KR100719208B1 - An Antifoaming and Dispersing Agent for an Photoresist Developer - Google Patents

Abstract

In the developing step of the photoresist using a developing solution, the antifoaming agent for resist developing agents which is excellent in the defoaming property with respect to foaming of a developing solution, and also excellent in the dispersibility of scum which generate | occur | produces in a developing solution is provided.

A photoresist developer comprising a mixed fatty acid having 5 to 300 parts by mass of a fatty acid having 6 to 14 carbon atoms to 100 parts by mass of a higher fatty acid having 15 or more carbon atoms and a partial fatty acid ester obtained by reacting an aliphatic trihydric alcohol. Antifoam Dispersant.

Description

Antifoaming and Dispersing Agent for an Photoresist Developer

INDUSTRIAL APPLICABILITY The present invention is directed to an antifoaming agent for a resist developer having excellent antifoaming property for foaming of a developer and excellent dispersibility of scum generated in a developer in a developing step of a photoresist (hereinafter simply referred to as a 'resist') using a developer. It is about.

Background Art Conventionally, resists are widely used in forming wiring patterns such as printed circuit boards, integrated circuits, and color filters. In the process of forming the wiring pattern, a film or liquid resist is usually laminated or coated on a substrate, and then the resist is irradiated with ultraviolet rays, X rays, electron beams, or the like to be exposed to light. After the resist has been cured in a pattern state, the resist is developed by removing the resist portion (non-irradiated portion) which has not been cured with a developer, thereby forming a resist film in a pattern state. As a developing solution, alkaline aqueous solution is used normally, As an alkali agent of a developing solution, inorganic alkaline compounds, such as alkali metal carbonate and alkali metal hydroxide, organic alkaline compounds, such as tetramethylammonium hydroxide, etc. are used.

In the alkaline developer, during development of the resist, the resin component of the uncured portion of the resist, dyes, pigments, polymerization initiators, crosslinking agents, and the like contained in the resist are dissolved and dispersed in the developer and mixed, and these are aggregated in the developer. Float on the surface of the developer or precipitate in the developer, so-called scum is generated in the developer. When the scum adheres to the developing apparatus at the time of development and prevents the development of the resist, and the scum adheres to the resist to be developed or the substrate on which the resist is provided at the time of development, the resolution of the resist is lowered and satisfactory. There is a problem that a resist pattern is not formed. Therefore, the developer requires the ability to disperse scum generated during development and prevent scum agglomeration.

On the other hand, when air is dried in the developing solution at the time of developing the resist, bubbles are generated in the developing solution. Since the developing solution is usually circulated and used, bubbles are accumulated in the developing solution when the defoaming of bubbles generated in the developing solution is insufficient. In particular, as the resist component (resin or the like) dissolved or dispersed in the developing solution increases due to the circulation use of the developing solution, bubbles formed in the developing solution hardly disappear. Such bubbles not only hinder good circulation of the developer, but also inhibit contact between the developer and the resist, thereby causing a problem that the uncured resist portion is not sufficiently removed and a good resist pattern is not formed. In recent years, in the spray development of a mainstream resist, since the developer is developed by spraying a developer from the spray nozzle onto the resist after exposure, foaming is likely to occur in the developer, and suppression of bubbles in the developer and defoaming are very important. It becomes a problem.

In order to suppress foaming of the developer, it is effective to add an antifoaming agent to the developer, but if the antifoaming agent aggregates in the developer and becomes an oil scum, the scum is adhered to the resist or its substrate during development. Not only is the resist pattern not formed, but there is a problem that the substrate on which the resist is formed is contaminated. In general, the antifoaming agent has a high antifoaming effect. However, since the antifoaming agent is easy to form an oily scum, as an antifoaming agent for a developer, for example, an acetylene alcohol-based surfactant (for example, Patent Document 1). Polyalkylene glycols or derivatives thereof (for example, see Patent Documents 2 to 7), mono higher fatty acid glycerin esters (for example, see Patent Document 8), and the like.

