KR101431487B1 - Acrylic compound substituted photosensitive-photoinitiator and method for manufacturing the same - Google Patents

Abstract

The present invention relates to an acrylic compound substituted with a photosensitive photoinitiator and a process for producing the same. Since the acrylic compound substituted with the photosensitive photoinitiator of the present invention is included as a component of the alkali-soluble binder resin, the solubility of the photosensitive photoinitiator separately contained in the photosensitive resin composition is lowered, It is advantageous to have excellent physical properties and process safety.

Photosensitive photoinitiator * Acrylic compound * Manufacturing method

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic compound substituted with a photosensitive photoinitiator and a process for producing the same.

The present invention relates to an acrylic compound substituted with a photosensitive photoinitiator and a process for producing the same. More specifically, there is no need to substitute a photosensitive photoinitiator in an acrylic compound to dissolve the photoinitiator separately, so that an alkali-soluble binder An acrylic compound useful as a component of a resin, and a process for producing the same.

The photosensitive resin composition is applied on a substrate to form a coating film, exposes a specific portion of the coating film by light irradiation using a photomask or the like, and then develops and removes the non-visible portion to form a pattern. Since such a photosensitive composition can be cured by irradiation with light, it is used for a photocurable ink, a photosensitive printing plate, various photoresists, a color filter photoresist for LCD, a photoresist for black matrix, or a transparent photoresist.

The photosensitive resin composition usually contains an alkali-soluble binder resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a solvent.

Among them, the alkali-soluble binder resin makes it possible to coat with an adhesive force to the substrate, to be able to form a fine pattern by melting in an alkaline developer solution, and at the same time to have strength in the obtained pattern, The giver plays a role. It also has a great influence on heat resistance and chemical resistance.

In general, since the photosensitive resin composition is formed of a coating film having a thickness of 3 탆 or more and most of the coating film should be developed, a large amount of the photosensitive resin composition should be soluble in a developing solution in a short time. In addition, if the phenomenon is not cleaned, it may cause not only direct spotting due to residues but also various display defects such as poor alignment of liquid crystals, so that the developability should be very good. When the photosensitive resin composition is applied to a large area glass substrate, the entire surface is difficult to be exposed. Therefore, when the sensitivity of the photosensitive resin composition is low, the time required for the exposure process becomes long and the productivity is lowered. Is required.

In addition, sufficient compressive strength and chemical resistance are required so as not to be destroyed by external pressure as well as thermal stability so that the shape and thickness do not change even in a high-temperature process of 200 DEG C or more. In addition, it is required to be able to stably exhibit desired characteristics without changing even in long-term storage, and therefore, superior stability over time is required. However, a photosensitive resin composition satisfactory in all of heat resistance, chemical resistance, developability, sensitivity and aging stability has not been developed yet.

In recent years, in order to improve the yield per unit time of the process in the process of using the photosensitive resin composition as described above, the exposure time and the development time are reduced. Thus, the sensitivity and developability of the conventional photosensitive resin composition are required to be improved.

As a method for increasing the photosensitivity of the photosensitive resin composition, a photoinitiator having a high photosensitivity is used or an amount of a photoinitiator is increased. However, photoinitiators having high photosensitivity are relatively expensive. In addition, there is a difficulty in selecting a solvent capable of dissolving it, and there is a problem that the photoinitiator is precipitated due to the solubility in a selected solvent, thereby acting as a foreign substance. In addition, when the amount of the photoinitiator is increased, there is a risk that contaminating foreign matters are generated in the post baking process to contaminate the oven or contaminate components such as liquid crystal in the LCD panel.

That is, the increase in the photoinitiator (PI) or the photosensitizer (PS) content in the photosensitizer composition leads to the difficulty in securing the stable property in the photosensitizer composition requiring high sensitivity and the increase in foreign matter in the LCD manufacturing process, Leading to failure.

In order to solve this problem, in recent years, attempts have been made to photo-crosslink an alkali-soluble resin with an ethylenically unsaturated compound in order to introduce a photopolymerizable functional group into the side chain of the alkali-soluble resin used in the photosensitive resin composition. However, since the photopolymerizable reactive group is introduced into the acid-labile part of the alkali-soluble binder resin, the proportion of the photopolymerizable reactive group in the alkali-soluble resin is high and the ratio of the photopolymerizable reactive group in the alkali- There is a problem that the ratio of the remaining acid groups remaining on the surface is lowered and the developability is lowered.

