JPH0545868A - Image forming composition, partial rugged image forming material and partially rugged image forming method - Google Patents

Abstract

PURPOSE:To form the image which has rugged parts and smooth parts on the surface of a sheet, article, etc., and has the high design characteristic colored with either of these parts. CONSTITUTION:An original 4 is brought into tight contact with the surface of the partial image forming material constituted by successively laminating a base material 1 having rugged shapes, a photosetting resin layer 2 contg. an image forming compsn. which develops a color with UV light and does not develop the color with visible light and a light transparent member 3. This material is irradiated with visible light vr. The exposed parts 2b do not develop color and are cured by being transferred with the ruggedness of the base material 1, by which the softening temp. is increased. The base material 1 is thereafter peeled and only the surfaces of the unexposed parts 2a are smoothed. The entire part of the partial rugged image forming material is then irradiated with the UV light to develop the color of the unexposed parts 2a. The smooth parts developing the color and the rugged parts without developing the color are thus obtd. on the same plane. The smooth parts without developing the color and the rugged parts developing the color are obtd. if the order of the irradiation with the visible light and the UV light is reversed. The workability is thus extremely improved.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel image forming composition, and a partially uneven image forming material using the image forming composition.
The present invention relates to a partial uneven image forming method using a partial uneven image forming material.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
A film that has been provided with the required pattern by various methods on a film that has been made uneven by embossing, sandblasting, etc.
It is used in various fields such as decorative films. But,
When an image is directly placed on the uneven surface, the image follows the unevenness, and the texture is significantly inferior to when the image is placed on the smooth surface.

For example, when a colored image is placed on an uneven surface by screen printing or the like, if the unevenness of the embossed film becomes deep, the colored image itself also becomes uneven, and the texture of the colored image becomes extremely inferior. Will be greatly reduced. As a solution to such a drawback, there is a method of forming a partial uneven image having an uneven portion and a smoothed image portion on the same surface by the present applicant (Japanese Patent Application No. 2-2).
29001). This is because the original is superposed on the light-transmissive member of the partially uneven image-forming material, which is formed by sequentially stacking a photo-curable resin layer and a light-transmissive member on a base material having an uneven shape,
After curing only the exposed portion of the photocurable resin layer into an uneven shape corresponding to the unevenness of the surface of the base material, the base material is peeled off,
Further, the entire surface of the photocurable resin layer is exposed to light to cure the surface of the previously unexposed portion to be smooth, thereby forming a partial uneven image.

Further, in order to color the partial unevenness image obtained by the above partial unevenness image forming material, the original is superposed on the light transmissive member of the partial unevenness image forming material and exposed, and only the exposed portion of the photocurable resin layer is exposed. Is cured into an uneven shape corresponding to the unevenness of the surface of the base material, after peeling the base material, the unexposed portion that is not formed in the uneven shape in which the adhesiveness remains, a transfer member in which a metal or the like is deposited, Alternatively, a method has been developed in which a coloring material is overlapped and the entire surface is exposed to light to transfer these transfer members, or to fix the coloring material to obtain a colored image (Japanese Patent Application No. 3-752).
No. 30).

However, according to these methods, it is possible to relatively easily obtain a partial unevenness image having a high design property by a dry process, but in order to obtain a colored image, such as lamination of transfer members or toning of colored powder. A process was needed. Further, the colored image can be formed only on the part where the surface of the partial uneven image is smooth, and it is impossible to color the uneven part.

The present invention has been made in order to eliminate the above-mentioned drawbacks, and is an image forming composition which is color-cured by irradiation with ultraviolet light and cured without being colored by irradiation with visible light. By providing a photocurable resin layer containing this image-forming composition, it is possible to obtain a partial uneven image that can be colored even in an uneven portion, a smooth portion, and a small amount of a large number of types. An object of the present invention is to provide an image forming material and a partial uneven image forming method using the same.

