KR20120030678A - Photoactive fluorinated polymer and the coating solution - Google Patents

Abstract

PURPOSE: A photo-curable fluorinated polymer compound is provided to remarkably reduce the optical transmission loss in optical communication region, to have very low birefringency, to control refractive ratio accurately, and to manufacture an optical device in short time at low temperatures. CONSTITUTION: A photo-curable fluorinated polymer compound is in chemical formula 1. In chemical formula 1, R1 is hydrogen, halogen, methyl or trifluoromethyl group, R2 is -CO-, a functional group in chemical formula 1-a or a functional group in chemical formula 1-b, Z1 and Z3 are empty, -O- or -S-, R3 is an aromatic alkyl group in which all or a part is substituted by fluorine, an alkylene oxide group, or an alkyl group in which aromatic group is contained, Z2 is NH-, -S-, -O- or -CH2CH(OH)-CH2-, R4 is substituent capable of thermal curing and UV curing, and a and b are molar fraction respectively, and a+b=1.

Description

Photocurable fluorinated polymer compound and composition thereof {Photoactive fluorinated polymer and the coating solution}

The present invention relates to a polymer compound consisting of a fluorine compound and a composition thereof. The fluorine compound for an optical waveguide device includes an optical switch, a variable optical attenuator (VOA), a variable and non-variable wavelength filter, a waveguide grating (Arrayed) It is a material used for core and cladding of various planar waveguide optical devices such as waveguide grating (AWG) devices.

    The present invention also relates to a compound used in the manufacture of polymers using fluorine compounds and cores and cladding materials of optical waveguide optical devices using the same.

    The polymer compound prepared in the present invention is easy to form a thin film by UV curing or thermosetting reaction, excellent thermal stability and chemical resistance, low loss due to light absorption and low birefringence can be produced an excellent optical waveguide type optical device. .

(Formula 1)

,

를 나타내고, 여기서 Ha는 H, 또는 같거나 서로 다른 할로겐 원소이며, Z_{1 ,} Z₃는 없거나, -O- 또는 -S- 이고, R₃는 불소로 전부 또는 일부가 치환된 지방족 알킬기, 알킬렌 옥사이드기 또는 방향족기가 함유된 알킬기이다. In formula (1), R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group, and R ₂ represents -CO-,

,

Wherein Ha is H or the same or different halogen, Z _{1 ,} Z ₃ is absent, -O- or -S-, and R ₃ is an aliphatic alkyl group, alkylene, all or part of which is substituted with fluorine; It is an alkyl group containing an oxide group or an aromatic group.

Z ₂ is —NH—, —S—, —O—, —CH 2 CH (OH) —CH 2 —, and R ₄ is a substituent capable of thermosetting and ultraviolet curing, a vinyl group, an allyl group, a (meth) acryl group, Styrene group acetylene group, alkenyl group, alkyne group or any one or more thereof may be included, all or part of these may be substituted with fluorine. R ₅ may be a linear or branched alkyl group, a cyclic alkyl group, an aromatic ring group or a complex substituent thereof, and may include an oxygen (oxo group) and a carbonyl group, and all or part of them may be substituted with fluorine.

a, b is a proportion of the copolymer a is at least 1 mol%, preferably contains 1 to 30 mol%, b is less than 99 mol%, preferably a random copolymer containing 70 to 99 mol%, Block copolymers or tapered copolymers.

In general, since an optical device made of a polymer material for an optical waveguide device is used in an indoor or outdoor communication network whose priority is reliability, the polymer material itself requires very high thermal and environmental stability.

     In addition, low light propagation loss, fine refractive index control, and low birefringence in the 1.3 ~ 1.55㎛ wavelength band directly affecting optical device characteristics are required.Adhesion between substrates, excellent coating property, and multilayer thin film formation are required for optical device fabrication. The use of various substrates is highly demanded.

In addition, an optical device using a polymer optical waveguide may perform various functions that are difficult to realize in an optical fiber type optical device. Optical dividers, wavelength multiplexers, optical switches, and optical attenuators, such as 8-channel or more, are optical devices that can highlight the advantages of optical waveguide devices. Polymer materials have various advantages in the fabrication of such optical waveguide devices. First, thin films can be formed through spin-coating and a simple curing process. This simple process eases the limitations of the device structure, allowing the fabrication of devices with unique structures.