However, these conventional antifoaming agents are not said to be sufficient in the dispersibility of scum generated in the developer, and this antifoaming agent has an antifoaming effect to some extent at the beginning of its use, but the resist component dissolved or dispersed in the developer increases. Therefore, there existed a fault that the defoaming effect fell rapidly and scum was easy to generate | occur | produce.

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-51020

[Patent Document 2] Japanese Patent Application Laid-Open No. 7-128865

[Patent Document 3] Japanese Patent Application Laid-Open No. 8-10600

[Patent Document 4] Japanese Patent Application Laid-Open No. 8-87382

[Patent Document 5] Japanese Patent Application Laid-Open No. 9-172256

[Patent Document 6] Japanese Patent Application Laid-Open No. 10-319606

[Patent Document 7] Japanese Patent Application Laid-Open No. 2001-222115

[Patent Document 8] Japanese Patent Application Laid-Open No. 9-293964

Accordingly, an object of the present invention is to develop a resist, even if the resist component to be dissolved or dispersed in the developer increases, while having a high anti-foaming property to the developer and excellent dispersibility of scum generated in the developer, An antifoaming agent for resist developer can be prevented from adhering to the substrate.

Accordingly, the present inventors have a medicament having anti-foaming property (hereinafter sometimes referred to simply as 'foaming property') to a developer and dispersibility to the scum generated in the developer solution (hereinafter sometimes referred to as 'scum dispersibility'). The present invention was completed by finding that the partial fatty acid ester of the mixed fatty acid and aliphatic trihydric alcohol having a specific fatty acid composition is excellent in the defoaming and scum dispersibility. That is, the present invention contains a mixed fatty acid having 5 to 300 parts by mass of a fatty acid having 6 to 14 carbon atoms to 100 parts by mass of a higher fatty acid having 15 or more carbon atoms and a partial fatty acid ester obtained by reacting an aliphatic trihydric alcohol. An antifoaming agent for resist developer (hereinafter sometimes referred to as "partial fatty acid ester"), and an alkaline resist developer containing the same.

The effect of the present invention is that when developing a resist with a developer, even if the resist component dissolved or dispersed in the developer increases, the foam having high defoaming property to the developer is excellent and the scum generated in the developer is excellent in dispersibility. It is to provide an antifoaming agent for a resist developer that can prevent adhesion to a resist or a substrate thereof.

Embodiment of the Invention

In the present invention, higher fatty acid refers to a fatty acid having 15 or more carbon atoms, and intermediate fatty acid refers to a fatty acid having 6 to 14 carbon atoms. Mixed fatty acid which is a raw material of the partial fatty acid ester of this invention is mixed fatty acid whose ratio of intermediate fatty acid with respect to 100 mass parts of higher fatty acids is 5-300 mass parts. This is because when the ratio of the intermediate fatty acid is less than 5 parts by mass, the scum dispersibility of the antifoam dispersant for the resist developer of the present invention is lowered, and when it exceeds 300 parts by mass, the antifoaming property of the foam generated in the developer is lowered. . It is preferable that the ratio of an intermediate fatty acid with respect to 100 mass parts of higher fatty acids is 10-200 mass parts, It is more preferable that it is 25-150 mass parts, It is most preferable that it is 40-100 mass parts.

As higher fatty acids having 15 or more carbon atoms, for example, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), 12-hydroxyoctadecanoic acid (12-hydroxystearic acid), eicosane Linear saturated fatty acids such as (arachinic acid), docoic acid (behenic acid), tetracoic acid (lignoseric acid), hexacoic acid (serotenic acid), and octacoic acid (montanoic acid); Branched fatty acids such as 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptyldodecanoic acid and isostearic acid; And unsaturated fatty acids such as palmitreic acid, oleic acid, isooleic acid, ellidinic acid, linoleic acid, linolenic acid, ricinolic acid, gardenic acid, erucic acid, ceracoreic acid, and the like. Among these higher fatty acids, fatty acids having 16 to 22 carbon atoms are preferred, fatty acids having 16 to 20 carbon atoms are more preferable, and fatty acids having 16 to 18 carbon atoms are most preferred.

