JPH06214382A - Photosensitive image receptive sheet - Google Patents

Abstract

PURPOSE:To provide the photosensitive image receptive sheet with which the formation of colored images of arbitrary colors by exposing and developing is possible and the images having excellent resilience are obtainable. CONSTITUTION:The photosensitive image receptive layer 1 of the photosensitive image receptive sheet 10 formed with the image receptive layer 1 on a base 2 is formed of a photopolymerizable resin compsn. consisting of (a) 100 pts.wt. linear copolymer of 20000 to 300000 weight average mol.wt. constituted of 10 to 70wt.% methyl methacrylate, 10 to 50wt.% butyl methacrylate, 10 to 25wt.% acrylic acid-2-ethyl hexyl and 10 to 30wt.% methacrylic acid, (b) 10 to 200 pts.wt. photopolymerizable unsatd. compd. and (c) 0.1 to 10 pts.wt. photopolymn. initiator to be sensitized by active rays.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive image receiving sheet used for obtaining a display panel or the like having a predetermined colored image pattern formed on a substrate. Such a display panel can be used, for example, as an instrument panel for various devices, a display panel on which a map or a landscape image is arranged, a dial for a vehicle speedometer, and the like.

[0002]

2. Description of the Related Art Conventionally, characters and numbers on a dial such as a meter are often formed on a substrate by printing, and screen printing is widely used. However, in recent years, as the trend toward higher grades and diversification of products have advanced,
Adds a sense of quality to images such as these letters and numbers,
In order to improve decorativeness and visibility, studies are underway to make images multicolored.

However, in multicolor printing by screen printing, a plate is required for each color, which complicates the printing process and requires drying and curing of the ink for each printing of one color, thus increasing the working speed. There is a problem of being late. Further, in offset printing suitable for multicolor printing, it is difficult to thicken the coating film, so that there is a problem that a sufficient color density for use as a display board cannot be obtained.

Further, in pattern formation by screen printing, since the ink used is a solvent type liquid, the solvent filled in the working environment becomes a source of offensive odor, and it is necessary to always pay attention to the danger of explosion or fire. There is a problem.

Moreover, in the printing ink, the solid content remains on the plate due to the evaporation of the solvent, which may cause the plate to be clogged.
There is also a problem that it takes time to adjust the viscosity suitable for screen printing.

Therefore, in recent years, a photopolymerizable ink has been proposed for the purpose of eliminating the solvent and shortening the curing time.
However, in order to adjust the viscosity suitable for screen printing, it is necessary to add a reactive diluent such as a low molecular weight monomer to the photopolymerizable ink, which shows the same behavior as a solvent and does not react. Is volatilized with time from the coating film.

Further, since the photopolymerizable ink is made to have a low molecular weight as a whole by the addition of such a reactive diluent,
Practicality was not sufficient because of the drawbacks of large shrinkage during curing, poor adhesiveness, and lack of flexibility.

In order to solve these problems, for example, JP-A-59-97140 discloses a method for forming a colored image using a colored photocurable composition.

In this manufacturing method, (1) a halftone dot photomask in which a desired image is color-separated in advance is prepared, and (2) a photocurable composition having a corresponding color through the photomask. The photocurable resin film obtained from (1) is irradiated with an actinic ray to be cured, (3) a color-separated halftone image is formed by developing and removing an uncured portion, (4) obtained. The halftone dot image is transferred and laminated for each color on an image receiving sheet having photopolymerization property. (5) A predetermined colored image is formed by photocuring the image receiving sheet.

Here, by using a colorant such as yellow, magenta or cyan in combination as the colored photopolymerizable composition, it is possible to display an arbitrary color.

The image layer of the above-mentioned image receiving sheet is formed from a photopolymerizable resin composition comprising a linear copolymer, a photopolymerizable unsaturated compound and a photopolymerization initiator. When a colored image is transferred onto an image receiving sheet having an image layer formed from the photopolymerizable composition described in 1 above, and retransferred onto a substrate, and then exposed and cured, the flexibility is lost as compared with that before the photocuring. When the obtained product such as the display panel is bent, there is a problem that cracks occur.

Further, there is a problem that the photopolymerizable composition is colored by the above-mentioned photopolymerization initiator, and further, the image receiving sheet is colored and yellowed due to a change with time after curing.

In order to solve such a coloring problem, Japanese Patent Publication No. 63-40799 discloses the use of an acylphosphine oxide compound such as benzoyldiphenylphosphine oxide as a photopolymerization initiator. There is.

The use of the acylphosphine oxide compound reduces yellowing of the photopolymerizable composition after curing, but the photopolymerizable composition relates to paints, varnishes, printing inks, recording materials and the like. , Its use in photosensitive image-receiving sheets is not mentioned.

[0015]

The present invention has been made in view of the above-mentioned drawbacks, and an object thereof is to form a colored image of any color by exposure and development, and
Another object of the present invention is to provide a photosensitive image-receiving sheet that can provide an image with excellent flexibility.

The present invention 2 has been made in view of the above-mentioned drawbacks, and an object thereof is to provide an image which can form a colored image of any color by exposure and development and which is excellent in yellowing resistance. It is to provide a photosensitive image-receiving sheet obtained.

[0017]

The present invention will be described below. The photosensitive image-receiving sheet of the present invention has a photosensitive image-receiving layer formed on one side of a support.

