KR20060043671A - Manufacturing method and photoresist composition of phenol resin for photoresist - Google Patents

Abstract

The phenol resin for photoresist which can reduce the contamination of the production line by the sublimation in a photoresist resin composition, and can improve productivity is manufactured at low cost and simple.

As a method for producing a phenol resin for photoresists, the method comprising: (a) a step of condensation reaction between phenols and aldehydes, and (b) heating the reaction system after the step (a) to remove water and unreacted monomers. In the step (a), a method for producing a photoresist phenol resin and a phenol resin composition for photoresists obtained by the production method are provided, wherein an acidic catalyst of 0.2 mol or more is used for 1 mole of the phenols.

Photoresist, Sublimation, Phenolic Resin, Condensation Reaction, Acid Catalyst

Description

Process for preparing phenolic resin for photoresist and photoresist composition {Process for preparing phenolic resin for photo-resist and photo-resist composition}

This invention relates to the manufacturing method of the phenol resin for photoresists, and the resin composition for photoresists.

Generally, the photosensitive agent which has quinonediazide groups, such as a naphthoquinone diazide compound, and alkali-soluble resin (for example, novolak-type phenol resin) are used for a positive photoresist. The positive photoresist having such a composition exhibits high resolution due to the development of an alkaline solution after exposure to light, and is used for manufacturing semiconductors such as IC and LSI, manufacturing display screen devices such as LCDs, and printing originals. It is used for manufacture. In addition, the novolak-type phenol resin also has high dry etching resistance due to the structure having a large number of aromatic rings to plasma dry etching, and thus contains a novolak-type phenol resin and a naphthoquinone diazide-based light modifier. Numerous positive photoresists have been developed and put into practical use, producing great results.

As the positive photoresist, a novolak-type phenol resin obtained by reacting m / p-cresol with formaldehyde in the presence of an acid catalyst is generally used. And in order to adjust or improve the characteristic of a photoresist, the ratio of m / p-cresol used as raw material phenols, the molecular weight of a phenol resin, molecular weight distribution, etc. have been examined.

However, in the photoresist to which the resin obtained by m / p-cresol and formaldehyde by the general method is applied, for example, in the manufacturing process of LCD, the component having few phenolic aromatic rings (nuclei) of the phenol resin in the photoresist is used. Sublimation of phosphorus low molecular weight component, that is, low nucleus component (mainly dinuclear component), causes the sublimation to be deposited and contaminated on the production line, resulting in lower yield of the product. It is becoming. For this reason, the reduction request | requirement of the binary nucleus component of a phenol resin becomes very high.

The phenol resin with few such nucleophile components is synthesize | combined by the removal of the binary nucleus component by methods, such as a solvent fraction (for example, patent document 1), vapor deposition (for example, patent document 2), etc. There is an example.

The solvent fractionation technique uses a solubility difference between phenolic resins for good solvents and poor solvents. However, since there is no clear solubility difference between low-nucleus components of phenolic resins, a binary nucleus component is selected. It is difficult to remove. For this reason, the excess resin powder was removed, and there existed a fault that batch production fell and it could not manufacture cheaply.

Moreover, since the removal efficiency of a binary nucleus component was low, it was necessary to repeat operation, the solution of the removal component generate | occur | produced in large quantities, and it was a manufacturing method with high load on an environment.

On the other hand, the steam distillation method is a method of blowing high pressure steam into the resin under vacuum conditions and forcibly removing the binary nucleus component by azeotropic action, but the low nucleus component of the phenol resin has a clear boiling point difference. The selectivity for dinuclear component removal is high. However, not only a robust facility that can withstand the dolby phenomenon caused by blowing steam into the high temperature resin is required, but also a large amount of thermal energy is required to keep the resin at a high temperature for a long time and generate high pressure steam. It is not possible to manufacture inexpensively, such as agglomerated water in which a binary nucleus component is dissolved in large quantities as industrial waste, and technical and environmental barriers in embodiments on an industrial scale It was a high manufacturing technology.

[Patent Document 1]

Japanese Patent Publication No. 2001-506294

[Patent Document 2]

Japanese Patent Publication No. 11-246643

The present invention provides a method for producing a photoresist phenol resin which can reduce the contamination of the production line by the sublimation in the photoresist resin composition and improve the productivity at low cost and for the photoresist obtained by the production method. It is providing the resin composition for photoresists using a phenol resin.

This object is achieved by the following invention (1)-(8).

(1) (a) a step of condensation reaction between phenols and aldehydes,

(b) A step of heating the reaction system after the step (a) to remove moisture and unreacted monomers.

