KR101491419B1 - Photocurable monomer and method for producing thereof - Google Patents

Abstract

A photocurable monomer compound according to an aspect of the present invention is convenient to use as the photocurable monomer compound has a refractive index higher than that of a photocurable monomer compound manufactured using 1,4-cyclohexanedimethanol (CHDM), and exists in a liquid state at room temperature. Also, the photocurable monomer compound according to an aspect of the present invention can reduce the rainbow effect of a cured film owing to the high refractive index. Moreover, the photocurable monomer compound according to an aspect of the present invention can be used for a photocurable resin composition, which is applied to materials for optical components, can be used as a surface coating material for plastic film substrates used for optical materials, or can be used to impart transparency to optical products, a high refractive index and high surface hardness of the cured articles, excellent productivity and excellent heat resistance as the high refractive index can be ensured.

Description

[0001] PHOTOCURABLE MONOMER AND METHOD FOR PRODUCING THEREOF [0002]

The present invention relates to a photo-curable monomeric compound and a process for its preparation.

The photocurable resin for coating should have good handling property after curing and it should be able to prevent appearance damages that may occur in handling process, and should have excellent workability without yellowing and proper viscosity. In addition, photo-curable resins should have a high refractive index in order to secure a high luminance. Representative examples of such resins include halogen-substituted resins. However, since these resins cause environmental problems or contain harmful components to the human body, Is limited.

1,4-cyclohexanedimethanol (hereinafter referred to as "CHDM") is used for the production of a diacrylate compound which is a photocurable monomer necessary for producing a photocurable resin, 4-Cyclohexanedimethanol (CHDM) can be used in various applications for paints, textile plastics, and the like.

For example, 1,4-cyclohexanedimethanol (CHDM)) is used in polyester synthesis to provide high value-added polymers that increase the thermal stability, corrosion resistance, hydrolysis resistance, moldability, gloss, transparency, And it is also advantageous to facilitate the development of new applications and improvement of the physical properties of the polyester-based resin and to handle it in a liquid state.

In addition, 1,4-cyclohexane dimethanol (CHDM) is used for the coating of a resin containing a hydorxy group together with a curing agent such as melamine, isocyanate and the like. In Korea, it is used as a raw material of PETG (polyethylene terephthalate glycoll) which is excellent in strength, processability and transparency, and 1,4-cyclohexanedimethanol (CHDM) used for PU binder etc. is added to a PET bottle It serves to increase transparency compared to IPA, and is used as a crosslinking agent for PU binders. In addition, it is used for heat-resistant engineering plastics, paints, PU binders, and liquid crystals of electronic circuit boards.

The photo-curable monomer compound, which is a diacrylate compound produced by using 1,4-cyclohexane dimethanol (CHDM) having various uses as described above, is excellent in permeability and curing hardness, but it is caused by a symmetrical chemical structure Which is crystallized at room temperature and is present as a solid, which is inconvenient to use.

Also, the photocurable coating composition obtained using crystalline diacrylate prepared from 1,4-cyclohexane dimethanol (CHDM) has a high viscosity, which results in a poor coating workability.

Therefore, a diacrylate compound having a hardness and a refractive index equal to or higher than those of a photocurable monomer compound produced by using 1,4-cyclohexane dimethanol (CHDM), amorphous and being liquid at room temperature, .

The present invention provides a photocurable monomer compound having high refractive index, amorphous property and being present as a liquid at room temperature and easy to use, and a method for producing the same.

The photocurable monomer compound according to one embodiment of the present invention is a material represented by the following formula (1)

[Chemical Formula 1]

A method for producing a photocurable monomer compound according to another embodiment of the present invention comprises the steps of: preparing a compound represented by the following formula (2);

A second step of adding the compound of Formula 2, an aromatic solvent, and an acid catalyst to a reactor and stirring the mixture;

A third step of further adding acrylic acid and methylhydroquinone to the reactor and stirring the mixture; And

And a fourth step of separating the first product from the product of the third step to prepare a photo-curable monomer compound of the formula (1).

In one embodiment of the present invention, the aromatic solvent is toluene, and the acid catalyst is methane sulfonic acid.

