を用いて、転写シート２０の基体シート１０側から熱及び圧力をかける。こうすることにより、転写シート２０が成形品３０の表面に接着し、成形品３０の表面の加飾がなされる。 Method for Producing Decorative Molded Product FIG. 4 is a diagram showing a method for producing a decorated molded product. With reference to FIG. 4, the decorative molded product can be obtained by transferring thetransfer sheet 20 including the base sheet 10, the protective layer 11, the pattern layer 12, and the adhesive layer 13 to the molded product 30 by hot roll transfer. . In the decorating method in the heat roll transfer, first, the position of the transfer sheet 20 is set so that the pattern layer 12 is arranged at a desired position of the molded product 30 in consideration of the position of the pattern layer 12 existing on the transfer sheet 20. decide. Next, the surface on the inner side (adhesive layer 13 side) of the transfer sheet 20 is superimposed on the surface of the molded product, and heat and heat are transferred from the base sheet 10 side of the transfer sheet 20 using a transfer machine such as a roll transfer machine or an up-down transfer machine. Apply pressure. By doing so, the transfer sheet 20 adheres to the surface of the molded product 30 and the surface of the molded product 30 is decorated.
図４は、加飾成形品の製造方法を示した図である。図４を参照して、加飾成形品は、基体シート１０、保護層１１、絵柄層１２、接着層１３からなる転写シート２０を、成形品３０に熱ロール転写することにより、得ることができる。熱ロール転写における加飾方法は、まず、転写シート２０に存在する絵柄層１２の位置を考慮して、成形品３０の所望の位置に絵柄層１２が配置されるように転写シート２０の位置を決定する。次いで、転写シート２０の内側（接着層１３側）の面を成形品の表面に重ね、ロール転写機、アップダウン転写機などの転写機を用いて、転写シート２０の基体シート１０側から熱及び圧力をかける。こうすることにより、転写シート２０が成形品３０の表面に接着し、成形品３０の表面の加飾がなされる。 Method for Producing Decorative Molded Product FIG. 4 is a diagram showing a method for producing a decorated molded product. With reference to FIG. 4, the decorative molded product can be obtained by transferring the
基体シートの材質はＰＥＴフィルムなどから構成される。保護層、絵柄層、接着層、成形品は、上述の材料から構成される。なお、保護層、絵柄層、接着層は、上記順番でグラビア印刷法、スクリーン印刷法、オフセット印刷法などの印刷方法によって基体シートの上に形成される。
The material of the base sheet is composed of PET film or the like. The protective layer, the picture layer, the adhesive layer, and the molded product are composed of the above-described materials. Note that the protective layer, the pattern layer, and the adhesive layer are formed on the substrate sheet by a printing method such as a gravure printing method, a screen printing method, and an offset printing method in the above order.
以下の実施例により本発明を具体的に説明するが、本発明はこれらに限定されない。尚、実施例中「部」又は「％」で表される量は特に断りなき限り重量基準である。
The present invention will be specifically described by the following examples, but the present invention is not limited thereto. In the examples, “part” or “%” is based on weight unless otherwise specified.
＜実施例１＞
<Example 1>
１．基材の製造
厚み０．８μｍのアルミ板（住友軽金属株式会社製、商品名：A５０５２）を基材として用意した。この基材をヘアライン加工機にセットした後、ヘアライン加工を施して、この基材の表面に凹凸形状を形成した。基材に形成された凹凸形状を、拡大鏡（日本電子株式会社製、商品名：走査電子顕微鏡（ＳＥＭ））で測定したところ、凹凸形状の凸部分の高さは、３．８μｍ、隣接する凸部の距離は９．８μｍであった。さらに、基材に形成された凹凸形状の表面粗さ（Ｒａ）を表面粗さ測定機（株式会社東京精密製、商品名：サーフコム）で測定したところ、０．６μｍであった。 1. Production of Base Material An aluminum plate having a thickness of 0.8 μm (manufactured by Sumitomo Light Metal Co., Ltd., trade name: A5052) was prepared as the base material. After setting this base material in a hairline processing machine, the hairline process was given and the uneven | corrugated shape was formed in the surface of this base material. When the concavo-convex shape formed on the substrate was measured with a magnifying glass (manufactured by JEOL Ltd., trade name: scanning electron microscope (SEM)), the height of the concavo-convex convex portion was 3.8 μm and adjacent. The distance between the convex portions was 9.8 μm. Furthermore, when the surface roughness (Ra) of the uneven | corrugated shape formed in the base material was measured with the surface roughness measuring machine (The Tokyo Seimitsu make, brand name: Surfcom), it was 0.6 micrometer.
