JPH0361983A - Relief hologram recording material - Google Patents

Abstract

PURPOSE:To facilitate fabrication of a hologram especially large in size by using a composition of an alkali-soluble polymer a polyfunctional monomer compatible with this polymer and a photopolymerization initiator composed of an organic dye and an organic peroxide. CONSTITUTION:This composition comprises the alkali-soluble polymer, preferably, such as a styrene-acrylic copolymer and a methyl methacrylate-acrylic copolymer, the polyfunctional monomer having compatibility with the alkali- soluble polymer and at least one ethylenically unsaturated bond, and the photopolymerization initiator composed of the organic dye and the organic peroxide, thus permitting the large-sized hologram recording material that has so far not been fabricated to be fabricated.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to relief hologram recording materials.

[Conventional technology]

Holography is a recording method that uses wavelengths with good coherence, such as lasers, and uses laser light as a half-mirror.
The transmitted light obtained from the object beam is classified into object beam and reference beam using This is a technology that reproduces the original image of an object by irradiating it with light.

As a recording material for a hologram, a silver salt photosensitive material having sufficient sensitivity at the wavelength of a general laser is generally used. However, this material is expensive and difficult to photograph or reproduce, so hologram products are expensive and unsuitable for mass production.

On the other hand, as one of the other types of holograms, there is a type of hologram (hereinafter referred to as a relief hologram) that records the interference fringes of hologram information as an uneven pattern on a recording material. By pressing, holograms can be reproduced in large quantities and at low cost.

Conventionally, a photosensitive resin (photoresist) is generally used as a recording material for this relief hologram.

[Problem to be solved by the invention]

The photosensitive resin that is the recording material for conventional relief holograms was originally developed for the purpose of manufacturing integrated circuits and printed circuit boards such as ICs and LSIs, and has excellent sensitivity to UV light sources. However, the Ar laser 488 does not have sufficient sensitivity to the wavelength of general lasers.
When a normal positive photoresist is used for n- light, an exposure amount of several hundred J/cm" is required, and an exposure dose of several tens of m
When photographing a subject at a corner, an exposure time of several minutes to ten minutes is required even if a high-output laser (5W) is used. The limit of exposure time is set to several tens of minutes or less due to the effects of vibrations, etc., and from this point of view, the maximum size of the copy must be limited to about 20 cm square, making it virtually difficult to form large-sized holograms. It becomes.

The present invention has been made based on the above background, and its purpose is to provide a high-sensitivity relief hologram recording material that can produce large holograms that could not be produced with conventional relief hologram recording materials. be.

[! Means to solve problem i]

Therefore, the relief hologram recording material of the present invention is characterized in that it consists of an alkali-soluble polymer, a polyfunctional monomer, and a photopolymerization initiator, and the photopolymerization initiator consists of an organic dye and an organic peroxide. That is.

The alkali-soluble polymer used in the present invention is (1), a styrene-acrylic acid resin, for example, manufactured by Johnson (2), trade name "Joncryl 683J (molecule 17300, acid value 1
50), same, product name "Jonkryl 586J (molecule f3 00, acid value 105), same, product name rscX611
J (molecular weight 6000, acid value 53) ■, Methyl methacrylate-acrylic acid resin, e.g. B
Manufactured by F Goodrich, product name "Carbocent XL"
-27J (molecular weight 40,000, acid value 80), product name "Carbocet 525J (molecular weight 260,000)
, acid value 80), product name ``Carboset 526'' (
Molecule t200000, acid value 100), ■, Styrene-monobutyl maleate resin (molecular weight 5000) ■, Methyl methacrylate-methacrylic acid resin, such as manufactured by Tansui Kagaku ■, trade name rSME-25J polymer, (molecular weight 300000) , 8-valent 91), (1), phenol novolac, Talesol novolanc resins, such as Gun-Ei Chemical (2), trade name "Regitop J PSF-2803J", etc. can be suitably used.

The polyfunctional monomer must be compatible with the alkali-soluble polymer described above. The polyfunctional monomer used in the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure. be. For example, they have chemical forms such as monomers, prepolymers, ie, dimers, trimers, and oligomers, mixtures thereof, and copolymers thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and the like.

Specific examples of monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol as acrylic esters. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate,
Dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,
Examples include tri(acryloyloxyethyl)isocyanurate 1 and polyester acrylate oligomer.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-(p-(3-methacrylate) Oxy-
Examples include 2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(acryloxyethoxyphenyl)dimethylmethane, and the like.

The above-mentioned polyfunctional monomer is used in an amount of 0.0% per 1 part by weight of the alkali-soluble polymer. It may be used in an amount of 1 part by weight to 3 parts by weight, more preferably 0.3 parts by weight to 1.5 parts by weight.

