JP2010046924A - Decorating method, decorating composition, and object to be decorated - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel decorating technology by which a pattern having excellent durability and also having a complicated shape can be easily attained. <P>SOLUTION: A decorating composition containing a sublimation dye, a thermoplastic resin and a solvent uniformly is closely stuck to the surface of an object to be decorated in a sheet form, the solvent is removed, and the decorating composition sheet is heated under pressure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel composition for decorating the surface of an article and a decoration technique using the composition.

  Electronic devices such as personal computers and mobile phones have become difficult to differentiate due to the common internal components such as CPUs. For this reason, in order to differentiate these electronic devices in appearance, the portability of the housing that is light and strong and the decorativeness of the housing such as color tone and gloss are important.

  As for the portability of the casing, in order to realize excellent portability in the casing for electronic devices, a casing using a lightweight Mg alloy, carbon fiber (CF) or glass fiber (GF) is polycarbonate. A casing using a highly rigid plastic added to a (PC) resin or a polyamide (PA) resin, a casing using a material obtained by impregnating a thermosetting plastic with carbon fiber, and the like are known.

  On the other hand, as a method of decorating the housing, there are 1) painting and 2) film insert. However, the most used painting often requires a great deal of labor and expense to impart a pattern or pattern. In addition, since a solvent is used, there is a problem that environmental load such as a volatile organic substance (VOC) is large.

  On the other hand, the film insert is a method of making a molded product in which a multilayer film composed of a base film, a printing layer, and an adhesive layer is set in a mold and then a resin is injection molded to adhere the film.

  In film insert molding, unlike painting, it is relatively easy to add a color, a pattern, or a pattern to a housing. Further, since no solvent is used, there is no VOC problem. However, since the film material is polyethylene terephthalate (PET), ABS resin, or the like, there is a disadvantage that the pencil hardness is low.

As a variation of the method using the film, there is a method of decorating by transfer. For example, there is a method in which a release sheet on which a pattern such as letters is copied is placed on the surface of a metal stay, and the pattern is transferred to the surface of the metal stay by hot pressing from there. However, when this method is applied to a casing, the durability of the dye often becomes a problem because a coloring matter (sometimes referred to as ink) cannot be fixed to the object to be decorated.
JP 2000-127691 A (Claims) JP 2001-30691 A (Claims) JP-A-2005-342023 (Claims)

  In view of the above circumstances, the following embodiment aims to provide a new decoration technique. Moreover, it aims at providing the decoration method and housing | casing for electronic devices which can implement | achieve either that it can decorate a color pattern easily and is excellent in durability. Still other objects and advantages will become apparent from the following description.

  According to one embodiment, a decorative composition comprising a sublimable dye, a thermoplastic resin and a solvent uniformly is adhered to the surface of the object to be decorated in a sheet form, the solvent is removed, and the composition is applied under pressure. A novel decorating method is provided that includes heating the decorative composition sheet. By this method, it is possible to realize a decorated case such as a decoration method or an electronic device that can realize either that a color pattern can be easily decorated or that it is excellent in durability.

  Such a method includes a decorating composition uniformly containing a sublimation dye, a thermoplastic resin, and optionally a solvent, and the decorating composition is formed into a sheet on the surface to be decorated. In the case of using a solvent, when the solvent is used before or after the adhesion or before and after the adhesion, and when the sheet is heated under pressure, the property that the sublimable dye moves to the surface to be decorated The composition for decorating which has can be used.

  According to the following embodiments, a novel decoration technique is realized. Moreover, the decoration technique which is excellent in durability can be realized. Complex patterns can often be easily realized. As an object to be decorated, a casing for an electronic device represented by a notebook personal computer, a mobile phone, or the like is particularly preferable.

  Hereinafter, various embodiments will be described with reference to the drawings, examples and the like. In addition, these figures, Examples, etc. and description illustrate the present invention, and do not limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.

  Here, “decoration” means decorating the surface of an article with a pigment such as painting, transferring, or printing. The decoration may be the entire surface of the target article (referred to as “decoration object” in the present specification) or a part thereof, and may be monochromatic or multicolored.

