KR101285701B1 - Process for preparing UV-curing organic-inorganic hybrid compound - Google Patents

Abstract

The present invention relates to a waveguide core and a cladding material of a high performance optical printed circuit board (O-PCB), and has a refractive index of the photocurable organic-inorganic hybrid compound including BPA and TPM. It relates to a manufacturing method.
According to the present invention, in the method for producing a photocurable organic-inorganic hybrid compound by reacting an alkoxysilane and a diol, 3-trimethoxysilylpropylmethacrylate (TPM) and bisphenol A (Bisphenol A; Sol-gel reaction of BPA) in the presence of a catalyst to produce an organic-inorganic hybrid precursor; And adding a photoinitiator to the organic-inorganic hybrid precursor to spin-coating and irradiating and crosslinking the light. It provides a method for producing a photo-curable organic-inorganic hybrid compound comprising a.

Description

Process for preparing UV-curing organic-inorganic hybrid compound

The present invention relates to a method for manufacturing a waveguide core and a cladding material of a high performance optical printed circuit board (O-PCB), and in detail, the refractive index can be adjusted, and bisphenol A (BPA) is used. ) And 3-trimethoxysilylpropylmethacrylate (TPM), the present invention relates to a method for producing a photocurable (UV curable) organic-inorganic hybrid compound.

Currently, an optical waveguide device is typically manufactured using a semiconductor manufacturing technology or a MEMS (Micro Electro-Mechanical System) technology, and when manufacturing an optical waveguide device on a flat substrate, a planar waveguide technology is used. In addition, researches for further integrating the functions of the optical waveguide device manufactured as described above have been continuously conducted.

In general, the manufacturing method of the optical waveguide device is as follows. First, a lower clad layer is formed on a substrate, and then a core layer is formed on the lower clad layer. Subsequently, a photoresist layer is formed on the core layer, and the photoresist pattern is exposed and developed to form a photoresist pattern. The core layer is etched and patterned using the obtained photoresist pattern. Thereafter, the optical waveguide is completed by forming an upper cladding layer over the patterned core layer.

The cladding layer and the core layer are usually formed by spin coating, and silica or polymers having different refractive indices are used as the forming material. However, when silica is used as the core and cladding layer forming material, the difference in refractive index with the core is obtained up to 75%. Therefore, in the case of using such a material, the size of the optical waveguide is limited, making it difficult to manufacture a passive device for micro optical communication.

US Pat. No. 6,054,253 discloses an optical waveguide using a photosensitive organic-inorganic hybrid material using a sol-gel method, which is related to the present invention. Using the difference, the solvent is used to etch away the unnecessary portions to form the optical waveguide. And US Pat. No. 6,144,795 discloses a method of forming an optical waveguide using an inorganic-organic hybrid material in a mold.

The present invention relates to a waveguide core and a cladding material for a high performance optical printed circuit board, specifically a refractive index of 10 ^- BPA, characterized in that to gain can be adjusted to a ^third scale, the desired refractive index (1.540, 1.560) and It is an object to provide a method for producing a photocurable organic-inorganic hybrid compound containing a TPM.

According to a preferred embodiment of the present invention, 3-trimethoxysilylpropylmethacrylate (TPM) and bisphenol A in the method for producing a photocurable organic-inorganic hybrid compound by reacting an alkoxysilane and a diol Sol-gel reaction of (Bisphenol A; BPA) in the presence of a catalyst to produce an organic-inorganic hybrid precursor; And adding a photoinitiator to the organic-inorganic hybrid precursor to spin-coating and irradiating and crosslinking the light. It provides a method for producing a photo-curable organic-inorganic hybrid compound comprising a.

According to another suitable embodiment of the invention, the catalyst is characterized in that the barium hydroxide monohydrate (Ba (OH) ₂ H ₂ O).

According to another suitable embodiment of the invention, the photoinitiator is characterized in that 2,2-dimethoxy-2-phenyl-acetophenone (2,2-dimethoxy-2-phenylacetophenone; DMPA).