[0007]

In order to achieve the above object, the image forming composition of the present invention comprises (a) a photo-oxidizing agent which produces an oxidizing substance upon irradiation with ultraviolet light, and (b) the oxidizing substance. It contains a leuco dye that develops a color, (c) a photoreducing agent that produces a reducing agent upon irradiation with visible light, (d) a hydrogen donor that supplies hydrogen to the photoreducing agent, and (e) a photopolymerizable compound.

The partially uneven image forming material of the present invention is
A base material having a concavo-convex shape on one surface, and (a) a photo-oxidizing agent, which is laminated on the concavo-convex surface of the base material, to generate an oxidative substance by irradiation with ultraviolet light, and (b) a dye leuco that develops a color by the oxidizable substance. And (c) a photoreducing agent that generates a reducing agent upon irradiation with visible light, (d) a hydrogen donor that supplies hydrogen to the photoreducing agent, and (e) a light comprising an image-forming composition containing a photopolymerizable compound. It is composed of a curable resin layer and a light-transmissive member laminated on the photocurable resin layer.

Further, according to the method for forming a partially uneven image of the present invention, (a) a photo-oxidizing agent which produces an oxidative substance by irradiation with ultraviolet light on the uneven surface of a substrate having an uneven shape on one surface, (b)
Leuco dye that develops color by the oxidizing substance, (c) a photoreducing agent that produces a reducing agent upon irradiation with visible light, (d) a hydrogen donor that supplies hydrogen to the photoreducing agent, (e) a photopolymerizable compound And a light-curable resin layer made of an image-forming composition containing a light-transmissive member, and a light-transmissive member formed on the light-transmissive member. After the exposed portion of the functional resin layer is not colored, the surface is cured into a shape corresponding to the irregularities of the surface of the base material, the base material is peeled off, and the whole surface is exposed to ultraviolet light to expose the visible light. By curing the surface smoothly along with developing the color, to form an uncolored concavo-convex portion on the same surface, and a colored smooth portion, or using a similar partial concavo-convex image forming material, the light The original is placed on the transparent member and UV light is applied. After curing accompanied on the surface when the color development the exposed part of the more exposed the photocurable resin layer in a shape corresponding to the unevenness of the substrate surface, and peeled off the base material,
Further, the entire surface is exposed to visible light, and the surface which has not been exposed to the ultraviolet light is cured while leaving the surface undeveloped, thereby forming a concavo-convex portion that is colored on the same surface and an uncolored smooth portion.

Each composition of the image forming composition of the present invention will be described below. (A) a photo-oxidizing agent in the image-forming composition,
The (b) dye leuco body is a component that develops color upon irradiation with ultraviolet light, and (a) a photo-oxidizing agent is preferably hexaallylbiimidazole. Particularly preferred hexaallyl imidazole is 2,2'-bis (o-chlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
And 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetrakis (m-methoxyphenyl)
Examples thereof include biimidazole.

(B) The leuco dye has a p-type having a substituent selected from an alkyl group, an alkoxy group and a halogen atom at the ortho position with respect to the methane carbon atom.
Aminotriarylmethanes containing at least two dialkylamino-substituted phenyl groups are suitable. Particularly preferred is tris (4-diethylamino-o-tolyl)
Examples include methane.

(C) a photoreducing agent in the image forming composition,
(D) The hydrogen donor is a component that fixes the image formed by irradiation with ultraviolet light, and as the (c) photoreducing agent, quinone having absorption mainly in the region of 400 to 500 nm is suitable. Particularly preferred is 9,10-phenanthrenequinone. (D) As the hydrogen donor,
An organic compound in which a hydrogen atom is easily activated is suitable, and particularly preferable one is triethanolamine triacetate.

