JPH03164783A - Hologram and production thereof - Google Patents

Abstract

PURPOSE:To improve the transparency to visible rays by forming the hologram of a polymer having specific constitutional units, a compd. selected from a group consisting of arom. aldehyde and arom. ketone which may have a substituent and a compd. having >=2 carbon-carbon double bonds. CONSTITUTION:This hologram consists of the polymer having 2 to 100 mol.% constitutional unit expressed by formula I, 0 to 98 mol.% constitutional unit expressed by formula II and 0 to 98 mol.% constitutional unit expressed by formula III, the compd. selected from the group consisting of the arom. aldehyde and arom. ketone which may have the substituent and the compd. having >=2 carbon-carbon double bonds. In the formula I, X<1> denotes a hydrogen atom or alkyl group; Y1 denotes a cycloalkenyl group, etc. In the formula II, X<2> denotes a hydrogen atom or alkyl group; Y<2> denotes a phenyl group, etc. In the formula III, X<3> denotes a hydrogen atom or alkyl group; Z<2> denotes a bivalent hydrocarbon group, R<4>, R<5>, R<6> respectively denote a hydrogen atom or alkyl group. The transparency to the visible rays is improved in this way.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to a hologram and a method for manufacturing the same.

[Prior Art] A hologram is a recording of the interference wavefront of coherent light such as a laser beam as a refractive index distribution or light absorption (shade) distribution, and is used in stereoscopic photographs, beam scanners of bar code reading devices, etc. It is used in optical elements, head-up displays for aircraft and automobiles, etc.

In order to use a hologram for the above purpose, it is necessary that the hologram has the following characteristics.

(I) High diffraction efficiency.

(2) Excellent moisture resistance, heat resistance, and light resistance.

(3) Be colorless and transparent.

(4) Less haze.

Known materials for holograms include bleached silver salts, photorenost, thermoplastics, dichromate gelatin, inorganic glass materials, and ferroelectric materials. Among these, bleached silver salts and dichromate gelatin has been put into practical use.

[Problems to be Solved by the Invention] When producing a hologram using the bleached silver salt described above, there are drawbacks such as the need for complicated processing and the resulting hologram having poor light resistance. . Further, the hologram provided by dichromate gelatin has drawbacks such as poor moisture resistance and heat resistance.

One object of the present invention is to provide a hologram that has good transparency to visible light, organic solvent resistance, and heat resistance, and high diffraction efficiency. Another object of the present invention is to provide a method for manufacturing the above-mentioned hologram.

[Means for Solving the Problems] According to the present invention, one of the above objects is achieved by the following - general formula (I
) (hereinafter referred to as structural unit (I)) from 2 to 100 mol%, a structural unit represented by the following general formula (ff) (hereinafter referred to as structural unit (■)) and a polymer (A) having 0 to 98 mol% of a structural unit represented by the following general formula (IF) (hereinafter referred to as structural unit (II[)), and a substituent A composition consisting of a compound (B) selected from the group consisting of aromatic aldehydes and aromatic ketones which may have This is achieved by providing a hologram.

Structural unit (■): 1 [In the formula, XI represents a hydrogen atom or an alkyl group, and Yl
represents a cycloalkenyl group or a group represented by the following general formula. Here, Zl represents a divalent hydrocarbon group, R1,
R1 and R3 each represent a hydrogen atom, an alkyl group or an alkenyl group. ] Structural unit (■): Y鵞 [In the formula, x2 represents a hydrogen atom or an alkyl group, and Yl
represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in general formula (II) may be substituted with a fluorine atom. ] Structural unit (■): ! 3 [wherein, X3 represents a hydrogen atom or an alkyl group, Z2
represents a divalent hydrocarbon group, and R4, R5 and R6 each represent a hydrogen atom or an alkyl group. ] The polymer (A) constituting the composition used in the present invention has a structural unit (I
), and contains 2 to 98 mol% of structural unit (III).
It is preferable that the structural unit (I) and the structural unit (I[I) are contained in an amount of 20 to 40 mol%.

x1 in the above structural unit ('I), structural unit (I
x8 in I) and x in the structural unit (I[I)
The alkyl group represented by 3 is preferably a lower alkyl group having 4 or less carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, or butyl group.