Accordingly, development of an alkali-soluble binder resin having excellent heat resistance, chemical resistance, developability, sensitivity and stability over time is required.

Accordingly, the present invention has the disadvantages of difficulty in securing stable physical properties in a photosensitive composition requiring high sensitivity due to an increase in photoinitiator (PI) or photosensitizer (PS) content in the conventional photosensitive resin composition, To solve problems such as difficulties of maintenances of process and defective products.

Accordingly, an object of the present invention is to provide an acrylic compound substituted with a photosensitive photoinitiator, which is contained in an alkali-soluble binder resin excellent in photosensitivity without securing a safe physical property in a photosensitive resin composition and causing no process problems such as foreign substances I have to.

Another object of the present invention is to provide a process for producing an acrylic compound substituted with the photosensitive photoinitiator.

Accordingly, in the present invention, it is possible to reduce the content of the photoinitiator contained in the photosensitive resin composition by preparing a compound in which various photosensitive photoinitiators are substituted with acrylic compounds and using the compound as a component of an alkali-soluble binder resin, It is possible to solve the problem that a problem or a foreign matter is generated, and it is possible to secure a safe physical property.

By replacing the photosensitive photoinitiator with an acrylic compound as a component of the binder resin as in the present invention, it is possible to solve various problems associated with the limitation of the solvent for dissolving the photoinitiator and the problems such as generation of foreign matter, .

In order to achieve the above object, the acrylic compound of the present invention is characterized in that a photosensitive photoinitiator is substituted.

According to another aspect of the present invention, there is provided a method for preparing an acrylic compound, which comprises reacting a photosensitive photoinitiator with a compound capable of introducing an acrylic group.

Hereinafter, the present invention will be described in more detail.

The acrylic compound according to the present invention is substituted with a photosensitive photoinitiator. "Photosensitive photoinitiator" used throughout the specification and claims of the present invention includes a photoinitiator and photosensitizer capable of exhibiting photosensitivity, and is collectively referred to as a photosensitive photoinitiator.

The acrylic compound substituted with the photosensitive photoinitiator of the present invention can be prepared by reacting various kinds of photosensitive photoinitiators with a compound capable of introducing an acryl group.

Specific examples of the photosensitive photoinitiator include 9-ethyl-2-hydroxycarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6- Dibromocarbazole, 3-amino-N-ethylcarbazole, 4-glycidyloxycarbazole, 4-hydroxycarbazole, 9-acetyl-3,6-diiodocarbazole, Carbazole-3-dicarboxaldehyde, 9-benzylcarbazole-3-dicarboxaldehyde, carbazole-N-carbonyl chloride, N- Carboxaldehyde, N - [(9-ethylcarbazol-3-yl) methylene] -2-methyl-1-indolinylamine, Carvedilol, And N-ethyl-N- (o-tolyl) hydrazone;

(4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2,4-trichloro (2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, and 3- {4- [2,4- Bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid;

1-one, 4- (2-hydroxyphenyl) -2-methylpropane-1- Benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-benzoin methyl ether, (4-methylthiophenyl) -2-morpholino-1-propan-1-one, and 2-benzyl-2-dimethylamino- Phenyl) -butan-1-one; < / RTI >

Methyl-propan-1-one, benzophenone, 4,4'-bis (dimethyl (2-methyl- Aminobenzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3-dimethyl-4-methoxybenzophenone , And 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Fluorene-based compounds selected from the group consisting of 9-fluorenone, 2-chloro-9-fluorenone, and 2-methyl-9-fluorenone;

From the group consisting of thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxytioxanthone, isopropylthioxanthone, and diisopropylthioxanthone Selected thioxantone compounds;

A xanthone based compound selected from xanthone, or 2-methylxanthone;

Anthraquinone selected from the group consisting of anthraquinone-2-carboxylic acid, anthraquinone, 2-methylanthraquinone, 2-ethyl anthraquinone, t -butylanthraquinone, and 2,6-dichloro-9,10- Nonnary compounds;

 (Dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) Amine-based compounds selected from the group consisting of cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, and 2,6-bis (4-diethylaminobenzal) -4-methyl- Synergest;

(Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- Benzoyl-7-methoxy-coumarin, and 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl ] -Benzopyrano [6,7,8-ij] -quinolizine-11-one;

A chalcone compound selected from 4-diethylaminokalcone, or 4-azidobenzalacetophenone;

2-benzoylmethylene; And

And 3-methyl-β-naphthothiazoline. However, it is not limited to these, and other photoinitiators and photosensitizers having photosensitivity known in the art may be used.

