JPH01302307A - Pattern forming method having refractive index difference and pattern transfer body used therein and image forming body - Google Patents

Abstract

PURPOSE:To easily form patterns having a refractive index difference by transferring a compd. B which changes the refractive index of a compd. A by reaction with a compd. A by sublimation or diffusion and bringing the same into reaction with the compd. A. CONSTITUTION:The transfer body 5 contg. the compd. B which changes the refractive index of the compd. A having a reactive functional group by reacting with the compd. A is brought into tight contact with an image forming body consisting of the layer 2 contg. compd. A and the base body 3. The compd. B is transferred from the transfer body to the image forming body by the sublimation or diffusion generated by the energy of electromagnetic waves such as light or heat and is brought into reaction with the compd. A, by which the change in the refractive index is generated. The formation is facilitated in this way and the excellent preservation stability is obtd. without having heat sensitivity and photosensitivity in the image forming body of an unrecorded state. The recording with many recording means is enabled by using the radiations of the heat, current, light, etc., as recording energy.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for creating a pattern with a difference in refractive index, and a pattern transfer member and an image forming member used therefor.

2. Description of the Related Art Conventionally, the first waveguide of a leading waveguide consisting of a pattern with a difference in refractive index has been used.
The following methods are known as methods for creating .

1. Providing a layer with a low refractive index on the base material.

2. On top of this, a material sensitive to radiation, such as a photoresist or an electron beam resist, is formed.

3. Sensitize only the area where the waveguide is desired (or the area other than the waveguide) to radiation using a mask or the like.

4. Remove the resist only at this location (or at other locations).

5. Remove the low refractive index layer at the location where the waveguide is desired to be formed by etching.

6. Construct a layer of high refractive index material.

7. Remove residual resist.

A second method is to create a holographic optical element or hologram using a refractive index difference (based on phase modulation) by exposing a hologram recording material such as dichromium gelatin to light and then processing it in a wet process. be.

In addition, as a new trend in the method of creating patterns having a difference in refractive index, as described in JP-A-60-166946, the refractive index is changed by reacting with light.
There is a method in which a film or the like is formed of different kinds of substances, the film is exposed in a pattern to react, and then one of the unreacted substances is removed. Another method is to create a pattern using only an exposure process by using a material that reacts and changes its refractive index only when irradiated with light of two different wavelengths.

Problems to be Solved by the Invention Among the above-mentioned methods for creating patterns having various refractive index differences, the first method requires complicated optical elements on which the pattern is formed and the processing required to obtain the recorded image. It's not easy. The second method is less complicated, but it is a little less easy to process in a wet process, and the storage stability of the unrecorded material is affected because the image forming body in the unrecorded state is photosensitive on its own. It is disadvantageous. The third method is a simpler method, but has the problem that a sufficient refractive index difference cannot be obtained unless one of the unreacted substances is sufficiently removed. The fourth method is designed with a gate in which a reaction accompanied by a change in refractive index occurs only when light of two wavelengths is applied, and it is also important in terms of storage stability of the material in the unrecorded state or in the recorded state. It's advantageous. However, the reality is that recording sensitivity sufficient for practical use has not been achieved.

In inventing a simple method for creating a pattern having a difference in refractive index, the present inventors decided to use the third method of the prior art described above, that is, to make the one with the lower refractive index by causing two types of substances to react with light. We focused on the method of increasing the refractive index of materials. Furthermore, by separating the energy required for a reaction accompanied by a change in refractive index and the signal energy for recording a pattern, we believe that pattern signals (information) can be recorded by more recording means, and we have invented the present invention. reached.

The present invention has a simple manufacturing method, has no heat or photosensitivity in the unrecorded image forming body, has excellent storage stability, and uses radiation such as heat, electric current, and light as recording energy.
It is an object of the present invention to provide a method for forming a pattern having a refractive index difference that can be recorded by many recording means, and a transfer body and an image forming body used therefor.

