Degradable photoresist resin monomer synthesized from trimethyl bicyclo[2.2.2]octanedione and synthesis method of degradable photoresist resin monomer

Abstract

The invention discloses a degradable photoresist resin monomer synthesized from trimethyl bicyclo[2.2.2]octanedione and a synthesis method of the resin monomer, and relates to the field of photoresistresin, the structural formula of the resin monomer is shown in the specification, R1 is saturated alkane or cycloalkane, R2 is hydrogen or methyl, and the synthesis method is as follows: under the protection of inert gas, making 1, 3, 3-trimethyl bicyclo[2.2.2]octane-5, 5-dione (I) react with an alkyl Grignard reagent or a cycloalkyl Grignard reagent, adding water for quenching after the reactionis finished, carrying out aftertreatment and purification to obtain an intermediate (II), reacting the intermediate (II) with acryloyl chloride or methacryloyl chloride under an alkaline condition, and carrying out aftertreatment and purification to obtain the resin monomer (III). Polymer resin formed by polymerizing the resin monomer provided by the invention and other resin monomers has betteretching resistance, is beneficial to improving the edge roughness of a developed pattern, and greatly improves the resolution of a photoetching pattern.

Description

Technical field

[0001] The invention relates to the field of photoresist resins, in particular to resin monomers and their synthesis methods.Background technique

[0002] Photolithography technology refers to the use of the chemical sensitivity of photolithography materials (specifically photoresist) under the action of visible light, ultraviolet rays, electron beams, etc., through exposure, development, etching and other processes, to design on the mask Graphic microfabrication technology in which the graphic is transferred to the substrate.

[0003] Photolithography material (specifically photoresist), also known as photoresist, is the most critical functional chemical material involved in photolithography technology. The main components are resin, photoacid generator, and corresponding additives and solvents. Such materials are chemically sensitive to light (including visible light, ultraviolet rays, electron beams, etc.), and their solubility in the developer changes after photochemical r...

Examples

Embodiment 1

[0023]

[0024]The first step: a. Preparation of methyl Grignard reagent: add magnesium chips (2.7g, 111mmol) to anhydrous ether (15mL), then add an iodine tablet, and then add methyl bromide (10.6g, 112mmol) Dissolve in ether (25mL) to prepare a solution. Under nitrogen protection, first add methyl bromide in ether solution (6mL) to the above reaction solution. After a few minutes, the reaction solution boils slightly and the color of iodine disappears. Continue stirring. Add the remaining ether solution of methyl bromide dropwise, add ether (20mL), increase the temperature and keep it boiling, and reflux for half an hour; b. Synthesis of intermediate 1-2: Under the protection of nitrogen, use the prepared methyl Grignard reagent Cool with ice water, add 1,3,3-trimethylbicyclo[2.2.2]octane-2,5-dione (10.0g, 55mmol) in ether (20mL) solution dropwise with stirring to control the dropping rate, Keep the reaction liquid slightly boiling. After the addition, continue to stir for half an ho...

Embodiment 2

[0027]

[0028]The first step: the operation steps and the amount of raw materials are the same as the first step reaction in Example 1, and the reaction obtains compound 2-2 (9.4 g, 44 mmol, 79.8%);

[0029]The second step: the operation steps are the same as the second step reaction of Example 1, wherein the reactants and the amount of feed are: Intermediate 1-2 (9.3g, 44mmol) is replaced by Intermediate 2-2 (9.4g, 44mmol), propylene The acid chloride (8g, 88mmol) was replaced by methacrylic acid chloride (9.3g, 89mmol), and the triethylamine (17.8g, 176mmol) was replaced by triethylamine (18.0g, 178mmol) to obtain compound 2-3 (13.2g, 38mmol, 85.6%).

