KR102179484B1 - 9-phenylacridine polymer photosensitizer and 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.Disclosed are 9-phenylacridine polymeric photosensitizers and methods and uses thereof. 9-phenylacridine polymer photosensitive agent contains at least one of the compounds having a structure represented by formula (I),

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

Description

9-phenylacridine polymer photosensitizer and its preparation method and use

The present invention pertains to the field of organic chemistry, and in particular, to 9-phenylacridine macromolecular photosensitizer and its preparation method, as well as its use in the field of photocuring.

The acridin compound is a macrocyclic conjugated system with a solid planar structure and very strong fluorescence, which is a good kind of fluorescent reagent. It can be used as a photoinitiator in a photopolymerization system, or it can also be used as a sensitizer for initiating a photoinitiator to perform photopolymerization. 9-phenylacridine is an acridine derivative and belongs to a biphenyl-type structure. They can initiate cross-linking curing of photocurable materials (photocurable paints, inks, photoresists, etc.) mainly composed of unsaturated resins and monomer materials thereof under irradiation of ultraviolet rays and X-rays. In addition, they have stable properties and have good photosensitive properties in a photocurable material composed of an unsaturated resin and a monomer material thereof. 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 a photosensitizer, these existing acridine compounds have some disadvantages of undesirable solubility and poor photosensitivity improvement effect. 9-Phenylacridine is one of the most widely used products used in conventional acridine photosensitizers. As micromolecular photosensitizers, they often cause problems such as difficult to separate from reactants, difficult to recover, poor miscibility with the system during the use process, and easily agglomerate and separate, reducing reaction efficiency and material properties. Affects In particular, 9-phenylacridine has a very low water solubility, which seriously affects its popularization and application as a photosensitizer in the field of photocuring, especially in the field of dry film photoresists. The unexposed part is typically washed away with an alkaline aqueous solution during dry film development, while 9-phenylacridine precipitates on the surface of the circuit board at this point due to their very low water solubility. Will be adsorbed. In this case, not only the use of the dry film will be affected, but the precision of the product will be poor. Therefore, a procedure for cleaning the circuit board surface needs to be added later, which complicates the process and increases the cost significantly.

Regarding the drawbacks of the prior art, an object of the present invention is to provide a 9-phenylacridine polymer photosensitizer. Compared to the conventional photosensitive agent, when used in a photo-curing system, the photosensitive agent of the present invention has good compatibility and good photosensitivity improvement effect, and the film produced therefrom has excellent resolution, adhesion, and high water solubility (with water). Easy to remove by washing).

Specifically, the 9-phenylacridine polymer photosensitizer of the present invention includes at least one of the compounds 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 oxygen, sulfur or 1,4-phenylene group, and ;

A each independently represents -[(CHR ₄ ) _x -O] _y -, where R ₄ each independently represents a hydrogen, a methyl group, or an ethyl group, x is an integer of 1-10, and y is 1-20 Is an integer of;

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

R ₃ represents hydrogen or a substituent; And

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

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

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

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,

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,

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,

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,

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,

.

In a preferred embodiment, A represents -[(CHR ₄ ) _x -O] _y -, where R ₄ each independently represents a hydrogen, a methyl group or an ethyl group, x is an integer of 1-10, and y is 1 It is an integer of -20. 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 represents 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 an oxygen or 1,4-phenylene group when two oxygens are not directly connected. Can be substituted with.

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 (eg 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.

Accordingly, the present invention also relates to a method for preparing the 9-phenylacridine polymer photosensitizer described above, comprising the following steps:

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

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

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

Here, the reaction equation is shown as follows:

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

The photosensitizer of the present invention is improved and optimized with respect to the structure of existing compounds. As shown by the reaction scheme described above, the synthesis involved in its preparation method relates to the construction of acridine structure, esterification, transesterification, etc., which are all common processes in the field of organic chemistry. If the synthesis process and its principle are clear, the specific process parameters will be readily determined by a person skilled in the art. For example, reference may be made to the content described in Chinese patent CN101525392A, 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, and is typically 150-220 °C, and the reaction time is 4-8 hours.

