JPH081487B2 - METHOD FOR CREATING OPTICAL ELEMENT HAVING PATTERN WITH DIFFERENTIAL INDEX, PATTERN TRANSFER PRODUCT AND IMAGE FORMING PRODUCT - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a pattern forming method having a difference in refractive index, and a pattern transfer body and an image forming body to be used therefor.

2. Description of the Related Art Conventionally, the following method has been known as a first method for producing an optical waveguide having a pattern having a refractive index difference.

1. A layer having a low refractive index is provided on the base material.

2. On top of this, once form a substance sensitive to radiation, such as a photoresistor or an electron beam resist.

3. Only the place where the waveguide is to be formed (or the place other than the waveguide) is made sensitive to radiation by using a mask or the like.

4. Remove the resist only at this place (or other than this place).

5. By etching, the low-refractive index layer at the location where the waveguide is to be formed is removed.

6. Construct a layer of high refractive index material.

7. Remove residual resist.

As a second method, as a holographic optical element or hologram using a difference in refractive index (by phase modulation), a hologram recording material such as heavy chromium gelatin is exposed and then processed by a wet process. There is.

Further, as a new flow of a pattern forming method having a difference in refractive index, as described in JP-A-60-166946, a film or the like is previously composed of two kinds of substances whose refractive index is changed by reacting with light. Then, there is a method in which a pattern is exposed to this to react it and then one of the unreacted substances is removed. There is also a method of forming a pattern only by an exposure process by using a material in which a reaction occurs and a refractive index changes only when light of two different wavelengths is irradiated.

Problems to be Solved by the Invention Of the methods for creating a pattern having a refractive index difference of the type described above, the first method is complicated in processing until an optical element in which a pattern is formed or a recorded image is obtained, and It's not easy. The second method is not complicated, but it is not so easy to perform in a wet process, and since the image-forming body in the unrecorded state has a single photosensitivity, the storage stability of the unrecorded material is improved. It is a disadvantage. The third method is a simpler method, but has a problem that a sufficient refractive index difference cannot be obtained unless one of the unreacted substances is sufficiently removed. The fourth method is a design with a gate in which a reaction involving a change in refractive index occurs only when light of two wavelengths is given,
It is also advantageous in terms of storage stability of the material in the unrecorded state or the state after recording. However, the reality is that the recording sensitivity is not sufficient for practical use.

The present inventor, in explaining a simple method for producing a pattern having a difference in refractive index, is the third method of the above-mentioned conventional technique, that is, one having a lower refractive index by reacting two kinds of substances with light. We paid attention to the method of increasing the refractive index of the substance. Further, by separating the energy required for the reaction involving the change in the refractive index and the signal energy for the pattern recording, it is considered that the pattern signal (information) can be recorded by a larger number of recording means. Came to.

INDUSTRIAL APPLICABILITY The present invention is easy to prepare and has excellent storage stability without heat sensitivity and photosensitivity in an unrecorded image forming body. By using radiation such as heat, current and light as recording energy, many recording means It is an object of the present invention to provide a method for forming a pattern having a difference in refractive index that enables recording, and a transfer body and an image forming body used for the method.

Means for Solving the Problems An image-forming body comprising a layer or a base material containing a compound A having a reactive functional group is bound to a compound B which changes the refractive index of the compound A by reacting with the compound A. The transfer material containing the material is brought into close contact, and the compound B is position-selectively transferred from the transfer material to the image forming body by sublimation or diffusion by electromagnetic waves such as light or heat energy, and reacted with the compound A to change the refractive index. Give rise to.

The reactive functional group of the image forming body in which the layer containing the compound A having a reactive functional group is formed, or the reactive functional group of the image forming body in which the substrate itself containing the compound A having a reactive functional group is the image forming body. With respect to the part of the layer or substrate containing the compound A having
The direction in which the portion containing compound B of the transfer body containing compound B and the binder that changes the refractive index of compound A by reacting with compound A are brought into close contact with each other, and the direction opposite to the side of the transfer body brought into close contact with the image forming body When an electromagnetic wave such as light or heat energy is applied from the transfer material, the compound B is position-selectively transferred from the transfer material to the image forming material by sublimation or diffusion, similarly to the sublimation transfer type thermal recording method. Compound A by the energy of radiation such as heat and light newly applied to the image forming body
A refractive index change can be caused by reacting with.