  A release sheet, in which a decorative composition comprising a sublimable dye and a thermoplastic resin is uniformly applied, is adhered to the surface of the object to be decorated, and the decorative composition sheet is heated under pressure. Then, when the release sheet is released from the object to be decorated, the sublimable dye moves to the surface side of the object to be decorated, and as a result, a thermoplastic resin layer is formed on the free surface side, and the dye is formed on the inside. It was found that a structure in which Such a technique has not been known at all. Moreover, it turned out that the decoration which is hard to peel from the decorating object by this, ie, was excellent in durability, can be implement | achieved.

  It is considered that such a phenomenon is observed because the dye used has sublimability and shifts to the decoration target side by heating. However, it is not required until all the sublimable pigments used have shifted to the decoration target side.

  1 to 3 are schematic views showing the state. FIG. 1 shows a part of a release sheet 2 in which a decorative composition 1 is applied in a sheet form. In the composition 1 for decorating, the sublimable pigment | dye 4 exists in the state which floated in the sea of a thermoplastic resin. FIG. 2 shows a state in which this release sheet is in close contact with the decoration object 3. After that, when the decorative composition (decorative composition sheet) is heated in a sheet form while pressing the press on the release sheet, the thermoplastic resin is softened or melted, and the sublimable dye 4 is sublimated. Then, as shown in FIG. 3, a structure in which the sublimable dye 4 moves to the surface side of the decoration object 3 and is covered with the thermoplastic resin 5 is obtained. When the surface to be decorated is porous, the sublimable dye enters the hole, so that a stronger bond is created. Since the surface of the sublimable dye 4 is covered with the thermoplastic resin 5, disappearance due to resublimation is prevented. Thereafter, the release sheet 2 is removed.

  In FIG. 1, the decorative composition 1 is shown in a state in which the sublimable dye 4 floats in the sea of the thermoplastic resin. It may be an aggregate of the like, or an intermediate one thereof, for example, a half-melted particulate thermoplastic resin. In the case of an aggregate of particles, it is difficult to maintain a sheet-like form, and thus a binder may be included.

  Although the thermoplastic resin will move to the free surface side on a macro scale, a part of the surface is in contact with the surface to be decorated as a result of this treatment. It seems.

  The decorating composition on the release sheet and the decorating composition applied on the decorating object are not monochromatic but may be multicolored or may contain some patterns and characters.

  The degree of “adhesion”, “pressurization” and “heating” in the above is not particularly limited, and is specifically determined by whether or not a decorative surface having a desired durability can be obtained after performing the above method. It is enough. Generally, the degree of “pressurization” can be 0.1 to 10 Pa. Generally, the degree of “heating” can be 60 to 200 ° C. Any method may be used for heating as long as the decorative composition can be heated. It may be by heat transfer from a decoration object or a pressurizing device, or the entire system may be placed in a heating device. The heating time may be appropriately determined according to the actual situation.

  There is no restriction | limiting in particular also about the thickness of the composition for decorating. 10-400 micrometers can be illustrated.

  About the said release sheet, it can select from a well-known thing suitably. In general, it is preferable that at least the release surface contains a fluorine compound or a silicone compound in terms of releasability.

  For pressurization and heating, it is convenient and preferable to use a press die. When the object to be decorated is not a uniform plane, it is preferable that the shape of the press die be a shape that matches the shape of the object to be decorated. When using a release sheet, it is often preferable to set the shape to a shape to be decorated.

  As will be described later, when the decorative composition on the release sheet contains a solvent, it may be necessary to consider that the solvent can be evaporated from the side of the press die. Alternatively, it is also preferable to provide an operation to stop the pressurization before or after pressurization, or before and after pressurization, and to evaporate the solvent by heating or decompression.

  Although there is no restriction | limiting in particular in the decorating object, The thing in which the surface has porosity is advantageous. This is because the sublimated dye penetrates into the pores, and the durability can be further improved. There is no particular limitation on the size of the pore, but if it is too large, the surface will be recognized as a rough surface, so if you want to avoid such recognition, a pore with a circular equivalent diameter of 5 μm or less is common Is preferable. Examples of such a porous material include formation by etching the surface.

  In view of the fact that such materials are often used as decoration objects and the strong need for durable decorative properties such as color tone and gloss as well as portability that is light and strong, an electronic device housing is particularly preferable. It is a use.

