KR100571367B1 - Light-sensitive photosensitive resin composition for light shielding of lenticular lens sheet and light-shielding pattern forming method using same - Google Patents

Abstract

The present invention provides a photosensitive colored resin composition used to form a light shielding pattern on a flat surface of a lenticular lens sheet to realize high contrast in a screen for a projection television, which uses a novolak resin as an alkali-soluble copolymer. By including a compound which generates an acid by irradiation with radiation, an adhesion promoter, a pigment and a solvent, it is excellent in adhesiveness and developability can be improved.

Description

Photoresist composition for light shielding of lenticular lens sheet and pattern formation method for light blocking photosensitive colored resin composition of lenticular lens sheet             

1 is a view showing a conventional projection screen,

Figure 2 is a schematic diagram showing a process of forming a light shielding pattern using the photosensitive colored resin composition of the present invention.

* Description of the symbols for the main parts of the drawings *

1-Projection Screen 2-Fresnel Lens Sheet

3-lenticular lens sheet 2a, 3a-base material

2b, 3b-Lens layer 2c, 3c-Lens surface

3d-shading

The present invention relates to a light-shielding photosensitive colored resin composition of a lenticular lens sheet and a light shielding pattern forming method using the same, and more particularly, to a light-shielding photosensitive colored resin composition forming a black matrix of a lenticular lens sheet of a projection screen and using the same A method for forming a black matrix pattern.

Since it is not practical in terms of technology and cost in order to realize a large screen of 30 inches or more using a conventional conventional CRT method, large screen displays such as liquid crystal display (LCD), plasma display panel (PDP), and projection television have begun to be developed.

Projection television refers to a television that is displayed on a large screen by reflecting the image to a mirror or by enlarging and projecting the image formed on the LCD panel using a high-performance CRT (Cathod Ray Tube) or LCD panel. Say.

In general, a projection television emits a display element having three primary colors of red, green, and blue light, and uses an projection lens and a reflector to project and magnify an image on the screen. It is a television system that allows the final image to be implemented.

Projection-type devices that display a desired image by enlarging and projecting an image signal by using a projection lens are largely classified into a front projection device and a rear projection device. Especially, a relatively bright image is displayed even in a bright environment. Displayable rear projection devices are becoming commonplace.

Since the projection television is a method of expanding and projecting a small original image, the image quality is inferior to that of the original image, and the screen is configured in such a way as to make up for the shortcomings.

A typical configuration of the screen has a structure in which a Fresnel lens sheet and a lenticular lens sheet are overlapped to form a single screen. This is shown in FIG.

In the Fresnel lens sheet, the center part of the surface of the lens layer 2b is bow-shaped and the outer part is sawtooth-shaped, which collects the image light incident from the projection lens provided in the light projection device to reduce the loss of light and make it parallel light. .

In addition, the lenticular lens sheet 3 is formed of lens-shaped protrusions as a whole to form and diffuse an image from parallel light emitted from the Fresnel lens.

In the lenticular sheet, the lens layer 3b is formed inside the support layer 3a, and the light shielding portion 3d is formed outside, that is, toward the screen.

In the screen, the lenticular lens sheet horizontally distributes the image signal that passes through the Fresnel lens horizontally through the sophisticated optical structure and serves to provide a wide viewing angle to the viewer. The difference in the brightness of the surroundings appeared, which caused the disadvantage that the surrounding image became dark and the viewing angle was narrowed. In addition, since diffuse reflection occurs, there is a problem in that clear image expression cannot be realized.

To secure the viewing angle in a projection television, the light passing through the lenticular lens must be diffused well. To this end, the photosensitive coloring resin composition is applied to a portion where light does not pass to form a black matrix (shading part / opening part). At the same time as control, a desired viewing angle can be secured.

The photosensitive colored resin composition used for this purpose must be particularly excellent in adhesion to the lenticular lens and high optical density is required.

On the other hand, as an example related to the technology of forming a light shielding portion on the flat surface of the lenticular lens sheet, Japanese Laid-Open Patent Publication No. 1997-120102 discloses a radiation curable resin layer formed on the flat surface of the lenticular lens sheet, and then exposed to light to expose the resin layer of the light collecting portion. Was cured. Next, the method of adhering colored bodies, such as a toner, was used using the adhesiveness of the resin layer of a non-condensing part.

