U.S. patent application number 12/530805 was filed with the patent office on 2011-03-03 for shaping sheet, resin decorative plate and method for manufacturing the same.
This patent application is currently assigned to DAI NIIPPON PRINTING CO., LTD.. Invention is credited to Takashi Iizuka, Seiichi Ishida, Kenichi Tachihara.
Application Number | 20110052880 12/530805 |
Document ID | / |
Family ID | 39759576 |
Filed Date | 2011-03-03 |
United States Patent
Application |
20110052880 |
Kind Code |
A1 |
Iizuka; Takashi ; et
al. |
March 3, 2011 |
SHAPING SHEET, RESIN DECORATIVE PLATE AND METHOD FOR MANUFACTURING
THE SAME
Abstract
A shaping sheet which has a delicate and daring concave-convex
shape, is capable of realizing minute shaping with excellent design
and touch feeling and having an air of luxuriousness and is
excellent in release properties; a resin decorative plate obtained
by using the shaping sheet; and a method for manufacturing a resin
decorative plate capable of shaping a body to be shaped using the
shaping sheet are provided. The shaping sheet is a sheet including
a base material having thereon at least an ink layer provided
partially or entirely and a surface shaping layer existing on the
ink layer, coming into contact therewith and covering over the
whole surface including a region where the ink layer is formed and
a region where the ink layer is not formed, wherein the surface
shaping layer is a layer obtained through crosslinking and curing
of a curable resin composition, and in the surface shaping layer,
the surface of the surface shaping layer which is located just
above the ink layer and in an upper part in the vicinity thereof
has a convex shape and further has a concave pattern.
Inventors: |
Iizuka; Takashi; (Saitama,
JP) ; Tachihara; Kenichi; (Chiba, JP) ;
Ishida; Seiichi; (Saitama, JP) |
Assignee: |
DAI NIIPPON PRINTING CO.,
LTD.
Shinjuku-ku
JP
|
Family ID: |
39759576 |
Appl. No.: |
12/530805 |
Filed: |
March 13, 2008 |
PCT Filed: |
March 13, 2008 |
PCT NO: |
PCT/JP2008/054627 |
371 Date: |
September 11, 2009 |
Current U.S.
Class: |
428/172 ;
264/132 |
Current CPC
Class: |
B30B 15/06 20130101;
B32B 5/024 20130101; B32B 27/306 20130101; B32B 23/08 20130101;
B32B 2262/106 20130101; B32B 27/20 20130101; B32B 2255/12 20130101;
B32B 2307/538 20130101; B32B 2270/00 20130101; B32B 27/10 20130101;
B32B 27/38 20130101; B32B 37/12 20130101; B32B 2274/00 20130101;
B32B 23/20 20130101; B32B 27/40 20130101; B44C 5/0469 20130101;
B32B 27/18 20130101; B32B 2262/0246 20130101; B32B 2307/75
20130101; B32B 3/28 20130101; B32B 2255/10 20130101; B32B 2262/0276
20130101; B44C 1/24 20130101; E04F 13/08 20130101; E04F 15/02
20130101; B32B 27/34 20130101; B32B 3/263 20130101; B32B 2260/046
20130101; B32B 27/22 20130101; Y10T 428/24612 20150115; B32B 7/12
20130101; B32B 2419/00 20130101; B32B 27/308 20130101; B32B
2262/101 20130101; B32B 27/302 20130101; B32B 27/304 20130101; B32B
27/32 20130101; B29C 59/04 20130101; B32B 27/12 20130101; B32B
27/365 20130101; B32B 38/00 20130101; B32B 2260/028 20130101; B32B
2479/00 20130101; B32B 2451/00 20130101; B32B 7/05 20190101; B32B
38/145 20130101; B32B 2255/26 20130101; B32B 2605/00 20130101; B32B
7/06 20130101; B32B 27/36 20130101; B32B 2264/02 20130101; B32B
27/283 20130101; B32B 27/281 20130101; B32B 2262/0261 20130101;
B32B 2262/10 20130101; B32B 2307/4026 20130101; B32B 5/022
20130101; B32B 5/145 20130101; B32B 27/42 20130101; B32B 3/30
20130101; B32B 2264/10 20130101; B32B 38/06 20130101; B32B 2307/306
20130101; B29C 59/02 20130101; B32B 27/08 20130101; B32B 27/16
20130101 |
Class at
Publication: |
428/172 ;
264/132 |
International
Class: |
B32B 3/10 20060101
B32B003/10; B29C 41/22 20060101 B29C041/22 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 14, 2007 |
JP |
2007-064861 |
Claims
1. A shaping sheet comprising a base material having thereon at
least a partially or entirely provided ink layer and a surface
shaping layer existing on the ink layer, coming into contact
therewith and covering over the whole surface including a region
where the ink layer is formed and a region where the ink layer is
not formed, wherein the surface shaping layer is a layer obtained
through crosslinking and curing of a curable resin composition, and
in the surface shaping layer, the surface of the surface shaping
layer which is located just above the ink layer and in an upper
part in the vicinity thereof has a convex shape and additionally
has a concave pattern.
2. The shaping sheet according to claim 1, wherein the surface
shaping layer contains a fine particle, and an average particle
size of the fine particle is a neighborhood value on a plus side of
a maximum thickness of the surface shaping layer which is located
just above the foregoing ink layer.
3. The shaping sheet according to claim 1, wherein the curable
resin composition is an ionizing radiation curable resin
composition.
4. The shaping sheet according to claim 3, wherein the ionizing
radiation curable resin composition is an electron beam curable
resin composition.
5. The shaping sheet according to claim 3, wherein an ink
constituting the ink layer contains a non-crosslinking urethane
resin as a binder, and the ionizing radiation curable resin
composition contains a (meth)acrylate monomer.
6. The shaping sheet according to claim 5, wherein the ink
constituting the ink layer contains a non-crosslinking urethane
resin and an unsaturated polyester resin as a binder.
7. A resin decorative plate prepared by laminating an adhesive
layer and a decorative sheet layer in this order on an upper
surface of a substrate, coating a resin composition on the
decorative sheet layer, subsequently bringing a shaping sheet into
contact therewith and integrally curing and then peeling the
shaping sheet to form a resin layer, wherein the shaping sheet is
the shaping sheet according to claim 1.
8. The resin decorative plate according to claim 7, wherein a resin
in the resin composition is an unsaturated polyester resin.
9. A resin decorative plate comprising a substrate having a resin
decorative sheet stuck thereto via an adhesive layer, said
decorative sheet prepared by inserting the shaping sheet according
to claim 1 between a molded article to be press molded between hot
press plates and a press plate and molding and then peeling the
shaping sheet.
10. The resin decorative plate according to claim 9, wherein the
resin decorative sheet is a melamine resin decorative plate.
11. The resin decorative plate according to claim 9, wherein the
resin decorative sheet is a diallyl phthalate (DAP) resin
decorative plate.
12. A method for manufacturing a resin decorative plate comprising
laminating an adhesive layer and a decorative sheet layer in this
order on an upper surface of a substrate, coating a resin
composition on the decorative sheet layer, subsequently bringing
the shaping sheet according to claim 1 into contact therewith and
integrally curing and then peeling the shaping sheet to form a
resin layer.
13. A method for manufacturing a resin decorative plate comprising
sticking onto a substrate via an adhesive layer a resin decorative
sheet prepared by inserting the shaping sheet according to claim 1
between a molded article to be press molded between hot press
plates and a press plate and molding and then peeling the shaping
sheet.
Description
TECHNICAL FIELD
[0001] The present invention relates to a shaping sheet, a resin
decorative plate obtained by using the shaping sheet and a method
for manufacturing a resin decorative plate using the shaping
sheet.
BACKGROUND ART
[0002] As building materials which are used as housing instruments
and interior materials, for example, furniture, desk tops, various
counters, doors, etc., there are in general widely used decorative
plates obtained by shaping a synthetic resin based material, for
example, thermosetting resin decorative plates, e.g., melamine
resin decorative plates, etc.
[0003] Hitherto, a thermosetting resin decorative plate having a
concave-convex shape on the surface thereof includes one obtained
by forming a concave-convex shape by an embossing die or a resin
concave-convex sheet and one obtained by forming a concave-convex
shape by a shaping sheet. However, when an embossing die having a
concave-convex shape formed thereon is used, since it is necessary
to subject the die to a surface treatment by blasting, etching,
etc., there are generated limitations in minuteness of a
concave-convex shape and a pattern. Furthermore, at the time of
manufacturing a thermosetting resin decorative plate, an expensive
template and a reserve template are necessary, and time and a load
of expenses for the preparation of a decorative plate increase, and
therefore, the manufacturing cost largely increases, resulting in
rendering a product expensive. Also, in case of a resin
concave-convex sheet, since a thermosetting resin decorative plate
is hardly peeled after the resin has been cured, it is necessary to
interpose an aluminum foil, a polypropylene film, etc. in a space
with a template, it is very difficult to sharply form a minute
concave-convex pattern.
[0004] Meanwhile, in recent years, according to the consumer's
orientation toward quality goods, an air of luxuriousness is also
required for furniture, desks, interior materials, etc., and those
having an appearance capable of giving an air of luxuriousness are
also desired in decorative plates to be used therefor. For that
reason, it is important to impart a texture, and various methods
for imparting a delicate concave-convex shape to a decorative plate
are proposed.
[0005] For example, there is proposed a shaping sheet having a
concave-convex shape with an ionizing radiation curable resin
provided on the surface of a base material sheet, which is able to
faithfully reproduce a desired pattern shape by providing a
crosslinking density such that when the shaping sheet is peeled,
the concave-convex shape is not broken, and which can be repeatedly
used (see Patent Document 1, claim 1). However, in preparing a
shaping sheet, a step of peeling it from a roll concave plate is
mediated, and therefore, when the concave part is thin, there is a
limitation in expressing the concave-convex shape. Also, according
to this method, when the concave part is thin, there is involved a
problem that unevenness does not clearly appear; whereas when the
concave part is thick to some extent, though a concave-convex
pattern is obtained on the base material surface, a convex part of
a height of the raised part or more is generated, and for example,
in case of a woodgrain pattern, there are involved problems that no
realist feeling is present and that appearance and touch feeling
are poor.
[0006] Furthermore, there is proposed a shaping sheet in which a
concave-convex layer is formed on the surface of a base material
sheet using a resin composition composed of an inorganic filler and
a binder resin, and only the resin composition for forming a fine
concave-convex layer which is coated on a design pattern formed of
a liquid-repellent resin is repelled to form the concave-convex
layer (see Patent Document 2, claims). However, there are involved
problems that since the concave-convex layer is formed by repelling
the resin composition for forming a concave-convex layer, the
design by a concave-convex shape is lacking in stability and that
since aging of a certain period of time is required for curing the
concave-convex layer, it takes a very long time to prepare the
shaping sheet so that it is impossible to rapidly respond to
diversified needs of consumers.
