CN1749032A - Decoration thin sheet and decoration material - Google Patents
Decoration thin sheet and decoration material Download PDFInfo
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- CN1749032A CN1749032A CN 200410099737 CN200410099737A CN1749032A CN 1749032 A CN1749032 A CN 1749032A CN 200410099737 CN200410099737 CN 200410099737 CN 200410099737 A CN200410099737 A CN 200410099737A CN 1749032 A CN1749032 A CN 1749032A
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- resin
- decorative laminate
- pearl
- ornament materials
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Abstract
The decoration sheet has base sheet, and thin decoration layer of pearl ink containing pearl pigment set on the base sheet. The pearl ink contains vinyl chloride-vinyl acetate copolymer as the adhesive and pearl pigment of mica coated with titania and metal oxide and/or metal hydroxide of Zr, Si, etc. The titania is preferably in rutile type, and the base sheet is preferably of acrylic resin. Laminating the thin decoration layer onto the base sheet constitutes the decoration sheet. The decoration sheet and decoration material of the present invention may be in decorating inside of automobile and other decoration purpose. The weather resistance of the pearl pigment may be improved via treatment with xenon lamp.
Description
Technical field
The present invention relates to a kind of decorative laminate, and this decorative laminate is layered in the ornament materials on the base materials such as resin forming article with light of pearl tone.Specifically, relate to and be suitable for automobile inside and other purposes etc. and require decorative laminate and the ornament materials high purposes of against weather, that against weather is good.
Background technology
Decorative laminate is used to build inside/outside decorative material, various uses such as building utensil, furniture or automobile inside/outside decorative material.In addition, require the situation of against weather and covering with paint sense also a lot of for decorative laminate.In this case, use the excellent acrylic resin thin slice of the transparency usually as the substrate sheet of face side.For example, begin to stack gradually the transparent acrylic resin thin slice as can on surfaces such as resin forming product, being shaped and the decorative laminate of stacked decorative laminate, can enumerating from face side, use the mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer and presented the ink lay of pattern as adhesive resin, used the bond layer of the mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer as adhesive resin, (with reference to patent documentations 1) such as decorative laminates that painted concealed resin flake constituted as the ABS resin (acrylonitrile-butadiene-styrene copolymer) of the resin flake of reverse side.
In addition, as the outward appearance of decorative laminate, the situation of lights such as sense of requirement metallic luster and pearly luster sense is arranged also.In order to give decorative laminate such light, the situation that the metal evaporation layer is set is also arranged, but make ink lay or resin flake etc. contain the example also more (with reference to patent documentation 2) of bright pigment such as metal powder or pearl pigment.As used bright pigment, under the situation that presents the metallic luster sense as light, use metal powders such as aluminium usually, under the situation that presents the pearly luster sense, use by the pearl pigments such as mica of coated by titanium dioxide usually.
[patent documentation 1]
The spy opens the 2001-232660 communique
[patent documentation 2]
The spy opens 2002-210907
Yet, can access more senior sensation although compare the pearly luster sense with the metallic luster sense, if common by the mica of coated by titanium dioxide as the pearl pigment use, wherein there is the low problem of against weather. If against weather is poor, the pearl ink lay that then can occur being added with pearl pigment in decorative laminate or the ornament materials such as peels off at the bad phenomenon. In the situation of against weather deficiency, usually adopt following countermeasure: in the resin of substrate sheet, use the resin of against weather excellence, perhaps in the resin of substrate sheet, add the light stabilizers such as ultra-violet absorber or hindered amines radical scavenger. But the interpolation of light stabilizer causes easily oozing out from the surface and produces the problem such as whiting, and therefore this means are also very limited.
In addition, the against weather evaluation is the artificial promotion exposure test in the laboratory simulation outdoor exposure, generally can obtain in the short period of time the good result of repeatability, and what often used as its test light source is the sunshine carbon arc lamp in the past. But, comparing with the sunshine carbon arc lamp, the result who obtains when using xenon arc lamp is closer to the against weather under the natural environment, and is therefore particularly nearest, very accurately estimates at needs in the situation of against weather, tends to adopt the test of using xenon arc lamp. In addition, the against weather of sometimes namely using the sunshine carbon arc lamp to estimate is good, the not so good situation of against weather when also useful xenon arc lamp is estimated.
Summary of the invention
That is, the objective of the invention is to improve the against weather of the decorative laminate that uses pearl pigment, this against weather also comprises the against weather when estimating with xenon arc lamp.In addition, provide the ornament materials that this decorative laminate is layered on the base materials such as resin forming product, for example for motor vehicle ornament materials such as automobile inside accessory.
