JP2001240823A - Multicolor patterned adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a multicolor patterned adhesive sheet having uniform multicolor patterns and especially useful as an interior and an exterior finish materials for buildings. SOLUTION: This multicolor patterned sheet comprises a multicolor patterned paint film layer formed by a spray coating method for forming multicolor patterns on a moving sheet using spray coating devices having >=2 discharge nozzles for coatings or inks in which the respective discharge nozzles are arranged toward a surface of the sheet to be coated, discharging the coatings or inks mutually different in coating colors from at least the >=2 discharge nozzles of the respective spray coating devices, forming a polychromatic sprayed pattern in which the coating or ink different in coating color are mixed and forming the multicolor pattern on the sheet in the adhesive sheet prepared by laminating (1) a mold releasable sheet layer, (2) an adhesive mass layer, (3) a base sheet layer and (4) the multicolor patterned paint film layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-colored pressure-sensitive adhesive sheet having a uniform multi-colored pattern, and particularly useful as an interior / exterior material for buildings. The multi-patterned pressure-sensitive adhesive sheet of the present invention can be provided with an easy-stain removal property and a photocatalytic function by providing a specific treatment agent layer.

[0002]

2. Description of the Related Art Conventionally, a multi-pattern pressure-sensitive adhesive sheet has been produced by making a pattern plate and performing gravure printing of inks of respective coating colors on a base sheet.
Such a method is useful when a small variety is mass-produced, but is unsuitable for a small variety with a large number of varieties because it takes a lot of man-hours to make a pattern plate. There is also a problem that the thickness of the obtained pattern layer is small and the pattern is poor in three-dimensional appearance.

[0003]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have a uniform, three-dimensional, and multicolored pattern layer excellent in cosmetics by a specific spray coating method. It was found that an adhesive sheet was obtained, and the present invention was completed.

That is, the present invention relates to an adhesive sheet comprising a laminate of a release sheet layer (1), an adhesive layer (2), a base sheet layer (3) and a multi-pattern coating film layer (4). A pattern coating film layer is a spray coating method for forming a colorful pattern on a moving sheet, wherein a paint or ink discharge nozzle is provided.
Using a spray coating device having two or more, each of the discharge nozzles are arranged facing the surface to be coated of the sheet, and paints or inks of different paint colors are applied from at least two or more discharge nozzles of each spray coating device. A multi-colored spray pattern formed by forming a multi-color pattern pattern on a sheet by discharging and forming a plurality of unit multi-color spray patterns in which the paints or inks of the different coating colors are mixed. A patterned pressure-sensitive adhesive sheet is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a release sheet layer (1) is located on one side of a pressure-sensitive adhesive layer (2) (the side opposite to a base sheet layer). It is a paper or sheet treated with a release agent or a sheet exhibiting releasability itself. The thickness of the sheet is about 1
It is in the range of 0-1000 μm, preferably about 20-250 μm.

In the present invention, the pressure-sensitive adhesive layer (2) is located between the release sheet layer (1) and the base sheet layer (3),
For example, it is a layer formed of a conventionally known pressure-sensitive and heat-sensitive adhesive such as natural rubber, acrylic resin, ethylene / vinyl acetate copolymer, polyurethane, polyester, silicone rubber, fluorine rubber, polyvinyl butyral, and the like.
The pressure-sensitive adhesive may include, for example, a tackifier, a pressure-adjusting agent, an antioxidant, a stabilizer, a coloring agent, and the like. The thickness of the pressure-sensitive adhesive layer (2) is in the range of about 10 to 1000 μm, preferably about 20 to 500 μm. As the pressure-sensitive adhesive, a pressure-sensitive pressure-sensitive adhesive is particularly preferable.

In the present invention, the base sheet layer (3) comprises:
The multi-layer pattern coating layer (4) provided on the surface of the base sheet layer (3) is fixed and can be attached to an adherend. For example, aluminum, iron, stainless steel, tinplate, copper Metal sheets such as polyvinyl chloride resin, polyethylene terephthalate resin, polyethylene resin, polyurethane resin, fluorine resin, polypropylene resin, polystyrene resin, polycarbonate resin,
Plastic sheets such as polybutylene terephthalate resin; sheets made of paper and the like. These base sheet layers (3) may be used alone or in combination, for example, metal vapor deposition or laminate. Further, these base sheet layers may themselves be colored. The thickness of the base sheet layer (3) is about 5-200 μm, preferably about 10-80 μm for metal sheets, and about 5-2000 μm, preferably about 10-1000 μm for plastic sheets and papers.
The range of m is preferred.

In the present invention, the multi-pattern coating film layer (4) comprises:
It is provided on the base sheet (3) by the following spray coating method.

That is, a spray coating method for forming a colorful pattern on a moving sheet, using a spray coating apparatus having two or more discharge nozzles for paint or ink, and applying each discharge nozzle to the surface to be coated of the sheet. And dispensing paints or inks of different paint colors from at least two or more discharge nozzles of each spray coating device to form a plurality of unit multicolor spray patterns in which the paints or inks of different paint colors are mixed. It is provided by a spray coating method in which individual pieces are formed and a multicolor pattern is formed on a sheet.

[0010] Examples of the spray coating apparatus having two or more paint or ink discharge nozzles used in the above method include a multi-nozzle spray gun and a multi-head spray gun.

The multi-nozzle spray gun is a coating machine having one coating gun head in a coating machine, and the coating gun head having two or more paint or ink discharge nozzles in close proximity. By discharging paints or inks of different paint colors from the respective discharge nozzles of the multi-nozzle spray gun, a multicolor spray pattern in which paints or inks of different paint colors are mixed can be formed.

As a multi-nozzle spray gun, for example,
A spray gun described in JP-A-9-299833 can be used. The position of the nozzle of the multi-nozzle spray gun may be any position where paints or inks of different colors discharged from each nozzle are mixed and a uniform pattern paint layer can be formed on the sheet. The nozzles may be arranged independently, or the nozzles may be arranged concentrically and integrally to form an inner nozzle and an outer donut-shaped nozzle.

An example of a spray coating apparatus in which two or more nozzles are independently arranged will be described with reference to FIGS. 1 and 2.

FIG. 1 is a front sectional view of the spray coating apparatus, and FIG. 2 is a left side view of the spray coating apparatus. FIG. 1 is a sectional view taken along the line AA of FIG. 2 which is a left side view.

In FIG. 1, the spray coating apparatus includes a gun body 1, a paint or ink discharge nozzle base 5, an air cap 15, and a retaining nut 14 for connecting and fixing them.

