JP2002321299A - Photosensitive resin laminate and photosensitive resin sign plate formed therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive sign plate which emits light even when illumination in a room is turned off and is excellent in designability. SOLUTION: (1) In a photosensitive resin laminate having at least a support and a photosensitive resin layer, the support contains a light accumulating agent. (2) In the photosensitive resin laminate, the total light transmittance of the support is at least 60%. (3) In the photosensitive resin sign plate having a relief obtained from the photosensitive resin laminate, the support contains the light accumulating agent. (4) In the photosensitive resin sign plate having the relief obtained from the photosensitive resin laminate, an afterglow time after the irradiation of light is at least 120 min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin laminate suitable for a display panel, a decorative shield, a name plate, a sign board such as a Braille display board, and a photosensitive resin sign board obtained therefrom. In particular, the present invention provides a photosensitive resin sign plate having excellent design properties.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive resin laminate using a photosensitive resin obtained by exposing a photosensitive resin layer through a pattern and then developing the same, Japanese Patent Laid-Open No.
It is disclosed in Japanese Unexamined Patent Publication No. 55927/1997 and Japanese Unexamined Patent Application Publication No. 9-6267, and is used for a Braille panel having a relief, a sign board including Braille, and the like. However, design requirements for the sign plate have recently been increased, and a conventional sign plate in which a concavo-convex pattern is formed and a convex portion is colored with a color paint cannot satisfy the demand. In addition, even in a dark place after turning off the light in the room, the function as a sign board may be required, but no sign board has satisfied the requirement.

[0003]

SUMMARY OF THE INVENTION The present invention relates to display panels,
For a decorative resin shield, a name plate, a sign board for a photosensitive resin composition used for a Braille display board, etc., a photosensitive resin sign board excellent in design which emits light even when indoor lighting is turned off by adding a storage material to a support. To provide.

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventors have sincerely studied and studied, and as a result, have finally completed the present invention. That is, the present invention provides a photosensitive resin laminate having at least a support and a photosensitive resin layer, wherein the support contains a luminous agent. The total light transmittance of the support is 6
The photosensitive resin laminate according to the above, which is 0% or more. A marker plate having a relief obtained from at least a photosensitive resin laminate having a support and a photosensitive resin layer, wherein the support contains a phosphorescent agent. At least a sign plate having a relief obtained from a photosensitive resin laminate having a support and a photosensitive resin layer, wherein the afterglow time after light irradiation is 120 minutes or more. It is a board.

[0005]

Next, the present invention will be described in more detail. In the present invention, the afterglow time after light irradiation of the photosensitive resin marker plate is defined as a value of 0.3 mcd / m3 of afterglow light after irradiation with 1,000 lx light of a common light source fluorescent lamp D65 specified in JIS Z8716 for 5 minutes. It is the time to decay to ² , in the present invention, 120 minutes or more,
Preferably, the time is 240 minutes or more, especially 360 minutes or more.

The luminous agent used in the present invention is a material which emits light in a dark place when it receives sunlight or electric light. 0.3mcd / m ² for light emission in dark place where brightness can be visually recognized by naked eyes
The above luminance is required, and it is preferable to use a luminous agent that has a long time until the luminance is reduced to 0.3 mcd / m ² (called afterglow time). As the phosphorescent agent, a commercially available phosphorescent agent can be used, and examples thereof include a sulfide-based phosphor and an aluminate phosphor. Among the above phosphors, an aluminate phosphor having a long emission time is preferable. As a specific example, (Ca, Sr) S: B
i phosphor, ZnS: Cu phosphor and the like, and aluminate phosphors include SrAl ₂ O ₄ : Eu phosphor,
SrAl ₂ O ₄ : Eu, Dy phosphor, CaAl ₂ O ₄ :
Eu, Nd phosphor, Sr ₄ Al ₁₄ O ₄ : Eu, Nd phosphor, Sr ₄ Al ₁₄ O ₂₅ : Eu, DY phosphor and the like.

The method of incorporating a luminous agent into the support of the present invention includes a method of producing the support by blending it with a resin used in the production of the support and a method of adding a luminous agent during polymerization of the resin for the support. And a method for producing a support using the above method.