Preferably, in step (2), R ₅ in the structure of the raw material c represents a C ₁ -C ₄ linear or branched alkyl group, in particular CH ₃ , CH ₂ CH ₃ and CH ₂ CH ₂ CH ₃ . The type of solvent used is not particularly limited as long as it can dissolve the raw material of the reaction and does not negatively affect the reaction, and examples thereof are acetone, acetonitrile, methanol, ethanol, and N,N-dimethylformamide. The acid binder may be sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxylate, pyridine, triethylamine, and the like. The reaction temperature is 40-100° C., and the reaction time is typically 4-18 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 for the reaction and does not negatively affect the reaction, and for example, toluene, xylene, benzene, cyclohexane, and the like. The catalyst may be one or a combination of two or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, methylsulfonic acid, p-toluenesulfonic acid, sulfuric acid and hypophosphorous acid. The amount of catalyst used is preferably 5%o-15%o of the total mass of the raw materials for the reaction. The reaction temperature is typically 70-130°C. The reaction time is typically 1-8 hours.

As can be seen from the transesterification reaction in step (3) by a person skilled in the art, m+n hydroxy groups capable of undergoing the transesterification reaction with the intermediate b are present in the raw material d. If m+n is greater than 1 and intermediate b is not sufficient with respect to the hydroxy group, the number of intermediates b reacting 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 scope of the definition of the 9-phenylacridine polymer photosensitizer described above.

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

Advantageous effects of the invention further include:

1. The energy transfer and intermolecular reaction in the polymer chain makes the polymer photosensitive agent more easily have high photosensitive activity;

2. Products with different reactivity are obtained by copolymerization with inert groups, by controlling and designing the distance between the photosensitive groups, or by changing the distance between the photoactive groups and the main chain;

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

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

Hereinafter, the present invention will be further illustrated in detail below with specific embodiments, but it should not be understood that the scope of the present invention is limited thereto.

Manufacturing example

Example One

(1) Preparation of intermediate 1a

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 (1.0 mol) of 85% phosphoric acid were added to 1000 ml of 4- It was added to the old flask, the temperature was increased to 200-210° C. with stirring, and the reaction was carried out for 6 hours. Then, the temperature was reduced to 130-140° C., 400 g of 30% sulfuric acid was added dropwise, and the temperature was maintained at 80° C. while stirring for 2 hours, and 300 g of water at 80° C. was added while stirring for 0.5 hour. , Water in the lower layer was separated by standing, and the above operation was repeated by additionally adding 300 g of water. 300 g of aqueous ammonia was finally added to the reaction flask to precipitate a large amount of orange solid. The material in the reaction flask was suction filtered at room temperature, rinsed with methanol and dried to give 257.4 g of a solid of intermediate 1a with a purity of 98%.

The structure of Intermediate 1a was confirmed by LCMS.

Mass spectrometric analysis was performed with the software attached to the instrument to obtain molecular fragment peaks at 272 and 273, and the molecular weight of the product was 271, which was 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, followed by heating at 80° C. under reflux. 12.0 g (0.11 mol) of methyl chloroacetate was added dropwise within about 1 hour. After completion of the dropping, the reaction was continued for 8 hours. After completion of the reaction, unreacted potassium carbonate was removed by filtration while hot, and most of the solvent was evaporated under reduced pressure to precipitate a solid. The material in the reaction flask was suction filtered, rinsed with methanol and dried to give 32.5 g of a pale yellow solid, intermediate 1b, with a purity of 98%.

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

Mass spectrometry was performed with the software attached to the instrument to obtain molecular fragment peaks at 344 and 345, and the molecular weight of the product was 343, which was 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) Preparation of product 1

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 were added to a 1000 mL 4-neck flask, and the internal temperature was set to 90-100°C. It was adjusted and heated while stirring. Methanol produced in the reaction was evaporated by heating, and toluene was appropriately supplemented until methanol no longer evaporated. Filtration was performed while hot, and the resulting filtrate was distilled under reduced pressure until the residual toluene was less than 5000 ppm, to obtain 304.4 g of a pale yellow viscous substance as product 1.