The gun body 1 has a paint or ink supply port 2 (a, b, c, d (c, d not shown)) and an atomizing air supply port 3 (a, b (however, b is not shown)), pattern air supply port 4 (a, b (b is not shown))
And a pilot air supply port 19 are formed. Further, the paint or ink path 6 (a, b, c, d (c, d is not shown)) from the supply port 2 to the left in FIG. Air path 9
(A, b (however, b is not shown)), the pattern air path 10 (a, b (however, b is not shown)) to the left from the pattern air supply port 4 and the upper right from the pilot air supply port 19. On the other hand, a pilot air path 20 is formed.

A paint or ink path 7 (a, b, c, d (however,
c, d are not shown)), the atomizing air path 11 (a, b,
c and d (however, c and d are not shown)) and a paint discharge nozzle 8 (a, b, c and d (however, c and d are not shown)) are formed. The air cap 15 has an atomized air jet 16 in the center and a pattern air jet 17 in the horn.
(A, b) are formed. By fixing the discharge nozzle base 5, the air cap 15, and the discharge nozzle position adjustment washer 18 with the retaining nut 14, the atomized air supply chamber 12 and the pattern air supply chamber 13 are formed.

At the time of painting, the path 6 of the gun body 1 is
The paint or ink is supplied to the discharge nozzle base path 7 from the left end of the path 6 of the gun body 1 and can be discharged from the discharge nozzle 8 in communication with the discharge nozzle base path 7. The atomizing air is supplied from the atomizing air path 9 of the gun body 1 to a chamber that communicates with the atomizing air path 11 of the discharge nozzle base, and from this chamber enters the atomizing air supply chamber 12 via the atomizing air path 11 and is atomized. It is ejected from the chemical air ejection port 16. The paint or ink discharged from the discharge nozzle 8 by the ejection of the atomizing air is atomized. The pattern air is supplied from the pattern air path 10 of the gun body 1 to the pattern air supply chamber 13 and is ejected from the pattern air ejection port 17. The ejection of the pattern air can promote the atomization of the paint or ink particles and increase the width of the paint or ink spray pattern.

The pilot air supplied from the pilot air supply port 19 of the gun body 1 is supplied to the pilot air path 2
0, the air is supplied to a sealed pilot air supply chamber 21 formed by the inner wall of the gun body 1 and the piston 24. By supplying the pilot air to the pilot air supply chamber 21, the piston 24 is pushed rightward and moves to expand the pilot air supply chamber 21. by this,
Needle connecting member 22 connected to piston 24 and needle 23 (a, b, c, d) connected to this member 22
(However, c and d are not shown)) move rightward. When the needle 23 moves to the right, the path 6 of the gun body 1 and the path 7 of the discharge nozzle base communicate with each other, so that the paint or the ink can be discharged.

When the pilot air is not supplied, the spring 25 pushes the piston 24 and the members interlocked therewith toward the left end, whereby the left end of the needle 23 closes the right end opening of the passage 7 of the discharge nozzle base. ,
The path 6 of the gun body 1 and the path 7 of the discharge nozzle base do not communicate with each other, and the paint or ink is not discharged. Further, by adjusting the position of the needle pull-down positioning member 27 with the needle pull-down adjusting screw 26, it is also possible to adjust the discharge amount of the paint or ink.

Next, in FIG. 2, four discharge nozzles 8 (a, b, c, d) are disposed at the center, and atomized air is jetted from the atomized air jet ports 16 around the nozzles. Further, pattern air is ejected from the pattern air ejection ports 17 (a, b). A multicolor pattern can be formed by using two or more of the four paint ejection nozzles, ejecting paint or ink of different colors from each nozzle, and ejecting atomized air and pattern air. .

By changing the arrangement of the discharge nozzles (a, b, c, d), the degree of mixing of the paint or ink particles can be adjusted. That is, as shown in FIG. 2, by bringing the discharge nozzle members close to each other so that they can come into contact with each other, the degree of mixing of the paint or ink particles discharged from each discharge nozzle can be increased.
When the discharge nozzle members are separated from each other, the degree of mixing of the paint or ink particles becomes smaller. Although the distance between the discharge nozzles is not particularly limited, it is usually preferable that the distance between the discharge nozzles is as small as possible, and the distance between the discharge nozzles is 15 mm or less, preferably 10 mm or less, more preferably 5 mm or less. Suitably, it is within the following range.

When the number of discharge nozzles of the multi-nozzle spray gun is three or more (four in FIG. 2), paints or inks of different colors may be discharged from each of the discharge nozzles, or a required number of nozzles may be discharged. Only one (eg, two of the four nozzles) may be used to spray different colors of paint or ink.

In the multi-head spray gun, the coating machine has two or more coating gun heads, each coating gun head has one discharge nozzle, and the discharge nozzles are not close to each other. With the discharge nozzles (two or more in total) of each coating head of the multi-head spray gun facing the sheet, spray patterns of paint or ink particles of different colors discharged from the two or more discharge nozzles are coated on the sheet. A multicolored paint film can be formed by forming a multicolor spray pattern in which two or more different colors of paints or inks are mixed by crossing each other before hitting a painted surface. Also, the direction of each nozzle of the two air spray guns is positioned so that each spray pattern crosses before hitting the surface to be coated to form a multi-color spray pattern and form a multi-color pattern coating on the sheet. By fixing it, the same operation as a multi-head spray gun can be performed.

Using the above spray coating device, at least two paints or inks having different coating colors are discharged from at least two discharge nozzles of a spray gun having two or more discharge nozzles. This forms a multicolor spray pattern in which paint or ink discharged from each nozzle is mixed. The degree of mixing of the paint or ink in the spray pattern may be determined according to the intended pattern within a range in which a multicolored coating film can be formed, and by appropriately adjusting the coating conditions such as viscosity and discharge amount. Can be adjusted. The viscosity of the paint at the time of application is usually in the range of 10 to 40 seconds, as measured by Ford Cup # 4 (20 ° C.). The atomizing air pressure of the paint or ink is usually in the range of 0.5 to ¹⁰ kgf / cm ² , and the pattern air pressure is usually 0.1 to 4 kgf / cm 2.
Suitably within the range of ² .

The shape of the unit multicolor spray pattern formed from each coating apparatus as described above may be a perfect circle or an ellipse, and is not particularly limited.
In the present invention, in the case where the moving speed of the sheet is relatively high, it is effective to use a plurality of coating apparatuses in order to perform coating without leaving unpainted areas.

In the above, a plurality of unit multicolor pattern patterns formed by a plurality of spray coating apparatuses are combined to form a multicolor pattern pattern in which adjacent unit multicolor pattern patterns overlap. The degree of overlap between adjacent unit multicolor pattern patterns is usually 1 /
Within the range of 6 to 1/2, preferably 1/3 to 1/2 (when each unit multicolor pattern is a circle, 1
/ 6 to ２, preferably 1/3 to）). In the present invention, the size of the unit multicolor pattern or the multiple multicolor pattern means the size of the effective spray pattern.