Means for Solving the Problems Transfer containing a compound B that changes the refractive index of the compound A by reacting with the compound A to an image forming body consisting of a layer or base material containing the compound A having a reactive functional group. The bodies are brought into close contact with each other, and compound B is transferred from the transfer body to the image forming body by sublimation or diffusion using electromagnetic waves such as light or thermal energy, and is caused to react with compound A, thereby causing a change in the refractive index.

Reactive functional group of an image forming body in which a layer containing a compound A having a reactive functional group or a substrate containing a compound A having a reactive functional group is itself an image forming body. A portion of a transfer body containing compound B, which changes the refractive index of compound A by reacting with compound A, is brought into close contact with a layer or a base material containing compound A, and the transfer body When energy such as electromagnetic waves such as light or heat is applied from the opposite direction to the side that is in close contact with the image forming body, compound B is transferred from the transfer body to the image forming body by sublimation or diffusion, similar to the sublimation transfer type thermal recording method. Further, a change in the refractive index can be caused by reacting with the compound A using thermal energy during transfer recording, heat newly applied to the image forming body, or radiation energy such as light.

Examples In the pattern creation method of the present invention, the reaction between compound A having a reactive functional group and compound B, which changes the refractive index of compound A by reacting with compound A, is not particularly limited. Compound A and compound B with different refractive indexes
Any material that can efficiently cause this reaction may be used. Since Compound A constitutes an image forming body, it is preferably stable even in the presence of unreacted reactive functional groups. Furthermore, polymer compounds are preferred since they are convenient for forming layers and films. Further, the compound B may be any compound that reacts with the reactive functional group of the compound A and can easily diffuse into the transfer body and the image forming body. For specific explanation, an example that can be used for the reaction of compound A and compound B will be given, and an example of compound A and compound B in which this reaction will be used will be given.

(1) Oxetane production reaction A photoreaction between an aromatic carbonyl compound and an olefin,
Generates a compound containing an oxetane ring as shown below (
“Organic Photochemical Reaction Theory” by Katsumi Tokumaru, published by Tokyo Kagaku Dojin)
.

The reaction of the photosensitive resin composition disclosed in JP-A No. 60-186948 mentioned above is also included in this category, but it is only a matter of time since the quantum yield of the reaction is relatively high.

As an example of compound A, a highly transparent substance is preferable,
When compound A is a compound having a carbon-carbon double bond, (meth)acrylic acid 3,3 as described in the claims of JP-A-60-186948 is used.
- In addition to dimethyl allyl ester alone or copolymer, (meth)acrylic acid 3-methyl-3-butenyl ester, 3-methyl allyl ester, allyl ester, 2-
Methyl allyl ester, 3-hebutenyl ester, 3.
There are homopolymers of 3-diethyl allyl ester, dicyclopentenyl ester, 2-furfuryl ester, divinylbenzene, and copolymers with other vinyl monomers. Compound B includes substituted or unsubstituted benzaldehyde, acetophenone, benzophenone, 1-
These include 1- or 2-naphthaldehyde, 1- or 2-naphthylmethylketone or 2-naphthylphenylketone. Substituted or unsubstituted benzaldehyde or benzophenone is preferred in terms of quantum yield of the oxetane production reaction. Furthermore, substituted or unsubstituted benzaldehydes include 4-fluorobenzaldehyde, 2-. 3
- or 4-chlorobenzaldehyde, 2-. 3- or 4-bromobenzaldehyde, 2. 4-, 3.
4- or 3°5-dichlorobenzaldehyde, 2.
4-, 3°4- or 3.5-dibromobenzaldehyde, 4-methylbenzaldehyde pyrubenzaldehyde, 4-cyclohexylbenzaldehyde, 2-. 3- or 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde3. 4.
5-) Dimethoxybenzaldehyde, 3-phenoxybenzaldehyde, 3-hydroxybenzaldehyde, phthalaldehyde, 4-cyanobenzaldehyde, and the like.

