Visible light photoinitiating system for preparing high diffraction efficiency hologram optical polymer material

Abstract

The present invention provides a visible light photoinitiating system for preparing a holographic photopolymer material with high-diffraction efficiency. The photoinitiating system comprises a photosensitizer and a co-initiator, and its mechanism is that the photosensitizer transforms from ground state to excited state after absorbing photons, and then interacts with the co-initiator through transfer of electrons and protons, which produces an alkyl (or aryl) free radical R and a ketyl radical K; wherein the free radical R initiates the addition polymerization of monomers that are capable of free radical polymerization, whereas the radical K inhibits the chain propagation of the macromolecular free radicals to a certain degree due to the steric hindrance effect, and thus delays the gelation time of the photopolymerization, which helps to increase the phase separation between the polymer and the functional components. A holographic photopolymer material with high-diffraction efficiency can be obtained by employing this visible light photoinitiating system.

Claims

1. A visible light photoinitiating system, comprising a photosensitizer and a co-initiator, within which system an alkyl or aryl free radical for initiating photopolymerization and a ketyl radical for inhibiting photopolymerization are generated upon exposure to a single laser beam, wherein said photosensitizer comprises one or more selected from the group consisting of C1, C2, C3, C4, and C5, said C1, C2, C3, C4, and C5 having the following structures, respectively: ##STR00002## wherein substitutes R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R6 may be same or different, and may be jointly, respectively or independent, and of SH, CN, NO.sub.2, C.sub.nH.sub.2n+1 (n0 to 8), C.sub.nH.sub.2n+1O (n=0 to 8), N(C.sub.nH.sub.2n+1).sub.2 (n=0 to 8), phenyl, thienyl, and thiazolyl.

2. The photoinitiating system according to claim 1, wherein a ratio by mass of the photosensitizer to the co-initiator is between 20:1 and 1:20.

3. The visible light photoinitiating system according to claim 1, wherein said co-initiator comprises one or more selected from the group consisting of N,N,N-triethylamine, N-Methyl maleimide, N-ethyl maleimide, triethanolamine N-phenyl glycine, acetyl phenyl glycine, p-chlorophenyl glycine, 3-bromine phenyl glycine, 3-nitrile phenyl glycine, N-phenyl glycine ethyl ester, 2,4,6-tri(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxy phenyl)-4,6-bi(trichloromethyl)-1,3,5-triazine.

4. The visible light photoinitiating system according to claim 1, wherein C2 is other than 3-acetylcoumarin.

5. The visible light photoinitiating system according to claim 1, wherein said photosensitizer comprises at least one photosensitizer or photosensitizer combination selected from the group consisting of: C1 and C2 in the proportion of 1:2, wherein R.sub.1R.sub.4N(C.sub.2H.sub.5).sub.2 and R.sub.2R.sub.3H); C2 and C4 in the proportion of 2:3, wherein R.sub.1C.sub.8H.sub.17, R.sub.2=thiazolyl, and R.sub.3OH; C3, wherein R.sub.1C.sub.8H.sub.17O, R.sub.2NH.sub.2, and R.sub.3=thienyl; C4, wherein R.sub.1N(C.sub.8H.sub.17).sub.2, R.sub.2NO.sub.2, and R.sub.3H; and C1 and C5 in the proportion of 1:1, wherein R.sub.1=phenyl, R.sub.2R.sub.3R.sub.5H, R.sub.4CN, and R.sub.6SH.

6. The visible light photoinitiating system according to claim 1, in combination with a non-epoxy polymerizable material.

7. The visible light photoinitiating system according to claim 5, wherein the non-epoxy polymerizable material comprises one or more selected from the group consisting of methyl methacrylate, methyl acrylamide, N-vinyl pyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, N-isopropyl acrylamide, ethylene dimethacrylate, trimethylolpropane trimethacrylate, N-vinyl carbazole, pentaerythritol tetraacrylate, and methylene diacrylamide.

8. The visible light photoinitiating system according to claim 1, wherein the laser beam has a wavelength of 441.6 nm.

Description

PARTICULAR EMBODIMENTS

Embodiment 1

(1) Add the visible light photoinitiating system (1:10 of photosensitizer to co-initiator by mass) consisting of a 0.1 wt % photosensitizer (C1 and C2 are in the proportion of 1:2; R.sub.1R.sub.4N(C.sub.2H.sub.5).sub.2, R.sub.2R.sub.3H) and a 1 wt % co-initiator (N,N,N-triethylamine, N-Methyl maleimide, and 3-bromine phenyl glycine in the proportion of 1:2:3) to the mixture system which consists of 70 wt % monomers (methyl methacrylate, methyl acrylamide, and N-vinyl pyrrolidone in the proportion of 1:3:1) and a 30 wt % polyvinyl alcohol agglomerant. Then, mix them ultrasonically to become a homogeneous emulsion and make a thin film of 20 m thick from the emulsion. Place the film into a 441.6 nm laser interference field for 30 seconds of holographic exposure at the exposure intensity of 50 mW/cm.sup.2 to obtain a holographic photopolymer material with a grating interval of 1 m and diffraction efficiency of 29%.