When the photocurable organic-inorganic hybrid compound according to the present invention has a high refractive index and does not lose transparency and stability even at a high temperature, the photocurable organic-inorganic hybrid compound is expected to be used as an encapsulant for a light emitting diode packaging material as well as a waveguide material of a high performance optical printed circuit board. do.

1 is a graph showing the change in refractive index according to the BPA content (mol%) for TPM in the photocurable organic-inorganic hybrid compound of the present invention.
Figure 2 is a photograph showing the thermal stability of the film formed with 56 mol%, 100 mol% BPA content for TPM in the photo-curable organic-inorganic hybrid compound of the present invention.

The photocurable organic-inorganic hybrid compound capable of controlling the refractive index according to the present invention and including BPA and TPM is synthesized by sol-gel reaction of alcoholic silane and diol without using water in the presence of a catalyst.

The alkoxysilane may include 3-trimethoxysilylpropylmethacrylate (TPM) or 3-acryloxypropyltrimethoxysilane (APTMS).

The diol may include bisphenol A or 4,4- (hexafluoroisopropylidine) diphenol (4,4-hexafluoroisopropylidenediphenol), preferably bisphenol A may be used.

In addition, the catalyst used in the sol-gel reaction may include strontium hydroxide monohydrate, calcium hydroxide monohydrate or barium hydroxide monohydrate. Preferably, barium hydroxide monohydrate can be used. The amount of catalyst at this time is 0.1 to 0.5 mol /% of TPM and preferably 0.3 mol%. If the amount of the catalyst is less than 0.1 mol%, the reaction is too slow, and if it exceeds 0.5 mol%, the physical properties of the organic-inorganic hybrid compound are lowered.

The sol-gel reaction is known to make various kinds of inorganic network from silicon or metal alkoxide unit precursor. In general, the sol-gel reaction process appears as a process of hydrolysis, water condensation, and alcohol condensation and requires a large amount of water. However, the sol-gel reaction according to the present invention uses a sol-gel method without using water by using a diol which does not require hydrolysis as a reactant.

Here, Scheme 1 shows a scheme for synthesizing the organic-inorganic hybrid compound by the sol-gel reaction according to the present invention.

[Reaction Scheme 1]

The photoinitiator is added to the resulting transparent solution material, spin-coated, and irradiated with light to crosslink.

The photoinitiator is 2-benzyl-2- (dimethylamino) -4'-morpholinobutyrophenone (2-benzyl-2- (dimethylamino) -4'-morpholinobutyrophenone) or 2,2-dimethoxy-2- Phenyl-acetophenone (2,2-Dimethoxy-2-phenyl-cetophenone) can be used, and preferably 2,2-dimethoxy-2-phenyl-acetophenone (DMPA) can be used. The amount of photoinitiator at this time is 1 to 2 mol /% of TPM and preferably 1.5 mol%. If the amount of the photoinitiator is less than 1 mol%, the crosslinking reaction becomes too slow, and if it exceeds 2 mol%, the physical properties of the organic-inorganic crosslinked product are lowered.

Then, a film having a uniform thickness and an even surface as a whole may be manufactured using a crosslinked product by irradiation with light after spin coating. Scheme 2 shows a crosslinking reaction by light irradiation.

[Reaction Scheme 2]

The method for producing a film using the crosslinked organic-inorganic hybrid composite material is as follows.

The product in a sol state is dropped on a desired substrate, and then covered with a PDMS mold and cured by irradiating UV, thereby producing a film having various patterns.

In addition, the refractive index of the organic-inorganic hybrid compound according to the present invention changes depending on the amount of the benzene group of the diol. As the amount of the diol increases, the amount of the benzene group increases, so the refractive index increases. That is, when the amount of bisphenol A, which is a diol, was 56 mol% based on the amount of alkoxysilane, that is, 3-trimethoxysilylpropyl methacrylate, the refractive index was 1.540, whereas when the amount of bisphenol A was 100 mol%, it increased to 1.560. The change in refractive index according to the amount of diol is shown in FIG. 1.