In order to achieve the above object, the structure of decorative laminate of the present invention is as follows: substrate sheet is provided with the decorative laminate of the pearl ink lay that contains pearl pigment, in this pearl ink lay, at least contain vinyl chloride-vinyl acetate copolymer as adhesive resin, as pearl pigment, contain the metal oxide of metals such as the zirconium that coated again on by the surface of the mica of coated by titanium dioxide except that titanium, silicon and/or the pearl pigment of metal hydroxides.
In above-mentioned structure, by titanium dioxide surface is coated with other material, suppressed in the past to be played the photochemical catalyst effect by its most surperficial titanium dioxide of the mica of coated by titanium dioxide and the photodissociation of the adhesive resin that promoted, thereby also can improve against weather even have the pearly luster sense as what pearl pigment used.In addition, also can improve with the against weather under the situation of xenon arc lamp evaluation.
In addition, decorative laminate of the present invention is that further setting titanium dioxide on the basis of structure in the above is the structure of rutile-type.
Compare with anatase,, can reduce titanium dioxide self photocatalysis more, so against weather is better by becoming this structure.
In addition, decorative laminate of the present invention is that the metal of further setting in metal oxide and/or the metal hydroxides on the basis of any structure is the structure of zirconium in the above.
Can positively improve against weather by forming this structure.
In addition, decorative laminate of the present invention is on the basis of any structure in the above, and further setting substrate sheet is the structure of the resin flake of acrylic resin.
By forming this structure, even consider that from the viewpoint of the resin that constitutes the substrate sheet material against weather also is excellent.
In addition, ornament materials of the present invention is that stacked above-mentioned any decorative laminate constitutes on the surface of resin forming article.
Said structure, it is the preferred example that is suitable for of above-mentioned various decorative laminates, by forming this structure, even the shape relatively except that thin slice is as article such as flat board, three-dimensional things, also can utilize above-mentioned various decorative laminate to give effect, and also can improve the against weather of ornament materials under the situation of promptly using xenon arc lamp etc. to estimate with pearly luster sense.
In addition, ornament materials of the present invention, be that the resin of further setting resin forming article on the basis of the ornament materials of above-mentioned formation is made of ABS resin, polycarbonate resin or this two kinds of resins, and the substrate sheet of decorative laminate is made of the resin flake of acrylic resin.
This structure is a kind of preferred form of above-mentioned ornament materials, as with the ornament materials of more common resin as the resin of resin forming article, can give the pearly luster sense when giving against weather.
In addition, a preferred form of ornament materials of the present invention is above-mentioned any ornament materials, and its purposes is for motor vehicle ornament materials.
The suitable purposes of above-mentioned any ornament materials has been shown in this structure, and for example the ornament materials of using as automobile inside can be given the pearly luster sense when giving against weather.
Description of drawings
Fig. 1 is the sectional view of the shape example of expression decorative laminate of the present invention and ornament materials.
Among the figure,
1 substrate sheet
2 pearl ink laies
3 bond layers
4 patterned layer
5 base materials (resin forming article etc.)
10 decorative laminates
20 ornament materials
The specific embodiment
Embodiments of the present invention are below described.
At first, Fig. 1 is the sectional view of several shape instance of expression decorative laminate of the present invention and the ornament materials that forms at folded this decorative laminate of layers on substrates such as resin forming article.
The decorative laminate 10 of Fig. 1 (A) is basic structure examples, wherein, forms the pearl ink lay 2 that contains the specific pearl pigment of the present invention on the single face of the substrate sheet 1 that is made of transparent acrylic resin thin slice etc.This pearl pigment is a cladding titanium dioxide on mica, coats metal such as the metal oxide of zirconium, silicon etc. and/or the pearl pigment of metal hydroxides except that titanium then in its surface.In addition, the pearl ink lay can be formed on whole, also can form floral designs.
In addition, the decorative laminate 10 of Fig. 1 (B) be on the architecture basics of Fig. 1 (A) on pearl ink lay 2 (drawing below) further formed the structure example of bond layer 3.In addition, the decorative laminate 10 of Fig. 1 (C) is the structure example that have the patterned layer 4 that is formed by the printing ink that does not contain pearl pigment between substrate sheet 1 and pearl ink lay 2.In addition, Fig. 1 (D) shows that various decorative laminates 10 such as Fig. 1 (A)-(C) for example for example are laminated in the sectional view of a kind of shape of the ornament materials 20 that forms on the base materials such as resin forming article 5 that are made of ABS resin etc.
