JP3339873B2 - Hologram forming material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel urethane compound which is cured by irradiation with ionizing radiation such as ultraviolet rays, electron beams and gamma rays, has a refractive index of 1.4 or less, and forms a flexible film. And a method of manufacturing the same.

[0002]

2. Description of the Related Art Urethane compounds having a tough cured film forming ability are widely used in binders in various coatings, adhesive compositions, coating material compositions, molding compositions for engineering plastics molded products, resists, and the like. It's being used.

[0003]

However, there are few conventional urethane compounds having a refractive index of 1.47 or less. In particular, as a hologram forming method, a recording medium comprising a matrix polymer, a photopolymerizable compound, and a photoinitiator, as described in Japanese Patent Application No. 3-104183, is exposed to laser light interference fringes. When the recording medium is immersed in a developer containing a compound capable of photopolymerization or heat polymerization, and then the recording medium is cured by heat or light, a (meth) acrylate monomer having a refractive index of 1.47 or less is used. is necessary.

In particular, when the film is swelled by development using this method to increase the pitch of the diffraction grating, it is desirable to have a flexible structure like a urethane compound. That is, the present invention provides a novel urethane compound containing fluorine, having a low refractive index and a flexible structure.

[0005]

The hologram-forming material of the present invention is a urethane compound represented by the following general formula (1).

[0006]

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R ₁ is a fluorine-containing hydrocarbon group, and the lower the refractive index, the more preferable the fluorine content. Examples of R ₁ include the following. C _m F _n H _{(2m + 1-n)} Here, when an alcohol or phenol is used as a starting material, the following are preferred.

(R)-(-)-2,2,2-trifluoro-1- (9-anthryl) ethanol, 2,2,2-
Trifluoro-1- (9-anthryl) ethanol,
(S)-(+)-2,2,2-trifluoro-1- (9
-Anthryl) ethanol α, α, α-trifluoro-o-cresol, CF ₃ C ₆ H ₄ OH 〃- ₄ -m-〃, 〃 〃-〃-p-〃, 〃α- (trifluoromethyl) benzyl alcohol _{C 6 H 5 CH (CF 3} ) OH 3- ( trifluoromethyl) phen ethyl alcohol _{CF 3 C 6 H 4 CH 2} CH 2 OH 7- ( trifluoromethyl) -4-quinolinol 2,3,5,6 - tetrafluoro phenol 2,2,3,3-tetrafluoro-1-propanol ^{_{n D 20 = 1.3210 F 2 CHCF}} 2 CH 2 OH 4,4'- difluoro benzhydrol (FC ₆ H) ₄ CHOH.

2,3-difluorobenzyl alcohol F ₂ C ₆ H ₃ CH ₂ OH 2,4- {} 2,5- {} 2,6- {} 3,4- {} 3,5- {} 2 , 3-Difluoro-6-nitrophenol F ₂ C ₆ H ₂ (NO ₂ ) OH 2,3-difluorophenol F ₂ C ₆ H ₃ CH 2,4- {2,5-} {2,6-} ３ ， 3,4-〃 〃 2-fluorobenzyl alcohol 〃 3-〃 ４− 4-〃 〃 4-fluoro-2-methylphenol FC ₆ H ₃ (CH ₃ ) OH 〃 〃 〃 2-fluorophenethyl alcohol _{FC 6 H 4 CH 2 CH 2} OH 4- undefined undefined.

2-fluorophenol FC ₆ H ₄ OH 3-〃 { ₄ -〃} 2,3,4,5,6-pentafluorobenzyl alcohol C ₆ F ₅ CH ₂ OH 2,3,4,5,6 -Pentafluoro-α- (nitromethylene) benzyl alcohol C ₆ F ₅ C (＝ CHNO ₂ ) OH pentafluorophenol C ₆ F ₅ OH 2,2,3,3,3-pentafluoro-1-propanol n _D ²⁰ = 1.2880 CF ₃ CF ₂ CF ₂ OH 4,4 ′-(hexafluoroisopropylidene) diphenol (CF ₃ ) ₂ C (C ₆ H ₄ OH) ₂ 1,1,1,3,3 3-hexafluoro-2-phenyl-2-propanol n _D ²⁰ = 1.2750 C ₆ H ₅ C (CF ₃ ) ₂ OH 2,2,3,3,4,4,4-heptafluoro-1-butanol n _D ²⁰ = 1.3000 CF ₃ CF ₂ CF ₂ CH ₂ OH Decafluorobenzhydrol (C ₆ F ₅ ) ₂ CHOH.

Particularly preferred are those having a high fluorine content and not containing an aromatic ring such as a benzene ring and a naphthyl ring.