厚み０．８μｍのアルミ板（住友軽金属株式会社製、商品名：A５０５２）を基材として用意した。この基材をヘアライン加工機にセットした後、ヘアライン加工を施して、この基材の表面に凹凸形状を形成した。基材に形成された凹凸形状を、拡大鏡（日本電子株式会社製、商品名：走査電子顕微鏡（ＳＥＭ））で測定したところ、凹凸形状の凸部分の高さは、３．８μｍ、隣接する凸部の距離は９．８μｍであった。さらに、基材に形成された凹凸形状の表面粗さ（Ｒａ）を表面粗さ測定機（株式会社東京精密製、商品名：サーフコム）で測定したところ、０．６μｍであった。 1. Production of Base Material An aluminum plate having a thickness of 0.8 μm (manufactured by Sumitomo Light Metal Co., Ltd., trade name: A5052) was prepared as the base material. After setting this base material in a hairline processing machine, the hairline process was given and the uneven | corrugated shape was formed in the surface of this base material. When the concavo-convex shape formed on the substrate was measured with a magnifying glass (manufactured by JEOL Ltd., trade name: scanning electron microscope (SEM)), the height of the concavo-convex convex portion was 3.8 μm and adjacent. The distance between the convex portions was 9.8 μm. Furthermore, when the surface roughness (Ra) of the uneven | corrugated shape formed in the base material was measured with the surface roughness measuring machine (The Tokyo Seimitsu make, brand name: Surfcom), it was 0.6 micrometer.
２．転写シートの製造
厚み５０μｍの２軸延伸ポリエチレンテレフタレートフィルムを基体シートとして用意した。この基体シートをヘアライン加工機にセットした後、ヘアライン加工を施して基体シートの表面に凹凸形状を形成した。基体シートに形成された凹凸形状を、走査電子顕微鏡（日本電子株式会社製、商品名：走査電子顕微鏡（ＳＥＭ））で測定したところ、凹凸形状の凸部分の高さは、０．４７μｍ、隣接する凸部の距離は０．８２μｍであった。さらに、基体シートに形成された凹凸の表面粗さ（Ｒａ）を表面粗さ測定機（株式会社東京精密社製、（商品名）サーフコム）で測定したところ、０．２５μｍであった。次に、基体シートを多色グラビア輪転印刷機にセットし、アクリレート系樹脂からなる紫外線硬化性材料を用いて、基体シートの凹凸形成された面に保護層を形成した。最後に、接着材料を用いて、保護層の上に接着層を形成し、転写シートを得た。 2. Production of Transfer Sheet A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was prepared as a base sheet. After this base sheet was set in a hairline processing machine, a hairline process was performed to form an uneven shape on the surface of the base sheet. When the concavo-convex shape formed on the base sheet was measured with a scanning electron microscope (trade name: Scanning Electron Microscope (SEM), manufactured by JEOL Ltd.), the height of the concavo-convex convex portion was 0.47 μm, adjacent. The distance of the convex part to perform was 0.82 micrometer. Furthermore, it was 0.25 micrometer when the surface roughness (Ra) of the unevenness | corrugation formed in the base | substrate sheet | seat was measured with the surface roughness measuring machine (The Tokyo Seimitsu Co., Ltd. make, (brand name) Surfcom). Next, the base sheet was set on a multicolor gravure rotary printing press, and a protective layer was formed on the surface of the base sheet on which the irregularities were formed using an ultraviolet curable material made of an acrylate resin. Finally, using the adhesive material, an adhesive layer was formed on the protective layer to obtain a transfer sheet.
厚み５０μｍの２軸延伸ポリエチレンテレフタレートフィルムを基体シートとして用意した。この基体シートをヘアライン加工機にセットした後、ヘアライン加工を施して基体シートの表面に凹凸形状を形成した。基体シートに形成された凹凸形状を、走査電子顕微鏡（日本電子株式会社製、商品名：走査電子顕微鏡（ＳＥＭ））で測定したところ、凹凸形状の凸部分の高さは、０．４７μｍ、隣接する凸部の距離は０．８２μｍであった。さらに、基体シートに形成された凹凸の表面粗さ（Ｒａ）を表面粗さ測定機（株式会社東京精密社製、（商品名）サーフコム）で測定したところ、０．２５μｍであった。次に、基体シートを多色グラビア輪転印刷機にセットし、アクリレート系樹脂からなる紫外線硬化性材料を用いて、基体シートの凹凸形成された面に保護層を形成した。最後に、接着材料を用いて、保護層の上に接着層を形成し、転写シートを得た。 2. Production of Transfer Sheet A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was prepared as a base sheet. After this base sheet was set in a hairline processing machine, a hairline process was performed to form an uneven shape on the surface of the base sheet. When the concavo-convex shape formed on the base sheet was measured with a scanning electron microscope (trade name: Scanning Electron Microscope (SEM), manufactured by JEOL Ltd.), the height of the concavo-convex convex portion was 0.47 μm, adjacent. The distance of the convex part to perform was 0.82 micrometer. Furthermore, it was 0.25 micrometer when the surface roughness (Ra) of the unevenness | corrugation formed in the base | substrate sheet | seat was measured with the surface roughness measuring machine (The Tokyo Seimitsu Co., Ltd. make, (brand name) Surfcom). Next, the base sheet was set on a multicolor gravure rotary printing press, and a protective layer was formed on the surface of the base sheet on which the irregularities were formed using an ultraviolet curable material made of an acrylate resin. Finally, using the adhesive material, an adhesive layer was formed on the protective layer to obtain a transfer sheet.
