JP3034336B2 - Display panel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display panel having an arbitrary colored pattern formed at a predetermined position on a substrate.

[0002]

2. Description of the Related Art Recently, tachometers used in vehicles,
2. Description of the Related Art A display panel provided with characters composed of colored patterns on a base is used for a speed meter or the like.

[0003] Conventionally, the characters and numerals on the display panel have been formed by printing on a substrate, and among them, screen printing is often used. However, in the pattern formation by screen printing, since the ink used is a solvent type liquid, the solvent filled in the working environment becomes a odor source, and it is necessary to always pay attention to the danger of explosion and fire. There was a problem.

[0004] In addition, the printing ink remains on the plate due to evaporation of the solvent, causing the clogging of the plate, and requires a long time to adjust the viscosity to be suitable for screen printing.

For this reason, photopolymerizable inks for the purpose of eliminating the solvent and shortening the curing time have been proposed in recent years.
However, photopolymerizable inks require the addition of a reactive diluent, such as a low molecular weight monomer, to adjust the viscosity to be suitable for screen printing. May evaporate over time from the coating film.

In addition, since the molecular weight has been reduced as a whole,
There are drawbacks such as a large shrinkage upon curing, a decrease in adhesiveness and a lack of flexibility, and the practicality was not sufficient. In order to solve the above-mentioned drawbacks, a film-like photopolymerizable resin composition using an acrylic polymer as a binder and urethane acrylate, epoxy acrylate, and polyol acrylate as a photopolymerizable compound is exposed through a negative mask and cured. A method of forming an image pattern by causing the image pattern to be formed is proposed in Japanese Patent Application Laid-Open No. 2-210219.

However, in the above method, it is not easy to form a pattern of an arbitrary shape at a predetermined position on a substrate because the resolution of the photopolymerizable resin composition used at the time of pattern formation is poor. In addition, there are drawbacks in that the adhesion between the formed pattern and the substrate, the flexibility of the formed pattern, heat resistance, light resistance and the like are inferior.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and an object of the present invention is to provide a pattern excellent in flexibility, heat resistance, light resistance and adhesion to a substrate.
In providing a display panel provided in an arbitrary shape at a predetermined position on a base,

[0009]

A display panel according to the present invention is a display panel in which an arbitrary image pattern is formed at a predetermined position on a substrate, wherein the image pattern is formed by curing a photopolymerizable resin composition. Made of things.

First, the present invention 1 will be described. In the present invention 1, the photopolymerizable resin composition comprises (A) a linear copolymer, (B) a photopolymerizable unsaturated compound, (C) a photopolymerization initiator sensitized by actinic rays, and D) It consists of a coloring agent.

The linear copolymer (a) comprises an α, β-unsaturated ethylenic monomer containing a carboxyl group and other α, β-unsaturated ethylenic monomers. . The carboxyl group-containing α, β-unsaturated ethylenic monomer includes a carboxyl group, α,
Any monomer copolymerizable with the β-unsaturated ethylenic monomer may be used. For example, (meth) acrylic acid, crotonic acid,
Unsaturated carboxylic acids such as maleic acid (anhydride), fumaric acid, itaconic acid and the like can be mentioned. Examples of other α, β-unsaturated ethylenic monomers include styrene, o-methylstyrene, m- Methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4
-Dimethylstyrene, pn-hexylstyrene, p-
Styrenes such as n-octylstyrene, p-methoxystyrene, p-phenylstyrene and 3,4-dimethylchlorostyrene; vinylnaphthalenes such as α-vinylnaphthalene; ethylene, propylene, butylene or C ₅
-C ₃₀ and more α- olefins, vinyl chloride,
Vinyl halides such as vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl (meth) acrylate, propyl (meth) acrylate, and n- (meth) acrylate Butyl,
Isobutyl (meth) acrylate, n (meth) acrylate
-Octyl, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid-
(Meth) acrylic esters such as 2-chloroethyl, α-chloromethyl (meth) acrylate, 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-vinyl compounds such as N-vinyl pyrrole and N-vinyl indole;
(Meth) acrylonitrile and (meth) acrylamides.

When the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer containing a carboxyl group in the components of the linear copolymer (a) becomes small, it becomes insoluble in an aqueous alkali solution. Development with an aqueous alkali solution is no longer possible. Conversely, if the amount is too large, the compatibility with the coating solvent or other components is reduced, and the resolution is also reduced. ~ 35% by weight. The amount of the component other than the portion corresponding to the α, β-unsaturated ethylenic monomer containing a carboxyl group in the constituent components of the linear copolymer (A) is 60 to 90% by weight.

The weight average molecular weight of the linear copolymer (a) is
When the size is reduced, so-called cold flow is apt to occur, and when stored in a roll, the photopolymerizable resin composition becomes wrinkled and cannot be used. Conversely, when the size is large, it is difficult to dissolve in an aqueous alkali solution and develop, and the resolution is reduced. Therefore, the content is limited to 20,000 to 500,000, and preferably 50,000 to 300,000.

The photopolymerizable unsaturated compound (b) used in the present invention 1 has the following general formulas (I), (II) and (III):
At least one selected from the group consisting of compounds represented by
More than one compound.

[0015]

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[0016]

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[0017]

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In the formula (I), R ¹ has 1 to 10 carbon atoms.
M is an integer of 1 to 100, R ² , R
³ is a hydrogen or methyl group, and X is a divalent hydrocarbon group having 2 to 20 carbon atoms.

