KR20120030478A - Compound for optical waveguide, copolymer thereof and optical waveguide using thereof - Google Patents

Abstract

PURPOSE: A compound for optical waveguide, copolymers thereof, and an optical waveguide using thereof are provided to minimize light loss and facilitate refractive index adjustment, thereby being used for manufacturing optical waveguide and applied to nano-imprint process. CONSTITUTION: A compound for optical waveguide is represented by chemical formula 3. In the chemical formula 3, X is either H or F. R stands for aromatic compound with 6-14 carbons which is substituted for one or more of fluorine. M stands for 0-6. A copolymer for optical waveguide is formed by polymerization reaction of a monomer of a compound which is expressed as chemical formula 3 with styrene based monomer which includes fluorine or acrylic monomer including fluorine. The monomer which is selected from the compound expressed as chemical formula 3 is included 10-30 parts by weight based on the copolymers. The optical waveguide includes clad layer and core which are formed by polymerization, and is manufactured by nano-imprint process. In the optical waveguide, refractive index difference between core and clad layer is 0.2-2.0%.

Description

Compound for optical waveguide, copolymer thereof and optical waveguide using same

The present invention relates to an optical waveguide compound, a copolymer thereof, and an optical waveguide using the same. Specifically, the present invention relates to a nanoimprint process capable of minimizing light loss and adjusting refractive index to increase a difference in refractive index between a core and a clad layer. It relates to possible optical waveguide compounds, copolymers thereof and optical waveguides using the same.

Currently, optical waveguide devices are typically manufactured using semiconductor fabrication technology or MEMS technology, and research for directing the optical waveguide fabricated on the plane and manufactured is being continuously conducted.

A general method for manufacturing an optical waveguide device is as follows. A lower clad layer is formed on the substrate, and a core is formed on the lower clad layer. Subsequently, patterns are formed on the core in various ways, and etched to pattern the cores. Thereafter, a planar optical waveguide is manufactured by forming an upper clad layer on the core. The clad layer or core is usually formed by spin coating or screen printing, and the forming material is a silica or a polymer having a different refractive index.

Most of the polymers developed to date can obtain a difference in refractive index between the cladding layer and the core up to 1%. Therefore, the size of the optical waveguide is limited, so it is difficult to manufacture a passive optical element for a micro optical communication. In addition, such silica or polymer material can be patterned by a complex process such as photolithography to form a core.

Currently, nanoimprint process that is simpler than photolithography process and easy to pattern of large area has been developed, but there is no development of polymer material for optical waveguide that can be applied thereto. In addition, polymers known to date have a problem in that it is not easy to control a difference in refractive index because the difference in refractive index is controlled by the fluorine group or chlorine group content in the monomer.

An object of the present invention to solve the above problems is to minimize the optical loss, easy to control the refractive index compound that can be applied to the optical waveguide for nanoimprint process that can increase the refractive index difference between the core and the clad, a copolymer thereof and using the same To provide an optical waveguide.

According to an aspect of the present invention,

It provides a compound for an optical waveguide represented by any one of the following formula (1):

<Formula 1>

(Formula 1,

n is an integer of 4 to 16,

에서 선택되며, m 은 0 내지 6 의 정수이다.)R is an aromatic compound substituted with at least one fluorine having 6 to 14 carbon atoms, or

M is an integer from 0 to 6.)

<Formula 2>

(Formula 2,

X is F or H,

에서 선택되며, m 은 0 내지 6 의 정수이며, n 은 1 내지 10 의 정수이다.) R is an aromatic compound of 6 to 14 carbon atoms substituted with one or more fluorine or

, M is an integer from 0 to 6, n is an integer from 1 to 10.)

<Formula 3>

(In Formula 3,

X is H or F,

이며, m 은 0 내지 6 이다.)
R is an aromatic compound of 6 to 14 carbon atoms substituted with one or more fluorine or

M is 0 to 6).

The present invention to achieve another object of the present invention,

At least one monomer selected from compounds represented by Formulas 1 to 3; And it provides a copolymer formed by the polymerization of at least one monomer selected from the group consisting of a styrene monomer containing fluorine and an acrylic monomer containing fluorine.