  The decorating composition used in such a method uniformly contains a sublimable dye and a thermoplastic resin. Here, “consisting uniformly” in the decorative composition or decorative composition sheet does not mean that they are mutually compatible, but as a mixture, one of the components is abnormally high It means to exclude the case where there is a portion (in extreme terms, the case where it consists of two layers of a sublimable dye and a thermoplastic resin). Such a state can be realized by uniformly mixing the sublimable dye into the sea of the integrated thermoplastic resin, or by uniformly mixing the sublimable dye into the particulate thermoplastic resin. However, for the purpose of realizing multiple colors and the like, when multiple types of decorating compositions are used side by side on the release sheet, it is sufficient if the above conditions are satisfied for each decorating composition. .

  Note that some or all of the pigments may be dissolved in the thermoplastic resin, but are generally incompatible with each other. Therefore, the sublimable dye is often in a state where the sublimable dye floats in the uniform sea of the thermoplastic resin on the release sheet, or in a mixture state of the particulate thermoplastic resin and the particulate sublimable dye.

  In such a decorative composition, a composition in a state in which a sublimable dye is dispersed or dissolved and a solvent for dissolving or dispersing a thermoplastic resin is mixed is applied onto a release sheet, and then the solvent is volatilized or dissolved. It can be obtained by removing by evaporation. When using heat to remove the solvent, care must be taken not to cause dye sublimation. It is useful to reduce the pressure if necessary to facilitate solvent removal. The removal of the solvent is usually performed before adhesion to the object to be decorated, but if possible, it may be performed after adhesion or a combination of both. The removal of the solvent may be incomplete. In this case, a solvent can be used as a binder. In this sense, a solvent having a high boiling point may be included. The solvent is used for the purpose of coating in the form of a sheet, but can play an important role in terms of adjusting the viscosity of the composition from the viewpoint of ease of handling.

  As said composition, it is a composition for decorating which contains a sublimation pigment | dye, a thermoplastic resin, and an optional solvent uniformly, Comprising: When using a solvent, decorating the composition for decorating When the sheet is adhered to the surface of the object, the solvent is removed before or after or before and after the adhesion, and the sheet is heated under pressure, the property that the sublimable dye moves to the surface of the object to be decorated. Any thing is acceptable as long as it has.

  In addition, although the above demonstrated the case where a release sheet was used altogether, if it is as follows, it is also possible to perform desired decoration, without using a release sheet. That is, a decorative composition comprising a sublimable dye, a thermoplastic resin and a solvent uniformly is adhered to the surface of the object to be decorated in a sheet form, the solvent is removed, and the decorative composition sheet under pressure is removed. Heat it. The solvent may be removed before or after the adhesion, or both. In relation to heating under pressure, any or all of them may be combined before, after, or simultaneously.

  In this case, the composition for decorating which has fluidity | liquidity is directly apply | coated to a decorating object, and it heats under pressure, for example with a press after that from above. In that case, since it is considered that the thermoplastic resin adheres to the surface of the pressurizing apparatus (for example, a press), it may be necessary to take measures such as releasing the surface of the pressurizing apparatus. A method of sandwiching a release sheet between them is also useful.

  In addition, arbitrary application | coating techniques and printing techniques can be suitably selected and used for application | coating of the composition to a release sheet or a decoration object. For example, any of ink jet printing, screen printing, letterpress printing, and gravure printing may be used.

  The composition that can be used in this method comprises a sublimable dye, a thermoplastic resin, and a solvent uniformly. The solvent dissolves the thermoplastic resin. As described above, the sublimable dye may be dispersed or dissolved in the solvent.

  As such a sublimable dye, it is important that it is sublimable, but what level of sublimation is required may be determined according to the actual situation. Here, “according to the actual situation” means that the above decoration method is actually carried out, and as a result, whether or not the desired durability has been realized is determined. It is not necessary to confirm that the pigment actually has sublimability, or to confirm that it shifts to the decoration target side by heating.