In the formula (II), R ⁴ has 1 to 1 carbon atoms.
10, a divalent hydrocarbon group, p is an integer of 1 to 100, q is an integer of 1 to 15, R ⁵ and R ⁶ are hydrogen or a methyl group, Y
Represents a divalent hydrocarbon group having 2 to 20 carbon atoms.

Further, in the formula (III), R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms, r is an integer of 1 to 100,
s is an integer of 1 to 15, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are hydrogen or a methyl group, and Z is a divalent hydrocarbon group having 2 to 20 carbon atoms.

Here, the divalent hydrocarbon group represented by X, Y, or Z includes a hydrocarbon group composed of a linear, branched, alicyclic or aromatic moiety, for example, Examples include a methylene group, a tolylene group and an isophorone group.

The unsaturated compound (b) may be produced by any method. For example, diisocyanate and diol may be mixed and reacted at a ratio corresponding to the required composition ratio of the compound, and an isocyanate group may be added to the terminal. After the formation of the urethane oligomer, a (meth) acrylate having a hydroxyl group may be added to react with the terminal isocyanate group. At this time, if necessary, the reaction may be carried out by dissolving in an organic solvent such as ethyl acetate, methyl ethyl ketone or toluene, or a catalyst such as dibutyltin dilaurate may be added.

When the amount of the unsaturated compound (b) in the photopolymerizable resin composition is small, the flexibility of the photopolymerizable resin composition layer after exposure and development is reduced, and when the amount is large, cold flow occurs. Since it becomes easier and the resolution is lowered, 5 to 100 parts by weight of the linear copolymer (A) is used.
It is 150 parts by weight, preferably 10 to 100 parts by weight.

When the weight average molecular weight of the unsaturated compound (b) is small, the flexibility of the resin composition layer after exposure and development is reduced, and when the weight average molecular weight is large, the development time is prolonged.
000 to 15,000, more preferably 1,
500 to 10,000.

Photopolymerization initiator (c) used in the present invention 1
Any substance may be used as long as it has the property of activating the unsaturated compound (b) with an actinic ray such as ultraviolet ray or visible ray and initiating polymerization. Examples of the substance activated by ultraviolet ray include sodium methyl. Dithiocarbamate sulfide, tetramethylthiuram monosulfide,
Sulfides such as diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide; thioxanthone, 2-ethylthioxanthone, 2-
Thioxanthone derivatives such as chlorothioxanthone and 2,4-diethylthioxanthone; diazo compounds such as hydrazone, azoisobutyronitrile, benzenediazonium; benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzylanthraquinone, aromatic carbonyl compounds such as t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketal, methylphenylglyoxylate; methyl p-dimethylaminobenzoate, p -Ethyl dimethylaminobenzoate, butyl p-dimethylaminobenzoate, isopropyl p-diethylaminobenzoate, etc. Dialkylaminobenzoates; peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9-phenylacridine, 9-p-methoxyphenylacridine, 9-acetyl Acridine derivatives such as aminoacridine and benzacridine; 9,10-dimethylbenzphenazine, 9-
Phenazine derivatives such as methylbenzphenazine, 10-methoxybenzphenazine; quinosaline derivatives such as 6,4 ', 4 "-trimethoxy-2,3-diphenylquinosaline; 2,4,5-triphenylimidazoyl dimer Is raised.

Examples of those activated by visible light include, for example, 2-nitrofluorene, 2,4,6-triphenylbrillium boron tetrafluoride, 2,4,6-tris (trichloromethyl)- 1,3,5-triazine,
3,3'-carbonylbiscoumarin, thiomicheller ketone and the like.

The amount of the photopolymerization initiator (c) in the photopolymerizable resin composition is 0.1 to 10 parts by weight based on 100 parts by weight of the linear copolymer (a). The coloring agent (c) used in the present invention 1 is used to impart a predetermined color to the photopolymerizable resin composition, and conventionally known pigments and dyes can be used.

The amount of the colorant (c) in the photopolymerizable resin composition is based on 100 parts by weight of the linear copolymer (a).
It is 0.01 to 10 parts by weight. Although the composition of the photopolymerizable resin composition used in the present invention is as described above, if necessary, a photopolymerizable monomer that is liquid at room temperature and can be cured by initiating a polymerization reaction with actinic rays is used. May be added.

Examples of the photopolymerizable monomer include triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and triethylene glycol (meth) acrylate. Propylene 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 Sulfonyl] propane, 2,2-bis [4- (methacryloxydiethoxyphenyl Siji ethoxy) phenyl] propane, 3-phenoxy-2-propanoyl acrylate,
Examples include 1,6-bis [3-acryloxy-2-hydroxypropyl) hexyl ether and urethane polyester acrylate oligomer.

When the amount of the photopolymerizable monomer is small, the curing after exposure tends to be insufficient, and when the amount is large, the adhesiveness of the unexposed portion becomes strong and a good pattern is obtained. The linear copolymer (a) 100
It is preferably added in an amount of 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on parts by weight.

The photopolymerizable resin composition used in the present invention 1 contains dioctyl phthalate, triethylene glycol diacetate, p-toluenesulfonamide, N-
Plasticizers such as ethyltoluenesulfonamide, hydroquinone, thermal polymerization inhibitors such as p-methoxyphenol, stabilizers, ultraviolet absorbers, antioxidants, methyl ethyl ketone,
A solvent such as toluene may be added.