 As a method for producing a phenol resin for photoresist having

 The said (a) process is a manufacturing method of the phenol resin for photoresists characterized by using an acidic catalyst of 0.2 mol or more with respect to 1 mol of said phenols.

(2) (a) a step of condensation reaction between phenols and aldehydes,

(b) A step of heating the reaction system after the step (a) to remove moisture and unreacted monomers.

 As a method for producing a phenol resin for photoresist having

 The said (b) process uses the acidic catalyst of 0.2 mol or more with respect to 1 mol of phenols used at the said (a) process, The manufacturing method of the phenol resin for photoresists.

(3) The method for producing a phenol resin for photoresist according to (1) or (2), wherein the acidic catalyst is oxalic acid.

(4) The said phenols are m-cresol and p-cresol in any one of (1)-(3), and the weight ratio (m-cresol / p-cresol) is 9/1-2/8 The manufacturing method of the phenol resin for photoresists.

(5) The manufacturing method of the phenol resin for photoresists in any one of (1)-(4) whose reaction molar ratio (F / P) of the said phenols (P) and aldehydes (F) is 0.5-1.0.

(6) The method for producing a phenol resin for photoresist according to any one of (1) to (5), wherein the aldehydes are formaldehyde.

(7) The manufacturing method of the phenol resin for photoresists in any one of (1)-(6) whose obtained phenol resin has the following characteristics.

(I) Content of binary nucleus component is 5% or less of the whole resin

(II) The weight average molecular weight measured by gel permeation chromatography is 1000-20000.

(8) The resin composition for photoresists containing the resin for photoresists obtained by the manufacturing method in any one of (1)-(7), a photosensitive agent, and a solvent.

According to the present invention, it is possible to produce a phenol resin for photoresist which is less expensive and simpler than the conventional method, and furthermore, has less binary nucleus components. By using the photoresist resin composition using the photoresist phenol resin manufactured by the manufacturing method of this invention, the contamination of a production line in an LCD manufacturing process etc. is reduced.

In addition, the yield can be improved when the phenol resin for photoresist is produced, and waste can be reduced to reduce the environmental load.

Hereinafter, the manufacturing method of the phenol resin for photoresists of this invention, and the resin composition for photoresists are demonstrated.

The manufacturing method of the phenol resin for photoresists of the present invention (hereinafter may be simply referred to as "manufacturing method"),

(a) a step of condensation reaction between phenols and aldehydes,

(b) A step of heating the reaction system after the step (a) to remove moisture and unreacted monomers.

As a method for producing a phenol resin for photoresist having

The step (a) is characterized by using an acid catalyst of 0.2 mol or more with respect to 1 mol of the phenols.

Moreover, the manufacturing method of the phenol resin for photoresists of this invention,

(a) a step of condensation reaction between phenols and aldehydes,

(b) A step of heating the reaction system after the step (a) to remove moisture and unreacted monomers.

As a method for producing a phenol resin for photoresist having

The step (b) is characterized in that an acid catalyst of 0.2 moles or more is used per mole of phenols used in the step (a).

Moreover, the resin composition for photoresists of this invention contains the resin for photoresists obtained by the manufacturing method of the said invention, the photosensitive agent, and a solvent, It is characterized by the above-mentioned.

First, embodiment of the manufacturing method of this invention is described.

In the present embodiment, first, (a) phenols and aldehydes are condensed to each other (hereinafter, referred to as "step a"). In addition, this reaction can be performed, for example under the reflux condition of water.

Although it does not specifically limit as phenols used by the manufacturing method of this invention, For example, cresols, such as a phenol, o-cresol, m-cresol, p-cresol, 2, 3- xylenol, 2, 4- size Xylenols such as silenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, In addition to ethylphenols such as p-ethylphenol, alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol, resorcin, catechol, hydroquinone, pyrogallol and flo And polyhydric phenols such as phloroglucine, and alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone (any alkyl group has 1 to 4 carbon atoms). These can be used individually or in combination of 2 or more types.

Among the above phenols, particularly preferably m-cresol and p-cresol, by using these phenols and adjusting the compounding ratio of both, various properties such as sensitivity and heat resistance as photoresist can be adjusted. .

When using m-cresol and p-cresol as said phenols, the ratio is not specifically limited, but weight ratio (m-cresol / p-cresol) = 9/1-2/8, Furthermore, 8/2-4/6 You can do When the ratio of m-cresol is too low, the sensitivity may decrease, while when too much, the heat resistance may decrease. When the ratio of m-cresol is included in the above range, the phenol resin for photoresist having excellent balance between both Can be obtained.

