JP2002328478A - Defoaming agent composition for photoresist dissolving liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a defoaming agent for a photoresist dissolving liquid less liable to generate a flocculate and having a satisfactory defoaming effect and a photoresist dissolving liquid obtained by adding the defoaming agent and to provide a method for dissolving a photoresist using the photoresist dissolving liquid. SOLUTION: The defoaming agent composition contains a compound A prepared by adding 8-20 mol ethylene oxide to an alcohol having 10-22 straight chain or branched chain alkyl groups and then adding 10-30 mol propylene oxide and a compound B prepared by adding propylene oxide to at least one selected from propylene glycol, glycerol and trimethylolpropane and then adding ethylene oxide and having a weight average molecular weight of 1,500-5,000 and 5-25 mass% proportion of polyethylene oxide groups in the entire compound as essential components. When the composition is used as a defoaming agent for a photoresist dissolving liquid, diminution of a flocculate and an excellent defoaming effect can be simultaneously satisfied.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifoaming composition for a photoresist solution, a photoresist solution obtained by adding the same, and a method for dissolving a photoresist using the photoresist solution. is there.

[0002]

2. Description of the Related Art Conventionally, a photoresist has been used as a material for forming a printed circuit, metal working of a lead frame or the like, forming a partition of a plasma display panel, and protecting a base material. When handling the photoresist, a photoresist solution is used, and as the main photoresist solution, a developer and a stripper are known. The photoresist has a difference in solubility in a developing solution between an unexposed portion and an exposed portion due to irradiation with actinic rays, and the developing solution is used to remove a portion exhibiting solubility. The part of the photoresist exposed to actinic radiation that shows insolubility in the developing solution forms a film on the substrate, and the exposed part of the substrate after development and removal of the photoresist is processed by etching, plating, etc., or is covered with the film Protects and exhibits the performance as a resist. The stripper is used to remove the photoresist film used for the processing from the substrate. Various solutions are used as the photoresist dissolving solution. In recent years, in addition to conventional organic solvents, an alkaline solution, particularly an alkaline aqueous solution, has recently been used for environmental reasons. As a method of dissolving the photoresist, a method of dripping a photoresist solution, supplying it to the resist surface by shower or spray, or a method of immersing in a photoresist solution is used, but it is often used in circulation, particularly An antifoaming agent is used because it is easy to foam by spraying. As a defoaming agent, it is generally known that a silicone type defoaming agent has a high defoaming effect. However, in the photoresist development step and the peeling step, the high covering power and water repellency of the silicone cause various problems in the processing step of the base material after development and the subsequent step after the peeling. Therefore, as a conventional defoaming agent, polyoxyalkylene monol or an esterified product thereof, a compound obtained by adding an alkylene oxide to a higher fatty acid, and the like have been used as the defoaming agent. These are disclosed in
-28865, JP-A-7-319170,
JP-A-8-10600, JP-A-8-160632
JP, JP-A-9-87380, JP-A-9-87
381, JP-A-9-87382, JP-A-9-87382
-293964, JP-A-10-319606, JP-A-11-258820, JP-A-11-3
It is known as a technique such as Japanese Patent No. 52700.

[0003] Since the photoresist solution is circulated, the insoluble content of the photoresist gradually precipitates when a processing device such as a developing device or a stripping device is used for a long period of time, or depending on the type of defoaming agent, the components of the photoresist. To produce oily substances or gel-like substances (hereinafter, aggregates).
Agglomerates adhere to the substrate surface, treatment tanks, piping, pumps, etc.
In some cases, it may solidify. Removing aggregates adhering to the processing tank, piping, pump, and the like is a troublesome operation such as scraping or disassembling and cleaning. Also,
Oily substances and agglomerates may cause defects or short-circuits in the parts to be processed by adhering to the base material, or may result in surface residues of exposed parts that are not protected and may cause poor bonding in the subsequent process. It becomes a problem. With the recent miniaturization of printed circuit width, lead frame pitch, plasma display panel partition wall pitch, etc., a spray-type processing apparatus for a photoresist solution has become mainstream. In this method, the spray pressure tends to be set higher to ensure the removal of the dissolved portion, so that the photoresist solution tends to foam, and a defoaming agent having a sufficient defoaming effect is required. In addition, with the miniaturization, the gap between the patterns of the photoresist film formed after development becomes narrower, so it is difficult to remove the aggregates generated when they adhere, and it is increasingly important to suppress the generation of aggregates. It has become. However, among the conventional antifoaming agents used in the developing solution and the stripping solution, the ester type antifoaming agent was inferior in its effect due to hydrolysis at a high alkali concentration. When the defoaming effect is lost, foaming of the photoresist solution becomes severe, causing a reduction in productivity due to the stop of the processing apparatus and an increase in cost due to replacement of the photoresist solution. Conventional ether-based antifoaming agents have a defoaming effect, but have poor dispersibility in photoresist solution, and act with photoresist components dissolved in developer and stripper to form aggregates. It tended to be more pronounced, causing product failure. On the other hand, photoresists are required to have high resolution in response to the miniaturization. It is known that a photoresist uses a polyfunctional monomer as a photopolymerizable monomer in a composition in order to increase the resolution.However, this polyfunctional monomer has a large hydrophobic structure, and depending on the amount added, it becomes a precipitate or an oily substance. It becomes an agglomerate due to the defoaming agent and the above-mentioned action, and becomes a problem. In particular, generation of aggregates was remarkably observed in the urethane monomer. In other words, the conventional antifoaming agent has a low generation of agglomerates, and none of the conventional antifoaming agents has sufficient performance of the antifoaming effect. In the conventional dissolution method using the method described above, the reduction in productivity and cost increase due to foaming, the generation of defective products due to the generation of agglomerates were not improved, and it was difficult to cope with a higher resolution photoresist.