(E) Photopolymerizable compounds include methacrylic acid, methyl methacrylate, butyl methacrylate, 2
-Methacrylic acid ester such as hydroxyethyl methacrylate, styrene, N-vinylpyrrolidone, acrylonitrile, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate , Low molecular weight photopolymerizable compounds such as pentaerythritol triacrylate, or urethane acrylate,
It is a high molecular weight photopolymerizable compound such as epoxy acrylate, polyester acrylate, and unsaturated polyester, and one or more of these can be used.

Further, as a photopolymerization initiator which is added as required, benzophenone, benzophenone such as 3,3-dimethyl-4-methoxybenzophenone, benzoin isopropyl ether, benzoin such as benzyl dimethyl ketal, 2-chlorothio, etc. Xanthone, 2,4-
One of the conventionally known photopolymerization initiators such as thioxanthone compounds such as diethylthioxanthone, acetophenone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-hydroxycyclohexylphenyl ketone. Alternatively, two or more kinds can be used.

Further, an organic polymer binder may be added. The organic polymer binder is a non-reactive polymer that is thermoplastic and has excellent compatibility with the photopolymerizable compound, and examples thereof include polyvinyl chloride, polymethacrylic acid, polyvinyl ether, polymethacrylic acid ester, and cellulose acetate. Butyrate, urethane resin, epoxy resin and the like can be used.

Further, as additives, dyes and pigments may be added to the extent that they do not inhibit the reaction by exposure. The partially uneven image forming material 10 of the present invention using the above image forming composition is a photocurable resin layer comprising a substrate 1 having an uneven shape on at least one surface as shown in FIG. 1 and an image forming composition. 2 and the light transmissive member 3 are sequentially laminated.

The base material 1 is provided with unevenness at least in the portion where the photocurable resin layer 2 is laminated by sandblasting or the like, and has an appropriate releasability.
The material is not particularly limited, but examples thereof include polyvinyl chloride film, polyethylene terephthalate film, acetate film, and glass plate. In some cases, a releasing agent or the like can be used to provide releasability.

The photo-curable resin layer 2 includes (a) a photo-oxidizing agent which produces an oxidizing substance upon irradiation with ultraviolet light, (b) a leuco dye which develops color by the oxidizing substance, and (c) reduction upon irradiation with visible light. A photoreducing agent for producing an agent, (d) a hydrogen donor for supplying hydrogen to the photoreducing agent, and (e) a photopolymerizable compound are contained. Includes organic polymer binders and other additives.

Examples of the light transmissive member 3 include polyethylene terephthalate film, acetate film, polyvinyl chloride film, and glass plate. If necessary, an easy adhesion treatment such as a corona treatment can be applied.
Here, the photo-curable resin layer 2 does not depend on the interfacial adhesion between the substrate 1 and the photo-curable resin layer 2 regardless of whether the photo-curable resin layer 2 is cured or not.
It is necessary to be smaller than the internal cohesive force and the interfacial adhesive force between the photocurable resin layer 2 and the light transmissive member 3.

A partially uneven image forming material 1 having such a constitution
In the partial uneven image forming method using 0, the original 4 on which a predetermined light-impermeable positive or negative pattern, characters 4a, etc. are formed is brought into close contact with the light-transmissive member 3 side. ,
Exposing with visible light vr. The exposed portion 2b of the photo-curable resin layer 2 which is exposed to visible light vr transmitted through a portion of the original 4 on which the characters 4a and the like are not formed has an uncolored state due to the inactivation of the coloring system and the surface of the substrate 1. It has an uneven surface corresponding to the unevenness of and is cured. The softened temperature of the cured exposed portion 2b rises, and a difference in softening temperature from that of the unexposed portion 2a occurs. Then, when the substrate 1 is peeled off as shown in FIG. 3, the exposed portion 2b forms an uneven portion 20b to which the unevenness of the substrate 1 is transferred at a temperature between the softening temperature of the exposed portion 2b and the unexposed portion 2a, and the unevenness is formed. While retaining its shape, the unexposed portion 2a flows and becomes a smooth portion 20a. That is, it is possible to obtain the partial unevenness image 20 in which only the exposed portion 2b has an uneven shape corresponding to the uneven shape of the substrate 1 in which no color is developed, and the unexposed portion 2a is uncured and smooth.