なお、接着材料は、ガラス転移温度（Ｔｇ）が２５～３０℃の両末端にカルボキシル基を有するポリエステルと、ガラス転移温度（Ｔｇ）が９５～１００℃のビスフェノール型エポキシ樹脂とコロイダルシリカ（日産化学工業株式会社、商品名：MEK-ST）を表１に示す割合で配合、攪拌して作成した。なお、接着材料のガラス転移温度（Ｔｇ）、重量平均分子量は表１の通りであり、接着材料は全体重量に対して、固形分が２０％の割合で存在しているものを使用した。
The adhesive material is made of polyester having carboxyl groups at both ends having a glass transition temperature (Tg) of 25 to 30 ° C., bisphenol type epoxy resin having a glass transition temperature (Tg) of 95 to 100 ° C. and colloidal silica (Nissan Chemical). Kogyo Co., Ltd., trade name: MEK-ST) was formulated and stirred at the ratio shown in Table 1. The glass transition temperature (Tg) and the weight average molecular weight of the adhesive material are as shown in Table 1, and the adhesive material having a solid content of 20% with respect to the total weight was used.
３．ヘアライン調加飾成形品の製造
上記で得られた転写シートと基材をロール転写機（ナビタス株式会社製、商品名：ＲＨ－３００）を用いて貼合した。最後に貼合した成形品から基体シートを剥離して、ヘアライン調加飾成形品を得た。 3. Production of hairline-like decorative molded product The transfer sheet obtained above and the substrate were bonded using a roll transfer machine (trade name: RH-300, manufactured by Navitas Co., Ltd.). The base sheet was peeled off from the finally bonded molded product to obtain a hairline-decorated molded product.
上記で得られた転写シートと基材をロール転写機（ナビタス株式会社製、商品名：ＲＨ－３００）を用いて貼合した。最後に貼合した成形品から基体シートを剥離して、ヘアライン調加飾成形品を得た。 3. Production of hairline-like decorative molded product The transfer sheet obtained above and the substrate were bonded using a roll transfer machine (trade name: RH-300, manufactured by Navitas Co., Ltd.). The base sheet was peeled off from the finally bonded molded product to obtain a hairline-decorated molded product.
＜実施例２～３、比較例１～３＞
基材に形成する凹凸の幅、高さ、及び基体シートに形成する凹凸の幅、高さを変更したこと以外は、実施例１と同様にしてヘアライン調加飾成形品を作成した。 <Examples 2 to 3, Comparative Examples 1 to 3>
A hairline-like decorative molded product was prepared 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.
基材に形成する凹凸の幅、高さ、及び基体シートに形成する凹凸の幅、高さを変更したこと以外は、実施例１と同様にしてヘアライン調加飾成形品を作成した。 <Examples 2 to 3, Comparative Examples 1 to 3>
A hairline-like decorative molded product was prepared 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.
実施例及び比較例は、以下の評価基準に基づいて評価した。
The examples and comparative examples were evaluated based on the following evaluation criteria.
１．耐指紋性
（１）指紋除去容易性
加飾成形品におけるハードコート層の表面をＪＩＳ Ｋ２２４６に記載されている指紋除去性試験方法に準拠して実施した。なお、指紋が除去されたか否かの判断は、試験片の人工指紋液を付着させた部分の外観を三波長光源下にて２０ｃｍ離して目視で観察することにより行い、評価は下記に従って行った。その結果を表１に示す。 1. Fingerprint resistance (1) Easiness of fingerprint removal The surface of the hard coat layer in the decorative molded product was carried out in accordance with the fingerprint removal test method described in JIS K2246. The determination of whether or not the fingerprint was removed was performed by visually observing the appearance of the part of the test piece to which the artificial fingerprint liquid was attached under a three-wavelength light source, and the evaluation was performed according to the following. . The results are shown in Table 1.
（１）指紋除去容易性
加飾成形品におけるハードコート層の表面をＪＩＳ Ｋ２２４６に記載されている指紋除去性試験方法に準拠して実施した。なお、指紋が除去されたか否かの判断は、試験片の人工指紋液を付着させた部分の外観を三波長光源下にて２０ｃｍ離して目視で観察することにより行い、評価は下記に従って行った。その結果を表１に示す。 1. Fingerprint resistance (1) Easiness of fingerprint removal The surface of the hard coat layer in the decorative molded product was carried out in accordance with the fingerprint removal test method described in JIS K2246. The determination of whether or not the fingerprint was removed was performed by visually observing the appearance of the part of the test piece to which the artificial fingerprint liquid was attached under a three-wavelength light source, and the evaluation was performed according to the following. . The results are shown in Table 1.