The present invention has been made to improve the high optical propagation loss, high birefringence and fine refractive index control, ease of optical device fabrication process, etc. of the polymer material for optical devices in the prior art prepared by using a fluorine-introduced compound In addition, by preparing a polymer according to the present invention rather than simply introducing a fluorine monomer, the optical transmission loss is remarkably lowered in the optical communication region, the optical birefringence is very small, precise refractive index control is possible, and the optical device manufacturing process in a short time at low temperature An object of the present invention is to provide a compound for an optical waveguide device and an optical waveguide optical device using the same.

In order to achieve the above object, a copolymer compound having two or more polymerized units having a polymerized unit as described below was prepared using a monomer made of fluorine.

(Formula 1)

In formula (1), R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group,

,

를 나타내고, 여기서 Ha는 H, 또는 같거나 서로 다른 할로겐 원소이며, Z_{1 ,} Z3는 없거나, -O- 또는 -S- 이고, R₃는 불소로 전부 또는 일부가 치환된 지방족 알킬기, 알킬렌 옥사이드기 또는 방향족기가 함유된 알킬기이다. R ₂ is -CO-,

,

Wherein Ha is H, or the same or different halogen, Z _{1 ,} Z 3 is absent, -O- or -S-, and R ₃ is an aliphatic alkyl group, alkylene oxide, all or part of which is substituted with fluorine An alkyl group containing a group or an aromatic group.

Z ₂ is NH-, -S-, -O-, -CH2CH (OH) -CH2-, R ₄ is a substituent capable of thermosetting and ultraviolet curing, vinyl group, allyl group, (meth) acryl group, styrene Group acetylene group, alkenyl group, alkyne group or any one or more thereof may be included, all or part of them may be substituted with fluorine, R ₅ is a linear or branched alkyl group, a cyclic alkyl group, an aromatic ring group or They are complex substituents, may include oxygen (oxo group), carbonyl group, all or part of them may be substituted with fluorine, a, b is a proportion of the copolymer, a contains at least 1 mol%, Preferably it is 1 to 30 mol%, b is a random copolymer, block copolymer or tapered copolymer containing 99 mol% or less, preferably 70 to 99 mol%.

     Although the molecular weight of this invention is not specifically limited, It is good to have a molecular weight of 2000-1 million based on a weight average molecular weight, More preferably, it is advantageous in processes, such as a process, having a molecular weight of 5000-50,000.

     Since the polymer of the present invention is capable of controlling the curing density, thin film formation is advantageous, and due to the constant structure of the polymer and the fluorine content control, optical birefringence is very small and precise refractive index can be controlled, thereby reducing optical transmission loss in the optical communication region, and According to the structural properties of the polymer it is possible to control a variety of properties. In addition, the optical device manufacturing process is possible in a short time at a low temperature, it is possible to provide an optical waveguide optical device of excellent performance.

In the present invention, the polymer of Formula 1 may include, for example, a polymer having a structure as follows, but is not limited thereto.

(Formula 2)

(k, l, m, n is the mole fraction of the copolymer, k or m is 0.01 or more, k + m has a mole fraction of 0.01 ~ 0.3, the sum of k + l + m + n is 1.)

Formula 1 according to the present invention is prepared by polymerizing the monomer of Formula 3 and Formula 4 to produce a polymer of Formula 5, and then vinyl, allyl, (meth) acryloyl, styrene, acetylene, alkenyl, alkyne Linear or branched or cyclic alkyl groups or aromatic ring groups or their complex substituents containing any one or more of them, and may include oxygen (oxo groups) or carbonyl groups, all or part of which are substituted with fluorine; It is prepared by grafting by reacting with a reactive monomer. Precursor materials of the reactive monomers to be grafted include, but are not limited to, (meth) acryloyl anhydride, (meth) acryloyl halide, and perfluorostyrene.

(Formula 3)

(Formula 4)

(Formula 5)

,할로겐 원자로 표현될 수 있다.Z4 is -NH2, -SH, -OH,

It can be represented by a halogen atom.

In the above formula, R 3 and R 5 include, but are not limited to, representative compounds of the following structures.

