JPH08269368A - Coating film composite material and decorative sheet - Google Patents

Abstract

PURPOSE: To prepare a decorative sheet which yields a uniform luminance independent of the angle of incidence of light or the visual angle of observer.

CONSTITUTION: The decorative sheet is composed to contain a support, a thermally expanded layer obtained through heat treatment from a thermally expandable layer which contains a thermoplastic resin and thermally expandable microcapsules dispersed in the resin and has an increased film thickness than the film thickness before the heat treatment and a colored layer containing a luster scaly material having an average particle size of from 12 to 250 μm.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating film composite and a decorative sheet using the same, and more particularly to a decorative sheet having a combination of a thermal expansion layer and a coloring layer containing a bright scale-like substance. The decorative sheet of the present invention, the orientation of the glittering scale-like substance of the colored layer above the expanded portion of the thermal expansion layer changes,
Since a uniform brightness can be obtained regardless of the incident angle of light and the viewing angle of an observer, it can be advantageously used as a label, a sticker, an emblem, and similar articles.

[0002]

2. Description of the Related Art Conventionally, various techniques have been used for manufacturing decorative articles such as labels, stickers and emblems. For example, Japanese Patent Laid-Open No. 60-246878 discloses a technique of using a printing ink containing microcapsules containing a foaming agent for producing a pattern print leather used particularly for automobile seats. Using this technique, first, as shown in FIG. 1 (A), a support layer 11 such as a woven cloth is provided with a film base layer 12 such as vinyl chloride.
Then, the pattern 14 is printed with a printing ink containing microcapsules containing a foaming agent, and the printed surface is covered with a protective layer 15 made of a transparent film or the like. Next, when the obtained composite is heated to a temperature capable of causing the expansion of the foaming agent in the microcapsules, the microcapsules expand in volume (No. 113) as shown in FIG. 1 (B).
Then, the pattern printing spot becomes a convex portion. Therefore,
It is possible to inexpensively manufacture pattern-printed leather with a very realistic texture without special embossing.

Japanese Patent Laid-Open No. 2-303573 discloses
Disclosed is a method for forming a coating film having a concavo-convex pattern, which is useful for the surface mounting of building materials, furniture, home appliances, etc., by using heat-expandable microcapsules. When this method is used, first, as shown in FIG. 2 (A), a base material 2 such as a galvanized steel sheet is used.
The entire surface (or one surface) of No. 2 is coated with an undercoat paint 24 containing thermally expandable microcapsules 23 dispersed therein. Next, the undercoat paint 24 is cured at a temperature lower than the foaming temperature of the microcapsules, and then the overcoat paint 25 is applied to the entire surface of the formed undercoat paint film 24, as shown in FIG. 2B.
To cover. Finally, when the obtained composite is heated to a temperature equal to or higher than the foaming temperature of the microcapsules, as shown in FIG.
As shown in FIG.
3), a coating film 125 having an uneven pattern is formed. According to this method, a coating film having a concavo-convex pattern can be formed on the surface of the base material at low cost without embossing unlike the conventional method.

However, the coatings formed by these conventional methods have significant deficiencies due to the presence of expanded microcapsules contained in the coatings. That is,
As is apparent from FIG. 3 showing the convex portion of FIG. 1B in an enlarged manner, a part of the volume-expanded microcapsule 113 projects from the original ink pattern layer 14 and reaches the protective layer 15. Such protrusions of microcapsules not only significantly impair the appearance of the resulting coating film, but are also aesthetically undesirable. In addition, in such a method, the capsules are expanded at the same time as or after the curing of the microcapsule-containing layer and the curing of the protective layer or the topcoat film, so that the stress caused by the expansion of the capsules causes stress in the protective layer or the topcoat layer. It is impossible to avoid deterioration of the coating film which is caused by the coating film and deterioration of weather resistance.