Hereinafter, the present invention will be described in more detail with reference to Examples, but embodiments according to the present invention can be modified in many different forms, and the scope of the present invention is construed as being limited to the embodiments described below. Can not be done.

Example

Example 1

10 g of TPM, 5.148 g of BPA, and 0.02 g of BaOH, which is a catalyst for a sol-gel reaction, are added to a reactor and stirred at 80 ° C. for at least 5 hours. Then, an alkyl group (-OCH ₃ ) of TPM and a hydroxyl group (-OH) of BPA condensate to form a covalent bond, forming a loose-shaped network (oligosilane). It is a very transparent and viscous liquid phase. After filtering it with a 35 syringe filter, 0.152 g of DMPA, a photoinitiator, was added, spin-coated, and cured using a UV lamp to form a rigid film. The refractive index was measured and shown in FIG. 1.

Example 2

The same procedure as in Example 1 was conducted except that 6.251 g of BPA and 3.285 g of p-xylene were used. The refractive index was measured and shown in FIG. 1.

* When synthesizing high content of BPA (65% or more), it tends to harden easily. In this case, p-xylene is used as a diluent.

Example 3

BPA was carried out in the same manner as in Example 1 except for using 7.722 g of p-xylene and 3.579 g of p-xylene. The refractive index was measured and shown in FIG. 1.

Example 4

BPA was carried out in the same manner as in Example 1 except that 9.192 g of p-xylene and 3.873 g of p-xylene were used. The refractive index was measured and shown in FIG. 1.

Table 1 below shows the contents of the materials used to prepare the organic-inorganic hybrid compound according to Examples 1 to 4.

BPA content for TPM TPM
(g) BPA
(g) BaOH
(g) DMPA
(g) p-xylene
(g) Example 1 56 mole% 10 5.148 0.02 0.152 - Example 2 68 mole% 10 6.251 0.02 0.152 3.285 Example 3 84 mole% 10 7.722 0.02 0.152 3.579 Example 4 100mole% 10 9.192 0.02 0.152 3.873

※ mole% is the molar ratio of comparative substance in%.

Example 5

Example 1 and Example 4 were annealed at 180 ° C. for 1 hour. This result is shown in FIG.

Referring to FIG. 1 as the initial object of the invention the refractive index ¹⁰ was possible to finely adjust the scale ^3, shows a very high linearity and reproducibility of the refractive index change according to the content of BPA. The refractive index value of 1.560 is very high among existing optical materials, and it is expected that the refractive index will be higher at contents of 100% or more.

2 shows the results of experiments of the thermal stability of Example 1 and Example 4, it can be seen that there is no change in color or transparency has a high thermal stability. By utilizing this property, it is expected to be used as a light emitting diode packaging material as well as a waveguide material for a high performance optical printed circuit board.

Claims (3)

In the method for producing a photocurable organic-inorganic hybrid compound capable of controlling the refractive index by reacting an alkoxysilane and a diol,
Sol-gel reaction of 3-trimethoxysilylpropylmethacrylate (TPM) and bisphenol A (BPA) in the presence of a catalyst to prepare an organic-inorganic hybrid precursor; And
Adding a photoinitiator to the organic-inorganic hybrid precursor to spin-coating and irradiating light to crosslink it;
Method for producing a photo-curable organic-inorganic hybrid compound comprising a. The method of claim 1,
The catalyst is a barium hydroxide monohydrate (Baruim hydroxide monohydrate; Ba (OH) ₂ H ₂ O) A method for producing a photo-curable organic-inorganic hybrid compound, characterized in that. The method of claim 1,
The photoinitiator is a 2,2-dimethoxy-2-phenyl-acetophenone (2,2-dimethoxy-2-phenylacetophenone; DMPA) method for producing a photocurable organic-inorganic hybrid compound.

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