[pearl ink lay]
In addition, if will will further be coated, for example can adopt from the corresponding metal salting liquid to make it precipitate into the known method on surface by the surface of coated by titanium dioxide with metal oxide, metal hydroxides or metal oxide and the metal hydroxides of metals such as zirconium, silicon.In addition, metal hydroxides for example under the situation that is zirconium, is the hydrate of zirconium dioxide, and it also is referred to as zirconium hydroxide.
In addition, as the titanium dioxide that coats mica surface, rutile-type better than the Detitanium-ore-type.This is because compare with Detitanium-ore-type, and the band gap of rutile-type (bandgap) is less, and (Detitanium-ore-type: 3.2eV, rutile-type: 3.0eV), so photocatalysis reduces, and the facilitation of the light aging of adhesive resin is less, so against weather is better.
In addition, in order to improve rerum natura such as dispersion stabilization, preferably further coat the surface of above-mentioned specific pearl pigment with organic coupling agent.For example can use silane coupling agent as organic coupling agent.In addition, can be as silane coupling agent according to suitably selection uses from known coupling agent such as purposes.
In addition, the particle diameter of pearl pigment can suitably be selected according to the outer impression of required pearl, transparent feel etc., for example is about 5-25 μ m.In addition, the shape of pearl pigment can be the flakey paillon foil identical with common pearl pigment.
In addition, the content of pearl pigment also can determine that suitably for example resinous principle is about 5-60 quality % relatively according to the outer impression of required pearl etc.
In addition, containing the thickness of the pearl ink lay of specific pearl pigment as described above, can for example can be about 1-10 μ m according to suitable thickness of selection such as the outer impressions of required pearl.
In addition,, have no particular limits basically, for example, can be arranged in surface, the back side, the positive and negative of substrate sheet, arbitrary position of inner face (under the situation of multi-layer substrate thin slice) the position of pearl ink lay and substrate sheet layer relation.But, consider that from the viewpoint of against weather substrate sheet is positioned at when observing side (daylight side), substrate sheet can prevent the bad pearl ink lay of light loss, therefore is preferred, in this, substrate sheet is positioned at the back side and inner face side wants the specific surface side good.
In addition, as the adhesive resin in the pearl ink lay, can suitably use polyurethane resin, mylar, acrylic resin etc. according to layer materials such as material resin of substrate sheet etc. basically.But, in the present invention, use vinyl chloride-vinyl acetate copolymer at least.Vinyl chloride-vinyl acetate copolymer also can be used alone as adhesive resin, but considers and cementability also can use with other resin, for example also can use the resin that mixes with acrylic resin.Among the present invention the special reason of using vinyl chloride-vinyl acetate copolymer be it with various resins such as acrylic resin bonding well.
In addition, vinyl chloride-vinyl acetate copolymer is that the against weather of specific pearl pigment of the present invention improves effect, the adhesive resin that is easy to significantly show in the weathering test that utilizes xenon arc lamp.This is that contained this wavelength components is more than the sunshine carbon arc lamp in the xenon arc lamp because it is 364nm that vinyl chloride-vinyl acetate copolymer is easy to by aging optical wavelength.In this, acrylic resin does not have this weak relatively light component, but vinyl chloride-vinyl acetate copolymer has the rerum natura that is difficult to give up at aspects such as cementabilities, even use this vinyl chloride-vinyl acetate copolymer, also can obtain to significantly improve the action effect of against weather under xenon arc lamp in the present invention.
In addition, the pearl ink lay can adopt any method by forming such as known forming method such as print process, rubbing method under situation about being formed on whole.In addition, in the decorative laminate shown in Fig. 1 (A)-Fig. 1 (C), pearl ink lay 2 is to form with whole form, but these just are used to the schematic diagram that illustrates, also comprise the situation that forms pattern form.
In addition, in the pearl ink lay,, can suitably add various additives, for example light stabilizers such as radical scavenger of colouring agent, filler, ultra-violet absorber and hindered amines as required in order to adjust rerum natura.
[substrate sheet]
As substrate sheet 1, have no particular limits basically, can suitably use resin flake, paper, metal forming etc. according to purposes.But, be positioned at respect to the pearl ink lay more when observing the position of side, need possess the transparency.In addition, describe in by vacuum forming, injection molded etc. under the situation of stretching decorative laminate, formability also is essential.The representative example of such substrate sheet is the resin flake that is made of thermoplastic resin.