In the method for producing a photocurable monomer compound according to one aspect of the present invention, a fifth step of neutralizing the first product with an alkali solution; And a sixth step of drying the neutralized product in the fifth step.

In the method for producing a photocurable monomer compound according to one aspect of the present invention, the seventh step of removing the toluene solvent from the product of the sixth step is further included.

In a method for producing a photocurable monomer compound according to one aspect of the present invention, the first product is an aromatic solvent phase.

In the method for producing a photocurable monomer compound according to one aspect of the present invention, the alkali solution is sodium hydroxide (NaOH) or potassium hydroxide (KOH).

In the method for producing a photocurable monomer compound according to one aspect of the present invention, magnesium sulfate (MgSO ₄ ) is used in the drying process of the sixth step.

A photocurable resin composition according to another embodiment of the present invention includes a photocurable monomer compound represented by the following formula (1)

[Chemical Formula 1]

The photocurable monomer compound according to one aspect of the present invention has a refractive index higher than that of the photocurable monomer compound prepared using 1,4-CHDM which is a diol having a monomer structure, is amorphous and exists in a liquid state at room temperature, . In addition, the photocurable monomer compound according to one aspect of the present invention can reduce the rainbow effect of the cured film because of its high refractive index.

Further, since the photocurable monomer compound according to one aspect of the present invention can secure a high refractive index, it can be usefully used in a photocurable resin composition applied to an optical component material, and can be used as a surface coating Or may be used to exhibit properties such as transparency in an optical product, high refractive index and hardness of a cured product, and excellent productivity and heat resistance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a process for synthesizing a photo-curable monomer compound prepared according to Example 1 on one side of the present invention. FIG.
2 is a ¹ H-NMR spectrum of a photocurable monomer compound prepared according to Example 1 on one side of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may unnecessarily obscure the subject matter of the present invention. In addition, the terms described below are established in consideration of the functions of the present invention, and these may vary depending on the intention of the manufacturer or custom in the industry, and the definition should be based on the contents throughout the specification.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a photocurable monomer compound according to one aspect of the present invention and a method for producing the same will be described in detail.

The photocurable monomer compound according to one aspect of the present invention is represented by the following formula (1).

[Chemical Formula 1]

A photocurable monomer compound according to one aspect of the present invention comprises a benzene ring and a flexible ether group (hereinafter, referred to as " compound ") in a photocurable monomer compound having a chemical symmetry structure (prepared by using 1,4- cyclohexane dimethanol (-O-) are further bonded to each other to show a structure in which crystallinity is lowered.

(3)

The photo-curable monomer compound prepared using 1,4-CHDM is solid at room temperature, whereas the photo-curable monomer compound according to one aspect of the present invention is colorless and transparent, and is conveniently used at room temperature. In addition, the photocurable monomer compound according to one aspect of the present invention can reduce the rainbow effect of the cured film because of its high refractive index.

Further, the photocurable acrylic coating composition prepared using the photocurable monomer compound according to one aspect of the present invention has high refractive index and surface hardness after coating film formation, and can be used as a surface coating material for a plastic film substrate used for optical materials, Excellent curing properties are exhibited, heat resistance and processability are ensured, and excellent transmittance is exhibited, ensuring transparency of the coating film.

The function and use of the photocurable monomer compound according to one aspect of the present invention can be used as an scratch resistant hard coat agent having workability.

The photocurable monomer compound according to one aspect of the present invention has a high refractive index and a low viscosity (liquid at room temperature), a refractive index of 1.4890, and a viscosity of 325 cps at 25 캜.

The photo-curable monomer compound according to one aspect of the present invention contains an ether functional group and has excellent adhesiveness, and can improve adhesion with various plastic substrates. In addition, it is possible to form a film excellent in both corrosion resistance, abrasion resistance and hardness because of its excellent transmittance and photo curability.

A schematic diagram of a method for producing the photocurable monomer compound of Formula 1 according to one aspect of the present invention is shown in FIG.

