阅读说明：本技术 光刻胶剥离剂组合物 (Photoresist stripper composition ) 是由 王腾芳 王勇军 于 2017-12-08 设计创作，主要内容包括：本发明涉及一种光刻胶剥离剂组合物,其包含：至少一种胆碱化合物；至少一种极性非质子溶剂；以及水。按组合物的总重量计,胆碱化合物的重量百分比为2.5-50重量％,优选为5-50重量％,更优选为7-30重量％,并且最优选为9-18重量％。该光刻胶剥离剂组合物表现出优异的光刻胶清洁性能和对基板的低蚀刻作用。(The present invention relates to a photoresist stripper composition comprising: at least one choline compound; at least one polar aprotic solvent; and water. The weight percentage of choline compounds is 2.5-50 wt%, preferably 5-50 wt%, more preferably 7-30 wt%, and most preferably 9-18 wt%, based on the total weight of the composition. The photoresist stripper composition exhibits excellent photoresist cleaning performance and low etching effect on a substrate.)

1. A photoresist stripper composition comprising:

(a) at least one choline compound;

(b) at least one polar aprotic solvent; and

(c) water;

wherein the choline compound is present in an amount of 2.5 to 50 wt% based on the total weight of the composition.

2. The photoresist stripper composition according to claim 1, wherein the choline compound is selected from the group consisting of choline hydroxide, choline bicarbonate, choline chloride, choline bitartrate, choline dihydrogen citrate, choline sulfate, and any combination thereof.

3. The photoresist stripper composition according to claim 1 or 2, wherein the choline compound has one hydroxyethyl group attached to a central nitrogen.

4. The photoresist stripper composition according to any of the preceding claims, wherein the amount of the choline compound is 5-50 wt%, preferably 7-30 wt%, more preferably 9-18 wt%, based on the total weight of the composition.

5. The photoresist stripper composition according to any of the preceding claims, wherein the amount of water is greater than or equal to 11 wt.%, preferably greater than or equal to 13 wt.%, and more preferably from 13 wt.% to 87.5 wt.%, based on the total weight of the composition.

6. The photoresist stripper composition according to any of the preceding claims, wherein the amount of the polar aprotic solvent is 10-90 wt.%, preferably 15-85 wt.%, and more preferably 15-75 wt.%, based on the total weight of the composition.

7. The photoresist stripper composition according to any of the preceding claims, wherein the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, propylene carbonate, and any combination thereof.

8. The photoresist stripper composition according to any of the preceding claims, further comprising at least one basic species.

9. The photoresist stripper composition according to any of the previous claims, wherein the basic substance is a weakly basic substance, preferably having a pKa value of 2 to 12, and more preferably a pKa value of 7 to 11, when dissolved in water at 25 ℃.

10. The photoresist stripper composition according to any of the preceding claims, wherein the basic substance is selected from the group consisting of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aminopyridine, butylamine, aminosulfane, diethanolamine, dimethylamine, dimethylimidazole, ephedrine, ethanolamine, ethylmorpholine, glycylglycine, hydroxypyrroline, piperidine, propylamine, methylamine, methylimidazole, triethylamine, triethanolamine, trimethylamine, tris (hydroxymethyl) aminomethanol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino-2-methyl-1-propanol, and any combination thereof.

11. The photoresist stripper composition according to any of the preceding claims, wherein the amount of the basic substance is 5-50 wt%, preferably 5-30 wt%, and more preferably 10-20 wt%, based on the total weight of the composition.

12. The photoresist stripper composition according to any of the preceding claims, comprising:

(a) 2.5-50% by weight of at least one choline compound;

(b) 10-90% by weight of at least one polar aprotic solvent;

(c)11-87.5 wt% water; and

(d)0 to 50 wt% of at least one alkaline substance;

wherein the weight percentages of all components add up to 100 weight%.

13. A method of making the photoresist stripper composition according to any of the preceding claims, comprising the step of mixing the components of the photoresist stripper composition.

14. A substrate obtained by removing a photoresist material coated on the substrate using the photoresist stripper composition according to any one of claims 1 to 12.

15. The method for evaluating the cleaning performance of a photoresist for the photoresist stripper composition according to any one of claims 1 to 12, comprising the steps of:

(a) heating the photoresist stripper composition;

(b) immersing the substrate covered with the photoresist material in the heated photoresist stripper composition;

(c) rinsing the substrate with water; and is

(d) Observing the removal of the photoresist material from the surface of the substrate.