   In addition, in the present invention, the above-mentioned compounds selected from the following Formula 3 (structure (1) or (2) of Formula 6) and Formula 4 (structures (3) to (7) of Formula 6) However, the present invention is not limited thereto.

(Formula 6)

  In another embodiment of the present invention, by mixing the polymers prepared in the formulas 7 and 8, the physical properties of the optical waveguide film can be improved. In particular, the formulas (7) and (8) are highly fluorinated polyfunctional compounds having excellent compatibility with the above formula (1), and are easy to control the viscosity for fabricating the optical device. In addition, it is possible to easily adjust the refractive index precisely by the change of the addition amount, and excellent heat resistance and chemical resistance by improving the curing density. In this embodiment of the present invention, it is preferable to use 10 to 80 parts by weight, preferably 30 to 70 parts by weight, based on 100 parts by weight of the polymer. Results were obtained and the thin film formation was excellent. In addition, the substrate adhesion is increased, it is advantageous to form a fine pattern of the optical waveguide.

(Formula 7)

R1, R2, R3, Z1, Z3, Ha are as defined above, and n is an integer of 2-4.

(Formula 8)

R1, R2, R3, Z1, and Z3 are the same as defined above, and R6 and R7 are aliphatic alkyl groups, alkylene oxide groups or alkyl groups containing aromatic groups.

In the present invention, as the structure of Formula 7, Formula 8 may be selected from the following, but is not limited thereto.

Formula 9

   Since the polymerization method according to the present invention may adopt a conventional radical polymerization method, the present invention is not limited thereto, and the prepared copolymer may be dissolved in a conventional solvent such as THF, ether, ketone, and aromatic compound. And polymerize by dissolving in a solvent such as a halogenated aromatic compound, a halogenated alkane, and a hydrocarbon compound. In addition, the polymerization initiator is not limited as long as it is a radical polymerization initiator, and examples thereof may include AIBN, peroxide, and the like.

   The solvent of the copolymer according to the present invention may also adopt the same one as the polymerization solvent of the polymer, or may adopt another one, for example, perfluorotoluene or the like.

The coating composition is spin-coated at various speeds of 500 to 5000 rpm on various kinds of substrates, preferably silicon wafer substrates, and then, using a mercury lamp under a nitrogen atmosphere, preferably 10 to 10 mW / cm ² of luminous intensity. To 50 mW / cm ² After curing for about 30 minutes to about 30 minutes of ultraviolet rays on a hot plate (hot plate) at 100 ~ 200 ℃ 0.5 ~ 1 hours by heat curing or drying to make a polymer thin film.

The copolymer according to the present invention has a much lower light propagation loss in the optical communication region than an optical waveguide device composed only of an acrylate-based monomer or a monomer into which perfluorostyrene is introduced. Since a copolymer of a monomer having a certain structure is manufactured, the optical birefringence of the polymer is very small, making it easy to manufacture a polarization-independent optical device and varying refractive index, physical properties, and curing conditions according to the monomer structure of the polymer. have. Therefore, by using the polymer of the present invention, it is easy to form a thin film by ultraviolet curing or thermosetting reaction, can express a variety of refractive index and physical properties, and excellent optical waveguide type optical device excellent in thermal stability and chemical resistance can be manufactured.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment aspect, A change, correction, and improvement can be made, as long as it does not deviate from the range of invention.

Preparation Example 1 Preparation of Compound Represented by Chemical Formula 6 (1)

20 g (103.04 mmol) of pentafluorostyrene and 27.01 g (103.04 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol under nitrogen atmosphere were completely dissolved in DMAc solvent. Dissolved. After stirring for 30 minutes, the temperature was raised to 50 ° C., followed by adding NaOH 5.36 g (133.95 mmol) and TBAB 1.66 g (5.15 mmol) for 1 hour, followed by stirring at room temperature for 1 hour. The mixture is extracted with deionized water and ether. The extracted ether layer is dehydrated using magnesium sulfate and distilled under reduced pressure to evaporate the ether. The concentrated compound was separated by column chromatography using silica gel, and then distilled under reduced pressure to obtain 27.86 g of the target chemical formula (6). (Yield 62%) 1 H-NMR (CDCl ₃ ): δ 4.07 (2H, t), 4.56 (1H, t), 4.61 (2H, t), 5.64 (1H, d), 6.01 (1H, d), 6.60 (1H, q)

