A modified fluorine-containing novolac epoxy resin, a preparation method thereof, a photoresist solution, and an optical waveguide device

Abstract

The application provides a modified fluorine-containing phenolic epoxy resin, a preparation method thereof, a photoresist solution and an optical waveguide device, and belongs to the field of optical waveguide materials. The alkyl chain or -C-F- chain increases the flexibility of the modified fluorine-containing phenolic epoxy resin. The optical absorption of the C-F bond is small, so when the fluorine-containing organic acid is used for modification, the fluorine content of the resin is further increased, the proportion of C-H bonds is further reduced, the optical transparency of the material in the optical communication waveband is increased, and the absorption loss is reduced, and the prepared optical waveguide device can be directly used in an optical interconnection device. The technical route disclosed by the application has a simple reaction process, has low requirements on equipment, and can be used for large-scale industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of optical waveguide materials, and particularly relates to a modified fluorine-containing phenolic epoxy resin, a preparation method thereof, a photoresist solution and an optical waveguide device. BACKGROUND

[0002] Low transmission loss optical waveguide material is one of the core materials in optical communication and optical interconnection technology. However, the photoresist of the phenolic epoxy resin series commonly used to prepare optical waveguide materials at present is mostly a rigid structure molecule, and the prepared optical waveguide material has the disadvantages of poor material toughness, high optical loss and the like, and is prone to end face cracking in the subsequent device polishing and polishing process, which also leads to large end face coupling loss of the optical communication device. Moreover, with the development of flexible electronic technology, the optical waveguide material needs to have a certain flexibility, and the rigid structure of the phenolic epoxy resin cannot be applied to the field of flexible optical waveguide. SUMMARY

[0003] The present application provides a modified fluorine-containing phenolic epoxy resin, a preparation method thereof, a photoresist solution and an optical waveguide device, and the modified fluorine-containing phenolic epoxy resin has excellent flexibility and low transmission loss.

[0004] The present application provides a modified fluorine-containing phenolic epoxy resin, which has a structural formula shown in Formula I:

[0005] Formula I;

[0006] The R includes -COC x H 2x+1 , -COC x F 2x+1 or -COC x H 2x+1 C y F 2y+1 ;

[0007] The x = 0-15, and the y = 0-15.

[0008] The n is greater than or equal to 1.

[0009] Preferably, the n = 3-10.

[0010] The present application also provides a preparation method of the modified fluorine-containing phenolic epoxy resin described in the above technical solution, which comprises the following steps:

[0011] The acid, the hexafluorobisphenol A type phenolic epoxy resin, the alkaline catalyst and the polar organic solvent are mixed and then subjected to grafting reaction to obtain the modified fluorine-containing phenolic epoxy resin.

[0012] The chemical formula of the acid includes CH 2x+1 COOH, CF 2x+1COOH or CH 2x+1 C y F 2y+1 COOH.

[0013] Preferably, the number average molecular weight of the hexafluorobisphenol A type novolac epoxy resin is 500-3000, the polymerization degree is 3-10, the epoxy equivalent weight is 220-500 g / mol, and the softening point is 65-70℃.

[0014] Preferably, the ratio of the amount of substance of the acid to the amount of substance of the epoxy group in the hexafluorobisphenol A type novolac epoxy resin is 0.1-0.8:1.

[0015] Preferably, the basic catalyst comprises one or more of NaOH, KOH, LiOH, aniline, benzylamine, NBu4Br, NBu4F, NBu4OH, and NMe4OH.

[0016] Preferably, the molar ratio of the acid to the basic catalyst is 0.5-10:1.

[0017] Preferably, the polar organic solvent comprises one or more of dichloromethane, petroleum ether, ethyl acetate, butyl acetate, toluene, xylene, butanone, cyclopentanone, ethylene glycol methyl ether, and propylene glycol methyl ether.

[0018] The present application also provides a photoresist solution comprising the following raw materials in mass fraction:

[0019] Modified fluorine-containing novolac epoxy resin 70-75%;

[0020] Photoinitiator 0.7-1%;

[0021] Polar organic solvent 23-28%;

[0022] The modified fluorine-containing novolac epoxy resin is one or more of the modified fluorine-containing novolac epoxy resins described in the above technical solution or one or more of the modified fluorine-containing novolac epoxy resins prepared by the preparation method described in the above technical solution.

