KR20190021362A - 9-phenylacridine polymer sensitizer, its preparation method and use - Google Patents

Abstract

여기에서,
R₁은 C₁-C₆₀ 선형 또는 분지형 (m+n)-원자가 알킬기이고, 여기에서 -CH₂-는 산소, 황 또는 1,4-페닐렌기로 선택적으로 치환될 수 있고; A는 각각 독립적으로 -[(CHR₄)_x-O]_y-을 나타내며, 여기에서 R₄는 각각 독립적으로 수소, 메틸기 또는 에틸기를 나타내고, x는 1-10의 정수이고, y는 1-20의 정수이며; R₂는 선형 또는 분지형 알킬렌기를 나타내며, 여기에서 -CH₂-는 산소, 황 또는 페닐렌기로 선택적으로 치환될 수 있고; R₃은 수소 또는 치환기를 나타내고; m은 0-20의 정수를 나타내고, n은 1-20의 정수를 나타낸다. 광경화성 시스템에서 사용할 때, 감광제는 양호한 상용성(compatibility)과 양호한 감광성 개선 효과를 갖고, 이로부터 제조된 필름은 우수한 해상도와 접착성 및 높은 수용성을 갖는다.9-phenylacridine polymer sensitizing agent, a process for producing the same, and uses thereof. The 9-phenylacridine polymer sensitizer comprises at least one of the compounds having the structure represented by formula (I)

From here,
R ₁ is a C ₁ -C ₆₀ linear or branched (m + n) -valent alkyl group, wherein -CH ₂ - may be optionally substituted with an oxygen, sulfur or 1,4-phenylene group; A represents independently - [(CHR ₄ ) _x -O] _y -, wherein each R ₄ independently represents hydrogen, a methyl group or an ethyl group, x is an integer of 1-10, y is 1-20 Lt; / RTI > R ₂ represents a linear or branched alkylene group, wherein -CH ₂ - may be optionally substituted with an oxygen, sulfur or phenylene group; R ₃ represents hydrogen or a substituent; m represents an integer of 0-20, and n represents an integer of 1-20. When used in a photocurable system, the photosensitizer has good compatibility and good photosensitizing effect, and the resulting film has excellent resolution, adhesion and high water solubility.

Description

9-phenylacridine polymer sensitizer, its preparation method and use

The present invention belongs to the field of organic chemistry and more particularly relates to 9-phenylacridine macromolecular photosensitizers and their use as well as their use in the field of photocuring.

The acridine compound is a macrocyclic conjugated system with a strong planar structure and very strong fluorescence, which is a good class of fluorescent reagent. It can be used as a photoinitiator in a photopolymerization system, or it can also be used as a sensitizer to initiate a photoinitiator and perform photopolymerization. 9-Phenacridine is an acridine derivative, belonging to the biphenyl-type structure. They can initiate crosslinking curing of photo-curable materials (photocurable paint, ink, photoresist, etc.) composed mainly of unsaturated resin and its monomer material under irradiation of ultraviolet ray and X-ray. In addition, they have stable properties and have good photosensitivity in a photo-curable material composed of an unsaturated resin and its monomer material. Therefore, they are widely used in the field of photocuring.

The use of acridine compounds as photosensitizers is well known. For example, the use of other acridine compounds in photosensitive resins is disclosed in Chinese patent applications CN101525392A, CN102675203A, and the like. However, when used as photosensitizers, these existing acridine compounds have some disadvantages of undesirable solubility, poor photosensitivity improvement. 9-Phenylacridine is one of the most widely used products for existing acridine sensitizers. As micromolecular photosensitizers, they are often difficult to separate from the reactants, are difficult to recover, are poorly miscible with the system during use, are easily agglomerated and separated, reduce the reaction efficiency, . In particular, 9-phenylacridine has very low water solubility, which seriously affects its popularization and application as photosensitizers in the field of photocuring, especially in the dry film photoresist sector. Unexposed parts are typically washed away in alkaline aqueous solution during dry film development whereas 9-phenylacridine is precipitated on the surface of the circuit board at this point due to their very low water solubility Lt; / RTI > In this case, the use of the dry film will not only be affected but also the accuracy of the product will deteriorate. Therefore, a cleaning procedure of the circuit board surface needs to be added later, which complicates the process and greatly increases the cost.