Preparation Example 2 Preparation of Compound Represented by Chemical Formula 6 (2)

Except for using 42.26 g (103.04 mmol) of perfluorotetraethylene glycol instead of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol in Preparation Example 1 Is the same as (Production Example 1). 33.71 g of Chemical Formula 6 (2) was obtained. (Yield 56%) 1 H-NMR (CDCl ₃ ): δ 3.90 (2H, t), 4.08 (1H, q), 4.49 (2H, t), 5.64 (1H, d), 6.01 (1H, d), 6.60 (1H, q)

Preparation Example 3 Preparation of Compound Represented by Chemical Formula 6 (3)

Under a nitrogen atmosphere, 10 g (51.52 mmol) of pentafluorostyrene were completely dissolved in a DMAc solvent. After stirring for 30 minutes, NaOH 3.09g (77.28mmol) and TBAB 0.42g (1.32mmol) were added and stirred at room temperature for 30 minutes. 20.50 g (51.52 mmol) of perfluorotriethylene glycol monomethyl ether was diluted in DMAc and slowly added dropwise, followed by stirring at room temperature for 1 hr. The mixture is extracted with deionized water and ether. The extracted ether layer is dehydrated using magnesium sulfate and distilled under reduced pressure to evaporate the ether. The concentrated compound was separated by column chromatography using silica gel, and then distilled under reduced pressure to obtain 26.82 g of Chemical Formula 6 (3). (Yield 91%) 1 H-NMR (CDCl ₃ ): δ 4.48 (2H, t), 5.63 (1H, d), 6.01 (1H, d), 6.56 (1H, q)

Preparation Example 4 Preparation of Compound Represented by Chemical Formula 6 (4)

Production Example 3 was the same as Production Example 3, except that 28.23 g (51.52 mmol) of perfluorotriethylene glycol monobutyl ether was used instead of perfluorotriethylene glycol monomethyl ether. 31.99 g of the chemical formula (6), which is the target product, was obtained. (Yield 86%) 1 H-NMR (CDCl ₃ ): δ 4.46 (2H, t), 5.64 (1H, d), 6.01 (1H, d), 6.56 (1H, q)

Preparation Example 5 Preparation of Compound Represented by Chemical Formula 6 (5)

Under nitrogen atmosphere, 10 g (54.33 mmol) of perfluorophenol were completely dissolved in DMAc solvent. After stirring for 30 minutes, NaOH 3.26g (81.49mmol) and TBAB 0.35g (1.08mmol) were added and stirred at room temperature for 30 minutes. 23.47 g (54.33 mmol) of 11H, 1H, 9H-perfluorononan-1-ol was diluted in DMAc and slowly added dropwise, followed by stirring at room temperature for 1 hour. The mixture is extracted with deionized water and ether. The extracted ether layer is dehydrated using magnesium sulfate and distilled under reduced pressure to evaporate the ether. The concentrated compound was completely dissolved in THF solvent, and then 6.04 g (59.76 mmol) of triethyleneamine was added and stirred for 30 minutes. 5.40 g (59.76 mmol) of acryloyl chloride was diluted in THF and slowly added dropwise, followed by stirring at room temperature for 1 hr. The mixture is extracted with deionized water and ether. The extracted ether layer is dehydrated using magnesium sulfate and distilled under reduced pressure to evaporate the ether. The mixture was separated by column chromatography using silica gel, and then distilled under reduced pressure to obtain 14.83 g of the chemical formula (6). (Yield 42%) 1 H-NMR (CDCl ₃ ): δ 4.62 (2H, t), 5.86, 6.00, 6.10 (1H, t, t, t), 5.92 (1H, d), 6.13 (1H, q), 6.46 (1 H, d)

Preparation Example 6 Preparation of Compound Represented by Chemical Formula 6 (6)