As the above-mentioned support, those which are chemically and thermally stable are preferable, for example, polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polyhalogenated such as polyvinyl chloride and polyvinylidene chloride. Vinyls; Polyamides;
A resin film such as polycarbonate can be used, and a biaxially stretched polyethylene terephthalate film is particularly preferable. These resin films are preferably subjected to a mold release treatment with a silicone-based or fluorine-based mold release agent in order to improve the mold release property at the time of thermal transfer.

The above-mentioned photosensitive image receiving layer is a photocurable resin comprising (a) a linear copolymer, (b) a photopolymerizable unsaturated compound and (c) a photopolymerization initiator sensitized by actinic rays. Formed from the composition.

The linear copolymer (a) is a quaternary copolymer containing methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and methacrylic acid as constituents.

Of the constituents of the linear copolymer (a), when the amount of methyl methacrylate is small, the copolymer (a) is
Since the softening point of the copolymer (a) decreases and the photosensitive image-receiving layer may cause cold flow if the flexibility of the copolymer decreases, the amount is limited to 10 to 70% by weight.

Among the constituent components of the linear copolymer (a), when the amount of butyl methacrylate is small, the copolymer (a) is
The softening point of the copolymer (a) is lowered and the softening point of the copolymer (a) is lowered, which may cause cold flow in the photosensitive image-receiving layer. Therefore, it is limited to 10 to 50% by weight.

Among the constituent components of the above linear copolymer (a), 2
-When the amount of ethylhexyl acrylate decreases, the flexibility of the copolymer (a) decreases, and when it increases, the softening point of the copolymer (a) decreases, and the photosensitive image receiving layer may cause cold flow. Therefore, it is limited to 10 to 25% by weight.

Among the constituents of the linear copolymer (a), when the amount of methacrylic acid is small, the surface hardness of the image-receiving layer after curing is lowered, and when it is large, the phase of the methacrylic acid and the coating solvent or other components is changed. Since the solubility is lowered and the flexibility of the copolymer (a) is lost, it is limited to 10 to 30% by weight, preferably 15 to
It is 25% by weight.

If the molecular weight of the above linear copolymer (a) becomes small, cold flow easily occurs, and if it is rolled and stored, the resulting photosensitive image-receiving sheet will be wrinkled and unusable, resulting in a large molecular weight. If so, it becomes difficult to dissolve in a solvent for coating, the viscosity increases and coating becomes difficult. Therefore, the weight average molecular weight is limited to 20,000 to 300,000, preferably 50,000 to 200,000.

As the method for producing the linear copolymer (a), any method may be adopted, and for example, it can be easily obtained by radical polymerization or the like in an organic solvent.

The unsaturated compound (b) is photopolymerizable, and is a urethane acrylate oligomer represented by the following general formula (1) or a liquid at room temperature which can be cured by starting a polymerization reaction by actinic rays. The photopolymerizable monomer and the like are preferable.

[0028]

[Chemical 1] In the general formula (1), R ¹ is a divalent hydrocarbon group, m is an integer of 5 to 100, n is an integer of 1 to 15, and X is a carbon number 2.
To 20 divalent hydrocarbon groups, respectively, and A is represented by the following general formula (2), (3) or (4).

[0029]

[Chemical 2] In the general formulas (2) to (4), R ² , R ³ and R ⁴ represent a hydrogen atom or a methyl group.

The divalent hydrocarbon group represented by R ¹ is a hydrocarbon group composed of linear, branched, alicyclic or aromatic moieties, such as ethylene group, propylene group, Examples include neopentyl group and the like.

The divalent hydrocarbon group represented by X is a hydrocarbon group composed of a straight chain, branched chain, alicyclic or aromatic moiety, such as a hexamethylene group or a tolylene group, Examples thereof include isophorone group.

Any method may be used for producing the unsaturated compound represented by the above general formula (1). For example, diisocyanate and diol are mixed and reacted at a ratio matching the composition ratio of the desired compound. After forming a urethane oligomer having an isocyanate group at the terminal, a (meth) acrylate having a hydroxyl group may be added and reacted with the isocyanate group at the terminal. At this time, if necessary, the reaction may be carried out by dissolving it in an organic solvent such as ethyl acetate, methyl ethyl ketone, or toluene, and a catalyst such as dibutyltin dilaurate may be added.

When the weight average molecular weight of the urethane acrylate oligomer increases, the amount of unsaturated groups relatively decreases, the photocurability deteriorates, and the sensitivity decreases.
It is preferably 50,000 or less, more preferably 8,000
It is the following.

Examples of the photopolymerizable monomer that is liquid at room temperature include polyfunctional and monofunctional (meth) acrylate monomers; polyester acrylate oligomers.

Examples of the polyfunctional (meth) acrylate monomer include, for example, triethylene glycol (meth).
Acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
Trimethylolpropane tri (meth) acrylate,
2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 3-phenoxy-2-
Examples thereof include propanoyl acrylate and 1,6-bis [3-acryloxy-2-hydroxypropyl] hexyl ether.

Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate monomer and benzyl (meth) acrylate monomer.

In the above photopolymerizable resin composition, when the content of the unsaturated compound (b) is small, surface curing after exposure becomes insufficient, and when it is large, cold flow easily occurs. It is limited to 10 to 200 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the combined (a).
It is 150 parts by weight.