With respect to the drawbacks of the prior art, the present invention aims to provide a 9-phenylacridine polymeric photoresist. Compared to conventional photosensitizers, the photosensitizer of the present invention has good compatibility and good photosensitivity improvement effects when used in a photocurable system, and the films produced therefrom have excellent resolution, adhesion and high water solubility Which is easy to remove by washing).

Specifically, the 9-phenylacridine polymer sensitizer of the present invention comprises at least one of the compounds having the structure represented by Formula (I): < EMI ID =

From here,

R ₁ represents a C ₁ -C ₆₀ linear or branched (m + n) valent alkyl group, wherein -CH ₂ - may be optionally substituted with an oxygen, sulfur or 1,4-phenylene group ;

Wherein A independently represents - [(CHR ₄ ) _x -O] _y -, wherein each R ₄ independently represents hydrogen, methyl or ethyl, x is an integer of 1-10, y is 1-20 Lt; / RTI >

R ₂ represents a C ₁ -C ₂₀ linear or branched alkylene group, wherein -CH ₂ - may be optionally substituted with an oxygen, sulfur or phenylene group;

R ₃ represents hydrogen or a substituent; And

m represents an integer of 0-20, and n represents an integer of 1-20.

In a preferred embodiment, R ₁ represents a C ₁ -C ₂₀ linear or branched (m + n) -valent alkyl group, wherein -CH ₂ -, when two oxygen atoms are not directly connected, And may be optionally substituted with a 4-phenylene group.

More preferably, in the structure represented by the above-described formula (I), R ₁ is selected from the following groups:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

.

In a preferred embodiment, A represents - [(CHR ₄ ) _x -O] _y -, wherein each R ₄ independently represents hydrogen, methyl or ethyl, x is an integer of 1-10, Lt; / RTI > The terminal oxygen atom of the - [(CHR ₄ ) _x -O] _y - group is connected to R ₁ .

More preferably, A is selected from the following groups:

_{- [CH 2 O] y -} , - [CH 2 CH 2 O] y -, - [CH 2 CH 2 CH 2 O] y -, - [CH 2 CH 2 CH 2 CH 2 O] y -, - [ _{CH (CH 3) -CH 2 O} ] y -, - [CH 2 -CH (CH 3) -CH 2 O] y -, where y is an integer of 1-20.

In a preferred embodiment, R ₂ represents a C ₁ -C ₈ linear or branched alkylene group, wherein -CH ₂ - is optionally substituted with oxygen or 1,4-phenylene if the two oxygen atoms are not directly connected . ≪ / RTI >

More preferably, R < ₂ > is selected from the following groups:

_{* CH 2 *, * CH 2} -CH 2 *, * CH 2 -CH 2 -CH 2 *, * CH (CH 3) -CH 2 *, * CH 2 CH 2 CH 2 CH 2 *, * CH 2 - O-CH ₂ *, * CH ₂ -CH ₂ -O-CH ₂ *, * CH ₂ -CH ₂ -O-CH ₂ -CH ₂ *.

Preferably, R ₃ is selected from H, CH _3, NO ₂ or halogen (e.g., F, Cl and Br).

Preferably, m represents an integer of 0-7, n represents an integer of 1-8, and the sum of m and n is an integer of 2-8.

The present invention therefore also relates to a process for the preparation of the 9-phenylacridine polymeric sensitizer described above, which comprises the following steps:

(1) carrying out a reaction between raw material a and raw material b in the presence of a catalyst to obtain an intermediate a;

(2) performing a reaction between the intermediate a and the starting material c in a solvent containing an acid binding agent to obtain an intermediate b;

(3) performing a transesterification reaction between the intermediate b and the starting material d in the presence of a catalyst to obtain a product;

Here, the reaction formula is shown as follows:

Wherein R ₅ represents a C ₁ -C ₈ linear or branched alkyl group.