13.68 g (54.73 mmol) of 4-trifluoromethyl-2,3,5,6-tetrafluorothiophenol was used instead of 11H, 1H, 9H-perfluorononan-1-ol in Preparation Example 5. Except for (Manufacture Example 5) except that. 12.59 g of Chemical Formula 6 (6) was obtained. (Yield 49%) 1 H-NMR (CDCl ₃ ): δ 5.93 (1H, d), 6.13 (1H, q), 6.47 (1H, d)

Preparation Example 7 Preparation of Compound Represented by Chemical Formula 6 (7)

Under nitrogen atmosphere, 30.0 g (75.36 mmol) of perfluorotriethylene glycol monomethyl ether was completely dissolved in THF solvent, and 15.25 g (150.72 mmol) of triethyleneamine was added thereto and stirred for 30 minutes. 8.18 g (90.43 mmol) of acryloyl chloride was diluted in THF and slowly added dropwise, followed by stirring at room temperature for 1 hr. The mixture is extracted with deionized water and ether. The extracted ether layer is dehydrated using magnesium sulfate and distilled under reduced pressure to evaporate the ether. The mixture was separated by column chromatography using silica gel, and then distilled under reduced pressure to obtain 28.28 g of the chemical formula 6 (7). (Yield 83%) 1 H-NMR (CDCl ₃ ): δ 4.52 (2H, t), 5.92 (1H, d), 6.13 (1H, q), 6.46 (1H, d)

Preparation Example 8 Preparation of Compound Represented by Chemical Formula 6 (8)

Production Example 7 was the same as Production Example 7, except that 30.0 g (54.73 mmol) of perfluorotriethylene glycol monobutyl ether was used instead of perfluorotriethylene glycol monomethyl ether. 26.68 g of Formula 6 (8) was obtained as a target product. (Yield 81%) 1 H-NMR (CDCl ₃ ): δ 4.51 (2H, t), 5.92 (1H, d), 6.13 (1H, q), 6.46 (1H, d)

Preparation Example 9 Preparation of Compound Represented by Chemical Formula 9 (1)

Under nitrogen atmosphere, 50 g (42.79 mmol) of perfluoro-tris- (9-hydroxymethyl-2,5,8-trioxanyl) methane was completely dissolved in THF solvent, followed by 20.78 g (205.4 mmol) of triethyleneamine. Stir for 30 minutes. 17.43 g (192.5 mmol) of acryloyl chloride was diluted in THF and slowly added dropwise, followed by stirring at room temperature for 1 hr. The mixture is extracted with deionized water and ether. The extracted ether layer is dehydrated using magnesium sulfate and distilled under reduced pressure to evaporate the ether. The mixture was separated by column chromatography using silica gel, and then distilled under reduced pressure to obtain 47.82 g of the chemical formula 9 (1). (84% yield) 1 H-NMR (CDCl ₃ ): δ 4.51 (6H, t), 5.92 (3H, d), 6.12 (3H, q), 6.45 (3H, d)

Preparation Example 10 Preparation of Compound Represented by Chemical Formula 9 (2)

In Production Example 9, perfluoro-tetrakis- (9-hydroxymethyl-2,5, instead of perfluoro-tris- (9-hydroxymethyl-2,5,8-trioxanyl) methane The same procedure as in (Preparation Example 9) except that 50.0 g (32.71 mmol) of 8-trioxanyl) methane was used. 43.94 g of Formula 9 (2) was obtained as a target product. (Yield 77%) 1 H-NMR (CDCl ₃ ): δ 4.51 (8H, t), 5.92 (4H, d), 6.13 (4H, q), 6.46 (4H, d)

Preparation Example 11 Preparation of Compound Represented by Chemical Formula 9 (3)

50 g (149.6 mmol) of hexafluoro-2,3-bis (trifluoromethyl) -2,3-butanediol (hereinafter referred to as perfluoropinacol) under a nitrogen atmosphere, and 38.95 g of 2-hydroxyethyl methacrylate (299.3) mmol), triphenylphosphine 172.3 g (685.5 mmol), and diethyl ether are mixed and stirred. After stirring for 30 minutes, the mixture was lowered to 0 ° C., diluted with diisopropyl azodicarboxylate (DIAD) 133.6 g (685.5 mmol) and diethyl ether, and slowly added dropwise thereto. After stirring for 24 hours at room temperature, the mixture is concentrated. The mixture was separated by column chromatography using silica gel, and then distilled under reduced pressure to obtain 62.67 g of the chemical formula 9 (3). (Yield 75%) ¹ H-NMR (CDCl ₃ ): δ 1.90 (6H, t), 4.36 (8H, m), 5.63 (2H, t), 6.09 (2H, t)

Example 1

The monomers of the contents shown in Table 1 were added, and the initiator (AIBN) was added in the molar equivalents specified in (Table 1) to the total moles of the added monomers.