When a multicolor pattern is formed on a sheet, the coating machine is reciprocated (short distance reciprocating) in the width direction of the sheet to reciprocate the multicolor pattern in the width direction of the sheet. You may. It is possible to improve the uniformity of the pattern by short reciprocating. For a wide sheet, the number of guns can be increased and the continuity of the pattern can be ensured.

In the present invention, when a multi-color pattern is formed by spray coating using a plurality of coating apparatuses, the formed multi-color pattern is located at a position that continuously covers the entire width of the sheet. When performing short reciprocating of a coating machine, short reciprocating is performed within a range where a multi-color pattern pattern continuously covers the entire width of an object to be coated.

The thickness of the multi-color coating film layer having the multi-color pattern formed on the sheet is not particularly limited, but is usually 1 to 100 μm in dry film thickness.
It is preferable that the thickness be in the range of 10 to 50 μm, from the viewpoints of the appearance of the resulting patterned coating film, prevention of foaming (foaming) of the coating film during drying and the like. The patterned coating film can be dried or cured by leaving it at room temperature, heating, or irradiating with active energy rays, depending on the type of paint or ink used.

As the paint or ink used above, for example, a non-curable type, a curable type at room temperature or by heating,
Further, a curable type by irradiation with an electron beam such as ultraviolet rays may be used. The non-curing type is, for example, a composition that forms a dry coating film only by evaporating an organic solvent. For example, a polyester resin, an alkyd resin, an epoxy resin, a vinyl acetate resin, a vinyl chloride resin, a vinyl acetate / Examples include those using a binder component such as a vinyl chloride copolymer resin, a fluorine resin, a urethane resin, a polyamide resin, a silicon resin, a rubber resin, and an acrylic resin. Curable resins include, for example, oxidation-curable resins (eg, resins having an oxidatively polymerizable unsaturated group such as alkyd resins), moisture-curable resins (eg, acrylic resins containing isocyanate groups and acrylic resins containing alkoxysilyl groups), and multi-liquid reactions. Curable resin (polyether polyol, polyester polyol,
A composition obtained by mixing a polyisocyanate or a melamine curing agent with a hydroxyl group-containing resin such as an acrylic polyol or a fluorine polyol, or a radical reaction-curable resin obtained by mixing a peroxide with an unsaturated polyester resin) and the like as a binder component. To do. Examples of the electron beam irradiation-curable type include those in which an electron beam-curable unsaturated group is bonded to an acrylic resin, a polyester resin, a silicone resin, a polyether resin, a fluororesin, or the like as a binder component.

In the present invention, if necessary, a clear coating layer (5) may be further provided on the multicolored coating layer (4). Examples of the clear coating layer (5) include molds generated on the interior material surface, cigarette dust, inks, markers,
From the viewpoint of prevention of contamination by foods and the like and easy removal of contamination, it is preferable to form by coating a silicone resin curable treatment agent, a treatment agent containing titanium sol having photocatalytic activity, and the like.

The silicone resin curable treating agent has a hydrolyzable silicon group which produces a hydroxyl group directly bonded to silicon by a hydrolysis reaction with water or moisture in the air,
In particular, a group in which a lower alkoxyl group such as methoxy, ethoxy, propoxy or the like is directly bonded to a silicon atom is preferable because of exhibiting excellent curability, and the following (I) to (VI)
Selected from any of

The treating agent (I) includes a hydroxyl-containing radically polymerizable unsaturated monomer (a), an epoxy-containing radically polymerizable unsaturated monomer (b), a hydroxyl group and / or a hydrolyzable group directly bonded to silicon. (C), a radically polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d), and optionally other radicals other than the above (a) to (d) A silicone resin curable treating agent containing an organosilicon copolymer (i) of a polymerizable unsaturated monomer (e) and a metal chelate compound (ii).

(A) Examples of the hydroxyl-containing radically polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. And) acrylates and hydroxyl-containing unsaturated monomers such as adducts of these with caprolactone.

Examples of the (b) epoxy group-containing radical polymerizable unsaturated monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and allyl glycidyl ether.

(C) Examples of the radically polymerizable unsaturated monomer having a hydroxyl group and / or a hydrolyzable group directly bonded to silicon include vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (2-methoxyethoxy). ) Silane, γ- (meth) acryloyloxypropyltrimethoxysilane, vinyltriacetooxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane and the like. Further, for example, Japanese Patent Application Laid-Open No.
No. 97423, which has an average of one polymerizable unsaturated bond in one molecule and at least two or more alkoxysilane groups and / or hydroxysilane groups in a terminal equivalent portion, and has a number average molecular weight of 400 to 100,000. Polysiloxane macromonomer can be used.

(D) A dimethylsiloxane bond is used as a main chain.
Radical polymerizable unsaturated monomers include, but are not limited to,
It has a radical polymerizable unsaturated group at the end and has
Tylsiloxane bond [-Si (CH_Three )_Two O-] unit
It is an unsaturated monomer containing two or more. The dimethylsi
Radical polymerization at one (left) end of oxane bond residue
And the other (right) end is [-S
i_Three ) (R_Four ) O-] unit (R_Three Or R_Four Is methyl, d
Alkyl groups such as tyl, propyl, and butyl; phenyl
Group, epoxy group, or SH group. However, R3 or
R4 does not include those which are both methyl groups. R3 or
In R4, the epoxy group and the SH group may be directly on Si.
Represents a hydrocarbon bond or an ether bond or a combination thereof.
They may be connected via a bond. Via)
Is directly [-Si (R_Three )_Three ] (R _Three Is the same as above.
Show the taste. R_Three Must be the same or different
Can be. ), R₁ (R₁ Indicates the same meaning as above
You. ) Or those with hydrogen atoms bonded
it can. Examples of the radical polymerizable unsaturated group include, for example, C
H _Two = CHCOOC_nH_2n-, CH_Two = CCH_Three COO
C_nH_2n(N is an integer of 1 to 5, especially
1-4 integers are preferred). The radical polymerizable unsaturated mono
In particular, CH_Two = CH (or CH_Three ) COO
C_Three H₆ − [Si (CH_Three )_Two O] m-Si (CH_Three )
_Three , And CH_Two = CH (or CH_Three ) COOC _Three H₆ −
[Si (CH_Three )_Two O] m-R1 (where m is 3 to 70)
Are preferred.) Specifically, for example
If CH_Two = CH (or CH_Three ) COOC _Three H₆ − [S
i (CH_Three )_Two O]₁₁-Si (CH_Three )_ThreeCH_Two = CH
(Or CH_Three) COOC_Three H₆ − [Si (CH_Three )_Two 
O]_{20 ~ 30} -Si (CH_Three )_ThreeCH_Two= CH (or CH_Three
 ) COOC_Three H₆ − [Si (CH_Three )_Two O]₆₅-Si
(CH _Three )_ThreeCH_Two = CH (or CH_Three ) COOC_Three H₆
 − [Si (CH_Three )_Two O]_{20 ~ 30} -CH_ThreeEtc.
Can be

(E) Other radically polymerizable unsaturated monomers other than the above (a) to (d) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl ( meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) such as such as acrylates (meth) C ₁ acrylic acid _{- 24} alkyl or cycloalkyl esters, styrene, vinyl toluene, (meth ) Acrylic nitrile and the like.