As the thermoplastic resin that is used for resin flake, that for example can enumerate has a polyethylene, polypropylene, polymethylpentene, polybutene, ionomer, ethylene-propylene copolymer, ethylene-propylene-butylene copolymer, polyolefin resins such as olefin hydrocarbons thermoplasticity elastic body, perhaps, polybutylene terephthalate, the polyesters thermoplastic elastomer (TPE), mylar such as complete noncrystal polyester, poly-(methyl) methyl acrylate, poly-(methyl) butyl acrylate, (methyl) methyl acrylate-(methyl) butyl acrylate copolymer, styrene-acrylic resins [in addition, (methyl) acrylic acid is meant acrylic or methacrylic acid] such as (methyl) methyl acrylate copolymer, polycarbonate resin, polystyrene resin, vinyl chloride resin etc.
Wherein, acrylic resin all is a kind of preferred resin from the angle of the transparency and against weather excellence.This is because acrylic resin has the excellent transparency, so it can give senior impressions such as covering with paint, lacquer, colour wash, etc. sense or lustrous surface.In addition, compare with the situation of using polyolefin resin etc., acrylic resin also has the good advantages of surface physical property such as against weather and marresistance.
In addition, in the resin flake,, can suitably add various additives as required in order to adjust rerum natura, for example lubricant, antifriction liniment, filler, colouring agent, perhaps, the light stabilizers such as radical scavenger of ultra-violet absorber and hindered amines.
In addition, under the situation of resin flake, can make suitable thickness according to cost, formability, aesthetic appearance (covering with paint, lacquer, colour wash, etc. sense) etc., suitable depth is usually about 30-200 μ m.
[bond layer]
Bonding force when improving adherends such as bonding and stacked decorative laminate and base material suitably is provided with bond layer 3[with reference to Fig. 1 (B) in case of necessity in the adherend side].As bond layer, can use known bonding agent according to purposes, for example, thermoplastic resins such as vinylacetate resin, vinyl chloride-vinyl acetate copolymer, thermoplastic polyester, polyamide, ionomer, chlorinated polyolefin resin, thermal plastic urethane resin, perhaps, cured resin such as phenolic resins, epoxy resin, perhaps, rubber resin etc.In addition, bond layer can form by known printing or covering with paint method.Thickness to bond layer has no particular limits, and for example is about 5-20 μ m.
[patterned layer]
[base material]
By on base materials such as resin, wood based panel, use the suitable stacked aforesaid decorative laminate of bonding agent, can become the ornament materials 20 shown in Fig. 1 (D).As base material 5, have no particular limits, can use known various base material according to purposes.In addition, the layered manner of decorative laminate and base material also has no particular limits, and can suitably adopt known various layered manner.For example, in the method for describing in the time of by injection molded, decorative laminate can be shaped and be layered on the surface of three-dimensional resin forming article.In addition, also mold for injection molding can be also used as the vacuum forming mould in the shaping of decorative laminate, also can be after forming thin slice by the vacuum forming particular manufacturing craft, the decorative laminate that is shaped is installed in carries out injection molded on the mold for injection molding.In addition, the latter also is inlay shaping a kind of.
In addition, have no particular limits, can suitably select to use known resin according to purposes as the resin of resin forming article.For example, in the vehicular applications of automobile inside product, the representative hybrid resin that ABS resin, polycarbonate resin, ABS resin/polycarbonate resin are arranged also can use acrylic resin etc. in addition.
[purposes of decorative laminate and ornament materials]
The purposes of decorative laminate of the present invention and ornament materials has no particular limits, and considers from applying flexibly this feature this point, especially preferably requires the purposes of against weather.In addition, as appearance requirement, the pearly luster sense purposes that is absolutely necessary.For instance, suitable purposes for example has automobile inside components, car body, decoration rope vehicle purposes such as vehicle exterior member such as (モ one Le) such as the water of screening instrument board, door skin, low level instrument board.In addition, the purposes outside the vehicle for example has, furniture such as construction material, desk, wardrobe such as window frame, doorframe, door, wallboard, bed board, revetment, claustra, roof surface material, canopy, door leaf, door pillar, door and window case.
[embodiment]
Illustrate in greater detail the present invention with Comparative Examples by the following examples.
[embodiment 1]
Be prepared as follows the decorative laminate 10 of Fig. 1 (B) structure.