In addition, R1 in structural unit (I). R1 and R3 and R4, R5 and R in structural unit (III)
The alkyl groups represented by 6 may have a branched chain or any substituent, and include methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, etc. A lower alkyl group having a carbon number h<s or less is preferable. R11R2 and R above
The alkenyl groups represented by 3 are 2-butenyl group, 3-
Methyl-2-butenyl group, 3-pentenyl group, and 4-methyl-3-pentenyl group are preferred. The divalent hydrocarbon group represented by Zl in the structural unit (I) and 2'' in the structural unit (■) is preferably an alkylene group having 2 to 8 carbon atoms which may have a branched chain.The structural unit (
Suitable examples of Yl in I) include allyl group; 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group/2-hebutenyl group, 3-hebutenyl group, 4-heptenyl group, 2- Methyl-2-butenyl group, 3-methyl-2
-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-3-butenyl group, 1,2-dimethyl-2-propenyl group; 2-hexenyl group, 3-hexenyl group, 4-hexenyl group , 5-hexenyl group, 1,1-dimethyl-2
-butenyl group, ■, 2-dimethyl-2-butenyl group, 1
．． 3-dimethyl-2-butenyl group, 2,3-dimethyl-2
-Butenyl group, 3-methyl-2-hebutenyl group, 2-methyl-2-heptenyl group: 2-methyl-2-cyclohexenyl group, 3-methyl-2-cyclohexenyl group, geranyl group, isogeranyl group , a neryl group, a lavandulyl group, a 6-methylgeranyl group, and a -mecyclogeranylgeranyl group. Y in structural unit (n)! Preferred examples of the alkoxycarbonyl group represented by are methoxycarbonyl group, ethoxycarbonyl group,
Examples include propoxycarbonyl group, butoxycarbonyl group, pentanoxycarbonyl group, hexanoxycarbonyl group, heptanoxycarbonyl group, and cyclohexanoxycarbonyl group.

Further, as the groups in the structural unit (III), 2.3-epoxypropyl group, 2.3-epoxybutyl group, 3.4-epoxybutyl group, 2.3-epoxy-2-methylpropyl group, 2-methyl -2,3-
Epoxybutyl group, 3-methyl-2,3-epoxybutyl group, 2.3-epoxyhebutyl group, 5.6-epoxyhebutyl group, 3-methyl-2,3-epoxybutyl group,
Examples include 4-methyl-2,3-epoxyheptyl group and 4-methyl-5°6-epoxyheptyl group.

The polymer (A) is obtained by homopolymerization of acrylic acid or its ester which may be substituted with an alkyl group at the α-position or copolymerization with a comonomer forming the structural unit (II), and then the polymer is obtained by copolymerization with a comonomer forming the structural unit (II). The structural unit (I) is formed by reacting the alcohol with the alcohol having the group Y3 or, if necessary, a mixture of this alcohol and the alcohol having the group Y3, or with an acrylic acid derivative forming the structural unit (I). It can be produced by copolymerization with acrylic acid derivatives or by copolymerization of these acrylic heptanoic acid derivatives and the above-mentioned co-O additives.