The photosensitizers of the present invention are improved and optimized with respect to the structure of existing compounds. As shown in the above-described reaction schemes, the synthesis involved in the method of preparation relates to acridine structure, esterification, construction of ester exchange, and the like which are all common processes in the field of organic chemistry. Where synthetic processes and their principles are apparent, specific process parameters will be readily determined by those skilled in the art. For example, the contents described in Chinese patent CN101525392A can be referred to, which is incorporated herein by reference in its entirety.

Preferably, in step (1), the catalyst is a composite catalyst of zinc chloride and 85% phosphoric acid. The reaction temperature varies slightly depending on the different kinds of raw materials, typically 150 - 220 캜, and the reaction time is 4 - 8 hours.

Preferably, in step (2), R ₅ in the structure of raw material c represents a C ₁ -C ₄ linear or branched alkyl group, especially CH ₃ , CH ₂ CH ₃ and CH ₂ CH ₂ CH ₃ . The type of the solvent to be used is not particularly limited as long as it can dissolve the raw material of the reaction and does not adversely affect the reaction. Examples thereof include acetone, acetonitrile, methanol, ethanol and N, N-dimethylformamide. The acid binding agent may be sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine, triethylamine, and the like. The reaction temperature is from 40 to 100 ° C., and the reaction time is typically from 4 to 18 hours.

Preferably, in step (3), the transesterification reaction is carried out in a solvent. Here, the type of the solvent is not particularly limited as long as it can dissolve the raw material of the reaction and does not adversely affect the reaction, and examples thereof include toluene, xylene, benzene, cyclohexane and the like. The catalyst may be one or a combination of one or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, methylsulfonic acid, p-toluenesulfonic acid, sulfuric acid and hypophosphorous acid. The amount of the catalyst to be used is preferably 5 to 15% of the total mass of the raw materials for the reaction. The reaction temperature is typically 70-130 占 폚. The reaction time is typically 1 to 8 hours.

As can be seen from the transesterification reaction in step (3) by the person skilled in the art, there are m + n hydroxy groups which can undergo an ester exchange reaction with intermediate b in raw material d. If m + n is greater than 1 and intermediate b is not sufficient for the hydroxy group, the number of intermediates b that react with a single molecule of R ₁ (AOH) _{m + n} will not match each other. Thus, the resulting product is not a compound having a single structure, but a mixture of compounds having the structure of formula (I). This mixture falls within the definition of the 9-phenylacridine polymer sensitizer described above.

The 9-phenylacridine polymer photoresist of the present invention has excellent water solubility and is particularly suitable for use as a photosensitizer in a photocurable system. This has a good photosensitizing effect, and the film produced therefrom has excellent resolution and adhesion. Thus, the present invention also relates to the use of a 9-phenylacridine polymeric photoresist in a photocurable composition. The photoinitiator used in the photo-curable composition is preferably selected from photo acid generators, photoinitiators and radical photoinitiators.

Advantageous effects of the present invention further include:

1. Energy transfer and intermolecular reaction in the polymer chain make the polymer sensitizer more easily have a high photosensitivity;

2. Products with different reactivities are obtained by copolymerization with inert groups, control and design of the distance between the photosensitive groups, or by changing the distance between the photoactive group and the main chain;

3. The movement of the photosensitive group is limited by the polymerization of the photosensitive group, thereby preventing yellowing and aging of the coating layer;

4. Since most of the photolysis fragments are still linked to the polymerization matrix, the odor and toxicity of the system can be reduced.

Hereinafter, the present invention will be further illustrated in detail below with reference to specific embodiments, but the scope of the present invention should not be construed as being limited thereto.

Manufacturing example

Example  One

(1) Preparation of intermediate 1a

A solution of 165.6 g (1.2 mol) of p-hydroxybenzoic acid, 169.0 g (1.0 mol) of diphenylamine, 244.8 g (1.8 mol) of zinc chloride and 115.3 g Was added to a globular flask, the temperature was increased to 200-210 DEG C with stirring and the reaction was carried out for 6 hours. The temperature was then reduced to 130-140 DEG C, 400 g of 30% sulfuric acid was added dropwise, the temperature was maintained at 80 DEG C with stirring for 2 hours and 300 g of water at 80 DEG C was added with stirring for 0.5 hour , The water in the lower layer was separated by standing, and the operation was repeated by addition of 300 g of water. 300 g of ammonia water was finally added to the reaction flask to precipitate a large amount of orange solids. The material in the reaction flask was suction filtered at room temperature, rinsed with methanol and dried to give 257.4 g of the intermediate 1a as a 98% pure.