The acryl-group-introducible compound may be prepared from a group consisting of 2-hydroxyethyl methacrylate, methacryloyl chloride, acryloyl chloride, dimethyl acryloyl chloride, vinyl chloroformate, and isopropenyl chloroformate Selected.

The reaction of the photosensitive photoinitiator with the compound capable of introducing an acryl group at a molar ratio of 1: 1 to 1: 1.5 is preferable from the viewpoints of solubility enhancement and exposure effect of the photosensitive photoinitiator. When the photosensitive initiator is used, the probability of detection of the solid material in the post-storage stability of the PR itself is reduced because the amount of the photoinitiator used in the photosensitive resin composition is reduced, the possibility of detecting solid matter in the baking step during the lithographic process is reduced, It is not good to use it because it reaches saturation at the limit.

Meanwhile, the photosensitive photoinitiator preferably includes at least one functional group selected from the group consisting of a hydroxyl group, a halogen atom, an aldehyde, an acid group, and an ester group in its structure for introduction of an acrylic group.

Therefore, the acrylic compound substituted with the photosensitive photoinitiator of the present invention may further be subjected to additional manufacturing processes depending on the photosensitive photoinitiator used. This is because, depending on which functional groups the photosensitive photoinitiator contains, a large number of side reactions may occur in the reaction of introducing an acryl group to lower the overall yield.

Specifically, in the case of a carbazole-based photosensitive photoinitiator having a hydroxy group, a compound capable of protecting it is first added to protect the hydroxy group, and then deprotected to introduce an acrylic group. As a result, the protection of the hydroxy group can be determined by selecting a substance as a photosensitive photoinitiator and whether the functional group participates in the intermediate synthesis route.

That is, the photosensitive photoinitiator containing a hydroxy group is prepared by the following process because protection of the functional group is required as mentioned above.

Adding a photosensitive photoinitiator containing a hydroxyl group and a compound capable of protecting a hydroxyl group contained in the photosensitive photoinitiator to protect the hydroxyl group, adding a photosensitizing auxiliary to the photosensitive photoinitiator, Deprotecting the protected hydroxy group of the photosensitive photoinitiator, and reacting the hydroxy group of the photosensitive photoinitiator with a compound capable of introducing an acryl group to prepare an acrylic compound substituted with the photosensitive photoinitiator.

In the first step, a compound capable of protecting a functional group such as benzyl bromide is added and reacted to protect the hydroxyl group contained in the photosensitive photoinitiator.

Examples of the compound capable of protecting the hydroxyl group include benzyl bromide, acetyl, methoxyethoxymethyl ether (MEM), methoxymethyl ether (MOM), p-methoxybenzyl ether PMB), methylthiomethyl ether, pivaloyl, tetrahydropyran, silyl ether, trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS) ), Triisopropylsilyl (TIPS), and methyl ether. The reaction ratio of the compound capable of protecting the functional group to the photosensitive photoinitiator containing a hydroxy group is 1: 1 to 1.3: 1.

The photosensitive photoinitiator and the compound capable of protecting the functional group are dissolved in an organic solvent, and K ₂ CO ₃ is added thereto, followed by reaction at room temperature for 24 hours. The reaction product is extracted with ethyl acetate and ammonium aqueous solution, and the organic solvent portion is extracted and concentrated by silica gel column separation using a developing solution (mobile liquid) containing hexane: ethyl acetate at a ratio of 5: 1.

In the second step, the resultant obtained in the above step 1 is dissolved in an organic solvent, and then a photosensitizing auxiliary agent for enhancing the photosensitive property of the photosensitive photoinitiator is added thereto and reacted in the presence of Lewis acid. The photosensitizer auxiliary added at this time is a compound containing at least one functional group selected from the group consisting of 2-toluoyl chloride, acetyl, thiophene, naphthalene, furan, pyridine, morpholine, amine and dioxolane, So that the photosensitivity of the photosensitive photoinitiator can be improved. The reaction product is washed, the water in the organic solution is removed, and the product is concentrated. The product is separated by a silica gel column separation method using a developing solution (mobile liquid) containing hexane: ethyl acetate at a ratio of 5: 1.