[0007] [Patent Document 1] JP-A-7-164519
[0008] [Patent Document 2] JP-A-5-92484
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] [FIG. 1] is a schematic view showing a section of a shaping
sheet of the present invention.
[0010] [FIG. 2] is a schematic view showing a section of a shaping
sheet of the present invention.
[0011] [FIG. 3] is a schematic view showing a section of a shaping
sheet of the present invention.
[0012] [FIG. 4] is a schematic view showing a section of a shaping
sheet of the present invention.
[0013] [FIG. 5] is a schematic view showing a section of a shaping
sheet of the present invention.
[0014] [FIG. 6] is a schematic view showing a section of a shaping
sheet of the present invention.
[0015] [FIG. 7] is a schematic view showing a section of a shaping
sheet of the present invention.
[0016] [FIG. 8] is a schematic view showing a section of a shaping
sheet of the present invention.
[0017] [FIG. 9] is a schematic view showing a section of a shaping
sheet of the present invention.
[0018] [FIG. 10] is a schematic view showing a section of a resin
decorative plate of the present invention.
[0019] [FIG. 11] is a schematic view showing a peeling process of a
shaping sheet of the present invention.
[0020] [FIG. 12] is a schematic view showing a section of a resin
decorative plate of the present invention.
DESCRIPTION OF REFERENCE NUMERALS AND SIGNS
[0021] 1: Shaping sheet
[0022] 2: Base material
[0023] 3: Ink layer
[0024] 3-a: Ink
[0025] 3-b: Ink
[0026] 3-c: Ink
[0027] 4: Interacting region
[0028] 4-a: Interacting region
[0029] 4-b: Interacting region
[0030] 4-c: Interacting region
[0031] 5: Surface shaping layer
[0032] 6: Penetration preventing layer
[0033] 7: Raised shape
[0034] 7-a: Raised shape
[0035] 7-b: Raised shape
[0036] 7-c: Raised shape
[0037] 8: Fine particle or baked kaolin particle
[0038] 8-a: Fine particle or baked kaolin particle
[0039] 8-b: Fine particle or baked kaolin particle
[0040] 9: Adhesive layer
[0041] 10: Substrate
[0042] 11: Resin decorative plate
[0043] 12: Fine raised shape
[0044] 13: Fine concave-convex surface
[0045] 14: Concave pattern
[0046] 15: Resin decorative sheet
[0047] 17: Decorative sheet layer
[0048] 17-a: Sheet layer
[0049] 17-b: Solid printing layer
[0050] 17-c: Design layer
[0051] 18: Resin layer
DISCLOSURE OF THE INVENTION
Problems that the Invention is to Solve
[0052] Under these circumstances, an object of the present
invention is to provide a shaping sheet which has a delicate and
daring concave-convex shape, is capable of realizing minute shaping
with excellent design and touch feeling and having an air of
luxuriousness and is excellent in release properties; a resin
decorative plate obtained by using the shaping sheet; and a method
for manufacturing a resin decorative plate using the shaping
sheet.
Means for Solving the Problems
[0053] In order to attain the foregoing object, the present
inventors made extensive and intensive investigations. As a result,
it has been found that a shaping sheet including an ink layer and a
surface shaping layer on a base material and further having a
concave-convex shape on the surface shaping layer upon application
with a concave pattern is able to solve the foregoing problems. The
present invention has been accomplished on the basis of such
knowledge.
[0054] That is, the present invention provides:
[0055] (1) A shaping sheet comprising a base material having
thereon at least an ink layer provided partially or entirely and a
surface shaping layer existing on the ink layer, coming into
contact therewith and covering over the whole surface including a
region where the ink layer is formed and a region where the ink
layer is not formed, wherein the surface shaping layer is a layer
obtained through crosslinking and curing of a curable resin
composition, and in the surface shaping layer, the surface of the
surface shaping layer which is located just above the ink layer and
in an upper part in the vicinity thereof has a convex shape and
further has a concave pattern;
[0056] (2) A resin decorative plate prepared by laminating an
adhesive layer and a decorative sheet layer in this order on an
upper surface of a substrate, coating a resin composition on the
decorative sheet layer, subsequently bringing a shaping sheet into
contact therewith and integrally curing and then peeling the
shaping sheet to form a resin layer, wherein the shaping sheet is
the shaping sheet as set forth above in (1); and
[0057] (3) A method for manufacturing a resin decorative plate
comprising laminating an adhesive layer and a decorative sheet
layer in this order on an upper surface of a substrate, coating a
resin composition on the decorative sheet layer, subsequently
bringing the shaping sheet as set forth above in (1) into contact
therewith and integrally curing and then peeling the shaping sheet
to form a resin layer.
Advantages of the Invention
[0058] According to the present invention, a shaping sheet which
has a delicate and daring concave-convex shape, is capable of
realizing minute shaping with excellent design and touch feeling
and having an air of luxuriousness and is excellent in release
properties; a resin decorative plate obtained by using the shaping
sheet; and a method for manufacturing a resin decorative plate
using the shaping sheet can be obtained. In particular, when used
for a delicate pattern such as a woodgrain pattern, a
concave-convex feeling of a vessel portion can be realistically
expressed, and a shaped decorative material is able to obtain the
same texture as in a material using an actual wood.
BEST MODES FOR CARRYING OUT THE INVENTION
[0059] The shaping sheet of the present invention comprises a base
material having thereon at least an ink layer provided partially or
entirely and a surface shaping layer existing on the ink layer,
coming into contact therewith and covering over the whole surface
including a region where the ink layer is formed and a region where
the ink layer is not formed, wherein the surface shaping layer is a
layer obtained through crosslinking and curing of a curable resin
composition, and in the surface shaping layer, the surface of the
surface shaping layer which is located just above the ink layer and
in an upper part in the vicinity thereof has a convex shape and
further has a concave pattern.
[0060] A structure of the shaping sheet of the present invention is
described with reference to FIGS. 1 to 7. FIGS. 1 to 7 are each a
schematic view showing a section of a shaping sheet 1 of the
present invention. An example shown in FIG. 1 is concerned with one
in which a penetration preventing layer 6 for covering evenly and
uniformly the whole surface, an ink layer 3 and a surface shaping
layer 5 obtained through crosslinking and curing of a curable resin
composition are laminated in this order on a base material 2, and a
fine concave-convex surface 13 is provided on the surface of the
surface shaping layer 5. The ink layer 3 is partially present, and
an interacting region 4 is formed on the surface shaping layer just
above the ink layer 3 and in the vicinity thereof. The interacting
region 4 is expressed by collection of dots in the drawing.
[0061] An upper part of the interacting region 4 in the uppermost
surface of the surface shaping layer 5 has a raised shape 7 which
has raised up with the formation of the ink layer 3. Furthermore, a
shaping sheet having a concave-convex shape as a whole and further
having a delicate and daring concave-convex shape is formed due to
a synergistic effect to be brought by applying a concave pattern 14
by embossing. Furthermore, as shown in FIG. 3, by changing a
thickness of the ink layer 3 to reveal the raised shape 7 on the
surface of the surface shaping layer 5 depending upon the
thickness, a more abundant concave-convex shape can be
imparted.
[0062] The degree of a spread of the interacting region 4 which is
formed in the surface shaping layer 5 is not particularly limited
so far as the effects of the present invention are brought, and as
shown in FIG. 1 or 2, the interacting region 4 may remain on the
way in the thickness direction from the surface of the ink layer 3
to the surface shaping layer 5, or may reach the uppermost surface
of the surface shaping layer 5.
[0063] Also, as shown in FIG. 4, a fine raised shape 12 which is
revealed by applying a fine particle or baked kaolin particle 8 to
the surface shaping layer 5 gives a partially fine raised shape to
the raised shape 7 and the fine concave-convex surface 13 which are
revealed over the whole of the surface of the surface shaping layer
5.
[0064] A shaping sheet having a delicate and daring convex shape
and capable of realizing minute shaping with excellent design and
touch feeling and having an air of luxuriousness is obtained by
effects of the fine concave-convex surface 13 to be brought due to
the interacting region 4 in this surface shaping layer 5, effects
of the fine raised shape 12 to be brought due to raising of the
fine particle on the surface of the surface shaping layer 5,
effects of the ink layer 3 and the raised shape 7 formed depending
upon its thickness and the concave pattern 14 to be applied by
embossing.
[0065] As shown in FIG. 5, when the ink layer 3 is provided over
the whole surface, the fine concave-convex surface and the concave
pattern 14 due to the fine concave-convex surface 13 are present on
the uppermost surface of the surface shaping layer 5, and
therefore, when this is used as the shaping sheet, a resin
decorative plate which is excellent in a touch feeling nevertheless
it is a matte can be obtained on the surface of a decorative plate
to be shaped. Even in that case, the facts that by changing a
thickness of the ink layer 3 as shown in FIG. 7, the raised shape 7
is obtained depending upon the ink thickness and that by adding the
fine particle or baked kaolin particle 8 to the surface shaping
layer 5 as shown in FIGS. 6 and 7, the fine raised shape 12 is
obtained are the same as those when the foregoing ink layer 3 is
partially provided. Also, the degree of a spread of the interacting
region 4 which is formed in the surface shaping layer 5 is the same
as that described previously and is not particularly limited so far
as the effects of the present invention are brought. The
interacting region 4 may remain on the way in the thickness
direction from the surface of the ink layer 3 to the surface
shaping layer 5, or may reach the uppermost surface of the surface
shaping layer 5.
[0066] Next, the respective layers configuring the shaping sheet of
the present invention are described in detail.
[Base Material 2]
[0067] The base material 2 which is used in the present invention
is not particularly limited so far as it is one used as a base
material for usual shaping sheets and can be subjected to
embossing, and various papers, plastic films, plastic sheets and
the like can be properly chosen depending upon applications. Though
these materials may be each used singly, laminates composed of an
arbitrary combination, for example, composites of papers each
other, composites of paper and a plastic film, etc. may be
used.
[0068] When such a base material, in particular a plastic film or a
plastic sheet is used as the base material, for the purpose of
enhancing adhesion to the layer to be provided thereon, a physical
or chemical surface treatment, for example, an oxidation process, a
roughening process, etc. can be applied to one surface or the both
surfaces thereof, if desired. Examples of the foregoing oxidation
process include, a corona discharge treatment, a chromium oxidation
treatment, a flame treatment, a hot air treatment, an
ozone/ultraviolet ray treatment process and the like; and examples
of the roughening process include a sand blast process, a solvent
treatment process and the like. Though such a surface treatment is
properly chosen depending upon the kind of the base material, in
general, a corona discharge treatment process is preferably adopted
from the standpoints of effects, workability and the like.
[0069] Also, the base material may be subjected to a treatment such
as formation of a primer layer, etc. for the purpose of
strengthening interlayer adhesion between the base material and
each layer.