Example In the pattern forming method of the present invention, the reaction between the compound A having a reactive functional group and the compound B which changes the refractive index of the compound A by reacting with the compound A is not particularly limited. It is only necessary that the reaction between the compound A and the compound B having different refractive indices can be caused efficiently. Since the compound A constitutes the image forming body, it is preferable that the compound A is stable even in the state where there is an unreacted reactive functional group.
Further, a polymer compound that is convenient in forming a layer or a film is preferable. The compound B may be any compound that reacts with the reactive functional group of the compound A and that easily diffuses in the transfer body and the image forming body. For the sake of concrete explanation, an example that can be used for the reaction between the compound A and the compound B is given, and further, the compound A and the compound B when the reaction is used.
Take the example of.

(1) Oxetane formation reaction The following compound having an octacene ring is formed by a photoreaction of an aromatic carbonyl compound and an olefin (Katsumi Tokumaru, "Organic Photochemical Reaction Theory," published by Tokyo Kagaku Dojin).

The reaction of the photosensitive resin composition described in JP-A-60-166946 mentioned above includes this, but it is useful because the quantum yield of the reaction is relatively high.

As an example of the compound A, a highly transparent substance is preferable, and when the compound A is a compound having a carbon-carbon double bond, it is described in the claims of JP-A-60-166946. In addition to homo- or copolymer of (meth) acrylic acid 3,3-dimethylallyl ester, 3-methyl-3-butenyl ester of (meth) acrylic acid,
3-methylallyl ester, allyl ester, 2-methylallyl ester, 3-heptenyl ester, 3,3-diethylallyl ester, dicyclopentenyl ester,
There are homopolymers such as 2-furfuryl ester or divinylbenzene and copolymers with other vinyl monomers. Compound B includes substituted or unsubstituted benzaldehyde, acetophenone, benzophenone, 1-, or 2-naphthaldehyde, 1- or 2-naphthylmethylketone or 2-naphthylphenylketone. A substituted or unsubstituted benzaldehyde or benzophenone is preferable from the viewpoint of the quantum yield of the oxetane production reaction. Further substituted or unsubstituted benzaldehydes such as 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, 4-is
o-Propylbenzaldehyde, 4-cyclohexylbenzaldehyde, 2-, 3- or 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde 3,4,5-trimethoxybenzaldehyde, 3-phenoxybenzaldehyde, 3-hydroxybenzaldehyde, phthalaldehyde or 4-cyanobenzaldehyde and the like. As the substituted or unsubstituted benzphenone, benzophenone, 2-, 3- or 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 2-, 3-
Alternatively, 4-bromobenzophenone, 4-methylbenzophenone, 4-propylbenzophenone, 4-methoxybenzophenone, 4-benzoylbenzophenone, or the like can be given.

(2) Cyclobutane formation reaction The following compounds having a cyclobutane ring are formed by a photoreaction between olefins or a conjugated enone and an olefin in the presence of a triplet sensitizer. There is also a compound that produces a cyclobutane ring from a singlet via an exciplex (Katsumi Tokumaru, "Organic Photochemical Reaction Theory," published by Tokyo Kagaku Dojin).

Similar to the above-mentioned oxetane formation reaction, there are also reactions with high quantum yield, which are 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 have such an ionization potential and an oxidation-reduction potential as long as they are appropriate. Reacts well. However, it is desirable that the recording enhancement layer containing the compound A has a low refractive index, and the compound A is preferably a copolymer of a divinylbenzene derivative having a vinyl group remaining and a (meth) acrylic acid ester. Examples of the compound B include vinylnaphthalene and vinylpyrene having a dialkylamino group and a cyano group.

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

The heat generated during recording is useful because not only the transfer of compound B but also the reaction between compound A and compound B occurs. The compound A includes substituted or unsubstituted polyacetylene and the like, and the compound B includes an aromatic compound having a vinyl group. It is preferable that the polyacetylenes are not stable and have less residual double bonds. Further, since polyacetylene has a conjugated double bond chain and has absorption in the visible region, a compound having a substituent having a butadiene structure is preferable when it is not suitable for use.