Next, the present invention 2 will be described. In the present invention 2, in place of the photopolymerizable resin composition, (e) a linear copolymer, (f) a photopolymerizable unsaturated compound, (g) an addition polymerizable compound, and (c) an actinic ray A photopolymerizable resin composition comprising a photopolymerization initiator sensitized by the above and a (d) colorant is used.

The linear copolymer (e) is composed of an α, β-unsaturated ethylenic monomer containing a carboxyl group, an α, β-unsaturated ethylenic monomer other than the above, and an imide monomer. The body is a constituent.

The α, β-unsaturated ethylenic monomer containing a carboxyl group and the α, β-unsaturated ethylenic monomer other than those described above are those used in the present invention 1 respectively. Can be.

When the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer containing a carboxyl group in the component of the linear copolymer (e) becomes small, it becomes insoluble in an alkaline aqueous solution. Development with an aqueous alkali solution is no longer possible. Conversely, if the amount is too large, the compatibility with the coating solvent or other components is reduced, and the resolution is also reduced. ~ 35% by weight. Then, the amount of a portion corresponding to an α, β-unsaturated ethylenic monomer other than the α, β-unsaturated ethylenic monomer containing a carboxyl group in the component of the linear copolymer (e) Is 40 to 80% by weight.

The imide monomer is a compound represented by the following general formula (IV).

[0037]

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In the formula (IV), R ¹² represents hydrogen or a methyl group, and R ¹³ , R ¹⁴ and R ¹⁵ represent an alkyl group or a hydroxyalkyl group having 10 or less carbon atoms, a phenyl group or a substituted phenyl group.

Examples of the imide monomer include, for example,
1,1,1-trimethylamine- (meth) acrylimide, 1,1,1-triethylamine- (meth) acrylimide, 1,1,1-tripropylamine- (meth) acrylimide, 1,1-dimethyl- 1-ethylamine-
(Meth) acrylimide, 1,1-dimethyl-1-propylamine- (meth) acrylimide, 1,1-dimethyl-1-phenylamine- (meth) acrylimide,
1,1-dimethyl-1- (2-hydroxypropyl) amine- (meth) acrylimide, 1,1-dimethyl-1
-(2-hydroxy-3-butoxypropyl) amine-
(Meth) acrylimide, 1-methyl-1-ethyl-1
-Phenylamine- (meth) acrylamide and the like.

When the amount of the portion corresponding to the imide monomer in the component of the linear copolymer (e) is reduced, the heat resistance is lost, and when it is increased, the resin becomes too hard. It is limited to 20% by weight, preferably 1 to 15% by weight.

The weight average molecular weight of the linear copolymer (e) is
When the size is reduced, so-called cold flow is apt to occur, and when stored in a roll, the photopolymerizable resin composition becomes wrinkled and cannot be used. Conversely, when the size is large, it is difficult to dissolve in an aqueous alkali solution and develop, and the resolution is reduced. Therefore, the content is limited to 20,000 to 500,000, and preferably 50,000 to 300,000.

The photopolymerizable unsaturated compound (f) used in the present invention 2 is at least one compound selected from the group consisting of the compounds represented by the above general formula (II). Any method may be adopted, for example, the method used in the first aspect of the present invention is used.

When the amount of the unsaturated compound (f) in the photopolymerizable resin composition decreases, the flexibility of the photopolymerizable resin composition layer after exposure and development decreases, and when the amount increases, cold flow occurs. Since it becomes easier and the resolution is lowered, 5 to 100 parts by weight of the linear copolymer (e) is used.
It is 150 parts by weight, preferably 10 to 100 parts by weight.

When the weight average molecular weight of the unsaturated compound (f) is small, the flexibility of the resin composition layer after exposure and development is reduced, and when the weight average molecular weight is large, the development time is prolonged.
000 to 15,000, more preferably 1,
500 to 10,000.

The addition polymerizable compound (g) used in the present invention 2 is a compound represented by the following general formula (V).

[0046]

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Wherein R ¹⁶ and R ¹⁷ are hydrogen or a methyl group;
l is an integer, and when l is small, the flexibility of the exposed photopolymerizable resin composition layer is reduced, and when l is large, the development time is long.

When the amount of the addition-polymerizable compound (g) in the photopolymerizable resin composition is small, the developability is reduced, and when the amount is large, the adhesiveness of the unexposed portion is increased, and the good pattern is obtained. Since it is difficult to obtain a copolymer, the linear copolymer (e) 1
It is limited to 5 to 80 parts by weight based on 00 parts by weight.

Photopolymerization initiator (c) used in the present invention 2
As the coloring agent (d), those used in the present invention 1 can be used. The amount of the photopolymerization initiator (c) in the photopolymerizable resin composition is 0.1 to 10 parts by weight based on 100 parts by weight of the linear copolymer (e), and the colorant (c) is used.
Is 0.01 to 10 parts by weight based on 100 parts by weight of the linear copolymer (A).

In the photopolymerizable resin composition used in the present invention 2, if necessary, the photopolymerizable monomer, plasticizer, thermal polymerization inhibitor, stabilizer and ultraviolet absorbing agent used in the present invention 1 are used. Agents, antioxidants, solvents and the like may be added.

When the amount of the photopolymerizable monomer is too large, the adhesiveness of the unexposed portion becomes strong and it becomes difficult to obtain a good pattern. Not more than 150 parts by weight, preferably not more than 100 parts by weight.