Further, Japanese Patent Laid-Open No. 6-127111 uses a screen printing method to manufacture a light-reflecting screen printed matter in which a printed pattern is three-dimensionally visible or disappears depending on an angle between a plane of the printed matter and a viewpoint. Disclosure. As shown in FIG. 4, a printed matter of this type has a pattern plate 32 having a concave portion 33, a convex portion 34, and a cutout portion 35 arranged on a face plate 31 of a screen printing machine, and a printing substrate 36 placed thereon. It can be produced by stacking and closely adhering, and screen-printing an ink or paint 37 containing the light-reflecting scaly particles in an amount of 5 to 60% by weight to a predetermined film thickness. As a result of the printing, as shown in the figure, the film thickness of the ink or paint 37 is high.
8 is thin, and the low level flat portion 39 is thick. Further, in the curved surface, the portion that is convex upward as shown by reference numeral 40 is the thinnest, and the portion that is concave upward as shown by 41 is the thickest. In this print,
Therefore, there is an effect that the pattern can be stereoscopically observed depending on the viewing angle of the observer. On the other hand, this printed matter has a drawback in that the observer cannot uniformly and stereoscopically observe the pattern from any position.

[0006]

The object of the present invention is therefore to overcome the drawbacks of the prior art as described above.
A decorative sheet that is easy to manufacture, does not have the drawbacks caused by the use of microcapsules, and that can even stereoscopically observe the pattern from any position regardless of the incident angle of light or the viewing angle of the observer, and Particularly, it is to provide a coating film composite useful for the production of such an observation sheet.

Other objects of the present invention will be readily apparent from the detailed description set forth below.

[0008]

According to the present invention, part 1
In one aspect, a heat-expandable layer containing a thermoplastic resin and heat-expandable microcapsules dispersed in the resin, and an average particle size of 12 to 250 applied to the heat-expandable layer.
There is provided a coating film composite comprising a colored layer containing a glittering scale-like substance of μm.

In the coating film composite of the present invention, preferably, the thermally expandable microcapsules are dispersed in the thermoplastic resin in an amount of 1 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin. . The glittering scale-like substance is preferably dispersed in the colored layer in an amount of 0.5 to 20% by weight. Here, the glittering scale-like substance dispersed in the colored layer is preferably a member selected from the group consisting of aluminum powder, iron oxide powder, metal evaporated glass flake and pearl pigment.

According to the present invention, on the other side thereof, the support and the support sequentially laminated on the support,
A heat-expandable layer formed from a heat-expandable layer containing a thermoplastic resin and heat-expandable microcapsules dispersed in the resin, the heat-expandable layer having an increased film thickness as compared with the film thickness before the heat treatment. And a colored layer containing a glittering scale-like substance having an average particle size of 12 to 250 μm.

The decorative sheet of the present invention preferably further has a clear layer made of a thermosetting resin on the colored layer. The coating film composite and the decorative sheet according to the present invention,
Preferably, various layer configurations can be used depending on various factors such as the desired effect. Although not limited to what is described below, typical layer configurations and details of each layer of the present invention will be further described with reference to the accompanying drawings.

FIG. 5 is a sectional view showing a preferred example of the coating film composite according to the present invention. As shown in the figure, this coating film composite comprises a heat-expandable layer 2 made of a thermoplastic resin in which heat-expandable microcapsules 3 are dispersed, and a colored layer 4 applied on this layer. . In the colored layer 4,
Although not particularly shown, the average particle size is 12 to 250 μ.
Includes m 3 glittering scales. The film thicknesses of the heat-expandable layer 2 and the colored layer 4 are generally preferably about 5 to 50 μm and about 3 to 50 μm, respectively.

The thermally expandable layer 2 contains a thermoplastic resin as a main component. The suitable thermoplastic resin is preferably a urethane-based resin, particularly a polyurethane resin, which can be softened at a temperature not higher than the foaming temperature of the heat-expandable microcapsules. A useful polyurethane resin is, for example, FL from Sumitomo 3M Limited.
It is available as 510 (trade name). Further, the heat-expandable microcapsules dispersed in such a thermoplastic resin are composed of a thin outer shell portion and a core substance encapsulated inside the thin outer shell portion, like the ordinary microcapsules.
The microcapsule used in the present invention is such that the outer shell portion is softened by heating and the core material inside is gasified and expanded, and the microcapsule itself expands. Although the temperature of the heating that causes such expansion of the microcapsules (also referred to herein as the "foaming temperature") can be widely varied depending on the conditions such as the constituent material of the membrane and core of the microcapsules,
Generally, about 100-180 ° C is advantageous.