Embodiment 2

(2) Add the visible light photoinitiating system (10:1 of photosensitizer to co-initiator by mass) consisting of a 1 wt % photosensitizer (C2 and C4 in the proportion of 2:3; R.sub.1C.sub.8H.sub.17, R.sub.2=thiazolyl, and R.sub.3OH) and a 0.1 wt % co-initiator (N-ethyl maleimide, N-phenyl glycine, and 2,4,6-tri(trichloromethyl)-1,3,5-triazine in the proportion of 2:2:1) to the mixture system, which consists of 70 wt % monomers (butyl acrylate, 2-Ethylhexyl acrylate, and N-isopropyl acrylamide in the proportion of 1:2:1) and a 30 wt % polyvinyl alcohol agglomerant. Then, agitate them ultrasonically to become a homogeneous emulsion and make a thin film of 20 m thick from the emulsion. Place the film into a 441.6 nm laser interference field for 30 seconds of holographic exposure at the exposure intensity of 50 mW/cm.sup.2 to obtain a holographic photopolymer material with a grating interval of 1 m and diffraction efficiency of 90%.

Embodiment 3

(3) Add the visible light photoinitiating system (20:1 of photosensitizer to co-initiator by mass) consisting of a 10 wt % photosensitizer C3 (R.sub.1C.sub.8H.sub.17O, R.sub.2NH.sub.2, and R3=thienyl) and a 0.5 wt % co-initiator (triethanolamine, acetyl phenyl glycine, and 3-nitrile phenyl glycine in the proportion of 2:1:1) to the mixed system, which consists of 60 wt % monomers (ethylene dimethacrylate, trimethylolpropane trimethacrylate, and vinyl carbazole in the proportion of 1:1:4) and a 29.5 wt % polyvinyl alcohol agglomerant. Then, mix them ultrasonically to become a homogeneous emulsion and make a thin film of 20 m thick. Place the film into a 441.6 nm laser interference field for 30 seconds of holographic exposure at the exposure intensity of 50 mW/cm.sup.2 to obtain a holographic photopolymer material with a grating interval of 1 m and diffraction efficiency of 80%.

Embodiment 4

(4) Add the visible light photoinitiating system (1:20 of photosensitizer to co-initiator by mass) consisting of a 0.5 wt % photosensitizer C4 (R.sub.1N(C.sub.8H.sub.17).sub.2, R.sub.2NO.sub.2, R.sub.3H) and a 10 wt % co-initiator (p-chlorophenyl glycine, N-phenyl glycine ethyl ester, and 2-(4-methoxy phenyl)-4,6-bi(trichloromethyl)-1,3,5-triazine in the proportion of 1:1:1) to the mixture system, which consists of 60 wt % monomers (N-vinyl carbazole, pentaerythritol tetraacrylate, and methylene diacrylamide in the proportion of 3:1:4) and a 29.5 wt % polyvinyl alcohol agglomerant. Then, mix them ultrasonically to become a homogeneous emulsion and make a thin film of 20 m thick from the emulsion. Place the film into a 441.6 nm laser interference field for 30 seconds of holographic exposure at the exposure intensity of 50 mW/cm.sup.2 to obtain a holographic photopolymer material with a grating interval of 1 m and diffraction efficiency of 76%.

Embodiment 5

(5) Add the visible light photoinitiating system (1:4 of photosensitizer to co-initiator by mass) consisting of a 2 wt % photosensitizer (C1 and C5 in the proportion of 1:1; R.sub.1=phenyl, R.sub.2R.sub.3R.sub.5H, R.sub.4CN, R.sub.6SH) and a 8 wt % co-initiator (p-chlorophenyl glycine, N-phenyl glycine ethyl ester, and 2-(4-methoxy phenyl)-4,6-bi(trichloromethyl)-1,3,5-triazine in the proportion of 1:1:1) to the mixture system, which consists of 60 wt % monomers (butyl acrylate, 2-Ethylhexyl acrylate, and N-vinyl carbazole in the proportion of 1:2:4) and a 30 wt % polyvinyl alcohol agglomerant. Then, mix them ultrasonically to become a homogeneous emulsion and make a thin film of 20 m thick from the emulsion. Place the film into a 441.6 nm laser interference field for 30 seconds of holographic exposure at the exposure intensity of 100 mW/cm.sup.2 to obtain a holographic photopolymer material with a grating interval of 1 m and diffraction efficiency of 89%.

Embodiment 6

(6) Add the visible light photoinitiating system (1:20 of photosensitizer to co-initiator by mass) consisting of a 0.5 wt % photosensitizer C4 (R.sub.1N(C.sub.8H.sub.17).sub.2, R.sub.2NO.sub.2, R.sub.3H) and a 10 wt % co-initiator (N-phenyl glycine ethyl ester) to the mixture system, which consists of 60 wt % monomers (N-vinyl carbazole, pentaerythritol tetraacrylate, and methylene diacrylamide in the proportion of 3:1:4) and a 29.5 wt % polyvinyl alcohol agglomerant. Then, mix them ultrasonically to become a homogeneous emulsion and make a thin film of 20 m thick. Place the film into a 441.6 nm laser interference field for 30 seconds of holographic exposure at the exposure intensity of 50 mW/cm.sup.2 to obtain a holographic photopolymer material with a grating interval of 1 m and diffraction efficiency of 86%.