[0070] As various papers which are used as the base material,
tissue papers, kraft papers, titanium papers and the like can be
used. These paper base materials may be one obtained by further
adding a resin such as acrylic resins, styrene-butadiene rubbers,
melamine resins, urethane resins and the like to such a paper base
material (resin impregnation after paper-making or internal
addition at the time of paper-making) for the purposes of enhancing
an interlayer strength between fibers of the paper base material or
between other layer and the paper base material and preventing
formation of fuzz. Examples thereof include interlayer reinforced
papers, rein-impregnated papers and the like.
[0071] In addition to the foregoing, various papers which are
frequently used in the building material field, such as linter
papers, paper boards, base papers for gypsum boards, raw fabrics
for vinyl wall papers in which a vinyl chloride resin layer is
provided on the surface of paper, etc. are exemplified.
Furthermore, coated papers, art papers, sulfate papers, glassine
papers, parchment papers, paraffin papers and Japanese papers,
which are used in the business field and usual printing or
packaging, etc., can also be used. Also, woven fabrics and
non-woven fabrics of various fibers which have an appearance and
properties similar to those of papers, though distinguished from
these papers, can be used as the base material. Examples of the
various fibers include inorganic fibers such as glass fibers,
asbestos fibers, potassium titanate fibers, alumina fibers, silica
fibers, carbon fibers and the like; and synthetic resin fibers such
as polyester fibers, acrylic fibers, vinylon fibers and the
like.
[0072] Examples of the plastic film or plastic sheet include
various films or sheets composed of a synthetic resin of every
sort. Examples of the synthetic resin include polyolefin resins,
for example, low density polyethylene resins (inclusive of linear
low density polyethylene resins), medium density polyethylene
resins, high density polyethylene resins, ethylene-.alpha.-olefin
copolymers, polypropylene resins, polymethylpentene resins,
polybutene resins, ethylene-propylene copolymers, propylene-butene
copolymers, olefin based thermoplastic elastomers, mixtures
thereof, etc.; vinyl based resins, for example, polyvinyl chloride
resins, polyvinylidene chloride resins, polyvinyl alcohol resins,
vinyl chloride-vinyl acetate copolymer resins, ethylene-vinyl
acetate copolymer resins, ethylene-vinyl alcohol copolymer resins,
mixtures thereof, etc.; polyester resins, for example, polyethylene
terephthalate resins, polybutylene terephthalate resins,
polyethylene naphthalate-isophthalate copolymer resins, polyester
based thermoplastic elastomers, etc.; acrylic resins, for example,
polymethyl(meth)acrylate resins, polyethyl(meth)acrylate resins,
polybutyl(meth)acrylate resins, etc.; polyamide resins represented
by nylon 6, nylon 66, etc.; cellulose based resins, for example,
cellulose triacetate resins, cellophane, etc.; polystyrene resins;
polycarbonate resins; polyallylate resins; polyimide resins; and
the like.
[0073] As the base material 2, plastic films or plastic sheets are
preferable, and these materials can be used singly or in admixture
of two or more kinds thereof. Of these, taking into account the
fact that no poisonous gas is generated at the time of burning and
costs, polyolefin resins are especially preferable.
[0074] A thickness of the base material 2 is not particularly
limited. When a sheet composed of a plastic as a raw material is
used, its thickness is in general in the range of from about 40 to
500 .mu.m, preferably from 20 to 150 .mu.m, and more preferably
from 30 to 100 .mu.m; and when a paper base material is used, its
basis weight is in general in the range of from about 20 to 150
g/m.sup.2, and preferably from 30 to 100 g/m.sup.2.
[Penetration Preventing Layer 6]
[0075] The penetration preventing layer 6 is a layer which is
provided, if desired and has a function of inhibiting an ink
constituting the ink layer 3 as described later and a curable resin
constituting the surface shaping layer 5 from penetration into the
base material 2, and it displays an effect particularly when the
base material 2 is a penetrative base material such as papers,
non-woven fabrics, etc. Accordingly, the penetration preventing
layer 6 may be located between the base material 2 and the ink
layer 3. In general, an even and uniform layer obtained through
crosslinking and curing of a curable resin having adhesion to the
curable resin constituting the surface shaping layer 5 is provided
between the base material 2 and the ink layer 3 as shown in FIG. 1.
According to this, the penetration preventing layer 6 also has a
function to enhance adhesiveness of the base material 2 to the ink
layer 3 and the surface shaping layer 5.
[Ink Layer 3]
[0076] The ink layer 3 in the shaping sheet of the present
invention is a layer which is laminated on the penetration
preventing layer 6 to be provided, if desired as shown in FIG. 1
and which produces the raised shape 7 and the fine concave-convex
surface 13 on the surface of the surface shaping layer 5.
[0077] The mechanism in which the fine concave-convex surface 13 is
produced on the surface of the surface shaping layer 5 has not been
sufficiently elucidated yet. However, from various experiments and
results of observation and measurement, it may be estimated that in
coating an uncured material of the curable resin composition for
forming the surface shaping layer 5 on the surface of the ink layer
3, the resin component of the ink layer 3 and the surface shaping
layer reveal an interaction such as partial elution, dispersion,
mixing, etc. by properly choosing a combination of respective
materials and a coating condition. On that occasion, it may be
considered that the respective resin components in the ink of the
ink layer 3 and the uncured material of the curable resin
composition do not become in a completely compatible state within a
short period of time but become in a suspended state to exist just
above the ink layer 3 and in the vicinity thereof, and a portion
which has become in the suspended state forms an interacting region
and reveals the fine concave-convex surface 13. It may be estimated
that when the surface shaping layer is crosslinked and cured while
keeping this suspended state, thereby fixing such a state, the
interacting region 4 is partially formed in the surface shaping
layer, thereby forming the fine concave-convex surface 13.
[0078] The ink for forming the ink layer 3 has properties capable
of revealing an interaction such as elution, dispersion, mixing,
etc. relative to the curable resin composition for forming the
surface shaping layer 5 and is properly chosen in relation with the
curable resin composition (uncured material). Specifically, the ink
is preferably an ink containing a non-crosslinking resin as a
binder resin, and for example, a thermoplastic (non-crosslinking)
urethane resin, etc. is suitable. Here, from the viewpoints of
making an interaction with the curable resin composition for
forming the surface shaping layer 5 stronger and obtaining a
further pattern concave-convex feeling, it is more preferable that
a content of the urethane resin is 50% by mass or more.
[0079] As the foregoing urethane resin, it is preferred to choose a
non-crosslinking type urethane resin, namely a thermoplastic resin
which is not one having a network three-dimensional molecular
structure upon being three-dimensionally crosslinked but one having
a linear molecular structure. Examples of such a crosslinking type
urethane resin include urethane resins obtained by a reaction
between, as a polyol component, a polyol such as acrylic polyols,
polyester polyols, polyether polyols, etc.; and, as an isocyanate
component, an isocyanate, for example, an aromatic isocyanate such
as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane
diisocyanate, etc., an aliphatic or alicyclic isocyanate such as
isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated
tolylene diisocyanate, etc., or the like. In general, the number of
hydroxyl groups in one molecule of the polyol and the number of
isocyanate groups in one molecule of the isocyanate are 2 in
average, respectively. Also, an average molecular weight of the
urethane resin is from about 10,000 to 50,000, and one having a
glass transition temperature (Tg) of from -70 to -40.degree. C. is
preferable for the purpose of revealing an interacting region.
[0080] Also, if desired, for the purpose of regulating the degree
of revealing an interacting region, namely the degree of the fine
concave-convex surface 13, a saturated or unsaturated polyester
resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer
or the like can be mixed. Of these, a polyester resin is
preferable, and an unsaturated polyester resin is especially
preferable. The addition amount of the unsaturated polyester resin
is preferably in the range of from 10 to 50% by mass relative to
the whole amount of the binder of the ink. When the addition amount
of the unsaturated polyester resin falls within this range, a
sufficient reinforcing effect for revealing an interacting region
is obtained. The unsaturated polyester resin is not particularly
limited so far as it is a reaction product between an unsaturated
dicarboxylic acid and a glycol. Examples of the unsaturated
dicarboxylic acid include maleic acid, fumaric acid, itaconic acid
and the like; and examples of the glycol include ethylene glycol,
diethylene glycol, propylene glycol, butylene glycol and the
like.
[0081] It is preferred to incorporate an extender pigment into the
ink composition for forming the ink layer 3. By incorporating an
extender pigment into the ink composition, thixotropy can be
imparted thereto, and in printing the ink layer 3 using a plate,
the shape of the ink composition is kept. According to this,
sharpness of the concave-convex shape in an end at which the convex
part transfers into the concave part can be emphasized, and it is
possible to express a modulated design.
[0082] The extender pigment which is used in the present invention
is not particularly limited and is properly chosen among, for
example, silica, talc, clay, barium sulfate, barium carbonate,
calcium sulfate, calcium carbonate, magnesium carbonate and the
like. Of these, silica which is a material having a high degree of
freedom of material design in oil absorbency, particle size, pore
volume, etc. and having excellent design properties, whiteness and
coating stability as an ink is preferable, and finely powdered
silica is especially preferable. A particle size of silica is
preferably in the range of from 0.1 to 5 .mu.m. When the particle
size of silica is 0.1 .mu.m or more, in adding to the ink, the
thixotropy of the ink does not become extremely high, and the
viscosity of the ink does not excessively increase, and therefore,
printing is easily controllable. In other words, the raised shape
is easily controlled. Also, in preparing a woodgrain pattern, when
it is intended to express a vessel pattern portion, a coating
thickness of the ink of the vessel pattern portion is usually not
more than 5 .mu.m. When the particle size of silica is smaller than
the coating thickness, the raising of the particle is relatively
suppressed and is not conspicuous, and therefore, the state of
revealing an interacting region becomes natural. Thus, an
uncomfortable feeling of the raised shape is hardly produced, and
natural finish is attained.
[0083] A content of such an extender pigment in the ink composition
is preferably in the range of from 5 to 15% by mass. When the
content of the extender pigment is 5% by mass or more, sufficient
thixotropy can be imparted to the ink composition, whereas when it
is not more than 15% by mass, a lowering of the effect for
imparting revealment of the raised shape 7 and the fine
concave-convex surface 13 is not observed at all, and therefore,
such is preferable.
[0084] A coating amount of the ink for forming the ink layer 3 is
preferably in the range of from 1 to 50 g/m.sup.2. When the coating
amount of the ink is 1 g/m.sup.2 or more, an interaction between
the foregoing ink and the resin composition takes place to obtain a
sufficient interacting region, and therefore, a sufficient
concave-convex shape is obtained on the shaping sheet surface. On
the other hand, when it is not more than 50 g/m.sup.2, there is no
mechanical restriction in printing the ink, and such is
economically advantageous. From the foregoing viewpoints, the
coating amount of the ink is more preferably in the range of from 1
to 30 g/m.sup.2, especially preferably from 1 to 10 g/m.sup.2, and
mostly preferably from 1 to 7 g/m.sup.2.