In addition, substituted or unsubstituted benzophenones include benzophenone, 2-. 3-* or 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 2-. Examples include 3- or 4-bromobenzophenone, 4-methylbenzophenone, 4-propylbenzophenone, 4-methoxybenzophenone, and 4-benzoylbenzophenone.

(2) Cyclobutane production reaction A photoreaction between olefins or between a conjugated enone and an olefin in the presence of a triplet sensitizer produces the following compound having a cyclobutane ring. There are also compounds that generate cyclobutane rings even from heavy polymers via exciplexes (Katsumi Mitsumi, ``Organic Photochemical Reaction Theory,'' published by Tokyo Kagaku Dojin).

Similar to the above-mentioned oxetane production reaction, there is also a reaction with a high m-plate ratio, which is useful.

For example, as a reaction via an exciplex, there is a cyclobutane ring formation reaction between aromatic vinyl compounds, and styrene, vinylnaphthalene, vinylpyrene, and their derivatives can undergo this type of reaction if their ionization potential, redox potential, etc. have an appropriate relationship. have a reaction. However, it is desirable that the recording image forming layer containing compound A has a low refractive index.
As the compound A, a copolymer of a divinylbenzene derivative with residual vinyl groups and a (meth)acrylic acid ester is preferable. Examples of the compound B include vinylnaphthalene and vinylpyrene having a dialkylamino group or a cyan group.

(3) Diels-Alder reaction A conjugated diene and an olefin having a carbon-carbon double bond through a carbon-carbon single bond undergo a Diels-Alder reaction to form a cyclohexene ring by heat or light.

The heat generated during recording causes not only the transition of compound B but also the reaction of compound A and compound B, which is useful.

Examples of the compound A include substituted or unsubstituted polyacetylene, and examples of the compound B include aromatic compounds having a vinyl group. Polyacetylenes do not have good stability, and it is preferable that the number of residual double bonds is small. Furthermore, since polyacetylenes have a conjugated double bond chain and have absorption in the visible range, compounds having a substituent having a butadiene structure are preferable if it is inappropriate for the purpose.

Various forms can be considered for the image forming body consisting of a layer or a base material containing compound A as described above, but mainly 1) a structure of only base material 1 containing compound A (Fig. 1) 2) compound Structure having at least a recorded image forming layer 2 containing compound A on a base material 3 not containing A (FIG. 2) 3) At least having a recorded image forming layer 2 containing compound A on a base material 1 containing compound A The following configuration (Figure 3) can be considered. When the image forming body functions as an optical element or the like by transmitting light, it must be transparent at least for necessary wavelengths. Therefore, the layer or base material constituting the image forming body that contains Compound A must be transparent for the necessary wavelengths;
Substances other than compound A are not particularly limited. In order to facilitate the diffusion of compound B, it is preferable that the glass transition temperature or heat distortion temperature is not too high, and is 40 to 150.
A polymer composition with a temperature of about ℃ is preferable. Furthermore, in consideration of crosslinking and curing during the reaction of Compound A and Compound B, if a compound (which may be Compound A) having a reactive functional group such as a 1,3-dioxolane ring is present, this limit may be applied. isn't it. Further, in the case of a base material that does not contain Compound A, in order to impart heat resistance to the image forming body, not only a polymer composition but also glass or the like may be used. When providing an image forming layer on a base material, a coating liquid is required for providing the image forming layer, but the solvent used may be one that dissolves the polymer composition other than Compound A and Compound B. For example, when these substances are acrylic, benzene, toluene, methyl ethyl ketone, monochlorobenzene, dichloromethane, etc. can be used. Although it is desirable that the thickness of the image forming layer be uniform, it can be formed satisfactorily by spin coating.