The monomer selected from the compound represented by Formula 1 may be included in 20 to 30 parts by weight based on the copolymer.

The monomer selected from the compound represented by Formula 2 may be included in 20 to 40 parts by weight based on the copolymer.

The monomer selected from the compound represented by Formula 3 may be included in 10 to 30 parts by weight based on the copolymer.

In order to achieve another object of the present invention,

It provides an optical waveguide comprising a clad layer and a core formed of the copolymer and manufactured by a nanoimprint process.

The optical waveguide may have a refractive index difference of 0.2 to 2.0% between the clad layer and the core.

The compound of the present invention can cause polymerization or crosslinking reaction by light without using an organic solvent.

The polymer of the present invention can minimize the light loss, can be used to manufacture the optical waveguide because the refractive index is easy to control, and can be applied to the nanoimprint process.

Since the optical waveguide having a large difference in refractive index between the core and the clad layer can be manufactured using the polymer of the present invention, it is possible to manufacture an optical waveguide having various sizes and shapes.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily practice.

The present invention provides a compound for an optical waveguide.

The optical waveguide compound of the present invention has two or more functional groups, and its copolymer may be applied to a UV nanoimprint process because crosslinking or polymerization may occur by UV.

Compound for an optical waveguide of the present invention can be represented by the following formula (1):

<Formula 1>

에서 선택되며, m 은 0 내지 6 의 정수이다. 상기 하나 이상의 불소로 치환된 탄소수 6 내지 14 의 방향족 화합물은 바람직하게는,

일 수 있다. In Formula 1, n is an integer of 4 to 16, R is an aromatic compound having 6 to 14 carbon atoms substituted with one or more fluorine or

Is selected from, and m is an integer from 0 to 6. Preferably the aromatic compound having 6 to 14 carbon atoms substituted with one or more fluorine,

Can be.

The optical waveguide compound represented by Chemical Formula 1 may be prepared by reacting an aliphatic fluorinated diol and acryloyl halide in the presence of a basic catalyst. As the aliphatic fluorinated diol, any aliphatic diol containing fluorine may be used without limitation, and specifically, octafluoro hexanediol or perfluoro octanediol may be used. However, the present invention is not limited thereto. The acryloyl halide may preferably use acryloyl chloride, but is not limited thereto. The basic catalyst may be triethylamine, trimethylamine, diphenylmethylamine or pyridine, but is not limited thereto. Preferably, triethylamine may be used.

The optical waveguide compound of the present invention may be represented by the following Chemical Formula 2:

<Formula 2>

에서 선택되며, 상기 m 은 0 내지 6 의 정수이며, 상기 n 은 1 내지 10 의 정수이다. 상기 하나 이상의 불소로 치환된 탄소수 6 내지 14 의 방향족 화합물은 바람직하게는,

일 수 있다.
In Formula 2, X is F or H, R is an aromatic compound having 6 to 14 carbon atoms substituted with one or more fluorine or

M is an integer from 0 to 6, and n is an integer from 1 to 10. Preferably the aromatic compound having 6 to 14 carbon atoms substituted with one or more fluorine,

Can be.

The compound represented by Chemical Formula 2 may be formed by the reaction of an aromatic compound containing a fluorine and at least two hydroxy groups and acryloyl halide. The aromatic compound including the fluorine and at least two or more hydroxy groups is specifically 2,2 '-(perfluoro-1,4-phenylene) bis (2,3,3,3-tetrafluoropropane-1- Ol) (2,2 ′-(perfluoro-1,4-phenylene) bis (2,3,3,3-tetrafluoropropane-1-ol)) may be used, but is not limited thereto. The acryloyl halide may preferably use acryloyl chloride, but is not limited thereto. The basic catalyst may be triethylamine, trimethylamine, diphenylmethylamine or pyridine, but is not limited thereto. Preferably, triethylamine may be used.

The optical waveguide compound of the present invention may be represented by the following Chemical Formula 3:

<Formula 3>

이며, m 은 0 내지 6 이다. 상기 하나 이상의 불소로 치환된 탄소수 6 내지 14 의 방향족 화합물은 바람직하게는,

일 수 있다. In Formula 3, X is H or F, R is an aromatic compound having 6 to 14 carbon atoms substituted with one or more fluorine or

And m is 0-6. Preferably the aromatic compound having 6 to 14 carbon atoms substituted with one or more fluorine,

Can be.