16. A metal etching evaluation method for the photoresist stripper composition according to any one of claims 1 to 12, comprising the steps of:

(a) measuring the thickness (omega) and initial resistivity (Rs) of a metal substrate_(pre))；

(b) Heating the photoresist stripper composition;

(c) soaking the metal substrate in the heated photoresist stripper composition and recording the soaking time (t);

(d) measuring the back resistivity (Rs) of the metal substrate_(post)) (ii) a And is

(e) The metal Etch Rate (ER) was calculated according to the following equation:

ER＝Rs_(pre)ω(1/Rs_(pre)-1/Rs_(post))/t。

Technical Field

The invention relates to a photoresist stripper composition. The photoresist stripper composition according to the present invention comprises at least one choline compound; at least one polar aprotic solvent; and water; the weight percentage of choline compounds is 2.5-50 wt%, preferably 5-50 wt%, more preferably 7-30 wt%, and most preferably 9-18 wt%, based on the total weight of the composition. The photoresist stripper composition according to the present invention shows excellent photoresist cleaning performance and low etching effect to a substrate.

Background

Liquid crystal displays (L CDs) have been widely used as display screens for various electronic devices, such as mobile phones, televisions, digital cameras, laptop computers, and notebook computers.

A conventional liquid crystal display (L CD) panel includes a liquid crystal layer laminated between a front glass panel and a rear glass panel.A thin film transistor array substrate (TFT array substrate) is formed on the rear glass panel to drive rotation of the liquid crystal and control display of each pixel, and a Color Filter (CF) layer is deposited on the front glass to form a color of each pixel.

In recent years, a new L CD panel has been developed, the CF layer is integrated into the TFT array substrate, and the new L CD panel has many advantages, such as improved contrast, increased aperture ratio, reduced alignment error, and light leakage.

The CF layer in the new L CD panel contains photoresist material combined with color pigments, however, the pigments in the CF layer are sometimes not properly distributed so that the color of the CF layer becomes non-uniform.

In addition, a new trend is to integrate the OC layer also into the TFT array substrate. The OC layer overlies the CF layer and contains a photoresist material that may be the same or different from the photoresist material in the CF layer. If there is any defect in the CF layer, the OC layer needs to be stripped together with the CF layer.

A variety of photoresist cleaners have been developed for removing photoresist material from TFT array substrates. Compared with the traditional cleaning agent, the photoresist cleaning agent for the TFT array substrate has higher requirements. For example, in order for the TFT array substrate to be reworkable, the photoresist cleaner must be able to effectively remove the photoresist material from the TFT array substrate while not damaging the metal electrodes disposed in the TFT array substrate below the CF layer.

Furthermore, most available photoresist cleaners are directed to positive photoresist materials. Positive photoresist materials generally adhere to substrates to a weak degree. It is more soluble and easier to remove in acetone or alkaline solutions. Negative photoresist materials, on the other hand, undergo a crosslinking reaction upon curing, and thus form a much stronger polymer on a substrate after curing than positive photoresist materials. Therefore, negative photoresist materials are more difficult to remove than positive photoresist materials.

Many photoresist cleaners on the market are based on tetramethylammonium hydroxide (TMAH). The cleaning performance of the cleaning agent containing TMAH is not good enough. More importantly, TMAH is toxic and detrimental to the environment and the health of workers who have been exposed to it.

Therefore, it is required to develop a photoresist cleaner having excellent photoresist cleaning performance, low etching for a metal electrode (e.g., copper) in a TFT array substrate, and low toxicity to health.

Disclosure of Invention

The present invention relates to a photoresist stripper composition comprising:

(a) at least one choline compound;

(b) at least one polar aprotic solvent; and

(c) water;

the weight percentage of choline compounds is 2.5-50 wt%, preferably 5-50 wt%, more preferably 7-30 wt%, and most preferably 9-18 wt%, based on the total weight of the composition.

The photoresist stripper composition has high photoresist cleaning efficiency and low etching to a metal electrode in a TFT array substrate.

The present invention also relates to a method of preparing a photoresist stripper composition comprising the step of mixing the components of the photoresist stripper composition.

The present invention also relates to a substrate obtained by removing a photoresist material coated on a substrate using the photoresist stripper composition.

The invention also relates to a method for evaluating the cleaning performance of the photoresist stripper composition, which comprises the following steps:

(a) heating the photoresist stripper composition;

(b) immersing the substrate covered with the photoresist material in a heated photoresist stripper composition;

(c) rinsing the substrate with water; and is

(d) The removal of the photoresist material from the substrate surface is observed.