[0004]

SUMMARY OF THE INVENTION The present invention provides an antifoaming agent composition for a photoresist dissolving solution, which has a small amount of agglomerates and has sufficient performance of an antifoaming effect, and a photoresist obtained by adding the same. An object of the present invention is to provide a resist dissolving solution and a method for dissolving a photoresist using the photoresist dissolving solution.

[0005]

Means for Solving the Problems The present inventors have studied to solve the above problems, and as a result, by using the following compound A and compound B as essential components of an antifoaming agent, the defoaming property and the dispersing property are improved. The present inventors have found that both performances are satisfied, and have reached the present invention. That is, the present invention has the formula _{(1) R-O (CH} 2 CH 2 O) m- (CH 2 CH (CH 3) O) n-H ···· (1) ( wherein, R is 10 carbon atoms 22 represents a straight-chain or branched-chain alkyl group, m represents a number of 8 to 20, and n represents a number of 10 to 30), and propylene glycol;
A compound obtained by adding propylene oxide to at least one selected from glycerin and trimethylolpropane and then adding ethylene oxide, and having a weight-average molecular weight of 1,500 to 5,000 and occupying in the entire polyethylene oxide group compound A defoaming agent composition for a photoresist solution, comprising a compound B having a ratio of 5 to 25% by mass as an essential component, and 0.01 to 1.00. A photoresist solution characterized by being added by volume%, a photoresist dissolution method characterized by using the photoresist solution, and a resist having a specific composition dissolved by using the solution. This is a method of dissolving the photoresist to be formed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In the present invention, compound A has 10 to 22 carbon atoms.
Can be easily synthesized by subjecting a higher alcohol having a linear or branched chain alkyl group to an addition reaction of ethylene oxide, followed by an addition reaction of propylene oxide. The ethylene oxide may contain a small amount of an alkylene oxide other than ethylene oxide (propylene oxide, butylene oxide, etc.), and the propylene oxide may contain a small amount of an alkylene oxide other than propylene oxide (ethylene oxide, butylene oxide, etc.). May be included. Examples of higher alcohols include decyl alcohol, lauryl alcohol, 2-butyl octanol, tridecyl alcohol, myristyl alcohol, 2-butyl decanol,
-Hexyl octanol, cetyl alcohol, 2-hexyl decanol, 2-octyl decanol, stearyl alcohol, 2-hexyl decanol, 2-octyl decanol, behenyl alcohol, and synthetic alcohols prepared from propylene polymers. When the carbon number of the present higher alcohol is less than 10, the defoaming property is very poor and does not function as an antifoaming agent. On the other hand, when the number of carbon atoms exceeds 22, the dispersibility decreases and the amount of aggregates increases.
The addition reaction of ethylene oxide and propylene oxide to these higher alcohols is synthesized by a conventional method. Compound A of the present invention can be obtained by subjecting ethylene oxide to an addition reaction followed by propylene oxide. When the order of the addition reaction is reversed, or when a mixture of ethylene oxide and propylene oxide is added, the defoaming properties are very poor and do not function as a defoaming agent. The addition number of ethylene oxide is suitably 8 to 20 mol, and the addition number of propylene oxide is suitably 10 to 30 mol.
If the number of additions of ethylene oxide is less than 8 moles or the number of additions of propylene oxide exceeds 30 moles, the dispersibility decreases and the amount of aggregate generation increases. When the number of additions of ethylene oxide exceeds 20 moles or the number of additions of propylene oxide becomes less than 10 moles, the defoaming property decreases.