Examples of the intermediate fatty acid having 6 to 14 carbon atoms include hexanoic acid (capronic acid), heptanoic acid, octanoic acid (capric acid), nonanoic acid (peralgonic acid), decanoic acid (capric acid), undecanoic acid, and dode. Linear saturated fatty acids such as cannoic acid (lauric acid), tridecanoic acid and tetradecanoic acid (myristin acid); Isohexanoic acid, isoheptanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, 2-propylheptanoic acid, isodecanoic acid, isoundecanoic acid, 2-butyloctanoic acid, isododecanoic acid, isotridecanoic acid Branched fatty acids such as; Unsaturated fatty acids, such as 10-undecenoic acid, are mentioned. Among these intermediate fatty acids, fatty acids having 7 to 14 carbon atoms are preferred, fatty acids having 8 to 13 carbon atoms are more preferred, and fatty acids having 10 to 12 carbon atoms are most preferred.

In addition, the mixed fatty acid which is a raw material of the partial fatty acid ester of the present invention is a mixed fatty acid containing linear saturated fatty acid and branched fatty acid or linear unsaturated fatty acid, rather than mixed fatty acid composed only of linear saturated fatty acid. Since the scum dispersibility in the developing solution by ester is good and the partial fatty acid ester becomes easy to disperse in the developing solution, it is preferable. It is preferable that the ratio of the branched fatty acid and linear unsaturated fatty acid in a mixed fatty acid is 5-80 mass% with respect to the mixed fatty acid whole quantity, It is more preferable that it is 10-70 mass%, It is most preferable that it is 15-60 mass%. Do.

On the other hand, the mixed fatty acid which is a raw material of the partial fatty acid ester of the present invention contains carboxylic acid other than the above-mentioned intermediate fatty acid and higher fatty acid as long as it does not adversely affect the defoaming or scum dispersibility of the antifoam dispersant for the resist developer of the present invention. You may be.                     

Examples of the aliphatic trihydric alcohol which is a raw material of the partial fatty acid ester of the present invention include glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-hydroxymethyl-1,3-propanediol, 2-methyl-1,2,3-propanetriol, 1,2,5-pentanetriol, 1,3,5-pentanetriol, 2-methyl-1,2,4-propanetriol, 2- Hydroxymethyl-1,3-butanediol, trimethylolethane, 1,3,5-hexanetriol, 1,2,6-hexanetriol, 3-hydroxymethyl-1,5-pentanediol, 3-methyl -1,3,5-pentane triol, trimethylol propane, trimethylol butane, 2, 5- dimethyl- 1,2, 5- hexane triol, etc. are mentioned. Among these aliphatic triols, from the viewpoint of scum dispersibility, aliphatic triols having 3 to 6 carbon atoms are preferable, and glycerin, 1,3,5-pentane triol, trimethylol ethane, 1,2,6-hexane triol and Trimethylolpropane is more preferred, glycerin, trimethylolethane and trimethylolpropane are more preferred, and glycerin is most preferred.

The partial fatty acid ester obtained by esterifying the mixed fatty acid with an aliphatic trihydric alcohol is usually a monofatty acid ester (hereinafter referred to as a 'monoester'), a difatty acid ester (hereinafter referred to as a 'diester'), and a trifatty acid ester (hereinafter referred to as an ester). It is a mixture of 'triester'). In the partial fatty acid ester of the present invention, when the content of the triester is too large, the scum dispersibility may decrease, so that the content of the triester is 20% by mass or less based on the total amount of the partial fatty acid ester. It is preferable that it is 10 mass% or less, and it is most preferable that it is 5 mass% or less. In addition, when there is too much content of diester, the defoaming property with respect to a developing solution may fall, and when it is too small, scum dispersibility may fall, so that the monoester and diester in the partial fatty acid ester of this invention may differ. It is preferable that the ratio is 5-1,500 mass parts of diester with respect to 100 mass parts of monoesters, It is more preferable that it is 10-500 mass parts, It is most preferable that it is 20-150 mass parts.