Although it does not specifically limit as aldehydes used by the manufacturing method of this invention, For example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine , Furfural, glyoxal, n-butylaldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. Can be mentioned.

Among them, it is most preferable in view of the use of formaldehyde and paraformaldehyde.

Although it does not specifically limit as reaction molar ratio (F / P) of the said phenols (P) and aldehydes (F), It is preferable to set it as 0.5-1.0. Thereby, the phenol resin which has a preferable molecular weight for use for a photoresist can be obtained.

If the reaction molar ratio is too large, the use of the photoresist may cause excessive high molecular weight or gelation depending on the reaction conditions, while if too small, it is difficult to sufficiently reduce the amount of the binary nucleus component. When contained in the range, the phenol resin for photoresists excellent in these balance can be obtained.

In the said process a, an organic solvent can be used suitably for reaction. As a solvent, if it can melt | dissolve a phenol resin, it can be used. For example, ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene Propylene glycol alkyl ether acetates such as glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate, ketones such as cyclohexanone and methyl amyl ketone, cyclic ethers such as dioxane and 2-hydroxypropionic acid Methyl, 2-hydroxypro Ethyl onion, 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl oxyacetate, 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Amides such as esters such as butyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate, and N, N'-dimethylformamide. These may be used individually by 1 type and may mix and use two or more types.

Although the usage-amount of a solvent is not specifically limited, When the acidic catalyst density | concentration in a reaction system becomes too low, since the reduction effect of a binary nucleus component will fall, it is preferable to set it as 20 weight% or less with respect to phenols.

Subsequently, (b) the reaction system of step a is heated to remove water and unreacted monomers (hereinafter referred to as "step b").

Although it does not specifically limit as a temperature raising process of the reaction system in process b, For example, most water can be removed by heating a reaction system at 120-200 degreeC under normal pressure.

Furthermore, for example, by raising the reaction system to 150 to 250 ° C under reduced pressure of 1 to 300 Torr, the remaining water can be removed and the unreacted monomer can be removed.

Moreover, it was discovered by the present inventors etc. that content of the binary nucleus component of the phenol resin for photoresists can also be reduced together. As a reason for content of a binary nucleus component being reduced, it can think as follows.

In the production method of the present invention, the reaction is considered to proceed in two steps. That is, in step a, a bond between monomers is formed by the reaction between phenols and aldehydes, and a phenol resin is synthesized. Subsequently, in step b, the reaction system after step a is raised to remove water and unreacted monomers, but the rearrangement of the phenol resin, for example, decomposition of high molecular weight components and reduction of low nucleus components are carried out by the elevated temperatures. Is generated, and it is considered that this action results in a reduced molecular weight distribution.

This rearrangement can hardly occur in the temperature range (40-250 degreeC) which synthesize | combines a novolak-type phenol resin when a normal amount of acidic catalyst is used. In the present invention, the rearrangement temperature can be reduced by using an acidic catalyst in a large amount, and this effect can be considered to be obtained within the reaction temperature range.

Hereinafter, the acidic catalyst used in this embodiment is demonstrated.

First, in the form of using an acidic catalyst

(1) Step (a) using an acid catalyst of 0.2 mol or more per 1 mole of phenols (hereinafter referred to as "form (1)"), and

(2) The form which uses 0.2 mol or more of acidic catalysts with respect to 1 mol of phenols used at the said process a in the process b (henceforth "form (2)").

There are two types.

In the said aspect (1), 0.2 mol or more of acidic catalysts are introduce | transduced into a reaction system with respect to 1 mol of phenols at the time of process a, ie, condensation reaction of phenols and aldehydes.

In the condensation reaction in step a, the acid catalyst usually used for the synthesis of the phenol resin remains as it is. For this reason, the said acidic catalyst exists in a reaction system also at the start of process b. By moving to step b and raising the reaction system in the presence of such an excessive amount of acidic catalyst, the above-described rearrangement reaction of the phenol resin occurs, thereby reducing the low nucleus components such as unreacted phenols and dinuclear components, and high molecular weight components. Decomposition occurs. Thereby, the phenol resin with few content of a binary nucleus component can be obtained, the yield of the phenolic monomer used for reaction can be improved, and the yield of a phenol resin can be improved significantly.

In addition, in the said aspect (2), in the process b, 0.2 mol or more of acidic catalysts are introduce | transduced into a reaction system with respect to 1 mol of phenols used at the said process a.