The photopolymerization initiator (c) may be any as long as it has a property of activating the unsaturated compound (b) by actinic rays such as ultraviolet rays and visible rays to initiate polymerization.

Among the above photopolymerization initiators (c), those which are activated by ultraviolet rays include, for example, sodium methyldithiocarbamate sulfide, tetramethylthiuram monosulfide, diphenylmonosulfide, dibenzothiazoyl monosulfide and disulfide. Sulfides such as; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; (di) azo compounds such as hydrazone, azobisisobutyronitrile, benzenediazonium; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzylanthraquinone, t-butyl Aromatic carbonyl compounds such as ntraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketal, methylphenylglyoxylate; methyl p-dimethylaminobenzoate, p-dimethylamino Dialkylaminobenzoic acid esters such as ethyl benzoate, butyl p-dimethylaminobenzoate and isopropyl p-diethylaminobenzoate;
Peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9-phenylacridine, 9
Acridine derivatives such as -p-methoxyphenylacridine, 9-acetylaminoacridine and benzacridine; phenazine derivatives such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine and 10-methoxybenzphenazine; 6,4 ', 4 "-Trimethoxy-
A quinoxaline derivative such as 2,3-diphenylquinoxaline; a 2,4,5-triphenylimidazoyl dimer; a halogenated ketone; an acylated phosphorus compound such as an acylphosphinoxide or an acylphosphonate.

As those which are activated with visible light, for example, 2-nitrofluorene, 2,4,6-triphenylpyrylylboron tetrafluoride salt, 2,4,6-tris (trichloromethyl)- 1,3,5-triazine,
3,3′-carbonylbiscoumarin, thiomichler ketone and the like can be mentioned.

In the above photopolymerizable resin composition, when the content of the photopolymerization initiator (c) is low, the image cannot be formed because the curing after the exposure is insufficient, and when the content is high, the photopolymerizable resin is cured. Since the resin composition turns yellow and becomes brittle, the amount is limited to 0.1 to 10 parts by weight with respect to 100 parts by weight of the linear copolymer (a).

Further, a plasticizer such as dioctyl phthalate, triethylene glycol diacetate, p-toluene sulfonamide, N-ethyltoluene sulfonamide or the like is added to the above photopolymerizable resin composition; thermal polymerization of hydroquinone or p-methoxyphenol or the like. Inhibitors; stabilizers; ultraviolet absorbers; antioxidants; solvents such as methyl ethyl ketone (MEK) and toluene may be added.

Next, the method for producing the photosensitive image-receiving sheet of the present invention will be described. To produce a photosensitive image-receiving sheet from the photopolymerizable resin composition, for example, a dilute solution of the photopolymerizable resin composition on a resin film support such as polyethylene terephthalate and stretched polypropylene,
A method of casting so as to have a constant thickness and drying is mentioned.

The above-mentioned support may be subjected to a release treatment in advance. Examples of the solvent used for dilution include methyl ethyl ketone, toluene and the like.

The thickness of the above-mentioned photosensitive image-receiving layer is not particularly limited, but when it is thin, it becomes difficult to handle, and it is difficult to sufficiently transfer a colored halftone dot image pattern onto the image-receiving sheet. Therefore, the thickness is preferably 1 to 200 μm.

The method of using the above-mentioned photosensitive image receiving sheet is as follows.
It is as follows. (1) First of all, the original image is yellow in advance by a color separation machine.
A yellow, magenta, and cyan halftone dot negative mask, which has been converted into halftone dots separated into magenta and cyan, and whose shades of color have been converted into halftone dots and large and small, is prepared.

(2) A photocurable resin layer is formed by applying at least three types of photocurable resin compositions colored in yellow, magenta, and cyan on each support to form a photocurable resin layer. Is exposed and cured through a halftone negative mask corresponding to that color, and the uncured portion is removed by development to form a halftone dot image pattern on each support.

(3) The halftone dot image pattern is peeled from the support, and transferred and laminated for each color on the photosensitive image receiving sheet.

(4) By retransferring the halftone dot image pattern laminated on the photosensitive image receiving sheet onto the substrate, an image consisting of the halftone dot image pattern can be formed on the substrate.

The photocurable resin composition comprises, for example, a linear copolymer (a), a photopolymerizable unsaturated compound (b), a photopolymerization initiator (c) and a colorant (d). Those are preferable.

The linear copolymer (a) is the linear copolymer (a) or α, β containing a carboxyl group.
A copolymer (e) containing an unsaturated ethylenic monomer and an α, β-unsaturated ethylenic monomer other than the above as a constituent component is preferable.

The α, β-unsaturated ethylene-based monomer containing a carboxyl group may be a monomer containing a carboxyl group and copolymerizable with the α, β-unsaturated ethylene-based monomer. For example, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid (including anhydride), fumaric acid and itaconic acid may be mentioned.

Examples of α, β-unsaturated ethylenic monomers other than the above are, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-
Styrenes such as methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-hexylstyrene, pn-octylstyrene, p-methoxystyrene, p-phenylstyrene, and 3,4-dimethylchlorostyrene. Vinylnaphthalenes such as α-vinylnaphthalene; ethylene, propylene, butylene or C _{5 to} C ₃₀
And higher α-olefins; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl (meth) acrylate, (meth ) Propyl acrylate, n-butyl (meth) acrylate, (meth)
Isobutyl acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, α-chloro (meth) acrylic acid methyl ester, (Meth) acrylic acid esters such as phenyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; N -N-vinyl compounds such as vinylpyrrole and N-vinylindole; (meth) acrylonitrile; (meth) acrylic acid amides.