The photopolymerization initiator consists of an organic dye and an organic peroxide. As the organic dye, a coumarin compound represented by the following formula (1) can be particularly used.

(In formula (1), R2, R1, and R3 each independently represent a hydrogen atom; a chloro atom; a lower alkoxy group; a lower dialkylamino group; a lower dialkenylamino group or an alicyclic amino group; 1 represents a heterocyclic group having a total number of heteroatoms of 5 to 9 or -C-Y, where Y is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms; a lower alkoxy group, a substituted or unsubstituted Phenyl group; represents a substituted or unsubstituted steryl group or a substituted or unsubstituted 3'-coumarino group.

Moreover, Z represents a hydrogen atom or a cyano group. ) The coumarin compound is shown by the above formula (1), and specific examples of R+, Rz, and Rz in the formula include a hydrogen atom: a chloro atom; a lower alkoxy group such as methoxy, ethoxy, and butoxy; diethylamino, diethylamino , a lower dialkylamino group such as N-methyl-N-propylamino;
Alicyclic amino groups such as N-molecular, N-piperidino;
Examples include lower dialkenylamino groups such as dibropenylamino and di(α-methylpropenyl)amino groups.

X represents a heterocyclic ring having a total number of carbon atoms and heteroatoms of 5 to 9 and -C-Y, and specific examples of the heterocyclic ring include 2-imidazole, 2-N-methylimidazole, 2-benz Imidazole, 2-(4-phenyl)-imidazole, 2-oxazole, 2-benzoxazole, 2-(4-phenyl)oxazole, 2
-thiazole4.2-benzthiazole, 2-(4-phenyl)thiazole, 2-(5-phenyl)thiadiazole, 2(5-tolyl)thiadiazole, 2-(5-
biphenyl)thiadiazole, 2-(5-phenyl)
Oxadiazole, 2-(5-p-methoxyphenyl)oxadiazole, 2-(5-p-chlorophenyl)
Examples include residues such as oxadiazole.

Specific examples 1 of Y in -〇-Y of formula (1) include methyl, ethyl, propyl, ^ xyl, β-
Substitutions such as cyanoethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, or C7-C of complex III
4 alkyl group; phenyl, p-cyanophenyl, p-
Substituted or unsubstituted phenyl groups such as methylphenyl, p-methoxyphenyl, m-hydroxycarbonylphenyl; steryl groups such as steryl, p-methoxysteryl, p-cyanosteryl, m-chlorsteryl, and the following general formula (f[ 3-coumarino group represented by ), (wherein Rr ,
Rx, Rx, and Z are the same as those in formula (1) above.

Preferred specific examples of the coumarin compound of formula (1) include the following. 3-acetyl-7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-5,7-simethoxycoumarin, 3-cinnamoyl-7-dinithylaminocoumarin, 3.3゜- Carbonylbis(5,7-simethoxyamino)coumarin, 7-dinithylamino5.7'-dimethoxy-3,3'-biscoumarin, 3-(5'phenylthiadiazoyl-2°)-7-dinithylamino 3.3° carbonyl bis(4-cyano-7-ethylamino)coumarin.

In addition to these, those represented by the following structural formulas can be particularly preferably used.

Ketocoumarin pigment Thiopyrylium pigment Thioxanthin pigment 0-C-CN3 others Organic dyes shown in can also be used.

Preferred organic peroxide compounds to be used in combination with the above organic dyes include methyl ketone oxide, cyclohexanone oxide, acetylacetone peroxide, t-butyl peroxide, cumene hydroperoxide, and diisopropylbenzene oxide.
Peroxide.

t-Butyl cumyl peroxide, dicumyl peroxide, α, α゛-bis t-butyl cumyl peroxyisopropyl> benzene, t-butyl, peroxyisopropyl carbonate, benzoyl peroxide, di(t
-Butylperoxy> Isophthalate, di(t-butylperoxy)terephthalate, di(t-butylperoxy)phthalate, t-butylperoxybenzoate,
3.3″, 4.4″-tetra-(t-butylperoxycarbonyl)benzophenone, 2.5-dimethyl, 2.
5-(dibenzoylperoxy)hexane, etc. are used, and among these, particularly preferred are di(1,-butylperoxy)isophthalate, di(t-butylperoxy)terephthalate, di(t-butylperoxy) peroxy)
phthalate, 3.3', 4.4°-tetra-(t-butylperoxycarbonyl)benzophenone.