The compound A according to the present invention is particularly excellent in defoaming property and sustainability as compared with the antifoaming agent found in the prior art. The compound disclosed in JP-A-8-10600 is
Propylene oxide is added to a linear or branched alkyl or alkenyl higher alcohol having 24 carbon atoms by
There is a compound in which ethylene oxide is added in an amount of 1 to 25 mol after addition of 60 mol. That is, the order of addition of propylene oxide and ethylene oxide is opposite to that of compound A of the present invention. As described above, when the order of the addition reaction is reversed, the defoaming property of the photoresist solution of the present invention was insufficient. The compound disclosed in JP-A-9-87380 is a straight-chain or branched-chain higher alcohol having 8 to 24 carbon atoms or an alkylphenol having 10 to 24 carbon atoms and 6 to 60 moles of propylene oxide and 2 to 2 moles of ethylene oxide. There is a compound obtained by adding 50 moles and then esterifying with a fatty acid having 10 to 24 carbon atoms. That is, unlike the compound A of the present invention, an ester group is introduced. As described above, in the photoresist solution of the present invention, the ester group was hydrolyzed by the alkali, and the defoaming effect was not maintained.

When Compound A alone was used in a photoresist solution, the formation of aggregates was suppressed and sufficient defoaming properties could not be obtained. Depending on the type of higher alcohol and the number of ethylene oxide and propylene oxide added, those with less generation of aggregates do not have sufficient defoaming properties, while those with sufficient defoaming generate more aggregates. However, both performances of defoaming and dispersibility could not be satisfied. On the other hand, when Compound B described below was used alone in a photoresist solution, the amount of aggregates generated was very small, but the defoaming property was very poor. Therefore, the present inventors prepared an antifoaming agent by using a compound A having excellent defoaming properties in combination with a compound B having an extremely small amount of aggregates. As a result, when compound B is used together with compound A within a predetermined range, compound B has an effect of reducing the amount of agglomerates without substantially reducing the defoaming property of compound A. Both defoaming and dispersing performances could be satisfied.

Compound B is obtained by adding propylene oxide to at least one selected from propylene glycol, glycerin and trimethylolpropane,
Then, it can be easily synthesized by subjecting ethylene oxide to an addition reaction. The ethylene oxide may contain a small amount of an alkylene oxide other than ethylene oxide (propylene oxide, butylene oxide, etc.), and the propylene oxide may contain a small amount of an alkylene oxide other than propylene oxide (ethylene oxide, butylene oxide, etc.). May be included. The addition reaction of ethylene oxide and propylene oxide to these polyhydric alcohols is synthesized by a conventional method. Compound B has a weight average molecular weight of 1,500 to 5,
000 is suitable. If the weight-average molecular weight is out of this range, the dispersibility decreases and the amount of aggregates generated increases. The ratio of the polyethylene oxide group of the compound B to the whole compound is suitably from 5 to 25% by mass. If this ratio is less than 5% by mass, the dispersibility decreases and the amount of aggregates generated increases, and if it exceeds 25% by mass, the defoaming property decreases.
In addition, one type of compound B may be used, or a plurality of types may be used. The proportion of the compound B in the antifoaming composition of the present invention is preferably 3 to 50% by mass, more preferably 5 to 2% by mass.
0 mass% is appropriate. When the proportion of the compound B is less than 3% by mass, the effect of reducing the aggregates does not appear, and when it exceeds 50% by mass, the defoaming property decreases.

The composition comprising Compound A and Compound B can be prepared as an antifoaming composition using a diluent component which does not adversely affect the antifoaming property and dispersibility. Includes diluent component to reduce product viscosity to facilitate removal from container, to improve diffusivity when added to photoresist solution, or to reduce product freezing point during winter The effect of not solidifying even during storage is obtained. Examples of the diluent component include ethylene glycol, propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, water, and the like, and one type may be used. , May be used.
As the diluent component, a component or a combination of components that are soluble in both the defoamer composition and the photoresist solution is generally selected. It is appropriate that the diluent component is used in an amount of not more than 47% by mass. When the ratio of the diluent component exceeds 47% by mass, the defoaming property decreases.