The optimum amount of the phosphorescent agent to be contained in the support of the present invention may be determined in consideration of the afterglow time until the luminance is reduced to 0.3 mcd / m ^2. If the content exceeds 30.0% by weight based on the weight of the photosensitive resin composition, the physical properties of the photosensitive resin layer are greatly reduced, which is not preferable.

As the photosensitive resin layer used in the present invention, known ones can be used, and specific photosensitive resin components include soluble polymer compounds (for example, polyvinyl alcohol, cationic polyamide, polyetherester). Amides, polyether amides, polyurethanes, etc.), photopolymerizable or photocrosslinkable monomers (eg, polyhydric alcohol acrylates, polyhydric alcohol epoxy acrylates, N-methylolacrylamide, etc.), photopolymerization initiators (eg, benzyldimethyl) Ketal, benzoin dimethyl ether, etc.), heat stabilizer, plasticizer,
A photosensitive resin composition containing a surfactant, an ultraviolet absorber, and the like. Note that a luminous agent may be added to the photosensitive resin layer for light emission in a dark place in terms of design. As the addition amount of the phosphorescent agent, an optimum addition amount may be determined in consideration of the afterglow time until the luminance is reduced to 0.3 mcd / m ^2.

Specific examples of commercially available transparent support resins used in the present invention include polyester resins such as polycarbonate resins and polyethylene terephthalate resins.
Examples include acrylic resins such as polymethyl methacrylate, copolymer resins of polymethyl methacrylate and styrene, and modified polyethylene terephthalate resins obtained by copolymerizing dicyclohexyl dimethanol and the like. Acrylic resins and copolymer resins of poly (methyl methacrylate) and styrene are preferred from the viewpoint of light resistance. These resins may be modified by blending to improve quality such as transparency, or may be modified by blending additives such as plasticizers.

The support used in the present invention is preferably transparent from the viewpoints of light irradiation on the luminous agent and design properties, and has a total light transmittance of 60% or more, preferably 65% or more, particularly preferably 70% or more. belongs to. If the total light transmittance is less than 60%, it is unsuitable for a sign plate which lacks quality when processed into a sign plate and has excellent design properties.

The thickness of the support used in the present invention is usually 1 m.
A thickness suitable for the application and design is selected in the range of m to 10 mm. With a support having a thickness of less than 1 mm, the resin plate itself tends to warp and is not suitable for use as a sign board. When the thickness exceeds 10 mm or more, the board cannot be easily cut or the weight becomes heavy, which is not preferable. .

The hardness of the support which can be used in the present invention is required to have a Shore D hardness of 35 ° or more, preferably 55 ° or more, particularly preferably 75 °. When the Shore D hardness is less than 35 °, the resin plate itself is warped or lacks the holding property as a sign plate, which is not preferable.

The photosensitive layer used in the present invention needs to have a thickness of at least 500 .mu.m, preferably 800 to 1200 .mu.m, for use in Braille applications. If it exceeds 1200 μm, the image reproducibility decreases, which is not preferable.

Next, as a method for producing the photosensitive resin laminate of the present invention, an adhesive described later is applied to the support, and a photosensitive resin layer is laminated by a known method. Body can be manufactured. As a method for laminating the photosensitive resin on the support, for example, hot pressing, casting, melt extrusion, solution casting, laminating and the like can be used to laminate the photosensitive resin on the support.

The photosensitive resin layer is prepared in advance by laminating a resin film such as polyethylene terephthalate on a support as a support (hereinafter referred to as a photosensitive resin laminate precursor). May be peeled off from the resin film and laminated on a resin support.

As a method for preparing the photosensitive resin laminate precursor, a method for producing a usual photosensitive resin laminate for a printing plate can be adopted. A cover which is coated with a transparent polymer having no tackiness and which is dispersed or dissolved in a developer (such as polyvinyl alcohol or cellulose, also referred to as a slip coat layer) to a thickness of 1 to 3 μm. A photosensitive resin layer precursor comprising a photosensitive resin layer, a slip coat layer, and a cover film is obtained between a film and a polyester film having a thickness of 125 μm, for example.