In the third step, a hydroxyl group substituted in the photosensitive photoinitiator protected in the first step is deprotected by adding a catalyst. At this time, Pd / C is used as the catalyst to be used and the reaction proceeds in a hydrogen gas atmosphere. In the third step reaction, the benzyl ether moiety generated in the second step reaction is removed and the hydroxyl group is substituted. In this step, the organic solution is concentrated, and a developing solution (5: 1 mixture of hexane: ethyl acetate The mobile phase is separated by silica gel column separation method.

In addition, an amine compound such as triethylamine may be added to couple the two substances and change the acid generated during the reaction to a salt.

In the fourth step, the resultant product of the third step is dissolved in an organic solvent, and a compound capable of introducing an acryl is added thereto to obtain an acrylic compound substituted with a photosensitive photoinitiator.

The reaction product thus obtained was extracted with ethyl acetate and an aqueous ammonium solution to concentrate the organic solvent, and then separated by silica gel column separation using a developing solution (mobile liquid) containing hexane: ethyl acetate at a ratio of 5: 1 .

The following Reaction Scheme 1 shows an example of preparation of an acrylic compound using a carbazole-based photosensitive photoinitiator containing a hydroxy group.

However, since the thioxanthone compound / xanthone compound / anthraquinone compound does not contain a hydroxy group functional group in the photosensitive photoinitiator, it is not necessary to add a compound capable of introducing an acrylic group into the compound to prevent the reaction, and the benzophenone compound is photosensitive When used as an initiator, there is a hydroxy group in the starting material, but no protection of the functional group is required.

Next, the production process of an acrylic compound is described using a thioxanthone / xanthone photosensitive photoinitiator. The thioxanthone / xanthone photosensitive photoinitiator is prepared by synthesizing each of the photosensitive photoinitiators and reacting the prepared photosensitive photoinitiator with a compound capable of introducing an acrylate group to prepare an acrylic compound substituted with the final photosensitive photoinitiator.

Specifically, thiophenol and acetic anhydride are added to a THF solution containing 3-nitropthalic anhydride, and 30% NaOH aqueous solution, benzyltriethylammonium chloride, methylene chloride And the reaction mixture is stirred at room temperature for 2 hours. When a xanthone-based photosensitive photoinitiator is prepared, phenol is used instead of the thiophenol.

When the reaction is complete, dilute with distilled water, separate the aqueous layer, acidify with HCl and extract with methylene chloride. The extracted organic layer was dried and then the solvent was evaporated. Acetic anhydride and toluene were added to the concentrate, and the solvent was evaporated from the resultant. The crude was recrystallized from CH ₂ Cl ₂ / hexane = 3/1 solution The product is obtained. The product is placed in 1,1,2,2-tetrachloroethane, 0.3 mol equivalent of AlCl ₃ is added, and the mixture is stirred. The mixture is reacted at 120 ° C for 3 hours and the solvent is evaporated. The remaining material is loaded with 2N HCl, the precipitate is filtered, washed well with distilled water, and then dried to obtain the respective thioxanthone / xanthone photosensitive photoinitiator.

Triphenylphosphine (PPh ₃ ) and 2-hydroxyethyl methacrylate were added to each of the above photosensitive photoinitiators in an organic solvent, stirred well, and diethyl azocarboxylate was dropwise added to the mixture, followed by reaction at room temperature for two days. After the reaction was completed, the solution was concentrated, and the final product was purified by column chromatography on hexane / EtOAc = 9/1 developing solution. The final product was recrystallized from ethanol to obtain an acrylate group ( acrylate can be obtained.

A process for producing an acrylic compound using a thioxanthone / xanthone compound as a photosensitive photoinitiator is shown in the following reaction formula (2).

When a benzophenone-based photosensitive photoinitiator is used, a compound capable of introducing an acryl group is directly added and reacted.

That is, an amine compound such as triethylamine is added to dissolve the benzophenone-based photosensitive photoinitiator in an organic solvent and then to add an acrylic compound capable of introducing an acryl group, For 6 hours. After the completion of the reaction, the resulting reaction product was extracted with ethyl acetate and an aqueous ammonium solution. The organic solvent was extracted and concentrated. The product was separated by a silica gel column separation method using a developing solution of hexane: ethyl acetate = 5: 1 to obtain a benzophenone photosensitive photoinitiator Can be obtained.