The antifoam composition of the present invention is used by adding to a photoresist solution. As a specific example of the photoresist solution, an alkaline solution having a pH of 8.0 to 14.0 is used. Although differences are seen depending on the photoresist used, examples of the developer include pH 8.0 to 13.0.
As an example of an alkaline solution at a temperature of 20 to 40 ° C and a stripper, an alkaline solution at a pH of 11.0 to 14.0 and a temperature of 30 to 60 ° C is often used. These alkaline solutions often use an alkaline aqueous solution containing a basic compound such as a basic alkali metal salt compound and an amine compound. Examples of the basic alkali metal salt compound include alkali metal carbonates such as sodium carbonate and potassium carbonate. Sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, alkali metal phosphates such as sodium phosphate and potassium phosphate, and sodium metasilicate. Examples of the amine compound include amines such as hydroxylamine, ethylamine, and monoethanolamine. Compounds or aqueous ammonia. These are often used alone or together with other compounds as an aqueous solution.

The amount of the defoamer composition of the present invention varies depending on various conditions such as the type and concentration of the photoresist solution and the purpose of defoaming. 0.01-1.00% by volume, often 0.05-0.50% by volume, is used. The method of addition may be the antifoaming composition as it is, or a solution diluted with water or a photoresist solution may be added. It may be added at the time of preparing the photoresist solution or may be added to the foamed photoresist solution. When it is used after dilution, it is added so that the addition amount of the antifoam composition becomes the above-mentioned amount.

The photopolymerization initiator used for the photoresist dissolved in the photoresist solution containing the antifoaming composition of the present invention is not particularly limited, and a known one can be used. Specific examples include aromatic ketones, benzyl derivatives, 2,4,5-triarylimidazole 2
Dimers, acridine derivatives, phenylglycine derivatives,
A diazonium compound, a thioxanthone derivative, or the like can be used. The content of the photopolymerization initiator is 0.05 to 30.00% by mass, preferably 0.05 to 2% by mass based on the total mass.
0.00% by mass, more preferably 0.10 to 15.00
% By mass. If the content is too small, sufficient photosensitivity cannot be obtained. If the content is too large, light absorption on the photoresist surface increases, and the photocuring inside tends to be insufficient.

The photopolymerizable monomer used for the photoresist dissolved in the photoresist solution containing the antifoaming composition of the present invention is a known one containing an ethylenically unsaturated double bond in the molecule. be able to. Examples of photopolymerizable monomers include polyol (meth) acrylates, acrylamides, (meth) acrylates modified and derived from bisphenol A, trimethylolpropane triacrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol. Di (meth) acrylate and the like can be mentioned.

A specific example of urethane di (meth) acrylate used for a photoresist dissolved in a photoresist solution containing the antifoaming composition of the present invention is a compound obtained by reacting a polyol with a diisocyanate. And a product obtained by reacting β-hydroxylalkyl (meth) acrylate. The molecular weight of the urethane di (meth) acrylate is from 500 to 30,000, preferably 5
00 to 25,000, more preferably 800 to 20,000
00. If the molecular weight is too small, the strength of the cured film will be insufficient, and if it is too large, the solubility in the photoresist solution will tend to deteriorate.

The vinyl copolymer used for the photoresist dissolved in the photoresist solution containing the antifoaming composition of the present invention is a vinyl copolymer obtained by using a vinyl monomer containing at least a carboxyl group as a copolymer component. Copolymers can be used. Known vinyl monomers containing a carboxyl group can be used. Specific examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, butyl acrylate, butyl methacrylate, 2-
Ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylonitrile, methacrylonitrile,
Acrylamide, methacrylamide, styrene and styrene derivatives are included. As the vinyl copolymer, those obtained by copolymerizing 2 to 5 kinds of these vinyl monomers by a known method are used.