Japanese Laid-Open Patent Publication No. 2002-182309 discloses a method of exposing a resin composition of a light shielding film containing a light absorbing agent to a flat surface of a lenticular lens to form a light shielding portion. Here, it is described that the opening is formed by the principle that the light absorption layer at the position corresponding to the condensing position of the lenticular lens is scattered and removed upon exposure.

Accordingly, an object of the present invention is to provide a light-sensitive photosensitive resin composition for light shielding of a lenticular lens sheet which improves the problem that high adhesion, developability, and high optical density are hardly obtained simultaneously in the photosensitive color resin composition and provides a desired viewing angle. It is done.                         

Another object of the present invention is to provide a method of forming a light shielding pattern of a lenticular lens sheet using such a light-shielding photosensitive colored resin composition.

The light-shielding colored resin composition of the lenticular lens sheet of the present invention for achieving the above object is 10 to 50% by weight of a novolak resin, 1 to 20% by weight of a compound that generates an acid by irradiation as an alkali-soluble copolymer , Characterized in that it comprises 0.1 to 5% by weight of the adhesion promoter, 10 to 60% by weight of the pigment and the remaining amount of the solvent.

Hereinafter, the compounding component used for the photosensitive colored resin composition of this invention and the usage method of this composition are demonstrated.

(1) alkali-soluble copolymer

In the present invention, a novolak resin is used as the alkali-soluble copolymer, but it is preferable to be soluble in an organic solvent and to be developed in a weak alkaline aqueous solution. In other words, the novolak resin of the alkali-soluble copolymer may be a novolak resin used as a film forming material in a positive photoresist composition. Especially, the novolak resin which melt | dissolves in aqueous alkali solution easily without swelling and is excellent in developability is preferable. The novolak resin can be obtained by condensing phenols, aldehydes and / or ketones in the presence of an acid catalyst. Such a novolak resin preferably has a mass average molecular weight of about 5,000 to 15,000 in view of improving solubility and heat resistance in an alkaline developer.

The content of such alkali-soluble copolymer is 10 to 50% by weight, preferably 20 to 40% by weight of the total composition, if the content is less than 10% by weight does not act as a binder, if more than 50% by weight Preservation stability falls.

(2) a compound which generates an acid by radiation irradiation

The compound which generates an acid by irradiation of an alkali-soluble copolymer crosslinks by heat at the time of prebaking, and forms the alkali-insoluble resist layer on the whole substrate surface. The compound which generate | occur | produces an acid by radiation irradiation should just generate | occur | produce an acid by exposure in an exposure part, and this acid may decompose | disassemble the said bridge | crosslinking and change the said insoluble resist layer to alkali solubility. The compound which produces | generates an acid by irradiating a radiation with such a function is what is called an acid generator used for a chemically amplified resist, and many things are proposed until now, and what is necessary is just to select arbitrarily from these. The compound which is irradiated with ultraviolet rays and which has high acid generation efficiency is preferable, and the compound which has high acid generation efficiency with respect to g-ray exposure is especially preferable.

For example, 2,1-diazonaphthoquinone-4-sulphonic ester or 2,1-diazonaphthoquinone-5-sulphonic ester is preferable.

The compound which generates an acid by such irradiation is contained in 1-20 weight%, Preferably it is 3-10 weight% in all the photosensitive coloring resin compositions. If the content is less than 1% by weight of the total composition can not sufficiently obtain the effect of preservation stability of the alkali-soluble copolymer solution, if the content is more than 20% by weight tends to deteriorate various properties of the photosensitive colored resin composition is not preferable.

(3) adhesion promoter

The photosensitive coloring resin composition of the present invention includes an adhesion promoter to improve the adhesion to the lenticular lens. Adhesion promoters include silane coupling agents, with functional silane coupling agents being particularly preferred. As a functional silane coupling agent, what has reactive substituents, such as a vinyl group, a methacryloyl group, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, is preferable.

Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyl Triethoxy silane, trimethoxysilyl benzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylethoxysilane, γ-methacryloxypropyltrimethoxy silane, γ-isocyanatepropyltrie Oxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned.