The following Reaction Scheme 3 shows the preparation process of an acrylic compound used as a benzophenone photosensitive photoinitiator.

When an anthraquinone-based photosensitive photoinitiator is used, a compound capable of introducing an acryl group is added and reacted directly.

Specifically, anthraquinone-2-carboxylic acid and 2-hydroxyethyl methacrylate were dissolved in an organic solvent containing PPh ₃ , azodicarboxylate was added dropwise and reacted at room temperature for 2 days. When the reaction is completed, the solution is concentrated, and the residue is separated by silica gel column separation using hexane: ethyl acetate = 9: 1 developing solution and recrystallization is carried out using ethanol to obtain an acrylic compound substituted with an anthraquinone-based photosensitive photoinitiator .

The following Scheme 4 shows a process for producing an acrylic compound using an anthraquinone-based photosensitive photoinitiator.

Further, it is also possible to use a triazine-based compound, a nonimidazole-based compound, an acetophenone-based compound, an O-acyloxime-based compound, a fluorenone-based compound, an acridine-based compound, a decarbonyl compound, a phosphine oxide- In the case of using a compound, a chalcone compound, 2-benzoylmethylene, and 3-methyl- beta -naphthothiazoline as a photosensitive photoinitiator, the compound can be produced by reacting with an acrylic-type-introducible compound through a similar process to the above-mentioned photosensitive photoinitiator Of course it is.

That is, in the case where the initial reaction starting material is a hydroxyl group or a halogen compound, a chemical reaction as shown in Reaction Scheme 3 or Reaction Scheme 4 can be used in the case where the reactant before the introduction of the acrylic group is a hydroxyl group or an acid group, The introduction of the acrylic monomer containing the photosensitive photoinitiator can be appropriately selected depending on the functional group substituted in the photosensitive photoinitiator.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Example 1: Production of acryl monomer substituted with carbazole-based photosensitive photoinitiator

211 g of 9-ethyl-2-hydroxycarbazole and 171 g of benzyl bromide were placed in a reactor, and then 500 g of DMF and 0.1 mol equivalent of K ₂ CO ₃ were added and reacted at room temperature for one day. After completion of the reaction, the reaction product was extracted with ethyl acetate and an aqueous ammonium solution, and the organic solvent was extracted. The organic solvent was extracted and concentrated by silica gel column separation using hexane: ethyl acetate = 5: 1. 100%.

300 g of the above substance A was dissolved in 500 g of dichloromethane, and 155 g of 2-toluoyl chloride was added at 0 캜. The solution was added with 0.3 mol equivalent of AlCl ₃ while stirring, and the reaction solution was reacted at 0 ° C for 2 hours and reacted at room temperature for one day. The reaction-terminated solution was poured into ice, and the organic solution layer was washed with an aqueous NaHCO ₃ solution and the water in the organic solution was removed using MgSO ₄ . The organic solution was concentrated and separated by silica gel column separation method using hexane: ethyl acetate = 5: 1 developing solution to obtain product B in a yield of 95%.

B material (398 g) was dissolved in 500 g of dichloromethane. Pd / C was added in an amount of 0.2 mole equivalent. Hydrogen gas was blown at room temperature for 12 hours to remove benzyl ether in the B material. The organic solution was concentrated and separated by silica gel column separation using hexane: ethyl acetate = 5: 1 developing solution to obtain product C in a yield of 90%.

C material (280 g) was dissolved in 500 g of THF. Then, 104 g of methacryloyl chloride and 2.3 moles of triethylamine were added thereto, followed by reaction at room temperature for about 6 hours. After the reaction was completed, the resulting reaction product was extracted with ethyl acetate and ammonium aqueous solution. The organic solvent was extracted and concentrated. The product was separated by a silica gel column separation method using hexane: ethyl acetate = 5: 1, To 80%.

The resulting monomer D, N-ethylcarbazole methacrylate, contains both toluoyl and acrylate with a carbazole as the center, and its ¹ H-NMR and GPC-based polystyrene reduced weight average Molecular weight (Mw), elemental analysis results are as follows.