To explain further, the heat-expandable microcapsule preferably comprises an outer shell made of a polymer material such as vinylidene chloride-acrylonitrile copolymer, and a liquid hydrocarbon such as isobutene is enclosed inside the outer shell. It can be prepared by Microencapsulation is
It can be advantageously carried out using a commonly used microencapsulation method, for example, a phase separation method, an interfacial polymerization method, a submerged drying method, an in-situ polymerization method, or the like. Although the size of the microcapsules can be widely changed in consideration of factors such as the film thickness of the heat-expandable layer, it is generally preferable that the microcapsules have a particle size of about 3 to 20 μm. Specifically, the microcapsules have, for example, a particle size of about 50 μm after foaming, when the particle size before foaming is about 15 μm.
μm. The heat-expandable microcapsules can be prepared according to a conventional method as described above, but commercially available microcapsules can be used if necessary. Useful microcapsules are available as, for example, Expancel 551DU (trade name) from Nippon Philite.

Dispersion of the microcapsules 3 in the thermoplastic resin of the heat-expandable layer 2 can be carried out according to various methods. For example, after preparing the microcapsules in advance, the microcapsules can be dispersed in the material of the heat-expandable layer. It may be dispersed and applied by a technique such as screen printing or knife coating, or microencapsulation and dispersion may be performed simultaneously. Here, the mixing ratio of the thermoplastic resin and the microcapsules is preferably about 100: 1 to 100: 4 by weight.
0, and more preferably about 100: 5 to 100:
Twenty. If the mixing ratio is less than 100: 1, the change in the glittering scale-like substance is small, so that it is impossible to distinguish the glitter feeling between the foamed portion and the non-foamed portion. On the contrary, when the mixing ratio of both is more than 100: 40, the content of the thermoplastic resin is small, so that the coating substrate of the present invention is advantageously applied to a printing substrate (“support” in the present specification). (Also referred to as)) is poor. If appropriate in terms of processing, a solvent such as thinner may be used together when dispersing the microcapsules. The heat-expandable microcapsules may be damaged by a ketone-based solvent, an alcohol-based solvent, or the like, so that it is preferable to use an aqueous solvent. In addition, when a solvent other than an aqueous solvent, particularly an organic solvent is used, it is necessary to evaluate in advance whether or not it has an adverse effect on the microcapsules.

The coloring layer 4 is used in combination with the heat-expandable layer 2. The colored layer 4 can preferably contain, as a main component, a resin which is the same as or similar to the thermoplastic resin used as the main component in the thermally expandable layer 2. this is,
This is because by selecting the resin in such a manner, the adhesion of the colored layer to the underlying thermally expandable layer is improved. The colored layer has an average particle size of 12 in addition to the thermoplastic resin.
It contains a colorant obtained by dispersing a brilliant scale-like substance having a size of ˜250 μm, that is, a pigment, a dye and the like. The colorant used is not particularly limited, and examples thereof include black ink FL545 (trade name) manufactured by Sumitomo 3M Limited. Further, the glittering scale-like substance dispersed in this colorant can be arbitrarily selected from a large number of known substances, and preferably flat aluminum powder, iron oxide powder, metal-deposited glass flake. And a member selected from the group consisting of pearl pigments. All of these flaky substances are easily available commercially, and for example, aluminum powder is available from Toyo Aluminum Co., Ltd. 0215M, 764.
0NS etc. (both are trade names), iron oxide powder from Sakai Chemical Co., Ltd. as PFO-1000, PFO-300 etc. (both are trade names), metal evaporated glass flakes from Nippon Sheet Glass Co., Ltd. 5150 PS, 5090 PS etc. HI-LITE GREEN is a pearl pigment from Marl
Available as FINE BLUE (trade name). The size (average particle size) of such a glittering scale-like substance is preferably about 12 to 250 μm, more preferably about 20 to 70 μm. If the average particle size of the scale-like substance used is less than 12 μm, the obtained glittering feeling is insufficient, and it is almost impossible to obtain the glittering difference between the foamed portion and the non-foamed portion. Further, as in the present invention, a method by silk printing is generally used for performing shape printing, but in this case, the glittering scale-like substance must be able to pass through the mesh plate. Here, the mesh may be roughened, but if it is too rough, the linearity of the edge of the finished shape is impaired. In order to avoid this, the limit that can pass through the mesh plate is 70 mesh, and the limit of the average particle size of the scale-like substance that can pass through this mesh is 250 μm.