The transfer body preferably has a structure in which a transfer material layer 5 is provided on one side of a base material 4 (FIG. 4). The base material supports the transfer material layer, and may be a film made of polyester, polyimide, aramid, cellophane, etc., or a plate-shaped material such as polystyrene, PMMA, polycarbonate, glass, etc. A heat-resistant lubricant layer may be provided for recording with a thermal head, or a conductive layer or a resistive layer may be provided to make it easier to use with an electrically conductive recording head or an induction heating head. Transfer material layer 5 of base material 4 for further optical recording
There may be a light absorption layer 6 on the side for converting light energy into heat (FIG. 5). The transfer material layer is composed of at least a transfer material (ie, compound B) and a binding material. The transfer material is as described above, and the binder may be a binder used in sublimation transfer type thermal recording materials. Namely, water-soluble resins such as cellulose-based, acrylic acid-based, and starch-based resins, organic solvent-soluble or water-soluble resins such as acrylic resin, polyphenylene oxide, polysulfone, polyethersulfone luulose, and acetylcellulose can be mentioned. In terms of recording sensitivity and storage stability of transfer material, heat distortion temperature (ASTM
D848) of 70 to 150°C is excellent.

Therefore, polystyrene, polyvinyl butyral, polycarbonate, methacrylic resin, acrylonitrile-styrene copolymer, polyester resin, urethane resin, chlorinated polyethylene, chlorinated polypropylene, and the like are preferred. The transfer material layer may also contain a plasticizer, a lubricant, a surfactant, etc. for the purpose of improving peeling from the image forming body after recording. In preparing the coating liquid for constituting the transfer material layer containing the above-mentioned transfer material/binder, etc., the solvents used are methanol, ethanol, propatool, alcohols such as butanol, methyl Cellosolves such as cellosolve and ethyl cellosolve, benzene,
Aromatics such as toluene and xylene, esters such as butyl acetate, ketones such as acetone, 2-butanone and cyclohexanone, N. Nitrogen compounds such as N-dimethylformamide, halogenated hydrocarbons such as dichloromethane, chlorobenzene, and chloroform can be used, but when using water-soluble or water-dispersible water-based resins as a binder, water or It is also possible to use a mixture of water and the above-mentioned solvents. Furthermore, as a method for applying the coating liquid onto a film-like base material, a reverse roll coater,
It can be carried out using a gravure coater, a rod coater, a flexible coater, an air doctor coater, etc. Spin coating is a typical method for coating on a plate-shaped base material.

Next, a more detailed example will be given and explained.

Example 1 First, 11 g of 3-methyl-2-buteno-1, 15 g of triethylamine, and 200 g of dioxane were mixed into 500 g of
A mixed solution of 16 g of methacroyl chloride and 50 g of dioxane was added dropwise to the mixture over 30 minutes while stirring. After stirring for another 30 minutes, add 1
00 g of water was added and stirred, and these reaction solutions were filtered. After further extracting the organic layer, it was washed with an aqueous sodium hydrogen carbonate solution and then with water. After removing dioxane from this using an evaporator, vacuum distillation was repeated twice.
0 g of methacrylic acid 3,3-dimethylallyl ester was obtained. 5 g of methacrylic acid 3,3-dimethylallyl ester and 15 g of methyl methacrylate obtained thereby,
Then, 0.1 g of AIBN was dissolved in 200 g of benzene, and radical polymerization was performed in a nitrogen atmosphere to obtain 15 g of a copolymer of 3,3-dimethylallyl methacrylate and methyl methacrylate. This copolymer was dissolved in dichloromethane to prepare a coating liquid. This coating liquid was used to spin code onto a glass substrate to obtain an image forming body IA having an image forming layer provided on the base material.

Next, 1 g of benzophenone and butyral resin (Tsukusui Kagaku)
Eslec B BX-1) 2g to toluene 21g1
It was dissolved in 9 g of methyl ethyl ketone to prepare coating liquid IB. Further, a coating liquid diluted to twice this amount was designated as coating liquid IB'. The recording and its results will be described later along with other examples.

Example 2 Methacroyl chloride and furfuryl methacrylic acid furfuryl ester was obtained in the same manner as in Example 1 using alcohol as raw materials. Furfuryl methacrylate ester 5g1
Methacrylic acid [2-methyl-2-(2-oxopropyl)-1,3-dioxolan-4-yl] ester 2g1
10 g of methyl methacrylate and 3 g of ethyl acrylate were similarly radically polymerized to obtain 15 g of a quaternary copolymer.