¹ H-NMR: 1.95 (3H), 1.57 (3H), 2.21 (3H), 4.09 (2H), 5.57 (1H), 6.07 (1H), 7.35-8.71

Mw: 397.48

C ₂₆ H ₂₃ NO ₃ : C 78.6%, H 5.8%, N 3.5%, O 12.1%.

Example 2: Preparation of acrylic monomer using thioxanthone-based photosensitive photoinitiator

11.0 g of thiophenol and 10 g of acetic anhydride were added to a THF solution containing 19.3 g of 3-nitropthalic anhydride. 10 g of a 30% NaOH aqueous solution, 7 g of benzyltriethylammonium chloride and 20 g of methylene chloride were added to the stirred solution. The reaction mixture was stirred at room temperature for 2 hours.

After the reaction was completed, the reaction solution was diluted with distilled water, the aqueous layer was separated, acidified with HCl, and extracted with methylene chloride. After the extracted organic layer was dried, the solvent was evaporated, and 10 g of acetic anhydride and 50 ml of toluene were added and the mixture was heated at 120 ° C for 1 hour. After evaporation of the solvent, the crude product was recrystallized from a CH ₃ Cl ₂ / hexane = 3/1 solution to obtain 4.4 g of a product E having a final yield of 17%.

4.4 g of the above substance E was placed in 20 ml of 1,1,2,2-tetrachloroethane and 0.3 mol equivalent of AlCl ₃ was added thereto, followed by stirring. The mixture was reacted at 120 DEG C for 3 hours, and then the solvent was evaporated. 3 ml of 2N HCl was added to the remaining material. The precipitate was filtered, washed well with distilled water, and dried to obtain 3.5 g of the product thioxanthone photosensitive photoinitiator F at a final yield of 82%.

Into the material F and 3.5g triphenylphosphine (PPh ₃₎ 1.0 mole equivalents, and 2-hydroxyethyl methacrylate 18g in 100 ml THF solvent and stirred well. 1.0 mole equivalent of diethylazocarboxylate was added dropwise to the mixture and reacted at room temperature for 2 days. When the reaction was completed, the solution was concentrated and the final product G was purified by column chromatography on hexane / EtOAc = 9/1 developing solution. The G material was recrystallized from ethanol to obtain 3.7 g in a yield of 60%.

The resulting monomer G contains an acrylate group around thioxanthone, and its ¹ H-NMR, GPC-weighted average molecular weight (Mw) in terms of polystyrene and elemental analysis results are as follows.

^{1 H-NMR: 1.94 (3H} ), 4.42 (2H), 4.69 (2H), 5.57 (1H), 6.08 (1H), 7.51-8.62 (7H)

Mw: 368.41

C ₂₀ H ₁₆ O ₅ S: 65.2%, H 4.4%, O 21.7%, S 8.7%.

Example 3 Preparation of Acrylic Monomer Using Xanthone-Based Photosensitive Photoinitiator

Monomer H was obtained in the same manner as in Example 2, except that phenol was used instead of thiophenol.

The polystyrene reduced weight average molecular weight (Mw) and elemental analysis results of ¹ H-NMR and GPC of the final product H are as follows.

^{1 H-NMR: 1.94 (3H} ), 4.43 (2H), 4.69 (2H), 5.57 (1H), 6.07 (1H), 7.41-8.35 (7H)

Mw: 352.35

C ₂₀ H ₁₆ O ₆ : C 68.2%, H 4.6%, O 27.2%.

Example 4: Preparation of acrylic monomer using benzophenone photosensitive photoinitiator

40 g of l- {4- [2- (4-benzoyl-phenoxy) -ethoxy] -phenyl} -2-hydroxy-2-methyl-propan- 1 -one was dissolved in 100 g of THF and methacryloyl chloride (methacryloyl chloride) and 2.3 mole equivalents of triethylamine were added, and the mixture was reacted at room temperature for about 6 hours. After the reaction was completed, the resulting reaction product was extracted with ethyl acetate and an aqueous ammonium solution, and then concentrated. The separated product was separated by a silica gel column separation method using a developing solution of hexane: ethyl acetate = 5: 1, To 80%.

The resulting monomer I contains both benzophenone and acrylate, and its ¹ H-NMR, weight average molecular weight (Mw) in terms of polystyrene using GPC, and elemental analysis results are as follows.