Such adhesion promoter is included in 0.1 to 5% by weight of the total photosensitive colored resin composition. If the content is less than 0.1% by weight, it is not possible to obtain the effect of improving the adhesiveness. If the content is more than 5% by weight, the heat resistance is lowered, and an excessive increase in the adhesive force causes a problem that the development is reduced in the developing process.

(4) Pigment

Since the photosensitive coloring resin composition of this invention contains a pigment in order to provide optical density, it can use 1 type (s) or 2 or more types of well-known various dyes and pigments. In addition, a colorant including a black pigment may be used by mixing carbon black and two or more color pigments. As carbon black, EX-3276, EX-3277 series etc. which are marketed by Mikuni company (Japan) can be used, for example. Mitsubishi Corporation (Japan) can also use Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, and Diagram SF. Also sold by Cabot (USA), Regal 250R, Regal 99R, Elftex 12, Raven 880 Ultra, Raven 860 Ultra, Raven 850, Raven 790 Ultra, Raven 760 Ultra, Raven 520 sold by Columbian Chemicals Company (USA). , Raven 500, Raven 460, Raven 450, etc. can be used.

The pigment is contained in 10 to 60% by weight, preferably 20 to 50% by weight of the total photosensitive colored resin composition. If the content is less than 10% by weight of the total composition, the optical density tends to be lowered, and if it is more than 60% by weight, all of the ultraviolet energy is absorbed in the exposure process for forming the pattern, thereby not being exposed.

(5) solvent

In the present invention, the use of alcohols, ethers, propylene glycol alkyl ether acetates is preferable.

Specific examples of the alcohols include methanol and ethanol. Specific examples of the ethers include tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like. Specific examples of the propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like.

Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate in view of solubility, reactivity with each component, and convenience of coating film formation; Ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanane; Methyl, ethyl, propyl, butyl ester of acetic acid, ethyl of 2-hydroxypropionic acid, methyl ester, ethyl ester of 2-hydroxy-2-methylpropionic acid, methyl, ethyl, butyl ester of hydroxyacetic acid, ethyl lactate, lactic acid Propyl, butyl lactate, methyl of methoxyacetic acid, ethyl, propyl, butyl ester, of methyl methyl, ethyl, propyl, butyl ester, of methyl butoxy, propyl, butyl ester, 2-methoxypropionic acid Methyl, ethyl, propyl, butyl ester, methyl of 2-ethoxypropionic acid, ethyl, propyl, butyl ester, methyl of 2-butoxypropionic acid, ethyl, propyl, butyl ester, methyl of methyl, ethyl, propyl Esters such as butyl ester, methyl, ethyl, propyl, butyl ester of 3-ethoxypropionic acid, methyl, ethyl, propyl, and butyl ester of 3-butoxypropionic acid Can.

In addition, it is also possible to use a high boiling point solvent together with the said solvent.

Specific examples of the high boiling point solvents include N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, and N, N-dimethyl acetyl. Amides and the like.

The photosensitive coloring resin composition of this invention can mix | blend various additives other than the said component etc. as needed in the range which does not impair the objective of this invention.

A process of forming a pattern using such a photosensitive colored resin composition is schematically illustrated in FIG. 2. First, the composition is homogenized, filtered, and then coated on the opposite side of the lens of the lenticular lens sheet to form a light-sensitive photosensitive resin layer. Forming ((2) of FIG. 2); Pre-bake the light-shielding photosensitive resin layer at a temperature of 70 to 150 ° C. for 30 seconds to 5 minutes; Exposing the preheated photosensitive resin layer; Developing with an alkaline developer; And post-bake for 30 seconds to 5 minutes at a temperature of 70 to 150 ° C. to form a light shielding pattern (FIG. 2 (3)).

More specifically, the composition of the present invention is added dropwise to the opposite surface of the lenticular lens, and then coated using a spin coater to a thickness of 3.5 μm (± 0.1 μm), followed by heating at 80 to 100 ° C. for 1 to 3 minutes on a hot plate. After removing a part of the solvent, when the coating film is formed, irradiated with 435nm UV light at 100-500mJ / cm 2, using an aqueous alkali solution as a developer, dissolving and removing unnecessary parts to form a pattern by remaining only the unexposed areas. This is again baked on a hot plate at 90 to 130 ° C. for 2 to 5 minutes to form a light shielding pattern on the lens opposite surface of the lenticular lens sheet.