  The sublimable dye is not particularly limited, and specifically includes azo, anthraquinone, quinophthalone, styryl, di- or triphenylmethane, oxazine, triazine, xanthene, methine, azomethine, acridine, diazine and other dyes. Can be mentioned. More specifically, 1,4-dimethylaminoanthraquinone, bromide or 1,5-dihydroxy-4,8-diaminoanthraquinone chloride, 1,4-diamino-2,3-dichloroanthraquinone, 1-amino-4- Hydroxyanthraquinone, 1-amino-4-hydroxy-2- (β-methoxyethoxy) -anthraquinone, 1-amino-4-hydroxy-2-phenoxyanthraquinone, 1,4-diaminoanthraquinone-2-carboxylic acid methyl, ethyl , Propyl, butyl ester, 1,4-diamino-2-methoxyanthraquinone, 1-amino-4-anilinoanthraquinone, 1-amino-2-cyano-4-anilino (or cyclohexylamino) -anthraquinone, 1-hydroxy- 2- (p-acetaminophenylazo) -4-me Rubenzen, 3-methyl-4- (nitrophenylazo) - Birazoron, 3-hydroxy quinophthalone like.

  Moreover, malachite green, methyl violet, etc. can be used as basic dye, Furthermore, the dye etc. which modified | denatured with sodium acetate, sodium etalate, sodium methylate, etc. can be mentioned.

  About the said solvent, if the temperature lower than the temperature of the said heating under said pressurization can be used for the removal, there will be no restriction | limiting in particular in others, It can select from a well-known solvent suitably. Specifically, aromatic hydrocarbons (toluene, xylene, styrene), chlorinated aromatic hydrocarbons (chlorobenzene, ortho-dichlorobenzene), chlorinated aliphatic hydrocarbons (dichloromethane, trichloromethane, tetrachloromethane) ), 1,2-dichloroethane, 1,1,1-trichloroethane, 1,2-dichloroethylene, trichloroethylene), alcohols (methanol, isopropyl alcohol, 1-butanol, 2-butanol), esters (Methyl acetate, ethyl acetate) ethers (ethyl ether, 1,4-dioxane), ketones (acetone, methyl ethyl ketone), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), alicyclic hydrocarbons ( Cyclohexanone, methylcyclohexanone), aliphatic hydrocarbons ( Rumaru hexane), and a mixture of aliphatic or aromatic hydrocarbons.

  Other additives may be added to the composition. Such additives can include so-called binders, viscosity modifiers, dispersants, and pH regulators. If these can overlap with the thermoplastic resin in terms of content, they may be considered to belong to either category as long as the intended purpose of the above embodiment is obtained. Examples of the binder include linseed oil and rosin-modified alkyd resin. Examples of the viscosity modifier include mineral oil.

  Some of these “other additives” may be used as a solvent. In such a case, the non-volatile component that exists even after the decoration in the above embodiment is completed should be considered as one of “other additives”, not a solvent.

  There is no restriction | limiting in particular about the content rate of each component in the composition for decorating. The sublimable dye may be determined based on whether or not the finally obtained color is as desired. For thermoplastics, it should be considered whether the required durability can be satisfied. The solvent can be determined in view of ease of handling. The weight ratio between the sublimable dye and the thermoplastic resin is generally between 50:50 and 90:10.

  There are no particular restrictions on the material to be decorated, and natural materials such as resin, metal, FRP (fiber reinforced plastic) made of CF (carbon fiber) or GF (glass fiber), wood, bamboo, paper, etc. are used. Can do.

  What is necessary is just to select suitably the said thermoplastic resin from execution in the said embodiment among well-known thermoplastic resins. Thermoplastic varnish, wax, polyester resin (for example, semi-aromatic polyester such as polyethylene terephthalate copolymerized with an aliphatic polyester resin or a third component) and the like can be suitably used. However, when exposed to a temperature higher than the temperature at which sublimation of the sublimable dye occurs, it may have a property of crosslinking and curing.

  Decoration target (surface) is polyethylene, polypropylene, polystyrene, ABS resin, PC (polycarbonate) -ABS resin, PC resin, polyamide resin, PC-ASA (acrylic-styrene-acrylic rubber) resin, PLA (polylactic acid) alloy When made of PPS (polyphenylene sulfide) resin or the like, the affinity for the object to be decorated is increased, and thus a decorated surface with excellent adhesion can be easily obtained. Moreover, it is often easy to obtain pencil hardness and durability equivalent to the object to be decorated.

