Tertiary amine photosensitizer, preparation method thereof, photosensitive resin composition containing same and application of photosensitive resin composition

Abstract

The invention discloses a tertiary amine photosensitizer, a preparation method thereof, a photosensitive resin composition containing the same and an application of the photosensitive resin composition. The tertiary amine photosensitizer contains at least one tertiary amine derivative shown in general formula (I); the tertiary amine photosensitizer of the present invention has high sensitivity to light sources with a wavelength of 350 to 410 nm, and the photosensitive resin composition prepared by adopting it has a high sensitivity to When using any single-wavelength light source for drawing, sufficient resolution and stable production capacity can be obtained, and this tertiary amine photosensitizer resin has good compatibility. After drying, the photosensitive resin composition added with the tertiary amine photosensitizer There will be no precipitates, and the direct drawing exposure method can be used to prepare photoresist films, resist patterns and printed circuit boards.

Description

technical field

[0001] The invention relates to the technical field of photosensitive materials, in particular, to a tertiary amine photosensitizer, a preparation method thereof, a photosensitive resin composition containing the photosensitive resin composition and the application of the photosensitive resin composition. Background technique

[0002] In recent years, printed circuit boards are mostly manufactured by photolithography. The so-called photolithography refers to coating a photosensitive resin composition on a substrate, exposing a pattern, polymerizing and curing the exposed part of the photosensitive resin composition, and then The unexposed part is removed with a developing solution, a resist pattern is formed on the substrate, and then etched or plated, and finally the resist pattern is peeled off from the substrate, thereby forming a conductor pattern on the substrate.

[0003] As a method of forming a resist pattern, the method of exposing through a photomas...

Examples

preparation example Construction

[0083] According to a typical embodiment of the present invention, a preparation method of the above-mentioned tertiary amine photosensitizer is provided. The preparation method comprises the following steps: 1) react raw material a and raw material b to obtain intermediate a; 2) react intermediate a and raw material c in an organic solvent containing a catalyst to obtain intermediate b; 3) react raw material d and raw material e in nitrogen Under the protection of the catalyst, the intermediate c is obtained; (4) the intermediate b and the intermediate c are obtained through the catalytic reaction of the catalyst under the protection of nitrogen to obtain the product; the reaction equation is as follows:

[0084]

[0085] In the case of knowing the above reaction scheme, the specific reaction conditions in steps 1) to 4) can be easily determined by those skilled in the art.

[0086] The reaction of step 1) can be carried out under catalyst-free and solvent-free conditions....

Embodiment 1

[0098] Component D is the preparation of the tertiary amine derivative shown in general formula (I)

[0099] (1) Preparation of intermediate a1

[0100]

[0101] Add 63 g of benzyl chloride and 100 g of triethyl phosphite into a 500 ml four-neck flask, stir and raise the temperature to 80-90° C., and react for 3 h. GC (gas chromatography) controls to benzyl chloride less than 1%, and the reaction ends. Distill at 90°C atmospheric pressure to remove the reaction by-product ethyl chloride, continue to distill under reduced pressure to remove unreacted triethyl phosphite, after no fraction is removed, cool down to 30°C to obtain 105g of intermediate a1 with a yield of 92.1% .

[0102] The structure of intermediate a1 via 1 H-NMR and LCMS confirmed.

[0103] 1 H-NMR (CDCl 3 , 500MHz): δ1.11 (6H, m), δ3.57 (4H, s), δ5.33 (2H, s), δ7.06-7.14 (5H, m).

[0104] MS (m / z): 229 (M+1).

[0105] (2) Preparation of intermediate b1

[0106]

[0107] Add 114g of intermediate a1...

Embodiment 2

[0124] (1) Preparation of intermediate c2

[0125]

[0126] Add raw materials 162.5g d2, 2-ethyl-6-methylaniline 216g, toluene 400g in a 1000mL four-necked flask, add sodium tert-butoxide 40g, tri-tert-butylphosphine 36g and tetrakis(triphenyl Phosphine)palladium 1.6g, heat up to 80-85°C and keep it warm for 10h, and control in HPLC until the reaction of raw material d2 and its intermediate monosubstituted product is complete (HPLC: <0.1%). Filtrate while hot, distill off the solvent from the mother liquor under reduced pressure, add 200 g of n-hexane, cool to 10° C., stir and crystallize, and filter with suction to obtain 197.1 g of intermediate c2 with a purity of 91%.