[0023] Preferably, the photoinitiator comprises one or more of iodonium salt, triphenyl sulfonium phosphate salt, triphenyl sulfonium antimony salt, triphenyl sulfonium triflate salt, and triphenyl sulfonium mesylate salt.

[0024] The present application also provides an optical waveguide device comprising an upper cladding layer, a core layer, and a lower cladding layer stacked in sequence.

[0025] The preparation raw materials of the upper cladding layer comprise the following in mass fraction:

[0026] First modified fluorine-containing novolac epoxy resin 70-75%;

[0027] The mass content of the first modified fluorine-containing phenolic epoxy resin in the upper cladding layer is greater than the mass content of the third modified fluorine-containing phenolic epoxy resin in the lower cladding layer.

[0028] The first photoinitiator is 0.7-1%;

[0029] The first polar organic solvent is 23-28%;

[0030] The raw materials for preparing the core layer include, in mass fraction:

[0031] The second modified fluorine-containing phenolic epoxy resin is 70-75%;

[0032] The second photoinitiator is 0.7-1%;

[0033] The second polar organic solvent is 20-28%;

[0034] The raw materials for preparing the lower cladding layer include, in mass fraction:

[0035] The third modified fluorine-containing phenolic epoxy resin is 70-75%;

[0036] The third photoinitiator is 0.7-1%;

[0037] The third polar organic solvent is 20-28%;

[0038] The first modified fluorine-containing phenolic epoxy resin, the second modified fluorine-containing phenolic epoxy resin and the third modified fluorine-containing phenolic epoxy resin are independently one or more of the modified fluorine-containing phenolic epoxy resins described in the above technical solution or one or more of the modified fluorine-containing phenolic epoxy resins prepared by the preparation method described in the above technical solution; and the refractive index of the second modified fluorine-containing phenolic epoxy resin is higher than that of the third modified fluorine-containing phenolic epoxy resin.

[0039] The alkyl chain or -C-F- chain increases the flexibility of the modified fluorine-containing phenolic epoxy resin. The optical absorption of the C-F bond is small, so when modified with a fluorine-containing organic acid, the fluorine content of the resin is further increased, the proportion of C-H bonds is further reduced, thereby increasing the optical transparency of the material in the optical communication waveband, reducing the absorption loss, and the prepared optical waveguide device can be directly used in optical interconnection devices.

[0040] The fluorine content of the modified fluorine-containing phenolic epoxy resin of the present application can be adjusted as needed, and the refractive index can also be adjusted, so that the refractive index range of the resin is larger, and the numerical aperture is better matched.

[0041] The technical route described in the present application has a simple reaction process and does not require high equipment, and can be mass-produced for industrialization.

[0042] Since the performance of waveguide devices in optical communication has different requirements, and the price of fluoric acid is generally high, when the performance of optical devices is not high in the field of device use, the alkyl chain organic acid without fluorine or with low fluorine content is selected to modify the resin, so as to reduce the production cost of photoresist. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 NMR spectra of hexafluorobisphenol A type phenolic epoxy resin grafted by different kinds of alkyl chain carboxylic acids;

[0044] Figure 2 Infrared spectra of hexafluorobisphenol A type phenolic epoxy resin grafted by different proportions of perfluoropentanoic acid;

[0045] Figure 3 UV-visible near infrared spectra of resins modified by different kinds of perfluorocarboxylic acids. DETAILED DESCRIPTION

[0046] The application provides a modified fluorine-containing phenolic epoxy resin, which has a structural formula shown in formula I.

[0047] Formula I;

[0048] The R includes -COC x H 2x+1 , -COC x F 2x+1 or -COC x H 2x+1 C y F 2y+1 ;

[0049] The x is 0-15, and the y is 0-15.

[0050] The n is greater than or equal to 1.

[0051] In specific embodiments of the application, the n is preferably 3-10, and in specific embodiments of the application, the n can be 3, 4, 5, 6, 7, 8, 9 or 10.

[0052] In specific embodiments of the application, the x can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15; and the y can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15.

[0053] The application also provides a preparation method of the modified fluorine-containing phenolic epoxy resin.

[0054] The modified fluorine-containing phenolic epoxy resin is obtained by grafting reaction after mixing the acid, hexafluorobisphenol A type phenolic epoxy resin, basic catalyst and polar organic solvent.

[0055] The chemical formula of the acid comprises C x H 2x+1 COOH, C x F 2x+1 COOH or C x H 2x+1 C y F 2y+1 COOH.