2,2,2-trifluoroethanol CF ₃ CH ₂ OH n _D ²⁰ = 1.2907 2,2,3,3-tetrafluoro-1-propanol F ₂ CHCF ₂ CH ₂ OH n _D ²⁰ = 1 .3210 2,2,3,3,3-pentafluoro-1-propanol _{CF 3 CF 2 CH 2 OH n} D 20 = 1.2880 1,1,1,3,3,3- hexafluoro-2-phenyl 2-propanol _{C 6 H 5 C (CF 3} ) 2 OH n D 20 = 1.2750 2,2,3,3,4,4,4- heptafluoro-1-butanol CF ₃ CF ₂ CF ₂ CH ₂ OH n _D ²⁰ = 1.3000.

R ₁ : When an amine is used as a starting material, the following may be mentioned.

CF ₃ CH ₂ NH ₂ 2,2,2-trifluoroethylamine FC ₆ H ₄ NH ₂ 2-fluoroaniline 3-fluoroaniline 4-fluoroaniline FC ₆ H ₃ (OCH ₃ ) NH ₂ 3-fluoro- o- aniline 3-fluoro -p- aniline _{FC 6 H 4 CH 3 NH 2} 2- fluoro - benzylamine 3-fluoro - benzylamine 4-fluoro - benzylamine 2-fluoro-4-iodoaniline, 2-fluoro-4-methyl Aniline, 2-fluoro-5-methylalanine, 3-
Fluoro-2-methylaniline, 3-fluoro-4-methylaniline, 4-fluoro-2-methylaniline, 5-fluoro-2-methylaniline, 2-fluoro-5-nitroaniline, 4-fluoro-2nitroaniline, 4-fluoro-3nitro Aniline, 3-fluoro-phenethylamine, 2,3-difluoroaniline, 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 3,5
-Difluoroaniline,
.

2,4-difluorobenzylamine, 2,
5-difluorobenzylamine, 2,6-difluorobenzylamine, 3,4-difluorobenzylamine,
2,3,4-trifluoroaniline, 2,3,6-trifluoroaniline, 2,4,5-trifluoroaniline, 2,4,6-trifluoroaniline, 2,2,2-
Trifluoroethylamine, 3-trifluoromethoxyaniline, 4-trifluoromethoxyaniline, 2-trifluoromethylbenzylamine, 3-trifluoromethylbenzylamine, 4-trifluoromethylbenzylamine.

2,3,4,5-tetrafluoroaniline, 2,3,5,6-tetrafluoroaniline, α,
α, α, 4-tetrafluoro-o-toluidine, α,
α, α-4-tetrafluoro-m-toluidine, α,
α, α-6-tetrafluoro-m-toluidine, α,
α, α-2-tetrafluoro-m-toluidine, α,
α, α-5-tetrafluoro-m-toluidine, α,
α, α-6-tetrafluoro-o-toluidine, 2,
3,4,5,6-Pentafluoroaniline Particularly preferably, one containing no aromatic ring is preferred for lowering the refractive index. R ₂ is a hydrocarbon group, and the starting material is preferably a diisocyanate compound. For example, the following are mentioned.

[0017]

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In particular, for lowering the refractive index, an HDI having an aromatic ring-free n _D ²⁰ of 1.4520 and an IDI of 1.483 is preferred.
PDI, HMDI, TMHMDI are preferred. R ₃ may be any as long as it is a (meth) acrylate group having a polymerizable unsaturated group. When hydroxy (meth) acrylate is used as a starting material, the following may be mentioned.

[0019]

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Hydroxybutyl acrylate, 4-hydroxycyclohexyl acrylate, 5-hydroxycyclooctyl acrylate, 5-hydroxycyclooctyl methacrylate, 2-hydroxy-3-phenyloxypropyl acrylate

[0021]

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Hereinafter, the method for producing the novel urethane compound of the present invention will be described. First, in the first step, a diisoanate compound [A], one or more fluorine atoms, and a hydroxyl group-containing compound [B] are reacted at a molar ratio of 1: 1. It is also effective to mix both reaction components and heat to 40 to 100 ° C.

As the solvent for the mixture, a monomer which is active against ionizing radiation may be used, but it is preferable to react in a solvent having no reactivity with isocyanate groups, or to react in a solvent-free state. You may. In this reaction system, an amine compound,
A catalyst such as an organotin compound may be added, and triethylamine, piperazine, triethanolamine, dibutyltin dilaurate, tin octoate, tin laurate,
Dioctyltin dilaurate or the like can be used.

Further, as a second step, the compound [C] obtained in the first step and the radically polymerizable compound [D] having a hydroxyl group at the terminal are combined while protecting the double bond in [D]. Let react. At this time, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, and 2,6-di-t-butyl-p-cresol may be added in an amount of about 10 to 1000 ppm.

[0025]

The novel urethane compound of the present invention acts as an ionizing radiation-curable urethane compound or a composition by itself or by mixing other additives and compounding agents. Further, by containing one or more fluorines, the refractive index becomes a low refractive index of 1.45 or less. The present compound is used as a hologram forming method in Japanese Patent Application No. 3-104.
No. 183, a recording medium comprising a matrix polymer, a photopolymerizable compound, and a photoinitiator is exposed to interference fringes of laser light, and then the recording medium contains a compound capable of photopolymerization or heat polymerization. Immersed in a developer
Then, it is useful as a host monomer or a guest monomer used in a method of curing a recording medium by heat or light, or as a coating agent for an optical fiber. In particular, when the hologram is used as a guest monomer in the hologram forming method, it has an advantage that it is easily incorporated into a binder due to flexibility due to urethane bonds.