When the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer containing a carboxyl group in the constituent components of the above copolymer (e) becomes small, it becomes insoluble in an alkaline aqueous solution. The development with an aqueous solution becomes impossible, and when the amount becomes large, the compatibility with the coating solvent or other components decreases, and the resolution also decreases. Therefore, the range of 10 to 40% by weight is preferable, and 15 to 35% by weight is more preferable. Is.

If the molecular weight of the above copolymer (e) is small, so-called cold flow is likely to occur, and conversely, if it is large, it becomes difficult to dissolve in an alkaline aqueous solution to make it difficult to develop, and the resolution is also lowered. Therefore, the weight average molecular weight is preferably in the range of 20,000 to 300,000, more preferably 50,000 to 200,000.

The unsaturated compound (b) is photopolymerizable, and a compound similar to the unsaturated compound (b) or a photopolymerizable monomer is preferably used.

The amount of unsaturated compound (b) in the photocurable resin composition is preferably in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the linear copolymer (a).

The photopolymerization initiator (c) is sensitized by an actinic ray, and a compound similar to the photopolymerization initiator (c) is preferably used.

The amount of the photopolymerization initiator (c) in the photocurable resin composition is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the linear copolymer (a). .

The colorant (d) is used for coloring the photocurable resin composition, and includes conventionally known pigments and dyes, and at least three types of yellow, magenta and cyan dyes. Is used.

Examples of yellow pigments include Hansa Yellow, Benzidine Yellow, Cadmium Yellow, Yellow Lead G, Zinc Chromate, Lemon Yellow, Strocian Yellow, Indian Yellow and the like.

As the magenta pigment, for example,
Rhodamine B lake, cadmium red, red iron oxide, chrome vermillion, pyrazolone red, resole red, red lead, watching red and the like.

Examples of cyan pigments include ultramarine blue, Prussian blue, cobalt blue, cerulean blue, manganese blue, and phthalocyanine blue.

Colorant (d) in the photocurable resin composition
Is preferably in the range of 1 to 300 parts by weight with respect to 100 parts by weight of the linear copolymer (a).

The method for producing a photocurable resin layer on a support from the above photocurable resin composition is, for example, a dilute solution of the photocurable resin composition on a resin film support such as polyethylene terephthalate or stretched polypropylene. In addition, there is a method of casting so as to have a constant thickness and drying.

Examples of the solvent for diluting the photocurable resin composition include methyl ethyl ketone, toluene and the like.

The above-mentioned support may be previously subjected to a release treatment with a silicone resin or the like, or may be treated with an alcohol-soluble polyamide, an acrylic copolymer, a vinyl chloride copolymer, a vinyl acetate copolymer or a polyvinyl acetate. A heat fusion layer made of butyral or the like may be provided.

The thickness of the photocurable resin layer is not particularly limited, but if it becomes thin, it becomes difficult to handle, and it becomes difficult to obtain a sufficient color density, and if it becomes thick, peeling easily occurs between layers. 0.5 to 20 μm is preferable.

The photo-curable resin layer is colored in at least three colors of yellow, magenta and cyan, and the color density per sheet is set to be thin and the number of layers to be stacked is adjusted. It is also possible to change the gradation of light and shade.

A method for forming a colored halftone dot image pattern using the above-mentioned photocurable resin layer will be described below. First, as shown in FIG. 3, a halftone dot negative mask 6 corresponding to cyan is superposed on the cyan-colored photocurable resin layer 3 and exposed through the halftone dot negative mask 6.
After curing, it is developed to form a halftone dot image pattern 7 corresponding to the halftone negative mask 6 as shown in FIG.

Then, by using the photo-curable resin film layers colored magenta and yellow respectively, yellow and magenta halftone dot image patterns can be formed by the same method as that for cyan.

In the above description, the halftone dot negative mask of three colors of yellow, magenta and cyan was used, but the number of colors is not limited to three, and photopolymerization of other colors (white, black, etc.) is also possible if necessary. The resinous resin film layer may be used to form a dot image pattern.

The light source for exposing the photocurable resin layer to light is not particularly limited, and a conventionally known light source can be used. For example, an ultrahigh pressure mercury lamp, a metal halide lamp or the like is preferably used.

The developing solution used for development is not particularly limited, but may be, for example, 0.5.
An aqueous solution of sodium carbonate having a concentration of ˜5% by weight is preferably used. The developing device used for development is not particularly limited, and a known device can be used.

The method for transferring the colored halftone dot image pattern to the photosensitive image receiving sheet will be described below. First, as shown in FIG. 4, a cyan halftone dot image pattern 7 formed on a support is superposed so that the image pattern 7 and the photosensitive image receiving layer 1 are in contact with each other,
While peeling the support 5 from the heat-sealing layer 4a, the support 5 is fused by pressure and heat to transfer the image pattern 7 to the photosensitive image-receiving sheet 10.