The partial fatty acid ester of this invention can be manufactured by a well-known method. As a known method, for example, (a) a method by direct esterification of a mixed fatty acid with an aliphatic trihydric alcohol, (b) a method by transesterification of a lower alcohol ester with an aliphatic trihydric alcohol of a mixed fatty acid and (c) a method by a transesterification reaction of a triester such as glycerin trifatty acid ester with an aliphatic trihydric alcohol. In addition, after completion | finish of reaction, you may refine | purify the produced | generated partial fatty acid ester as needed. For example, the refine | purification by molecular distillation etc. can obtain the partial fatty acid ester with a high monoester or diester content.

The defoaming dispersion for the resist developer of the present invention further contains a polyether polyol ester of a higher fatty acid having 10 to 20 carbon atoms, thereby improving scum dispersibility and antifoaming property. Such polyether polyol ester is obtained by making a C10-20 fatty acid react with the alkylene oxide adduct of polyhydric alcohol or polyhydric phenol.

As the polyhydric alcohol, in addition to the aliphatic trihydric alcohol, for example, ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, neopentyl glycol, isoprene glycol (3-methyl-1,3-butanediol ), Dihydric alcohols such as 1,6-hexanediol; Other trihydric alcohols such as triethanolamine and triisopropanolamine; Tetrahydric alcohols such as pentaerythritol, diglycerin, sorbitan, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine; And tetrahydric alcohols such as methylglucoside, dipentaerythritol, and sucrose.

As said polyhydric phenol, For example, Bivalent phenol, such as bisphenol A, bisphenol F, catechol, hydroquinone; Trihydric phenols such as tris (4-hydroxyphenyl) methane and tris (4-hydroxyphenyl) ethane.

Among these polyhydric alcohols and polyhydric phenols, dihydric alcohols are preferred, ethylene glycol, propylene glycol and 1,2-butanediol are more preferred, and propylene glycol is most preferred.

Examples of the alkylene oxide added to the polyhydric alcohol or polyhydric phenol include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-butylene oxide), long chain α-olefin oxide, styrene oxide and the like. Can be mentioned. The additional form may be homopolymerization of one type of alkylene oxide, random copolymerization of two or more types of alkylene oxide, block copolymerization or random / block copolymerization. Especially preferable is copolymerization of ethylene oxide and propylene oxide, In this case, it is preferable that the ratio of ethylene oxide with respect to 100 mass parts of propylene oxide is 5-100 mass parts, It is more preferable that it is 10-60 mass parts, 15- It is most preferable that it is 40 mass parts. This is because when the ratio of ethylene oxide is less than 5 mass parts, scum dispersibility in a developing solution may become inadequate, and when it exceeds 100 mass parts, the foamability of a developing solution will become high.

20-200 are preferable, as for the addition mole number of the alkylene oxide of the alkylene oxide adduct of the said polyhydric alcohol or polyhydric phenol, 30-150 are more preferable, and 40-120 are the most preferable.

Moreover, also in the said C10-C20 or more fatty acid, a C10-16 fatty acid is preferable from a scum dispersibility viewpoint, a C10-14 fatty acid is more preferable, C10-C14 linear saturated fatty acid is especially preferable, From the viewpoint of suppression, fatty acids having 14 to 20 carbon atoms are preferable, fatty acids having 16 to 18 carbon atoms are more preferable, and linear saturated fatty acids of saturated fatty acids having 16 to 18 carbon atoms are most preferred.

The antifoaming agent for resist developing solution of this invention may contain another component in the range which does not impair the performance. As such a component, Water-soluble solvents, such as ethanol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, butanediol, hexanediol; The alkylene oxide adduct of monohydric alcohol or monohydric phenol, its fatty acid ester, a coloring agent, etc. are mentioned.