Further, as shown in FIG. 4, when the partial concave-convex image 20 is entirely exposed with the ultraviolet light ur, the unexposed portion 2a (FIG. 2), that is, the smooth portion 20a (FIG. 3) is cured in a smooth state and The leuco dye develops color. Therefore, it is possible to obtain the partial unevenness image 21 having the uncolored uneven portion 21b and the colored smooth portion 21a on the same surface. Figure 5 here
As shown in FIG. 3, the partial unevenness image 20 (FIG. 3) is laminated on the surface of the article 5 by using the adhesiveness of the unexposed portion, and the whole surface is exposed to the ultraviolet light ur from the light transmissive member 3 to unexpose it. A smooth portion 21a which is color-cured on the smooth portion 20a (FIG. 3) and fixed to the surface of the article, and the color is developed on the article 5;
It is also possible to obtain a partial concavo-convex image 21 having an uncolored concavo-convex portion 21b.

Similarly, as shown in FIG. 6, the original 4 on which a predetermined light-opaque positive or negative pattern, characters 4a, etc. are formed is closely attached to the light-transmissive member 3 side of the partially uneven image forming material 10. And expose to ultraviolet light ur. The exposed portion 2d of the photocurable resin layer 2 that is exposed to the ultraviolet light ur that has passed through the portion where the characters 4a and the like of the original 4 are not formed is colored and has an uneven surface corresponding to the unevenness of the surface of the substrate 1. Hardened. The cured exposed portion 2d has a higher softening temperature, and the unexposed portion 2d
The difference between c and the softening temperature is generated. Therefore, as shown in FIG.
When peeled off, the exposed portion 2d forms an uneven portion 23d to which the unevenness of the base material 1 is transferred at a temperature between the softening temperature of the exposed portion 2d and the unexposed portion 2c to retain the uneven shape, whereas The portion 2c flows and becomes a smooth portion 23c.
That is, it is possible to obtain a partial unevenness image 23 having an uneven shape corresponding to the uneven shape of the substrate 1 in which only the exposed portion 2d is colored and the unexposed portion 2c being uncured and smooth.

Further, as shown in FIG. 8, if the partial concave-convex image 23 is entirely exposed with the visible light vr, the unexposed portion 2c (FIG. 6), that is, the smooth portion 24c is cured in a smooth state and the leuco dye is colored. do not do. Therefore, it is possible to obtain the partial uneven image 24 having the uncolored smooth portion 24c and the colored uneven portion 24d on the same surface. Here, as shown in FIG. 9, the partial concavo-convex image 23 (FIG. 7) is laminated on the surface of the article 5 by using the adhesiveness of the unexposed portion, and the whole surface is exposed by the visible light vr from the light transmitting member 3. The unexposed smooth portion 23c (FIG. 7) is cured while still uncolored and fixed to the surface of the article, and the uneven portion image 24 having the uncolored smooth portion 24c and the colored uneven portion 24d on the article 5 is formed. You can also get

Further, as shown in FIG. 10, by utilizing the adhesiveness of the smooth portion 23c of the partial concavo-convex image 23 shown in FIG. 7, a colored powder or a transfer layer 6 is placed on the smooth portion 23c, and then the light transmissive member is applied. It is also possible to obtain the partial unevenness image 26 in which the smooth portion 23c is colored by exposing and fixing with visible light. The above description is one example of the present invention, and the present invention is not limited to this. That is, not only an image having an uneven portion that has developed color on the same plane and an undeveloped smooth portion or an image that has a smooth portion that has developed color and an undeveloped uneven portion,
Ultraviolet light and visible light exposure are sequentially repeated using multiple originals to form uneven parts that have developed color on the same plane and uneven parts that have not developed color, and the smooth part that has developed after peeling the base material and the undeveloped part A desired image can be obtained by forming a smooth portion and appropriately mixing color-developed and non-color-developed uneven portions and a smooth portion. Further, in addition to such a smoothed portion and uneven portion that have been colored, an uncolored smooth portion and uneven portion, an image having a smoothed portion that is colored by a colored powder or a transfer layer can be formed on the same plane.