Next, the present invention 3 will be described. In the present invention 3, in place of the photopolymerizable resin composition, (h) a linear copolymer, (g) an addition polymerizable compound, (iii) a photopolymerization initiator sensitized by actinic rays, and (d) ) A photopolymerizable resin composition comprising a colorant is used.

The linear copolymer (H) comprises an α, β-unsaturated ethylenic monomer having a carboxyl group, (meth) acrylonitrile, and another α, β-unsaturated ethylenic monomer. It is a component.

The α, β-unsaturated ethylene monomer containing a carboxy group and the other α, β-unsaturated ethylenic monomer other than those described above may be the same as those used in the present invention 1. it can.

When the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer having a carboxyl group in the constituents of the linear copolymer (H) becomes small, it becomes insoluble in an aqueous alkali solution. Development with an aqueous alkali solution is no longer possible. Conversely, if the amount is too large, the compatibility with the coating solvent or other components is reduced, and the resolution is also reduced. Therefore, the content is limited to 10 to 40% by weight, preferably 15 to 40% by weight. 35% by weight.

When the amount of the portion corresponding to (meth) acrylonitrile in the components of the linear copolymer (H) decreases, the adhesiveness decreases remarkably, and when the amount increases, the developability and resolution deteriorate. Since it is significantly reduced, it is limited to 5 to 30% by weight. Then, the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer other than the α, β-unsaturated ethylenic monomer containing a carboxy group in the component of the linear copolymer (H) Is 30 to 85% by weight.

The weight average molecular weight of the linear copolymer (H) is
When the size is reduced, so-called cold flow is apt to occur, and when stored in a roll, the photopolymerizable resin composition becomes wrinkled and cannot be used. Conversely, when it gets bigger,
Since it is difficult to dissolve in an aqueous solution of an ant and development becomes difficult, and the resolution is reduced, it is limited to 20,000 to 500,000, and preferably 50,000 to 300,000.

The addition polymerizable compound (g) used in the present invention 3 is a compound represented by the general formula (V).
When the amount of the addition polymerizable compound (g) in the photopolymerizable resin composition is small, the developability is reduced. On the contrary, when the amount is large, the tackiness of the unexposed portion is increased, and it is difficult to obtain a good image. Therefore, the amount is limited to 5 to 80 parts by weight based on 100 parts by weight of the linear copolymer (H).

The photopolymerization initiator (c) used in the present invention 3
As the coloring agent (d), those used in the present invention 1 can be used. The amount of the photopolymerization initiator (c) in the photopolymerizable resin composition is 0.1 to 10 parts by weight based on 100 parts by weight of the linear copolymer (h), and the colorant (d)
Is 0.01 to 10 parts by weight based on 100 parts by weight of the linear copolymer (H).

In the photopolymerizable resin composition used in the present invention 3, if necessary, the photopolymerizable monomer, plasticizer, thermal polymerization inhibitor, stabilizer and ultraviolet absorbing agent used in the present invention 1 are added. Agents, antioxidants, solvents and the like may be added.

When the amount of the photopolymerizable monomer is too large, the adhesiveness of the unexposed portion becomes strong and it becomes difficult to obtain a good pattern. Therefore, 100 parts by weight of the linear polymer (h) is used. 150 parts by weight or less, preferably 100 parts by weight or less.

Next, the present invention 4 will be described. In the present invention 4, in place of the photopolymerizable resin composition, (i) a linear copolymer, (v) a photopolymerizable liquid at room temperature, (iii) a photopolymerization initiator sensitized by actinic rays, and (D) A photopolymerizable resin composition comprising a colorant is used.

The linear copolymer (e) is composed of an α, β-unsaturated ethylenic monomer containing a carboxyl group, an α, β-unsaturated ethylenic monomer other than the above, and a macromer. And

The α, β-unsaturated ethylenic monomer containing a carboxyl group and the other α, β-unsaturated ethylenic monomer other than those described above are those used in the present invention 1, respectively. Can be.

When the amount of the α, β-unsaturated ethylenic monomer containing a carboxyl group in the components of the linear copolymer (i) becomes small, it becomes insoluble in an aqueous alkali solution and is developed with an aqueous alkali solution. On the other hand, if the content is too large, the compatibility with the coating solvent or other components is reduced, and the resolution is also reduced. Therefore, the content is limited to 10 to 40% by weight, and preferably 1 to 40% by weight.
5 to 35% by weight. And, the α, β-unsaturated ethylenic monomer other than the α, β-unsaturated ethylenic monomer containing a carboxyl group is limited to 5 to 60% by weight.

The macromer is a polymer monomer represented by the following general formula (VI).

[0067]

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In the formula, R ¹⁸ , R ¹⁹ and R ²⁰ represent hydrogen or a methyl group, R ²¹ represents an alkyl group having 5 or less carbon atoms, and A represents a styrene-based polymer. When the molecular weight of the styrene-based polymer decreases, the flexibility and toughness after curing of the photopolymerizable resin composition decreases, and when the molecular weight increases, the resolution and developability decrease. It is limited to 20,000, preferably from 1,000 to 20,000.

Examples of the macromer include 2-polystyrylethyl (meth) acrylate, 2-polystyrylpropyl (meth) acrylate, 2-polystyryl-1-methylethyl (meth) acrylate and 2-polystyryl-1-methyl Propyl (meth) acrylate and the like.