The developing solution in which the defoaming dispersant for resist developing solution of the present invention is used is an alkaline developing solution. As an alkali agent of a developing solution, For example, Alkali metal carbonate, such as lithium carbonate, sodium carbonate, potassium carbonate; Alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; Alkali metal borate salts such as lithium borate, sodium borate and potassium borate; Alkali metal silicates such as lithium silicate, sodium silicate and potassium silicate; Inorganic alkali compounds such as alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Organic alkaline compounds such as ethylenediamine, propylenediamine, pyrrolidine, morpholine, piperazine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, and the like. Can be. Among these alkaline agents, alkali metal carbonates and organic alkaline compounds are preferable, and sodium carbonate and tetramethylammonium hydroxide are more preferable.

The concentration of the alkali agent in the developer is different depending on the type of alkali agent to be used and the type of resist to which the developer is applied. However, in the case of alkali metal carbonate, it is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of water, and 0.3 to It is more preferable that it is 3 mass parts, and it is most preferable that it is 0.5-2 mass parts. Moreover, in the case of an organic alkaline compound, it is preferable that the density | concentration of the alkali agent in a developing solution is 0.5-25 mass parts with respect to 100 mass parts of water, It is more preferable that it is 1-15 mass parts, It is 1.5-10 mass parts Most preferred

As for the temperature of the developing solution at the time of developing a resist using the said developing solution, 15-50 degreeC is preferable, 20-40 degreeC is still more preferable, 25-35 degreeC is the most preferable. This is because when the temperature of the developing solution is lower than 15 ° C, dissolution of the uncured resist portion may be insufficient, and when it exceeds 50 ° C, the cured resist portion may peel off from the substrate.

 In addition, the developing solution for resists of the present invention includes additive components conventionally used in the developing solution for resists, for example, various known surfactants, lubricants, stabilizers, dissolving aids, and the like, in a range where the object of the present invention is not impaired. You may add it suitably.

The amount of the antifoaming agent for the resist developer of the present invention is not particularly limited, and the amount of the antifoaming agent can be selected according to various conditions such as the type of developer, the concentration of the developer, the developing method, and the type of resist. For example, in the case of developing a dry film (resist in a film state) using a 1 mass% aqueous sodium carbonate solution as a developing solution, the antifoaming agent for the resist developing solution of the present invention is 0.005 in terms of net glycerin partial fatty acid ester in terms of the developer. It is preferable to use -0.2 mass%. In addition, a partial fatty acid ester may be used as an addition method, and what diluted the partial fatty acid ester with water may be added. In addition, the partial fatty acid ester or the partial fatty acid ester diluted with water may be added at the time of preparing a developing solution, and may be added to a foamed developing solution. The partial fatty acid ester according to the present invention may be used alone or in combination of two or more kinds thereof.

On the other hand, any resist can be used as the resist used as the developing object of the developer of the present invention, as long as it can be developed using an alkaline aqueous solution, regardless of whether it is negative or positive. Specifically, For example, (1) Positive resist containing a naphthoquinone diazide compound and a novolak resin; (2) a positive resist containing a compound which generates an acid upon exposure, a compound which is decomposed by an acid and has increased solubility in an alkaline aqueous solution and an alkali soluble resin; (3) a positive resist containing a compound which generates an acid upon exposure and an alkali soluble resin having a group which is decomposed by an acid and has increased solubility in an alkaline aqueous solution; (4) a negative resist containing a compound which generates an acid upon exposure, a crosslinking agent, and an alkali soluble resin; (5) negative type resist containing compound which generate | occur | produces a radical by exposure, a crosslinking agent, and alkali-soluble resin; (6) Negative-type resist containing the compound which generate | occur | produces a radical by exposure, alkali-soluble resin which has a radical polymerizable group, etc. are mentioned.                     

EXAMPLE

Hereinafter, an Example and a comparative example demonstrate this invention further more concretely. In addition, "part" and "%" in a following example and a comparative example are a mass reference | standard unless there is particular notice.

The antifoamer of Examples 1-9 and Comparative Examples 1-10 shown below were used for the test. Examples 1 to 7 and Comparative Examples 1 and 2 are partial fatty acid esters obtained by esterifying mixed fatty acids with aliphatic trihydric alcohols, and Table 1 shows the fatty acid composition (%) and ester composition (%). On the other hand, the fatty acid composition was subjected to methyl esterification after desensitizing the sample in accordance with the standard maintenance analysis method, and measured by gas chromatography (detector: FID). In addition, ester composition was measured by TLC-FID method (Yatron company, form Itarosscan MK5).