[0025]

EXAMPLES The present invention will be described below with reference to examples. Example 1 A photocurable resin solution having the following composition was prepared. Cellulose acetate butyrate 18 g Pentaerythritol triacrylate 12 g Tris (4-diethylamino-O-tolyl) methane 1.0 g 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1 2'-biimidazole 3.0 g P-toluenesulfonic acid monohydrate 2.0 g 9,10, phenanthrenequinone 0.2 g triethanolamine triacetate 5.0 g 4,4'diethylaminobenzophenone 0.2 g methyl ethyl ketone 170 g toluol 70 g This solution was coated on a 100 μm polyester film with a wire bar and dried in an oven at 100 ° C. for 120 seconds to obtain a photocurable resin layer of about 10 μm.

The processed surface of the sandblasted polyester film is aligned with the photocurable resin layer and laminated at 50 ° C. for 3 m / min using a heat laminator to form a partially uneven image forming material 10 as shown in FIG. Obtained. As shown in FIG. 2, the original was brought into close contact with it and exposed for 60 seconds through a visible light transmission filter from a 2 kW high-pressure mercury lamp 1 m away, after which the sandblasted polyester film was peeled off and the exposed portion became matt. A partial matte film 20 which is the image of the partial unevenness shown in No. 3 was obtained.

Further, as shown in FIG. 4, the entire surface was exposed to ultraviolet light, and the unexposed portion of the photocurable resin was color-cured and cured to blue. The partial matte film 21, which is a partial uneven image easily obtained in this way, has a high designability with a part having an uncolored uneven shape and a smooth colored part on the same surface, and is matte, The resolution was sufficient. Example 2 Partially uneven image-forming material 1 obtained in the same manner as in Example 1
As shown in Fig. 6, the original was brought into close contact with the original and exposed for 40 seconds from a 2kW high-pressure mercury lamp 1m away through an ultraviolet light transmitting filter, and then the sandblasted polyester film was peeled off, and the exposed portion developed a blue color and was matted. Partial matte film 2 which is the partial uneven image shown in FIG.
Got 3.

Further, as shown in FIG. 8, the entire surface was exposed to visible light and the unexposed portion of the photocurable resin was fixed and cured. The partial matte film 24, which is an image of partial unevenness easily obtained in this way, has a high degree of designability and has a mattness with a colored portion and an uncolored and smooth portion on the same surface. , And the resolution was sufficient. Example 3 Partial matte film 23 obtained by the same method as in Example 2
In addition, an aluminum vapor deposition film in which a 100-nm-thick aluminum thin film is provided on one side of a polyester film having a thickness of 50 μm by vacuum vapor deposition is used. It was laminated at 3 m / min. Further, the entire surface is exposed for 60 seconds from a 2 kW high pressure mercury lamp 1 m away from the polyester film side of the partial matte film 23 through a visible light transmitting filter, and then the aluminum vapor deposition film is peeled off. As shown in FIG. Thus, a partial matte film 26 in which is formed is obtained.

By this method, it is possible to obtain a film of extremely high designability, which cannot be obtained by the conventional method of having a colored portion having a concavo-convex shape on the same surface and a metallic gloss image portion.

[0030]

As is apparent from the above examples, according to the partial unevenness image forming method of the present invention, partial unevenness containing an image-forming composition that develops color upon irradiation with ultraviolet light and does not develop upon irradiation with visible light. Since the image forming material is used, it is possible to easily obtain a partial matte film which has a portion having unevenness and a smooth portion on the same surface in a dry process, and in which any one of them is colored. Therefore, the workability can be significantly improved, and the cost in the production of a large number of small-lot types can be significantly reduced.