^{1 H-NMR: 1.45 (6H} ), 1.85 (3H), 5.57 (1H), 6.08 (1H), 3.97 (2H), 4.0 (2H), 6.94-7.65 (13H)

Mw: 472.54

C ₂₉ H ₂₈ O ₆ : C 73.7%, H 6.0%, O 20.3%.

Example 5: Preparation of acrylic monomer using an anthraquinone-based photosensitive photoinitiator

25 g of anthraquinone-2-carboxylic acid and 13 g of 2-hydroxyethyl methacrylate were dissolved in 70 g of THF containing 1.5 mole equivalents of PPh ₃ , 0.5 mole equivalent of azodicarboxylate was added dropwise, Lt; / RTI > When the reaction was completed, the solution was concentrated and the product was separated by silica gel column separation using hexane: ethyl acetate = 9: 1 developing solution. Recrystallization using ethanol gave 19 g of final product J at a yield of 60%.

The resulting monomer J contains both an anthraquinone and an acrylate group. Its ¹ H-NMR, weight average molecular weight (Mw) in terms of polystyrene using GPC, and elemental analysis results are as follows.

¹ H-NMR: 1.85 (3H), 5.57 (1H), 6.07 (1H), 7.80-8.97 (7H)

Mw: 320.30

B

C

D

E

(X는 S를 의미)
F

(X는 S를 의미)
G

(X는 S를 의미) H

(X는 O를 의미)
I

J

C ₁₉ H ₁₂ O ₅ : C 71.3%, H 3.8%, O 25.0%.
The structures of A to J of Examples 1 to 5 are shown in Table 1 below.
division Chemical structure
A

B

C

D

E

(X means S)
F

(X means S)
G

(X means S) H

(X means O)
I

J

Claims (15)

As the acrylic compound substituted with the photosensitive photoinitiator, Compounds represented by the following formulas (1), (3) and (4). [Chemical Formula 1]

(3)

[Chemical Formula 4]

delete delete Ethyl-2-hydroxycarbazole to produce a compound represented by the following formula (1-1): (1) protecting the hydroxy group of 9-ethyl-2-hydroxycarbazole by adding benzyl bromide to 9-ethyl-2-hydroxycarbazole; Preparing a compound represented by the following formula (1-2) by adding 2-toluoyl chloride to a compound represented by the following formula (1-1); And deprotecting the protected hydroxy group of the compound represented by the following formula (1-2) to prepare a compound represented by the following formula (1-3); And 1. A process for preparing a photosensitive material, comprising the steps of: preparing a compound represented by the following formula (1), which is an acrylic compound substituted with a photosensitive photoinitiator, by adding methacryloyl chloride to a compound represented by the following formula A process for producing a compound represented by the formula (1). [Chemical Formula 1]

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

delete delete delete delete delete delete 5. The method according to claim 4, wherein the catalyst is Pd / C, wherein the photosensitive photoinitiator is a substituted acrylic compound. delete Adding thiophenol or phenol to 3-nitrophthalic anhydride to prepare a compound represented by the following formula (2-1); Preparing a compound represented by the following formula (2-2) by adding a compound represented by the following formula (2-1) and AlCl ₃ to 1,1,2,2-tetrachloroethane; And 2-hydroxyethyl methacrylate is added to a compound represented by the following formula (2-2) to prepare a compound represented by the following formula (2), which is an acrylic compound substituted with a photosensitive photoinitiator: Wherein the compound is a compound represented by the following formula (2). (2)

(Wherein X in the general formula (2) is S or O) [Formula 2-1]

(In the above formula (2-1), X is S or O) [Formula 2-2]

(In the above formula (2-2), X is S or O) Methacryloyl chloride was added to 1- {4- [2- (4-benzoyl-phenoxy) -ethoxy] -phenyl} -2-hydroxy-2-methyl- (3), wherein the photosensitive photoinitiator is a substituted acrylic compound, wherein the photosensitive photoinitiator is a substituted acrylic compound. (3)

2-hydroxyethyl methacrylate to an anthraquinone-2-carboxylic acid to prepare a compound represented by the following general formula (4), which is an acrylic compound substituted with a photosensitive photoinitiator, wherein the photosensitive photoinitiator is a substituted acrylic compound Lt; RTI ID = 0.0 > (4) < / RTI > [Chemical Formula 4]