The compound represented by Chemical Formula 3 may be produced by reacting acryloyl halide with a product obtained by reacting a triazine compound with an aromatic compound containing at least two hydroxy groups in the presence of a basic catalyst. The basic catalyst may be triethylamine, trimethylamine, diphenylmethylamine or pyridine, but is not limited thereto. Preferably, triethylamine may be used. Specifically, 1,3,5-triazine-2,4,6-tricarbonyltrichloride (1,3,5-triazine-2,4,6-tricarbonyltrichloride) 1 equivalent and 3 equivalents of 2,2 ′ -(Perfluoro-1,4-phenylene) bis (2,3,3,3-tetrafluoropropan-1-ol) is reacted under a base catalyst to obtain an intermediate product to which acryloyl It can be obtained by reacting 3 equivalents of halide.

The present invention also relates to a polymerization reaction of at least one monomer selected from the compounds represented by Formulas 1 to 3; and at least one monomer selected from the group consisting of styrene monomers containing fluorine and acrylic monomers containing fluorine. To provide a copolymer formed.

Copolymers polymerized with the compounds represented by the formulas (1) to (3) of the present invention as monomers may have low light loss and easily produce a refractive index.

When the copolymer is formed using the compound represented by Chemical Formula 1 as a monomer, the compound represented by Chemical Formula 1 may be included in an amount of 20 to 30 parts by weight based on the copolymer. When the compound represented by Chemical Formula 1 is included in less than 20 parts by weight, the effect of adjusting the refractive index is insignificant, and may be undesirable.

The compound represented by Chemical Formula 1 used as a monomer in the copolymer may be a compound represented by Chemical Formula 4 below:

<Formula 4>

The compound represented by Formula 2 has a high content of fluorine and an aromatic compound, and thus the copolymer copolymerized with the monomer may reduce light absorption loss and increase refractive index. When the compound represented by Formula 2 is used as a monomer, the compound represented by Formula 2 may be included in an amount of 20 to 40 parts by weight based on the copolymer. When included in less than 20 parts by weight it may be undesirable to reduce the light absorption loss, but the effect of increasing the refractive index may be insignificant. If it is included in more than 40 parts by weight, the curing reaction is rapidly increased to increase the flexibility of the produced copolymer It may decrease, which may degrade the optical waveguide function, which may be undesirable.

The compound represented by Formula 2 used as a monomer in the copolymer may preferably be a compound represented by Formula 5 below:

<Formula 5>

Compound represented by the formula (3) is easy to crosslinking reaction is suitable for increasing the refractive index. When using the compound represented by Formula 3 as a monomer may be included in 10 to 30 parts by weight based on the copolymer. When included in less than 10 parts by weight the effect of increasing the refractive index is insignificant, when contained in more than 30 parts by weight of the curing reaction is sharply increased to decrease the flexibility of the prepared copolymer to reduce the optical waveguide function is not desirable Can be.

The compound represented by Chemical Formula 3 used as a monomer in the copolymer may be a compound represented by Chemical Formula 6 below:

<Formula 6>

The present invention also provides an optical waveguide comprising a clad layer and a core formed of the above-described copolymer and manufactured by a nanoimprint process. The above-mentioned copolymer contains two or more functional groups, and a small amount of photopolymerization initiator facilitates photopolymerization and crosslinking reactions, and thus can be applied to nanoimprint processes.

Method for manufacturing an optical waveguide using the nanoimprint process may be used without limitation methods known in the art, the optical waveguide may employ a structure known in the art.

The optical waveguide may have a refractive index difference of 0.2 to 2.0% between the clad layer and the core. When the copolymer is used to form the clad layer and the core, the refractive index may be adjusted, and thus the optical waveguide may be manufactured to have a refractive index difference in the above range, and thus an optical waveguide having various sizes and shapes may be manufactured. .

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. This is for the purpose of illustrating the invention only, and thus the scope of the invention is not limited.