The structure of intermediate 1a was confirmed by LCMS.

Mass spectrometric analysis was performed with software attached to the instrument to obtain molecular fragment peaks at 272 and 273, and the molecular weight of the product was 271, consistent with T + 1 and T + 2.

(2) Preparation of intermediate 1b

27.1 g (0.1 mol) of Intermediate 1a, 16.6 g (0.12 mol) of potassium carbonate and 167 g of acetonitrile were added to a 500 mL four-necked flask and then heated at 80 DEG C under reflux. 12.0 g (0.11 mol) of methyl chloroacetate was added dropwise in about 1 hour. After completion of the dropwise addition, the reaction was continued for 8 hours. After completion of the reaction, unreacted potassium carbonate was removed by filtration by hot filtration and most of the solvent was evaporated under reduced pressure to precipitate the solid. The material in the reaction flask was suction filtered, rinsed with methanol and dried to give 32.5 g of a light yellow solid of intermediate 1b in 98% purity.

The structure of intermediate 1b was confirmed by LCMS and ¹ H-NMR.

Mass spectrometry was performed with software attached to the instrument to obtain molecular fragment peaks at 344 and 345, and the molecular weight of the product was 343, consistent with T + 1 and T + 2.

_{^{1 H-NMR (CDCl 3,}} 500MHz): 3.6721 (3H, s), 4.9034 (2H, s), 6.7254-6.8351 (2H, d), 7.2812-7.3708 (2H, d), 7.3424-7.4765 (2H, d ), 7.5432-7.6278 (4H, d), 7.9234-8.0509 (2H, d).

(3) Production of the product 1

To a 1000 mL four-necked flask were added 154.3 g (0.45 mol) of intermediate 1b, 166.2 g (0.3 mol) of raw material 1d, 1.3 g of lithium hydroxide and 540 g of toluene, And heated with stirring. Methanol produced in the reaction was heated to evaporate, and toluene was appropriately replenished until the methanol was no longer evaporated. Filtration was carried out while hot, and the resulting filtrate was distilled under reduced pressure until the residual toluene content was less than 5000 ppm to obtain 304.4 g of a pale yellow viscous product of Product 1.

It is easy to understand that three hydroxy groups with the same or similar activity were present in raw material 1d and that product 1 contained products 1-1, 1-2 and 1-3 due to the different reaction ranges of a single molecule of raw material 1d Will be.

Example  2

(1) Preparation of intermediate 2a

169.0 g (1.0 mol) of diphenylamine, 244.8 g (1.8 mol) of zinc chloride and 115.3 g (1.0 mol) of 85% phosphoric acid were added to 1000 mL four-necked flask, the temperature was increased to 200-210 DEG C with stirring, and the reaction was carried out for 6 hours. Liquid phase tracking was performed until the reaction was complete. The temperature was reduced to 130-140 캜, 400 g of 30% sulfuric acid was added dropwise, the temperature was maintained at 80 캜 while stirring for 2 hours, 300 g of water was added at 80 캜 with stirring for 0.5 hours, The mixture was allowed to stand and separated, and 300 g of water was further added thereto to repeat the above operation. 300 g of ammonia water was finally added to the reaction flask to precipitate a large amount of orange solids. The material in the reaction flask was suction filtered, rinsed with methanol and dried to give 300.2 g of the intermediate 2a, a 98% purity and 95% yield.

The structure of intermediate 2a was confirmed by LCMS.

Mass spectrometry was performed with software attached to the instrument to obtain molecular fragment peaks at 317 and 318, and the molecular weight of the product was 316, consistent with T + 1 and T + 2.