When the projection television screen is manufactured using the photosensitive colored resin composition provided by the present invention by the above-described method, it exhibits better adhesiveness, higher optical density, and higher developability than conventional projection television screens.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Production Example  1: Preparation of Alkali Soluble Copolymer

After mixing m-cresol, p-cresol and 2,5-xylenol in a molar ratio of 4: 5: 1 in a reaction vessel equipped with a stirrer, using oxalic acid as an acid catalyst and formaldehyde and salicylic as a condensing agent Condensation reaction was carried out using an aldehyde to synthesize a novolak resin which is an alkali-soluble copolymer. The novolak resin produced after the synthesis was a cresol formaldehyde novolak resin with a mass average molecular weight of 8,500.

Examples 1 to 4 and Comparative Examples 1 to 2

As shown in Table 1 below, the black photosensitive coloring resin composition was prepared by premixing with an alkali-soluble copolymer, a compound which generates an acid by irradiation, an adhesion promoter, a pigment, and a solvent, and then dispersing it with a gray bead mill. Got it.

After homogenizing the obtained photosensitive colored resin composition, the resultant was filtered using a 0.1 to 5 μm filter, added dropwise to the flat surface of the lenticular lens sheet, and then applied to a thickness of 3.5 μm (± 0.1 μm) using a spin coater, and then applied on a hot plate. After removing a part of the solvent by heating at 1 to 100 ° C. for 1 to 3 minutes, when a coating film is formed, ultraviolet rays of g line (435 nm) are irradiated at 100 to 500 mJ / cm 2, and unnecessary portions are dissolved using an aqueous alkali solution as a developer. After removing and remaining only the unexposed portions to form a pattern, it was again baked on a hot plate at 90 to 130 ° C. for 2 to 5 minutes to form a light shielding pattern on the flat surface of the lenticular lens sheet.

Example Comparative example One 2 3 4 One 2 Alkali Soluble Copolymers ⁽¹⁾ 26.1 26.1 26.1 26.1 26.1 26.1 Acid-generating compounds ⁽²⁾ 5.9 5.9 5.9 5.9 5.9 5.9 Adhesion Promoter ⁽³⁾ 0.2 0.7 2.0 4.0 - 7.0 Pigment Carbon black 24.5 24.5 24.5 24.5 24.5 24.5 Solvent ⁽⁴⁾ 43.3 42.8 41.5 39.5 43.5 36.5 Sum 100 100 100 100 100 100 (1) Cresol formaldehyde novolac resin (2) 2,1-diazonaphthoquinone-4-sulfonic ester (3) 3-glycidoxypropyltrimethoxysilane (4) propylene glycol methyl ether acetate

For the projection television screen on which the coating film was formed, the adhesiveness and optical density were evaluated as well as the required properties of the projection screen generally required, and the results are shown in Table 2 below.

1) Adhesion: Measured by the method of ASTM D3359-B (Elcomer Cross Cutting Tape Test). The evaluation score of the adhesion test is shown below.

5B: Both sides of the line are thin and smooth and there is no peeling off of the intersection on the square scale

4B: There is a slight peeling (falling) at the intersection where the line is drawn, and there is no peeling (falling) at each square, and the damage area is within 5% of the square area.

3B: There is peeling (falling) at both sides of the line and the intersection, and the area of the damaged part is 5 to 15% of the square area.

2B: The peeled off part of the line is wide and the area of the damaged part is 15 ~ 35% of the square area.

1B: The peeled off part of the line is wider than 2B and the damaged part is 35 ~ 65% of the square area.

0B: The area of peeling (falling off) is not less than 65% of the square area

2) Optical Density: Using the transmittance value at 550 mm wavelength using MCPD 3000 was calculated by the following equation. The smaller the transmittance, the greater the optical density, the better.