At first, as substrate sheet 1, the water white thickness of preparing to be made of PMMA (polymethyl methacrylate) is the resin flake of 125 μ m.Rear side in this substrate sheet is carried out intaglio printing with printing ink, this printing ink is grouped into by following one-tenth: with respect to the weight ratio by vinyl chloride-vinyl acetate copolymer and acrylic resin is adhesive resin 15 mass parts of 1: 1 hybrid resin formation, contains mica surface is added up to 3 mass parts, solvent 67 mass parts with pearl pigment 15 mass parts, dispersion stabilizer and the plasticizer that rutile titanium dioxide, zirconium dioxide, silane coupling agent coat successively.When dry (following identical), forming thickness is whole the pearl ink lay 2 of 2 μ m.Then, on the pearl ink lay, also form the bond layer 3 that the thickness that is made of vinyl chloride-vinyl acetate copolymer is 2 μ m through intaglio printing, thus the decorative laminate 10 of preparation shown in Fig. 1 (B).
Next, with this decorative laminate 10 on the mold for injection molding that is also used as the vacuum forming mould (former), thermoplastic and vacuum forming on the heating plate of 340 ℃ radiation heating formulas, afterwards, under the condition of 50 ℃ of mold temperatures, 235 ℃ of injection temperatures with the ABS resin injection molded, be layered on the base material 5 of the resin forming article that forms by ABS resin, make the ornament materials 20 shown in Fig. 1 (D).
[embodiment 2]
Use the decorative laminate of preparation among the embodiment 1, be stacked on the base material 5 of resin forming article with embodiment 1 same formation, just when the preparation ornament materials, utilize special-purpose vacuum forming mould to carry out after the vacuum forming of decorative laminate, be loaded in the mold for injection molding, afterwards with the ABS resin injection molded, thus the preparation ornament materials 20 required as Fig. 1 (D).
[comparative example 1]
In embodiment 1, as the pearl pigment that is used for the pearl ink lay, used the pigment that has just coated mica surface with rutile titanium dioxide, other and embodiment 1 prepare decorative laminate and ornament materials in the same manner.
[comparative example 2]
In embodiment 1, as the pearl pigment that is used for the pearl ink lay, used the pigment that has just coated mica surface with anatase titanium dioxide, other and embodiment 1 prepare decorative laminate and ornament materials in the same manner.
[comparative example 3]
In embodiment 2, use the decorative laminate in the Comparative Examples 1 to replace the decorative laminate among the embodiment 1 to prepare ornament materials, other and embodiment 2 prepare ornament materials in the same manner.
[comparative example 4]
In embodiment 2, use the decorative laminate in the Comparative Examples 2 to replace the decorative laminate among the embodiment 1 to prepare ornament materials, other and embodiment 2 prepare ornament materials in the same manner.
[performance evaluation]
With the ornament materials that makes in embodiment and the Comparative Examples, promote exposure test to estimate against weather through artificial with xenon arc lamp.Experimental condition: 89 ℃ of blackboard temperatures, humidity 50RH%, Continuous irradiation (have only illumination to penetrate, do not rain), irradiation time 500 hours.After the test, estimate (reticulate pattern) adhesiveness by the reticulate pattern strips method, do 100 (10 * 10 in length and breadth) little lattice with cutting knife, with the cellophane adhesive tape bonding with it after, peel off quickly, not and adhesive tape peel off together and residual little lattice number be 100 (100/100) be considered as well also be considered as bad even there is 1 little lattice to be peeled (below 99/100).
Its result is as shown in table 1, and the adhesiveness of embodiment is all good, and is also good with the against weather that xenon arc lamp is estimated.But the adhesiveness of Comparative Examples is all bad, can not obtain enough against weathers.
[table 1]
Performance evaluation result
| Against weather | ||
| The reticulate | ||
| Embodiment | ||
| 1 | 100/100 | |
| Embodiment | ||
| 2 | 100/100 | Well |
| Comparative Examples 1 | 38/100 | Bad |
| Comparative Examples 2 | 11/100 | Bad (very poor) |
| Comparative Examples 3 | 38/100 | Bad |
| Comparative Examples 4 | 11/100 | Can (not very poor) |
(1) according to decorative laminate of the present invention, even the mica that uses cladding titanium dioxide is as pearl pigment, (because its surface also is coated with the metal oxide and/or the metal hydroxides of other metal except that titanium) decomposed and can be inhibited by the light of the adhesive resin that the photocatalysis of titanium dioxide causes, and can improve against weather when giving the pearly luster sense.In addition, with also having good against weather under the situation of xenon arc lamp evaluation.