Then, as shown in FIG. 6, the magenta halftone dot image pattern 8 is transferred onto the cyan heat fusion layer 4b by pressure and lamination. Similarly, the yellow dot image pattern 8 is pressed, laminated and transferred onto the magenta heat fusion layer 4c to transfer the photosensitive receptor sheet 1.
On 0, a stack of three color image patterns 7, 8 and 9 is obtained.

As a method for transferring and laminating the above-mentioned halftone dot image pattern laminated body to the photosensitive image receiving layer 2, for example,
A method of applying pressure and fusion while heating each halftone image pattern of each color with a laminator roll is mentioned.
At this time, the temperature of the laminator roll is determined by the heat resistance of the substrate used, the softening temperature of the photocurable resin film layer 1 and the like, but is generally preferably 50 to 130 ° C.

A method of retransferring the laminate of the halftone dot image patterns 7, 8 and 9 on the photosensitive image receiving sheet 10 to the substrate 12 will be described below. First, as shown in FIG. 8, the yellow image pattern 9 is superposed so as to be in contact with the heat fusion layer 4 provided on the substrate 12, and is heated and pressed by a laminating roll or the like to be fused to the substrate. Thus, the above laminated body can be retransferred.

Next, the support 2 is peeled off, and a light source such as an ultrahigh pressure mercury lamp is irradiated from the cyan halftone dot image pattern 7 side to cure the photosensitive image receiving layer 1.

When the support 2 is light transmissive, it may be re-transferred to the substrate 12 after being irradiated with light to be cured before being peeled off. Curing with the support 2 attached is easy with little oxygen damage, and peeling of the support 2 is easy because the image receiving layer 1 is cured.

When the light irradiation amount is small, the curing is insufficient and the surface hardness is insufficient, so that the obtained image is easily scratched, and when the light irradiation amount is large, yellowing occurs.
000 mJ / cm ² is preferred.

The above-mentioned substrate is not particularly limited, and in general, a plastic plate such as an acrylic resin, a polycarbonate resin, a polyester resin; a glass plate; a ceramic plate; a metal plate, etc. It is preferably used and is selected in consideration of necessary properties such as flexibility, transparency and heat resistance. These substrates may be colored.
Further, a primer layer or an adhesive layer may be provided on these substrates in advance in order to improve the adhesion.

The present invention 2 will be described below. The photosensitive image-receiving sheet used in the present invention 2 has a photosensitive image-receiving layer formed on one side of a support.

As the support, the same support as that used in the present invention is preferably used.

The photosensitive image receiving layer is a photopolymerizable resin composition comprising a linear copolymer (d), a photopolymerizable unsaturated compound (b) and an acylphosphine oxide photopolymerization initiator (e). Formed from things.

The linear copolymer (d) is a copolymer similar to the linear copolymer (a).

The unsaturated compound (b) is the same as the unsaturated compound used in the present invention.

In the above photopolymerizable resin composition, when the content of the unsaturated compound (b) is small, the surface hardening after exposure becomes insufficient, and when it is large, cold flow easily occurs. The amount is limited to 10 to 200 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the combined body (d).
It is 150 parts by weight.

The photopolymerization initiator (e) is an acylphosphine oxide type compound, and is, for example, 2,4,6-
Trimethylbenzoylphenylphosphine oxide, pivaloyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide, versatoyl-diphenylphosphine oxide,
4-methylbenzoyl-phenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoyl-phosphinic acid diethyl ester and the like can be mentioned.

The above-mentioned photopolymerization initiator (e) may be used alone, but may be used in combination with a photopolymerization initiation aid in order to accelerate the curing rate and alleviate oxygen damage.

Examples of the photopolymerization initiation aid include triethanolamine, dialkylaminobenzoic acid esters and the like.

Examples of photopolymerization initiation assistants other than the above include, for example, sulfides such as dibenzothiazoyl monosulfide; thioxanthone derivatives such as 2,4-diethylthioxanthone; (di) azo compounds such as benzenediazonium; benzyl. Aromatic carbonyl compounds such as dimethyl ketal; acetophenone derivatives such as α-hydroxy-α, α′-dimethyl-acetophenone; peroxides such as dicumyl peroxide; acridine derivatives such as benzacridine; 9-methylbenzphenazine and the like. Phenazine derivative; 6,4 ', 4 "-trimethoxy-2,3
-Quinosaline derivatives such as diphenylquinosaline; 2,
4,5-Triphenylimidazoyl dimer; halogenated ketone; 2,4,6-tris (trichloromethyl)-
1,3,5-triazine and the like can be mentioned.

In the above photopolymerizable resin composition, when the content of the photopolymerization initiator (C) is low, the image cannot be formed due to insufficient curing after exposure, and when the content is high, the cured photocurable composition is cured. Since the resin composition turns yellow and becomes brittle, it is limited to 0.1 to 10 parts by weight with respect to 100 parts by weight of the linear copolymer (d).

The constitution of the photosensitive image-receiving sheet of the present invention is
As described above, the image-receiving sheet is used to form the above-mentioned image pattern of dots as in the present invention.