The concentration of the bright scale-like substance in the colored layer is preferably about 0.5 to 20% by weight, more preferably
It is about 1.0 to 15% by weight. The scale-like substance concentration is 0.
When the amount is less than 5% by weight, the glittering feeling is insufficient like the above-mentioned average particle diameter, so that it is almost impossible to provide the glittering feeling difference between the foamed portion and the non-foamed portion. Further, if the scale-like substance is more than 20% by weight, the cohesive force of the colored layer itself becomes poor, and cohesive failure is inevitable.

The coating film composite of the present invention can be preferably prepared by sequentially coating the heat-expandable layer 2 and the coloring layer 4 described above on a support. The coating of such layers can be advantageously carried out using printing techniques such as silk screen printing, as is conventional in the coatings art. In addition, as a usable technique other than the printing technique, for example, a coating method such as a knife coating method or a spray coating method can be used. Although the film thickness of such a layer can be variously changed according to the layer constituent material used and other factors, in general,
It is about 5 to 50 μm (thermally expandable layer) and about 3 to 50 μm (colored layer). Here, the colored layer may be coated as a single layer or, if desired, in the form of two or more composite layers. When coating the heat-expandable layer 2 and the colored layer 4, attention must be paid to selection of a solvent for dissolving the base resin. This is because it is necessary to perform drying at a temperature lower than the foaming temperature of the heat-expandable microcapsules in the heat-expandable layer 2 when the layers are dried after coating, in order to prevent early expansion of the microcapsules. Because it is.

The coating composite of the present invention may preferably have a clear layer on its colored layer after the thermal expansion of the microcapsules is completed, as detailed below. Examples of the material of the clear layer include materials having excellent adhesion to the underlying colored layer, for example, colorless paints such as thermosetting urethane paints and ultraviolet (UV) curable paints. Also, this clear layer is preferably applied after the thermal expansion of the microcapsules in the heat-expandable layer has been completed, so that it can be dried and cured independently of the foaming temperature of the microcapsules, but of the microcapsules. It is desirable to dry and cure below the foaming temperature.

FIG. 6 shows another example of the coating film composite according to the present invention.
It is sectional drawing which showed two preferable examples. This coating composite uses the support 1 for the support of the heat-expandable layer, except that the heat-expandable layer 2 is arranged not in the entire surface but in a pattern as shown. And is similar to the coating film composite of FIG. As the support 1, an appropriate material can be selected from the materials widely used as the support in known decorative sheets and the like. Suitable support materials are, for example, paper, coated paper, metal sheets or sheets, glass sheets or sheets, for example polyvinyl chloride (PVC), polyurethane, polyethylene terephthalate (PET) or other plastic material sheets or sheets, Others can be mentioned. Although the thickness of the support is not particularly limited, it is generally about 20 to 2
It is preferably 000 μm. Also, if necessary,
As will be described in detail below, a means such as a release sheet may be attached to the surface of the support opposite to the colored layer.

The heat-expandable layer 2 is coated on the support 1 in a pattern according to a desired decorative pattern. This pattern coating can be advantageously carried out using printing techniques such as silk screen printing, as is commonly done in the coating art, but other printing techniques or coatings may be used if desired. Method may be used.