In the present invention, when a photosensitive resin layer (which may have a slip coat layer or a cover film) is bonded to the resin support, a known adhesive is used as an adhesive layer to be used. Specific examples thereof include a polyester urethane-based adhesive and an epoxy-based adhesive obtained by curing a soluble polyester with a polyvalent isocyanate. Among them, a polyester urethane-based adhesive is preferable because of excellent adhesion to a photosensitive resin, and among polyester urethane-based adhesives, an adhesive composed of polyester and an isocyanurate-type polyisocyanate is particularly preferable from the viewpoint of low-temperature drying. Other minor components can be added to the adhesive layer composition. As an additive,
Examples include plasticizers, dyes, ultraviolet absorbers, antihalation agents, and photopolymerizable vinyl monomers.

As a method of providing the adhesive layer on the support,
Generally, the solvent is removed after applying the adhesive layer composition solution to a predetermined thickness. As a coating method, a known method such as a roll coater, a curtain flow coater, a slit die coater, a gravure coater, or a spray can be used. The drying treatment of the adhesive layer after coating the support is generally performed by blowing hot air in a drying oven. The drying temperature of the adhesive layer used in the present invention is 15 ° C to 80 ° C.
Is preferably less than 20 ° C and 70 ° C. If the temperature exceeds 80 ° C., the support is undesirably deformed such as warpage.
If the temperature is lower than 15 ° C., the drying time becomes longer, which is not preferable.

The thickness of the adhesive layer needs to be in the range of 0.5 μm to 100 μm. When the thickness is 0.5 μm or less, the adhesive force between the photosensitive resin layer and the adhesive layer does not appear. On the other hand, if the thickness of the adhesive layer exceeds 50 μm, there is a problem that the time required for drying the coating liquid becomes long. For such a reason, the thickness of the adhesive layer needs to be in the range of 0.5 μm to 100 μm, and preferably 1 μm to 50 μm.

As described above, the method for producing the sign board of the present invention from a photosensitive resin laminate having a support plate, an adhesive layer, and a photosensitive resin layer (which may further have a slip coat layer or a cover film) is described. The method can be adopted to produce a normal printing plate, for example, through a slip coat layer on the photosensitive resin layer, or without, without contact, a negative film having a transparent image portion is closely adhered and overlapped, When exposure is performed by irradiating an actinic ray from above, only the exposed portions are insolubilized and photocured. Actinic rays are usually 300 to 4
A high-pressure mercury lamp centered on a wavelength of 5 nm, an ultra-high-pressure mercury lamp,
A light source such as a metal halide lamp and a xenon lamp can be used.

Next, a relief plate having a clear image area is obtained by dissolving and removing the non-exposed portion with an appropriate solvent, particularly, neutral water in the present invention. For this purpose, a spray developing device, a brush developing device, or the like can be used.

[0023]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
The afterglow time and the total light transmittance were measured by the following methods. Afterglow time: The time required for the afterglow light to decay to 0.3 mcd / m ² after being irradiated with 1000 lx light of a common light source fluorescent lamp D65 specified in JIS Z 8716 for 5 minutes was measured. Total light transmittance: measured using a turbidity meter (Hazemeter, NDH-1001DP) manufactured by Nippon Denshoku Industries Co., Ltd.

Example 1 An acrylic plate (polymethyl methacrylate resin) having a total light transmittance of 92% was used as a resin of a support, and a fine powder of yellow-green SrAl ₂ O ₄ : Eu phosphor was contained as a luminous agent. The mixture was blended so that the ratio became 20% by weight, and a support having a thickness of 2.0 mm was obtained by a melt extrusion molding method. The adhesive layer used a polyester urethane-based adhesive, and the composition solution for the adhesive layer was prepared as follows. 80 parts by weight of polyester resin "Byron RV-200" manufactured by Toyobo Co., Ltd.
It was heated and dissolved at 80 ° C. in 1940 parts by weight of a mixed solvent of methyl ethyl ketone = 80/20 (weight ratio). After cooling, 20 parts by weight of "Desmodur HL" isocyanurate-type polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd. using hexamethylene diisocyanate and toluene diisocyanate as raw materials as isocyanurate-type polyisocyanate, and triethylenediamine 0 as a curing catalyst 0.06 parts by weight and stirred for 10 minutes. The composition solution for an adhesive layer thus obtained was applied on a 2.0 mm-thick acrylic plate so as to have a film thickness of 12 μm.
The substrate was dried and cured for 10 minutes to obtain a support coated with an adhesive layer.