EXAMPLES The present invention will be described below based on examples. (Example 1) (1) Preparation of unsaturated compound capable of photopolymerization In a 5 liter four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer and a mechanical stirrer, 504 g (3 mol equivalent) of hexamethylene diisocyanate was added. , Dry methyl ethyl ketone (hereinafter referred to as MEK) 8 as a solvent
26 g and dibutyltin dilaurate (catalyst) 1 g were added and polyethylene glycol 916 g with stirring
(2 mol equivalent, average molecular weight: 458) was added and the mixture was refluxed for 5 hours. Next, 596 g (2 mol equivalent) of pentaerythritol triacrylate was added dropwise, the mixture was refluxed for another 5 hours for reaction, and MEK was evaporated to prepare a photopolymerizable unsaturated compound (hereinafter referred to as U-1).
[The unsaturated compound is represented by the formula (1) in which R ¹ =
(CH ₂ ) ₂ , X = (CH ₂ ) ₆ , m = 10, n = 2,
A was represented by the general formula (2) (R ² = H in the formula), and the weight average molecular weight was 2016. ]

(2) Preparation of Photopolymerizable Resin Composition-Linear Copolymer (A) 100 parts by Weight (Methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid = 31/31/13/25 ( Weight ratio), weight average molecular weight = 150,000) -Unsaturated compound (U-1) 100 parts by weight-Unsaturated compound (photopolymerizable monomer) 50 parts by weight (Nippon Kayaku Co., Ltd. "KAYARAD R-" 167 ")-Photopolymerization initiator (component: benzyl dimethyl ketal) 2 parts by weight (" Irgacure 651 "manufactured by Ciba-Geigy) The above components are dissolved in 400 parts by weight of MEK to prepare a photopolymerizable resin composition solution. did.

(3) Preparation of Photosensitive Image Receiving Sheet The above photopolymerizable resin composition solution was cast on a polyethylene terephthalate (hereinafter referred to as PET) film having a thickness of 75 μm and dried at 80 ° C. for 5 minutes. A photosensitive image receiving sheet having a photosensitive image receiving layer having a thickness after drying of 25 μm was produced.

(4) Preparation of Photocurable Resin Composition 100 parts by weight of linear copolymer (a) (methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid = 31/31/13/25 ( (Weight ratio), weight average molecular weight = 100,000) -Unsaturated compound 67 parts by weight (component: trimethylolpropane triacrylate) -Photopolymerization initiator (component: benzyl dimethyl ketal) 2 parts by weight (Ciba Geigy's "IRGA" Cure 651 ")-Yellow pigment (Dainichi Seika's" FPF-27E Yellow ") 10 parts by weight or-Magenta pigment (Dainichi Seika's" FPF-96Q Red ") 10 parts by weight or-Cyan pigment (Large) "FPF-CP2 Blue" manufactured by Nissei Chemical Co., Ltd.) 10 parts by weight The above substances are dissolved in 400 parts by weight of methyl ethyl ketone, Yellow and magenta and cyan, solutions of each colored three photocurable resin composition was prepared.

(5) Preparation of Colored Photocurable Resin Layer First, alcohol-soluble polyamide (“CM-8000” manufactured by Toray Industries, Inc.) 10 was formed on a PET film having a thickness of 75 μm.
Casting a solution of 90 parts by weight of methanol and 90 parts by weight of methanol,
It was dried at 100 ° C. for 5 minutes to provide a heat fusion layer having a thickness of 2 μm. A solution of the photo-curable resin composition colored in yellow was cast on the heat-sealing layer, dried at 80 ° C. for 5 minutes, and then dried to a thickness of 5 μm to obtain a yellow photo-curable layer. A resinous layer was prepared. Similarly, photo-curable resin layers colored magenta and cyan were prepared.

(6) Formation of Colored Halftone Image Pattern First, a halftone dot negative mask corresponding to cyan is overlaid on a cyan-colored photo-curable resin layer, and a halftone dot negative mask is placed on the halftone dot negative mask. 400 mJ / cm ^{2 with} ultra-high pressure mercury lamp
Was irradiated with light to cure. Then, at 20 ° C., a 1% by weight aqueous solution of sodium carbonate was added at a pressure of ² kg / cm ² to 4
By spraying for 5 seconds and developing, and dissolving and removing the unexposed portion, a halftone dot image pattern corresponding to a cyan halftone negative mask was formed. In the same manner, a halftone image pattern corresponding to magenta and yellow colors was formed using the photocurable resin layers colored in magenta and yellow.

(7) Transfer of Halftone Image Pattern to Photosensitive Image Receiving Sheet The halftone image pattern corresponding to the cyan color is overlaid so that the image pattern side is in contact with the photosensitive image receiving layer, and 110 A laminator roll at 4 ° C. and a pressure of 4 kg / cm ² at 2 m / min to heat and press,
At the same time when the halftone dot image pattern and the image receiving layer were fused, the support was peeled off, and the image pattern was transferred to the photosensitive image receiving sheet together with the heat fusion layer. Similarly, the image patterns corresponding to magenta and yellow were transferred onto the above-mentioned photosensitive image receiving sheet to obtain a photosensitive image receiving sheet in which image patterns of three colors were laminated.

(8) Retransfer of halftone dot image pattern onto substrate First, a photosensitive image receiving sheet having three color image patterns laminated thereon was used, the heat-sealing layer thereof and a white polycarbonate sheet substrate having a thickness of 1 mm. And a laminator roll were passed at a rate of 2 m / min to heat and press to fuse the layers, and the laminate of three-color dot image patterns was retransferred onto the substrate. Then, using an ultra high pressure mercury lamp, 40
After irradiation with light of 0 mJ / cm ² to cure the image receiving layer, the support was peeled off to prepare a display board having a colored image.