As will be apparent from the following description, FIG.
And the coating film composite of the present invention illustrated in FIG. 6 can be advantageously used particularly in the production of the decorative sheet of the present invention. FIG. 7 is a sectional view showing a preferred example of the decorative sheet according to the present invention. The illustrated decorative sheet is a support 1
The thermal expansion layer 102 is coated in a pattern on the
Then, the colored layer 4 containing the glittering scale-like substance is covered thereover. As shown in the figure, the coloring layer 4 is raised by the expansion amount as a result of the expansion of the underlying thermal expansion layer 102. Although expanded microcapsules 103 are dispersed in the thermal expansion layer 102, all the capsules are contained in the thermal expansion layer. The respective constituent elements of the illustrated decorative sheet can be formed in the same manner as the constituent elements described above with reference to FIGS. 5 and 6. Unless otherwise specified, the respective constituent elements of the coating film composite and the decorative sheet, which will be described below with reference to the drawings, can be formed in the same manner as described above.
The decorative sheet as shown can be observed as having a uniform light intensity no matter where it is observed.

FIG. 8 is a sectional view showing an example in which a clear layer 5 is further applied to the decorative sheet shown in FIG. The clear layer is formed from a material having excellent adhesion to the underlying colored layer, for example, a colorless paint such as a thermosetting urethane paint or an ultraviolet (UV) curable paint, as briefly described above. Preferably. To form this clear layer, for example,
Techniques such as silk screen printing can be used. Although the thickness of the clear layer is not particularly limited, it is generally preferably about 5 to 15 μm in consideration of its function as a protective layer. The use of the clear layer is expected to have effects such as protection of the underlayer, prevention of contamination, improvement of weather resistance, addition of gloss, and other effects.

FIG. 9 is a sectional view showing a modified example of the coating film composite shown in FIG. The illustrated coating film composite is the same as the coating film composite of FIG. 6 in that the support 1, the heat-expandable layer 2 and the coloring layer 4 correspond to each other, except that the support 1
6 is different from that shown in FIG. 6 in that the adhesive layer 6 and the release paper 7 are provided on the back surface (the surface not having the heat-expandable layer and the coloring layer). The adhesive layer used here can be composed of, for example, an acrylic resin-based adhesive, and the film thickness thereof is usually
It is about 10 to 50 μm. Further, the release paper can be, for example, paper coated with a release agent such as silicone resin, or a sheet or film of polyethylene terephthalate or the like. A product in which a release paper with an adhesive layer is laminated on the back surface of the support is, for example, Scotchcal ^™ S / C.
It is available as 3650 (brand product of Sumitomo 3M Limited). Thus, by laminating the release paper with the adhesive layer on the back surface of the support, it is possible to facilitate the application of the coating film composite and the decorative sheet obtained therefrom and to apply it to various parts. .

FIG. 10 is a sectional view of a decorative sheet manufactured using the coating film composite shown in FIG. Further, the illustrated decorative sheet corresponds to the decorative sheet of FIG. 8 except that a release paper having an adhesive layer is laminated on the back surface of the support 1. As illustrated, the microcapsules 103 that have been expanded as a result of the expansion of the microcapsules 3 (FIG. 9) by heating.
The thermal expansion layer 102 containing and disperse | distributed is obtained, and the coloring layer 4 and the clear layer 5 containing the bright scale-like substance above the thermal expansion layer 102 are also piled up by this. The effect of improving the brilliance obtained is as described above.

[0026]

The decorative sheet of the present invention is formed as a result of heat treatment from a support and a heat-expandable layer containing a thermoplastic resin and heat-expandable microcapsules dispersed in the resin. The thermal expansion layer has a film thickness increased from the film thickness and the colored layer contains a bright scale-like substance having an average particle diameter of 12 to 250 μm. First, since the colored layer is lifted by the underlying thermal expansion layer, the orientation of the glittering scale-like substance contained in the colored layer changes, and the glittering is uniform regardless of the angle of incident light and the diopter during observation. You will get a feeling. Also, by functionally separating the decorative coating film into two layers, a thermal expansion layer and a colored layer, it is possible to maintain a uniform coating color even if the coating film is a thin film with a thickness of 50 μm or less. It is also possible to prevent the disadvantage that the microcapsules project from the colored layer. Furthermore, when the heat-expandable layer on the support is provided in a pattern, different glittering feelings can be obtained in the foamed portion and the non-foamed portion of the capsule due to the glittering scale-like substance in the colored layer. Furthermore,
When the clear layer is used in combination, it is not necessary to foam the microcapsules at the same time as or after the curing of the clear layer, so that the problem of deterioration of the obtained coating film can be solved.