30 wt% of the total grams of the THF was heated to 65 DEG C while stirring for 30 minutes under a nitrogen atmosphere, and according to the mole% specified in Table 1, the monomer 8 (1), the monomer formula 8 (3), and the total initiator The solution dissolved in 30% of THF with respect to grams was slowly added dropwise for 12 hours. After the addition was completed, the mixture was further stirred for 12 hours, and cooled to room temperature. At room temperature, triethylamine was added dropwise to 2 molar equivalents to mole of compound 8 (1), followed by stirring for 30 minutes, and then methacrylic anhydride to 2 molar equivalents to mole of compound 8 (1). Was added dropwise. After stirring for 4 hours at room temperature, the reaction solution is precipitated in methanol. The precipitate is dried under reduced pressure at 30 ° C./12 hours. Precipitation was carried out three times to obtain polymer 1. The molecular weight of the prepared polymer was measured using a column of Polymer Laboratories' GPC apparatus (trade name mixed-B 2, 500 Å 1). (The solvent is MC and polystyrene was measured as a standard.)

1.0 g of the polymer prepared above was mixed with 0.42 g of octafluoro rutoluene (OFT), 0.015 g of photoinitiator I184C (CIBA GEIGY, Irgacure 184), and 0.005 g of TPO (CIBA GEIGY, Irgacure TPO), and then the solution was mixed with a 0.2 μm Teflon filter. Filtration produces a coating solution for use as core and cladding layers in the optical waveguide device.

The coating solution was spin-coated at a speed of 3500 rpm on a silicon wafer substrate, and then cured for 5 minutes in an ultraviolet light of 14 mW / cm ² using a mercury lamp under a nitrogen atmosphere, and then 0.5 hours at 200 ° C. on a hot plate. Thermally cured to form a polymer thin film. Table 2 below was used to measure the refractive index, Thermo-optic coefficient (dn / dT) using a prism coupler at a wavelength of 1550nm for the polymer thin film prepared in the above Example, the optical progress loss is a method of combining the slab waveguide using the refractive index matching solution Measured using.

Examples 2-10 Polymer Preparation (see Table 1)

Examples 2 to 10 differed only in the type, monomer mole%, and molar equivalents of the monomers prepared in Synthesis Examples 2 to 9 shown in Table 1, and the polymerization method was performed under the same conditions as in Example 1, and in the same manner. The coating composition was prepared and coated to measure physical properties.

Comparative Examples 1 and 2 Preparation of Polymer (see Table 1)

1.0 g of the polymer prepared above using the polymers of Comparative Examples 1 and 2 were mixed with 0.42 g of octafluoro rutoluene, 0.015 g of photoinitiator I184C (CIBA GEIGY, Irgacure 184), and 0.005 g of TPO (CIBA GEIGY, Irgacure TPO). The solution was then filtered through a 0.2 μm Teflon filter to prepare a coating solution for use as the core and cladding layer of the optical waveguide device.

The coating solution was spin-coated at a speed of 3500 rpm on a silicon wafer substrate, and then cured for 5 minutes in an ultraviolet light of 14 mW / cm ² using a mercury lamp under a nitrogen atmosphere, and then 0.5 hours at 200 ° C. on a hot plate. The polymer film was thermally cured to produce a polymer thin film, and the results thereof were measured by the method of Example 1 and listed in Table 2.

As shown in Table 2, polymers 1 to 6 showed various refractive index results depending on the structure of the monomers. Polymers 7 to 10 showed various refractive index results according to three or more monomers and the mole% of the monomers, and by using three or more monomers, not only the refractive index of the polymer but also the physical properties of the polymer can be adjusted. In addition, the polymers 1 to 10 may have a birefringence of about 10 to 100 times lower than that of Comparative 1 and 2, thereby lowering the polarization dependence of the optical device by 10 to 100 times. In addition, the thermo-optic coefficient (T / O coef.) Is 1.5 to 3 times higher, which reduces the driving power of the thermo-optic device by 2 to 3 times. Birefringence, light loss, high T / O coef. The results came out.