評価基準
○ ：５回未満で加飾成形品の表面に付着した指紋を完全に除去できた。
△ ：５回以上１０回未満で加飾成形品の表面に付着した指紋を完全に除去できた。
× ：加飾成形品の表面を１０回以上拭いたが完全には指紋を除去できなかった。 Evaluation criteria ○: The fingerprint adhering to the surface of the decorative molded product was completely removed in less than 5 times.
(Triangle | delta): The fingerprint adhering to the surface of the decorative molded product was completely removed by 5 times or more and less than 10 times.
X: The surface of the decorative molded product was wiped 10 times or more, but the fingerprint could not be completely removed.
○ ：５回未満で加飾成形品の表面に付着した指紋を完全に除去できた。
△ ：５回以上１０回未満で加飾成形品の表面に付着した指紋を完全に除去できた。
× ：加飾成形品の表面を１０回以上拭いたが完全には指紋を除去できなかった。 Evaluation criteria ○: The fingerprint adhering to the surface of the decorative molded product was completely removed in less than 5 times.
(Triangle | delta): The fingerprint adhering to the surface of the decorative molded product was completely removed by 5 times or more and less than 10 times.
X: The surface of the decorative molded product was wiped 10 times or more, but the fingerprint could not be completely removed.
（２）指紋付着困難性
加飾成形品の表面を複数回接触させ、何回目で加飾成形品の表面に指紋が付着するかを試験した。指紋が付着したかどうかの判断は、試験片の指が接触した部分の外観を三波長光源下にて２０ｃｍ離して目視で観察することにより行い、評価は下記に従って行った。その結果を表１に示す。 (2) Fingerprint adhesion difficulty The surface of the decorative molded product was contacted multiple times, and it was tested how many times the fingerprint adhered to the surface of the decorative molded product. Judgment as to whether or not the fingerprint was attached was made by visually observing the appearance of the part of the test piece touched by the finger under a three-wavelength light source, and the evaluation was performed as follows. The results are shown in Table 1.
加飾成形品の表面を複数回接触させ、何回目で加飾成形品の表面に指紋が付着するかを試験した。指紋が付着したかどうかの判断は、試験片の指が接触した部分の外観を三波長光源下にて２０ｃｍ離して目視で観察することにより行い、評価は下記に従って行った。その結果を表１に示す。 (2) Fingerprint adhesion difficulty The surface of the decorative molded product was contacted multiple times, and it was tested how many times the fingerprint adhered to the surface of the decorative molded product. Judgment as to whether or not the fingerprint was attached was made by visually observing the appearance of the part of the test piece touched by the finger under a three-wavelength light source, and the evaluation was performed as follows. The results are shown in Table 1.
評価基準
○ ：１０回以上、加飾成形品の表面に指を接触させても、加飾成形品の表面には指紋が付着しなかった。
△ ：５回以上１０回未満、加飾成形品の表面に指を接触させると、加飾成形品の表面に指紋が付着した。
× ：１回加飾成形品の表面に指を接触させると、加飾成形品の表面に指紋が付着した。 Evaluation criteria ○: Even when the finger was brought into contact with the surface of the decorative moldedproduct 10 times or more, the fingerprint did not adhere to the surface of the decorative molded product.
(Triangle | delta): When the finger was made to contact the surface of a decorative moldedproduct 5 times or more and less than 10 times, the fingerprint adhered to the surface of the decorative molded product.
X: When a finger was brought into contact with the surface of the decorative molded product once, a fingerprint adhered to the surface of the decorative molded product.
○ ：１０回以上、加飾成形品の表面に指を接触させても、加飾成形品の表面には指紋が付着しなかった。
△ ：５回以上１０回未満、加飾成形品の表面に指を接触させると、加飾成形品の表面に指紋が付着した。
× ：１回加飾成形品の表面に指を接触させると、加飾成形品の表面に指紋が付着した。 Evaluation criteria ○: Even when the finger was brought into contact with the surface of the decorative molded
(Triangle | delta): When the finger was made to contact the surface of a decorative molded
X: When a finger was brought into contact with the surface of the decorative molded product once, a fingerprint adhered to the surface of the decorative molded product.
２．触感性
加飾成形品の表面を指でなぞり、加飾成形品にヘアライン加工製品特有のでこぼこした触感があるかどうか試験した。接触性の評価は、５０人がヘアライン金属板（会社名 志摩鋼業株式会社 商品名 ＳＵＳ３０４ＨＬ）と上記加飾成形品を、それぞれ触ったときに感じる触感の差異についてアンケート調査することにより行った。なお、触感性の評価基準は下記に示す通りである。その結果を表１に示す。 2. The surface of the tactile decorative molded product was traced with a finger to test whether the decorative molded product had a tactile sensation peculiar to hairline processed products. The evaluation of the contact property was performed by conducting a questionnaire survey on the difference in tactile sensation felt when 50 people touched the hairline metal plate (company name: Shima Steel Co., Ltd., trade name: SUS304HL) and the decorative molded product. The evaluation criteria for tactile sensation are as shown below. The results are shown in Table 1.