According to one aspect of the present invention, there is provided a process for preparing the photo-curable monomer compound of Formula 1, which comprises reacting di- (4-hydroxy methyl cyclohexylmethyl) ether ≪ / RTI >

(2)

The photocurable monomer compound of Formula 1 is produced by reacting a diol reaction product of a dimer type having a flexible ether functional group of Formula 2 with acrylic acid or methacrylic acid Is an amorphous diacrylate compound having a dimer chemical structure containing an ether group.

In order to prepare the diacrylate compound of Formula 1, a small amount of methane sulfonic acid, which is an acid catalyst for the ester reaction, is required, and toluene, which forms an azeotropic ratio to remove water as a byproduct of the reaction, is used as a reaction solvent , Dean Stark trap (Dean Stark trap) device is used to remove the reaction by-product water. At this time, the reaction temperature is maintained at 118 ° C to 120 ° C at which toluene is sufficiently refluxed so that water can be removed smoothly. In order to prevent thermal polymerization of the acrylate formed during the esterification, a small amount of a methylhydroquinone polymerization inhibitor is added, and an esterification reaction is carried out by additionally introducing air having a polymerization inhibiting function into the reactor. .

As the reaction solvent, an aromatic solvent may be used. Examples thereof include benzene, toluene, xylene, etc., and toluene is preferably used. As the catalyst for the ester reaction, an acid catalyst may be used, and methane sulfonic acid may be preferably used. As the polymerization inhibitor, a hydrocoupling polymerization inhibitor may be used, and methylhydroquinone may preferably be used.

An alkaline solution is used to neutralize the first product formed with the aromatic solvent, and the alkaline solution may be sodium hydroxide (NaOH) or potassium hydroxide (KOH).

Hereinafter, a method for producing a photocurable monomer compound (Comparative Example) produced using Example 1 of the present invention and 1,4-CHDM will be described in detail.

The photocurable monomer compound of the formula (1)

Di- (4-hydroxy methyl cyclohexylmethyl) ether of formula (2): di- (4-hydroxymethylcyclohexylmethyl)

(2)

Example

A process for producing a photocurable monomer compound of formula (1)

, 270.42 g (1.0 mol) of di- (4-hydroxymethyl cyclohexylmethyl) ether of Formula 2, 300 ml of toluene, 300 ml of methane sulfonic acid 1 g (0.01 mol) of acetic acid were added to a four-necked 1 L round-bottom flask reactor with a magnetic stir bar and stirred.

Then, a Dean-Stark trap, a condenser, and an air injector are attached to a four-neck round flask reactor to remove water as a reaction by-product.

173 g (2.4 mol) of acrylic acid and 200 mg (1.611 mmol) of methylhydroquinone were further charged into the four-neck round flask reactor and then reacted under air conditions for 6 hours to 8 hours at 118-120 And the reaction is terminated when 36 ml of water (H ₂ O) is obtained as a by-product in the Dean-Stark trap.

After completion of the reaction, the reaction mixture is cooled at room temperature, placed in a separating funnel, and washed three more times with distilled water.

The toluene phase is neutralized with 15 g of sodium hydroxide (NaOH) and dried with 10 g of magnesium sulfate (MgSO ₄ ).

The toluene solvent is removed using a rotary evaporator to give 378 g of a clear liquid product.

The yield was 100% and the product prepared was 4,4 '- [oxybis (methylene)] bis-cyclohexyldimethyl-1,1'-diacrylate (4,4' - [Oxybis (methylene)] bis-cyclohexyldimethyl-1,1'-diacrylate).

2 is a ¹ H-NMR spectrum of a photocurable monomer compound prepared according to Example 1 on one side of the present invention. Referring to FIG. 2, the methylene peak bonded to the ester functional group was observed at 3.9 ppm, and the hydrogen peak of the acrylate double bond was observed at 5.8 - 6.4 ppm. The photocurable monomer compound represented by Formula 1 was synthesized .

Comparative Example

The material used as a comparative example is CD-406 (Cyclohexane dimethanol diacrylate) of Sartomer Company, which is currently commercialized and commercially available.

The comparative charts of the photocurable monomer compounds prepared from the above Examples and Comparative Examples of the present invention are as follows.