[0085] Also, by changing the coating amount of the ink composition,
the thickness of the ink constituting the ink layer 3 can be made
non-uniform, and the degree of a difference of elevation of the
raised portion to be revealed thereby changes stepwise or
continuously. As a result, the pattern of the shaping sheet can be
rendered to be a gradation pattern in which the raised shape
changes stepwise or a continuous pattern in which an undulation of
raising changes continuously.
[0086] It may be considered that this is caused due to the fact
that as the coating amount of the ink layer 3 relatively increases,
the interaction between the ink layer 3 and the surface shaping
layer 5 relatively increases, whereby the degree of the suspended
state becomes higher, and the undulation of the raised shape
becomes larger.
[0087] This is hereunder described in detail with reference to
FIGS. 3 and 7. In FIGS. 3 and 7, inks 3-a, 3-b and 3-c each
constituting the ink layer 3 have a different thickness from each
other. That is, the film thickness become relatively thin stepwise
in the order of 3-a, 3-b and 3-c. According to this, interacting
regions 4-a, 4-b and 4-c can be changed stepwise, and the obtained
raised shape rises up stepwise in the order of 7-c, 7-b and 7-a. It
may be considered that this is caused due to the fact that the
thickness of the ink constituting the ink layer 3 is not uniform,
and coating is achieved such that the thickness of the ink
decreases in the order of 3-a, 3-b and 3-c, and therefore, in a
portion where the thickness of the ink is large, the undulation of
the raised shape becomes more remarkable, whereby the thickness of
the ink changes such that the undulation of the convex shape
becomes small stepwise in the order of 3-a, 3-b and 3-c. By more
finely changing the thickness of the ink, the concave-convex shape
can be changed continuously, too.
[0088] By the shaping sheet having such a structure, it is possible
to impart a much more colorful and delicate texture. In general, a
method for changing the thickness of the ink constituting the ink
layer 3 can be easily carried out by changing the coating amount of
the ink, and by changing the coating amount of the ink
continuously, the foregoing stepwise change can be changed
continuously in a stepless manner.
[0089] Next, in an example shown in FIG. 8, the ink layer 3 is
laminated on the base material 2 such that the thickness changes
continuously in a parallel surface to the base material surface
(the central part is thick, and the thickness becomes thin toward
the side part), and the surface shaping layer 5 obtained through
crosslinking and curing of a curable resin composition is laminated
thereon. Similar to the example shown in FIG. 3, the surface
shaping layer just above the ink layer and in the vicinity thereof
forms an interacting region. In the example shown in FIG. 8, in
response to the fact that the film thickness of the ink layer
becomes thick in the order of 3-c, 3-b and 3-a, the undulation of
the raised shape increases continuously in the order of the
interacting regions 4-c, 4-b and 4-a. As a result, in the surface
shaping layer 5, the undulation of the raised shape increases
continuously in this order.
[Surface Shaping Layer 5: Curable Resin Composition]
[0090] As described previously, the surface shaping layer 5 is
constituted of a material obtained through crosslinking and curing
of a curable resin composition. Here, the curable resin composition
is composed of a curable resin, components to be added, if desired,
various additives and the like. For example, when the curable resin
is an ionizing radiation curable resin as described later, the
curable resin composition is referred to as an ionizing radiation
curable resin composition.
[0091] In order to form the surface shaping layer by means of
printing, the curable resin composition is required to have
printability. Also, in order to form a pattern by means of
printing, when a pattern is transferred from a gravure plate into a
shaping sheet, it is necessary to set up the curable resin
composition such that a transferred pattern does not sag. For these
reasons, it is necessary to chiefly use a resin having a high
viscosity at the ordinary temperature. Specifically, it is
preferred to enhance the thixotropy of the curable resin
composition using a polymerizable oligomer or a prepolymer as a
principal resin and adding an extender pigment thereto. As the
extender pigment, those which are used in the foregoing ink layer 3
can be preferably used. Furthermore, solvent dilution is carried
out to decrease the viscosity to a printable range, after forming a
pattern by means of printing, the solvent is dried by heating, and
crosslinking and curing are then carried out by a method such as
heating, irradiation with an ionizing radiation, etc. Also, in
order to increase heat resistance and crosslinking density, a
polyfunctional polymerizable monomer may be added.
[0092] Though the curable resin in the curable resin composition is
not particularly limited, examples thereof include thermosetting
resins and ionizing radiation curable resins such as melamine
based, urea based, epoxy based, ketone based, diallyl phthalate
based, unsaturated polyester based and phenol based resins and the
like. Of these, ionizing radiation curable resins are preferable
from the viewpoint of enhancing the surface strength of the shaping
sheet.
[0093] The ionizing radiation curable resin as referred to herein
refers to a resin having an energy quantum at which a molecule can
be crosslinked and polymerizing in electromagnetic waves or charged
particle rays, namely a resin capable of being crosslinked and
cured upon irradiation with ultraviolet rays, electron beams or the
like. Specifically, polymerizable monomers and polymerizable
oligomers or prepolymers which have hitherto been customarily used
as an ionizing radiation curable resin can be properly chosen and
used.
[0094] Representatively, the polymerizable monomer is suitably a
(meth)acrylate monomer having a radical polymerizable unsaturated
group in a molecule thereof. In view of the fact that the
(meth)acrylate monomer is included, an interaction with the
foregoing ink composition constituting an ink layer is produced,
thereby suitably forming a difference in the undulation of the
raised shape. From the viewpoints of making the interaction with
the ink composition stronger and obtaining a further difference in
the undulation of the raised shape and a fine concave-convex
surface, a content of the (meth)acrylate monomer is more preferably
50% by mass or more.
[0095] A polyfunctional (meth)acrylate is preferable as the
(meth)acrylate monomer. The "(meth)acrylate" as referred to herein
means "acrylate or methacrylate". The polyfunctional (meth)acrylate
is not particularly limited so far as it is a (meth)acrylate having
two or more ethylenically unsaturated bonds in a molecule thereof.
Specific examples thereof include ethylene glycol di(meth)acrylate,
propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,
1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
polyethylene glycol di(meth)acrylate, neopentyl glycol
di(meth)acrylate hydroxypivalate, dicyclopentanyl di(meth)acrylate,
caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene
oxide-modified phosphoric acid di(meth)acrylate, allylated
cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate,
trimethylolpropane tri(meth)acrylate, ethylene oxide-modified
trimethylolpropane tri(meth)acrylate,
dipentaerythritoltri(meth)acrylate,propionicacid-modified
dipentaerythritol tri(meth)acrylate, pentaerythritol
tri(meth)acrylate, propylene oxide-modified trimethylolpropane
tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic
acid-modified dipentaerythritol penta(meth)acrylate,
dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified
dipentaerythritol hexa(meth)acrylate, caprolactone-modified
dipentaerythritol hexa(meth)acrylate and the like. These
polyfunctional (meth)acrylates may be used singly or in
combinations of two or more kinds thereof.
[0096] In the present invention, a monofunctional (meth)acrylate
can be properly used together with the foregoing polyfunctional
(meth)acrylate for the purpose of reducing a viscosity of the
polyfunctional (meth)acrylate so far as the object of the present
invention is not impaired. Examples of the monofunctional
(meth)acrylate include methyl(meth)acrylate, ethyl(meth)acrylate,
propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate,
hexyl(meth)acrylate, cyclohexyl(meth)acrylate,
2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate,
stearyl(meth)acrylate, isobornyl(meth)acrylate and the like. These
monofunctional(meth)acrylates may be used singly or in combinations
of two or more kinds thereof.
[0097] Next, examples of the polymerizable oligomer include
oligomers having a radical polymerizable unsaturated group in a
molecule thereof, for example, epoxy(meth)acrylate based,
urethane(meth)acrylate based, polyester(meth)acrylate based and
polyether(meth)acrylate based oligomers, etc. Here, the
epoxy(meth)acrylate based oligomer can be obtained by, for example,
allowing an oxirane ring of a relatively low molecular weight
bisphenol type epoxy resin or novolak type epoxy resin to react
with (meth)acrylic acid to achieve esterification. Also, a
carboxyl-modified epoxy(meth)acrylate oligomer obtained by
partially modifying this epoxy(meth)acrylate based oligomer with a
dibasic carboxylic anhydride can be used. The
urethane(meth)acrylate based oligomer can be obtained by, for
example, esterifying a polyurethane oligomer obtained through a
reaction between a polyether polyol or a polyester polyol and a
polyisocyanate, with (meth)acrylic acid. The
polyester(meth)acrylate based oligomer can be obtained by, for
example, esterifying a hydroxyl group of a polyester oligomer
having a hydroxyl group on the both ends thereof, which is obtained
through condensation between a polyvalent carboxylic acid and a
polyhydric alcohol, with (meth)acrylic acid, or esterifying a
hydroxyl group on an end of an oligomer obtained by adding an
alkylene oxide to a polyvalent carboxylic acid, with (meth)acrylic
acid. The polyether(meth)acrylate based oligomer can be obtained by
esterifying a hydroxyl group of a polyether polyol with
(meth)acrylic acid.
[0098] Furthermore, examples of the polymerizable oligomer include,
in addition to the foregoing, polybutadiene(meth)acrylate based
oligomers having high hydrophobicity and having a (meth)acrylate
group on a side chain of a polybutadiene oligomer;
silicone(meth)acrylate based oligomers having a polysiloxane bond
on a principal chain thereof; aminoplast resin (meth)acrylate based
oligomers obtained by modifying an aminoplast resin having a number
of reactive groups in a small molecule thereof; and oligomers
having a cation polymerizable functional group in a molecule
thereof, for example, novolak type epoxy resins, bisphenol type
epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers,
etc.
[0099] In the present invention, as described previously, an
interaction between the ink composition constituting the ink layer
3 and the ionizing radiation curable resin composition constituting
the surface shaping layer 5 is important, and suitable ink
composition and ionizing radiation curable resin composition are
chosen from this viewpoint. It is preferable that the curable resin
in the ionizing radiation curable resin composition contains a
polyfunctional (meth)acrylate monomer.
[0100] When an ultraviolet ray curable resin is used as the
ionizing radiation curable resin, it is desirable that a
photopolymerization initiator is added in an amount of from about
0.1 to 5 parts by mass based on 100 parts by mass of the curable
resin composition. The photopolymerization initiator can be
properly chosen among those which have hitherto been customarily
used and is not particularly limited. Examples of the
photopolymerization initiator for the polymerizable monomer or
polymerizable oligomer having a radical polymerizable unsaturated
group in a molecule thereof include benzoin, benzoin methyl ether,
benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl
ether, benzoin isobutyl ether, acetophenone,
dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone,
2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl
phenyl ketone,
2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one,
4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone,
p-phenylbenzophenone, 4,4'-diethylaminobenzophenone,
dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone,
2-tert-butylanthraqunione, 2-aminoanthraquinone,
2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone,
2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl
ketal, acetophenone dimethyl ketal and the like.