As described above, the step b is a step of removing condensed water by heating after completion of the reaction of the step a, followed by a demonomer under normal pressure reduction.

Here, as a method of using the acidic catalyst in step b, as in the embodiment (1), a predetermined amount of acidic catalyst is used in step a, and this is usually present in the reaction system or in step a. There is a method of condensation reaction with a small amount of acid catalyst and introducing an additional acid catalyst in step b.

In the case of the method of additionally introducing the acidic catalyst in the step b, the timing for introducing the acidic catalyst is not particularly limited. For example, at the start of the step b, after the dehydration treatment of the step b, or the demonomer of the step b. It can be added after the end of the treatment. Even if it adds at any timing, the rearrangement reaction of the above-mentioned phenol resin generate | occur | produces, the reduction of low nucleus component, such as unreacted phenols and a binary nucleus component, and decomposition of a high molecular weight component arise. Thereby, the phenol resin with few content of a binary nucleus component can be obtained.

In addition, at the start of step b or after completion of dehydration of step b, in addition to the above effects, the yield of monomers of phenols used in the reaction is improved in the same manner as in the case of the above aspect (1), and the yield of phenol resin Can greatly improve.

By introducing an acidic catalyst as described above, an excess acidic catalyst can be present at least in step b, thereby reducing waste and reducing environmental load as compared with the conventional production method.

The amount of the acidic catalyst used in the above aspect (1) or (2) is usually 0.2 mol or more, preferably 0.2 to 1.0 mol with respect to 1 mol of phenols used in step a. If the amount of the acidic catalyst is too small, it may be difficult to sufficiently reduce the low nucleus component such as the nucleophile component from the phenol resin. On the other hand, if the amount of the acid catalyst is too high, there is no problem about the effect of reducing the low nucleus component. It is not economical to use, and it may be difficult to remove the acidic catalyst from the reaction system after the step b, and the removal efficiency may be lowered. Therefore, by using the amount of the acidic catalyst in the above range, these balances are excellent. It can be set as the manufacturing method of a phenol resin.

Although it does not specifically limit as an acidic catalyst used in the manufacturing method of this invention, For example, organic acids, such as inorganic acids, such as hydrochloric acid, a sulfuric acid, phosphoric acid, a phosphoric acid, oxalic acid, diethylsulfonic acid, paratoluenesulfonic acid, an organic phosphonic acid, etc. And metal salts such as zinc acetate and the like. These can be used individually or in combination of 2 or more types.

Among these, it is preferable to use oxalic acid. Oxalic acid can be easily removed from the phenol resin because it is gasified by heating at a high temperature in the step (b).

In addition, since oxalic acid has less metal corrosion than other acidic catalysts, corrosion of production equipment such as a reaction apparatus can be suppressed, and the incorporation of metal components due to corrosion can be minimized. Thereby, the phenol resin with little content of the metal impurity especially suitable for photoresists can be manufactured efficiently.

In addition, in the case of using a catalyst other than oxalic acid, the acidic catalyst in the phenol resin can be removed by neutralizing, washing with water, or using an ion exchange resin or a special filter after completion of the reaction. .

Although it does not specifically limit as a weight average molecular weight of the phenol resin obtained by this embodiment, The weight average molecular weight measured by gel permeation chromatography (GPC) may be 1000-20000, and also 1500-15000 may be sufficient. Thereby, it can be set as having a characteristic suitable as resin for photoresists. In other words, if the weight average molecular weight is too small, the heat resistance tends to be lowered. If the weight average molecular weight is too large, the sensitivity as a photoresist may be insufficient, and by setting the weight average molecular weight in the above range, a phenol resin for photoresist excellent in these balances can be obtained. Can be.

In addition, content of the binary nucleus component in resin for photoresists obtained by this embodiment may be 5% or less, for example, and may also be 4% or less. When content of this binary nucleus component is too large, the effect about productivity improvement in manufacturing processes, such as LCD, by reducing the sublimation contained in a phenol resin may fall, and content of a binary nucleus component is in the said range. This productivity can be further improved.

Here, the weight average molecular weight of a phenol resin and content of a binary nucleus component can be measured by gel permeation chromatography (GPC measurement). The weight average molecular weight can be calculated based on a calibration curve drawn using polystyrene standards. In addition, content of a binary nucleus component can be computed from the area ratio (%) of the binary nucleus component with respect to the whole phenol resin from the molecular weight distribution curve obtained as a result of GPC measurement. GPC measurement can be performed, for example using tetrahydrofuran as an elution solvent, on the conditions of 1.0 ml / min of flow rates, and the column temperature of 40 degreeC.