The organosilicon copolymer (i) can be produced by a conventionally known radical polymerization method, for example, a solution polymerization method.

The average molecular weight of the organosilicon copolymer (i) is preferably in the range of about 3000 to 80000, particularly preferably in the range of about 8000 to 50,000. If the molecular weight is less than about 3,000, the workability of the coating film is reduced, and if it is more than about 80,000, the coating and printing workability is undesirably reduced.

Examples of the metal chelate compound (ii) include aluminum tris (ethylacetoacetate), aluminum tris (n-propylacetoacetate), aluminum tris (isopropylacetoacetate), and tris (n-butylacetoacetate). Aluminum, aluminum isopropoxybis (ethylacetoacetate), aluminum diisopropoxyethylacetoacetate, aluminum tris (acetylacetonato), aluminum tris (propionylacetonato), aluminum diisopropoxypropionylacetonato, aluminum acetylacetonate bis Propionylacetonato) aluminum, monoethyl acetoacetate bis (acetylacetonato) aluminum, acetylacetonato aluminum Aluminum chelate compounds such as di-sec-butylate, methyl acetoacetate aluminum di-tert-butylate, bis (acetylacetonato) aluminum mono-sec-butylate, di (methylacetoacetate) aluminum mono-tert-butylate; Titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetonato) titanate and di-n-butoxybis (acetylacetonato) titanate; for example, tetrakis Examples include zirconium chelate compounds such as (acetylacetonato) zirconium, tetrakis (n-propylacetoacetate) zirconium, and tetrakis (ethylacetoacetate) zirconium.

The treating agent (I) is an organosilicon copolymer (i)
It is obtained by blending about 0.01 to 20 parts by weight, particularly about 0.1 to 10 parts by weight of the metal chelate compound (ii) with respect to 100 parts by weight. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

The treating agent (II) includes a hydroxyl-containing radically polymerizable unsaturated monomer (A), an epoxy-containing radically polymerizable unsaturated monomer (B), a hydroxyl group and / or a hydrolyzable group directly bonded to silicon. (C) and optionally (a) to (c) above
And an organic silicon copolymer (iii) of a radical polymerizable unsaturated monomer (e), a dimethylpolysiloxane-based compound (iv), and a metal chelate compound (ii).

The hydroxyl group-containing radically polymerizable unsaturated monomer (b) and the epoxy group-containing radically polymerizable unsaturated monomer (b) used in the organosilicon copolymer (iii), a hydroxyl group directly bonded to silicon and / or Radical polymerizable unsaturated monomers containing a hydrolyzable group (c), and other radical polymerizable unsaturated monomers used as required
(E) includes those similar to the organosilicon copolymer (i).

The organosilicon copolymer (iii) can be produced by a conventionally known radical polymerization method, for example, a solution polymerization method.

The average molecular weight of the organosilicon copolymer (iii) is about 3000 to 80000, especially about 8000 to 5000
A range of 0 is preferred. If the molecular weight is less than about 3,000, the workability of the coating film is reduced, and if it is more than about 80,000, the coating and printing workability is undesirably reduced.

Dimethyl polysiloxane compound (iv)
Is a dimethylsiloxane bond [-Si (CH
₃ ) ₂ O—] units, two or more, preferably 3 to 100, of which one (left) molecular terminal is —OSi (R ₅ )
(R ₆ ) (R ₇ ) (R ₅ , R ₆ or R ₇ is methyl,
Ethyl, lower alkyl group of C _{1 ~ 3,} such as propyl, phenyl group, hydroxyl group and the like shown. ), Also the other (right) molecular end _{-Si (R 5) (R 6} ) (R 7) (R 5
, R ₆ or R ₇ have the same meaning as described above. ). Among R ₅ , R ₆ and R ₇ , it is preferable that all three of them are a methyl group or two methyl groups and a hydroxyl group. [-Si (R)
_{8) (R 9) O -} .] (R 8 or R _9, represents methyl, ethyl, lower alkyl group of C _{1 ~ 3,} such as propyl, phenyl group, hydroxyl group, etc. However, R _8, and R ₉ is Both do not include those having a methyl group.) About 1 to 50 units can be combined. The average molecular weight of the dimethylpolysiloxane compound (iv) is about 310 to 80.
00, especially about 380-5000. When the average molecular weight is less than about 310, the adhesion to the base film layer is reduced or the durability of the effect is reduced. On the other hand, when the average molecular weight is more than about 8000, the effect of stain resistance is reduced, which is not preferable.

Specific examples of dimethylpolysiloxane (iv) include, for example, SH200 oil (dimethylpolysiloxane), PRX413, and BY16-80 (trade names, manufactured by Toray Dow Corning Silicone Co., Ltd.).
1, BY16-817 (above, dimethylpolysiloxane having a terminal silanol group), SH510, SH550, S
H710, SH556 (above, phenyl-modified dimethylpolysiloxane), SH203, SH230, BX16-
811F (dimethylpolysiloxane modified with an alkyl group other than a methyl group) and the like.

The treating agent (II) comprises an organosilicon copolymer (i)
ii) It is obtained by blending about 1 to 10 parts by weight, particularly about 1 to 5 parts by weight, of the dimethylpolysiloxane compound (iv) with respect to 100 parts by weight. If the compounding ratio is less than about 1 part by weight, the stain resistance, surface hardness and the like are inferior.
If the amount is more than 0 parts by weight, the surface smoothness, curability, transparency, adhesion to the substrate, etc. are poor, and therefore it is not preferable.

The mixing ratio of the metal chelate compound (ii) is about 0.01 to 20 parts by weight, especially about 0 to 20 parts by weight of the metal chelate compound (ii) per 100 parts by weight of the organosilicon copolymer (iii). 0.1 to 10 parts by weight is preferred. About 0.0
If the amount is less than 1 part by weight, the low-temperature curability decreases, while about 20 parts
Exceeding the weight part is not preferred because the cost increases and the processability decreases.

The treating agent (III) includes a hydroxyl group-containing radically polymerizable unsaturated monomer (a), an epoxy group-containing radically polymerizable unsaturated monomer (b), a hydroxyl group and / or a hydrolyzable group directly bonded to silicon. (C), a radically polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d), and optionally other radicals other than the above (a) to (d) Organosilicon copolymer (i) of polymerizable unsaturated monomer (e), dimethylpolysiloxane compound (iv), and metal chelate
(Ii) the compound (ii).