[0056] In the present application, the ratio of the amount of substance of the acid to the amount of substance of the epoxy group in the hexafluorobisphenol A type phenolic epoxy resin is preferably 0.1-0.8:1, and in specific embodiments of the present application, the molar ratio of the acid to the hexafluorobisphenol A type phenolic epoxy resin can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1 or 0.8:1; the chemical formula of the acid comprises C x H 2x+1 COOH, C x F 2x+1 COOH or C x H 2x+1 C y F 2y+1 COOH; the acid preferably comprises one or more of butyric acid, hexanoic acid, perfluorobutyric acid, perfluorohexanoic acid, perfluorooctanoic acid, heptafluorooctanoic acid, heptanoic acid, perfluoroheptanoic acid and heptafluoroheptanoic acid; the epoxy equivalent weight of the hexafluorobisphenol A type phenolic epoxy resin is preferably 220-500 g / mol, the softening point is preferably 65-70°C, the molecular weight is preferably 500-3000, and the polymerization degree is preferably 3-10, and in specific embodiments of the present application, the epoxy equivalent weight can be 220 g / mol, 250 g / mol, 280 g / mol, 300 g / mol, 350 g / mol, 400 g / mol, 450 g / mol, 480 g / mol or 500 g / mol, the softening point can be 65°C, 66°C, 67°C, 68°C, 69°C or 70°C, the molecular weight can be 500, 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800 or 3000, and the polymerization degree can be 3, 4, 5, 6, 7, 8, 9 or 10.

[0057] In the present application, the molar ratio of the acid to the basic catalyst is preferably 0.5-10:1, and in specific embodiments of the present application, the molar ratio can be 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1; the basic catalyst preferably includes one or more of NaOH, KOH, LiOH, aniline, benzylamine, NBu4Br, NBu4F, NBu4OH and NMe4OH.

[0058] In the present application, the solid-liquid ratio of the hexafluorobisphenol A type novolac epoxy resin to the polar organic solvent is preferably 4g:9mL; the polar organic solvent preferably includes one or more of dichloromethane, petroleum ether, ethyl acetate, butyl acetate, toluene, xylene, butanone, cyclopentanone, ethylene glycol methyl ether and propylene glycol methyl ether.

[0059] In the present application, the temperature of the grafting reaction is preferably 80-120℃, and the time is preferably 2-10h, and in specific embodiments of the present application, the temperature of the grafting reaction can be 80℃, 90℃, 100℃, 110℃ or 120℃, and the time can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.

[0060] In the present application, the grafting reaction is preferably carried out in a protective atmosphere, and the protective atmosphere preferably includes nitrogen.

[0061] In the present application, the grafting reaction is preferably carried out under stirring.

[0062] After the grafting reaction, the present application preferably further includes: washing, concentrating the product obtained by the grafting reaction, then mixing the obtained solid with hydrochloric acid to neutralize the basic catalyst, and after solid-liquid separation, washing, drying the obtained solid.

[0063] The present application also provides a photoresist solution, which includes the following raw materials in mass fraction:

[0064] Modified fluorine-containing novolac epoxy resin 70-75%;

[0065] Photoinitiator 0.7-1%;

[0066] Polar organic solvent 23-28%;

[0067] The modified fluorine-containing novolac epoxy resin is one or more of the modified fluorine-containing novolac epoxy resins described in the above technical solution or one or more of the modified fluorine-containing novolac epoxy resins prepared by the preparation method described in the above technical solution.

[0068] In the present application, the raw material of the photoresist solution includes 70-75% of modified fluorine-containing phenolic epoxy resin by mass fraction, and specifically can be 70%, 71%, 72%, 73%, 74% or 75%.

[0069] In the present application, the raw material of the photoresist solution includes 0.7-1% of photoinitiator by mass fraction, and in the specific embodiments of the present application, the mass fraction of the photoinitiator in the raw material of the photoresist solution can be 0.7%, 0.8%, 0.9% or 1%; the photoinitiator preferably includes one or more of iodonium salt, triphenyl sulfonium phosphate, triphenyl sulfonium antimony salt, triphenyl sulfonium triflate and triphenyl sulfonium mesylate.

[0070] In the present application, the raw material of the photoresist solution includes 23-28% of polar organic solvent by mass fraction, and specifically can be 23%, 24%, 25%, 26%, 27% or 28%; the polar organic solvent preferably includes one or more of dichloromethane, petroleum ether, ethyl acetate, butyl acetate, toluene, xylene, butanone, cyclopentanone, ethylene glycol methyl ether and propylene glycol methyl ether.