Comparative 1 and 2 are polymers in which perfluorostyrene is introduced at the end and are used for fabricating an optical waveguide type optical device, and have excellent properties. Comparing the results of the birefringence, the light loss, and the T / O coef. Of the polymers 1 to 10 and the polymers 1 to 2 prepared in the present invention, the polymers 1 to 10 showed very excellent characteristics compared to the comparative examples 1 and 2.

As shown in the results, the polymer according to the present invention can be used to finely adjust the refractive index and physical properties of the monomer by the structure and mole%, and the low birefringence and light loss, high T / O coef compared to the conventional optical waveguide polymer. As a result, an excellent optical device can be manufactured.

[Examples 11-13]

In applying the polymer prepared in the present invention to an optical device, an excellent polymer thin film can be manufactured by adding a compound of Formula 9 to control polymer properties required for easier polymer thin film production. That is, by mixing the polymer described in (Table 3) and the compound having a polyfunctional group of (Formula 9), it is possible to control various physical properties such as viscosity control, curing density control, thin film lamination, complementary adhesion to the substrate

Mixtures 1 to 3 were mixed with polymers, monomers, photoinitiators, and solvents (octafluorotoluene) in the contents specified in Table 3, and then the solution was filtered through a 0.2 μm Teflon filter.

The coating solution was spin-coated at a speed of 1500 rpm on a silicon wafer substrate, and then cured for 5 minutes in an ultraviolet light of 14 mW / cm ² using a mercury lamp under nitrogen atmosphere, and then 0.5 hours at 200 ° C. on a hot plate. Thermally cured to form a polymer thin film.

As shown in Table 3, a mixture of Compound 9 (1) and Compound 9 (2) in the mixture 1, 2 has a lower refractive index, light loss, and higher T / O coef than the properties of Polymer 7. The results were obtained, and the curing density was increased, and the thin film formation was excellent. Although the mixture 3 had low light loss, the adhesion of the substrate, which is an important property of the optical device manufacturing process, was increased, and the formation of fine patterns in the optical waveguide was advantageous due to the increase of the curing density.

The polymer prepared by the present invention has various physical properties depending on the structure and content of the monomer, and the refractive index control, low birefringence, light loss, and high T / O coef. Have In addition, the physical properties of the polymer can be finely adjusted by mixing the polymer with a multifunctional compound.

Claims (16)

A polymer having the following structure.

R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group,
R ₂ is -CO-, ,

Wherein Ha is H, or the same or different halogen, Z _{1 ,} Z 3 is absent, -O- or -S-, and R ₃ is an aliphatic alkyl group, alkylene oxide, all or part of which is substituted with fluorine An alkyl group containing a group or an aromatic group. Z ₂ is NH-, —S—, —O—, —CH 2 CH (OH) —CH 2 —, R ₄ is a substituent capable of thermosetting and ultraviolet curing, and a vinyl group, an allyl group, a (meth) acryl group, and styrene Group acetylene group, alkenyl group, alkyne group or any one or more thereof may be included, all or part of them may be substituted with fluorine, R ₅ is a linear or branched alkyl group, a cyclic alkyl group, an aromatic ring group or These are complex substituents, and may include oxygen (oxo group), carbonyl group, and all or part of them may be substituted with fluorine. A and b represent the mole fraction of the copolymer, and a + b is 1.


The method of claim 1,
A is 0.01 to 0.3, and b is 0.7 to 0.99. The method of claim 1,
The polymer has the following structure.

The k, l, m, n is a mole fraction of the copolymer, k or m is 0.01 or more, k + m has a mole fraction of 0.01 ~ 0.3, the sum of k + l + m + n is 1.
The method of claim 1,
R3 and R5 have the following structure.