(2) Preparation of intermediate 2b

31.6 g (0.1 mol) of intermediate 2a, 16.6 g (0.12 mol) of potassium carbonate and 156 g of acetonitrile were added to a 500 mL four-necked flask and heated at 80 DEG C under reflux. 13.4 g (0.11 mol) of ethyl chloroacetate was added dropwise in about 1 hour. After completion of the dropwise addition, the reaction was continued for 8 hours. After completion of the reaction, the unreacted potassium carbonate was removed by filtration by hot filtration and most of the solvent was evaporated under reduced pressure to precipitate a solid. The solid was suction filtered, rinsed with methanol and dried to obtain 36.8 g of intermediate 2b A pale yellow solid was obtained with a purity of 98% and a yield of 91.5.

The structure of intermediate 2b was confirmed by LCMS.

Mass spectrometry was performed with software attached to the instrument to obtain molecular fragment peaks at 403 and 404, and the molecular weight of the product was 402, which was consistent with T + 1 and T + 2.

The structure of intermediate 2b was confirmed by ¹ H-NMR.

¹ H-NMR (CDCl ₃ , 500 MHz): 3.6721-3.7232 (3H, t), 4.9034-4.9985 (2H, q), 7.0942 (2H, s), 7.3424-7.4765 , q), 7.6082-7.6191 (2H, d), 7.7634-7.7705 (2H, d), 7.9234-8.0509 (2H, d), 8.3233 (1H, s).

(3) Production of product 2

A solution of 180.4 g (0.45 mol) of intermediate 2b, 79.8 g (0.3 mol) of raw material 2d, 1.3 g of lithium hydroxide and 540 g of toluene was added to a 1000 mL four-necked flask and the temperature was adjusted to 90-100 And heated with stirring. Methanol produced in the reaction was heated to evaporate, and toluene was appropriately replenished until the methanol was no longer evaporated. Filtration was carried out while hot, and the resulting filtrate was distilled under reduced pressure until the residual toluene content was less than 5000 ppm to obtain 221 g of a pale yellow viscous substance of product 2 in a yield of 92.4%.

Example  3 - 9

Referring to the method of Example 1 or 2, the product 3-9 having the following structure was synthesized.

Product 3:

Product 4:

Product 5:

Product 6:

Product 7:

Product 8:

Product 9:

Evaluation of characteristics

The application characteristics of the photosensitizer of the present invention were evaluated by formulating an exemplary photocurable composition.

1. Manufacture of objects for characterization

≪ Preparation of photosensitive resin laminate >

The photosensitive resin composition having the composition shown in Table 1 and propylene glycol monoethyl ether acetate were thoroughly stirred and mixed, and uniformly coated on the surface of a polyethylene terephthalate thin film having a thickness of 19 mu m as a support using bar coating And then dried in a dryer at 95 캜 for 4 minutes to form a photosensitive resin layer having a thickness of 40 탆. Then, a polyethylene thin film having a thickness of 23 mu m was adhered as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate thin film was not laminated to obtain a photosensitive resin laminate.

≪ Leveling of Substrate Surface >

As a substrate for use in evaluating photosensitivity and resolution, the use of a copper clad laminate treated with a spray washing mill at a spray pressure of 0.20 MPa .

<Lamination>

While the surface was planarized, the polyethylene thin film of the photosensitive resin laminate peeled off. The laminate was laminated on a copper clad laminate preheated to 60 占 폚 by a hot roller laminator at a roller temperature of 105 占 폚, wherein the gas pressure was 0.35 MPa and the laminating speed was 1.5 m / min.

<Exposure>

By using an h-ray type direct drawing exposure apparatus (Digital Light Processing), an exposure amount of 8 steps in the step-by-step exposure apparatus is obtained according to the photosensitivity evaluation described below. Exposure was performed.