As the acrylic acid derivative forming the structural unit (I),
Allyl methacrylate, allyl acrylate, 2 (or 3)-butenyl methacrylate, 2 (or 3)-butenyl acrylate, 2-methyl-2-propenyl methacrylate, 2-methyl-2-propenyl acrylate, 2 (or 3 or 4) )-hebutenyl methacrylate, 2 (or 3 or 4)-hebutenyl acrylate,
2-Methyl-2 (or 3)-butenyl methacrylate, 2-methyl-2 (or 3)-butenyl acrylate, 2-ethyl-2-propenyl methacrylate, 2-ethyl-2-propenyl acrylate, 1.2- Dimethyl-2-propenyl methacrylate, 1,2-dimethyl-
2-propenyl acrylate, 2 (or 3 or 4 or 5)-hexenyl methacrylate, 2 (or 3 or 4 or 5)-hexenyl acrylate, 1.1 (
or 1.2 or 1.3 or 2.3)-dimethyl-
2-butenyl methacrylate, ■, ■ (or 1.2 or 1.3 or 2.3)-dimethyl-2-butenyl acrylate, 2 (or 3)-methyl-2-hebutenyl methacrylate, 2 (or 3) Acrylic acid derivatives in which alcohol residues are chained, such as -methyl-2-heptenyl acrylate; 2 (or 3)-methyl-2-
Acrylic acid derivatives in which alcohol residues are cyclic, such as cyclohexenyl methacrylate and 2 (or 3)-methyl-2-cyclohexenyl acrylate; geranyl methacrylate, geranyl acrylate, neryl methacrylate, neryl acrylate, isogeranyl methacrylate, Isogeranyl acrylate, lavandulyl methacrylate, lavanduryl acrylate, 6-methylgeranyl methacrylate, rylate, 6-ethylgeranyl methacrylate, 6-ethylgeranyl acrylate, perylyl methacrylate, perillyl acrylate, etc. Esters of chain or cyclic terpene alcohol and acrylic acid or methacrylic acid: non-military double bonds such as farnesyl methacrylate, farnesyl acrylate, geranylgeranyl methacrylate, geranylgeranyl acrylate, β-cyclogeranylgeranyl methacrylate, β-cyclogeranylgeranyl acrylate, etc. Examples include esters of chain or cyclic terpene-based alcohols having three or more of the following and acrylic acid or methacrylic acid. Among these, allyl methacrylate, 2-methyl-2-propenyl methacrylate, 2-butenyl methacrylate, 2-methyl-2
-Butenyl methacrylate, 2-hexenyl methacrylate, 3-hexenyl methacrylate, and geranyl methacrylate are preferred from the viewpoint of easy availability of alcohol as a raw material and ease of ester synthesis.

In addition, examples of the acrylic acid derivatives forming the structural unit (III) include 2,3-epoxypropyl methacrylate, 2
．． 3-Epoxypropyl acrylate, 2,3-epoxybutyl methacrylate, 2.3-epoxybutyl acrylate, 3.4-epoxybutyl methacrylate, 3
．． 4-epoxybutyl acrylate, 2-methyl-2,
3-epoxypropyl methacrylate, 2-methyl-2
, 3-epoxypropyl acrylate, 2.3-epoxyhebutyl methacrylate, 5.6-epoxyhebutyl methacrylate, 2.3-epoxyhebutyl acrylate, 5.6-epoxyhebutyl acrylate, 2 (or 3)-methyl -2,3-epoxybutyl methacrylate, 2(or 3)-methyl-2,3-epoxybutyl acrylate, 4-methyl-2,3-epoxyhebutyl methacrylate, 4-methyl-5,6-epoxyheptyl acrylate Can be mentioned. Among these, 2.3-
Epoxypropyl methacrylate, 2,3-epoxypropyl methacrylate, 2,3-epoxybutyl methacrylate, and 3,4-epoxybutyl methacrylate are preferred from the viewpoint of ease of ester synthesis.

Comonomers forming the structural unit (It) include methacrylic acid; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, amyl methacrylate, and cyclohexyl methacrylate; Ester/acrylic acid; Acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, amyl acrylate, cyclohexyl acrylate; Methacrylic acid amide; Acrylic acid amide : Styrene, substituted styrene such as α-methylstyrene, etc. The hydrogen atom in the structural unit (n) may be substituted with a fluorine atom.

Polymer (A) has a polystyrene equivalent number average molecular weight determined by gel permeation chromatography of 1.0.
A value in the range of 00 to 1,000.000 is preferred. The polymer (^) has a number average molecular weight of 100,000 to 80
A value in the range of 0.000 is more preferable.