Acryloyl chloride used in the following Examples and Comparative Examples is wako, Cyanuric chloride, 1,3,5-Benzenetricarbonyl trichloride, 2,2,3,4,4,4-Hexafluoro butyl acrylate, 2-Hydroxy-2-methyl -propiophenone, 2,6-Di-tert-Butyl-4-methoxy phenol, Chloroform-d, Acetone-d is aldrich, 2,2,3,3,4,4,5,5-Octafluoro-1,6 -Hexanediol, 4,4 '-(Hexafluoroisopropylidene) diphenol, 1H, 1H-Perfluoro-1-octanol, 1H, 1H-Perfluoro-1-decanol is alfa, 1,4-Bis (hexafluoro-α-hydroxy -isopropyl) Benzene and Pyrogallol were purchased from TCI. Tetrahydrofuran, Dimethyl chloride, and Chloroform were used to purify Duksan Chemical, and H ₂ 0 was used as distilled water.

All synthesized compounds were confirmed by 1 H-NMR. 1 H-NMR was recorded using Bruker's 400 MHz Spectrometer, and all chemical mobility was reported in ppm based on tetramethylsilane (TMS), an internal standard.

Example 1 Synthesis of Compound Represented by Chemical Formula 1

2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate

1.389 g (0.005 mol) of 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol is dissolved in 50 ml of Dichloromethane, and then 1.0 ml (0.0125 mol) of acryloyl chloride is added. It was. 1.9 ml (0.0125 mol) triethylamine was slowly added to the droplet at 0 ° C. and the mixture was reacted at room temperature for 3 hours. The mixture was washed three times with 100 ml of distilled water and the organic layer was extracted using Chloroform. After drying using magnesium sulfate, it was filtered through a filter and the solvent was removed to give the title product. Yield is about 50% and 1 H-NMR: δ6.40 (d, 3H), 6.12 (m, 3H), 5.82 (d, 3H), 4.15 (m, 12H)

Example 2 Synthesis of Compound Represented by Chemical Formula 1

2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate

Dissolve 1.11 g (0.003 mol) of 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol in 50 ml of DCM, then add 0.50 ml (0.006 mol) of acryloyl chloride To this was slowly added 1.0 ml (0.007 mol) triethylamine. The reaction was allowed to react at room temperature for 3 hours or more, washed three times with 100 ml of distilled water, dried using Magnesium sulfate, filtered through a filter and the solvent was removed to obtain the title product. Yield is about 95% and 1 H-NMR: δ6.53 (d, 1H), 6.20 (m, 1H), 5.99 (d, 1H), 4.68 (m, 2H)

Example 3 Synthesis of Compound Represented by Chemical Formula 2

2,2 '-(perfluoro-1,4-phenylene) bis (2,3,3,3-tetrafluoropropane-2,1-diyl) diacrylate

2.590 g (0.005 mol) of 2,2 '-(perfluoro-1,4-phenylene) bis (2,3,3,3-tetra fluoropropane-1-ol) was dissolved in 50 ml of Dichloromethane and then 1.0 ml ( 0.0125 mol) of acryloyl chloride was added. 1.9 ml (0.0125 mol) triethylamine was slowly added to the droplet at 0 ° C. and the mixture was reacted at room temperature for 3 hours. The mixture was washed three times with 100 ml of distilled water and the organic layer was extracted using Chloroform. After drying using magnesium sulfate, it was filtered through a filter and the solvent was removed to give the title product. Yield is about 70% and 1 H-NMR: δ6.45 (d, 4H), 6.18 (m, 2H), 3.78 (m, 4H)

Example 4 Synthesis of Compound Represented by Chemical Formula 3

tris (2- (4- (3- (acryloyloxy) -1,1,1,2-tetrafluoropropan-2-yl) -2,3,5,6- tetrafluorophenyl) -2,3,3,3-tetrafluoropropyl) 1,3,5-triazine-2,4,6-tricarboxylate