The device is for example

Body: HLC-8020 made by TOSOH

Detector: UV-8011 made by TOSOH set to wavelength 280 nm

Analysis column: Showa Electric Works, SHEXEX KF-802: 1, KF-803: 1, KF-805: 1

Can be used.

Next, embodiment of the phenol resin composition for photoresists (Hereinafter, it may only be called "composition") using the phenol resin for photoresists obtained by the manufacturing method of the said embodiment is demonstrated.

Although the composition using the phenol resin for photoresists is not specifically limited other than the phenol resin for photoresist mentioned above, For example, a quinonediazide group containing compound can be contained as a photosensitizer. Moreover, it is preferable to melt | dissolve using the solvent which melt | dissolves these, and to use it in the form of a solution.

Here, as said quinonediazide group containing compound, it is a, for example.

(1) 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzo Phenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3 ', 4,4', 6-pentahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,5-pentahydroxy Polyhydroxybenzoates such as benzophenone, 2,3 ', 4,4', 5 ', 6-hexahydroxybenzophenone, 2,3,3', 4,4 ', 5'-hexahydroxybenzophenone Phenon,

 (2) bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl Propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- ( 2 ', 3', 4'-trihydroxyphenyl) propane, 4,4 '-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, 3 Bis [(poly) hydroxyphenyl] alkanes such as, 3'-dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol ,

(3) tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl)- 4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane , Bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane Tris (hydroxyphenyl) methanes such as methyl substituents thereof,

(4) bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclo Hexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy Hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl ) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl)- 3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenyl Methane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4- Bis (cyclohexyl hydroxyphenyl) (hydroxyphenyl) methanes, such as methylphenyl) -2-hydroxyphenylmethane and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane Or quinone diazide groups such as naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid and orthoanthraquinonediazidesulfonic acid And full ester compounds, partial ester compounds, amidates or partial amidates with containing sulfonic acids.

Here, as said quinonediazide group containing compound component, you may contain individually by 1 type, and may contain two or more types. Moreover, this component is mix | blended in the range of 5-100 weight part normally, Preferably it is 10-50 weight part with respect to 100 weight part of said phenol resins.

When there is too little compounding quantity of this quinone azide group containing compound component, it will become difficult to obtain a faithful image in a predetermined pattern, and transferability may fall, while when too large, the sensitivity as a photoresist may fall, and this compounding quantity By making it into the said range, the phenol resin composition for photoresists excellent in these balance can be obtained.

Moreover, as a solvent for melt | dissolving each component of the phenol resin composition for photoresists, ethylene glycol alkyl, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, for example. Diethylene glycol dialkyl ethers such as ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate Propylene glycol alkyl ether acetates such as ethylene glycol alkyl ether acetates, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, acetone, methyl ethyl ketone, cyclohexanone, methyl ace Ketones such as milk ketones, cyclic ethers such as dioxane, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl oxyacetate, 2- Esters such as hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate Can be. These may be used individually by 1 type and may mix and use two or more types.

Although the usage-amount of the said solvent is not specifically limited, Solid content concentration of a composition can be 30-65 weight%. If the solid content concentration of the composition is too large using a solvent, the fluidity of the composition tends to be lowered, so that handling becomes difficult, and application by the spin coating method becomes difficult, and it becomes difficult to obtain a uniform resist film, even if it is too small. Handling becomes difficult, and by using the solvent whose solid content concentration of a composition becomes the said range, handling becomes easy at the time of use of a composition, and it becomes easy to obtain a uniform resist film.

Moreover, in addition to the component demonstrated above, you may use various additives, such as surfactant, an adhesion promoter, and a dissolution promoter, for this composition as needed.

Although it does not specifically limit as a preparation method of this composition, When a filler and a pigment are not added to a composition, it does not only mix and stir the said component by a conventional method, but also adds a dissolver when adding a filler and a pigment. What is necessary is just to disperse | distribute and mix using dispersing apparatuses, such as a homogenizer and a three roll mill. Moreover, you may filter using a mesh filter, a membrane filter, etc. further as needed.

By exposing to the composition obtained in this way through a mask, a structural change arises in a composition in an exposure part, and the solubility with respect to alkali developing solution is accelerated | stimulated. On the other hand, in the non-exposed part, low solubility with respect to alkali developing solution is maintained. Thus, the resist function is provided by the difference in solubility which generate | occur | produced.

Hereinafter, the present invention will be described by the following experimental examples. However, the present invention is not limited by these experimental examples. In addition, "part" described in each experiment example represents "weight part", and "%" represents "weight%."