[0071] The present application also provides an optical waveguide device comprising an upper cladding layer, a core layer and a lower cladding layer which are sequentially laminated;

[0072] The preparation raw material of the upper cladding layer includes, by mass fraction:

[0073] 70-75% of the first modified fluorine-containing phenolic epoxy resin;

[0074] The mass content of the first modified fluorine-containing phenolic epoxy resin in the upper cladding layer is greater than the mass content of the third modified fluorine-containing phenolic epoxy resin in the lower cladding layer;

[0075] 0.7-1% of the first photoinitiator;

[0076] 23-28% of the first polar organic solvent;

[0077] The preparation raw material of the core layer includes, by mass fraction:

[0078] 70-75% of the second modified fluorine-containing phenolic epoxy resin;

[0079] 0.7-1% of the second photoinitiator;

[0080] 23-28% of the second polar organic solvent;

[0081] The preparation raw material of the lower cladding layer includes, by mass fraction:

[0082] 70-75% of the third modified fluorine-containing phenolic epoxy resin;

[0083] Third photoinitiator 0.7~1%;

[0084] Third polar organic solvent 23~28%;

[0085] The first modified fluorine-containing phenolic epoxy resin, the second modified fluorine-containing phenolic epoxy resin and the third modified fluorine-containing phenolic epoxy resin are independently one or more of the modified fluorine-containing phenolic epoxy resins described in the above technical solution or one or more of the modified fluorine-containing phenolic epoxy resins prepared by the preparation method described in the above technical solution; and the refractive index of the second modified fluorine-containing phenolic epoxy resin is higher than that of the third modified fluorine-containing phenolic epoxy resin.

[0086] In the present application, the resin type of the first modified fluorine-containing phenolic epoxy resin is preferably the same as that of the third modified fluorine-containing phenolic epoxy resin.

[0087] In the present application, the mass fraction of the first modified fluorine-containing phenolic epoxy resin, the second modified fluorine-containing phenolic epoxy resin and the third modified fluorine-containing phenolic epoxy resin is preferably independently the mass fraction of the modified fluorine-containing phenolic epoxy resin in the photoresist solution.

[0088] The type and mass fraction of the first photoinitiator, the second photoinitiator and the third photoinitiator are preferably independently the type and mass fraction of the photoinitiator in the photoresist solution.

[0089] The type and mass fraction of the first polar organic solvent, the second polar organic solvent and the third polar organic solvent are preferably independently the type and mass fraction of the modified fluorine-containing phenolic epoxy resin in the photoresist solution.

[0090] The present application also provides a preparation method of the optical waveguide device described in the above technical solution, which preferably comprises the following steps:

[0091] After mixing the preparation raw materials of the lower cladding layer, the lower cladding layer is formed on the substrate by first baking, first exposure and first curing.

[0092] After mixing the preparation raw materials of the core layer, the core layer is formed on the surface of the lower cladding layer by second baking, second exposure, third curing, development, washing, drying and fourth curing.

[0093] After mixing the preparation raw materials of the upper cladding layer, the upper cladding layer is formed on the surface of the core layer by third baking, third exposure and fifth curing, thereby obtaining the optical waveguide device.

[0094] In the present application, the preparation raw materials of the lower cladding layer are mixed and then coated on the substrate, and then the lower cladding layer is formed by first baking, first exposure and first curing.

[0095] In the present application, the substrate preferably includes a silicon wafer, an epoxy plate, glass, a polyimide or a polyester resin plate.

[0096] In the present application, the coating preferably includes pouring the preparation material of the lower clad layer onto the substrate and then placing it in a spin coater to perform the coating.

[0097] In the present application, the rotation speed of the spin coater is preferably 300-3000 r / min, and in a specific embodiment of the present application, the rotation speed can be 300 r / min, 500 r / min, 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, 2000 r / min, 2500 r / min or 3000 r / min.

[0098] In the present application, the temperature of the first baking is preferably 90°C, and the time is preferably 10-60 min, and in a specific embodiment of the present application, the time of the first baking can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.

[0099] After the first baking, the present application preferably restores the optical waveguide material obtained after the first baking to room temperature before the first exposure.

[0100] In the present application, the wavelength of the light used for the first exposure is preferably 365 nm, the light intensity is preferably 20 mW / cm 2 , and the irradiation time is preferably 0.1-60 s, and in a specific embodiment of the present application, the irradiation time can be 0.1 s, 5 s, 10 s, 20 s, 30 s, 40 s, 50 s or 60 s.