The photoresist dissolved in the photoresist solution containing the antifoaming composition of the present invention is provided in a conventionally employed form. As a form of the photoresist, a solution or a dry film resist is widely used. The photoresist in the solution is obtained by applying a solution obtained by dissolving the components of the photoresist in a solvent onto a substrate by a method such as a spin coater, a dip coater, a roll coater, and a curtain coater, and then drying to obtain a photoresist film.
A dry film resist is prepared by applying a solution obtained by dissolving a photoresist component in a solvent on a supporting film using a method such as a die coater or kiss dipping and drying to form a photoresist layer, and then bonding a cover film as necessary. And usually provided in a roll. After the cover film is peeled off, the dry film resist is hot-pressed with a hot roll type laminator or the like so that the photoresist layer is on the base material to obtain a photoresist film.
The support film on the opposite side of the photoresist layer from the substrate is peeled off before development or exposure. As a method of dissolving the photoresist, a method of supplying a photoresist solution on the photoresist film to be dissolved, a method of immersing the entire substrate on which the photoresist film is formed in the photoresist solution, and the like are used. As a specific example, a pipe in which a spray nozzle, a hole, and the like are arranged is installed in a tank whose periphery is covered with resin or metal, and a photoresist solution is dropped or sprayed with a pump. The substrate is conveyed by a conveyor or a jig, and a portion of the substrate surface where the photoresist is dissolved is dissolved by a photoresist dissolving solution supplied by dropping or spraying. The used photoresist solution is circulated by a pump. Piping is often installed parallel to the transport surface. Examples of immersion in a photoresist solution include immersion in a tank filled with a photoresist solution by a method such as mounting a base material on a jig, and, if necessary, stirring, lifting, ultrasonic vibration and the like. In these dissolving methods, the base material is treated for a desired time, washed with water or the like, and then moved to the next step.

Hereinafter, the present invention will be described based on examples and comparative examples, but the present invention is not limited to these examples.

Compound A-1 In a 5 liter autoclave, 200.0 g of branched tridecyl alcohol and 2.3 g of potassium hydroxide were charged, and the system was purged with nitrogen.
The solution was dehydrated under a reduced pressure of about 100 kPa at 30 ° C. for 30 minutes to perform alcoholation. Next, 528.0 g of ethylene oxide
Was introduced at 100 to 110 ° C. and 100 to 500 kPa over about 3 hours to cause an addition reaction. Next, 1044.0 g of propylene oxide was added at 100 to 110 ° C and 100 to
The mixture was introduced at 500 kPa for 7 to 8 hours to carry out an addition reaction. After the completion of the reaction, the alkali value of the product was measured by a titration method, and the catalyst was neutralized with a small excess amount of an aqueous lactic acid solution. The compound obtained here is an adduct of 12 mol of ethylene oxide and 18 mol of propylene oxide of a branched tridecyl alcohol. This was designated as compound A-1.

Compound A-2 214.0 g of n-tetradecyl alcohol and 2.3 g of potassium hydroxide were charged into an autoclave, and Compound A-1 was charged.
616.0 g of ethylene oxide and 1624.0 g of propylene oxide were subjected to an addition reaction in the same manner as described above to carry out a neutralization treatment. The compound obtained here is an adduct of 14 mol of ethylene oxide and 28 mol of propylene oxide of n-tetradecyl alcohol. The compound A-
And 2.

Compound A-3 158.0 g of n-decyl alcohol and 2.3 g of potassium hydroxide were charged into an autoclave, and 352.0 g of ethylene oxide and then 1740.0 g of propylene oxide were added and reacted in the same manner as in Compound A-1. And a neutralization treatment was performed. The compound obtained here is an adduct of n-decyl alcohol with 8 mol of ethylene oxide and 30 mol of propylene oxide. This was designated as compound A-3.

Compound A-4 326.0 g of behenyl alcohol and potassium hydroxide
3 g was charged into an autoclave, and in the same manner as in Compound A-1, 880.0 g of ethylene oxide and then 1740.0 g of propylene oxide were subjected to an addition reaction to carry out a neutralization treatment. The compound obtained here was 20 moles of ethylene oxide of behenyl alcohol and 30 moles of propylene oxide.
It is a molar adduct. This was designated as compound A-4.

Compound A-5 326.0 g of behenyl alcohol and potassium hydroxide
3 g was charged in an autoclave, and 352.0 g of ethylene oxide and then 580.0 g of propylene oxide were subjected to an addition reaction in the same manner as in the compound A-1 to perform a neutralization treatment. The compound obtained here is a behenyl alcohol adduct of 8 mol of ethylene oxide and 10 mol of propylene oxide. This was designated as compound A-5.

Compound B-1 A propylene oxide / ethylene oxide block adduct of trimethylolpropane having a weight average molecular weight of 4,50.
A commercially available surfactant in which the ratio of ethylene oxide to the total amount of ethylene oxide was 10% by mass was designated as Compound B-1.

Compound B-2 A commercially available surfactant which is an ethylene oxide adduct of polypropylene glycol and has a weight average molecular weight of 2,200 and a proportion of ethylene oxide in the whole compound of 20% by mass is referred to as Compound B-2.