1. Synthesis of Phenolic Resin for Photoresist

(1) Experimental Example 1

To 1000 parts of phenols which mixed m-cresol and p-cresol in the ratio of molar ratio (m-cresol: p-cresol) = 7: 3 to the 3 L four neck flask provided with the stirrer, a thermometer, and a heat exchanger, 638 parts of 37% aqueous formalin solution (F / P = 0.85) and 420 parts of oxalic acid (0.5 mole to 1 mole of phenols) were added, and the reaction was carried out at reflux for 4 hours. Then, dehydration was carried out to normal temperature 170 degreeC under normal pressure, and further dehydration and demonomerization was carried out to 200 degreeC under reduced pressure of 70 torr, and the weight average molecular weight 3500 and 1080 parts of phenol resins for photoresists of 3.7% of binary nucleus components were obtained.

(2) Experimental Example 2

In the same apparatus as in Experimental Example 1, 620 parts of 37% formalin aqueous solution (F / F) with respect to 1000 parts of phenols mixed with m-cresol and p-cresol in a molar ratio (m-cresol: p-cresol) = 6: 4 P = 0.83) and 250 parts of oxalic acid (0.3 mol with respect to 1 mol of phenols) were put, and reaction was performed under reflux for 4 hours. Then, dehydration was carried out to normal temperature 170 degreeC under normal pressure, and further dehydration and demonomerization was carried out to 200 degreeC under the pressure reduction of 70 torr, and the weight average molecular weight 4100 and 990 parts of phenol resins for photoresists of 3.5% of nucleus component components were obtained.

(3) Experimental Example 3

660 parts of 37% formalin aqueous solution (1000 parts) with respect to 1000 parts of phenols which mixed m-cresol and p-cresol in the ratio of molar ratio (m-cresol: p-cresol) = 8: 2 in the apparatus similar to Experimental example 1 /P=0.88) and 750 parts of oxalic acid (0.9 mol to 1 mol of phenols) were put in, and the reaction was carried out at reflux for 4 hours. Then, dehydration was carried out to normal temperature 170 degreeC under normal pressure, and further, dehydration and demonomerization was carried out to 200 degreeC under reduced pressure of 70 torr, and the weight average molecular weight 5200 and 970 parts of phenol resins for photoresists of 3.0% of nucleus component components were obtained.

(4) Experimental Example 4

In the same apparatus as in Experimental Example 1, 630 parts of 37% formalin aqueous solution (F / F) was used for 1000 parts of phenols obtained by mixing m-cresol and p-cresol in a ratio of molar ratio (m-cresol: p-cresol) = 7: 3. P = 0.84) and 21 parts of oxalic acid (0.03 mol with respect to 1 mol of phenols) were put, and reaction was performed under reflux for 4 hours. Then, after dehydrating under normal pressure to 140 degreeC internal temperature, 309 parts of oxalic acid (0.38 mol with respect to 1 mol of phenols) were added, and also it heated up to 170 degreeC. Furthermore, dehydration and demonomerization were performed to 200 degreeC under reduced pressure of 70 torr, and 1060 parts of phenol resins for photoresists of the weight average molecular weight 3000 and the nucleus component amount 3.8% were obtained.

(5) Experimental Example 5

In the same apparatus as in Experimental Example 1, 620 parts of 37% formalin aqueous solution (F / F) with respect to 1000 parts of phenols obtained by mixing m-cresol and p-cresol in a molar ratio (m-cresol: p-cresol) = 7: 3. P = 0.83) and 21 parts of oxalic acid (0.03 mol with respect to 1 mol of phenols) were put, and reaction was performed under reflux for 4 hours. Next, 479 parts (0.58 mol with respect to 1 mol of phenols) of oxalic acid were added, and it heated up to 170 degreeC of internal temperature under normal pressure. Furthermore, dehydration and demonomerization were performed to 200 degreeC under reduced pressure of 70 torr, and 1070 parts of phenol resins for photoresists with a weight average molecular weight of 3900 and 4.0% of a binary nucleus component were obtained.