The proportion of the organic peroxide added to the organic dye is 0.1 parts by weight to 50 parts by weight, preferably 0.5 parts by weight to 2 parts by weight, per 1 part by weight of the former. The photopolymerization initiator consisting of the above-mentioned alkali-soluble polymer 10
It is used in a proportion of 0.5 parts by weight to 30 parts by weight, preferably 1 part to 25 parts by weight.

The hologram recording material of the present invention contains an alkali-soluble polymer, a polyfunctional monomer, and a photopolymerization initiator in a predetermined ratio as a solvent such as benzene, chlorobenzene, tetrahydrofuran, 1,4-dioxane, 1,2-dichloroethane, and dichloromethane. , chloroform, etc., and coated on a support such as glass or a transparent resin film, or it may be formed into a film itself. The photosensitive plates obtained in this way are, for example, 4579 people, 488 people
0 people, 5145 people, 5287 people, etc. are sensitive to laser light with bright lines, and 4880 people are sensitive to 1 to 211 J.
/C1l'' and high sensitivity.

A hologram is produced using this recording material through the steps of exposing it to an interference pattern of radiation, and etching the exposed recording medium with an alkaline developer to form a relief.

The radiation used in the present invention is preferably a laser beam or radiation emitted from a light source such as a mercury lamp.

A hologram is formed by irradiating the recording material surface with two coherent beams of radiation at a predetermined offset angle (θ) as shown in FIG.

In the development process, uncured monomers and alkali-soluble polymers are eluted with an alkaline developer, thereby forming a relief in which the parts where light mutually strengthens due to light interference are convex parts and the parts where light mutually weakens are concave parts. The alkaline developer used here can be any type of inorganic or organic alkali, and is usually a 1 to 10% by weight aqueous sodium carbonate solution.

[Effect]

The hologram recording material of the present invention is characterized by comprising an alkali-soluble polymer, a polyfunctional monomer, and an organic dye and an organic peroxide as a photopolymerization initiator.
First, the organic dye is excited by light irradiation, and the excitation energy is transmitted to the organic peroxide, decomposing the peroxide and generating radicals.

This radical attacks the polyfunctional monomer and the polymerization reaction proceeds. The resulting polymer matrix and alkali-soluble polymer become entangled and become insoluble in the developer.

Since such a reaction does not occur in areas not exposed to light, the alkali-soluble polymer and unreacted monomer are dissolved in the developer and removed. In this way, insolubilization occurs depending on the amount of light, information can be recorded in an analog manner, and a negative relief pattern can be formed.

[Example] Fig. 1 is a conceptual diagram of a relief hologram forming apparatus of the present invention, in which 1 is a Fresnel hologram and 2 is an Ar''
3 is a ξ mirror, 4 is a half mirror 55, 6 is a lens, 7 is a mirror, 8 is a lens, and 9 is a photosensitive plate.

The following formulation: Alkali-soluble polymer BF Manufactured by Goodrich Co., Ltd., trade name “Carbosesoto
L-44J ・・・・・・ 4g・
Multifunctional polymer pentaerythritol triacrylate...
4g ・Organic dye 33'-carbonylbis(7-dinithylaminocoumarin) 0.2g ・Organic peroxide 3.3',4,4°-tetra-(t-butylperoxycarbonyl) Benzophenone ・・・・・・ 0.
Dissolve 2g in 20g of monochlorobenzene,
Use photosensitive liquid. Filter this with a 0.5 μm filter,
20 to a film thickness of 066 μm after drying on a glass plate.
Spin code with 0 Or, p, m.

After drying in an oven at 60°C for 20 minutes, PVA liquid [polyvinyl alcohol (polymerization degree 500,
saponification degree 87%)) 10g dissolved in 100cc water) at 1000r, ρ1. After drying, overcoat to a film thickness of 1 to 2 μm.

The photosensitive plate thus obtained was exposed (2
s+J/cm") L, after removing the PVA overcoat layer by washing with water, developing with 1% by weight sodium carbonate,
Obtain a relief hologram.

〔Effect of the invention〕

The relief hologram recording material of the present invention can obtain sufficient sensitivity to laser light with an exposure amount of only a few taJ/cm'', so the exposure time can be short, and it is suitable for creating not only small-sized holograms but especially large-sized holograms. It's easy to use.

[Brief explanation of drawings]

FIG. 1 is a conceptual diagram of a relief hologram forming apparatus of the present invention, in which 1 is a Fresnel hologram, 2 is an Ar laser, 3 is a mirror, 4 is a half mirror 15, 6 is a lens, 7 is a mirror, 8 9 indicates a lens, and 9 indicates a photosensitive plate.

Claims (1)

[Claims] (1) A relief hologram recording material comprising an alkali-soluble polymer, a polyfunctional monomer, and a photopolymerization initiator, the photopolymerization initiator comprising an organic dye and an organic peroxide.