As the organosilicon copolymer (i), the dimethylpolysiloxane compound (iv), and the metal chelate compound (ii), those similar to the above can be used.

The treating agent (III) is blended with about 1 to 10 parts by weight, particularly about 1 to 5 parts by weight, of the dimethylpolysiloxane compound (iv) based on 100 parts by weight of the organosilicon copolymer (i). . If the compounding ratio is less than about 1 part by weight, the stain resistance and surface hardness are inferior. Absent.

The compounding ratio of the metal chelate compound (ii) is about 0.01 to 20 parts by weight, particularly about 0 to 20 parts by weight of the metal chelate compound (ii) per 100 parts by weight of the organosilicon copolymer (i). 0.1 to 10 parts by weight is preferred. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

The treating agent (IV) may be a hydroxyl-containing radically polymerizable unsaturated monomer (a), an epoxy-containing radically polymerizable unsaturated monomer (b), a hydroxyl group and / or a hydrolyzable group directly bonded to silicon. (C), a radically polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d), and optionally other radicals other than the above (a) to (d) polymerizable unsaturated monomers - organosilicon copolymer (e) (i), the general formula _{(1) Si (oR 1)} 4 ( wherein, the hydrocarbon group R ₁ is C ₁ ~ ₄ same or different 0) to 90% by weight of the organosilicon compound (A) represented by
And general formula _{(2) R 2 Si (OR1} ) 3 ( wherein, R ₁ represents the same meaning as above, R ₂ represents a C ₁ ~ _{1 2} hydrocarbon group) the organosilicon compound represented by ( B) and / or an organosilicon condensate (v) obtained by condensing a mixture of 10 to 100% by weight of a low condensate thereof, and a metal chelate compound (i)
i).

As the organosilicon copolymer (i) and the metal chelate compound (ii), the same compounds as described above can be used.

[0058] In the organic silicon compound (A), the hydrocarbon group of C _{1 ~ 4} of R ₁ represented by the general formula (1), include methyl, ethyl, propyl, alkyl groups such as butyl it can. The alkyl group may be branched or unbranched. As the low condensate, those having a polymerization degree of 2 to 10 are preferable. Specific examples of the organic silicon compound (A) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like.

In the organosilicon compound (B), R ₁ represented by the general formula (2) may be the same as described above. The hydrocarbon group of C _{1 ~ 12} of the R _2, for example, methyl, ethyl, propyl, butyl,
Alkyl groups such as hexyl and octyl (the alkyl groups may be branched or unbranched), aryl groups such as phenyl, toluyl and xylyl, cycloalkyl groups such as cyclohexyl, cyclobutyl and cyclopentyl; Can be mentioned. As the low condensate, those having a polymerization degree of 2 to 10 are preferable.

Specific examples of the organosilicon compound (B) include:
For example, methyltrimethoxysilane, methyldimethoxyethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like can be given.

The organosilicon condensate (v) comprises the organosilicon compound (A) and / or its low condensate in an amount of 0 to 90% by weight, preferably 20 to 80% by weight, and the organosilicon compound (B) and / or its low condensate. 10 to 100% by weight, preferably 20 to 100% by weight of condensate
It is obtained by condensing a mixture with 80% by weight.
The above-mentioned condensation reaction is described in, for example, Japanese Patent Publication No. 4-22953.
The method can be performed by the method described in Japanese Patent Application Laid-Open Publication No. HEI 10-76, pp. The organosilicon condensate (v) is a three-dimensional condensate, having a degree of condensation of at least 20 and a molecular weight of about 3,000 to 2,000.
00.

The treating agent (IV) comprises an organosilicon condensate (v)
The mixing ratio of the organic silicon copolymer (i) to the organic silicon condensate (v) is 1 to 50% by weight, preferably 1 to 30% by weight. ~ 99
% By weight, especially 70 to 99% by weight. When the amount of the organosilicon condensate (v) is less than 1% by weight (the amount of the organosilicon copolymer (i) exceeds 99% by weight), the stain resistance decreases, while the amount of the organosilicon condensate (v) is 50% by weight. % (The content of the organosilicon copolymer (i) is less than 50% by weight) is not preferred because the processability decreases.

The mixing ratio of the metal chelate compound (ii) is based on 100 parts by weight of the total amount of the organic silicon condensate (v) and the organic silicon copolymer (i).
Is preferably about 0.01 to 20 parts by weight, particularly preferably about 0.1 to 10 parts by weight. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

The treating agent (V) includes a hydroxyl-containing radically polymerizable unsaturated monomer (a), an epoxy-containing radically polymerizable unsaturated monomer (b), a hydroxyl group and / or a hydrolyzable group directly bonded to silicon. An organosilicon copolymer of a radical polymerizable unsaturated monomer (c) and optionally other radical polymerizable unsaturated monomers (e) other than the above (a) to (c), (iii), dimethyl polysiloxane compound (iv), the general formula (1) Si (oR _{1) 4} (wherein, R ₁ represents the same or different represent a hydrocarbon group of C ₁ ~ ₄ in) organic silicon compounds represented by ( A) and / or 0 to 90% by weight of a low condensate thereof and a compound of the general formula (2) R ₂ Si
(OR ₁ ) ₃ (wherein, R ₁ has the same meaning as described above;
₂ C ₁ ~ _{1 2} hydrocarbon groups showing a) the organosilicon compound represented by (B) and / or its low condensate 10 to 100% by weight of the mixture condensed organosilicon condensates obtained by (v ),
And a metal chelate compound (ii).

The same organic silicon copolymer (iii), dimethylpolysiloxane compound (iv), organic silicon condensate (v), and metal chelate compound (ii) as described above can be used.

In the treating agent (V), the compounding ratio of the organosilicon condensate (v) and the organosilicon copolymer (iii) is 1 to 50% by weight based on the total weight of the two. Preferably 1 to 30% by weight of the organosilicon copolymer (i
ii) 50-99% by weight, especially 70-99% by weight, is preferred. When the amount of the organosilicon condensate (v) is less than 1% by weight (the amount of the organosilicon copolymer (iii) exceeds 99% by weight),
The stain resistance is reduced, while the organosilicon condensate (v) is 50%.
If the content is more than 50% by weight (the content of the organosilicon copolymer (iii) is less than 50% by weight), the processability is undesirably reduced.

Dimethylpolysiloxane compound (iv)
Of the organic silicon condensate (v) and the organic silicon copolymer (iii) in an amount of about 1 to 1 based on a total weight of 100 parts by weight.
0 parts by weight, especially about 1 to 5 parts by weight, is preferred. If the compounding ratio is less than about 1 part by weight, stain resistance, surface hardness, etc. are inferior,
On the other hand, if it exceeds about 10 parts by weight, the surface smoothness, curability, transparency, adhesion to the substrate and the like are inferior, so that it is not preferable.