Examples of the compound (B) include benzaldehyde, benzophenone, or derivatives thereof, which may have substituents, and specifically, compounds represented by the following general formula (■), general formula (V), or general formula (VI). It will be done.

x'' [wherein, X4, X5, x6, x7, x8, x9, XIO
, X port and X port each represent a hydrogen atom, an alkyl group or alkoxy group having 7 or less carbon atoms, or a halogen atom;
n is 0.1 or 2. Preferred compounds (B) include benzophenone; 3 (or 4)-methylbenzophenone, 3 (or 4)-methoxybenzophenone, 3.3' (or 4.4')
-dimethylbenzophenone, 3,3' (or 4,4
°)-dimethoxybenzophenone, 2.3 (or 2.
4)-Substituted penzophenones such as -chlorobenzophenone, 3.4.5-trimethoxybenzophenone; 3-benzoylbenzophenone; 3 (or 4)-methylbenzoyl-3° (or 4')-methylbenzophenone;
(or 4)-methoxybenzoyl-3° (or 4°
)-methoxybenzophenone, 3.3'-dibenzoylbenzophenone, meta-substituted benzophenones such as 1.3.5-tribenzoylbenzene, benzaldehyde; 3 (or 4)-methylbenzaldehyde, 3 (or 4)-methoxybenzaldehyde , 3,4-dimethylbenzaldehyde, and 3,4-dimethoxybenzaldehyde. Among these, benzaldehyde, benzophenone,
3-benzoylbenzophenone, 3.3°-dibenzoylbenzophenone and 1,3.5-tribenzoylbenzene are preferred from the viewpoint of ease of synthesis, and 3-benzoylbenzophenone and 1,3.5-tribenzoylbenzene are preferred because of their ease of synthesis. It is particularly preferable because it has good reactivity, it is possible to increase the difference in refractive index between exposed and unexposed areas, and the produced hologram has high solvent resistance and heat resistance.

Preferred compounds (C) include alkylene glycol dimethacrylate, alkylene glycol diacrylate, or polymers thereof; glycerin dimethacrylate, glycerin trimethacrylate, glycerin diacrylate, glycerin triacrylate, neopentyl glycol dimethacrylate, and neopentyl glycol dimethacrylate. Acrylate, pentaerythritol dimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 2.2-bis[4-methacryloyl ethoxyphenyl]propane, 2.2- Bis[4-methacryloylboriethoxyphenylcopropane, 2.2-bis[4-acryloylethoxyphenylcopropane, 2.2-bis[4
-acryloylpolyethoxyphenyl]propane, 2-
Polyacrylates or polymethacrylates of polyols having a urethane main chain structure such as hydroxy-1-acryloyl-3-methacryloylpropane, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane triacrylate. ; or N,! Examples include 1'-methylenebisacrylamide, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimesotate, trimethacrylic cyanurate, trimethacrylylisocyanurate, triallyl cyanurate, and triallyl isocyanurate. can. Among these 2
Compounds having more than one acryloyl or methacryloyl group are preferred.

The composition ratio of polymer (A) and compound (B) is lO:1~
The range of 1:lG (weight ratio) is preferable, and 3:1-1:2
(weight ratio) is more preferable. The ratio of the structural unit (I) and the compound (B) that the polymer (A) has is 1O:1 to
The range is 1:20 (molar ratio), preferably 5:1 to
The range is 1:10 (molar ratio). In addition, the ratio of the structural unit (I) and the compound (C') that the polymer (^) has is 30
The range is from 0:1 to 2:l (molar ratio), preferably 3
The range is from 0:1 to 5:l (molar ratio).

According to the present invention, another object of the above is a method for manufacturing a hologram made of the above composition, which comprises the following steps (a), ([I) and (8). This is achieved by providing

(a) A step of forming a thin film of the above composition.

(0) A step of partially irradiating the thin film with ultraviolet rays according to a desired pattern.

(c) Step of removing unreacted compound (B) from the thin film.

In the above step (a), the polymer (A) and the compound (B) are dissolved in a solvent that dissolves them, and the resulting solution is used to form a thin film by a casting method, a barcode method, a spin code method, etc. do. If necessary, the solvent is removed from the thin film by subjecting it to reduced pressure treatment or heat treatment. The method for forming the thin film is selected depending on the desired thickness or form of the thin film. The thickness of the thin film is preferably in the range of 0.5 to 50 μm. Generally, when the thickness is large, the scanning scan method is used, and when the thickness is small, the bar code method or spin code method is used.