  The above thermoplastic resin can also be suitably used for FRP (fiber reinforced plastic) or the like whose surface to be decorated includes metal, CF (carbon fiber), GF (glass fiber), or the like. Moreover, you may give the metal decoration object etc. the coating based on thermosetting resin which consists of urethane, an acryl, etc. previously.

  It is important that the melting point and softening point of the thermoplastic resin are such that the sublimable dye can be sublimated and the object to be decorated is not deformed or altered. For example, polyester resins have a melting point ranging from a very high melting point exceeding 300 ° C. to a very low one of several tens of degrees C. Therefore, a thermoplastic resin should be selected according to the type of decoration object to be used.

  The technology according to the above-described embodiment can be used for any decoration target, but has excellent durability and a large need for realizing complex patterns, such as personal computers, digital cameras, digital video cameras, mobile phones, etc. An electronic device casing that accommodates the electronic device is a particularly preferable application.

  Next, specific examples and comparative examples will be described in detail.

[Example 1]
FIG. 4 shows an electronic device casing that is a decoration target. The casing was made of an Al alloy (A5052), and a large number of pores having a diameter of about 1 μm were present on the surface by etching.

  40 parts by weight of a sublimable dye and 10 parts by weight of a thermoplastic polyester resin powder were added to 50 parts by weight of a solvent (ethylene glycol monomethyl ether) and mixed uniformly.

  This mixed composition was printed on a release paper coated with a silicone coating using a screen printing to form a pattern consisting of a pattern and letters, and then dried at room temperature to remove the solvent.

  After the release paper was brought into close contact with the surface of the casing, it was heated under pressure at 180 ° C. and 0.1 Pa for 2 minutes.

  As a result of observing the cross-section of the decorative surface thus obtained using an electron microscope, as shown in the cross-sectional view of FIG. 5, the sublimable dye moves to the surface of the object to be decorated, and on the free surface side. It was found that the thermoplastic polyester layer was formed. In FIG. 5, the decoration object 3, the layer of the sublimable dye 4, the thermoplastic resin layer 5, and the space 6 are shown in layers from the bottom. In addition, the code | symbol 7 is the surface part which can be seen because the decoration object is seen from diagonally, and is unrelated to the said layered structure.

  As a result of performing the following cross-cut test (JIS K5400) on this decorative surface, it was found that there was no peeling of the decorative surface, and the decorative layer was firmly fixed to the surface of the casing. After (MIL STD-106D-202E), the crosscut test was performed again. As a result, it was found that the decorative surface was not peeled off and showed high durability.

[Example 2]
FIG. 4 shows an electronic device casing that is a decoration target. The material of the casing was Mg alloy (AZ91D). The Mg alloy has been subjected to chemical conversion treatment that provides rust prevention and adhesion. Fine irregularities were formed on the surface by the chemical conversion treatment.

  In the same manner as in Example 1, 40 parts by weight of a sublimable dye and 10 parts by weight of a thermoplastic polyester resin powder were added to 50 parts by weight of a solvent (ethylene glycol monomethyl ether) and mixed uniformly.

  This mixed composition was printed on a release paper coated with a silicone coating using a screen printing to form a pattern consisting of a pattern and letters, and then dried at room temperature to remove the solvent.

  After the release paper was brought into close contact with the surface of the casing, it was decorated by being heated under pressure at 180 ° C. and 0.1 MPa for 2 minutes.

  As a result of performing the following cross-cut test on this decorative surface, it was found that the decorative surface was not peeled off and the decorative layer was firmly fixed to the housing surface. Furthermore, after the temperature and humidity cycle (MIL STD-106D-202E), the cross-cut test was performed again. As a result, it was found that the decorative surface was not peeled off and showed high durability.

[Comparative Example 1]
The same electronic device casing as in Example 1 was used as a decoration target. The casing was made of an Al alloy (A5052), and a large number of pores having a diameter of about 1 μm were present on the surface by etching.

  In addition to 40 parts by weight of the same sublimable dye powder as in Example 1 and 50 parts by weight of solvent (ethylene glycol monomethyl ether), they were mixed uniformly.

  This mixed composition was printed on a release paper coated with a silicone coating using a screen printing to form a pattern consisting of a pattern and letters, and then dried at room temperature to remove the solvent.