The invention also relates to a metal etching evaluation method of the photoresist stripper composition, which comprises the following steps:

(a) measuring the thickness (omega) and initial resistivity (Rs) of a metal substrate_(pre))；

(a) Heating the photoresist stripper composition;

(c) soaking the metal substrate in the heated photoresist stripper composition and recording the soaking time (t);

(d) measuring the post resistivity (Rs) of a metal substrate_(post)) (ii) a And is

(e) The metal Etch Rate (ER) was calculated according to the following equation:

ER＝Rs_(pre)ω(1/Rs_(pre)-1/Rs_(post))/t。

the invention also relates to a stability test of the photoresist stripper composition, which comprises the following steps:

(a) heating the photoresist stripper composition;

(b) immersing the substrate covered with the photoresist material in a heated photoresist stripper composition;

(c) rinsing the substrate with water;

(d) observing the removal of the photoresist material on the surface of the substrate; and is

(e) Repeating steps (b), (c) and (d) for a new substrate covered with the photoresist material at predetermined time intervals.

Drawings

Fig. 1 shows the surface of a TFT array substrate after cleaning by the photoresist stripper composition of example 1, observed under a microscope at a magnification of 75 times;

FIG. 2 shows the surface of a TFT array substrate after cleaning by the photoresist stripper composition of example 4, observed under a microscope at a magnification of 75 times;

FIG. 3 shows the surface of a TFT array substrate after cleaning by the photoresist stripper composition of example 10, observed under a microscope at a magnification of 75 times;

FIG. 4 shows the surface of a TFT array substrate after cleaning by the photoresist stripper composition of example 14, observed under a microscope at a magnification of 75 times; and

fig. 5 shows the surface of the TFT array substrate after cleaning by the photoresist stripper composition of example 17, observed under a microscope at a magnification of 75 times.

Detailed Description

The present invention will be described in more detail in the following paragraphs. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

In the context of the present invention, the terms used will be construed according to the following definitions, unless the context indicates otherwise.

As used herein, the singular forms "a," "an," and "the" include both singular and plural referents unless the context clearly dictates otherwise.

As used herein, the terms "comprising," "comprises," and "comprising" are synonymous with "including," "includes," or "containing," "contains," and are inclusive or open-ended, without precluding additional unrecited members, elements, or process steps.

The recitation of numerical endpoints includes all numbers and fractions within the corresponding range, as well as the recited endpoints.

All references cited in this specification are incorporated herein by reference in their entirety.

Unless defined otherwise, all terms (including technical and scientific terms) used in disclosing the invention have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to provide a better understanding of the teachings of the present invention.

In the context of the present disclosure, a number of terms should be utilized.

The term "protic solvent" according to the present invention refers to a solvent containing hydrogen linked to oxygen or nitrogen, thereby being able to form hydrogen bonds or donate protons.

The term "polar aprotic solvent" according to the present invention refers to a polar solvent which does not contain acidic hydrogen and does not act as a hydrogen bond donor.

Choline compounds

The choline compound of the present invention refers to a choline compound or a choline derivative compound in the form of hydroxide or salt.

The choline compounds include, but are not limited to, monocholine compounds, bischoline compounds, tricholine compounds, higher choline compounds, or derivatives thereof. Preferably, the choline compound is selected from the group consisting of choline hydroxide, choline bicarbonate, choline chloride, choline bitartrate, choline dihydrogen citrate, choline sulfate, and any combination thereof.

Specific examples of the choline compound are shown below.

Examples of commercially available choline compounds are, for example, the monocholine compound from TCI (choline hydroxide (48-50% in water)) and the tricaholine compound from TCI (tris (2-hydroxyethyl) methylammonium hydroxide (45-50% in water)).

In some embodiments of the invention, the amount of choline compound is from 2.5 to 50 wt.%, preferably from 5 to 50 wt.%, more preferably from 7 to 30 wt.%, and most preferably from 9 to 18 wt.%, based on the total weight of the composition. Choline compounds at concentrations greater than 50% are unstable and prone to color change, which can lead to failure of subsequent properties of the photoresist stripper composition.

In some embodiments of the present invention, a monocholine compound or its derivative, i.e., a choline compound having only one hydroxyethyl group attached to the central nitrogen, is preferably included in the photoresist stripper composition. When a bishydrocholic compound or a trihydrocholic compound is used, the photoresist stripper composition can be kept stable for one or two days at its working temperature (e.g., 78 ℃). Further experiments have shown that a photoresist stripper composition comprising a monocholine compound can be used for more than three days at its operating temperature (e.g., 78 deg.C) and still effectively remove photoresist material from a TFT array substrate.