Table 1

Example Comparative example One 2 3 4 5 6 7 One 2 Aliphatic trihydric alcohol G G G G G TP TP G G Fatty Acid Composition (%) Octanoic acid 2 - 2 5 - 2 - - - Isononan - 30 - 5 - - 30 - - Decanoic acid 2 - 2 10 6 2 - - One Dodecanosan 10 - 10 - - 10 10 - 98 Tetradecanoic acid 38 3 24 - - 38 - - One Hexadecanoic acid 4 19 2 One 3 4 24 39 - Octadecanoic acid 4 13 28 8 11 4 36 61 - Palmitic Acid - - - 2 2 - - - - Oleic acid 34 2 30 68 77 34 - - - Linoleic acid 6 3 2 One One 6 - - - Ricinolic acid - 30 - - - - - - - Intermediate mountain total 52 33 38 20 6 52 40 0 100 Premium Mountain Total 48 67 62 80 94 48 60 100 0 Total divergence and unsaturated volcanoes 40 65 32 76 80 40 30 0 0 Ester Composition (%) Monoester 42 16 69 43 79 65 95 45 98 Diester 50 83 22 55 17 31 5 51 2 Triester 8 One 9 2 4 4 0 4 0

In the table, G represents glycerin and TP represents trimethylolpropane.

Example 8

A mixture of 100 parts of a partial fatty acid ester of Example 1 and 50 parts of a polyether polyol ester (80 moles of propylene oxide of propylene glycol and bisoctadecanoic acid ester of 30 moles of ethylene oxide).

Example 9

A mixture of 100 parts of a partial fatty acid ester of Example 2 and 50 parts of a polyether polyol ester (50 moles of propylene oxide of trimethylolpropane and 30 parts of random adducts of 30 moles of ethylene oxide).

Comparative Example 3

10 mole adduct of ethylene oxide of 2,4,7,9-tetramethyldeca-5-yne-4,7-diol.

Comparative Example 4

Polypropylene glycol (number average molecular weight 700).

Comparative Example 5

Polyoxypropylene glyceryl ether (number average molecular weight 1,000).

Comparative Example 6

Octadecanoic acid (stearic acid) ester of a block addition of 40 mol of propylene oxide and 8 mol of ethylene oxide of octadecanol (stearyl alcohol).

Comparative Example 7

Block addition product of 20 mol of propylene oxide and 20 mol of ethylene oxide of 2,2-diethyl-1,3-propanediol.

Comparative Example 8

Octadecanoic acid ester of the block addition product of Comparative Example 7.

Comparative Example 9

Bisoctadecanoic acid ester of the block addition of 80 mol of propylene oxide and 30 mol of ethylene oxide of propylene glycol.

Comparative Example 10

Dodecanoic acid ester of 50 mol of propylene oxide and 30 mol of ethylene oxide of trimethylolpropane.

<Preparation of Test Solution>

1% sodium carbonate (Na ₂ CO ₃₎ were 100 parts of an aqueous solution, Examples 1 to 9 and Comparative developer solution was added 0.05 part each of the anti-foaming agent Examples 1 to 10. What melt | dissolved the dry film produced from the acrylic photosensitive resin which was not exposed to this developing solution so that the density | concentration of this resin may be 0.2 g / L was used for the following tests as test liquid. In addition, the same test was done also about 2.5% tetramethylammonium hydride (TMAH) aqueous solution instead of 1% sodium carbonate aqueous solution.

<Vesicle test>

50 mL of the test solution was placed in a 100 mL volume stopper measuring cylinder, and shaken 50 times for 1 minute. After standing still, the state of foam was observed, and the antifoaming property was evaluated according to the following criteria.

: 15초 미만에서 거품이 사라지고, 소포성이 양호.