加飾成形品の表面を指でなぞり、加飾成形品にヘアライン加工製品特有のでこぼこした触感があるかどうか試験した。接触性の評価は、５０人がヘアライン金属板（会社名 志摩鋼業株式会社 商品名 ＳＵＳ３０４ＨＬ）と上記加飾成形品を、それぞれ触ったときに感じる触感の差異についてアンケート調査することにより行った。なお、触感性の評価基準は下記に示す通りである。その結果を表１に示す。 2. The surface of the tactile decorative molded product was traced with a finger to test whether the decorative molded product had a tactile sensation peculiar to hairline processed products. The evaluation of the contact property was performed by conducting a questionnaire survey on the difference in tactile sensation felt when 50 people touched the hairline metal plate (company name: Shima Steel Co., Ltd., trade name: SUS304HL) and the decorative molded product. The evaluation criteria for tactile sensation are as shown below. The results are shown in Table 1.
評価基準
○ ：５０人中４０人以上が、両者の触感に差異はないと回答した。
△ ：５０人中、２５～４０未満の人が、両者の触感に差異はないと回答した。
× ：５０人中２５人未満の人が、両者の触感に差異はないと回答した。 Evaluation criteria ○: 40 or more out of 50 responded that there was no difference in the tactile sensation between the two.
Δ: Out of 50 people, less than 25 to 40 answered that there was no difference in touch between the two.
X: Less than 25 people out of 50 answered that there was no difference in both tactile sensations.
○ ：５０人中４０人以上が、両者の触感に差異はないと回答した。
△ ：５０人中、２５～４０未満の人が、両者の触感に差異はないと回答した。
× ：５０人中２５人未満の人が、両者の触感に差異はないと回答した。 Evaluation criteria ○: 40 or more out of 50 responded that there was no difference in the tactile sensation between the two.
Δ: Out of 50 people, less than 25 to 40 answered that there was no difference in touch between the two.
X: Less than 25 people out of 50 answered that there was no difference in both tactile sensations.
３．意匠性
加飾成形品の意匠性について試験した。意匠性の評価は、５０人がヘアライン金属（志摩鋼業株式会社 商品名 ＳＵＳ３０４ ＨＬ）と上記加飾成形品を、それぞれ３０ｃｍ離れた距離から観察したときに感じる意匠性の差異についてアンケート調査することにより行った。なお、意匠性の評価基準は下記に示す通りである。その結果を表１に示す。 3. The design property of the decorative decorative molded product was tested. The evaluation of designability is to conduct a questionnaire survey on the difference in designability that 50 people feel when they observe the hairline metal (Shima Steel Co., Ltd., trade name SUS304 HL) and the above-mentioned decorative molded product from a distance of 30 cm from each other. It went by. In addition, the evaluation criteria of the designability are as shown below. The results are shown in Table 1.
加飾成形品の意匠性について試験した。意匠性の評価は、５０人がヘアライン金属（志摩鋼業株式会社 商品名 ＳＵＳ３０４ ＨＬ）と上記加飾成形品を、それぞれ３０ｃｍ離れた距離から観察したときに感じる意匠性の差異についてアンケート調査することにより行った。なお、意匠性の評価基準は下記に示す通りである。その結果を表１に示す。 3. The design property of the decorative decorative molded product was tested. The evaluation of designability is to conduct a questionnaire survey on the difference in designability that 50 people feel when they observe the hairline metal (Shima Steel Co., Ltd., trade name SUS304 HL) and the above-mentioned decorative molded product from a distance of 30 cm from each other. It went by. In addition, the evaluation criteria of the designability are as shown below. The results are shown in Table 1.
評価基準
○ ：５０人中４０人以上が、両者の美感に差異はないと回答した。
△ ：５０人中、２５～４０未満の人が、両者の美感に差異はないと回答した。
× ：５０人中２５人未満の人が、両者の美感に差異はないと回答した。 Evaluation criteria
○: More than 40 out of 50 responded that there was no difference in their aesthetics.
Δ: Out of 50 people, less than 25 to 40 answered that there was no difference in their aesthetics.
X: Less than 25 people out of 50 answered that there was no difference in both aesthetics.
○ ：５０人中４０人以上が、両者の美感に差異はないと回答した。
△ ：５０人中、２５～４０未満の人が、両者の美感に差異はないと回答した。
× ：５０人中２５人未満の人が、両者の美感に差異はないと回答した。 Evaluation criteria
○: More than 40 out of 50 responded that there was no difference in their aesthetics.
Δ: Out of 50 people, less than 25 to 40 answered that there was no difference in their aesthetics.