It is easy to understand that three hydroxy groups having the same or similar activity were present in raw material 1d, and product 1 should include 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

219.6 g (1.2 mol) 4-hydroxy-3-nitrobenzoic acid, 169.0 g (1.0 mol) diphenylamine, 244.8 g (1.8 mol) zinc chloride and 115.3 g (1.0 mol) 85% phosphoric acid were added to 1000 ml of a four-necked flask, the temperature was increased to 200-210° C. with stirring, and the reaction was carried out for 6 hours. Liquid phase tracking was performed until reaction. The temperature was reduced to 130-140° C., 400 g of 30% sulfuric acid was added dropwise, and the temperature was maintained at 80° C. while stirring for 2 hours, and 300 g of water at 80° C. was added while stirring for 0.5 hour, and water of the lower layer Was allowed to stand to separate, and 300 g of water was further added to repeat the above operation. 300 g of aqueous ammonia was finally added to the reaction flask to precipitate a large amount of orange solid. The material in the reaction flask was suction filtered, rinsed with methanol and dried to give 300.2 g of a solid as intermediate 2a with a purity of 98% and a yield of 95%.

The structure of Intermediate 2a was confirmed by LCMS.

Mass spectrometry was performed with the software attached to the instrument to obtain molecular fragment peaks at 317 and 318, and the molecular weight of the product was 316, which was 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, followed by heating at 80° C. under reflux. 13.4 g (0.11 mol) of ethyl chloroacetate was added dropwise within about 1 hour. After completion of the dropping, the reaction was continued for 8 hours. After completion of the reaction, unreacted potassium carbonate was removed by filtration while hot, and most of the solvent was evaporated under reduced pressure to precipitate a solid, and this solid was filtered with suction, rinsed with methanol and dried, and 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 the 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 , 500MHz): 3.6721-3.7232 (3H, t), 4.9034-4.9985 (2H, q), 7.0942 (2H, s), 7.3424-7.4765 (2H, d), 7.5432-7.6278 (2H , q), 7.6082-7.6191 (2H, d), 7.7634-7.7705 (2H, d), 7.9234-8.0509 (2H, d), 8.3233 (1H, s).

(3) Preparation of product 2

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 were added to a 1000 mL 4-neck flask, and the temperature was adjusted to 90-100°C. And heated while stirring. Methanol produced in the reaction was evaporated by heating, and toluene was appropriately supplemented until methanol no longer evaporated. Filtration was performed while hot, and the resulting filtrate was distilled under reduced pressure until the residual toluene was less than 5000 ppm, thereby obtaining product 2, 221 g of a pale yellow viscous substance in a yield of 92.4%.

Example 3-9

With reference to the method of Example 1 or 2, products 3-9 having the following structure were synthesized.

Product 3:

Product 4:

Product 5:

Product 6:

Product 7:

Product 8:

Product 9:

Evaluation of characteristics

By formulating an exemplary photocurable composition, the application properties of the photosensitizer of the present invention were evaluated.

1. Fabrication of objects to evaluate properties

<Production of photosensitive resin laminate>

The photosensitive resin composition having the composition shown in Table 1 and propylene glycol monoethyl ether acetate are sufficiently stirred and mixed, and uniformly coated on the surface of a polyethylene terephthalate thin film having a thickness of 19 µm as a support using a bar coating. Then, it was dried in a dryer at 95° C. for 4 minutes to form a photosensitive resin layer having a thickness of 40 μm. Thereafter, a polyethylene thin film having a thickness of 23 µm was attached 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 the substrate surface>

As a substrate for use in evaluating photosensitivity and resolution, a copper clad laminate treated with a spray pressure of 0.20 MPa using a spray washing mill was used. Was prepared.

<Lamination>

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

<exposure>

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

<development>

After peeling off the polyethylene terephthalate thin film, development was performed at 23° C. for 2 minutes using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to dissolve and remove the unexposed portion of the photosensitive resin layer. Then, washing was performed for 1 minute with ultra-pure water. 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 development time.