[0101] In the present application, the temperature of the first curing is preferably 90°C, and the time is preferably 10-60 min, and in a specific embodiment of the present application, the time of the first curing can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.

[0102] After the formation of the lower clad layer, the present application mixes the preparation material of the core layer, coats it on the surface of the lower clad layer, performs the second baking, the second exposure, the third curing, the development, the washing, the drying and the fourth curing to form the core layer.

[0103] In the present application, the coating preferably includes pouring the preparation material of the core layer onto the surface of the lower clad layer and then placing it in a spin coater to perform the coating.

[0104] In the present application, the rotation speed of the homogenizer is preferably 300-3000 r / min, and in specific embodiments of the present application, the rotation speed can be 300 r / min, 500 r / min, 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, 2000 r / min, 2500 r / min or 3000 r / min.

[0105] In the present application, the temperature of the second baking is preferably 90°C, and the time is preferably 10-60 min, and in specific embodiments of the present application, the time of the second baking can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.

[0106] After the second baking and before the second exposure, the present application preferably restores the optical waveguide material obtained after the second baking to room temperature.

[0107] In the present application, the wavelength of the light used for the second exposure is preferably 365 nm, the light intensity is preferably 20 mW / cm 2 , and the irradiation time is preferably 0.1-60 s, and in specific embodiments of the present application, the irradiation time can be 0.1 s, 5 s, 10 s, 20 s, 30 s, 40 s, 50 s or 60 s.

[0108] In the present application, the second exposure is performed under the action of a mask plate.

[0109] In the present application, the temperature of the third curing is preferably 90°C, and the time is preferably 10-60 min, and in specific embodiments of the present application, the time of the third curing can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.

[0110] In the present application, the temperature of the fourth curing is preferably 90°C, and the time is preferably 10-60 min, and in specific embodiments of the present application, the time of the fourth curing can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.

[0111] After the formation of the core layer, the present application mixes the preparation raw materials of the upper cladding layer, coats them on the surface of the core layer, performs third baking, third exposure and fifth curing, forms the upper cladding layer, and obtains the optical waveguide device

[0112] In the present application, the coating preferably comprises pouring the preparation raw materials of the upper cladding layer onto the surface of the core layer and then placing them in a homogenizer for coating.

[0113] In the present application, the rotation speed of the homogenizer is preferably 300-3000 r / min, and in specific embodiments of the present application, the rotation speed can be 300 r / min, 500 r / min, 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, 2000 r / min, 2500 r / min or 3000 r / min.

[0114] In the present application, the temperature of the third baking is preferably 90°C, and the time is preferably 10-60 min, and in specific embodiments of the present application, the time of the third baking can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.

[0115] After the third baking and before the third exposure, the present application preferably restores the optical waveguide material obtained after the third baking to room temperature.

[0116] In the present application, the wavelength of the light used for the third exposure is preferably 365 nm, the light intensity is preferably 20 mW / cm 2 , and the irradiation time is preferably 0.1-60 s, and in specific embodiments of the present application, the irradiation time can be 0.1 s, 5 s, 10 s, 20 s, 30 s, 40 s, 50 s or 60 s.

[0117] In the present application, the temperature of the fifth curing is preferably 90°C, and the time is preferably 10-60 min, and in specific embodiments of the present application, the time of the fifth curing can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min.

[0118] After the fifth curing, the present application preferably further performs cutting, polishing and polishing to obtain the optical waveguide device.

[0119] The modified fluorine-containing novolac epoxy resin provided by the present application, the preparation method thereof, the photoresist solution and the optical waveguide device will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0120] Examples 1-5

[0121] In a 250 mL reaction bottle, 20 g of hexafluorobisphenol A type phenolic epoxy resin (softening point 65-70°C) was added, 45 mL of ethyl acetate was added, dissolved under stirring, the volume concentration was 15%, and after nitrogen was filled for 1 h, an alkali catalyst sodium hydroxide and an alkyl chain carboxylic acid were added, and the reaction was carried out at 80°C for 8 h. After washing with ethanol and acetone, an appropriate amount of 2 mol / L hydrochloric acid aqueous solution was added and stirred for 2 h, then washed with a large amount of water, and finally dried to obtain a hexafluorobisphenol A type phenolic epoxy resin with side chain branched alkyl chains.