X: Less than 25 people out of 50 answered that there was no difference in both aesthetics.
４．表面硬度
加飾成形品における、ハードコート層の表面硬度をＪＩＳ Ｋ５６００－５－４に記載されている引っかき硬度（鉛筆法）に準拠して測定した。なお、表面硬度の評価基準は下記に示す通りである。その結果を表１に示す。 4). In the surface hardness decorative molded product, the surface hardness of the hard coat layer was measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4. The evaluation criteria for the surface hardness are as shown below. The results are shown in Table 1.
加飾成形品における、ハードコート層の表面硬度をＪＩＳ Ｋ５６００－５－４に記載されている引っかき硬度（鉛筆法）に準拠して測定した。なお、表面硬度の評価基準は下記に示す通りである。その結果を表１に示す。 4). In the surface hardness decorative molded product, the surface hardness of the hard coat layer was measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4. The evaluation criteria for the surface hardness are as shown below. The results are shown in Table 1.
評価基準
○ ：引っかき硬度（鉛筆硬度）がＨ～２Ｈの範囲であった。
△ ：引っかき硬度（鉛筆硬度）がＨＢ～Ｆの範囲であった。
× ：引っかき硬度（鉛筆硬度）がＢ以下の範囲であった。 Evaluation criteria ○: Scratch hardness (pencil hardness) was in the range of H to 2H.
Δ: Scratch hardness (pencil hardness) was in the range of HB to F.
X: Scratch hardness (pencil hardness) was in the range of B or less.
○ ：引っかき硬度（鉛筆硬度）がＨ～２Ｈの範囲であった。
△ ：引っかき硬度（鉛筆硬度）がＨＢ～Ｆの範囲であった。
× ：引っかき硬度（鉛筆硬度）がＢ以下の範囲であった。 Evaluation criteria ○: Scratch hardness (pencil hardness) was in the range of H to 2H.
Δ: Scratch hardness (pencil hardness) was in the range of HB to F.
X: Scratch hardness (pencil hardness) was in the range of B or less.
５．接着性
加飾成形品における接着層と基材の接着性について測定した。接着性の測定方法は、ＪＩＳ Ｋ５６００－５－６に記載されているクロスカット法に準拠して行った。なお、接着性の評価基準は下記に示す通りである。その結果を表１に示す 5). It measured about the adhesiveness of the contact bonding layer and a base material in an adhesive decoration molded product. The adhesiveness was measured according to the cross-cut method described in JIS K5600-5-6. In addition, the evaluation criteria of adhesiveness are as showing below. The results are shown in Table 1.
加飾成形品における接着層と基材の接着性について測定した。接着性の測定方法は、ＪＩＳ Ｋ５６００－５－６に記載されているクロスカット法に準拠して行った。なお、接着性の評価基準は下記に示す通りである。その結果を表１に示す 5). It measured about the adhesiveness of the contact bonding layer and a base material in an adhesive decoration molded product. The adhesiveness was measured according to the cross-cut method described in JIS K5600-5-6. In addition, the evaluation criteria of adhesiveness are as showing below. The results are shown in Table 1.
評価基準
○ ：カットの縁が完全に滑らかで、どの格子の目にも剥がれが観察されなかった。
△ ：カットの交差点における塗膜に小さな剥がれが確認でき、その剥がれは接着層と基材との間で発生していた。剥がれは、クロスカットを行った部分の５％未満であった。
× ：カットの交差点における塗膜に小さな剥がれが確認でき、その剥がれは接着層と基材との間で発生していた。剥がれは、クロスカットを行った部分の５％以上であった。
Evaluation criteria ○: The edges of the cut were completely smooth, and no peeling was observed in any lattice eye.
(Triangle | delta): The small peeling could be confirmed to the coating film in the intersection of cut, and the peeling had generate | occur | produced between the contact bonding layer and the base material. Peeling was less than 5% of the cross-cut portion.
X: A small peeling was confirmed in the coating film at the intersection of the cuts, and the peeling occurred between the adhesive layer and the substrate. Peeling was 5% or more of the cross-cut portion.
○ ：カットの縁が完全に滑らかで、どの格子の目にも剥がれが観察されなかった。
△ ：カットの交差点における塗膜に小さな剥がれが確認でき、その剥がれは接着層と基材との間で発生していた。剥がれは、クロスカットを行った部分の５％未満であった。
× ：カットの交差点における塗膜に小さな剥がれが確認でき、その剥がれは接着層と基材との間で発生していた。剥がれは、クロスカットを行った部分の５％以上であった。
(Triangle | delta): The small peeling could be confirmed to the coating film in the intersection of cut, and the peeling had generate | occur | produced between the contact bonding layer and the base material. Peeling was less than 5% of the cross-cut portion.
X: A small peeling was confirmed in the coating film at the intersection of the cuts, and the peeling occurred between the adhesive layer and the substrate. Peeling was 5% or more of the cross-cut portion.