[0027]

EXAMPLES The present invention will be described below in terms of its implementation.
In addition, the embodiment described below is a preferred example,
It should be understood that the present invention is not limited to these examples. Example 1 A coating film composite having a cross section shown in FIG. 9 was prepared. A product in which a release paper with an adhesive layer is laminated on the back surface of a support, Scot
chcal ^™ S / C3650 (Sumitomo 3M brand product) was prepared, and the heat-expandable layer was screen-printed in a pattern on the non-adhesive layer side. For this screen printing, polyurethane resin, FL510 (trade name, manufactured by Sumitomo 3M Limited), thermally expandable microcapsules, EXP
ANCEL (Expansel) 551DU (trade name, manufactured by Nippon Philite) is 0, 1.0, 5.0 or 10.0.
It is mixed in a weight% amount, diluted with a thinner (S / 63911, manufactured by Sumitomo 3M Limited) so that it can be subjected to silk screen printing, printed with a 270 mesh silk screen printing plate, and dried at 80 ° C. for 45 minutes. It was

After drying the heat-expandable layer, a colored layer was formed thereon. To form a colored layer, a colorant, black ink,
FL545 (trade name, manufactured by Sumitomo 3M) with a film thickness of about 5
μm, then polyurethane resin, FL510
(Trade name, manufactured by Sumitomo 3M Limited), glittering scale-like substance, aluminum powder manufactured by Toyo Aluminum Co., Ltd., Alpaste (trade name), 0215M (average particle size 8 μm), 7
680NS (average particle size 12 μm), 7640NS (average particle size 17.2 μm), MG600 (average particle size 20.5 μm)
m), MG1000 (average particle size 29.4 μm) or MG
1300 (average particle size 43.5 μm) 0.5, 1.0,
Mixtures mixed in in amounts of 2.5, 5.0 or 10.0% by weight were applied to a film thickness of about 5 μm and dried at 80 ° C. for 45 minutes.

After completion of drying, the resulting coating composite (see FIG. 9)
Reference) was heated at 120 ° C. for 4 minutes to expand the microcapsules in the expandable layer. A clear layer was then coated over the colored layer, which was partially raised as a result of the expansion of the expandable layer. For clear layer coating, clear paint, G
A-3 (trade name, manufactured by Sumitomo 3M Limited) was printed on a 270 mesh silk screen printing plate, and dried and cured at 80 ° C. for 1.5 hours. A decorative sheet having a cross section shown in FIG. 10 was obtained. Evaluation of brilliance Using the obtained decorative sheets, the brilliance of each sheet was evaluated according to the observation method shown in FIGS. 11 and 12.

Light source used: 60 W incandescent bulb Angle of incident light from the light source: 45 degrees (FIG. 11) or 90
Degree (Fig. 12) Distance from light source to sample under test (reference numeral 10 in the figure): 40 cm Viewing angle of observer (see Fig. 11 and Fig. 12): 45 ° backward with respect to incident light angle 45 ° (Arrow A), 90 degrees upward (arrow B), 45 degrees lateral (arrow C), 45 degrees forward (arrow D).

90 ° upward (arrow E) and 45 ° lateral (arrow F) with respect to the incident light angle of 90 ° Distance from sample to observer: 40 cm Prepare 6 panelists, inflated part and non-expanded part The glitter feeling of each part was visually evaluated based on the following sensitivity test criteria.

[Sensitivity Test Criteria] O ... A sensation of luster is felt regardless of the viewing angle. Δ: The brightness is uniformly felt regardless of the viewing angle, but the light brightness is weak. X: There is a remarkable difference depending on the viewing angle between where the glitter is felt and where it is not.

The results obtained are shown in Table 1 below.