When the amount of the portion corresponding to the macromer in the constituents of the linear copolymer (i) decreases, the toughness of the cured photopolymerizable resin composition layer decreases. Since the resolution is lowered, the content is limited to 5 to 60% by weight, preferably 10 to 60% by weight.

When the weight average molecular weight of the linear polymer (i) is small, so-called cold flow is likely to occur, and when it is wound and stored in a roll, the photopolymerizable resin composition becomes wrinkled and cannot be used. On the other hand, when the size is large, it is difficult to dissolve in the aqueous solution of alkali and development is difficult, and the resolution is reduced. Therefore, the content is limited to 20,000 to 500,000, and preferably 50,000 to 300,000.

The photopolymerizable monomer (nu) used in the present invention 4 is a compound which is liquid at room temperature and can be cured by initiating a polymerization reaction by actinic rays. Can be used.

When the amount of the photopolymerizable monomer (N) in the photopolymerizable resin composition is small, the tackiness of the unexposed portion becomes strong, so that it becomes difficult to obtain a good image, and conversely, when the amount is large, the amount becomes large. Since curing after exposure is likely to be insufficient, the amount is limited to 5 to 150 parts by weight based on the linear copolymer (i).

The photopolymerization initiator (c) used in the present invention 4
As the coloring agent (d), those used in the present invention 1 can be used. The amount of the photopolymerization initiator (c) in the photopolymerizable resin composition is 0.1 to 10 parts by weight based on 100 parts by weight of the linear copolymer (h), and the colorant (d)
Is 0.01 to 10 parts by weight based on 100 parts by weight of the linear copolymer (II).

In the photopolymerizable resin composition used in the present invention 4, if necessary, the plasticizer, thermal polymerization inhibitor, stabilizer, ultraviolet absorber, antioxidant, solvent Etc. may be added.

In the display panel of the present invention, the above-described four types of photopolymerizable resin compositions are exposed and developed to form a pattern of an arbitrary shape comprising a cured product of the photopolymerizable resin composition on a substrate. Is provided.

The substrate used in the present invention is not particularly limited as long as it is transparent, but is generally a plastic plate such as an acrylic resin, a polycarbonate resin or a polyester resin. The body is preferably used.

As a method of forming a pattern on the substrate, any method can be used. For example, a photopolymerizable resin composition layer is provided on a substrate, and a predetermined layer is formed on the photopolymerizable resin composition layer. After overlaying the negative mask to obtain the pattern,
A method of irradiating light from above the negative mask to cure only the patternable portion of the photopolymerizable resin composition layer and remove the uncured portion by development.

The method for forming the photopolymerizable resin composition layer includes, for example, a method of directly applying the photopolymerizable resin composition on a substrate, and a method of laminating a photopolymerizable resin composition layer separately formed on a substrate. -Transfer method to the substrate by a method and the like, as the substrate used in the latter method, for example,
Polyethylene terephthalate (hereinafter referred to as PET),
Transparent plastic sheets such as polypropylene, polyethylene, and polyvinyl chloride can be used. In addition, the said base material can also be used for the purpose of protecting a photopolymerizable resin composition layer, when superposing and exposing to a negative mask. In the latter method, a film having good releasability such as polyethylene or polypropylene may be provided on the photopolymerizable resin composition layer in order to protect the photopolymerizable resin composition layer until use.

The thickness of the photopolymerizable resin composition layer is appropriately determined depending on the cross-sectional shape of the pattern. However, if the thickness is too small or too large, the visibility is poor. Therefore, the thickness is preferably 2 to 100 μm. Preferably it is 5-50 micrometers, More preferably, it is 7-15 micrometers.

The pattern constituting the display panel of the present invention is obtained by exposing and developing the photopolymerizable resin composition layer as described above, but the light source for exposing is not particularly limited. Instead, a conventionally known one can be used. For example, a high-pressure mercury lamp is suitably used. The developer used for the development is not particularly limited. For example, an aqueous solution of sodium carbonate having a concentration of 0.5 to 5% by weight is preferably used.

The display panel of the present invention can have various configurations according to the purpose by using the above-described pattern forming method. For example, by repeating a series of steps of forming, exposing, and developing a photopolymerizable resin composition layer, a structure in which patterns of different colors are combined can be obtained. FIG. 1 shows an example.

In FIG. 1, 1 is a substrate and 2 is a white pattern.
Reference numeral 3 denotes a red pattern, and reference numeral 4 denotes a black pattern. The display panel thus configured has a reflective pattern in the daytime.
Each color pattern is visually recognized as a pattern, and at night, a color pattern other than the black pattern is seen by the transmitted light due to the backlight from the back surface of the base.

It is also possible to form desired patterns on a plurality of substrates, respectively, and to combine them.

[0085]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Example 1 Preparation of Photopolymerizable Unsaturated Compound A reflux condenser, a dropping funnel, a thermometer and a mechanical stirrer were installed.
Hexamethylene diisocyanate 504
Parts by weight (3 mol equivalent), 826 parts by weight of dry methyl ethyl ketone and 1 part by weight of dibutyltin dilaurate (catalyst) as a solvent, and 916 parts by weight of polyethylene glycol (2 mol equivalent, average molecular weight: 4) with stirring.
58) and refluxed for 5 hours.