In step (0) following step (a), the thin film is partially irradiated with ultraviolet light having a wavelength of 200 to 450 nm in accordance with the hologram pattern. The light source is a high pressure mercury lamp, N.

A gas laser, e-Cd laser, Ar laser, etc. are used. As a method for forming a hologram pattern, a mask exposure method using a photomask, an interference exposure method, a laser beam direct writing method, etc. are employed.

Removal of unreacted compound (B) in step (8) following step ([+)] is usually carried out by heat treatment under reduced pressure or normal pressure. The temperature of the heat treatment is preferably in the range of 50 to 100°C. As a result, a hologram is obtained in which the exposed portion has a higher refractive index than the unexposed portion and is thicker.

In the hologram manufacturing method of the present invention, a step (=) of irradiating the entire surface of the thin film on which the hologram pattern is formed with ultraviolet light may be provided after the step (c). By going through this step (d), the organic solvent resistance and heat resistance of the manufactured hologram are further improved. The ultraviolet rays to be irradiated preferably have an intensity of 1O to 40fflW/cIIl'' and a wavelength of 200 to 450 nm.The time of ultraviolet irradiation is preferably in the range of 30 seconds to 5 minutes.Also, step (8) Next to or as required (
After step (d), a step (iv) of performing heat treatment at a higher temperature than the heat treatment temperature in step (eight) may be provided. By passing through this step (iv), the organic solvent resistance and heat resistance of the manufactured hologram are further improved. The heat treatment in the (main) step is preferably performed at a temperature in the range of 105 to 230°C for 15 minutes to 40 hours. Heat treatment at a temperature in the range of 150-200℃ for 1-5 hours or 110-140℃
A heat treatment at a temperature in the range of 10 to 25 hours gives more favorable results.

After the step (a), a step (f) may be provided in which the entire surface of the thin film made of the above composition is irradiated with ultraviolet rays under conditions in which only a portion of the compound (B) reacts.

Note that a hologram having a desired refractive index difference and unevenness difference can also be obtained by partially irradiating a thin film made of the above composition with ultraviolet rays according to the hologram pattern and then immersing it in a solvent.

The hologram of the present invention has a pitch in the range of 0.2 to 5 μ-, and a refractive index difference between the exposed and non-exposed portions of 0.2 μm.
The range of 0.001 to 0.1 is preferred.

The hologram of the present invention has high diffraction efficiency, small variation, good transparency, and little haze. Therefore, the hologram of the present invention is preferably used in head-up displays for automobiles.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 2-butenyl methacrylate 13 was added to the reaction vessel after h substitution.
0g, 2.3-epoxypropyl methacrylate 13
0g, methyl methacrylate 140g, azobisisobutyronitrile 200B and dioxane 1200+07
! The tube was sealed and heated in a water path at 55 to 60'C for 24 hours to carry out a polymerization reaction. The obtained reaction This polymer (A) was found to have a molar ratio of 2-putenyl methacrylate to 2.3-epoxypropyl meccrylate to methyl methacrylate from the results of NMR measurements: 1:1:2.
It was confirmed that it was a copolymer of In addition, the number average molecular weight of this polymer (^) in terms of polystyrene determined by gel permeation chromatography is 260,
It was 000. A composition consisting of 10 parts of polymer (A), 8 parts of 3-benzoylbenzophenone, and 2 parts of a triacrylisocyanurate derivative (M-315 manufactured by Toagosei Co., Ltd.) represented by the following formula % was added to toluene. The obtained solution was used to form a thin film (thickness: 12 μs) on a glass substrate by a spin code method.

This thin film was exposed to a hologram grid pattern using an interference exposure apparatus shown in FIG. In the interference exposure apparatus, an Ar laser 1 having a wavelength of 36311 nm is emitted, and the light incident on the interference optical system 2 is reflected by a mirror 3 and then split into two by a beam splitter 4. The two-split light is reflected by the mirror 5 (6) and then passes through the lens system 7 (8).
), the light becomes parallel, forming interference fringes on the exposure surface 9.

In this example, the period of the obtained hologram is 0.43
Interference exposure was performed by adjusting the lens system and mirror so that the distance was .mu.m.