<Development>

After the polyethylene terephthalate thin film was peeled off, development was carried out at 23 DEG C for 2 minutes using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to dissolve and remove unexposed portions of the photosensitive resin layer. Then, cleaning was performed with ultra-pure water for 1 minute. At this time, the minimum amount of time required to completely dissolve the photosensitive resin layer in the non-exposed portion was regarded as the minimum developing time.

sign Example
One Example
2 Example
3 Example
4 Example
5 Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4





Photosensitive
Suzy
Composition
(Parts by weight) P-1 41 41 41 41 41 41 41 41 41 P-2 100 100 100 100 100 100 100 100 100 M-1 14 14 14 14 14 14 14 14 14 M-2 20 20 20 20 20 20 20 20 20 M-3 5 5 5 5 5 5 5 5 5 M-4 5 5 5 5 5 5 5 5 5 TPS 4 4 4 4 4 4 4 4 Product 1 0.4 Product 2 0.4 Product 3 0.4 Product 5 0.4 Product 7 0.4 A-1 0.4 A-2 0.4 B-1 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 B-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Note: The name / composition of the components indicated by designation in Table 1 is shown in Table 2.

sign ingredient P-1 Wherein the copolymer contains 30 mass% of the copolymer and the copolymer has a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (mass ratio 70/20/10) An acid equivalent of 334 and a weight average molecular weight of 120000. P-2 Wherein the copolymer contains 43 mass% and the copolymer has a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (weight ratio 50/30/20) An acid equivalent weight of 340 and a weight average molecular weight of 50,000. M-1 The urethanization product of hexamethylene diisocyanate and pentapropylene glycol monomethacrylate M-2 Dipentaerythritol hexaacrylate M-3 Tetra-nonylphenylheptaethylene glycol dipropylene glycol acrylate M-4 Triacrylate of trimethylolpropane with an average of 3 moles of cyclohexane added TPS Tribromomethylphenylsulfone (photo acid generator) A-1 9-phenylacridine A-2 4,4-bis (diethylamino) benzophenone B-1 Malachite green B-2 Leuco crystal violet

2. Methods for evaluating characteristics

(1) Compatibility Test

The photosensitive resin composition having the composition shown in Table 1 was thoroughly stirred and mixed and uniformly coated on the surface of a polyethylene terephthalate thin film having a thickness of 19 mu m as a support using a bar coating and dried in a dryer at 95 DEG C for 4 minutes Thereby forming a photosensitive resin layer. Thereafter, the coated surface was visually inspected and evaluated as follows.

◇: Coated surface was uniform.

◆: Insoluble material deposited on the coated surface.

(2) Evaluation of photosensitivity

The substrate was exposed to light for 15 minutes using a 21-stage step-by-step exposure apparatus produced by a Stouffer, whose brightness varied from transparent to black to 21, and its photosensitivity was evaluated. After the exposure, development was carried out for twice the minimum development time, and the evaluation was carried out according to the exposure amount of 8 in the stepwise exposure apparatus in which the resist film remained completely, as follows.

?: The exposure dose was 20 mJ / cm ² or less.

?: Exposure dose was 20 mJ / cm ² - 50 mJ / cm ² (end point value excluded).

●: The exposure dose was 50 mJ / cm ² or more.

(3) Evaluation of resolution

The substrate was exposed for 15 minutes after lamination with a line pattern mask having a width ratio of 1: 1 of the exposed portion to the unexposed portion. Next, development was performed for twice the minimum development time, and the minimum mask line width at which the cured resist line was normally formed was used as the resolution value. Evaluation was performed as follows.

?: The resolution value was 30 占 퐉 or less.

⊚: The resolution value was 30 탆 - 50 탆 (the end point value was excluded).

●: The resolution value was 50 μm or more.

(4) Evaluation of adhesiveness

The substrate was exposed for 15 minutes after lamination with a line pattern mask having a width ratio of the exposed portion to the unexposed portion of 1: 100. Then, developing was performed for a time that was twice the minimum developing time, and the minimum mask line width at which the cured resist line was normally formed was used as the adhesion value. The evaluation was carried out as follows.

?: Adhesion value was 30 占 퐉 or less.

?: Adhesion value was 30 占 퐉 to 50 占 퐉 (the end point value was excluded).

●: Adhesion value was 50 μm or more.

(5) Evaluation of water solubility

After the polyethylene terephthalate thin film was peeled off, development was carried out at 23 DEG C for 2 minutes using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to dissolve and remove unexposed portions of the photosensitive resin layer. Then, cleaning was performed for one minute with ultra pure water. Evaluation was performed as follows.