Then, 592 parts by weight (2 mol equivalents) of trimethylolpropane triacrylate was added dropwise, and the mixture was refluxed for 5 hours to react. After that, methyl ethyl ketone was evaporated to obtain a photopolymerizable unsaturated compound.

[Preparation of Photopolymerizable Resin Composition] 100 parts by weight of linear copolymer (methyl methacrylate / butyl methacrylate / methacrylic acid = weight ratio 50/25/25, weight average molecular weight Mw = 150,000) Polymerizable unsaturated compound 100 parts by weight Photopolymerization initiator (component: benzyldimethyl ketal) 2 parts by weight (“Irgacure 651” manufactured by Ciba-Geigy) Pigment (“FPF-96Q” (red) manufactured by Dainichi Seika) 2 parts by weight Part The above substance was dissolved in 400 parts by weight of methyl methyl ethyl ketone to prepare a solution of the photopolymerizable resin composition.

[Preparation of Photopolymerizable Film] A solution of the above photopolymerizable resin composition was applied to a thickness of 25 μm as shown in FIG.
Is applied on a PET substrate 5 so that the thickness after drying is 10 μm, and dried at 80 ° C. for 10 minutes to form a photopolymerizable resin composition layer 6, and a polyethylene protection layer is formed thereon. The colored photopolymerizable film 8 was produced by attaching the film 7.

[Measurement of Physical Properties] The photopolymerizable film 8 was subjected to the following physical property tests. (Resolution and Sensitivity Test) While peeling off the protective film 7 of the photopolymerizable film 8, the photopolymerizable resin composition layer 6 was pressed on a transparent acrylic plate having a thickness of 2 mm to form a laminate. 100 mJ / c with a 3 KW high-pressure mercury lamp through a resolution measurement pattern and a sensitivity measurement pattern (Stofa 21-step tablet)
It was irradiated with light of m ² intensity.

Next, the substrate 5 was peeled off, and spray-developed with a 1% aqueous solution of sodium carbonate at 30 ° C. under a pressure of 10 kg / cm ² , and the resolution and sensitivity were measured.
60 μm and 9 steps.

(Adhesion Test) After irradiating the laminate with light having an intensity of 1000 mJ / cm ² by an ultra-high pressure mercury lamp,
The base material 5 was peeled off, and the cured photopolymerizable resin composition layer 6 was coated with 2
Eleven cuts were made in each of the vertical and horizontal directions at mm intervals, and 100 grid patterns were created.

After the cellophane tape was strongly pressed on the grid, the cell was peeled off and the percentage of the peeled grid was counted. The peeled grid was 0. (Cross cut test: based on JIS K 5400)

(Flexibility test) After irradiating the above laminate with light having an intensity of 100 mJ / cm ² through a negative film having a line of 100 μm, the substrate 5 was peeled off and spray-developed with a 1% aqueous solution of sodium carbonate at 30 ° C. Thus, a pattern was formed.

Next, the laminated body on which the pattern was formed was wrapped around a round bar having a diameter of 2 mm, and the presence or absence of peeling of the line was examined with the naked eye, but no peeling was observed.

(Durability test) After processing the laminate after forming the pattern under the following conditions, the adhesion, the flexibility, the color change,
When each test of glossiness and color density (light fastness) was performed, there was no change in the pattern in all items.

Table 3 shows the results of the durability test. However,
The case where there was no change under the following conditions was marked with “○”, and the case where there was a change was marked with “x”. (Conditions) (1) Heat at 90 ° C. for 1,000 hours. (2) A cycle of cooling at −30 ° C. for 1 hour and then heating at 100 ° C. for 1 hour is repeated 1,000 times. (3) Heating at 90 ° C. and 95% RH for 1,000 hours. (4) Irradiation for 5,000 hours with a sunshine meter.

Examples 2 to 6, Comparative Example 1 Photopolymerizable unsaturated compounds having the compositions shown in Table 1 were obtained in the same manner as in Example 1 (the details of the obtained unsaturated compounds are shown in Table 2). Shown). Thereafter, an unsaturated compound, a photopolymerization initiator, and a pigment were added to the linear copolymer in the same manner as in Example 1 to obtain a photopolymerizable resin composition.

Example 1 Using the Photopolymerizable Resin Composition
After preparing a photopolymerizable film in the same manner as in Example 1, the physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

Examples 7 and 8, Comparative Example 2 [Preparation of Photopolymerizable Resin Composition] A photopolymerizable unsaturated compound having the composition shown in Table 4 was prepared in the same manner as in Example 1.

[0104]

[Table 4]

The following composition was dissolved in 826 parts by weight of methyl ethyl ketone to prepare a solution of a photopolymerizable resin composition.

100 parts by weight of linear copolymer (imide-100 (imide monomer manufactured by Inui Corporation) / butyl methacrylate / methacrylic acid = weight ratio 10/65/25, Mw = 150,000) Photopolymerizable Unsaturated compound (see Table 4) 50 parts by weight Addition polymerizable compound (component: 1,6-bis (3-acryloxy 20 parts by weight c-2-hydroxypropyl) -hexyl ether) (Nippon Kayaku's “R- 167 ") 2 parts by weight of a photopolymerization initiator (component: benzyl methyl ketal) (Irgacure 651 manufactured by Ciba Geigy) 2 parts by weight of pigment (" FPF-96Q "(red) manufactured by Dainichi Seika)

The details of the imide monomer (general formula (IV)) and the photopolymerizable monomer (general formula (II)) are shown in Table 5.
Table 6 shows details of the photopolymerizable resin composition. Using a solution of the photopolymerizable resin composition, in the same manner as in Example 1,
After preparing the photopolymerizable film, the same resolution, sensitivity, adhesion, and flexibility tests as in Example 1, and the following flexibility test and thermal shock test were performed. The results are shown in Table 7. .