This was hot press molded to obtain a plate with a thickness of 11. This was designated as image forming body 2A.

Next, a coating liquid 2B12B' containing 4-bromobenzaldehyde as compound B was obtained in the same manner as in Example 1.

Example 3 4 g of p-divinylbenzene and 16 g of methyl methacrylate
was subjected to radical polymerization in the same manner as in Example 1 to obtain 13 g of a copolymer in which unreacted vinyl groups of divinylbenzene remained. This was dissolved in toluene and a 211m thick PMMA cast plate (
An image-forming body 3A was obtained by spin coating on Kyowa Gas Kagaku Kogyo Co., Ltd. (Balaclas).

Next, 1 g of 2-vinylnaphthalene and 2 g of AS resin (Denka Styrol AS-SU, manufactured by Denki Kagaku Kogyo Co., Ltd.) were dissolved in 21 g of toluene and 9 g of methyl ethyl ketone.
- Coating liquid 3B containing vinylnaphthalene as compound B was prepared.

This was further diluted to 20% and designated as coating liquid 3B'.

Example 4 10 parts by weight of polyphenylacetylene and 90 parts by weight of PMMA were dissolved in toluene and spin coated onto glass to obtain an image forming member 4A.

Next, in the same manner as in Example 3, 2-vinylnaphthalene was added to compound B.
Coating liquid 4B and coating liquid 4B'' were prepared.

Recording and Results of Examples 1 to 4 (Recording Method 1) Examples 1 to 4 were recorded on the side of a 4 μm PET film provided with a heat resistant slip layer made of a photocurable resin and silica fine particles, on which the heat resistant slip layer was not provided. Coating liquids 1 to 4B were applied using a wire bar to form a transfer material layer of about 1 μm to form transfer bodies 1 to 4C. The transfer material layer of the transfer body and the image forming layer of the image forming body are overlapped so that they are in contact with each other (in the case of the image forming body 2A which does not have an image forming layer, either side is fine), and the heat-resistant slipping layer of the transfer body is Recording was performed from the side using a thermal head under the following conditions.

Thermal head recording conditions Main scanning linear density: 4 dots/■■ Sub-scanning linear density 28 dots/corresponding Recording power: 0.7 W/dot Head heating time: 8 ms/dot Recording only one line in the sub-scanning direction After irradiating each of the subsequent image forming bodies 1 to 4A with a 300W high-pressure mercury lamp for 30 seconds, two prisms were placed at a distance from each other on the recording line, and helium-neon laser light was incident from one of the prisms. For each image forming body, it was possible to observe that the light that had been guided through the leading waveguide of the recording line was emitted from the other prism. Furthermore, it was confirmed that the light was guided only in the recording line portion due to diffuse reflection caused by foreign matter mixed in the image forming layer.

(Recording method 2) Coating liquids 1 to 4B of Examples 1 to 4 were applied with a wire bar to a carbon-containing aramid film (thickness: 8 μm, 1 sheet resistance: approximately IKΩ/hole) to form a transfer material layer of approximately 1 μm. hand,
Transfer bodies 1 to 4D were used. The transfer member and the image forming member were placed one on top of the other in the same manner as in Recording Method 1, and recording was performed from the film side of the transfer member using a line-type current-carrying head under the following conditions.

Current-carrying head recording conditions Linear density of main scanning: 1o dots/am Linear density of sub-scanning: 2o dots/dragon Applied voltage: 5
0V Applied pulse width = 80μs Recording only one line in the sub-scanning direction After performing the same processing as in recording method 1, a similar experiment with a leading wave was conducted, and it was found that every image forming body functioned as a leading wave path. This was confirmed.