After interference exposure, the patterned thin film was heat treated in a vacuum dryer at 98°C and 0.2avHg for 17 hours.
Unreacted compound (B) was removed from the thin film. Thereafter, a hologram was obtained by irradiating the entire surface of the thin film with ultraviolet rays of 2 hW/am'' for 6 minutes.

The diffraction efficiency of the obtained hologram for light having a wavelength of 632 Jnm was 40% for light polarized in the same direction as the lattice pattern of the hologram, and 16% for light polarized in the perpendicular direction. Next, FIG. 2 shows a spectral transmission characteristic diagram of this tenogram for visible light. Here, FIG. 2 shows the results obtained by arranging the hologram so that the diffraction efficiency for light with a wavelength of 632.8 nm is maximized and measuring it. As is clear from FIG. 2, the above hologram has a transmittance of 90% or more for light of wavelengths other than the wavelength at which diffracted light is generated, and has extremely good transparency for visible light. Furthermore, when the hologram was left in saturated vapor of methyl methacrylate at 50° C. for 100 hours, its diffraction efficiency did not change. From this, it was determined that the refractive index of this hologram did not change.

Further, this hologram was heated at 180° C. (normal pressure) for 2 hours, but the diffraction efficiency did not change.

Examples 2 to 9 In the same manner as in Example 1, M-309 manufactured by Toagosei Co., Ltd. shown in Table 1 is expressed by the following formula %, and Toa Gosei M-309 is expressed by the following formula %. Manufactured by Seimei Co., Ltd. M-325 or the above M
-315 was used. Holograms were prepared as in Example I using the compositions shown in Table 1.

Example 1 using the holograms manufactured in each example
The organic solvent resistance and resistance were also good.

In Table 1, parts indicate parts by weight.

Below is a margin Example IO N in the reaction vessel, 2-butenyl methacrylate 1 after substitution
05g, methyl methacrylate) 225g, azobisisobutyronitrile 300B and dioxane 1100I
IIQ was charged, the tube was sealed, and the tube was heated in a water bath at 55 to 60° C. for 24 hours to perform a polymerization reaction. The obtained reaction solution was poured into 4,500 ml of methanol to precipitate the product, and by drying, 231 g of polymer (A) was obtained.
Obtained. From the results of NMR measurements, this polymer (A)
It was confirmed that the copolymer had a molar ratio of 2-butenyl methacrylate to methyl methacrylate of 1:3. Further, the number average molecular weight of this polymer (A) in terms of polystyrene, determined by gel permeation chromatography, was 290,000. 10 parts of polymer (A), 8 parts of 3-benzoylbenzophenone, and the above N-3
A thin film (thickness: 12 μm) was formed on a glass substrate using the spin code method using the obtained solution, and interference exposure was performed under the same conditions as in Example 1. I did it. After interference exposure, it was heat-treated in a vacuum dryer at 98° C. and 0.2 part mHg for 17 hours to remove unreacted compound (B). After that, the entire surface of the thin film was irradiated with 25 d/am' ultraviolet rays for 5 minutes, and 18
A hologram was manufactured by performing heat treatment at 0° C. (normal pressure) for 2 hours.

This hologram had high diffraction efficiency like the hologram of Example 1, and had good organic solvent resistance, heat resistance, and transparency.

Example 11 N in reaction vessel, 39 g of geranyl methacrylate after substitution
, 2.3-epoxypropyl methacrylate 26g1
38 g of methyl methacrylate, azobisisobutyronitrile 90B and 300 g of dioxane were charged, the tube was sealed and heated in a water bath at 55 to 60° C. for 24 hours to perform a polymerization reaction. The resulting reaction solution was poured into 112 methanol to precipitate the product, which was then dried to obtain 45 parts of polymer (A). This polymer (A) is N M
From the measurement results by R, geranyl methacrylate vs. 2.
It was confirmed that the copolymer had a molar ratio of 3-epoxypropyl methacrylate to methyl methacrylate of 1:1:2. Further, the number average molecular weight of this polymer (A) in terms of polystyrene determined by the gel permeation chromatography method was 190. It was Goo. Polymer (
A) 10 parts, O 1.3.5-8 parts of tribenzoylbenzene, and the above.
-315, 2 parts is dissolved in toluene,
Using the obtained solution, a thin film (thickness: 12 μm) was formed on a glass substrate by a spin code method, and interference exposure was performed under the same conditions as in Example 1. After interference exposure, it was heat-treated in a vacuum dryer at 98° C. and 0.2 V++Hg for 17 hours to remove unreacted compound (B). Thereafter, a hologram was manufactured by irradiating the entire surface of the thin film with 20mf/am'' ultraviolet rays for 6 minutes and heat-treating it at 120°C (normal pressure) for 24 hours. It had high diffraction efficiency, and good organic solvent resistance, heat resistance, and transparency.