(Flexibility test) The photopolymerizable film was treated with 10
After cutting the sample to a size of × 100 mm and exposing the sample to 1,000 mJ / cm ² with an ultra-high pressure mercury lamp, the support film and the protective film were peeled off, and the sample was cut to 100 mm.
A tensile test was performed at a rate of / min, and the elongation until breaking was measured, which was defined as a flexibility test.

(Thermal Shock Test) The photopolymerizable film was cooled at −30 ° C. for 1 hour, and then heated at 100 ° C. for 1 hour. After 1,000 times of thermal shock cycles, the same adhesion as in Example 1 was obtained. Force, flexibility, and flexibility tests were performed.

Example 9 The following composition was dissolved in 826 parts by weight of methyl methyl ethyl ketone to prepare a solution of a photopolymerizable resin composition.

60 parts by weight of linear copolymer (butyl acrylate / acrylonitrile / acrylic acid = weight ratio 50:25:25, Mw = 150,000) Addition polymerizable compound (component: 1,6-bis (3-acryloxy) 15 parts by weight C-2-hydroxypropyl) -hexyl ether) (“R-167” manufactured by Nippon Kayaku) 15 parts by weight of photopolymerizable monomer (component: tetraethylene glycol dimethacrylate) Photopolymerization initiator (component: Benzyl dimethyl ketal) 2 parts by weight (“Irgacure 651” manufactured by Ciba Geigy) Pigment (“FPF-96Q” (red) manufactured by Dainichi Seika) 2 parts by weight The details of the photopolymerizable resin composition are shown in Table 6. Was.

Using the solution of the photopolymerizable resin composition, a photopolymerizable film was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 7. The results are shown in Table 7.

Example 10 As a linear copolymer, butyl methacrylate / methacrylonitrile / methacrylic acid copolymer (weight ratio: 50: 2)
5:25, Mw = 150,000) and 1,8-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether as an addition polymerizable compound.
Example 1 was prepared in the same manner as in Example 9 except that bis (3-acryloxy-2-hydroxypropyl) -octyl ether was used, and the solution of the obtained photopolymerizable resin composition was used. After preparing a photopolymerizable film in the same manner as in the above, physical properties were measured in the same manner as in Example 7, and the results are shown in Table 7.

Comparative Example 3 In Example 9, 1,6-bis (3-acryloxy-
Except for using trimethylolpropane triacrylate instead of (2-hydroxypropyl) -hexyl ether, adjustment was performed in the same manner as in Example 9, and using the obtained solution of the photopolymerizable resin composition, After preparing a photopolymerizable film in the same manner as in Example 1, physical properties were measured in the same manner as in Example 7, and the results are shown in Table 7.

Example 11 A linear copolymer was mixed with a photopolymerizable monomer at the ratio shown below.
The photopolymerization initiator and the pigment were dissolved in 200 parts by weight of methyl ethyl ketone to prepare a solution of the photopolymerizable resin composition.

50 parts by weight of linear copolymer (macromer (A) / methyl methacrylate / methacrylic acid = weight ratio 40:35:25, Mw = 150,000) Photopolymerizable monomer 15 parts by weight (component: tri (Methylolpropane triacrylate) 15 parts by weight of photopolymerizable monomer (component: tetraethylene glycol dimethacrylate) 2 parts by weight of photopolymerization initiator (component: benzyldimethyl ketal) Pigment (“FPF-96Q” manufactured by Dainichi Seika (red) )) 2 parts by weight The macromer (A) in the linear copolymer is represented by R ¹² = R ¹³ = R ¹⁵ = H and R ¹⁴ = C ₄ H in the general formula (VI).
₉ , A = polystyrene (Mw = 5000). Table 6 shows details of the photopolymerizable resin composition.

Using the solution of the photopolymerizable resin composition, a photopolymerizable film was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 7. The results are shown in Table 7.

Example 12 As a linear copolymer, macromer (B) / methyl methacrylate / methacrylic acid (weight ratio 35:40:25, Mw
= 180,000), except that the copolymer was used.
In the same manner as in the above, a solution of the photopolymerizable resin composition was prepared.

Macromer (B) in the above linear copolymer
In the general formula (VI), R ¹² = R ¹³ = R ¹⁵ =
H, R ¹⁴ = C ₄ H ₉ , A = poly-α-methylstyrene (Mw = 5000). Table 6 shows details of the photopolymerizable resin composition.

Using the solution of the above photopolymerizable resin composition, a photopolymerizable film was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 7. The results are shown in Table 7.

Comparative Example 4 As a linear copolymer, macromer (A) / methyl methacrylate / methacrylic acid (weight ratio 40:35:25, Mw
= 150,000), except that the copolymer was used.
In the same manner as in the above, a solution of the photopolymerizable resin composition was prepared.

Using the solution of the photopolymerizable resin composition, a photopolymerizable film was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 7. The results are shown in Table 7.

[0123]

[Table 5]

[0124]

[Table 6]

[0125]

[Table 7]

[0126]

Each display panel of the present invention can form an arbitrary colored image only by curing and developing a predetermined portion of a specific photopolymerizable resin composition.