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Photosensitive
Suzy
Composition
(Part 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: Table 2 shows the names/compositions of ingredients indicated by designation in Table 1.

sign ingredient P-1 As an acrylic copolymer in a methyl ethyl ketone solution, wherein the copolymer contains 30% by mass, the copolymer has a composition of methyl methacrylate/methacrylic acid/n-butyl acrylate (mass ratio 70/20/10), It has an acid equivalent of 334 and a weight average molecular weight of 120000. P-2 As an acrylic copolymer in a methyl ethyl ketone solution, wherein the copolymer contains 43% by mass, the copolymer is a composition of methyl methacrylate/methacrylic acid/n-butyl acrylate (mass ratio 50/30/20), It has an acid equivalent weight of 340 and a weight average molecular weight of 50000. M-1 Urethane products of hexamethylene diisocyanate and pentapropylene glycol monomethacrylate M-2 Dipentaerythritol hexaacrylate M-3 Tetra-nonylphenyl heptaethylene glycol dipropylene glycol acrylate M-4 Trimethylolpropane triacrylate with an average of 3 moles of cyclohexane added TPS Tribromomethyl phenyl sulfone (mine 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 properties

(1) Compatibility Test

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

◇: The coated surface was uniform.

◆: Insoluble matter precipitated on the coated surface.

(2) Evaluation of photosensitivity

The photosensitivity was evaluated by exposing the substrate for 15 minutes after lamination using a 21-stage stepwise exposure apparatus produced by a Stopper, whose brightness varies from transparent to black in 21 steps. After exposure, development was carried out for twice the minimum development time, and evaluation was performed as follows according to the exposure amount of the stepwise exposure apparatus in which the resist film remained completely and the number of steps was 8.

○: The exposure amount was 20 mJ/cm ² or less.

◎: exposure amount is 20 mJ / cm ² - was 50 mJ / cm ² (end values except under).

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

(3) Evaluation of resolution

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

(Circle): The resolution value was 30 micrometers or less.

◎: The resolution value was 30 µm-50 µm (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 an exposed portion to an unexposed portion of 1:100. Then, development was performed for a time twice the minimum development time, and the minimum mask line width in which the cured resist line is normally formed was used as the adhesiveness value. Evaluation was carried out as follows.

(Circle): The adhesiveness value was 30 micrometers or less.

◎: The adhesiveness value was 30 µm-50 µm (end point value was excluded).

-: The adhesiveness value was 50 µm or more.

(5) Evaluation of water solubility

After peeling off the polyethylene terephthalate thin film, development was performed at 23° C. for 2 minutes using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to dissolve and remove the unexposed portion of the photosensitive resin layer. Then, washing was performed with ultrapure water for 1 minute. Evaluation was carried out as follows.

◇: Completely dissolved, no solid remained.

◆: A solid precipitated on the coated surface.

3. Evaluation result of characteristics

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

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4 Compatibility rank ◇ ◇ ◇ ◇ ◇ ◆ ◇ ◇ ◇ Photosensitive mJ/cm ² /
rank 14/○ 20/○ 14/○ 18/○ 20/○ 71/● 30/◎ 90/● *One resolution um/grade 28/○ 30/○ 25/○ 30/○ 28/○ 100/● 40/◎ 100/● *One Adhesiveness um/grade 30/○ 25/○ 25/○ 28/○ 30/○ 79/● 36/◎ 100/● *One receptivity rank ◇ ◇ ◇ ◇ ◇ ◆ ◇ ◆ *One

Note: ^* 1-Resist lines could not be formed, were 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, when the other components are the same, the composition of the present invention using a 9-phenylacridine photosensitive agent (embodiments 1-5) has very good compatibility, high photosensitivity, and very It has good resolution, adhesion, and good water solubility, and is significantly superior to Comparative Example 1-2 using the existing photosensitive agent. With respect to Comparative Example 3, when only the TPS photoacid generator is contained, the compatibility, photosensitivity, resolution, adhesion, and water solubility of the composition are the composition of the present invention using a 9-phenylacridine photosensitive agent (Embodiment Examples 1-5 ) Was much lower than 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.