: Bubble disappears in less than 15 seconds, and defoaming is good.

(Triangle | delta): Foam disappears in 15 to 60 second, and an defoaming property is slightly bad.

: 60초를 넘어 경과하더라도 거품이 사라지지 않고, 소포성이 불량.

: Bubble does not disappear even after over 60 seconds, poor defoaming.

<Scum dispersibility test 1>

300 mL of the said test liquids were put into the glass container with a cap of 400 mL of capacity, and it stood still for 1 week in 30 degreeC dark place, and the amount of sediment was observed visually and judged, and scum dispersibility was evaluated based on the following reference | standard.

(Double-circle): A sediment cannot be seen and scum dispersibility is favorable.

: 침강물을 약간 볼 수 있고, 스컴분산성이 약간 양호.

: Some sediments can be seen and scum dispersibility is slightly good.

(Triangle | delta): A small amount of sediment is seen, and scum dispersibility is slightly bad.

: 침강물을 다량으로 볼 수 있고, 스컴분산성이 불량.

: A large amount of sediment can be seen, and scum dispersibility is poor.

<Scum dispersibility test 2>

Laminate the dry film made of acrylic photosensitive resin on the printed board, partially expose it with a mercury lamp, and then spray-treat with the test solution (liquid temperature 30 ° C, spray time 10 seconds, spray pressure 150kPa) to dry film or substrate. The scum dispersibility was evaluated by visually observing adhesion of scum on the basis of the following.

◎: No adhesion of scum is seen, and scum dispersibility is good.

: 스컴의 부착을 약간 볼 수 있고, 스컴분산성이 약간 양호.

: Scum adheres slightly, and scum dispersibility is slightly good.

(Triangle | delta): A small amount of scum adhesion is seen, and scum dispersibility is slightly bad.

: 스컴의 부착을 다량으로 볼 수 있고, 스컴분산성이 불량.

: A large amount of scum can be seen, and scum dispersibility is poor.

TABLE 2

Defoamer of test solution Na ₂ CO ₃ Test Solution TMAH Test Solution Antifoam Dispersibility 1 Dispersibility 2 Antifoam Dispersibility 1 Dispersibility 2 Example One

◎ ◎

◎ ◎ 2

3

◎ ◎

◎ ◎ 4

◎ ◎

◎ ◎ 5

◎

◎ 6

◎

◎ 7

◎

◎

8

◎ ◎

◎ ◎ 9

◎

◎ Comparative Example One

△

2

△

△

3

△ △ △ △

4 △

△ 5 △

△

6 △

△ △

7

△

8 △

△ △

△ 9 △

△

10

△

According to the present invention, in developing the resist, even if the resist component dissolved or dispersed in the developer is increased, it has a high anti-foaming property to the developer and excellent dispersibility of the scum generated in the developer, and the scum is applied to the resist or its substrate. The antifoaming agent for resist developing solutions which can prevent sticking can be provided.

Claims (6)

A photoresist developer comprising a mixed fatty acid having 5 to 300 parts by mass of a fatty acid having 6 to 14 carbon atoms to 100 parts by mass of a higher fatty acid having 15 or more carbon atoms and a partial fatty acid ester obtained by reacting an aliphatic trihydric alcohol. Antifoam Dispersant. The antifoaming agent for photoresist developer according to claim 1, wherein the ratio of the diester to 100 parts by mass of the monoester in the partial fatty acid ester is 5 to 1,500 parts by mass. The antifoaming agent for photoresist developer according to claim 1 or 2, wherein the content of the branched fatty acid and the linear unsaturated fatty acid in the mixed fatty acid is 5 to 80% by mass based on the total amount of the mixed fatty acids. The antifoaming agent for a photoresist developer according to claim 1 or 2, wherein the aliphatic trihydric alcohol is an aliphatic trihydric alcohol having 3 to 6 carbon atoms. The antifoaming agent for photoresist developer of Claim 1 or 2 containing the polyether polyol ester of a C10-20 fatty acid. An alkaline photoresist developer comprising the antifoaming agent for photoresist developer according to claim 1.