The compounding ratio of the metal chelate compound (ii) is based on 100 parts by weight of the total amount of the organosilicon condensate (v) and the organosilicon copolymer (iii).
i) is preferably about 0.01 to 20 parts by weight, especially about 0.1 to 10 parts by weight. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

The treating agent (VI) is a hydroxyl group-containing radical polymer.
Compatible unsaturated monomer (a), epoxy group-containing radical polymer
Compatible unsaturated monomer (b), directly bonded hydroxyl group and / or
Or radically polymerizable unsaturated mono-containing hydrolyzable group
(C) Radical having dimethylsiloxane bond as main chain
Cal-polymerizable unsaturated monomer (d) and, if necessary,
(A) Other radically polymerizable unsaturated monomers other than (d)
Noma (e) organosilicon copolymer (i), dimethylpoly
Siloxane compound (iv), general formula (1) Si (OR
₁ )_Four (Where R₁ Are the same or different C₁~_Four of
An organosilicon compound (A) represented by the following formula:
And / or 0 to 90% by weight of a low condensate thereof and the general formula (2)
R_Two Si (OR₁ )_Three (Where R₁ Has the same meaning as above
And R _Two Is C₁ ~₁₂Represents a hydrocarbon group)
Organosilicon compound (B) and / or low condensate thereof 10-1
Organic silicon condensate obtained by condensing a 00% by weight mixture
(V) and a metal chelate compound (ii).
Can be

In the treating agent (VI), the organic silicon copolymer (i) and the dimethylpolysiloxane compound (i)
As v), the organosilicon condensate (v), and the metal chelate compound (ii), those similar to the above can be used.

In the treating agent (VI), the blending ratio of the organosilicon condensate (v) and the organosilicon copolymer (i) is 1 to 50% by weight of the organosilicon condensate (v), Preferably 1 to 30% by weight, 50 parts of organosilicon copolymer (i)
-99% by weight, particularly preferably 70-99% by weight. When the amount of the organosilicon condensate (v) is less than 1% by weight (the amount of the organosilicon copolymer (i) exceeds 99% by weight), the stain resistance decreases, while the amount of the organosilicon condensate (v) is 50% by weight. % (Organic silicon copolymer (i) is less than 50% by weight)
Is not preferred because the processability is reduced.

Dimethyl polysiloxane compound (iv)
Is preferably about 1 to 10 parts by weight, particularly preferably about 1 to 5 parts by weight, based on 100 parts by weight of the organosilicon copolymer (i). If the compounding ratio is less than about 1 part by weight, the stain resistance and surface hardness are inferior. Absent.

The mixing ratio of the metal chelate compound (ii) is based on 100 parts by weight of the total amount of the organic silicon condensate (v) and the organic silicon copolymer (i).
Is preferably about 0.01 to 20 parts by weight, particularly preferably about 0.1 to 10 parts by weight. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

The silicone resin-curable treating agents (I) to (VI) can be obtained by dissolving or dispersing the above-mentioned compound in an organic solvent, and further adding a coloring pigment, a filler,
It can be produced by mixing additives and the like.

On the other hand, as a treating agent containing a titanium sol having photocatalytic activity, for example, an organic solvent is added to an aggregate of (a) a curable silicone resin and (b) a hydrated titanium oxide sol, and then water is added. An organic solvent-based titanium sol having a photocatalytic activity obtained by removal is included.

As the curable silicone resin (a), there can be used, without particular limitation, conventionally known thermosetting resins and room-temperature curing resins. In particular, the resin contains a tetrafunctional silicon structural unit or a trifunctional silicon structural unit. It is preferable to use a resin containing 50 mol% or more. The functional groups used for curing include:
For example, a hydrolyzable group directly bonded to a silicon atom (for example,
Lower alkoxy group, acyl group, acetoxy group, butanoxime group), hydroxysilyl group and the like. The hydrolyzable group or hydroxysilyl group can be cured by, for example, a reaction with an organometallic compound or an epoxy group. In addition, the curable silicon-based resin may have a functional group such as an epoxy group and an unsaturated group in addition to the above-described functional group as needed.

Examples of the compound having a tetrafunctional silicon structural unit include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, triacetoxysilane, and about 2 to 10-mers thereof. And the like. Examples of the trifunctional silicon structural unit include, for example, trimethoxymethylsilane, trimethoxyethylsilane, trimethoxycypropylsilane, trimethoxybutylsilane, trimethoxyphenylsilane, triethoxymethylsilane, tripropoxymethylsilane, and tributoxyphenylsilane. , Vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxytrimethoxysilane, 2-styrylethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethoxysilane, γ-glycidoxypropyltrimethoxysilane And the like.

The curable silicone resin may have a bifunctional silicon structural unit or a monofunctional silicon structural unit in addition to the tetrafunctional silicon structural unit and the trifunctional silicon structural unit. These include monoalkoxysilanes such as methoxytrimethylsilane, methoxytriethylsilane, ethoxytriethylsilane, and ethoxytriphenylsilane; and dialkoxysilanes such as dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiphenylsilane, and diethoxydimethylsilane. . The organic solvent-based titanium sol (b) having photocatalytic activity is obtained by blending an organic solvent with an aggregate of a hydrated titanium oxide sol and then removing water. Furthermore, an anionic surfactant is added to the hydrated titanium oxide sol obtained by hydrolyzing the aqueous solution of titanium sulfate to aggregate the hydrated titanium oxide particles, and if necessary, alkali washing is performed to remove the inorganic acid. This is an organic solvent-based titanium sol obtained by blending an organic acid and an organic solvent after removal, and then removing water. The hydrated titanium oxide sol is added with a basic aqueous solution to an aqueous solution of titanium sulfate to adjust the pH to 1.
It is preferable that the sol is a transparent hydrated titanium oxide sol having a particle diameter of 200 nm or less, particularly 100 nm or less.
The amount of the organic solvent-based titanium sol (b) having photocatalytic activity is 5 to 70 parts by weight based on 100 parts by weight of the total solids in the treating agent.
Suitably it is parts by weight.

The organic solvent-based titanium sol (b) having photocatalytic activity is excited by absorbing ultraviolet rays such as sunlight and artificial illumination light, for example, ultraviolet rays having a wavelength of 400 or less, to excite holes (holes) and OH radicals. They exhibit strong oxidizing performance, decompose dirt in the air, and oxidize them when they come in contact with nitrogen oxides or sulfurous acid gas in the air to change them into nitric acid or sulfuric acid. The nitric acid or sulfuric acid acts as a catalyst for hydrolyzing the alkoxysilyl group in the coating film, hydrophilizes the surface of the coating film, and enhances the self-cleaning property of the coating film itself.