(Recording method 3) An ethyl cellulose solution in which carbon black was dispersed was spin-coded onto a glass substrate having a thickness of 1.1 mm, an outer diameter of 130 mm, and an inner diameter of 15 m, to provide a light absorption layer of 2 μm. Furthermore, coating liquids 1 to 4B' of Examples 1 to 4 were spin-coded to provide a transfer material layer of 1 μm to prepare transfer bodies 1 to 4E. An image forming body previously processed to have an outer diameter of 130 mm and an inner diameter of 15 mm was brought into close contact with the transfer body so that the recorded image forming layer and the transfer material layer of the transfer body overlapped. This was recorded on an optical recording deck for optical discs at a linear velocity of 10 m/s, 16 mL, and a radial feed pitch of 2 μm, with no modulation. After recording, the transfer member and the image forming member were separated, and the image forming member was irradiated with light for 30 seconds using a 300 W high pressure mercury lamp.

When a 0.5 mW helium-neon laser was vertically incident on these image forming bodies, diffracted light could be observed, and it was found that it was possible to create optical elements such as diffraction gratings.

Effects of the Invention The method for creating a pattern having a refractive index difference based on the present invention provides a method for forming a pattern having a refractive index difference by reacting with the compound A on an image forming body consisting of a layer or a base material containing the compound A in which a reactive functional group is present. By bringing a transfer body containing compound B that changes the refractive index of A into close contact with each other, and transferring compound B from the transfer body to an image forming body by sublimation or diffusion using electromagnetic waves such as light or thermal energy, and reacting with compound A. Because the refractive index changes, the preparation method is simple, and the unrecorded image forming body has no heat or photosensitivity and has excellent storage stability.
By using radiation such as light as recording energy, recording can be performed with many recording means.

[Brief explanation of the drawing]

1 to 3 are schematic cross-sectional views of an image forming body in an embodiment of the present invention, and FIGS. 4 and 5 are schematic cross-sectional views of a pattern transfer body in an embodiment of the present invention. 1...Base material containing compound A, 2...Recording image forming layer containing compound A, 3. Old...Base material not containing compound A, 4... Base material, 5. Old transfer material layer,
6. Old...Light absorption layer. Name of agent: Patent attorney Toshio Nakao (1 person) Figure 1 Figure 2 Figure 3

Claims (5)

[Claims] (1) A transfer body containing a compound B that changes the refractive index of the compound A by reacting with the compound A is brought into close contact with an image forming body consisting of a layer or a base material containing a compound A having a reactive functional group. , has a refractive index difference characterized by causing a change in refractive index by transferring Compound B from the transfer body to the image forming body by sublimation or diffusion using electromagnetic waves such as light or heat energy, and causing a change in the refractive index by reacting with Compound A. How to create a pattern. (2) The method for creating a pattern having a refractive index difference according to claim 1, wherein compound A and compound B are the following compounds. (a) Compound A is a homopolymer of an ester of a substituted or unsubstituted allyl group and (meth)acrylic acid, or an ester of a substituted or unsubstituted allyl group and (meth)acrylic acid at 5% by weight or more. Compound B is a copolymer (co)polymer with other vinyl monomers containing a double bond of a substituted or unsubstituted allyl group, and in which a double bond of a substituted or unsubstituted allyl group remains. Benzaldehyde, benzophenone or naphthylphenyl ketone with substituents (3) The method for creating a pattern having a refractive index difference according to claim 1, wherein compound A and compound B are the following compounds. (a) Compound A is a homopolymer of 3,3-dimethylallyl ester of (meth)acrylic acid or a polymer containing 3,3-dimethylallyl ester of (meth)acrylic acid with another vinyl monomer containing 5% by weight or more. (2) Compound B is a copolymer in which a double bond of 3,3-dimethylallyl group remains in the polymer. or naphthylphenyl ketone (4) An image forming body comprising a layer or a base material containing a compound A having a reactive functional group, which is subjected to the method for creating a pattern having a refractive index difference according to claim 1. (5) A transfer recording material containing a compound B that changes the refractive index of the compound A by reacting with the compound A, which is used in the method for creating a pattern having a refractive index difference according to claim 1.