(6) Experimental Example 6

In the same apparatus as in Experimental Example 1, 520 parts of 37% formalin aqueous solution (F / F) with respect to 1000 parts of phenols mixed with m-cresol and p-cresol in a ratio of molar ratio (m-cresol: p-cresol) = 7: 3 P = 0.69) and 40 parts of oxalic acid (0.05 mol with respect to 1 mol of phenols) were added, and reaction was performed for 4 hours under reflux. Then, it heated up to 170 degreeC internal temperature under normal pressure, and further performed dehydration and demonomerization to 200 degreeC under reduced pressure of 70 torr. Then, 50 parts of ethylene glycol monomethyl ether was added while cooling, and it cooled to internal temperature 130 degreeC. Oxalic acid 380 parts (0.46 mol with respect to 1 mol of phenols) were added here, and it heated up again to normal temperature 170 degreeC under normal pressure, and further performed dehydration and demonomerization to 200 degreeC under reduced pressure of 70 torr, and weight average molecular weight 4300, 820 parts of phenol resins for photoresists of 2.8% of binary nucleus component amount were obtained.

(7) Experimental Example 7

In the same apparatus as in Experimental Example 1, 450 parts of 37% formalin aqueous solution against 1000 parts of phenols mixed with m-cresol and p-cresol in a ratio of molar ratio (m-cresol: p-cresol) = 4: 6 (F / P = 0.60) and 21 parts of oxalic acid (0.03 mol with respect to 1 mol of phenols) were put, and reaction was performed under reflux for 4 hours. Then, dehydration was carried out to normal temperature 170 degreeC under normal pressure, and further dehydration and demonomerization was carried out to 200 degreeC under reduced pressure of 70 torr, and the weight average molecular weight 3500 and 730 parts of phenol resins for photoresists of 11.0% of binary nucleus components were obtained.

(8) Experimental Example 8

506 parts of 37% formalin aqueous solution (F / F) with respect to 1000 parts of phenols which mixed m-cresol and p-cresol in the ratio of molar ratio (m-cresol: p-cresol) = 7: 3 in the apparatus similar to Experimental example 1 P = 0.67) and 8 parts of oxalic acid (0.01 mol with respect to 1 mol of phenols) were added, and reaction was performed for 4 hours under reflux. Then, dehydration was carried out to normal temperature 170 degreeC under normal pressure, and further dehydration and demonomerization was carried out to 200 degreeC under reduced pressure of 70 torr, and the weight average molecular weight 2500 and 800 parts of phenol resins for photoresists of 8.7% of binary nucleus components were obtained.

It shows in Table 1 about the phenol resin for photoresists obtained by Experimental Examples 1-8.

yield(%) Mw Nucleotide component amount (%) Experimental Example 1 108 3500 3.7 Experimental Example 2 99 4100 3.5 Experimental Example 3 97 5200 3.0 Experimental Example 4 106 3000 3.8 Experimental Example 5 107 3900 4.0 Experimental Example 6 82 4300 2.8 Experimental Example 7 73 3500 11.0 Experimental Example 8 80 2500 8.7

2. Preparation of Photoresist Composition

(1) Experimental Example 9

70 parts of phenol resins for photoresists obtained in Experimental Example 1 and 15 parts of 2,3,4-trihydroxybenzophenone esters of naphthoquinone 1,2-diazide-5-sulfonic acid were PGMEA (propylene glycol monomethyl ether Acetate) and dissolved in 150 parts, and filtered using a membrane filter having a pore size of 1.0 μm to obtain a positive photoresist composition.

(2) Experimental Example 10

A composition was obtained in the same manner as Experimental Example 9 except that the phenolic resin for photoresist obtained in Experimental Example 2 was used instead of the phenolic resin for photoresist obtained in Experimental Example 1.

(3) Experimental Example 11

A composition was obtained in the same manner as Experimental Example 9 except that the phenolic resin for photoresist obtained in Experimental Example 3 was used instead of the phenolic resin for photoresist obtained in Experimental Example 1.

(4) Experimental Example 12

A composition was obtained in the same manner as Experimental Example 9 except that the phenolic resin for photoresist obtained in Experimental Example 4 was used instead of the phenolic resin for photoresist obtained in Experimental Example 1.

(5) Experimental Example 13

A composition was obtained in the same manner as Experimental Example 9 except that the phenolic resin for photoresist obtained in Experimental Example 5 was used instead of the phenol resin for photoresist obtained in Experimental Example 1.

(6) Experimental Example 14

A composition was obtained in the same manner as Experimental Example 9 except that the phenolic resin for photoresist obtained in Experimental Example 6 was used instead of the phenolic resin for photoresist obtained in Experimental Example 1.

(7) Experimental Example 15

A composition was obtained in the same manner as Experimental Example 9 except that the phenolic resin for photoresist obtained in Experimental Example 7 was used instead of the phenolic resin for photoresist obtained in Experimental Example 1.