◇: completely dissolved, no solid remained.

◆: Solids settled on the coated surface.

3. Evaluation results of characteristics

The evaluation results of the characteristics are listed in Table 3.

Example
One Example
2 Example
3 Example
4 Example
5 Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Compatibility Rating ◇ ◇ ◇ ◇ ◇ ◆ ◇ ◇ ◇ Photosensitive mJ / cm ² /
Rating 14 / ○ 20 / ○ 14 / ○ 18 / ○ 20 / ○ 71 / ● 30 / ◎ 90 / ● *One resolution um / rating 28 / O 30 / ○ 25 / O 30 / ○ 28 / O 100 / ● 40 / ◎ 100 / ● *One Adhesiveness um / rating 30 / ○ 25 / O 25 / O 28 / O 30 / ○ 79 / ● 36 / ◎ 100 / ● *One receptivity Rating ◇ ◇ ◇ ◇ ◇ ◆ ◇ ◆ *One

Note: ^* 1 - The resist line could not be formed, was not fully cured and could not be used for evaluation of resolution and adhesion.

As can be seen from the evaluation results in Table 3, the compositions of the present invention (Examples 1 to 5) using 9-phenylacridine-based photosensitizers exhibit very good compatibility, high photosensitivity, It has good resolution, adhesion and good water solubility and is remarkably superior to Comparative Example 1-2 using a conventional photosensitive agent. With respect to Comparative Example 3, compatibility, photosensitivity, resolution, adhesiveness and water solubility of the composition when only the TPS photoacid generator was contained were measured using a composition of the present invention using the 9-phenylacridine sensitizer ) Were much lower than those of. Comparative Example 4 shows that the composition could not be cured at all in the absence of TPS and photosensitizer.

4. Additional Characterization

A photosensitive resin composition having a formulation as shown in Table 4 was formulated.

sign Example
6 Example
7 Example
8 Example
9 Example
10 Example
11 Example
12 Example
13 Example
14



Photosensitive
Suzy
Composition
(Parts by weight) P-1 41 41 41 41 41 41 41 41 41 P-2 100 100 100 100 100 100 100 100 100 M-1 14 14 14 14 14 14 14 14 14 M-2 20 20 20 20 20 20 20 20 20 M-3 5 5 5 5 5 5 5 5 5 M-4 5 5 5 5 5 5 5 5 5 Product 1 0.4 0.2 0.2 0.2 0.2 PBG305 0.4 0.2 PAG201 0.4 0.2 HABI101 0.4 0.2 PBG314 0.4 0.2 B-1 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 B-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Note: The names / composition of the components indicated by symbols in Table 4 are shown in Table 5.

sign ingredient P-1 Wherein the copolymer contains 30 mass% of the copolymer and the copolymer has a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (mass ratio 70/20/10) An acid equivalent of 334 and a weight average molecular weight of 120000. P-2 Wherein the copolymer contains 43 mass% and the copolymer has a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (weight ratio 50/30/20) An acid equivalent weight of 340 and a weight average molecular weight of 50,000. M-1 The urethanization product of hexamethylene diisocyanate and pentapropylene glycol monomethacrylate M-2 Dipentaerythritol hexaacrylate M-3 Tetra-nonylphenylheptaethylene glycol dipropylene glycol acrylate M-4 Triacrylate of trimethylolpropane with an average of 3 moles of cyclohexane added PBG305 1- (4-phenylthiophenyl) - (3-cyclopentyl) -propane- 1, 2-dione-2-benzoic acid oxime ester PAG201 (Di [4-biphenylthiophenyl] sulfide dihexafluoroantimonate) HABI101 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole PBG314 Ethylcarbazol-3-yl) -3-cyclopentyl-propan-1-one-acetic acid oxime ester B-1 Malachite Green B-2 Ryuko Crystal Violet

The photosensitivity was evaluated with reference to the evaluation method. The evaluation results are listed in Table 6.