The treating agent containing the titanium sol having photocatalytic activity may further contain additives such as a pigment, a filler and a flow regulator, if necessary.

Before applying the treatment agent containing the photocatalytically active titanium sol, a primer may be applied as necessary. As the primer, for example, the components described in the above-mentioned silicone-based resin curable treating agent can be blended and used. In particular, a hydroxyl-containing radically polymerizable unsaturated monomer (A) and an epoxy-containing radically polymerizable unsaturated monomer can be used. -(B) a radical polymerizable unsaturated monomer (c) containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon, and if necessary, other radical polymerizable unsaturated monomer (e). An organosilicon copolymer (iii) obtained by copolymerization, Si (OR ₁ ) _{4 represented by the} general formula (1):
₁ organic silicon compound represented by the same or different represent a hydrocarbon group of C ₁ ~ ₄ in) (A) and / or its low condensate 0-90 wt% and the general formula ₍₂₎ R ₂ Si (OR
₁ ) ₃ (wherein, R ₁ has the same meaning as described above, and R ₂ is C
_{1-1 2} hydrocarbon groups showing a) the organosilicon compound represented by (B) and / or condensed with organosilicon condensate obtained its low condensate 10 to 100% by weight of the mixture (v), and Those containing the metal chelate compound (ii) are preferred.

As a method of applying (including printing) the silicone resin curable treating agent, a conventionally known method, for example, spray, brush, roller, etc., and printing (screen, gravure, etc.) can be used. ) Can be performed. The film thickness is about 0.1-30 microns in cured film thickness,
Particularly, a range of about 1 to 20 microns is suitable. Curing can be carried out at room temperature, but it can be usually carried out in a heating range of 40 to 200 ° C.

[0083]

According to the present invention, a pressure-sensitive adhesive sheet having a uniform, three-dimensional and multicolored pattern layer excellent in cosmetics can be obtained by a specific spray coating method, and is particularly useful as an interior / exterior material for buildings. is there. In addition, by providing a specific treatment agent layer, it is possible to have easy stain removal properties and a photocatalytic function.

[0084]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Preparation of Silicone Resin Curing Agent 35 g of styrene, 20 g of glycidyl methacrylate and 20 g of 2-hydroxyethyl acrylate, CH ₂ =
_{CCH 3 COOC 3 H 6 - [} Si (CH 3) 2 O] 2 0 ~
_{30 -Si (CH 3) 3 5g} , macromonomer - (Note 1)
A monomer mixture comprising 20 g was subjected to a radical copolymerization reaction according to a usual acrylic production method to obtain an organosilicon copolymer a having a number average molecular weight of about 20,000.

The organosilicon copolymer a (solid content) 100
g and aluminum tris (ethyl acetoacetate
G) Toluene was added to 2 g for dispersion to obtain a treating agent. (Note 1) Macromonomer: methylmethoxysilane 272
A mixture of 0 g, 230 g of γ-methacryloxypropyltrimethoxysilane, 1130 g of deionized water, 2 g of 1% formic acid, and 1 g of hydroquinone was reacted at 80 ° C. for 5 hours to obtain a polysiloxane macromonomer having a number average molecular weight of 2,000. .

Preparation of Primer Toluene was added to 70 g of organosilicon copolymer b (Note 2) (solid content), 30 g of organosilicon condensate c (Note 3) (solid content) and 2 g of aluminum tris (ethyl acetoacetate). The mixture was added and dispersed to obtain a primer. (Note 2) Organic silicon copolymer b: 42 g of isobornyl acrylate, 20 g of 3,4-epoxycyclohexylmethyl methacrylate, 2-hydroxyethyl methacrylate
A monomer mixture consisting of 18 g of a polymer and 20 g of a macromonomer (Note 1) is subjected to a radical copolymerization reaction according to a usual acrylic production method, and the number average molecular weight is about 20,000.
Was obtained. (Note 3) Organic silicon condensate c: 62 g (0.3 mol) of tetraethoxysilane, 125 g (0.7 mol) of methyltrimethoxysilane and 187 of ethyl alcohol in a reaction vessel.
g of the mixture and heated to 80 ° C.
g was added and reacted at 80 ° C. for 10 hours. Next, 30 g of triethylamine was added to the reaction product to adjust the pH to 7 or more, and a condensation reaction was carried out at 80 ° C. for 2 hours. 100 g of benzene was blended, the solvent was removed until the solid content became 40% by weight, and a varnish having a viscosity of 5.8 mPa · s was obtained. Obtained.

Processing Including Titanium Sol Having Photocatalytic Activity
Preparation of Agent 100 g (solid content) of the above-mentioned organic silicon condensate c is used as a curable silicon-based resin, and an organic solvent-based titanium sol “TK
S-260 "(manufactured by Teica Co., Ltd., trade name, anatase crystal form, average particle diameter 100 °, toluene medium, titanium sol) 100 g (solid content), and benzoylacetonato bis (acetylacetonato) aluminum 2 g were mixed,
After adjusting the organic solvent, butyl acetate and toluene were used as the organic solvent, and the heating residue was 47% and the viscosity was 3.0 poise (25
° C).

Preparation of Multicolored Pattern Sheet Example 1 As a paint for obtaining a multicolored pattern layer, "Rethane PG80
White "(Kansai Paint Co., Ltd., acrylic urethane resin top coat, white) and" Rethane PG Black "
(Acrylic urethane resin top coat, black, manufactured by Kansai Paint Co., Ltd.) was used after adjusting the viscosity to 15 seconds (Ford Cup # 4/20 ° C.). Fig. 3
, Ie, using three multi-nozzle guns. As an object to be coated, a transparent polyethylene terephthalate (PET) film having a corona treatment (50 μm thick)
m), and the moving speed (line speed) of the object to be coated is 4
0 m / min.

Each multi-nozzle gun has four nozzles and the members of the nozzles come into contact with each other (a distance between nozzles of 4 m).
m), when all the four nozzles are used to discharge and paint the two kinds of paints, white and black, the distance from the nozzle tip to the surface of the work is 40 cm, and the effective pattern width is 30 cm. Was formed, and a multiplex multicolor pattern was formed such that adjacent spray patterns overlapped with each other by half of the diameter of the spray pattern.

In each multi-nozzle gun, the atomizing air pressure of the paint is 1.0 kgf / cm ² and the pattern air pressure is 1.0 kf.
gf / cm ^2, and the discharge amount of the paint from each multi-nozzle gun was 200 cc / min for both the white paint and the black paint. Baking was performed at 180 ° C. for 30 seconds.

On the PET film side of the obtained colorful pattern sheet, a pressure-sensitive adhesive layer of 30 μm and a release sheet 250
The sheet laminated with μm was applied under pressure so that the PET film layer and the pressure-sensitive adhesive layer were in contact with each other to obtain a multi-pattern adhesive sheet.