Although various forms are conceivable as the image-forming body comprising the layer or the base material containing the compound A as described above, mainly, 1) the constitution of only the base material 1 containing the compound A (FIG. 1) 2) the compound A structure having at least the recording image forming layer 2 containing the compound A on the base material 3 not containing A (FIG. 2) 3) Having at least the recording image forming layer 2 containing the compound A on the base material 1 containing the compound A A configuration (Fig. 3) is possible. When the image forming body functions as an optical element or the like by transmitting light, it must be transparent at least for the necessary wavelength. for that reason,
The layer or substrate constituting the image forming body containing the compound A must be transparent for the necessary wavelength, but the substance other than the compound A is not particularly limited. In order to facilitate the diffusion of the compound B, it is preferable that the glass transition temperature or heat distortion temperature is not too high.
A polymer composition at 0 ° C. is preferable. Further, in consideration of crosslinking and curing during the reaction between the compound A and the compound B, if a compound having a reactive functional group such as 1,3-dioxolane ring (may be the compound A) is present, this is not. In the case of a base material containing no compound A, not only the polymer composition but also glass or the like may be used in order to impart heat resistance to the image forming body. When an image forming layer is provided on a base material, a coating liquid for providing the image forming layer is required, and the solvent used is a solvent that dissolves a polymer composition other than compound A and compound B. Although good, for example, when these substances are acrylic, benzene, toluene, methyl ethyl ketone, monochlorobenzene, dichloromethane and the like can be used. The image forming layer preferably has a uniform thickness, but can be favorably formed by the spin coating method.

The transfer body preferably has a transfer material layer 5 on one surface of the base material 4 (FIG. 4). The base material supports the transfer material layer, and films such as polyester, polyimide, aramid, and cellophane, and plate-shaped materials such as polystyrene, PMMA, polycarbonate, and glass can be used. A heat resistant slipping layer may be provided for recording with a thermal head, and a conductive layer or a resistance layer may be provided for easy recording by an electric recording head or an induction heating head. Further, a light absorption layer 6 for converting light energy into heat may be provided on the transfer material layer 5 side of the substrate 4 for performing optical recording (FIG. 5). The transfer material layer is composed of at least a transfer material (that is, compound B) and a binder. The transfer material is as described above, and as the binder, a binder that is used in a sublimation transfer thermal recording medium can be used. That is, water-soluble resins such as cellulose-based, acrylic acid-based, and starch-based resins, acrylic resins, polyphenylene oxide, polysulfone, polyether sulfone, ethyl cellulose, acetyl cellulose, and other organic solvents or water-soluble resins can be mentioned. In terms of recording sensitivity and storage stability of the transfer material, the heat distortion temperature (ASTM D648) is 70 to 15
Those at 0 ° C are excellent. Therefore, polystyrene, polyvinyl butyral, polycarbonate, methacrylic resin, acrylonitrile / styrene copolymer, polyester resin, urethane resin, chlorinated polyethylene, chlorinated polypropylene and the like are preferable. Further, the transfer material layer may contain a plasticizer, a lubricant for the purpose of improving separation from the image forming body after recording, a surfactant and the like. And when preparing a coating liquid for forming the transfer material layer containing the transfer material, the binder, etc., as the solvent to be used, alcohols such as methanol, ethanol, propanol, butanol, methyl cellosolve, Cellosolves such as ethyl cellosolve, aromatics such as benzene, toluene and xylene, esters such as butyl acetate, acetone, 2-
Ketones such as butanone and cyclohexane, nitrogen compounds such as N, N-dimethylformamide, halogenated hydrocarbons such as dichloromethane, chlorobenzene and chloroform can be used, but a water-soluble or water-dispersible aqueous resin is bound. When used as a material, water or a mixture of water and the above solvent may be used. Further, as a method of applying the coating liquid on a film-shaped substrate, it can be carried out by using a reverse roll coater, a gravure coater, a rod coater, a flexo coater, an air doctor coater, etc. Spin coating is a typical method for coating the material.

 Next, a more detailed example will be described.