(9) Performance Evaluation of Display Board The obtained display board was subjected to the following bending test, and the results are shown in Table 1. [Flexibility test] The display board was wound around a round bar having a diameter of 10 mm so that the bending angle was 90 degrees, and the presence or absence of cracks or cracks was visually observed on the surface of the photosensitive image receiving layer. . The folding direction was such that the image receiving layer was on the outside and inside.

(Examples 2 to 4) A display having a colored image was obtained in the same manner as in Example 1 except that the composition and molecular weight of the linear copolymer (a) were changed as shown in Table 1. After making the board, a bending test was conducted in the same manner as in Example 1,
The results are shown in Table 1.

(Examples 5 to 7) As the photopolymerizable unsaturated compound, only the following unsaturated compound (hereinafter referred to as U-2) was used, and the composition and molecular weight of the linear copolymer (a) are shown. After producing a display board having a colored image in the same manner as in Example 1 except that the change was made as shown in Example 1, the same flexibility test as in Example 1 was performed, and the results are shown in Table 1. Indicated. [Preparation of Unsaturated Compound (U-2)] Hexamethylene diisocyanate (504 g (3 mol equivalent)) was dried as a solvent in a 5-liter four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer and a mechanical stirrer. 826 g of methyl ethyl ketone (hereinafter referred to as MEK) and 1 g of dibutyltin dilaurate (catalyst) were added, and 916 g of polyethylene glycol (2 mol equivalent, average molecular weight: 458) was added with stirring and refluxed for 5 hours. Then
232 g of 2-hydroxyethyl acrylate (2 mol
(Equivalent) was added dropwise, and the mixture was refluxed for another 5 hours to react,
By evaporating MEK, a photopolymerizable unsaturated compound (U
-2) was prepared. [The unsaturated compound is represented by the formula (1) in which R ¹ = (CH ₂ ) ₂ and X = (CH ₂ ) _2
6 , m = 10, n = 2, A was represented by the general formula (3) (in the formula, R ³ = H), and the weight average molecular weight was 1652. ]

(Examples 8 to 10) R-167 was used alone as the photopolymerizable unsaturated compound, and the composition and molecular weight of the linear copolymer (a) were changed as shown in Table 1. In the same manner as in Example 1, after producing a display board having a colored image, a bending test was conducted in the same manner as in Example 1, and the results are shown in Table 1.

[0106]

[Table 1]

Comparative Examples 1 to 10 Coloring was carried out in the same manner as in Example 1 except that the composition and blending amount of the linear copolymer (a) and the unsaturated compound were changed as shown in Table 1. After the display panel having the above image was prepared, a bending test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

[0108]

[Table 2]

Example 11 (1) Preparation of Photopolymerizable Resin Composition and Preparation of Photosensitive Image Receiving Sheet 100 parts by weight of linear copolymer (d) (methyl methacrylate / butyl methacrylate / 2-ethylhexyl ac) Relate / methacrylic acid = 31/31/13/25 (weight ratio), weight average molecular weight = 100,000) ・ Unsaturated compound (U-1) 100 parts by weight ・ Unsaturated compound ("R" manufactured by Nippon Kayaku Co., Ltd. -167 ") 50 parts by weight Photopolymerization initiator (component: 2,4,6-trimethylbenziyldiphenylphosphine oxide) 1.5 parts by weight (BASF's" Lucirin TPO ") 400 parts by weight of each of the above components To prepare a photopolymerizable resin composition solution. Then, using this photopolymerizable resin composition solution, a photosensitive image-receiving sheet was prepared in the same manner as in Example 1.

(2) Preparation of Photocurable Resin Composition and Preparation of Photocurable Resin Layer As the photopolymerization initiator, 2,4,6-trimethylbenzoylphenylphosphine was used in place of 2 parts by weight of "Irgacure 651". Oxide (Lucirin TP manufactured by BASF
O ”) was used, and a photocurable resin composition colored in yellow, magenta, and cyan was prepared in the same manner as in Example 1 except that 1.5 parts by weight was used. Next, using the solutions of the respective photocurable resin compositions, in the same manner as in Example 1, three types of photocurable resin film layers colored yellow, magenta, and cyan were prepared.

(3) Preparation of Display Board After forming a halftone dot image pattern on the above-mentioned photocurable resin film layer in the same manner as in Example 1, the image pattern was transferred to a photosensitive image receiving sheet, and further, A display board having a colored image was prepared by retransferring onto the substrate.

(4) Sensitivity Test of Photosensitive Image Receiving Sheet The photosensitive image receiving sheet obtained in (1) was used in a thickness of 1 mm.
Samples were prepared by stacking on a white polycarbonate substrate (1) and stacking by applying pressure and heating with a laminator roll. This sample was treated with a high pressure mercury lamp at 50 m with a support attached to prevent curing inhibition by oxygen.
Sensitivity was defined as the cumulative irradiation amount of light irradiated by J / cm ² until the surface hardness reached the pencil hardness H, and the values are shown in Table 3.