Accordingly, unlike the printing method, there is no need to prepare a plate and no ink is required, so that problems such as contamination of the working environment due to evaporation of the solvent and clogging of the plate do not occur.
Further, since the specific photopolymerizable resin composition is used, the pattern made of the cured product is excellent in flexibility, light resistance, heat resistance and the like, and also excellent in adhesion to the substrate.

[Brief description of the drawings]

FIG. 1 is a partially enlarged schematic cross-sectional view showing an example of a display panel of the present invention.

FIG. 2 is a schematic sectional view showing an outline of a photopolymerizable film used in Examples of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base 2 white pattern 3 red pattern 4 black pattern 5 substrate 6 photopolymerizable resin composition layer 7 protective film 8 photopolymerizable film

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) G01D 13/02 C08F 220/36

Claims (4)

(57) [Claims] 1. A display panel in which an arbitrary image pattern is formed at a predetermined position on a substrate, wherein said image pattern is made of a cured product of a photopolymerizable resin composition. (A) 10 to 40% by weight of an α, β-unsaturated ethylenic monomer containing a carboxy group and 60 to 90% by weight of the other α, β-unsaturated ethylenic monomer 100 parts by weight of a linear copolymer having a weight average molecular weight of 20,000 to 500,000, and (b) at least one selected from the group consisting of compounds represented by the following general formulas (I), (II) and (III). 5 to 150 parts by weight of at least one kind of photopolymerizable unsaturated compound, (Wherein, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, m
Is an integer of 1 to 100, n is an integer of 1 to 15, R ² , R ³
Represents a hydrogen or methyl group, and X represents a divalent hydrocarbon group having 2 to 20 carbon atoms. ) (Wherein R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, p
Is an integer of 1 to 100, q is an integer of 1 to 15, R ⁵ and R ⁶
Represents a hydrogen or methyl group, and Y represents a divalent hydrocarbon group having 2 to 20 carbon atoms. ) (Wherein, R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms, r
Is an integer of 1 to 100, s is an integer of 1 to 15, R ⁸ ,
R ⁹ , R ¹⁰ , and R ¹¹ are hydrogen or a methyl group; Z is carbon number 2
And represents a divalent hydrocarbon group of -20. (C) Photopolymerization initiator sensitized by actinic rays 0.1 to 1
A display panel comprising 0 parts by weight and (d) 0.01 to 10 parts by weight of a coloring agent. 2. The display panel according to claim 1, wherein the photopolymerizable resin composition comprises (e) 10 to 40% by weight of an α, β-unsaturated ethylenic monomer containing a carboxy group, and Of 40 to 80% by weight of an α, β-unsaturated ethylenic monomer and 1 to 20% by weight of an imide monomer represented by the following general formula (IV): 100,000 parts by weight of 500,000 linear copolymer, (Wherein R ¹² is hydrogen or a methyl group, R ¹³ , R ¹⁴ , R ¹⁵
Represents an alkyl group or a hydroxyalkyl group having 10 or less carbon atoms, a phenyl group or a substituted phenyl group. (F) 5 to 150 parts by weight of at least one or more photopolymerizable unsaturated compounds selected from the group consisting of the compounds represented by formula (II) according to claim 1; V) addition-polymerizable compound 5 represented by
80 parts by weight (Wherein, R ¹⁶ and R ¹⁷ are hydrogen or a methyl group, and l is 4 to 1)
Indicates an integer of 2. A display panel comprising (c) 0.1 to 10 parts by weight of the photopolymerization initiator according to claim 1 and (d) 0.01 to 10 parts by weight of the colorant according to claim 1. 3. The display panel according to claim 1, wherein the photopolymerizable resin composition comprises: (h) 10 to 40% by weight of an α, β-unsaturated ethylenic monomer containing a carboxy group; ) 100 parts by weight of a linear copolymer having a weight average molecular weight of 20,000 to 500,000 containing 5 to 30% by weight of acrylonitrile and 30 to 85% by weight of an α, β-unsaturated ethylenic monomer other than the above. (F) 5 to 80 parts by weight of an addition polymerizable compound represented by the general formula (V) according to claim 2, (c) 0.1 to 10 parts by weight of the photopolymerization initiator according to claim 1, A display panel comprising the colorant according to claim 1 in an amount of 0.01 to 10 parts by weight. 4. The display panel according to claim 1, wherein the photopolymerizable resin composition comprises a (li) carboxy group-containing α, β-
10 to 40% by weight of an unsaturated ethylene monomer, 5 to 60% by weight of an α, β-unsaturated ethylenic monomer other than the above and 5 to 60% by weight of a macromer represented by the following general formula (VI) 100 parts by weight of a linear copolymer having a weight average molecular weight of 20,000 to 500,000 as a constituent component, (Wherein R ¹⁸ , R ¹⁹ and R ²⁰ are hydrogen or methyl, R ²¹
Represents an alkyl group having 5 or less carbon atoms, and A represents a weight average molecular weight of 50.
0 to 20,000 styrenic polymers are shown. (D) 5 to 150 parts by weight of a photopolymerizable monomer which is liquid at ordinary temperature; (c) 0.1 to 10 parts by weight of the photopolymerization initiator according to claim 1; and (d) the colorant according to claim 1. A display panel comprising 0.01 to 10 parts by weight.