(2) in addition, if titanium dioxide is rutile-type, its against weather is better than the situation of Detitanium-ore-type.
(3) in addition, if the metal zirconium of above-mentioned metal oxide and/or metal hydroxides then can improve against weather really.
(4) in addition, if the resin flake of substrate sheet acrylic resin then also can have good against weather aspect the resin material of substrate sheet.
(5) according to ornament materials of the present invention, can obtain and the corresponding various effects of above-mentioned decorative laminate, can when giving the pearly luster sense, improve against weather, the ornament materials that forms at resin forming article upper strata closed assembly decorations thin slices such as ABS resin, polycarbonate resins can be used for vehicular applications etc.In addition, with also having good against weather under the situation of xenon arc lamp evaluation.
Claims (7)
1, a kind of decorative laminate, it is the decorative laminate that substrate sheet is provided with the pearl ink lay that contains pearl pigment, it is characterized in that, in this pearl ink lay, at least contain vinyl chloride-vinyl acetate copolymer as adhesive resin, as pearl pigment, contain the metal oxide of metals such as the zirconium that coated again on by the surface of the mica of coated by titanium dioxide except that titanium, silicon and/or the pearl pigment of metal hydroxides.
2, decorative laminate as claimed in claim 1, wherein titanium dioxide is rutile-type.
3, decorative laminate as claimed in claim 1 or 2, wherein the metal in metal oxide and/or the metal hydroxides is a zirconium.
4, as each described decorative laminate among the claim 1-3, wherein substrate sheet is the resin flake of acrylic resin.
5, a kind of ornament materials is the ornament materials of each described decorative laminate among the stacked requirement 1-4 that has the right on the surface of resin forming article.
6, ornament materials as claimed in claim 5, wherein the resin of resin forming article is made of ABS resin, polycarbonate resin or this two kinds of resins, and the substrate sheet of decorative laminate is made of the resin flake of acrylic resin.
7, a kind of for motor vehicle ornament materials is claim 5 or 6 described ornament materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410099737 CN1749032A (en) | 2004-09-16 | 2004-09-16 | Decoration thin sheet and decoration material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410099737 CN1749032A (en) | 2004-09-16 | 2004-09-16 | Decoration thin sheet and decoration material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1749032A true CN1749032A (en) | 2006-03-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410099737 Pending CN1749032A (en) | 2004-09-16 | 2004-09-16 | Decoration thin sheet and decoration material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099203B (en) * | 2008-09-30 | 2013-01-02 | 日本写真印刷株式会社 | Decorative material, method for producing decorative material, and molded article |
| CN107206744A (en) * | 2015-02-06 | 2017-09-26 | 大日本印刷株式会社 | Cosmetic sheet and the decorative element for possessing the cosmetic sheet |
| CN108274849A (en) * | 2017-01-06 | 2018-07-13 | 株式会社御牧工程 | The manufacturing method and ornament of ornament |
| CN108569006A (en) * | 2017-03-07 | 2018-09-25 | 卡西欧计算机株式会社 | The manufacturing method of thermal expansivity thin slice and thermal expansivity thin slice |
| CN111150561A (en) * | 2018-11-08 | 2020-05-15 | 尤妮佳股份有限公司 | Absorbent article package and package of absorbent article package |
-
2004
- 2004-09-16 CN CN 200410099737 patent/CN1749032A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099203B (en) * | 2008-09-30 | 2013-01-02 | 日本写真印刷株式会社 | Decorative material, method for producing decorative material, and molded article |
| CN107206744A (en) * | 2015-02-06 | 2017-09-26 | 大日本印刷株式会社 | Cosmetic sheet and the decorative element for possessing the cosmetic sheet |
| CN108274849A (en) * | 2017-01-06 | 2018-07-13 | 株式会社御牧工程 | The manufacturing method and ornament of ornament |
| CN108569006A (en) * | 2017-03-07 | 2018-09-25 | 卡西欧计算机株式会社 | The manufacturing method of thermal expansivity thin slice and thermal expansivity thin slice |
| CN108569006B (en) * | 2017-03-07 | 2020-09-15 | 卡西欧计算机株式会社 | Thermally expandable sheet, and method for producing molded article |
| CN111150561A (en) * | 2018-11-08 | 2020-05-15 | 尤妮佳股份有限公司 | Absorbent article package and package of absorbent article package |
| CN111150561B (en) * | 2018-11-08 | 2023-07-11 | 尤妮佳股份有限公司 | Absorbent article package and package of absorbent article package |
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Application publication date: 20060322 |