(5) Yellowing degree of the photosensitive image-receiving sheet (Δ
E) Measurement A sample similar to that prepared in (4) was irradiated with light until the surface hardness reached a pencil hardness H in the same manner as in (4), and then the photosensitive image-receiving sheet was peeled from the substrate. Then, using a "SM-3 color computer" manufactured by Suga Test Instruments Co., Ltd., the color difference of the photosensitive receiving sheet before and after curing is measured by the reflection method (JI
According to SK7013), the measured value is defined as the yellowing degree (ΔE) of the photosensitive image-receiving sheet, and the measured values are shown in Table 3. Further, using the same sample as that prepared in (4), the sample after the heat resistance test at 90 ° C. × 900 hours and the fade resistance test according to JIS K5400 were subjected to the light resistance test for 100 hours. The yellowing degree (ΔE) was measured in the same manner for the subsequent samples, and the measured values are shown in Table 3.

(6) Evaluation of Yellowing Degree (ΔE) of Display Panel Using the display panel prepared in (3) as a sample, the sample was measured by JI.
10 with a fade meter conforming to SK5400
With respect to those subjected to the 0-hour light resistance test, the yellowing degree of the photosensitive image-image receiving sheet was visually observed and evaluated according to the following criteria, and the results are shown in Table 3. ◯: No yellow coloring is observed, ×: Yellow coloring is observed, XX: Very yellow coloring is observed.

(Examples 12 to 20) In the same manner as in Example 1 except that the kinds of the linear copolymer, the unsaturated compound and the photopolymerization initiator and the compounding parts were changed as shown in Table 3. After preparing a light-sensitive image-receiving sheet and a display board having a colored image, a sensitivity test and yellowing degree (ΔE) measurement of the light-sensitive receiving sheet, and a yellowing degree (ΔE) of the display board
Evaluation was performed in the same manner as in Example 11, and the results are shown in Table 3.
It was shown to.

[0116]

[Table 3]

(Comparative Examples 11 to 20) In the same manner as in Example 1 except that the kinds of linear copolymers, unsaturated compounds and photopolymerization initiators and the compounding parts were changed as shown in Table 3. After preparing a light-sensitive image-receiving sheet and a display board having a colored image, a sensitivity test and yellowing degree (ΔE) measurement of the light-sensitive image-receiving sheet and a yellowing degree (ΔE) of the display board were performed.
E) Evaluation was performed in the same manner as in Example 11, and the results are shown in Table 4.

[0118]

[Table 4]

[0119]

Since the photosensitive image-receiving sheet of the present invention contains a specific quaternary linear copolymer imparted with flexibility, a colored image transferred onto the photosensitive image-receiving sheet is obtained. The final product such as a display panel obtained by re-transferring the above-mentioned to the substrate can be colored in any color and has excellent flexibility. Since the photosensitive image-receiving sheet of the present invention 2 contains a photopolymerization initiator having high sensitivity and less yellowing, the colored image transferred on the photosensitive image-receiving sheet is retransferred onto the substrate. The final product such as a display board thus obtained can be colored in any color and has excellent yellowing resistance (weathering resistance).

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing a photosensitive image-receiving sheet of the present invention.

FIG. 2 is a schematic cross-sectional view showing a colored photocurable resin film used in the present invention.

FIG. 3 is a schematic cross-sectional view showing a state of exposing a photocurable resin film layer through a halftone negative mask.

FIG. 4 is a schematic cross-sectional view showing a colored halftone dot image pattern obtained by developing an exposed photocurable resin film layer.

FIG. 5 is a schematic cross-sectional view showing a state in which a halftone dot image pattern is transferred and laminated on the photosensitive image receiving sheet of the present invention.

FIG. 6 is a schematic cross-sectional view showing an image obtained by transferring and laminating halftone dot image patterns of three colors on the photosensitive image receiving sheet of the present invention.

FIG. 7 was obtained on a photosensitive image receiving sheet of the invention,
It is a schematic cross section which shows the situation which re-transfers the image which consists of a 3-color halftone dot image pattern to a base | substrate.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photosensitive image receiving layer 2 Support 3 Photocurable resin layer 4 Thermal fusion layer 5 Support 6 Halftone dot negative mask 7 Halftone dot image pattern colored in cyan 8 Halftone dot image colored in magenta Pattern 9 Yellow-dotted image pattern 10 Photosensitive image receiving sheet 11 Photocurable resin film 12 Substrate

Claims (2)

[Claims] 1. A photosensitive image receiving sheet having a photosensitive image receiving layer formed on a support, wherein the image receiving layer comprises:
(A) Methyl methacrylate 10-70% by weight, butyl methacrylate 10-50% by weight, 2-ethylhexyl acrylate 10-25% by weight and methacrylic acid 10-30.
100 parts by weight of a linear copolymer having a weight average molecular weight of 20,000 to 300,000 composed of 10% by weight, (b) 10 to 200 parts by weight of a photopolymerizable unsaturated compound, and (c) light sensitized by an actinic ray. A photosensitive image-receiving sheet formed of a photopolymerizable resin composition comprising 0.1 to 10 parts by weight of a polymerization initiator. 2. A photosensitive image-receiving sheet having a photosensitive image-receiving layer formed on a support, wherein the image-receiving layer comprises:
(D) 100 parts by weight of a linear copolymer having an α, β-unsaturated ethylenic monomer as a constituent and having a weight average molecular weight of 20,000 to 300,000, and (b) a photopolymerizable unsaturated compound 10 to 200. A photosensitive image-receiving sheet comprising a photopolymerizable resin composition comprising 0.1 to 10 parts by weight of a (pho) acylphosphine oxide-based photopolymerization initiator.