3) Developing performance: The composition of the present invention is added dropwise to the opposite side of the lenticular lens, and then applied using a spin coater to a thickness of 3.5 μm (ㅁ 0.1), on a hot plate for 1 to 3 minutes at 80 to 100 ° C. After removing a part of the solvent by heating, when a coating film is formed, it is irradiated with ultraviolet rays of 435 nm, using an aqueous alkali solution as a developer to dissolve and remove unnecessary portions, leaving only the unexposed areas to form a pattern, and then hot again. The light-shielding pattern was formed on the opposite side of the lens of the lenticular lens sheet by baking for 2 to 5 minutes at 90 to 130 ℃ on the plate. Then, the presence or absence of the residue was visually examined under a halogen lamp.

○: Excellent processability-No residue on pattern.

(Triangle | delta): Good processability-There exists some residue on a pattern.

X: poor processability-Many residues remain on the pattern.

Adhesive Optical density Developability Example 1 4B 4.0 ○ Example 2 5B 4.0 ○ Example 3 5B 4.0 ○ Example 4 5B 4.0 ○ Comparative Example 1 2B 4.0 × Comparative Example 2 5B 4.0 △

As shown in Table 2, Examples 1 to 4 containing 3-glycidoxypropyltrimethoxysilane, which is an adhesion promoter, as an example of the present invention within the range of 0.1 to 5% by weight, have very high adhesion and developability. It can be seen that the comparative example 1, which does not include the adhesion promoter, is markedly inferior in adhesion as 2B, and Comparative Example 2, which includes the adhesion promoter at 7 wt% in excess of 5 wt%, has improved adhesion. It turns out that developability is inferior. Determining the optical density here shows the same result as using the same pigment as the pigment in the above Examples and Comparative Examples as the pigment.

As described in detail above, the lenticular is made using a photosensitive colored resin composition comprising a compound, an adhesion promoter, a pigment and a solvent that generates an acid by irradiation using an novolak resin as an alkali-soluble copolymer according to the present invention. When the light shielding pattern is formed on the flat surface of the lens sheet, the adhesion is excellent and the optical density can be increased, thereby ultimately achieving high contrast in the screen for a projection television.

Claims (7)

Alkali-soluble copolymer includes 10 to 50% by weight of novolak resin, 1 to 20% by weight of compound which generates acid by irradiation, 0.1 to 5% by weight of adhesion promoter, 10 to 60% by weight of pigment and residual solvent Light-sensitive photosensitive resin composition for light shielding of a lenticular lens sheet. The light-sensitive photosensitive resin composition for light shielding of a lenticular lens sheet according to claim 1, wherein the novolak resin is obtained by condensation of phenols and aldehydes, phenols and ketones, and phenols and aldehydes and ketones in the presence of an acid catalyst. The light-sensitive photosensitive resin composition for light shielding of a lenticular lens sheet according to claim 1, wherein the novolac resin has a mass average molecular weight of 5,000 to 15,000. The light-sensitive photosensitive resin composition for light shielding of a lenticular lens sheet according to claim 1, wherein the novolak resin is a cresol formaldehyde novolak resin. The light-sensitive photosensitive resin composition for light shielding of a lenticular lens sheet according to claim 1, wherein the adhesion promoter is a functional silane coupling agent having a vinyl group, methacryloyl group, hydroxyl group, amino group, isocyanate group or epoxy group. The method of claim 5, wherein the adhesion promoter is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethic. Methoxysilane, 3-aminopropyltriethoxy silane, trimethoxysilyl benzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylethoxysilane, γ-methacryloxypropyltrimethoxy silane and (gamma) -isocyanatepropyltriethoxysilane and (gamma) -glycidoxypropyltrimethoxysilane. The photosensitive colored resin composition for light shielding of a lenticular lens sheet characterized by the above-mentioned. Homogenizing and filtering the photosensitive colored resin composition of any one of claims 1 to 6 and then coating the opposite side of the lens of the lenticular lens sheet to form a light-sensitive photosensitive resin layer; Pre-bake the light-shielding photosensitive resin layer at a temperature of 70 to 150 ° C. for 30 seconds to 5 minutes; Exposing the preheated photosensitive resin layer; Developing with an alkaline developer; And A method of forming a light shielding pattern of a lenticular lens sheet, comprising: forming a light shielding pattern by post-bake for 30 seconds to 5 minutes at a temperature of 70 to 150 ° C.

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