Polar aprotic solvent

Polar aprotic solvents include, but are not limited to, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), 1, 3-dimethyl-2-imidazolidinone (DMI), Propylene Carbonate (PC), and any combination thereof.

Examples of commercially available polar aprotic solvents are, for example, N-methylpyrrolidone (NMP) from Sinopharm Group Co. L td., DMSO from Sinopharm Group Co. L td. and 1, 3-dimethyl-2-imidazolidinone from Sinopharm Group Co. L td..

In some embodiments of the invention, the amount of polar aprotic solvent is from 10 to 90 weight percent, preferably from 15 to 85 weight percent, and more preferably from 15 to 75 weight percent, based on the total weight of the composition.

Water (W)

Unlike conventionally available photoresist cleaners which contain substantially no or very little water, the amount of water in the present invention is preferably greater than or equal to 11%, more preferably greater than or equal to 13%, and even more preferably from 13% to 87.5% by weight of the total composition.

Without wishing to be bound by theory, it is believed that having sufficient water content in the photoresist stripper composition allows for easier establishment of an alkaline environment that helps dissolve the photoresist material.

Alkaline substance

The basic substance of the present invention means any substance that readily accepts hydrogen ions in solution.

The basic substance includes an inorganic basic substance, an organic basic substance, or a combination thereof, preferably having a pKa value of 2 to 12, more preferably a pH value of 7 to 11, when dissolved in water at 25 ℃. In some embodiments, it was found that photoresist stripper compositions comprising a basic species having a pKa value greater than 12 are prone to attack metal electrodes in TFT array substrates during the cleaning process.

Suitable inorganic substances include, but are not limited to, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, and any combination thereof. Suitable organic materials include, but are not limited to, ethanolamine (MEA), aminopyridine, butylamine, aminosulfane (chlor), diethanolamine, dimethylamine, dimethylimidazole, ephedrine, ethylmorpholine, glycylglycine, hydroxypyrroline, piperidine, propylamine, methylamine, methylimidazole, triethylamine, triethanolamine, trimethylamine, tris (hydroxymethyl) aminomethanol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino-2-methyl-1-propanol, and any combination thereof.

Examples of commercially available alkaline substances are, for example, ethanolamine from Sinopharm Group Co. L td. and 2- (2-aminoethoxy) ethanol from Aladdin.

In some embodiments of the invention, the amount of alkaline material is from 0 to 50 weight percent, preferably from 5 to 30 weight percent, and more preferably from 10 to 20 weight percent, based on the total weight of the composition.

In a preferred embodiment, the photoresist stripper composition comprises:

(a) 2.5-50% by weight of at least one choline compound;

(b) 10-90% by weight of at least one polar aprotic solvent;

(c)11-87.5 wt% water; and

(d)0 to 50 wt% of at least one alkaline substance;

wherein the weight percentages of all components add up to 100 weight%.

The photoresist stripper composition of the present invention can be prepared by mixing the components of the photoresist stripper composition.

The substrate may be obtained by removing the photoresist material coated on the substrate using the photoresist stripper composition.

The photoresist cleaning performance of the photoresist stripper composition can be evaluated by a method comprising the steps of:

(a) heating the photoresist stripper composition;

(b) immersing the substrate covered with the photoresist material in a heated photoresist stripper composition;

(c) rinsing the substrate with water; and is

(d) The removal of the photoresist material from the substrate surface is observed.

The metal etch of the photoresist stripper composition can be evaluated by a method comprising the steps of:

(a) measuring the thickness (omega) and initial resistivity (Rs) of a metal substrate_(pre))；

(a) Heating the photoresist stripper composition;

(c) soaking the metal substrate in the heated photoresist stripper composition and recording the soaking time (t);

(d) measuring the post resistivity (Rs) of a metal substrate_(post)) (ii) a And is

(e) The metal Etch Rate (ER) was calculated according to the following equation:

ER＝Rs_(pre)ω(1/Rs_(pre)-1/Rs_(post))/t。

the stability of the photoresist stripper composition can be evaluated by a method comprising the steps of:

(a) heating the photoresist stripper composition;

(b) immersing the substrate covered with the photoresist material in a heated photoresist stripper composition;

(c) rinsing the substrate with water;

(d) observing the removal of the photoresist material on the surface of the substrate; and is

(e) Repeating steps (b), (c) and (d) for a new substrate covered with the photoresist material at predetermined time intervals.