[0122] The differences of Examples 1-5 are shown in Table 1.

[0123] Table 1 Differences of Examples 1-5

[0124]

[0125] Conclusion: From the data in the table, it can be seen that after modification of the alkyl chain carboxylic acid side chain, the epoxy value of the resin is reduced, indicating that the carboxyl group of the alkyl acid reacts with the epoxy group to form an ester group. The refractive index of the grafted resin is significantly reduced, indicating that the method of side chain grafting can achieve the purpose of adjusting the refractive index of the resin by the reaction ratio of raw materials.

[0126] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the hexafluorobisphenol A type phenolic epoxy resin grafted with different types of alkyl chain carboxylic acid (wherein the modification ratio is shown in Table 1). From the Figure 1 it can be found that after grafting, the peak of the epoxy group in the chemical shift 3.32-3.35 (2H,, m), 2.73-2.90 (4H, m) is obviously reduced, and the peak of -CH2 in the alkyl chain at 4.06 ppm is gradually enhanced, which is due to the grafting reaction of the alkyl chain carboxylic acid with the epoxy group, indicating that the carboxylic acid molecules are successfully grafted.

[0127] Examples 6-10

[0128] In a 250 mL reaction bottle, 20 g of hexafluorobisphenol A type phenolic epoxy resin (softening point 65-70°C) was added, 45 mL of ethyl acetate was added, and it was dissolved under stirring, with a volume concentration of 15%, and then 1 hour of nitrogen was added. After adding the basic catalyst sodium hydroxide and fluorine-containing carboxylic acid, it was reacted at 80°C for 8h. After washing with ethanol and acetone, an appropriate amount of 2 mol / L hydrochloric acid aqueous solution was added and stirred for 2h, then washed with a large amount of water, and finally dried to obtain a hexafluorobisphenol A type phenolic epoxy resin grafted with a fluorine-containing alkyl chain on the side.

[0129] The differences of Examples 6-10 are shown in Table 1.

[0130] Table 2 Differences of Examples 6-10

[0131]

[0132] Conclusion: The data in the table show that the epoxy value of the resin decreased after modification with fluorinated organic acids of different fluorine contents compared to the initial value. This indicates that the fluorinated carboxylic acid underwent a ring-opening reaction with the epoxy group, forming a covalent bond structure. Furthermore, the epoxy values ​​obtained with octanoic acid of different fluorine contents varied slightly, indicating differences in the reactivity of the carboxyl and epoxy groups. The refractive index of the grafted resin decreased significantly with increasing fluorine content, demonstrating that adjusting the fluorine content of the side chains can adjust the refractive index of the resin. Moreover, since the refractive index of fluorinated organic acids is lower than that of ordinary organic acids, the modified epoxy resin has an even lower refractive index.

[0133] Examples 11-15

[0134] The differences from Examples 6-10 are shown in Table 3, and the rest are the same as Examples 6-10.

[0135] Table 3. Differences between Examples 11-15 and Examples 6-10

[0136]

[0137] Figure 2 Infrared spectra of perfluorovalerate grafted with hexafluorobisphenol A type phenolic epoxy resins in different proportions.

[0138] from Figure 2 It can be observed that after the reaction is complete, at 1754 cm... -1 The appearance of a vibrational absorption peak at 3442 cm⁻¹ indicates that perfluoropentanoic acid and the epoxy group underwent a ring-opening reaction to form an ester group. -1 The absorption peak of the generated -OH group gradually increased with the increase of the modification ratio, and reached 928 cm⁻¹. -1 There are still residual epoxy group peaks at 1606.5 and 1509.1 cm⁻¹. -1 It retains the characteristic absorption peaks on the benzene ring of hexafluorobisphenol A type phenolic epoxy resin and the 1126~1300 cm⁻¹ peak. -1 The absorption peaks of C–F.

[0139] Figure 3 The ultraviolet-visible-near-infrared spectra of different types of perfluorocarboxylic acid modified resins are shown in Table 2.

[0140] By replacing hydrogen atoms in carbon-hydrogen bonds with fluorine atoms, the absorption band was shifted away from the communication bands (1310 and 1550 nm). The results are derived from... Figure 3It can be proved that there is no obvious absorption peak at 1310 nm and 1550 nm wavelength, which shows that the proportion of C-H bond with large optical absorption in the hexafluorobisphenol A type novolac epoxy resin is reduced, and the absorption of C-F bond with low optical absorption is very small, which can reduce the absorption loss of the material in the optical communication band, so as to achieve the purpose of reducing the optical loss.