Example 1 First, 11 g of 3-methyl-2-butenol-1, 15 g of triethylamine and 200 g of dioxane were placed in a 500 ml three-necked flask, and a mixed solution of 16 g of metacloyl chloride and 50 g of dioxane was added dropwise over 30 minutes while stirring. 30 more
After leaving to stir for minutes, 100 g of water was added to this and stirred, and these reaction solutions were filtered. After extracting the organic layer further,
It was washed with an aqueous sodium hydrogen carbonate solution and then with water. After removing dioxane with an evaporator, vacuum distillation was repeated twice to obtain 20 g of methacrylic acid 3,3-dimethylallyl ester. The thus obtained 5 g of methacrylic acid 3,3-dimethylallyl ester, 15 g of methyl methacrylate, and 0.1 g of AIBN were dissolved in 200 g of benzene, and radically polymerized under a nitrogen atmosphere to give 15 g of methacrylic acid 3,3.
A copolymer of dimethylallyl ester and methyl methacrylate was obtained. This polymer was dissolved in dichloromethane to obtain a coating liquid. A glass substrate was spin-coated with this coating liquid to prepare an image forming body 1A in which an image forming layer was provided on a substrate.

Next, 1 g of benzophenone and butyral resin (Sekisui Chemical
2 g of S-REC B BX-1) was dissolved in 21 g of toluene and 9 g of methyl ethyl ketone to prepare a coating liquid 1B. A coating solution obtained by doubling this was designated as coating solution 1B '. The recording and the result thereof will be described later together with other examples.

Example 2 Methacrylic acid furfuryl ester was obtained by the same procedure as in Example 1 using methacryloyl chloride and furfuryl alcohol as raw materials. Methacrylic acid furfuryl ester 5 g, methacrylic acid [2-methyl-2- (2-oxopropyl)-
Similarly, 2 g of 1,3-dioxolan-4-yl] ester, 10 g of methyl methacrylate and 3 g of ethyl acrylate were radically polymerized to obtain 15 g of a quaternary copolymer. This was hot press molded to obtain a plate having a thickness of 1 mm. This was designated as image forming body 2A.

Then, in the same manner as in Example 1, coating solutions 2B and 2B 'containing 4-bromobenzaldehyde as the compound B were obtained.

Example 3 4 g of p-divinylbenzene and 16 g of methyl methacrylate were radical-polymerized 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 spin-coated on a 2 mm-thick PMMA cast plate (Kyowa Gas Chemicals Co., Ltd. Paragrass) to obtain image forming body 3A.

Next, 1 g of 2-vinylnaphthalene and 2 g of AS resin (Denkastyrol AS-SU manufactured by Denki Kagaku Kogyo Co., Ltd.) were mixed with 21 g of toluene,
A coating liquid 3B containing 2-vinylnaphthalene as the compound B was dissolved in 9 g of methyl ethyl ketone to prepare a coating liquid 3B. Further, this was diluted twice to obtain 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 on glass to prepare an image forming body 4A.

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

Recording and Results of Examples 1 to 4 (Recording Method 1) Examples 1 to 4 on a surface of a PET film of 4 μm provided with a heat resistant slip layer composed of a photocurable resin and silica fine particles without the heat resistant slip layer. Coating liquids 1 to 4B were coated with a wire bar to form a transfer material layer having a thickness of about 1 μm to obtain transfer bodies 1 to 4C. The transfer material layer of these transfer bodies and the image forming layer of the image forming body are superposed so as to be in contact with each other (image forming body 2A having no image forming layer
In either case, either side may be used), but recording was performed under the following conditions with a thermal head from the heat resistant slipping layer side of the transfer member.

Thermal head recording conditions Linear density in main scanning: 4 dots / mm Linear density in sub-scanning: 8 dots / mm Recording power: 0.7 W / dot Head heating time: 8 ms / dot Recording one line in sub-scanning fragrance After recording After irradiating each of the image forming bodies 1 to 4A with a 300 W high pressure mercury lamp for 30 seconds, two prisms are placed on the recording line at a distance from each other, and helium
When a neon laser beam was incident, it was possible to observe that the light guided through the optical waveguide of the recording line was emitted from the other prism of any image forming body. It was also confirmed that the light was guided only in the recording line portion from the irregular reflection by the foreign matter mixed in the image forming layer.

(Recording Method 2) A carbon-containing aramid film (thickness 8 μm, sheet resistance about 1 kΩ / □) was applied with a wire bar of coating liquids 1 to 4B of Examples 1 to 4 to form a transfer material layer of about 1 μm. , And transfer bodies 1 to 4D. The transfer member and the image forming member were superposed in the same manner as in the recording method 1, and recording was performed from the film side of the transfer member using a line-type energizing head under the following conditions.