The obtained multi-color patterned pressure-sensitive adhesive sheet had a multi-colored pattern layer having a uniform dry film thickness of about 20 μm, a three-dimensional appearance, and excellent cosmetic properties. And no pencil peeling H).

Example 2 In Example 1, after the formation of the multi-color pattern layer, the treatment agent produced as described above was further applied on the multi-color pattern surface (the surface opposite to the PET film surface) to a dry film thickness of 1 μm. Was coated with a gravure coater and dried and cured at 160 ° C. for 30 seconds. Thereafter, a sheet in which a pressure-sensitive adhesive layer of 30 μm and a release sheet of 250 μm are laminated on the surface of the PET film is applied by applying pressure so that the PET film layer and the pressure-sensitive adhesive layer are in contact with each other. A patterned adhesive sheet was obtained.

The obtained multi-pattern pressure-sensitive adhesive sheet was attached to an aluminum plate (0.8 × 150 × 100 mm) to prepare a test plate, an oil-based magic was drawn on the surface thereof, and after 24 hours, the magic was wiped off by dry wiping. Was very easily wiped off.

Example 3 In Example 1, after the formation of the multi-color pattern layer, the primer produced as described above was further applied on the multi-color pattern surface (opposite to the PET film surface) to a dry film thickness of 1 μm. After coating with a bar coater and drying at 120 ° C. for 1 minute, the treatment agent was coated with a bar coater so as to have a dry film thickness of 1 μm.
It was coated with a tar and dried and cured at 160 ° C. for 1 minute. Thereafter, a sheet in which a pressure-sensitive adhesive layer of 30 μm and a release sheet of 250 μm are laminated on the surface of the PET film is applied by applying pressure so that the PET film layer and the pressure-sensitive adhesive layer are in contact with each other. A patterned adhesive sheet was obtained.

The obtained multi-pattern pressure-sensitive adhesive sheet was attached to an aluminum plate (0.8 × 150 × 100 mm) to prepare a test plate.
The test plate was set at an angle of 0 degree, and an outdoor exposure test was performed. The lightness difference (the lightness difference ΔL * value in the CIE color system) of the surface of the treatment agent layer after 12 months of outdoor exposure from the unexposed initial coated plate was 0.9 in each case.

[Brief description of the drawings]

FIG. 1 is a front sectional view of an example of a multi-nozzle spray gun.

FIG. 2 is a left side view of an example of a multi-nozzle spray gun.

FIG. 3 is a schematic view showing one example of spray coating in the present invention.

[Explanation of symbols]

1 Gun body 2 (a, b, c, d) Paint supply port 3 (a, b) Atomizing air supply port 4 (a, b) Pattern air supply port 5 Paint discharge nozzle base 6 (a, b, c, d) Paint path of gun body 7 (a, b, c, d) Paint path based on paint discharge nozzle 8 (a, b, c, d) Paint discharge nozzle 9 (a, b) Atomized air path of gun body 10 (a, b) Pattern air path of gun body 11 (a, b, c, d) Atomizing air path of paint discharge nozzle base 12 Atomizing air supply chamber 13 Pattern air supply chamber 14 Retaining nut 15 Air cap 16 Atomizing air jet 17 (a, b) Pattern air jet 18 Paint washer nozzle position adjustment washer 19 Pilot air supply port 20 Pilot air path 21 Pilot air supply chamber 22 Needle connecting member 23 (a, b, c, ) Needle 24 piston 25 spring 26 needle pulling white adjustment screw 27 needle pulling white positioning member 28 multi nozzle spray gun 29 coating gun fixed frame (short reciprocating device) 30 sheets

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B05D 7/24 302 B05D 7/24 302Y B32B 27/00 B32B 27/00 M 33/00 33/00 (72 Inventor: Masato Kikuta, Kansai Paint Co., Ltd. 4-1-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture 72) Inventor Junichi Mogi 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture, Kansai Paint Co., Ltd. (72) Inventor Satoru 4-1-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture, Kansai Paint Co., Ltd. (72) Inventor Shoichi Shin-Oda 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term (reference) in Kansai Paint Co., Ltd. 4D075 AA39 AA55 AA83 AA85 AE0 3 CA47 CB36 DA04 DB31 DC02 DC05 EA02 EA05 EA43 EC02 4F033 AA01 EA02 PA11 PB31 QA01 QC02 4F100 AA21E AH06 AK12 AK25 AK42 AK52E AL01 AR00A AR00B AR00E AT00J J00A BA00L01 J10 BA10L BA10L BA10L AA04 AA05 AA06 AA07 AA08 AA10 AA11 AA14 AA15 AB01 CA02 CA03 CA04 CA05 CA06 CA08 CB02 CC02 CC03 CD01 CD06 DA02 DA04 DB02 FA01 GA01 GA02

Claims (5)

[Claims] 1. A release sheet layer (1), an adhesive layer (2),
In a pressure-sensitive adhesive sheet formed by laminating a base sheet layer (3) and a multi-colored coating film layer (4), the multi-colored coating film layer is a spray coating method for forming a multi-colored pattern on a moving sheet. Using a spray coating device having two or more ink discharge nozzles, disposing each discharge nozzle toward the surface to be coated of the sheet, and applying different paint colors from at least two or more discharge nozzles of each spray coating device. The paint or ink is ejected to form a multi-color spray pattern in which the paints or inks of the different coating colors are mixed, and provided by a spray coating method in which a multicolor pattern is formed on a sheet. Multi-colored adhesive sheet. 2. A spray coating method in which a multi-color pattern coating layer forms a multi-color pattern on a moving sheet, comprising a spray coating apparatus having two or more paint or ink discharge nozzles.
Using more than one table, disposing each discharge nozzle toward the surface to be coated of the sheet, discharging paints or inks of different paint colors from at least two or more discharge nozzles of each spray coating device, A plurality of unit multicolor spray patterns in which paints or inks of the paint colors are mixed are formed, and a plurality of unit multicolor pattern patterns formed by the plurality of unit multicolor spray patterns are adjacent to each other on a sheet. 2. The multi-colored pressure-sensitive adhesive sheet according to claim 1, wherein the multi-colored pressure-sensitive adhesive sheet is provided by a spray coating method in which a unit multi-colored pattern pattern formed by a color spray pattern is overlapped to form a multiple multi-colored pattern pattern covering the entire width of the sheet. 3. The multicolored pressure-sensitive adhesive sheet according to claim 1, further comprising a clear coating layer (5) provided on the multicolored coating layer (4). 4. The multicolor patterned pressure-sensitive adhesive sheet according to claim 3, wherein the clear coating layer (5) is a silicone resin curable treating agent. 5. The multi-colored pressure-sensitive adhesive sheet according to claim 3, wherein the clear coating layer (5) is a treating agent containing a titanium sol having photocatalytic activity.