[0026]

EXAMPLES Specific examples of the novel urethane compound of the present invention and the method for producing the same will now be described with reference to Examples. Example 1 Into a 500 ml four-neck flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel, 22.2 g (1 mol) of isophorone diisocyanate and dilaurylic acid were added.
0.1 ml of di-N-butyltin and 45 g of acetone were charged, and 10.0 g (1 mol) of 2,2,2-trifluoroethanol was added dropwise at a temperature of 60 ° C. 60 ° C after dropping
Was maintained for 2 hours while stirring.

The IR spectrum of the obtained substance measured by an infrared spectrophotometer was 2330 cm for isophorone diisocyanate as a raw material as shown in FIG.
^-1 isocyanate group is reduced, and -CH ₂ having high reactivity among two isocyanate groups It is presumed that alcohol selectively reacted with -N = C = O side.

Further, 11.6 g (1 mol) of 2-hydroxyethyl acrylate and 0.01 g of hydroquinone were added dropwise under the same conditions and stirred for 5 hours. Thus IR spectrum of the resulting solution distilled under reduced pressure to remove the acetone material as shown in FIG. 1 (b), the isocyanate groups of 2330Cm ^-1 has completely disappeared, and,

[0029]

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Had an absorption. Also, the obtained sample was dissolved in methanol, and filtered with a filter.
Liquid chromatography (Shimadzu LC-9)
A, LC-8A) showed no unreacted isophorone diisocyanate, 2,2,2-trifluoroethanol, or 2-hydroxyethyl acrylate, and showed almost a single peak. further,
Mass spectrometer (Shimadzu GCMS-QP200
Analyzed by A). FIG. 2 shows the obtained spectrum. From the above results, the obtained substance was represented by the chemical structural formula:

[0031]

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It was confirmed that the compound was a urethane compound corresponding to The refractive index n _D ²⁰ was 1.45. A matrix polymer and a photopolymerizable compound,
After exposing the recording medium comprising a photoinitiator to interference fringes of laser light, the recording medium is immersed in a developer containing a light or heat polymerizable compound, and then the recording medium is cured by heat or light. When used as a guest monomer under the following conditions, good results were obtained.

The conditions for forming the hologram are shown below. Polyvinyl carbazole (manufactured by Anan Sangyo Co., Ltd., Tubicol No. 210), tribromophenol methacrylate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., BR-31M) 3,3 ′, 4,4′-tetra (t-butyl) A composition comprising peroxycarbonylbenzophenone squarylium dye was formed into a photosensitive film, and a 633 nm He-N
Interference fringes were recorded with an e-laser. This film was immersed in a 50% acetone solution of the urethane compound of the present invention for 30 seconds. As a result, the diffraction efficiency was 53% and the peak wavelength was 730n.
m, which was bright and shifted by a long wavelength.

Example 2 Instead of 2,2,2-trifluoroethanol in Example 1, 1,1,1,3,3,3-hexafluoro-2-
A similar synthesis was performed using phenyl-2-propanol. In the same manner as in Example 1, the reaction product of the first step and the second step
FIG. 3 shows an IR spectrum of the reaction product of the step.

[0035]

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A urethane compound corresponding to the above was obtained. The refractive index n _D ²⁰ was 1.44.

When used as a guest monomer for forming a hologram, the diffraction efficiency was 62% and the peak wavelength was 7%.
A bright one with a long wavelength shift of 40 nm was obtained.

Comparative Example 1 The following urethane acrylate containing no fluorine as a guest monomer

[0039]

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In the case where is used, the diffraction efficiency was 43% because the refractive index n _D ²⁰ was as high as 1.49.

Comparative Example 2 When a fluorine-containing acrylate heptadecafluoropropyl acrylate, which is not urethane, was used as the guest monomer, the diffraction peak wavelength hardly shifted to 640 nm.

[0042]

The novel urethane compound of the present invention is cured by irradiation with ionizing radiation, has a low refractive index and has flexibility, and is useful as a coating material for hologram recording materials and optical fibers.

Further, according to the method for producing a urethane compound of the present invention, a urethane compound having the above properties can be obtained reliably and easily.

[Brief description of the drawings]

FIG. 1 is a view for explaining an IR spectrum showing one example of a novel urethane compound of the present invention.

FIG. 2 is a view for explaining a mass spectrometry spectrum showing one example of the novel urethane compound of the present invention.

FIG. 3 is a view for explaining an IR spectrum showing another example of the novel urethane compound of the present invention.

Claims (1)

(57) [Claims] 1. A hologram-forming material represented by the following general formula (1). Embedded image In the formula, R ₁ is a hydrocarbon group containing fluorine R ₂ is a hydrocarbon group R ₃ is a (meth) acrylate group having a polymerizable unsaturated group