  This mixed composition was printed on a release paper coated with a silicone coating using a screen printing to form a pattern consisting of a pattern and letters, and then dried at room temperature to remove the solvent.

  After the release paper was brought into close contact with the surface of the casing, it was heated under pressure at 180 ° C. and 0.1 MPa for 2 minutes.

  As a result of performing the following cross-cut test on this decorative surface, there was no peeling of the decorative surface, and the decorative layer adhered to the housing surface. However, after the temperature / humidity cycle (MIL STD-106D-202E), the cross-cut test was performed again. As a result, the decorative surface of the 95/100 mass was peeled off, and strong adhesion was not obtained, and there was no durability. I understood.

  In addition, the embodiment shown to the following additional remark can be derived from the content disclosed above.

  (1) A decorative composition comprising a sublimable dye, a thermoplastic resin and a solvent uniformly is adhered to the surface of the object to be decorated in a sheet form, the solvent is removed, and the decorative composition under pressure is applied. A decoration method including heating an object sheet.

  (2) A release sheet obtained by coating a decorative composition comprising a sublimable dye and a thermoplastic resin in a sheet shape is brought into close contact with the surface to be decorated, and the decorative composition is applied under pressure. A decoration method including heating a sheet and then releasing the release sheet from the decoration target.

  (3) The decoration method according to appendix 1 or 2, wherein a press die is used for pressure heating.

  (4) The decorating method according to any one of appendices 1 to 3, wherein the sublimable dye is any one of pyridoneazo, anthraquinone, indoaniline, azo and quinoline dyes, or a mixture thereof.

  (5) The decorating method according to any one of appendices 1 to 4, wherein the thermoplastic resin is any one of thermoplastic varnish, wax and polyester resin, or a mixture thereof.

  (6) The decorating method according to any one of appendices 1 to 5, wherein the surface of the decorating object has porosity.

(7) A decorative composition comprising a sublimable dye, a thermoplastic resin, and optionally a solvent uniformly,
When the decoration composition is adhered to the surface of the object to be decorated in the form of a sheet and a solvent is used, the solvent is removed before, after, or before and after the adhesion, and the sheet is heated under pressure The sublimable dye has a property of transferring to the surface of the object to be decorated,
Composition for decoration.

  (8) The decorative composition according to appendix 7, which is bonded to a release sheet.

  (9) An electronic device casing decorated with the decorative composition according to appendix 8 or 9.

It is a schematic diagram showing a part of release sheet which apply | coated the composition for decorating in the sheet form. It is a schematic diagram which shows the state which closely_contact | adhered the release sheet to the decoration object. It is a schematic diagram which shows the structure which the sublimation pigment | dye moved to the surface side of the decoration object, and it covered with the thermoplastic resin. It is a perspective view which shows the electronic device housing | casing which is an example of the decorating object. It is a cross section of the decoration object after decoration.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Composition for decorating 2 Release sheet 3 Decorating object 4 Sublimation dye 5 Thermoplastic resin 6 Space 7 Surface part

Claims (5)

  A decorative composition comprising a sublimable dye, a thermoplastic resin and a solvent uniformly is adhered to the surface of the object to be decorated in a sheet form, the solvent is removed, and the decorative composition sheet is applied under pressure. A decoration method including heating.   A release sheet, in which a decorative composition comprising a sublimable dye and a thermoplastic resin is uniformly applied, is adhered to the surface of the object to be decorated, and the decorative composition sheet is heated under pressure. Then, the decorating method including releasing the said release sheet from the said decorating object.   The decoration method according to claim 1 or 2, wherein a press die is used for pressure heating.   The decorating method according to any one of claims 1 to 3, wherein the thermoplastic resin is any one of thermoplastic varnish, wax and polyester resin, or a mixture thereof. A decorative composition comprising a sublimable dye, a thermoplastic resin, and optionally a solvent uniformly,
When the decoration composition is adhered to the surface of the object to be decorated in the form of a sheet and a solvent is used, the solvent is removed before, after, or before and after the adhesion, and the sheet is heated under pressure The sublimable dye has a property of transferring to the surface of the object to be decorated,
Composition for decoration.