Compound B-3 A commercially available surfactant having a weight average molecular weight of 3,000 and a proportion of ethylene oxide in the total compound of 20% by mass, which is a propylene oxide / ethylene oxide block adduct of glycerin, was designated as Compound B-3. .

Compound B-4 A commercially available surfactant which is an ethylene oxide adduct of polypropylene glycol and has a weight average molecular weight of 2,300 and a proportion of ethylene oxide in the whole compound of 10% by mass is referred to as Compound B-4.

Compound ZA-1 130.0 g of 2-ethylhexyl alcohol and 2.3 g of potassium hydroxide were charged into an autoclave, and Compound A-
In the same manner as in 1, 352.0 g of ethylene oxide and then 1740.0 g of propylene oxide were subjected to an addition reaction,
A neutralization treatment was performed. The compound obtained here is an adduct of 2-ethylhexyl alcohol with 8 mol of ethylene oxide and 30 mol of propylene oxide. This is compound Z
A-1 is a comparative example in which the number of carbon atoms in R of compound A is out of the preferred range.

Compound ZA-2 214.0 g of n-tetradecyl alcohol and 2.3 g of potassium hydroxide were charged into an autoclave, and Compound A-1 was charged.
In the same manner as described above, 220.0 g of ethylene oxide and then 2030.0 g of propylene oxide were subjected to an addition reaction to carry out a neutralization treatment. The compound obtained here is an adduct of n-tetradecyl alcohol with 5 mol of ethylene oxide and 35 mol of propylene oxide. This was compounded with Compound ZA-2.
This is a comparative example in which the number of additions of ethylene oxide and propylene oxide of the compound A is out of the preferred range.

Compound ZB-1 A commercially available surfactant having an ethylene oxide adduct of polypropylene glycol having a weight average molecular weight of 4,100 and an ethylene oxide addition ratio of 50% by mass was added to Compound ZB.
B-1 is a comparative example in which the proportion of polyethylene oxide in compound B is out of the preferred range.

[0031]

Example 1 96 parts by mass of compound A-1 and compound B-1
Was mixed in an amount of 4 parts by mass to obtain an antifoaming composition.

Example 2 95 parts by mass of compound A-2 and compound B-2
Was mixed in an amount of 5 parts by mass to obtain an antifoaming composition.

Example 3 95 parts by mass of compound A-3 and compound B-2
Was mixed in an amount of 5 parts by mass to obtain an antifoaming composition.

Example 4 95 parts by mass of compound A-4, compound B-2
Was mixed in an amount of 5 parts by mass to obtain an antifoaming composition.

Example 5 Compound A-5 (95 parts by mass), Compound B-2
Was mixed in an amount of 5 parts by mass to obtain an antifoaming composition.

Example 6 Compound A-2 was 50 parts by mass, Compound B-2
Was mixed with 7 parts by weight of 3-methyl-1,5-pentanediol and 3 parts by weight of water to obtain an antifoaming composition.

Example 7 Compound A-2 (75 parts by mass), Compound B-3
Was mixed with 7 parts by weight of 3-methyl-1,5-pentanediol and 3 parts by weight of water to obtain an antifoaming composition.

Example 8 70 parts by mass of compound A-2 and compound B-4
Was mixed with 17 parts by weight of 3-methyl-1,5-pentanediol and 3 parts by weight of water to obtain an antifoaming composition.

[0032]

Comparative Example 1 Compound A-1 alone.

Comparative Example 2 Compound A-2 alone.

Comparative Example 3 95 parts by mass of compound ZA-1 and compound B-
2 were mixed in an amount of 5 parts by mass to obtain a composition.

Comparative Example 4 Compound ZA-2 (95 parts by mass), Compound B-
2 were mixed in an amount of 5 parts by mass to obtain a composition.

Comparative Example 5 70 parts by mass of compound A-2 and compound ZB-
10 parts by mass, 17 parts by weight of 3-methyl-1,5-pentanediol and 3 parts by weight of water were mixed to obtain a composition.

Comparative Example 6 A commercially available defoamer containing silicone, SN Deformer 470 (manufactured by San Nopco Co., Ltd.).

Comparative Example 7 SN Deformer 265 (manufactured by San Nopco Co., Ltd.), a commercially available antifoaming agent for higher fatty acid alkylene oxide adducts.

Comparative Example 8 SN Deformer 170 (manufactured by San Nopco Co., Ltd.), a commercially available antifoaming agent obtained by adding propylene oxide and ethylene oxide in this order to a higher alcohol.