[0101] Also, examples of the photopolymerization initiator for the
polymerizable oligomer having a cation polymerizable functional
group in a molecule thereof include aromatic sulfonium salts,
aromatic diazonium salts, aromatic iodonium salts, metallocene
compounds, benzoin sulfonic acid esters and the like.
[0102] Also, for example, p-dimethyl benzoic acid esters, tertiary
amines, thiol based sensitizers and the like can be used as a
photosensitizer.
[0103] In the present invention, it is preferred to use an electron
beam curable resin as the ionizing radiation curable resin. This is
because the electron beam curable resin can be used in the absence
of a solvent and is more preferable from the environmental or
healthy viewpoint, and also, it does not require a
photopolymerization initiator and provides a stable curing
characteristic.
[Surface Shaping Layer 5: Fine Particle]
[0104] Also, it is preferable that the curable resin composition
which is used in the present invention is further blended with a
fine particle. As this fine particle, one whose average particle
size is a neighborhood value on a plus side of a maximum thickness
of the surface shaping layer 5 which is located just above the
foregoing ink layer 3 is used. The shaping sheet of the present
invention having a fine particle blended therein is described in
detail with reference to FIG. 4. FIG. 4 is a schematic view showing
a section of a shaping sheet having a fine particle blended in a
curable resin composition.
[0105] In the fine particle 8 (8-a and 8-b) blended in the surface
shaping layer, its average particle size d.sub.A is a neighborhood
value on a plus side of a maximum thickness t.sub.M of the surface
shaping layer 5 which is located just above the ink layer 3, namely
d.sub.A is slightly larger than t.sub.M, and raising of the fine
particle 8-a takes place from the surface of the surface shaping
layer 5 which is located just above the ink layer 3. Since a
portion where this raising has taken place forms the fine raised
shape 12, a fine concave-convex feeling can be formed. At the same
time, in the inside of the surface shaping layer 5, the interacting
region 4 for revealing a raised shape just above the ink layer 3
and in the vicinity thereof is formed due to an interaction between
the ink in the ink layer 3 and the curable resin composition
constituting the surface shaping layer 5.
[0106] On the other hand, the fine particle 8-b which is located in
a portion not just above the ink layer 3 neither rises up nor
contributes to revealment of a concave shape. In this way, the
effect for revealing a concave shape depending upon the location of
a fine particle within the surface shaping layer is diverse.
[0107] Accordingly, the concave-convex shape which is revealed on
the surface of the surface shaping layer by the effect of the fine
raised shape 12 to be brought by raising of the fine particle on
the fine concave-convex surface 13 by the interacting region 4 in
this surface shaping layer 5 and the surface of the surface shaping
layer 5, the effect of the raised shape 7 formed depending upon the
foregoing ink layer 3 and its thickness and the concave pattern 14
to be applied by embossing is delicate, daring and excellent in
design and touch feeling, has an air of luxuriousness and is
minute.
[0108] With respect to the maximum thickness t.sub.M of the surface
shaping layer 5 which is located just above the ink layer 3, when a
convex shape following the formation of the foregoing ink layer 3
is not formed, it means a thickness of the surface shaping layer 5,
and when the convex shape is formed, it means a thickness including
the subject portion, respectively.
[0109] With respect to the foregoing fine particle, what the
particle size distribution is closer to a monodispersed system is
preferable because not only it is easy to set up its use amount,
but the foregoing effects are displayed well in a low use
amount.
[0110] In the present invention, a coefficient of variation CV
value of particle size distribution of the fine particle
[{(standard deviation of particle size)/(average particle
size)}.times.100] is preferably not more than 30%. When the
foregoing CV value is not more than 30%, the fine particle has
practically useful particle size distribution, and the foregoing
effects can be sufficiently displayed in an appropriate use amount.
This CV value is more preferably not more than 20%, and further
preferably not more than 15%.
[0111] Furthermore, when an average particle size of the fine
particle is defined as d.sub.A, a maximum thickness of the surface
shaping layer which is located just above the ink layer is defined
as t.sub.M, and a thickness of the surface shaping layer in a
region where the ink layer is not present is defined as t.sub.G, it
is preferable that a relationship of the expression (I) is
satisfied.
1.05.times.t.sub.M.ltoreq.d.sub.A.ltoreq.t.sub.G (I)
[0112] When the average particle size d.sub.A of the fine particle
is 1.05.times.t.sub.M or more, even if settling of the fine
particle is generated in the ink layer, raising of the fine
particle is generated on the surface of the surface shaping layer
which is located just above the ink layer, and the foregoing
effects are sufficiently displayed. Also, when d.sub.A is not more
than t.sub.G, raising of the fine particle is suppressed in the
surface shaping layer in a region where the ink layer is not
present.
[0113] The shape of the fine particle is not particularly limited,
and spherical, ellipsoidal and polyhedral fine particles and the
like can be used, with spherical fine particles being preferable.
In the present invention, the particle size of the fine particle
having a shape other than a spherical shape is defined to be a
value expressed by a diameter of a circumscribing sphere.
[0114] A content of the fine particle in the curable resin
composition varies depending upon the average particle size of the
fine particle, the coefficient of variation CV value of particle
size distribution and the like and is usually chosen within the
range of from 2 to 20% by mass. When this content is 2% by mass or
more, the effects to be brought due to incorporation of the fine
particle are displayed, and when it is not more than 20% by mass, a
concave-convex feeling of the concave-convex shape formed on the
shaping sheet surface is good. The content of the fine particle is
preferably from 4 to 16% by mass, and more preferably from 4 to 13%
by mass.
[0115] The fine particle may be any of an inorganic fine particle
or an organic fine particle. As the fine particle, examples of
inorganic particles include particles of silica, alumina,
aluminosilicate, kaolinite, calcium carbonate, barium sulfate,
glass, etc.; and examples of organic fine particles include
particles of acrylic resins, polycarbonate resins, urethane based
resins, urea based resins, benzoguanamine resins,
benzoguanamine-melamine-formaldehyde condensates, etc.
[0116] Though these fine particles may be used singly or in
combinations of two or more kinds thereof, silica particles are
preferable in view of the effects of the present invention. Also,
the fine particle may be used in combinations with the foregoing
baked kaolin particle having the same effect.
[Surface Shaping Layer 5: Baked Kaolin Particle]
[0117] It is preferable that the curable resin composition which is
used in the present invention contains a baked kaolin particle. By
incorporating the baked kaolin particle in the surface shaping
layer, not only the concave-convex shape of the shaping sheet
surface becomes delicate due to the formation of the fine raised
shape 12, but marring resistance is enhanced. The marring as
referred to herein means the fact that when the sheet surface is
abraded, a small abrasion is generated, and excellence in the
marring resistance as referred to herein means the fact that an
abrasion is hardly formed. By imparting such a performance to the
shaping sheet, the surface shaping layer is reinforced, whereby a
shaping sheet which is able to withstand the use for a longer
period of time can be obtained, and the manufacturing costs of a
resin decorative plate can be reduced.
[0118] The baked kaolin particle which is used for the purpose of
imparting finer concave-convex shape and marring resistance to the
shaping sheet surface is a kaolin particle obtained by baking a
general (hydrated) kaolin particle, and by adding the baked kaolin
particle as a filler, an improvement in the marring resistance
which could not be realized by a silica particle or a hydrated
kaolin particle before baking is realized. A particle size of the
baked kaolin particle may be properly chosen depending upon
applications, required physical properties, etc., and for example,
particles having an average particle size of from about 0.5 to 2
.mu.m are useful. Also, though the addition amount of the baked
kaolin particle may be properly chosen depending upon applications,
required physical properties, etc., it is, for example, from about
5 to 50 parts by mass based on 100 parts by mass of the curable
resin composition.
[0119] Also, the baked kaolin particle is more excellent in coating
stability than the hydrated kaolin particle.
[0120] As the baked kaolin particle, a baked kaolin particle, the
surface of which has been further surface treated, may be used.
Using this surface treated baked kaolin particle, an effect for
enhancing the marring resistance can be further increased. Examples
of the surface treatment include a surface treatment with a silane
coupling agent. Examples of the silane coupling agent include known
silane coupling agents containing an alkoxy group, an amino group,
a vinyl group, an epoxy group, a mercapto group, a chlorine group,
etc. Examples thereof include .gamma.-aminopropyltriethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-methacryloxypropylmethyldimethoxysilane,
.gamma.-methacryloxypropyldimethylmethoxysilane,
.gamma.-methacryloxypropyltriethoxysilane,
.gamma.-methacryloxypropyldimethylethoxysilane,
.gamma.-acryloxypropyltrimethoxysilane,
.gamma.-acryloxypropylmethyldimethoxysilane,
.gamma.-acryloxypropyldimethylmethoxysilane,
.gamma.-acryloxypropyltriethoxysilane,
.gamma.-acryloxypropylmethyldiethoxysilane,
.gamma.-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane, etc.
[Surface Shaping Layer 5: Reactive Silicone]
[0121] It is preferable that the curable resin composition which is
used in the present invention further contains a reactive silicone.
This is because by incorporating the reactive silicone into the
surface shaping layer 5, release properties are enhanced, and
resistance to the repetitive continuous use is enhanced. Also, when
an additive or a filler such as pearlescent pigments, etc. is
incorporated into a body to be shaped, there is brought an effect
for suppressing separation of the additive or filler incorporated
in the body to be shaped in a manufacturing process of a decorative
plate.
[0122] The "reactive silicone" as referred to herein means a
modified silicone oil in which an organic group is introduced in a
side chain or an end thereof and which has reactivity depending
upon properties of the organic group to be introduced. Specific
examples of the reactive silicone include modified silicone oil
side-chain types, modified silicone oil dual-end types, modified
silicone oil single-end types, modified silicone oil side-chain
dual-end types and the like, in which the organic group to be
introduced is an organic group introduced by amino modification,
epoxy modification, mercapto modification, carboxyl modification,
carbinol modification, phenol modification, methacryl modification,
modification with different functional groups or the like.
[0123] The foregoing reactive silicone reacts with and bonds to the
curable resin at the time of curing of the surface shaping layer,
whereby the both are integrated. Accordingly, in molding the
decorative plate of the present invention by means of hot press
molding, since the reactive silicone does not bleed out onto the
surface of the decorative plate, it is possible to remarkably
enhance adhesion between the shaping sheet of the present invention
and the decorative plate and to shape a decorative material with a
delicate design having a fine concave-convex shape.
[0124] The use amount of the foregoing reactive silicone is in the
range of from about 0.1 to 50 parts by mass, and preferably in the
range of from about 0.5 to 10 parts by mass based on 100 parts by
mass of the curable resin. When the use amount of the reactive
silicone is 0.1 parts by mass or more, peeling of the decorative
plate from the surface of the shaping sheet is sufficient so that
the concave-convex shape of the surface of the shaping sheet is
kept and is able to withstand the use for a longer period of time.
On the other hand, when the use amount of the reactive silicone is
not more than 50 parts by mass, since repelling is not generated in
coating the curable resin composition on the base material, the
coating surface does not become rough so that the coating stability
is enhanced.