Comparative example example! Example 1 Using a composition consisting of 10 parts of polymer (A) having the same composition as in Example 0 and 8 parts of 3-benzoylbenzophenone! Holograms were manufactured under the same conditions as in . When this hologram was heated at 180° C. (normal pressure) for 2 hours, the hologram pattern was deformed and the diffraction efficiency changed.

[Effects of the Invention] According to the present invention, a hologram is provided that has good transparency to visible light, organic solvent resistance, and heat resistance, and high diffraction efficiency. In this hologram, the exposed portion has a higher refractive index than the non-exposed portion and is thicker. Further, according to the present invention, a method of manufacturing the above-mentioned hologram is provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of an interference exposure apparatus used for manufacturing the hologram of the present invention, and FIG. 2 is a diagram of the spectral transmission characteristics of the hologram of Example 1 for visible light. l...Ar laser, 4...beam splitter, 7.8...lens system, 9...exposure surface.

Claims (1)

[Claims] 1. The following general formula (I) (I)▲ Numerical formulas, chemical formulas, tables, etc.▼ [In the formula, X^1 represents a hydrogen atom or an alkyl group, and Y
^1 represents a cycloalkenyl group or a group represented by the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼. Here, Z^1 represents a divalent hydrocarbon group, and R^1, R^2 and R^3 each represent a hydrogen atom, an alkyl group or an alkenyl group. ] 2 to 100 mol% of the structural unit represented by the following general formula (
II) (II)▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^2 represents a hydrogen atom or an alkyl group, and Y
^2 represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in general formula (II) may be substituted with a fluorine atom. ] 0 to 98 mol% of structural units represented by the following general formula (III) (III) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^3 represents a hydrogen atom or an alkyl group, and Z
^2 represents a divalent hydrocarbon group, and R^4, R^5 and R^6 each represent a hydrogen atom or an alkyl group. ]
A polymer having 0 to 98 mol% of the structural unit represented by (A
), a compound (B) selected from the group consisting of aromatic aldehydes and aromatic ketones which may have substituents, and a compound (B) having two or more carbon-carbon double bonds (C
) A hologram consisting of a composition consisting of. 2. A hologram comprising the composition according to claim 1, wherein the compound (C) has two or more acryloyl groups or methacryloyl groups. 3. (a) The following general formula (I) (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X^1 represents a hydrogen atom or an alkyl group, and Y
^1 represents a cycloalkenyl group or a group represented by the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼. Here, Z^1 represents a divalent hydrocarbon group, and R^1, R^2 and R^3 each represent a hydrogen atom, an alkyl group or an alkenyl group. ] 2 to 100 mol% of the structural unit represented by the following general formula (
II) (II)▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^2 represents a hydrogen atom or an alkyl group, and Y
^2 represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in general formula (II) may be substituted with a fluorine atom. ] 0 to 98 mol% of structural units represented by the following general formula (III) (III) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^3 represents a hydrogen atom or an alkyl group, and Z
^2 represents a divalent hydrocarbon group, and R^4, R^5 and R^6 each represent a hydrogen atom or an alkyl group. ]
A polymer having 0 to 98 mol% of the structural unit represented by (A
), a compound (B) selected from the group consisting of aromatic aldehydes and aromatic ketones which may have substituents, and a compound (B) having two or more carbon-carbon double bonds (C
), (b) partially irradiating the thin film with ultraviolet rays according to a desired pattern, and (c) removing unreacted compound (B) from the thin film. A method for manufacturing a hologram, comprising: .