１…成形品、
２…接着層、
３…絵柄層、
４…保護層、
５…凸部、
６…凹部、
７…微細凸部、
８…微細凹部、
１０…基体シート、
１１…保護層、
１２…絵柄層、
１３…接着層、
２０…転写シート、
３０…成形品、
１００…加飾成形品、
５００…加飾成形品、
５１０…成形品、
５１１…接着層、
５１２…接着層、
５１３…保護層、
５１４…凸部、
５１５…凹部、
６００…指、 1 ... Molded product
2 ... adhesive layer,
3 ... pattern layer,
4 ... protective layer,
5 ... convex part,
6 ... recess,
7 ... fine convex part,
8 ... fine recesses,
10: Base sheet,
11 ... Protective layer,
12 ... Picture layer,
13: Adhesive layer,
20 ... transfer sheet,
30 ... molded product,
100 ... decorative molded product,
500 ... decorative molded product,
510 ... molded product,
511 ... adhesive layer,
512 ... adhesive layer,
513 ... Protective layer,
514 ... convex portion,
515 ... concave,
600 ... finger,
２…接着層、
３…絵柄層、
４…保護層、
５…凸部、
６…凹部、
７…微細凸部、
８…微細凹部、
１０…基体シート、
１１…保護層、
１２…絵柄層、
１３…接着層、
２０…転写シート、
３０…成形品、
１００…加飾成形品、
５００…加飾成形品、
５１０…成形品、
５１１…接着層、
５１２…接着層、
５１３…保護層、
５１４…凸部、
５１５…凹部、
６００…指、 1 ... Molded product
2 ... adhesive layer,
3 ... pattern layer,
4 ... protective layer,
5 ... convex part,
6 ... recess,
7 ... fine convex part,
8 ... fine recesses,
10: Base sheet,
11 ... Protective layer,
12 ... Picture layer,
13: Adhesive layer,
20 ... transfer sheet,
30 ... molded product,
100 ... decorative molded product,
500 ... decorative molded product,
510 ... molded product,
511 ... adhesive layer,
512 ... adhesive layer,
513 ... Protective layer,
514 ... convex portion,
515 ... concave,
600 ... finger,
Claims (7)
- ヘアライン調の意匠を備える加飾成形品において、
複数の凸部を一方の面に備え、前記凸部の高さが１～１０μｍであり、前記凸部の隣接頂点間距離が１～１００μｍである成形品と、
前記成形品の前記凸部が形成された面に形成される接着層と、
前記接着層の上に形成され、前記接着層と接する面とは反対方向の面に微細凸部を備え、前記微細凸部の高さが０．１～１μｍであり、前記微細凸部の近接頂点間距離が０．１～１００μｍである保護層と、
を備える加飾成形品。 In decorative molded products with hairline-like designs,
A molded product having a plurality of convex portions on one surface, the height of the convex portions is 1 to 10 μm, and the distance between adjacent vertices of the convex portions is 1 to 100 μm;
An adhesive layer formed on the surface on which the convex portion of the molded product is formed;
A fine convex portion is provided on the surface opposite to the surface in contact with the adhesive layer, the height of the fine convex portion is 0.1 to 1 μm, and the proximity of the fine convex portion is formed on the adhesive layer A protective layer having a distance between vertices of 0.1 to 100 μm;
Decorative molded product with - 前記保護層の表面における算術平均粗さ（Ｒａ２）が、前記成形品と前記接着層との間における算術平均粗さ（Ｒａ１）より小さい請求項１の加飾成形品。 The decorative molded product according to claim 1, wherein the arithmetic average roughness (Ra2) on the surface of the protective layer is smaller than the arithmetic average roughness (Ra1) between the molded product and the adhesive layer.
- 前記成形品と前記接着層との間における算術平均粗さ（Ｒａ１）が、０．１～１０μｍである請求項１～２の加飾成形品。 The decorative molded product according to claim 1 or 2, wherein an arithmetic average roughness (Ra1) between the molded product and the adhesive layer is 0.1 to 10 µm.
- 前記保護層の表面における算術平均粗さ（Ｒａ２）が、０．０１～１μｍである請求項１～３の加飾成形品。 The decorative molded product according to claims 1 to 3, wherein the arithmetic average roughness (Ra2) on the surface of the protective layer is 0.01 to 1 µm.