[Surface Shaping Layer 5: Various Additives]
[0125] Also, the curable resin composition which is used in the
present invention is blended with various additives depending upon
desired physical properties of the obtained cured resin layer.
Examples of the additive include weatherability improving agents,
abrasion resistance enhancing agents, polymerization inhibitors,
crosslinking agents, infrared ray absorbers, antistatic agents,
adhesiveness enhancing agents, antioxidants, leveling agents,
thixotropy imparting agents, coupling agents, plasticizers,
defoaming agents, fillers, solvents and the like.
[0126] Here, an ultraviolet ray absorber and a light stabilizer can
be used as the weatherability improving agent. These materials are
added for the purpose of contriving to use the shaping sheet for a
long period of time. The ultraviolet ray absorber may be any of an
inorganic or organic ultraviolet ray absorber. As the inorganic
ultraviolet ray absorber, titanium dioxide, cerium oxide, zinc
oxide and the like each having an average particle size of from
about 5 to 120 nm can be preferably used. Also, examples of the
organic ultraviolet ray absorber include benzotriazole based
compounds, specifically 2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole,
3-[3-(benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic
acid ester of polyethylene glycol and the like. On the other hand,
examples of the light stabilizer include hindered amine based
compounds, specifically bis(1,2,2,6,6-pentamethyl-4-piperidyl)
2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2'-n-butylmalonate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate
and the like. Also, a reactive ultraviolet ray absorber or light
stabilizer having a polymerizable group such as a (meth)acryloyl
group, etc. in a molecule thereof can be used as the ultraviolet
ray absorber or light stabilizer.
[0127] Examples of the abrasion enhancing agent include inorganic
materials, for example, spherical particles of .alpha.-alumina,
silica, kaolinite, iron oxide, diamond, silicon carbide and the
like. Though the particle shape is not particularly limited,
examples thereof include a spherical shape, an ellipsoidal shape, a
polyhedral shape, a flaky shape and the like, with a spherical
shape being preferable. Examples of organic materials include beads
of a synthetic resin such as a crosslinked acrylic resin, a
polycarbonate resin and the like. A particle size thereof is
usually from about 30 to 200% of the film thickness. Of these,
spherical .alpha.-alumina is especially preferable because it has a
high hardness and a large effect for enhancing the abrasion
resistance, and a spherical particle is relatively easily
obtainable.
[0128] Examples of the polymerization inhibitor which is used
include hydroquinone, p-benzoquinone, hydroquinone monomethyl
ether, pyrogallol, t-butyl catechol and the like; and examples of
the crosslinking agent which is used include polyisocyanate
compounds, epoxy compounds, metal chelate compounds, aziridine
compounds, oxazoline compounds and the like.
[0129] Examples of the filler which is used include barium sulfate,
talc, clay, calcium carbonate, aluminum hydroxide and the like.
[0130] Examples of the infrared ray absorber which is used dithiol
based metal complexes, phthalocyanine based compounds, diimmonium
compounds and the like.
[Formation of Surface Shaping Layer 5]
[0131] In the present invention, a curable resin such as a
polymerizable monomer, a polymerization oligomer and the like as
the foregoing curable component, components which are added, if
desired and various additives are homogenously mixed in prescribed
proportions, respectively, thereby preparing a curable resin
composition. A viscosity of this curable resin composition is not
particularly limited so far as it is a viscosity at which an
uncured resin layer can be formed on the surface of a base material
by a coating method as described later.
[0132] In the present invention, the thus prepared curable resin
composition is coated on the surface of a base material in a
thickness after curing of from 1 to 20 .mu.m by a known method such
as gravure coating, bar coating, roll coating, reverse roll
coating, Komma coating and the like, and preferably gravure
coating, thereby forming an uncured resin layer. When the thickness
after curing is 1 .mu.m or more, a cured resin layer (surface
shaping layer) having a desired function is obtained. The thickness
of the surface shaping layer after curing is preferably from about
2 to 20 .mu.m.
[0133] In the present invention, the thus formed uncured resin
layer is heated or irradiated with an ionizing radiation such as
heat, electron beams, ultraviolet rays and the like, thereby curing
the uncured resin layer and obtaining a surface shaping layer.
Here, when electron beams are used as the ionizing radiation,
though its accelerating voltage can be properly chosen depending
upon the resin to be used or the thickness of the layer, in
general, it is preferred to cure the uncured resin layer at an
accelerating voltage of from about 70 to 300 kV.
[0134] In the irradiation with electron beams, the higher the
accelerating voltage, the larger the transmission ability is.
Therefore, when a base material which is deteriorated by electron
beams is used as the base material, by choosing the accelerating
voltage such that a transmission depth of the electron beams is
substantially equal to a thickness of the uncured resin layer, the
irradiation with excessive electron beams onto the base material
can be suppressed, and deterioration of the base material by the
excessive electron beams can be kept to a minimum.
[0135] An irradiation dosage is preferably an amount at which a
crosslinking density of the curable resin in the surface shaping
layer is saturated and is in general chosen within the range of
from 5 to 300 kGy (0.5 to 30 Mrad), and preferably from 10 to 50
kGy (1 to 5 Mrad).
[0136] Furthermore, an electron beam source is not particularly
limited, and various electron beam accelerators, for example, a
Cockroft-Walton type, a van de Graaff type, a resonance transformer
type, an insulating core transformer type, a linear type, a
Dynamitron type, a high frequency type and the like can be
used.
[0137] When ultraviolet rays are used as the ionizing radiation, a
radiation including ultraviolet rays having a wavelength of from
190 to 380 nm is irradiated. An ultraviolet ray source is not
particularly limited, and for example, a high pressure mercury
lamp, a low pressure mercury lamp, a metal halide lamp, a carbon
arc lamp and the like are useful.
[0138] Various additives can also be added to the thus formed
surface shaping layer to impart various functions, for example, a
so-called hard coat function having a high hardness and abrasion
resistance, a defogging coat function, an antifouling coat
function, an antiglare coat function, an antireflection coat
function, an ultraviolet ray shielding coat function, an infrared
ray shielding coat function and the like.
[Concave Pattern 14]
[0139] The concave pattern 14 is provided on the shaping sheet by
means of embossing or the like and by giving a deeper concave shape
on the surface of the surface shaping layer 5, imparts a design and
an air of luxuriousness with an excellent touch feeling by the
shaping sheet.
[0140] This concave pattern 14 can be formed by heating and
pressurization by an embossing plate from an upper surface of the
surface shaping layer, namely from the outermost layer side when
the shaping sheet of the present invention reaches a temperature at
which embossing is possible by any means during the manufacturing
process. As shown in FIGS. 1 to 9, as to unevenness which is formed
by heating and pressurization by an embossing plate, its deepest
portion preferably reaches the upper surface of the base material
2, and an area where the concave pattern 14 is formed is not
particularly limited. A depth of the unevenness of the concave
pattern 14 varies depending upon the thickness of the shaping sheet
and is usually from 20 to 80 .mu.m, and preferably from 30 to 60
.mu.m. In forming the concave pattern 14, a well-known sheet-fed or
rotary embossing machine is used. Examples of the shape of the
concave pattern 14 include woodgrain vessel channel, stone board
surface unevenness, cloth surface texture, satin finished surface,
grain, hairline, linear streak and the like. Also, by coordinating
the concave pattern 14 with the pattern applied to the foregoing
ink layer 3, the effects of the present invention become much more
remarkable, but even when the concave pattern 14 is not coordinated
with the pattern applied to the foregoing ink layer 3, the effects
are sufficiently obtainable.
[Resin Decorative Plate: Resin Decorative Plate-1]
[0141] The resin decorative plate of the present invention is not
particularly limited so far as it is prepared by using the shaping
sheet of the present invention. As a preferred embodiment thereof,
there is exemplified a resin decorative plate shown in FIG. 10,
which is obtained by laminating an adhesive layer and a decorative
sheet layer in this order on an upper surface of a substrate,
coating a resin composition on the decorative sheet layer,
subsequently bringing the shaping sheet of the present invention
into contact therewith and integrally curing and then peeling the
shaping sheet to form a resin layer.
[Resin Decorative Plate-1: Substrate 10]
[0142] Though a substrate 10 of the resin decorative plate of the
present invention is not particularly limited, plastic films,
plastic sheet metal plates, wood based plates such as woods, etc.,
ceramic based raw materials and the like can be properly chosen
depending upon applications. When such a substrate, in particular a
plastic sheet is used as the substrate, for the purpose of
enhancing adhesion to the decorative material, a physical or
chemical surface treatment, for example, an oxidation process, a
roughening process, etc. can be applied to one surface or the both
surfaces thereof, if desired. The foregoing oxidation process and
roughening process are the same as those described previously in
the base material of the shaping sheet of the present
invention.
[0143] The plastic film and plastic sheet are the same as those
described previously in the base material of the shaping sheet of
the present invention.
[0144] As the metal plate, those made of, for example, aluminum,
iron, stainless steel, copper or the like can be used, and those
obtained by plating with such a metal can also be used.
[0145] Examples of the wood based plate include woody materials
such as sliced veneers, veneers, plywood, particle boards and
medium density fiber (MDF) boards of various raw materials, for
example, Japanese cedar, Japanese cypress, Japanese zelkova, pine,
lauan, teak, Melapi, etc., and the like. These materials can be
used alone or in the form of a laminate. The wood based plate
includes not only woody plates but paper powder-containing plastic
plates and papers having a reinforced strength.
[0146] Examples of the ceramic based raw material include ceramic
based building materials such as gypsum boards, calcium silicate
boards, wood chip cement boards and the like; pottery and
porcelain, glass, enamels, baked tiles, boards composed of volcanic
ash as a main raw material and the like.
[0147] In addition to the foregoing materials, composites of
various raw materials such as plates of a fiber-reinforced plastic
(FRP), plates obtained by sticking an iron plate on the both
surfaces of a paper honeycomb, plates obtained by interposing a
polyethylene resin by two aluminum plates and the like.
[Resin Decorative Plate-1: Adhesive Layer 9]
[0148] An adhesive layer 9 is a layer which is provided for the
purpose of bonding the substrate 10 and a decorative sheet layer 17
to each other.
[0149] An adhesive which is used for the adhesive layer 9 is coated
using a coating device such as a spray, a spreader, a bar coater
and the like. Urea based, vinyl acetate resin based, urea resin
based, melamine resin based, phenol resin based and isocyanate
based adhesives and the like can be used as this adhesive. Such an
adhesive is used singly or as a mixed adhesive as an arbitrary
mixture. If desired, the adhesive can be added to and mixed with an
inorganic powder such as talc, calcium carbonate, clay, titanium
white and the like, wheat flour, wood flour, plastic flour, a
colorant, an insecticide, an antiseptic or the like. In general,
the adhesive has a solids content of from 35 to 80% by mass and is
coated in a coating amount in the range of from 50 to 300 g/m.sup.2
on the surface of the substrate.