Further, in this partial uneven image, a metal image or the like can be formed on a smooth portion, and the product thus obtained has a high designability and is an excellent decorative sheet.

[Brief description of drawings]

FIG. 1 is a sectional view of a partially uneven image forming material according to the present invention.

FIG. 2 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 3 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 4 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 5 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 6 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 7 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 8 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 9 is a diagram illustrating a partial uneven image forming method according to the present invention.

FIG. 10 is a diagram illustrating a partial uneven image forming method according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Photocurable resin layer 3 ... Light transmissive member 4 ... Original document 10 ... Partially uneven image forming material 20, 21, 23, 24, 26 ... Partial uneven image 20a, 21a, 23c, 24c ... Smooth part 20b, 21b, 23d, 24d ... Uneven part

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03F 7/029 9019-2H

Claims (4)

[Claims] 1. A photo-oxidizing agent which produces an oxidizing substance upon irradiation with ultraviolet light, (b) a leuco dye which develops a color by said oxidizing substance, and (c) a photo-reducing substance which produces a reducing agent upon irradiation with visible light. An image forming composition comprising an agent, (d) a hydrogen donor that supplies hydrogen to the photoreducing agent, and (e) a photopolymerizable compound. 2. A base material having a concavo-convex shape on one surface, and (a) a photo-oxidizing agent which is laminated on the concavo-convex surface of the base material to generate an oxidizing substance by irradiation with ultraviolet light, and (b) the oxidizing substance. A leuco dye that develops a color by (c) a photoreducing agent that produces a reducing agent upon irradiation with visible light, (d) a hydrogen donor that supplies hydrogen to the photoreducing agent, and (e) an image formation containing a photopolymerizable compound. A partially uneven image forming material comprising a photocurable resin layer made of a composition and a light transmissive member laminated on the photocurable resin layer. 3. A photo-oxidizing agent which produces an oxidative substance upon irradiation with ultraviolet light (a) on a concavo-convex surface of a base material having a concavo-convex shape on one surface, (b) a leuco dye which develops a color by the oxidizable substance, c) a photoreducing agent that produces a reducing agent upon irradiation with visible light, (d) a hydrogen donor that supplies hydrogen to the photoreducing agent,
(E) Visible by superimposing an original on the light-transmitting member of the partially uneven image-forming material formed by sequentially stacking a light-curable resin layer made of an image-forming composition containing a photopolymerizable compound and a light-transmitting member. After exposing the exposed portion of the photocurable resin layer to light by light to cure the surface into a shape corresponding to the irregularities of the surface of the base material, the base material is peeled off, and the whole surface is exposed to ultraviolet light. A method for forming a partial uneven image, wherein an unexposed uneven portion and a developed smooth portion are formed on the same surface by causing the surface of the unexposed portion to be colored by visible light to be cured smoothly. .. 4. A photo-oxidizing agent which produces an oxidative substance by irradiation with ultraviolet light on a concave-convex surface of a base material having an irregular shape on one surface, and (b) a leuco dye which develops a color by the oxidative substance. c) a photoreducing agent that produces a reducing agent upon irradiation with visible light, (d) a hydrogen donor that supplies hydrogen to the photoreducing agent,
(E) An ultraviolet ray is formed by superimposing an original on the light-transmissive member of the partially uneven image-forming material formed by sequentially laminating a light-curable resin layer made of an image-forming composition containing a photopolymerizable compound and a light-transmissive member, and then ultraviolet rays. The exposed portion of the photocurable resin layer is exposed to light to develop a color, and the surface is cured into a shape corresponding to the unevenness of the base material surface, and then the base material is peeled off and further exposed to visible light. The uneven surface image forming method, characterized in that an uneven portion that has developed color on the same surface and an undeveloped smooth portion are formed by smoothly curing the surface while leaving the unexposed area by the ultraviolet light undeveloped. ..