[0034]

[Table 1]

From the results shown in Table 1 above, in the case of the sample in which the glittering scale-like substance (aluminum powder) used had a small average particle size, and in the case of the sample in which the thermally expandable layer was not present as the base of the colored layer, It can be seen that a uniform glittering feeling cannot be obtained. Example 2 A coating film composite and a decorative sheet were prepared according to Example 1 above. Scotchcal ^™ S / C3650 (Sumitomo 3M brand product), a product in which a release paper with an adhesive layer was laminated on the back surface of a support, was prepared, and a thermally expandable layer was screen-printed on the non-adhesive layer side in a pattern. . For this screen printing, polyurethane resin, FL510
(Product name, manufactured by Sumitomo 3M Limited), thermally expandable microcapsules, EXPANCEL 551D
U (trade name, manufactured by Nippon Philite Co., Ltd.) was mixed in an amount of 5.0% by weight, diluted with thinner (S / 63911, manufactured by Sumitomo 3M Co., Ltd.) to an extent suitable for silk screen printing, and then a 270 mesh silk screen. It was printed on a printing plate and dried at 80 ° C. for 45 minutes.

After drying the heat-expandable layer, a colored layer was formed thereon. To form a colored layer, a colorant, black ink,
FL545 (trade name, manufactured by Sumitomo 3M) with a film thickness of about 5
μm, then polyurethane resin, FL510
(Trade name, manufactured by Sumitomo 3M Co., Ltd.), glittering flaky substances, aluminum powder manufactured by Toyo Aluminum Co., Ltd., Alpaste (trade name), 0215M (average particle size 8 μm), or pearl pigment manufactured by Marl Co., Ltd. Brand name), HI-LIGHT GREEN (average particle size 6-
48 μm), FINE BLUE (average particle size 4 to 32 μm
m), RUSSET (average particle size 6 to 48 μm), BRI
GHT SILVER (average particle size 8 to 48 μm) or B
RIGHT GOLD (average particle size 8-48 μm) 15
Apply the mixture mixed in the amount of wt% to a film thickness of about 5 μm,
It was dried at 80 ° C. for 45 minutes.

After completion of the drying, the resulting coating film composite was treated with 12
The microcapsules in the expandable layer were expanded by heating at 0 ° C for 4 minutes. A clear layer was then coated over the colored layer, which was partially raised as a result of the expansion of the expandable layer. For coating the clear layer, a clear paint, GA-3 (trade name, manufactured by Sumitomo 3M Limited) was printed on a 270 mesh silk screen printing plate, and dried and cured at 80 ° C. for 1.5 hours. The intended decorative sheet was obtained.

Evaluation of Brightness Using the obtained decorative sheet, the bright feeling of each sheet was evaluated according to the method described in Example 1 above. In this example, six panelists were prepared, and the glitter feelings of the expanded portion and the non-expanded portion were visually evaluated based on the following sensitivity test criteria.

[Sensitivity Test Criteria] A point system of 1 to 5 was adopted. 1 ... No glitter. 2 ... I feel a little glitter. 3 ... I feel a sense of radiance normally. 4 ... Slightly bright feeling. 5: I feel a very strong radiance. The results obtained are shown in Table 2 below. The numerical values shown in the table are average values obtained from the total points.

[0040]

[Table 2]

Next, the brightness average value at each evaluation site is obtained from the data in Table 2 (see Table 3 below), and the light brightness rate (%) for each viewing angle is based on the average value. Was determined for each of the expanded part and the non-expanded part. The results shown in Table 3 below were obtained.

[0042]

[Table 3]

In the column of "Judgment" in Table 3 above, since the average value of brilliance is 2.0 or more and the brilliance is uniform regardless of the viewing angle, the brilliance at each viewing angle is Those in the range of 70 to 130% of the average feeling value were judged to have a uniform glittering feeling, and were evaluated as OK (OK). That is, NG in the “determination” column means “not possible”.

From the results shown in Table 3 above, in the case of the sample having a small average particle size of the glittering scale-like substance (aluminum powder or pearl pigment) used, and the sample having no thermally expansive layer as the base of the colored layer In the case of, it can be seen that a uniform glittering feeling cannot be obtained.