Example
6 Example
7 Example
8 Example
9 Example
10 Example
11 Example
12 Example
13 Example
14 Photosensitive mJ / cm ² /
Rating *One 18 / ○ 14 / ○ 25 / ◎ 20 / ○ 18 / ○ 15 / ○ 36 / ◎ 25 / ◎

Note: ^* 1 - Not fully cured.

It has been found experimentally that the photoresist of the present invention did not exhibit a good photosensitive effect when used alone, and that the composition can not be fully cured. When used in conjunction with photoinitiators such as radical photoinitiators, photoinitiators, etc., the photosensitizer exhibited a higher sensitivity when the total amount was not changed compared to when the photoinitiator was used alone.

In summary, the photosensitizer of the present invention exhibits excellent coating performance in the field of photocuring and has wide applicability. Further, the photosensitizer of the present invention is not limited to the application field as shown by the above-mentioned formulations. All systems such as photocurable paints, inks, photoresists, etc. fall within the scope protected by this patent as long as they use the photosensitizer of the present invention.

Claims (10)

As a 9-phenylacridine polymer sensitizer,
A composition comprising at least one compound having a structure represented by formula (I)

From here,
R ₁ represents a C ₁ -C ₆₀ linear or branched (m + n) -valent alkyl group, wherein -CH ₂ - may be optionally substituted with an oxygen, sulfur, or 1,4-phenylene group Have;
A represents independently - [(CHR ₄ ) _x -O] _y -, wherein each R ₄ independently represents hydrogen, a methyl group or an ethyl group, x is an integer of 1-10, y is 1-20 Lt; / RTI &gt;
R ₂ represents a C ₁ -C ₂₀ linear or branched alkylene group, wherein -CH ₂ - may be optionally substituted with an oxygen, sulfur or phenylene group;
R ₃ represents hydrogen or a substituent; And
m is an integer of 0 to 20, and n is an integer of 1-20. The method according to claim 1,
R ₁ represents a C ₁ -C ₂₀ linear or branched (m + n) -valent alkyl group, wherein -CH ₂ - is an oxygen or 1,4-phenylene group when two oxygen atoms are not directly connected Lt; RTI ID = 0.0 &gt; 9-phenylacridine &lt; / RTI &gt; polymeric sensitizer. The method according to claim 1,
A represents - [(CHR ₄ ) _x -O] _y -, wherein each R ₄ independently represents hydrogen, a methyl group or an ethyl group, x is an integer of 1-10 and y is an integer of 1-20 9-phenylacridine polymeric photoresist. The method according to claim 1 or 3,
_{- [(CHR 4) x -O} ] y - group terminal oxygen atoms, 9-phenyl acridine polymeric photosensitive agent, characterized in that coupled to the R _1. The method according to claim 1,
R ₂ represents a C ₁ -C ₈ linear or branched alkylene group, wherein -CH ₂ -, when two oxygen atoms are not directly connected, may be optionally substituted with oxygen or a 1,4-phenylene group &Lt; / RTI &gt; 9-phenylacridine polymeric photoresist. The method according to claim 1,
R ₃ is selected from H, CH ₃ , NO ₂ or halogen. The method according to claim 1,
m is an integer of 0 to 7, n is an integer of 1 to 8, and the sum of m and n is an integer of 2 to 8. 9. The 9-phenylacridine polymer sensitizer according to claim 1, 9. A method for producing a 9-phenyl acridine polymer sensitizer according to any one of claims 1 to 7,
(1) carrying out a reaction between raw material a and raw material b in the presence of a catalyst to obtain an intermediate a;
(2) performing a reaction between the intermediate a and the starting material c in a solvent containing an acid binding agent to obtain an intermediate b;
(3) carrying out a transesterification reaction between the intermediate b and the starting material d in the presence of a catalyst to obtain a product
Including,
The reaction scheme is illustrated as follows:

Here, R ₅ is a process for producing a C ₁ -C ₈ linear or branched alkyl group represents a, 9-phenyl acridine polymeric photosensitizer. Use of a 9-phenyl acridine polymeric sensitizer according to any one of claims 1 to 7 in a photocurable composition. 10. The method of claim 9,
Wherein the photoinitiator used in the photo-curable composition is selected from photoacid generators, photoinitiators, and radical photoinitiators.