[0127] The structure of product 1 was determined by LCMS and 1 H-NMR confirmed.

[0128] 1 H-NMR (CDCl 3 , 500MHz): δ1.24-2.59 (16H, m), δ4.01 (2H, s), δ6.28-7.15 (12H, m), δ10.1 (1H, s).

[0129] MS (m / z): 434 (M+1).

[0130] (2) Preparation of product 2

[0131]

[0132] Add 208g of intermedia...

technical field

[0001] The invention relates to the technical field of photosensitive materials, in particular, to a tertiary amine photosensitizer, a preparation method thereof, a photosensitive resin composition containing the photosensitive resin composition and the application of the photosensitive resin composition. Background technique

[0002] In recent years, printed circuit boards are mostly manufactured by photolithography. The so-called photolithography refers to coating a photosensitive resin composition on a substrate, exposing a pattern, polymerizing and curing the exposed part of the photosensitive resin composition, and then The unexposed part is removed with a developing solution, a resist pattern is formed on the substrate, and then etched or plated, and finally the resist pattern is peeled off from the substrate, thereby forming a conductor pattern on the substrate.

[0003] As a method of forming a resist pattern, the method of exposing through a photomas...

Examples

preparation example Construction

[0083] According to a typical embodiment of the present invention, a preparation method of the above-mentioned tertiary amine photosensitizer is provided. The preparation method comprises the following steps: 1) react raw material a and raw material b to obtain intermediate a; 2) react intermediate a and raw material c in an organic solvent containing a catalyst to obtain intermediate b; 3) react raw material d and raw material e in nitrogen Under the protection of the catalyst, the intermediate c is obtained; (4) the intermediate b and the intermediate c are obtained through the catalytic reaction of the catalyst under the protection of nitrogen to obtain the product; the reaction equation is as follows:

[0084]

[0085] In the case of knowing the above reaction scheme, the specific reaction conditions in steps 1) to 4) can be easily determined by those skilled in the art.

[0086] The reaction of step 1) can be carried out under catalyst-free and solvent-free conditions....

Embodiment 1

[0098] Component D is the preparation of the tertiary amine derivative shown in general formula (I)

[0099] (1) Preparation of intermediate a1

[0100]

[0101] Add 63 g of benzyl chloride and 100 g of triethyl phosphite into a 500 ml four-neck flask, stir and raise the temperature to 80-90° C., and react for 3 h. GC (gas chromatography) controls to benzyl chloride less than 1%, and the reaction ends. Distill at 90°C atmospheric pressure to remove the reaction by-product ethyl chloride, continue to distill under reduced pressure to remove unreacted triethyl phosphite, after no fraction is removed, cool down to 30°C to obtain 105g of intermediate a1 with a yield of 92.1% .

[0102] The structure of intermediate a1 via 1 H-NMR and LCMS confirmed.

[0103] 1 H-NMR (CDCl 3 , 500MHz): δ1.11 (6H, m), δ3.57 (4H, s), δ5.33 (2H, s), δ7.06-7.14 (5H, m).

[0104] MS (m / z): 229 (M+1).

[0105] (2) Preparation of intermediate b1

[0106]

[0107] Add 114g of intermediate a1...

Embodiment 2

[0124] (1) Preparation of intermediate c2

[0125]

[0126] Add raw materials 162.5g d2, 2-ethyl-6-methylaniline 216g, toluene 400g in a 1000mL four-necked flask, add sodium tert-butoxide 40g, tri-tert-butylphosphine 36g and tetrakis(triphenyl Phosphine)palladium 1.6g, heat up to 80-85°C and keep it warm for 10h, and control in HPLC until the reaction of raw material d2 and its intermediate monosubstituted product is complete (HPLC: <0.1%). Filtrate while hot, distill off the solvent from the mother liquor under reduced pressure, add 200 g of n-hexane, cool to 10° C., stir and crystallize, and filter with suction to obtain 197.1 g of intermediate c2 with a purity of 91%.

[0127] The structure of product 1 was determined by LCMS and 1 H-NMR confirmed.

[0128] 1 H-NMR (CDCl 3 , 500MHz): δ1.24-2.59 (16H, m), δ4.01 (2H, s), δ6.28-7.15 (12H, m), δ10.1 (1H, s).

[0129] MS (m / z): 434 (M+1).

[0130] (2) Preparation of product 2

[0131]

[0132] Add 208g of intermedia...

Images