[0150] In general, sticking of the decorative sheet layer 17 onto
the substrate 10 is carried out by a method in which the adhesive
layer 9 is formed on a back surface of the decorative sheet layer
17, and the substrate 10 is then stuck thereonto; a method in which
an adhesive is coated on the substrate 10, and the decorative sheet
layer 17 is then stuck thereonto; or the like. Sticking can be
carried out by a sticking device such as a cold press, a hot press,
a roll press, a laminator, a wrapping machine, an edge-sticking
machine, a vacuum press and the like.
[Resin Decorative Plate-1: Decorative Sheet Layer 17]
[0151] The decorative sheet layer 17 gives decorative properties to
the resin decorative plate of the present invention and is a layer
in which a solid printing layer 17-b and a design layer 17-c which
are provided, if desired are provided in this order on the sheet
layer 17-a.
[0152] The sheet layer 17-a is not particularly limited so far as
it is a material which is used as a base material of usual
decorative sheets, and various papers, plastic films and plastic
sheets and the like can be properly chosen depending upon
applications. Though these materials may be respectively used
singly, a laminate composed of an arbitrary combination such as
composites of papers each other, composites of paper and a plastic
film and the like may be used.
[0153] When such a base material, in particular a plastic film or a
plastic sheet is used as the base material, for the purpose of
enhancing adhesion to the layer which is provided thereon, a
physical or chemical surface treatment, for example, an oxidation
process, a roughening process, etc. can be applied to one surface
or the both surfaces thereof, if desired. The foregoing oxidation
process and roughening process are the same as those described
previously in the base material of the shaping sheet of the present
invention. Also, the substrate may be subjected to a treatment such
as formation of a primer layer and the like, or may be previously
coated for the purpose of regulating a tint or formed with a
pattern from the design viewpoint.
[0154] The various papers, plastic films and plastic sheets which
are used as the sheet layer 17-a are the same as those described
previously in the base material of the shaping sheet of the present
invention.
[0155] A thickness of the sheet layer 17-a is not particularly
limited. When a sheet made of a plastic as a raw material is used,
its thickness is in general in the range of from about 20 to 150
.mu.m, and preferably from 30 to 100 .mu.m; and when a paper base
material is used, its basis weight is in general in the range of
from about 20 to 150 g/m.sup.2, and preferably from 30 to 100
g/m.sup.2.
[0156] The solid printing layer 17-b which is provided on the sheet
layer 17-a is a layer which is provided, if desired for the purpose
of enhancing design properties of the resin decorative plate of the
present invention and which is also called a hiding layer. When the
sheet layer 17-a itself is colored, or color irregularity is
present, the solid printing layer 17-b is formed by regulating the
color of the surface of the sheet layer 17-a, thereby giving an
intended tint to the surface on the sheet layer 17-a. In general,
though the solid printing layer 17-b is frequently formed of an
opaque color, there may be the case where the solid printing layer
17-b is formed of a colored transparent color, thereby making the
best of a pattern which the backing has. When it is intended to
make the best of a white color of the sheet layer 17-a, or when the
sheet layer 17-a itself is adequately colored, it is not necessary
to form the solid printing layer 17-b.
[0157] As the ink which is used for forming the solid printing
layer 17-b, an ink obtained by properly mixing a binder with a
colorant such as pigments, dyes and the like, an extender pigment,
a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent,
etc. is useful. The binder is not particularly limited, and
materials selected among, for example, polyurethane based resins,
vinyl chloride/vinyl acetate based copolymer resins, vinyl
chloride/vinyl acetate/acrylic copolymer resins, chlorinated
polypropylene based resins, acrylic resins, polyester based resins,
polyamide based resins, butyral based resins, polystyrene based
resins, nitro cellulose based resins, cellulose acetate based
resins and the like are used singly or in admixture of two or more
kinds thereof.
[0158] Examples of the colorant which is used include inorganic
pigments such as carbon black (semi), iron black, titanium white,
antimony white, chrome yellow, titanium yellow, red iron oxide,
cadmium red, ultramarine blue, cobalt blue and the like; organic
pigments or dyes such as quinacridone red, isoindolinone yellow,
phthalocyanine blue and the like; metal pigments composed of a
flaky foil piece of aluminum, bronze, etc.; pearlescent (pearl)
pigments composed of a flaky foil piece of titanium dioxide-coated
mica, basic lead carbonate, etc.; and the like.
[0159] The design layer 17-c gives decoration properties to the
sheet layer 17-a and is formed by printing various patterns on the
sheet layer 17-a or the solid printing layer 17-b using a printer.
Examples of the pattern include woodgrain patterns, stone-grain
patterns imitating the surface of a rock such as a marble pattern
(for example, a travertine marble pattern), etc., fabric patterns
imitating a texture or cloth-like pattern, tiling patterns, brick
work patterns and the like and also include composite patterns
thereof such as a parquetry pattern, a patchwork pattern and the
like. Such a pattern is formed by multicolor printing with process
colors including yellow, red, blue and black of usual colors and in
addition thereto, is formed by multicolor printing with special
colors by preparing plates of individual colors.
[0160] The same inks as those used in the solid printing layer 17-b
can be used as the design inks to be used in the design layer
17-c.
[Resin Decorative Plate-1: Resin Layer 18]
[0161] A resin layer 18 is a layer formed by coating a resin
composition on the decorative sheet layer 17, subsequently bringing
a shaping sheet into contact therewith and integrally curing and
then peeling the shaping sheet. A thickness of the resin layer 18
is preferably from 100 to 500 g/m.sup.2, more preferably from 100
to 350 g/m.sup.2, and further preferably from 150 to 250
g/m.sup.2.
[0162] The resin composition is a composition composed of a
polymerization initiator, a polymerization accelerator, a
polymerization inhibitor and other additives, each of which is
added, if desired as well as a resin.
[0163] The resin in the resin composition which is used in the
present invention is not particularly limited so far as it is cured
at the ordinary temperature or by heating. Examples thereof include
silicone resins, unsaturated polyester resins, saturated polyester
resins, melamine resins, diallyl phthalate (DAP) resins,
polycarbonate resins, phenol resins, polyamides, ketone resins,
epoxy resins, urethane resins, urea resins, acrylic resins, vinyl
resins, alkyd resins, amino alkyd resins, hydrocarbon resins
(aromatic and aliphatic hydrocarbon resins), rubber based resins,
fluorocarbon resins and the like. Of these, unsaturated polyester
resins are preferable.
[0164] The polymerization initiator, the polymerization accelerator
and the polymerization inhibitor are added for the purpose of
regulating a curing rate of the resin composition.
[0165] The polymerization initiator is properly chosen and used
among, for example, peroxides such as methyl ethyl ketone peroxide,
benzoyl peroxide, hydroperoxide and the like; and radical
initiators such as azobisisobutyronitrile. The addition amount of
the polymerization initiator in the resin composition is preferably
from 0.5 to 3% by mass, and more preferably from 0.5 to 2.0% by
mass.
[0166] As the polymerization accelerator, for example, a metal
compound such as a cobalt compound, e.g., cobalt naphthenate, etc.,
a vanadium compound, a manganese compound, etc., an amine based
compound such as dimethyl nitrile, etc. or the like is used
preferably in a proportion of from 0.1 to 2.0% by mass, and more
preferably from 0.3 to 1.0% by mass in the resin composition. As
the polymerization inhibitor, for example, hydroquinone,
trihydroquinone,benzoquinone, trihydrobenzene and the like can be
used. As other additives, for example, for the purposes of
regulating the coating viscosity and crosslinking the resin, there
can be preferably exemplified vinyl group-containing compounds such
as a styrene monomer and the like. The addition amount thereof is
preferably from 10 to 40% by mass, and more preferably from 15 to
30% by mass in the resin composition.
[0167] These curing rate regulators and other additives can be used
singly or in combinations.
[Resin Decorative Plate: Resin Decorative Plate-2]
[0168] As a preferred embodiment of the resin decorative plate of
the present invention, there is exemplified a resin decorative
plate shown in FIG. 12, in which a resin decorative sheet obtained
by inserting a shaping sheet of the present invention between a
molded article to be press molded between hot press plates and a
press plate and molding and then peeling the shaping sheet is stuck
to a substrate via an adhesive layer.
[0169] Examples of a resin decorative sheet 15 include melamine
resin decorative sheets, diallyl phthalate (DAP) resin decorative
sheets, polycarbonate resin decorative sheets and polyester
decorative sheets because they have a hard surface, are excellent
in heat resistance and antifouling properties, and are able to
choose abundant multicolored patterns from the design standpoint.
Of these, melamine resin decorative sheets and diallyl phthalate
(DAP) resin decorative sheets are especially preferable. Also, the
substrate 10 serving as an adherend and an adhesive which is used
for the adhesive layer 9 are the same as those described
previously.
[Resin Decorative Plate: Manufacturing Method of Resin Decorative
Plate-1]
[0170] The resin decorative plate of the present invention is
preferably a resin decorative plate shown in FIG. 10, which is
obtained by laminating the adhesive layer 9 and the decorative
sheet layer 17 in this order on an upper surface of the substrate
10, coating a resin composition on the decorative sheet layer,
subsequently bringing the shaping sheet of the present invention
into contact therewith and integrally curing and then peeling the
shaping sheet to form the resin layer 18. Peeling of the shaping
sheet 1 is carried out in the manner shown in FIG. 11, thereby
obtaining a resin decorative plate 11 having a certain shape shaped
thereon.
[Resin Decorative Plate: Manufacturing Method of Resin Decorative
Plate-2]
[0171] Also, the resin decorative plate of the present invention is
preferably a resin decorative plate shown in FIG. 12, which is
obtained by sticking the resin decorative sheet 15 having a certain
shape shaped thereon, which is obtained by inserting a shaping
sheet between a molded article to be press molded between hot press
plates and a press plate and molding and after hot press molding,
peeling the shaping sheet from a body to be shaped, to the
substrate 10 via the adhesive layer 9. Peeling of the shaping sheet
1 is carried out in the manner shown in FIG. 11, thereby obtaining
the resin decorative plate 11 having a certain shape shaped
thereon.
[0172] On that occasion, a press plate onto the surface of which
embossing has been applied can be suitably used as the foregoing
press plate. Using such a press plate, an air of texture with a
further increased touch feeling can be imparted to the resin
decorative plate of the present invention. A depth of the
unevenness of embossing by this press plate is usually from 20 to
80 .mu.m, and preferably from 30 to 60 .mu.m, and examples of the
shape include woodgrain vessel channel, board surface unevenness,
cloth surface texture, satin finished surface, grain, hairline,
linear streak and the like. Also, by coordinating the pattern with
the pattern applied to the foregoing ink layer 3, the effects of
the present invention become much more remarkable, but even when
the pattern is not coordinated with the pattern applied to the
foregoing ink layer 3, the effects are sufficiently obtainable.