The photosensitive resin composition to be laminated is composed of 525 parts of ε-caprolactam as a soluble polymer, nylon salt 40 of N- (2-aminoethyl) piperazine and adipic acid.
0 parts and 75 parts of a nylon salt of 1,3-bis (aminomethyl) cyclohexane and adipic acid were melt-polycondensed in an autoclave to obtain a copolymer nylon containing a nitrogen atom.
After dissolving 55 parts of the obtained polymer in 200 parts of methanol at 60 ° C., 2 parts of glycidyl methacrylate was added and stirred for 3 hours to react glycidyl methacrylate on the polymer terminal. 4 parts of methacrylic acid are added to this solution, and then acrylate 3 obtained by the open addition reaction of diglycidyl ether of glycerin and acrylic acid.
5 parts, N-ethyltoluenesulfonamide 5 parts, hydroquinone monomethyl ether 0.1 part, and benzyldimethyl ketal 1.0 part were added to obtain a solution of the photosensitive resin composition. This solution was cast on a polyester film coated with 2 μm of polyvinyl alcohol having a saponification rate of 98%, and methanol was removed by evaporation.
A photosensitive resin layer precursor having a thickness of 00 μm was obtained. The bonding method of the thus obtained photosensitive resin layer precursor and the support coated with the adhesive layer is performed by aligning the photosensitive resin composition surface and the support surface, and then injecting water therebetween. . The photosensitive resin layer was pressure-bonded at a room temperature of 25 ° C. through a rubber roller whose gap clearance was adjusted according to the thickness of the laminated layers, thereby producing a photosensitive resin laminated body. After leaving the photosensitive resin laminate for one day, it is cut into a predetermined size with a circular saw-toothed cutter, placed on a negative, exposed, developed, dried and post-exposed to obtain a display plate on which a relief is created. Was. The afterglow time of light emission after light irradiation was evaluated for the obtained relief of the marker plate. 0.3m afterglow after 5 minutes
The time required for the decay to cd / m ² was 700 minutes. After the indoor certification was turned off, yellowish green light was emitted, and the signboard was excellent.

COMPARATIVE EXAMPLE 1 The same operation as in Example 1 was carried out to obtain a relief of an ordinary marker plate without a luminous agent added to the support. The afterglow time of light emission after light irradiation was evaluated in the same manner as in Example 1. There was no afterglow after irradiating for 5 minutes, and no function as a sign board after turning off the indoor certification was observed.

Example 2 The support used in Example 1 was applied to the support as a luminous agent with purple blue Ca
A display panel was prepared in which fine powder of Al ₂ O ₄ : Eu, Nd phosphor was blended so as to have a content of 30%, a luminous agent was blended in the support, and a relief was prepared in the same manner as in Example 1. Obtained.
The afterglow time of light emission after light irradiation was evaluated for the obtained relief of the marker plate. The afterglow after irradiation for 5 minutes is 0.
The time to decay to ³ mcd / m ² is 400 minutes,
It turned out to be purple blue after the indoor certification was turned off, and was an excellent sign board.

[0028]

As described above, the photosensitive resin marker plate of the present invention can provide a photosensitive resin laminate suitable as a marker plate having excellent design properties, and thus greatly contributes to the industry.

Continued on front page F-term (reference) 2H025 AA00 AB20 AC01 AD01 DA17 FA17 4F100 AA19 AH03 AH04 AK01B AK25 AK41 AK48 AL01 AT00A BA02 BA07 CB00 EH17 EJ17 GB90 HB00 JN08A JN13 JN13A JN17BFA03A

Claims (4)

[Claims] 1. A photosensitive resin laminate having at least a support and a photosensitive resin layer, wherein the support contains a luminous agent. 2. The photosensitive resin laminate according to claim 1, wherein the total light transmittance of the support before containing the luminous agent is 60% or more. 3. A sign plate having a relief obtained from at least a photosensitive resin laminate having a support and a photosensitive resin layer, wherein the support contains a phosphorescent agent. Resin sign board. 4. A sign plate having a relief obtained from at least a photosensitive resin laminate having a support and a photosensitive resin layer, wherein the afterglow time after light irradiation is 120 minutes or more. Photosensitive resin signboard.