Comparative Example
(CD-406 from Sartomer Company, USA) Example 1 constitutional formula

Empirical formula C ₁₄ H ₂₀ O ₄ C ₂₂ H ₃₄ O ₅ Appearance (25 ℃) solid Colorless transparent liquid Viscosity (cps, 25 캜)
Measured with a Brookfield Viscometer NA (solid at room temperature) 325 Refractive index (RI, 25 DEG C) 1.4800 1.4890 Pencil hardness HB B Pendulum hardness 47 42

Properties and Viscosity

The comparative photocurable monomer compound is solid at ambient temperature, and the photocurable monomer compound prepared according to Example 1 of the present invention is a colorless transparent liquid and has a viscosity of 325 cps at 25 占 폚. That is, the viscosity of the photocurable monomer compound prepared according to Example 1 of the present invention is 325 cps at 25 캜, which is lower than other acrylate compounds containing cyclohexyl functional groups.

Refractive index

The refractive index of the photo-curable monomer compound of the comparative example was 1.4800. The refractive index of the photo-curable monomer compound prepared in Example 1 of the present invention was 1.4890, which was relatively higher than that of the comparative example And exhibits a high refractive index.

Hardness

In the comparative table, the hardness shows the physical properties of the coating film measured after coating the photocurable monomer compound according to the comparative example and the example 1 using a glass substrate, and photocuring. The thickness of the coating was 250 탆, and the photoinitiator was 5 phr (part per hundred, using 5 g of photoinitiator when 100 g of monomer was used).

The hardness of the photocurable monomer compound of Comparative Example was slightly higher than that of the photocurable monomer compound prepared according to Example 1 of the present invention. However, the photocurable monomer compound prepared according to Example 1 of the present invention had a higher impact resistant coating film than Comparative Example .

From this, it can be seen that the photocurable monomer compound prepared according to Example 1 of the present invention exhibits the same level of refractive index and hardness as compared with the photocurable monomer compound of the comparative example already on the market, and shows a colorless transparent liquid And showed 325 cps viscosity, which is superior to the comparative example.

As a result, the photocurable monomer compound according to one aspect of the present invention has a hardness and a refractive index equal to or higher than those of a commercially available photocurable monomer compound, is amorphous, and is present as a liquid at room temperature, .

In addition, the photocurable monomer compound according to one aspect of the present invention can reduce the rainbow effect of the cured film because of its high refractive index. Further, since the photocurable monomer compound according to one aspect of the present invention can secure a high refractive index, it can be usefully used in a photocurable resin composition applied to an optical component material, and can be used as a surface coating Or may be used to exhibit properties such as transparency in an optical product, high refractive index and hardness of a cured product, and excellent productivity and heat resistance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be understood that various modifications and applications are possible. For example, each component specifically shown in the embodiments can be modified and implemented. It is to be understood that all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (9)

1. A photocurable monomer compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

A first step of preparing a compound represented by the following formula (2);
(2)

A second step of adding the compound of Formula 2, an aromatic solvent, and an acid catalyst to a reactor and stirring the mixture;
A third step of further adding acrylic acid and methylhydroquinone to the reactor and stirring the mixture; And
A fourth step of separating, from the product of the third step, a first product comprising a photocurable monomer compound represented by the following formula (1);
[Chemical Formula 1]

The method for producing a photocurable monomer compound according to claim 1,
3. The method of claim 2,
The aromatic solvent is toluene,
Wherein the acid catalyst is methane sulfonic acid. ≪ RTI ID = 0.0 > 11. < / RTI >
3. The method of claim 2,
A fifth step of neutralizing the first product with an alkali solution; And
A sixth step of drying the neutralized product in the fifth step;
≪ / RTI > further comprising a photoinitiator.
5. The method of claim 4,
And a seventh step of removing the toluene solvent from the product of the sixth step.
3. The method of claim 2,
Wherein the first product is an aromatic solvent phase. ≪ RTI ID = 0.0 > 11. < / RTI >
5. The method of claim 4,
Wherein the alkali solution is sodium hydroxide (NaOH) or potassium hydroxide (KOH).
5. The method of claim 4,
Wherein magnesium sulfate (MgSO ₄ ) is used in the drying step of the sixth step.
1. A photocurable resin composition comprising a photocurable monomer compound represented by the following formula
[Chemical Formula 1]

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