[0141] Application Example 1

[0142] Preparation of optical waveguide device by matching different kinds of alkyl chain carboxylic acid modified proportion resins

[0143] Preparation of n-octanoic acid modified hexafluorobisphenol A type novolac epoxy resin optical waveguide material cladding and n-butyric acid modified hexafluorobisphenol A type novolac epoxy resin optical waveguide core material:

[0144] Lower cladding: 50 g of n-octanoic acid modified hexafluorobisphenol A type novolac epoxy resin, 20 mL of cyclopentanone, stirring and dissolving, 0.5 g of initiator triphenyl sulfonium phosphate, stirring and dissolving, filtering through 0.45 um filter membrane, and obtaining a light yellow transparent and uniform photoresist solution.

[0145] Core layer: 50 g of n-octanoic acid modified hexafluorobisphenol A type novolac epoxy resin, 20 mL of cyclopentanone, stirring and dissolving, 0.5 g of initiator triphenyl sulfonium phosphate, stirring and dissolving, filtering through 0.45 um filter membrane, and obtaining a light yellow transparent and uniform photoresist solution.

[0146] Upper cladding: 50 g of n-octanoic acid modified hexafluorobisphenol A type novolac epoxy resin, 17 mL of cyclopentanone, stirring and dissolving, 0.5 g of initiator triphenyl sulfonium phosphate, stirring and dissolving, filtering through 0.45 um filter membrane, and obtaining a light yellow transparent and uniform photoresist solution.

[0147] Preparation process of lower cladding:

[0148] Pour the above cladding glue solution on a clean silicon wafer substrate, and then put it into a spin coater with a rotation speed of 2000 rpm. After spin coating, move it to a heating plate and bake at 90℃ for 10 min.

[0149] After baking, restore room temperature and expose the entire cladding. The wavelength of the exposure machine is 365 nm, the light intensity is 20 mW / cm 2 , and the irradiation time is 5 s.

[0150] After exposure, heat to 90℃ again and bake for 10 min for curing, and obtain a lower cladding with a thickness of 10 μm.

[0151] The manufacturing process of the core layer is as follows:

[0152] The core layer glue solution is poured on the cleaned substrate coated with the lower cladding layer, and then the substrate is placed in a spin coater with a rotation speed of 2000 rpm for spin coating.

[0153] After the spin coating is completed, the substrate is moved to a heating plate and baked at 90℃ for 10 minutes. 2 After the baking is completed, the substrate is exposed to light under the action of a mask plate.

[0154] After the exposure is completed, the substrate is heated again to 90℃ for baking for 10 minutes.

[0155] After the baking time is completed, the substrate is naturally cooled to room temperature with the platform, and then developed with a developing solution for 60 seconds.

[0156] The substrate is baked again at 90℃ for 10 minutes, and a core layer with a thickness of 10 microns is obtained.

[0157] The manufacturing process of the upper cladding layer is as follows:

[0158] The core layer glue solution is poured on the cleaned substrate coated with the lower cladding layer, and then the substrate is placed in a spin coater with a rotation speed of 2000 rpm for spin coating.

[0159] After the spin coating is completed, the substrate is moved to a heating plate and baked at 90℃ for 10 minutes. 2 After the baking is completed, the substrate is exposed to light under the action of a mask plate.

[0160] After the exposure is completed, the substrate is heated again to 90℃ for baking for 10 minutes.

[0161] After the baking time is completed, the substrate is naturally cooled to room temperature with the platform, and then developed with a developing solution for 60 seconds.

[0162] The core layer, the lower cladding layer and the upper cladding layer are cut, polished and polished to obtain a waveguide device with a waveguide morphology (the size is 10 cm long, and the end face size is 50*50 microns).

[0163] The transmission loss of the optical waveguide device of Application Example 2 was measured by the Cut-back method to be as low as 0.1 dB / cm.

[0164] Application Example 2

[0165] Preparation of optical waveguide devices by matching different kinds of perfluorocarboxylic acid-modified resins

[0166] Preparation of a perfluorooctanoic acid-modified hexafluorobisphenol A type novolak epoxy resin cladding layer and a perfluorobutyric acid-modified hexafluorobisphenol A type novolak epoxy resin core layer material:

[0167] Lower cladding layer: A 250 mL round-bottom flask or an Erlenmeyer flask was charged with 50 g of perfluorooctanoic acid-modified hexafluorobisphenol A type novolak epoxy resin, 20 mL of cyclopentanone was added, and dissolved with stirring, 0.5 g of an initiator, sulfonium salt, was added, and dissolved with stirring, and a light yellow transparent uniform photoresist solution was obtained after filtration through a 0.45 μm filter.