Energizing head recording conditions Linear density in main scanning: 10 dots / mm Linear density in sub-scanning: 20 dots / mm Applied voltage: 50 V Applied pulse width: 80 μs Recording only one line in the sub-scanning direction Same processing as in recording method 1 After that, the same optical waveguide experiment was conducted, and it was confirmed that any image forming body functions as an optical waveguide.

(Recording Method 3) A glass substrate having a thickness of 1.1 mm, an outer diameter of 130 mm and an inner diameter of 15 mm was spin-coated with an ethylcellulose solution in which carbon black was dispersed to provide a 2 μm light absorbing layer. Further, the coating liquids 1 to 4B 'of Examples 1 to 4 were spin-coated to provide a transfer material layer having a thickness of 1 μm to obtain transfer bodies 1 to 4E. An image forming body which was 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 recording image forming layer and the transfer material layer of the transfer body were overlapped. This was recorded on an optical recording deck for optical disks with a linear velocity of 10 m / s, 6 mW, a radial feed pitch of 2 μm, and no modulation. After recording, the transfer body and the image forming body were separated, and the image forming body was irradiated with light from a 300 W high-pressure mercury lamp for 30 seconds.

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

EFFECTS OF THE INVENTION The method of forming a pattern having a difference in refractive index according to the present invention comprises reacting a compound A with an image-forming body comprising a layer or a base material containing the compound A having a reactive functional group. The compound B that changes the refractive index of the compound B and a transfer body containing a binder are brought into close contact with each other, and the compound B is regioselectively transferred by sublimation or diffusion from the transfer medium to the image forming body by electromagnetic waves such as light or energy of heat, Since the reaction with Compound A causes a change in the refractive index, the preparation method is simple, the image-forming body in the unrecorded state does not have heat sensitivity and photosensitivity, and has excellent storage stability. By using it as recording energy, recording can be performed by many recording means.

[Brief description of drawings]

1 to 3 are schematic sectional views of the image forming body in the embodiment of the present invention, and FIGS. 4 and 5 are schematic sectional views of the pattern transfer body in the embodiment of the present invention. 1 ... Substrate containing Compound A, 2 ... Recording image forming layer containing Compound A, 3 ... Substrate not containing Compound A, 4 ... Substrate, 5 ... Transfer material layer, 6 ... Light Absorption layer.

Claims (5)

[Claims] 1. An image-forming body comprising a layer or a base material containing a compound A having a reactive functional group, a compound B which changes the refractive index of the compound A by reacting with the compound A, and a binder. The compound B is regioselectively transferred by sublimation or diffusion from the transfer member to the image-forming material by electromagnetic energy such as light or heat energy, and the refractive index of the transferred part is reacted. A method for producing an optical element having a pattern having a difference in refractive index, which is characterized by causing a change. 2. The method for producing an optical element having a pattern having a difference in refractive index according to claim 1, wherein compound A and compound B are the following compounds. (A) Compound A contains homopolymerization of an ester of substituted or unsubstituted allyl alcohol and (meth) acrylic acid, or 5% by weight or more of an ester of substituted or unsubstituted allyl alcohol and (meth) acrylic acid. A (co) polymer (B) which is a copolymer with another vinyl monomer and in which a double bond of a substituted or unsubstituted allyl alcohol remains in the polymer, Group containing benzaldehyde, benzophenone or naphthylpheniketone 3. The method for producing an optical element having a pattern with a difference in refractive index 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 another vinyl monomer containing 5% by weight or more of 3,3-dimethylallyl ester of (meth) acrylic acid. (Co) polymer which is a copolymer and has double bond of 3,3-dimethylallyl group remaining in the polymer (b) Compound B is a benzaldehyde or benzophenone having an unsubstituted or substituted group. Or naphthyl phenyl ketone 4. An image-formed body comprising a layer or a substrate containing a compound A having a reactive functional group, which is used in the method for producing an optical element having a pattern having a difference in refractive index according to claim 1. 5. A transfer containing a compound B which reacts with the compound A and changes the refractive index of the compound A, which is used in the method for producing an optical element having a pattern having a refractive index difference according to claim 1. Record body.