Embodiment 3

[0031]

[0032]The first step: the operation steps are the same as the first step of Example 1, wherein methyl bromide (10.6g, 112mmol) is changed to ethyl bromide (12.1g, 111mmol) to obtain compound 3-2 (10.3g, 43mmol, 77.2 %);

[0033]The second step: the operation steps are the same as the second step reaction of Example 1, wherein the reactants and the amount of feed are: Intermediate 1-2 (9.3g, 44mmol) is replaced by Intermediate 3-2 (10.3g, 43mmol), propylene The acid chloride (8g, 88mmol) was replaced by acryloyl chloride (7.8g, 86mmol), and the triethylamine (17.8g, 176mmol) was replaced by triethylamine (17.4g, 172mmol) to obtain compound 3-3 (12.5g, 36mmol, 83.7 %).

Technical field

[0001] The invention relates to the field of photoresist resins, in particular to resin monomers and their synthesis methods.Background technique

[0002] Photolithography technology refers to the use of the chemical sensitivity of photolithography materials (specifically photoresist) under the action of visible light, ultraviolet rays, electron beams, etc., through exposure, development, etching and other processes, to design on the mask Graphic microfabrication technology in which the graphic is transferred to the substrate.

[0003] Photolithography material (specifically photoresist), also known as photoresist, is the most critical functional chemical material involved in photolithography technology. The main components are resin, photoacid generator, and corresponding additives and solvents. Such materials are chemically sensitive to light (including visible light, ultraviolet rays, electron beams, etc.), and their solubility in the developer changes after photochemical r...

Examples

Embodiment 1

[0023]

[0024]The first step: a. Preparation of methyl Grignard reagent: add magnesium chips (2.7g, 111mmol) to anhydrous ether (15mL), then add an iodine tablet, and then add methyl bromide (10.6g, 112mmol) Dissolve in ether (25mL) to prepare a solution. Under nitrogen protection, first add methyl bromide in ether solution (6mL) to the above reaction solution. After a few minutes, the reaction solution boils slightly and the color of iodine disappears. Continue stirring. Add the remaining ether solution of methyl bromide dropwise, add ether (20mL), increase the temperature and keep it boiling, and reflux for half an hour; b. Synthesis of intermediate 1-2: Under the protection of nitrogen, use the prepared methyl Grignard reagent Cool with ice water, add 1,3,3-trimethylbicyclo[2.2.2]octane-2,5-dione (10.0g, 55mmol) in ether (20mL) solution dropwise with stirring to control the dropping rate, Keep the reaction liquid slightly boiling. After the addition, continue to stir for half an ho...

Embodiment 2

[0027]

[0028]The first step: the operation steps and the amount of raw materials are the same as the first step reaction in Example 1, and the reaction obtains compound 2-2 (9.4 g, 44 mmol, 79.8%);

[0029]The second step: the operation steps are the same as the second step reaction of Example 1, wherein the reactants and the amount of feed are: Intermediate 1-2 (9.3g, 44mmol) is replaced by Intermediate 2-2 (9.4g, 44mmol), propylene The acid chloride (8g, 88mmol) was replaced by methacrylic acid chloride (9.3g, 89mmol), and the triethylamine (17.8g, 176mmol) was replaced by triethylamine (18.0g, 178mmol) to obtain compound 2-3 (13.2g, 38mmol, 85.6%).

Embodiment 3

[0031]

[0032]The first step: the operation steps are the same as the first step of Example 1, wherein methyl bromide (10.6g, 112mmol) is changed to ethyl bromide (12.1g, 111mmol) to obtain compound 3-2 (10.3g, 43mmol, 77.2 %);

[0033]The second step: the operation steps are the same as the second step reaction of Example 1, wherein the reactants and the amount of feed are: Intermediate 1-2 (9.3g, 44mmol) is replaced by Intermediate 3-2 (10.3g, 43mmol), propylene The acid chloride (8g, 88mmol) was replaced by acryloyl chloride (7.8g, 86mmol), and the triethylamine (17.8g, 176mmol) was replaced by triethylamine (17.4g, 172mmol) to obtain compound 3-3 (12.5g, 36mmol, 83.7 %).

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