(In the above structure, Ha is H, or the same or different halogen element, m ~ v is a natural number from 0 to 100) A photocurable composition comprising the polymer of claim 1 and at least one compound selected from formula (6) or formula (7).
(Formula 6)

(Formula 7)

In the above, R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group,
R ₂ is -CO-,

,

Wherein Ha is H, or a halogen element, Z _{1 ,} Z 3 is absent, or -O- or -S-, and R ₃ is an aliphatic alkyl group, alkylene oxide group or aromatic group in which all or part is substituted with fluorine; It is an alkyl group contained, and R6, R7 is an alkyl group containing an aliphatic alkyl group, an alkylene oxide group or an aromatic group, n has a natural number of 2 to 4.
6. The method of claim 5,
Photocurable composition, characterized in that the compound is any one or more selected from the following.

A photocurable polymer coating composition comprising any one of the polymers selected from claims 1 to 4, a photoinitiator and a solvent. A photocurable coating composition comprising the composition of claim 5. In the optical waveguide type optical device including a lower cladding layer formed on a flat substrate, a core layer formed on the lower cladding layer, and an upper cladding layer formed on the core layer, the core layer or cladding layer described above. The optical waveguide device comprising any one of the polymers selected from the above 1 to 4. In the optical waveguide type optical device including a lower cladding layer formed on a flat substrate, a core layer formed on the lower cladding layer, and an upper cladding layer formed on the core layer, the core layer or cladding layer described above. An optical waveguide type optical device manufactured by including any one of the coating compositions selected from the above. A polymer having the following structure.

In formula (1), R ₁ represents a hydrogen, halogen, methyl, trifluoromethyl group,
Ha is H or the same or different halogen, R ₃ is an alkyl group containing an aliphatic alkyl group, an alkylene oxide group or an aromatic group, all or part of which is substituted with fluorine, and R ₅ is a linear or branched alkyl group, a cyclic alkyl group , An aromatic ring group or a complex substituent thereof, and may include an oxygen (oxo group) and a carbonyl group, all or part of which may be substituted with fluorine, and k, l, m, and n are mole fractions of the copolymer. , k or m is 0.01 or more, k + m has a mole fraction of 0.01 ~ 0.3, the sum of k + l + m + n is 1. Monomer of the formula (3).
(Formula 3)

R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group,
R ₂ is -CO-,

,

Wherein Ha is H, or a same or different halogen element, Z ₁ is absent, -O- or -S-, and Z4 is -NH2, -SH, -OH,

Or a halogen group and R ₃ is an alkyl group containing an aliphatic alkyl group, an alkylene oxide group, or an aromatic group, all or part of which is substituted with fluorine. The method of claim 12,
Monomer characterized in that the R3 has the following structure

Monomer of Formula

R1, R2, R3, R5 and Z1, Z3 are the same as in claim 1 above.
R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group,
R ₂ is -CO-,

,

Wherein Ha is H, or the same or different halogen, Z ₁ is absent, -O- or -S-, and R ₃ is an aliphatic alkyl group, an alkylene oxide group substituted with all or part of fluorine, or Is an alkyl group containing an aromatic group, and R5 is a linear or branched alkyl group, a cyclic alkyl group, an aromatic ring group or a complex substituent thereof, and may include oxygen (oxo group) and carbonyl group, all or part of which is substituted with fluorine It may be. Monomers of the formula

n has a natural number of 2-4, and R <1>, R <2>, R <3>, Z <1>, Z <3> and Ha are the same as said 1st term.

In the above, R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group, R ₂ represents -CO-,, wherein Ha is H, or a halogen element, Z _{1 ,} Z 3 is absent, -O- or- S-, R ₃ is an alkyl group containing an aliphatic alkyl group, an alkylene oxide group or an aromatic group all or part of which is substituted with fluorine, n has a natural number of 2 to 4. Polyfunctional compound of the following formula.

R6 and R7 are aliphatic alkyl groups, alkylene oxide groups or alkyl groups containing aromatic groups, and R1, R2, Z1, and Z3 are the same as those of claim 1.
In the above, R ₁ represents hydrogen, a halogen element, methyl, trifluoromethyl group,
R ₂ is -CO-,

,

Wherein Ha is H or a halogen element, Z _{1 and} Z 3 are absent, -O- or -S-, and R 6 and R 7 are an alkyl group containing an aliphatic alkyl group, an alkylene oxide group or an aromatic group.