[0173] A method for manufacturing the foregoing resin decorative
sheet 15 is not particularly limited so far as it is a generally
employed method. Above all, the preferred melamine resin decorative
sheet and diallyl phthalate (DAP) resin decorative sheet are
generally obtained according to the following manufacturing
method.
[0174] The melamine resin decorative sheet is obtained by
laminating a melamine resin-impregnated sheet on about four sheets
of phenol resin-impregnated core papers and further laminating a
melamine resin-impregnated overlay paper thereon, interposing the
laminate between two mirror finished metal plates, inserting the
foregoing shaping sheet into the surface, hot pressing the
resultant, for example, at 0.98 MPa and 160.degree. C. for 20
minutes and after allowing to stand for cooling to room
temperature, peeling the foregoing shaping sheet.
[0175] Also, the diallyl phthalate (DAP) resin decorative sheet is
obtained by superimposing a diallyl phthalate resin-impregnated
paper successively on a plate-shaped base material, hot pressing
the resultant at 140 to 150.degree. C. and 0.98 MPa for about 10
minutes using the foregoing shaping sheep between mirror finished
metal plates in the same manner as in the manufacturing method of a
melamine resin decorative sheet and after allowing to stand for
cooling to room temperature, peeling the foregoing shaping sheet.
In any case, a delicate and daring decorative plate having a
concave-convex shape is produced.
[0176] The thus obtained resin decorative sheet 15 can be used as a
resin decorative plate upon being stuck to various substrates.
Specifically, as shown in FIG. 12, the resin decorative plate 11 is
obtainable by sticking the decorative plate 11 to the substrate 10
via the adhesive layer 9. The substrate 10 serving as an adherend
and an adhesive and an adhesion method to be used for the adhesive
layer 9 are the same as those described previously.
[Resin Decorative Plate]
[0177] The resin decorative plate which is manufactured by the
method of the present invention is delicate and daring, is
excellent in design and touch feeling and has an air of
luxuriousness due to the effect of a raised shape formed depending
upon the ink layer in the shaping sheet of the present invention
and its thickness, the effect to be brought by the fine
concave-convex surface, the effect to be brought due to raising of
a fine particle (fine raised shape), the effect to be brought by a
concave pattern applied by embossing, the effect to be brought by
embossing against a hot press plate which is used for preparing a
resin decorative plate and the like. From the viewpoint of bringing
these effects, a surface roughness of the resin decorative plate in
an area applied by embossing is preferably from 20 to 80 .mu.m, and
more preferably from 30 to 60 .mu.m. Also, a surface roughness of
the resin decorative plate in an area corresponding to the raised
shape and fine concave-convex surface is preferably from 0.1 to 10
.mu.m, and more preferably from 1 to 8 .mu.m.
[0178] The resin decorative plate of the present invention can be
cut into an arbitrary size, and the surface or butt end part
thereof can be subjected to arbitrary decorating works such as
grooving work, chambering work and the like using a cutting work
machine such as a router, a cutter and the like. The resin
decorative plate of the present invention can be used for various
applications, for example, interior or exterior materials for
buildings such as walls, ceilings, floors and the like, surface
decorative plates for fittings such as window frames, doors,
balustrades, base boards, verandahs, malls and the like, surface
decorative plates of cabinets for kitchen wares, furniture, light
electrical appliances, OA appliances and the like, interior and
exterior decorations for vehicles and the like.
Examples
[0179] The present invention is hereunder described in more detail
with reference to Examples and Comparative Example, but it should
not be construed that the present invention is limited thereto.
(Evaluation Methods)
[0180] Shaping sheets and decorative plates obtained in the
respective Examples were evaluated by the following methods.
(1) Measurement of Surface Roughness:
[0181] A decorative plate having a size of 400 mm long by 400 mm
wide was measured for a surface roughness (arithmetic average
surface roughness) using a three-dimensional non-contact surface
profilometer system (MICROMAP, manufactured by Ryoka System
Inc.).
(2) Peeling Properties:
[0182] A peeling strength of a shaping sheet was measured using a
tensile/compression tester (RTC-1250A, manufactured by Orientec
Co., Ltd.). An objective sample for evaluation had a size of 25 mm
wide by 50 mm long, and the test was carried out at a peeling speed
of 300 mm/min and a peeling direction of 180.degree. (vertical
direction) in a load cell load of 10 N at a measurement
environmental temperature of 23.degree. C. (room temperature).
(3) Continuous Moldability:
[0183] Molding was carried out 10 times using the same shaping
sheet, a peeling strength was measured at every molding, and
peeling stability was measured during repeated use of the shaping
sheet.
Example 1
Preparation of Shaping Sheet
[0184] A primer ink (acrylic resin "EBF Coordinated Primer",
manufactured by Showa Ink manufacturing Co., Ltd.) was subjected to
gravure printing over the entirety of an easy adhesion-treated
surface of a polyester film ("A4100 (50 .mu.m)", manufactured by
Toyobo Co., Ltd.) which had been previously subjected to an easy
adhesion treatment, thereby forming a penetration preventing layer
6 (primer layer).
[0185] Subsequently, using a pattern printing plate, an ink (a
urethane based vessel ink "VESSEL MINI (A)", manufactured by The
Intec Inc.) was printed on a vessel portion of a woodgrain pattern,
thereby forming an ink layer 3. Furthermore, an electron beam
curable resin composition prepared by adding 5% by mass of a baked
kaolin particle and 2% by mass of a reactive silicone methacrylate
to an electron beam curable resin ("REB-GE", manufactured by
Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was coated in a
coating amount of 4 g/m.sup.2 on these ink layers by a gravure
offset coater method. After coating, electron beams were irradiated
at an accelerating voltage of 175 kV and an irradiation dose of 30
kGy (3 Mrad) to cure the electron beam curable resin composition,
thereby forming a surface shaping layer 5. Furthermore, a concave
pattern which is coordinated with the thus formed ink layer 3 was
applied by means of embossing from the side of the surface shaping
layer 5 through offline. The shaping sheet was a film having an air
of luxuriousness and an expression of a delicate woodgrain.
Example 2
Preparation of Resin Decorative Plate
[0186] A melamine resin-impregnated sheet was laminated on about
four sheets of phenol resin-impregnated core papers, and a melamine
resin-impregnated overlay paper of about 35 g/m.sup.2 was further
laminated thereon; the laminate was interposed between two mirror
finished metal plates (in which the metal plate coming into contact
with the surface side of the resin decorative plate had been
subjected to embossing); the shaping sheet prepared in Example 1
and having a concave-convex shape formed on the surface thereof was
inserted; and the resultant was hot pressed at 0.98 MPa and
160.degree. C. for 20 minutes. After allowing to stand for cooling
to room temperature, the shaping sheet was peeled, thereby
obtaining a melamine resin decorative sheet having a delicate and
daring concave-convex shape, excellent design and touch feeling and
an air of luxuriousness, in which a surface roughness of the fine
concave-convex surface of the shaping sheet and an area shaped by
the concave-convex shape by a raised shape was from 2 to 4 .mu.m,
and a surface roughness of an area having been subjected to
embossing was from 10 to 12 .mu.m. Also, in the obtained melamine
resin decorative sheet, a concave-convex feeling of the vessel
portion was realistically expressed, and the same texture as in a
material using an actual wood was displayed.
[0187] Also, the shaping sheet obtained in Example 1 was rich in
durability, and even when molding was repeated 10 times, the
surface shape and the peeling properties (easiness for peeling)
after shaping did not change at all.
Example 3
[0188] An interlayer-reinforced paper for building material having
a basis weight of 30 g/m.sup.2 was used as a base material, one
surface of which was then provided with a solid printing layer
having a coating amount of 5 g/m.sup.2 by means of gravure printing
using an ink containing an acrylic resin and nitrocellulose as a
binder and titanium white, red iron oxide and chrome yellow as a
colorant. A design layer having a woodgrain pattern was formed
thereon by means of gravure printing using an ink containing
nitrocellulose as a binder and a colorant composed of red iron
oxide as a principal component, thereby obtaining a decorative
sheet layer. Subsequently, after roll coating a urea-vinyl acetate
based adhesive on MDF of the substrate, the obtained decorative
sheet layer was stuck.
[0189] Thereafter, a polyester resin composition obtained by mixing
an unsaturated polyester and a peroxide was coated in a coating
amount of 200 g/m.sup.2 over the entirety of an upper surface of
the decorative sheet layer; the shaping sheet obtained in Example 1
was covered thereon and brought into contact therewith while being
registered at a register mark; the resultant was rolled and
deaerated five times at 0.98 MPa/930 m/m using a rubber roll such
that the registered position was not deviated; heating was carried
out at 40.degree. C. for 2 hours; and the polyester resin was cured
at room temperature. After curing, the resultant was aged for one
hour and allowed to stand for cooling to room temperature; and the
shaping sheet was peeled to obtain a polyester decorative sheet in
which the same concave-convex feeling of the vessel portion as in
Example 2 was realistically expressed and which had the same
texture as in a material using an actual wood.
[0190] Also, the shaping sheet obtained in Example 1 was rich in
durability, and even when molding was repeated 10 times, the
surface shape and the peeling properties (easiness for peeling)
after shaping did not change at all.
Comparative Example 1
[0191] A convex pattern layer made of a urethane acrylate based
ultraviolet ray curable resin (XD-808, manufactured by manufactured
by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was formed
on an easy adhesion-treated surface of a PET film ("A4100 (100
.mu.m)", manufactured by Toyobo Co., Ltd.) which had been
previously subjected to an easy adhesion treatment by means of a
drum printing film (hereinafter referred to as "DPS") mode.
[0192] A concave-convex pattern with a woodgrain design (depth: 70
.mu.m, each of width of convex part and width of concave part: 35
.mu.m) was provided on a roll concave plate surface by an etching
method. A line speed of the DPS mode was regulated at 10 m/min, and
two 160-W ozone high-pressure mercury lamps (manufactured by Japan
Storage Battery Co., Ltd.) were used for irradiation with
ultraviolet rays.
[0193] The thus obtained shaping sheet had a concave-convex shape.
Using the thus obtained shaping sheet, the same operation as in
Example 2 was followed, thereby preparing a melamine resin
decorative plate.
[0194] Though the decorative plate according to Comparative Example
1 had a good expression of a dynamic concave-convex feeling, it
could not express a delicate concave-convex shape. Also, the film
was required to use a thick sheet with nerve in view of an issue of
manufacture, and the manufacturing costs were high. The durability
and peel properties were equal to those in Example 2.
INDUSTRIAL APPLICABILITY
[0195] Since the shaping sheet of the present invention has a
delicate and daring concave-convex shape, is capable of realizing
minute shaping with excellent design and touch feeling and having
an air of luxuriousness and is excellent in release properties, a
resin decorative plate can be obtained by using this shaping sheet.
In particular, when used for a delicate pattern such as a woodgrain
pattern, a concave-convex feeling of a vessel portion can be
realistically expressed, and a shaped decorative material is able
to obtain the same texture as in a material using an actual
wood.
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