[0168] Core layer: A 250 mL round-bottom flask or an Erlenmeyer flask was charged with 50 g of perfluorobutyric acid-modified hexafluorobisphenol A type novolak epoxy resin, 20 mL of cyclopentanone was added, and dissolved with stirring, 0.5 g of an initiator, sulfonium salt, was added, and dissolved with stirring, and a light yellow transparent uniform photoresist solution was obtained after filtration through a 0.45 μm filter.

[0169] Upper cladding layer: A 250 mL round-bottom flask or an Erlenmeyer flask was charged with 50 g of perfluorooctanoic acid-modified hexafluorobisphenol A type novolak epoxy resin, 17 mL of cyclopentanone was added, and dissolved with stirring, 0.5 g of an initiator, sulfonium salt, was added, and dissolved with stirring, and a light yellow transparent uniform photoresist solution was obtained after filtration through a 0.45 μm filter.

[0170] The preparation process of the optical waveguide device was the same as in Application Example 1

[0171] The transmission loss of the optical waveguide device of Application Example 2 was measured by the Cut-back method to be as low as 0.05 dB / cm.

[0172] The above only describes preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which should also be considered within the scope of protection of the present application.

Claims

1. An optical waveguide device, characterized by, The upper clad layer, the core layer and the lower clad layer are sequentially stacked; The preparation raw materials of the upper clad layer include, in mass fraction: The first modified fluorine-containing phenolic epoxy resin 70-75%; The first photoinitiator 0.7-1%; The first polar organic solvent 23-28%; The preparation raw materials of the core layer include, in mass fraction: The second modified fluorine-containing phenolic epoxy resin 70-75%; The second photoinitiator 0.7-1%; The second polar organic solvent 20-28%; The preparation raw materials of the lower clad layer include, in mass fraction: The third modified fluorine-containing phenolic epoxy resin 70-75%; The third photoinitiator 0.7-1%; The third polar organic solvent 20-28%; The refractive index of the second modified fluorine-containing phenolic epoxy resin is higher than that of the third modified fluorine-containing phenolic epoxy resin; The mass content of the first modified fluorine-containing phenolic epoxy resin in the upper clad layer is greater than the mass content of the third modified fluorine-containing phenolic epoxy resin in the lower clad layer; The first modified fluorine-containing phenolic epoxy resin, the second modified fluorine-containing phenolic epoxy resin and the third modified fluorine-containing phenolic epoxy resin have one of the structural formulas shown in Formula I; Formula I; The R is -COC x H 2x+1 C y F 2y+1 ; The x=0-15, and the y=0-15; The n≥1.

2. The optical waveguide device according to claim 1, wherein, The n=3-10.

3. The optical waveguide device of claim 1, wherein, The preparation method of the first modified fluorine-containing phenolic epoxy resin, the second modified fluorine-containing phenolic epoxy resin and the third modified fluorine-containing phenolic epoxy resin includes the following steps: The acid, the hexafluorophenol A type phenolic epoxy resin, the basic catalyst and the polar organic solvent are mixed and then subjected to grafting reaction to obtain the modified fluorine-containing phenolic epoxy resin; The acid is COOH x H 2x+1 C y F 2y+1 .

4. The optical waveguide device of claim 3, wherein, The number average molecular weight of the hexafluorophenol A type phenolic epoxy resin is 500-3000, the polymerization degree is 3-10, the epoxy equivalent weight is 220-500 g / mol, and the softening point is 65-70℃.

5. An optical waveguide device according to claim 3 or 4, c h a r a c t e r i z e d in that The ratio of the amount of substance of the acid to the amount of substance of the epoxy group in the hexafluorophenol A type phenolic epoxy resin is 0.1-0.8:

1.

6. The optical waveguide device of claim 3, wherein, The basic catalyst includes one or more of NaOH, KOH, LiOH, aniline, benzylamine, NBu4Br, NBu4F, NBu4OH and NMe4OH.

7. An optical waveguide device according to claim 3 or 6, c h a r a c t e r i z e d in that The molar ratio of the acid to the basic catalyst is 0.5-10:1.

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