[0045]

As described above, according to the present invention,
Since the colored layer is lifted by the underlying thermal expansion layer, the orientation of the brilliant scale-like substance contained in the colored layer changes, and a brilliant feeling is uniformly produced regardless of the angle of incident light and the diopter during observation. You will get it. Also, by functionally separating the decorative coating film into two layers, a thermal expansion layer and a colored layer, it is possible to maintain a uniform coating color even if the coating film is a thin film with a thickness of 50 μm or less. It is also possible to prevent the disadvantage that the microcapsules project from the colored layer. Furthermore, when the heat-expandable layer on the support is provided in a pattern, different glittering feelings can be obtained in the foamed portion and the non-foamed portion of the capsule due to the glittering scale-like substance in the colored layer. Furthermore, when the clear layer is used in combination, it is not necessary to foam the microcapsules at the same time as or after the curing of the clear layer, so that the problem of deterioration of the obtained coating film can be solved.

[Brief description of drawings]

1A to 1C are cross-sectional views sequentially showing a manufacturing process of a pattern print leather by a conventional method.

2A to 2D are cross-sectional views sequentially showing a manufacturing process of a coating film with an uneven pattern by a conventional method.

FIG. 3 is a cross-sectional view showing a drawback of using microcapsules in a conventional method.

FIG. 4 is a cross-sectional view showing a structure of a light-reflecting screen printed matter according to a conventional method.

FIG. 5 is a sectional view showing a preferred example of a coating film composite according to the present invention.

FIG. 6 is a sectional view showing another preferred example of the coating film composite according to the present invention.

FIG. 7 is a sectional view showing a preferred example of the decorative sheet according to the present invention.

FIG. 8 is a sectional view showing another preferable example of the decorative sheet according to the present invention.

FIG. 9 is a cross-sectional view showing another preferable example of the coating film composite according to the present invention.

FIG. 10 is a sectional view showing another preferable example of the decorative sheet according to the present invention.

FIG. 11 is a perspective view showing a first method of visually evaluating a glitter feeling.

FIG. 12 is a perspective view showing a second method for visually evaluating a glitter feeling.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Support body 2 ... Thermal expansion layer 3 ... Thermal expansion microcapsule 4 ... Coloring layer 5 ... Clear layer 10 ... Decorative sheet 102 ... Thermal expansion layer 103 ... Thermal expansion microcapsule

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 7/12 PSJ C09D 7/12 PSJ

Claims (10)

[Claims] 1. A heat-expandable layer containing a thermoplastic resin and heat-expandable microcapsules dispersed in the resin,
Average particle size of 12 to 250 μm applied on the heat-expandable layer
And a colored layer containing a glittering scale-like substance,
Coating composite. 2. The thermally expandable microcapsules are contained in the thermoplastic resin in an amount of 1 per 100 parts by weight of the thermoplastic resin.
Dispersed in the range of ˜40 parts by weight.
The coating film composite as described in 1. 3. The coating film composite according to claim 1, wherein the glittering scale-like substance is dispersed in the colored layer in an amount of 0.5 to 20% by weight. 4. The glittering scale-like substance is a member selected from the group consisting of aluminum powder, iron oxide powder, metal vapor-deposited glass flakes and pearl pigments. Coating complex. 5. Formed as a result of heat treatment from a support and a thermally expandable layer comprising a thermoplastic resin and thermally expandable microcapsules dispersed in the resin, sequentially laminated on the support. A decorative sheet comprising the thermal expansion layer having a film thickness increased from the film thickness before the heat treatment, and the colored layer containing a bright scale-like substance having an average particle diameter of 12 to 250 μm. 6. The thermoexpandable microcapsule is contained in the thermoplastic resin in an amount of 1 per 100 parts by weight of the thermoplastic resin.
6. Dispersed in the range of about 40 parts by weight.
The decorative sheet described in. 7. The decorative sheet according to claim 5, wherein the glittering scale-like substance is dispersed in the colored layer in an amount of 0.5 to 20% by weight. 8. The glittering scale-like substance is a member selected from the group consisting of aluminum powder, iron oxide powder, metal vapor-deposited glass flakes and pearl pigments. Decorative sheet. 9. The decorative sheet according to claim 5, wherein the thermal expansion layer is laminated on at least a part of the surface of the support. 10. The decorative sheet according to claim 5, wherein a clear layer made of a thermosetting resin is further laminated on the colored layer.