Using the samples of Examples 1 to 8 and Comparative Examples 1 to 8, the following performance evaluation tests were performed.

[0034]

[Test Result 1] A development test solution was prepared using a dry film resist AQ-4067 manufactured by Asahi Kasei (a photoresist composition comprising a photopolymerizable monomer, a photopolymerization initiator, a vinyl copolymer, a dye, etc.) having a thickness of 40 μm on a support film. so as to be applied, and the temperature control of the photoresist layer 0.25 m ² of the unexposed photoresist) provided in roll form a three-layer structure laminated cover film 30 ° C. 1
immersed in 1% by weight sodium carbonate aqueous solution dm ^3, a solution prepared by stirring for 2 hours to dissolve. The 1% by weight aqueous solution of sodium carbonate used herein had a pH of 11.4, and the unexposed photoresist composition was immersed and dissolved in the solution.
0.5. 120 ml of this development test solution and 0.24 ml of the defoamer sample were put into a commercially available 1-liter glass measuring cylinder, and air was sent from the glass ball filter at a rate of 6,000 ml / min while controlling the temperature in a 30 ° C. water bath. This was performed by recording the height of the foam 30 minutes after aeration. Table 1 shows the results.

[0035]

[Test result 2] The peeling test solution was prepared by immersing 0.75 m ² of the exposed portion of the above photoresist in a 3% by mass aqueous solution of 1 dm ³ sodium hydroxide adjusted to 50 ° C. and stirring for 2 hours. Is a solution at room temperature for 22 hours with immersion, and then the undissolved photoresist is removed. The 3% by weight aqueous solution of sodium hydroxide used here had a pH of 13.5, and the pH of the liquid in which the exposed photoresist composition was immersed was 13.5. 120 ml of the peel test liquid and 0.06 ml of the defoamer sample were placed in a commercially available 1 liter glass measuring cylinder, and 50 ml of the peel liquid was added.
While controlling the temperature in a water bath at ℃, air is sent from the glass ball filter at a rate of 6,000 ml / min.
This was performed by recording the height of the foam 8 hours after aeration. Table 2 shows the results.

The test for the amount of agglomerates is performed by taking a developer and a stripping solution after the defoaming test is completed in a glass bottle, covering with a lid and allowing to stand at room temperature for about 20 hours, and then reducing the pressure with a membrane filter having a pore size of 5 micrometers. Filtration was performed by a method in which the increase in the mass of the filter when the membrane filter was dried with a dryer at 50 ° C. for 3 hours was recorded as the amount of aggregates. Tables 1 and 2 show the performance test results of each sample.

The criteria for the defoaming were that the foam height was less than 60 mm, that the height was 60 mm or more and less than 120 mm, and that the foam height was 120 mm or more. Less than 30 mg and not more than 30 mg were considered unacceptable.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Test Result 3] The dissolved portion of the dry film resist was dissolved with a developer using a photoresist dissolution apparatus having the following specifications. This developer was circulated to observe the height of bubbles and the formation of aggregates. Processing equipment: Conveyor-type automatic dissolution processing equipment Supply of liquid: Supply to the substrate surface by a spray nozzle. The developer collects in the lower part of the tank and is circulated and supplied to the spray nozzle by a pump. Conveyor: Conveyor Developing solution: 1% by mass of sodium carbonate controlled at 30 ° C
Aqueous solution defoamer: 0.05% by volume of the defoamer composition of Example 8, Comparative Example 6, Comparative Example 8 Test substrate: Dry film resist made by Asahi Kasei on copper-clad laminate R-1766 (Matsushita Electric Works) AQ-4067 substrate thermocompressed with a hot roll laminator Test method: A test substrate in which a support film on the surface of a dry film resist is peeled and an unexposed photoresist composition is exposed is put into the above-mentioned dissolution apparatus by a conveyor. The photoresist layer was dissolved in a dissolving tank with a developer supplied from a spray nozzle. The substrate was charged until the amount of dissolution of the unexposed photoresist layer reached 0.25 m ² / dm ³ . The spray operation by the pump was continued to measure the foam height, and stopped after 24 hours, and the generation of aggregates was confirmed. The results are summarized in Table 3.