3.108 g (0.006 mol) of 2,2 '-(perfluoro-1,4-phenylene) bis (2,3,3,3-tetrafluoropropane-1-ol in 50 ml of tetrahydrofuran, 0.34 g (0.002) mol) of cyanuric chloride was dissolved in 25 ml tetrahydrofuran and slowly added 1.0 ml (approximately 0.007 mol) of triethylamine as droplets to the solution at 0 ° C. The mixture was allowed to react overnight and 0.25 ml (0.003 mol) of acryloyl After the addition of chloride, 0.5 ml (about 0.0035 mol) of triethylamine were slowly added to the droplets at 0 ° C. After the salt was filtered off, the solvent was removed to give the title product.The yield was about 46% and 1 H-NMR: δ6.49 (d, 6H), 6.13 (m, 3H), 3.59 (m, 6H)

Example 5 Preparation of Copolymer

2,2,3,4,4,4-Hexafluorobutyl acrylate and 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate synthesized in Example 1 and in Example 3 Synthesized 2,2 '-(perfluoro-1,4-phenylene) bis (2,3,3,3-tetrafluoropropane-2,1-diyl) diacrylate in a mass ratio of 5: 2: 3 and copolymerized. The polymerization reaction was carried out using photopolymerization reaction and 2-Hydroxy-2-methyl-propiophenone, a photoinitiator in the ultraviolet region. The mixture of the two monomers and the photoinitiator was applied to a slide glass or a silicon wafer and reacted for 10 minutes using an ADAC Cure zone2 exposure machine using ultraviolet light near a wavelength of 345 nm to obtain a product in the form of a film. Thus produced copolymer has a refractive index of about 1.48 in the wavelength band of about 650nm and T _d (10 wt%) is 312 ℃.

Example 6 Preparation of Copolymer

2,2,3,4,4,4-Hexafluorobutyl acrylate and monomers represented by Formulas 1 and 2,2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate and 2, 2 '-(perfluoro-1,4-phenylene) bis (2,3,3,3-tetrafluoropropane-2,1-diyl) diacrylate and fluorine-substituted styrene, a pentafluoro styrene, in a mass ratio of 3: 2: 2 Copolymerized by mixing at 3: 3. The polymerization reaction was carried out using photopolymerization reaction and 2-Hydroxy-2-methyl-propiophenone, a photoinitiator in the ultraviolet region. A mixture of the two monomers and the photoinitiator was applied to a slide glass or a silicon wafer and reacted for 5 minutes using ultraviolet light near a wavelength of 345 nm to obtain a product in the form of a film. Thus produced copolymer has a refractive index of about 1.51 in the wavelength band of about 650nm and T _d (10 wt%) is 352 ℃. The composition of the copolymer was 3.6: 1.8: 1.7: 2.9 and the absorption loss of the copolymer was 0.002 dB / cm at 850 nm.

The copolymer of the present invention can change the optical properties of the copolymer by controlling the content of each monomer. The copolymer of the present invention is a copolymer of a monomer having two or three polymerization functional groups mixed with a monomer having one polymerization functional group and copolymerized. Crosslinked polymers. As the content of the monomer having 2 to 3 polymerizable functional groups of Formulas 1 to 3 of the present invention increases, the crosslinking density of the copolymer of the present invention increases. The copolymer of the present invention can be used for various applications as a device for a new optical waveguide.

Claims (5)

Compound for an optical waveguide, characterized in that represented by the formula
<Formula 3>

(In Formula 3,
X is H or F,
R is an aromatic compound of 6 to 14 carbon atoms substituted with one or more fluorine or

M is 0 to 6). At least one monomer selected from compounds represented by Formula 3 of claim 1; Wow
An optical waveguide copolymer, characterized in that formed by the polymerization of at least one monomer selected from the group consisting of styrene monomers containing fluorine and acrylic monomers containing fluorine. The method of claim 2,
The optical waveguide copolymer, characterized in that the monomer selected from the compound represented by the formula (3) is contained in 10 to 30 parts by weight based on the copolymer. An optical waveguide comprising a cladding layer and a core formed of the copolymer of claim 2 or 3 and manufactured by a nanoimprint process. The method of claim 4,
The optical waveguide is an optical waveguide, characterized in that the refractive index difference between the cladding layer and the core is 0.2 to 2.0%.