- 前記保護層と前記接着層との間に、ポリ塩化ビニル樹脂、アクリル樹脂、ポリウレタン樹脂、セルロースエステル樹脂及びポリビニルアセタール樹脂のいずれかを少なくとも一種を含む絵柄層を備え、
前記成形品が金属であり、
前記接着層が両末端にカルボキシル基を有するポリエステルとビスフェノール型エポキシ樹脂を、７５／２５～９０／１０の重量比で反応させて得られる、ガラス転移温度３０～１００℃及び分子量２００００～３００００のエポキシ変性ポリエステル樹脂を含み、その厚みが５～１０μｍである請求項１～４の加飾成形品。 Between the protective layer and the adhesive layer, comprising a pattern layer containing at least one of polyvinyl chloride resin, acrylic resin, polyurethane resin, cellulose ester resin and polyvinyl acetal resin,
The molded article is a metal;
Epoxy having a glass transition temperature of 30 to 100 ° C. and a molecular weight of 20000 to 30000 obtained by reacting a polyester having a carboxyl group at both ends with a bisphenol type epoxy resin at a weight ratio of 75/25 to 90/10. 5. The decorative molded product according to claim 1, which comprises a modified polyester resin and has a thickness of 5 to 10 μm. - 前記接着層が、前記エポキシ変性ポリエステルに対して、重量比０．０５～０．１の量でコロイダルシリカを含有する請求項１～５の加飾成形品。 The decorative molded product according to any one of claims 1 to 5, wherein the adhesive layer contains colloidal silica in an amount of 0.05 to 0.1 with respect to the epoxy-modified polyester.
- 前記接着層が、硬化剤としてブロックイソシアネートを含有する請求項１～６の加飾成形品。 The decorative molded product according to claims 1 to 6, wherein the adhesive layer contains blocked isocyanate as a curing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011233447A JP2013091191A (en) | 2011-10-24 | 2011-10-24 | Hairline-like decorative molded article having sense of touch peculiar to hairline processing and function of fingerprint resistance |
| JP2011-233447 | 2011-10-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013061689A1 true WO2013061689A1 (en) | 2013-05-02 |
Family
ID=48167529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/072259 WO2013061689A1 (en) | 2011-10-24 | 2012-08-31 | Hairline-like decorative molded article providing sensation unique to hairline processing and providing fingerprint resistance |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2013091191A (en) |
| TW (1) | TW201332800A (en) |
| WO (1) | WO2013061689A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018154023A (en) * | 2017-03-17 | 2018-10-04 | 大日本印刷株式会社 | Decorative molded article and method of manufacturing decorative molded article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI667151B (en) * | 2017-02-13 | 2019-08-01 | 彩碁科技股份有限公司 | Colorful fibric board structure and manufacturing method thereof |
| JP7274690B2 (en) * | 2018-09-25 | 2023-05-17 | 国立大学法人 熊本大学 | Concave-convex body manufacturing method and concavo-convex body |
| KR20210114774A (en) * | 2020-03-11 | 2021-09-24 | 삼성전자주식회사 | Rear cover of electronic device and manufacturing method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63272596A (en) * | 1987-04-30 | 1988-11-10 | 日本写真印刷株式会社 | Delustering transfer material |
| JPH04189200A (en) * | 1990-11-22 | 1992-07-07 | Nissha Printing Co Ltd | Uneven surface transfer foil |
| JPH0827544A (en) * | 1994-07-14 | 1996-01-30 | Nkk Corp | Thin steel sheet for floppy disk shutter excellent in fingerprinting resistance |
| JP2008110519A (en) * | 2006-10-30 | 2008-05-15 | Riken Technos Corp | Metal like sheet and metal like decorative material using it |
| JP2008126529A (en) * | 2006-11-21 | 2008-06-05 | Shin Etsu Polymer Co Ltd | Decorative molded form |
| JP2010168655A (en) * | 2008-12-25 | 2010-08-05 | Aichi Steel Works Ltd | Stainless steel having excellent oil stain resistance and reduced fingerprint visibility |
-
2011
- 2011-10-24 JP JP2011233447A patent/JP2013091191A/en active Pending
-
2012
- 2012-08-31 WO PCT/JP2012/072259 patent/WO2013061689A1/en active Application Filing
- 2012-10-23 TW TW101138998A patent/TW201332800A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63272596A (en) * | 1987-04-30 | 1988-11-10 | 日本写真印刷株式会社 | Delustering transfer material |
| JPH04189200A (en) * | 1990-11-22 | 1992-07-07 | Nissha Printing Co Ltd | Uneven surface transfer foil |
| JPH0827544A (en) * | 1994-07-14 | 1996-01-30 | Nkk Corp | Thin steel sheet for floppy disk shutter excellent in fingerprinting resistance |
| JP2008110519A (en) * | 2006-10-30 | 2008-05-15 | Riken Technos Corp | Metal like sheet and metal like decorative material using it |
| JP2008126529A (en) * | 2006-11-21 | 2008-06-05 | Shin Etsu Polymer Co Ltd | Decorative molded form |
| JP2010168655A (en) * | 2008-12-25 | 2010-08-05 | Aichi Steel Works Ltd | Stainless steel having excellent oil stain resistance and reduced fingerprint visibility |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018154023A (en) * | 2017-03-17 | 2018-10-04 | 大日本印刷株式会社 | Decorative molded article and method of manufacturing decorative molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013091191A (en) | 2013-05-16 |
| TW201332800A (en) | 2013-08-16 |
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