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Photosensitive
Suzy
Composition
(Part 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: Table 5 shows the names/compositions of ingredients indicated by the symbols in Table 4.

sign ingredient P-1 As an acrylic copolymer in a methyl ethyl ketone solution, wherein the copolymer contains 30% by mass, the copolymer has a composition of methyl methacrylate/methacrylic acid/n-butyl acrylate (mass ratio 70/20/10), It has an acid equivalent weight of 334 and a weight average molecular weight of 120000. P-2 As an acrylic copolymer in a methyl ethyl ketone solution, wherein the copolymer contains 43% by mass, the copolymer is a composition of methyl methacrylate/methacrylic acid/n-butyl acrylate (mass ratio 50/30/20), It has an acid equivalent weight of 340 and a weight average molecular weight of 50000. M-1 Urethane product of hexamethylene diisocyanate and pentapropylene glycol monomethacrylate M-2 Dipentaerythritol hexaacrylate M-3 Tetra-nonylphenyl heptaethylene glycol dipropylene glycol acrylate M-4 Trimethylolpropane triacrylate 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 dihexafluoroantimonyate) HABI101 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole PBG314 1-(6-thiophenecarbonyl-9-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.

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

Note: ^* 1-Not sufficiently cured.

It was found by experiment that the photosensitive agent of the present invention did not show a good photosensitive effect when used alone, and that the composition could not be completely cured. When used together with a photoinitiator such as a radical photoinitiator or a photobase generator, the photosensitizer exhibited higher sensitivity when the total amount did not change compared to when the photoinitiator was used alone.

In summary, the photosensitive agent of the present invention exhibits very good coating performance in the photocurable field and has a wide applicability. In addition, the photosensitizer of the present invention is not limited to the field of application as indicated by the above formulation. All systems, such as photocurable paints, inks, photoresists, etc., fall within the scope covered by this patent as long as they use the photosensitizer of the present invention.

Claims (10)

9-phenylacridine polymer photosensitive agent,
It contains at least one of the compounds 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 oxygen, sulfur, or 1,4-phenylene group. There is;
A each independently represents -[(CHR ₄ ) _x -O] _y -, where R ₄ each independently represents a hydrogen, a methyl group or an ethyl group, x is an integer of 1-10, and y is 1-20 Is an integer of;
R ₂ represents a C ₁ -C ₂₀ linear or branched alkylene group, wherein -CH ₂ -may be optionally substituted with oxygen, sulfur or phenylene group;
R ₃ represents hydrogen or a substituent; And
m represents an integer of 0-20, n represents an integer of 1-20, 9-phenylacridine polymer photosensitizer. The method of claim 1,
R ₁ represents a C ₁ -C ₂₀ linear or branched (m+n)-atom is an alkyl group, where -CH ₂ -is an oxygen or 1,4-phenylene group when two oxygens are not directly connected 9-phenylacridine polymer photosensitizer, characterized in that it can be optionally substituted. The method of claim 1,
A represents -[(CHR ₄ ) _x -O] _y -, where R ₄ each independently represents a hydrogen, a methyl group or an ethyl group, x is an integer of 1-10, and y is an integer of 1-20 Characterized in, 9-phenylacridine polymer photosensitizer. The method of claim 1 or 3,
-[(CHR ₄ ) _x -O] _y -9-phenylacridine polymer photosensitizer, characterized in that the terminal oxygen atom of the group is connected to R ₁ . The method of claim 1,
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 group when two oxygens are not directly connected. Characterized in that, 9-phenylacridine polymer photosensitizer. The method of claim 1,
R ₃ is H, CH ₃ , NO ₂ or halogen, characterized in that selected from, 9-phenylacridine polymer photosensitizer. The method of claim 1,
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, 9-phenylacridine polymer photosensitizer. As a method for preparing the 9-phenylacridine polymer photosensitizer of claim 1,
(1) performing a reaction between a raw material a and a raw material b in the presence of a catalyst to obtain an intermediate a;
(2) performing a reaction between the intermediate a and the raw 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 raw material d in the presence of a catalyst to obtain a product
Including,
The reaction scheme is shown below:

Here, R ₅ represents a C ₁ -C ₈ linear or branched alkyl group, a method of preparing a 9-phenylacridine polymer photosensitizer. delete delete