[0041]

[Table 3]

[0042]

As can be seen from the examples, the antifoaming composition of the present invention has both good antifoaming properties and good dispersibility in a photoresist solution. This is more effective than the conventional antifoaming technology. The defoaming agent composition of the present invention and a photoresist dissolving solution obtained by adding the same, and a method for dissolving a photoresist using the photoresist dissolving solution only have an excellent defoaming effect in a photoresist developing step and a peeling step. However, since the generation of agglomerates is low, problems such as the adhesion of aggregates to the substrate, the stoppage of processing equipment due to foaming, the replacement of the photoresist solution, the cleaning of equipment, etc. due to the adhesion of agglomerates, as seen with conventional antifoaming agents Useful for improving points.

[Procedure amendment]

[Submission Date] May 24, 2002 (2005.2.
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

2. Description of the Related Art Conventionally, a photoresist has been used as a material for forming a printed circuit, metal working of a lead frame or the like, forming a partition of a plasma display panel, and protecting a base material. When handling the photoresist, a photoresist solution is used, and as a main photoresist solution, a developer and a stripper are known. The photoresist has a difference in solubility in a developing solution between an unexposed portion and an exposed portion due to irradiation with actinic rays, and the developing solution is used to remove a portion showing the solubility. The part of the photoresist exposed to actinic radiation that shows insolubility in the developing solution forms a film on the substrate, and the exposed part of the substrate after development and removal of the photoresist is processed by etching, plating, etc., or is covered with the film Protects and exhibits the performance as a resist. The stripper is used to remove the photoresist film used for the processing from the substrate. Various solutions are used as the photoresist dissolving solution. In recent years, in addition to the conventional organic solvent, an alkaline solution, particularly an alkaline aqueous solution, has been increasingly used for environmental reasons. As a method of dissolving the photoresist, a method of dropping a photoresist solution, a method of supplying the photoresist to the resist surface by shower or spray, and a method of dipping in a photoresist solution are used, but often used in circulation, An antifoaming agent is used because it is easy to foam by spraying. As a defoaming agent, it is generally known that a silicone type defoaming agent has a high defoaming effect. However, in the photoresist development step and the peeling step, various problems arise in the processing step of the base material after development and the subsequent step after the peeling due to the high covering power and water repellency of the silicone, so that it is avoided. Therefore, as a conventional defoaming agent, polyoxyalkylene monol or an ester thereof, a compound obtained by adding an alkylene oxide to a higher fatty acid, and the like have been used as the defoaming agent. These are disclosed in
JP-A-128865, JP-A-7-319170, JP-A-8-10600, JP-A-8-1606
No. 32, JP-A-9-87380, JP-A-9-87
87381, JP-A-9-87382, JP-A-9-293964, JP-A-10-319606
JP, JP-A-11-258820, JP-A-11-258820
It is known as a technique such as Japanese Patent No.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasuhiko Kinoshita 2 Samejima, Fuji-shi, Shizuoka Prefecture Asahi Kasei Corporation F-term (reference) 2H096 AA26 AA28 BA05 GA10 GA11 LA30 4D011 CB02 CB06 CC01 5F046 LA03 LA12

Claims (6)

[Claims] 1. Formula (1) R—O (CH ₂ CH ₂ O) m— (CH ₂ CH (CH ₃ ) O) n—H (1) (where R is 10 to 10 carbon atoms) 22 represents a linear or branched alkyl group, m represents a number of 8 to 20, n represents a number of 10 to 30), and propylene glycol;
A compound obtained by adding propylene oxide to at least one selected from glycerin and trimethylolpropane and then adding ethylene oxide, and having a weight-average molecular weight of 1,500 to 5,000 and occupying in the entire polyethylene oxide group compound An antifoaming composition for a photoresist solution, comprising a compound B having a ratio of 5 to 25% by mass as an essential component. 2. A compound A comprising 50 to 97% by mass of a compound B
The defoaming agent composition according to claim 1, comprising 3 to 50% by mass. 3. An anti-foaming composition according to claim 1, which is an alkaline solution having a pH of 8.0 to 14.0.
A photoresist solution, which is added in an amount of from 0.01 to 1.00% by volume. 4. A method for dissolving a photoresist, comprising using the photoresist dissolving solution according to claim 3. 5. A photoresist comprising 0.05 to 30.00% by mass of a photopolymerization initiator based on the total mass and a photopolymerizable monomer having an ethylenically unsaturated double bond in the molecule of 15.00.
The photoresist according to claim 4, comprising from 15.00 to 84.95% by mass of a vinyl copolymer obtained by using a vinyl monomer containing at least a carboxyl group as a copolymer component. Dissolution method. 6. The method according to claim 5, wherein the photoresist contains 10% by mass or more of urethane di (meth) acrylate having a molecular weight of 500 to 30,000 as a photopolymerizable monomer.