(8) Experimental Example 16

A composition was obtained in the same manner as Experimental Example 9 except that the phenolic resin for photoresist obtained in Experimental Example 8 was used instead of the phenolic resin for photoresist obtained in Experimental Example 1.

The characteristic evaluation shown below was performed using the photoresist composition obtained in Experimental Examples 9-16. The results are shown in Table 2.

Sublimation amount (mg) Membrane Reduction (%) Experimental Example 9 10 One Experimental Example 10 9 <1 Experimental Example 11 5 <1 Experimental Example 12 15 One Experimental Example 13 10 <1 Experimental Example 14 4 <1 Experimental Example 15 135 5 Experimental Example 16 50 13

3. Evaluation method of characteristics

3.1 Phenolic Resin for Photoresist

(1) yield

It calculated by the following formula.

Yield (%) = (weight of obtained resin / weight of phenol monomer put) x100

(2) Weight average molecular weight (Mw) and content of binary nucleus component

It was measured by gel permeation chromatography (GPC measurement). Weight average molecular weights were calculated based on calibration curves prepared using polystyrene standards. Content of a binary nucleus component was computed from the molecular weight distribution curve by the area ratio (%) of the binary nucleus component with respect to the whole resin. GPC measurement was carried out using tetrahydrofuran as the elution solvent, under a flow rate of 1.0 ml / min and a column temperature of 40 ° C.

The device is

Body: TOSOH, HLC-8020

Detector: made by TOSOH, set at wavelength 280 nm, "UV-8011"

Column for analysis: Showa Electric Works, "SHODEX KF-802: 1, KF-803: 1, KF-805: 1"

Was used.

3.2 Photoresist Composition

(1) sublimation test

The photoresist composition was applied on a 3 inch silicon wafer with a spin coater to a thickness of about 1 μm and dried for 100 seconds on a 110 ° C. hotplate. At the time of drying, the silicon wafer was covered with a petri dish to collect the sublimate. Ten pieces of this work were carried out, and the weight of the substance attached to the petri dish was measured.

(2) membrane reduction rate

The photoresist composition was applied on a 3 inch silicon wafer with a spin coater to a thickness of about 1 μm and dried for 100 seconds on a 110 ° C. hotplate. The wafer was immersed in a developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, washed with water, and dried for 100 seconds on a 110 캜 hot plate. The amount of reduction in the film thickness when immersed in the developer was expressed as a percentage of the film thickness before being immersed in the developer, and was set as the film reduction rate.

Experimental examples 1-6 are the phenol resins for photoresists obtained by the manufacturing method of this invention.

And Experimental example 9-14 is a composition using this photoresist resin. As shown in Table 1, in Experimental Examples 9-14, the amount of sublimation was small compared with Experimental Examples 15-16 which are compositions using the phenol resin obtained in Experimental Examples 7-8, and also the film reduction rate was also excellent. In particular, in Experimental Examples 1 to 5, the phenol resin yield was significantly improved in addition to the above effects. From this fact, it became clear that the phenol resin for photoresists obtained by the manufacturing method of this invention is suitable for the process aimed at LCD manufacture.

The manufacturing method of this invention can manufacture the phenol resin for photoresists with few content of a binary nucleus component efficiently. Therefore, since the composition for photoresists using the photoresist phenol resin obtained by the manufacturing method of this invention can reduce the contamination of a production line, and can improve productivity, it is the display of semiconductor manufacture, such as IC and LSI, LCD etc. It can use suitably for manufacture of a screen apparatus, manufacture of a printing original plate, etc.

Claims (8)

(a) a step of condensation reaction between phenols and aldehydes, (b) A step of heating the reaction system after the step (a) to remove moisture and unreacted monomers. As a method for producing a phenol resin for photoresist having The said (a) process is a manufacturing method of the phenol resin for photoresists characterized by using an acidic catalyst of 0.2 mol or more with respect to 1 mol of said phenols. (a) a step of condensation reaction between phenols and aldehydes, (b) A step of heating the reaction system after the step (a) to remove moisture and unreacted monomers. As a method for producing a phenol resin for photoresist having The said (b) process uses the acidic catalyst of 0.2 mol or more with respect to 1 mol of phenols used at the said (a) process, The manufacturing method of the phenol resin for photoresists. The method of claim 1 or 2, wherein the acidic catalyst is oxalic acid. The phenols of claim 1 or 2, wherein the phenols are m-cresol and p-cresol, and the weight ratio (m-cresol / p-cresol) is 9/1 to 2/8 of the phenol resin for photoresist. Manufacturing method. The manufacturing method of the phenol resin for photoresists of Claim 1 or 2 whose reaction molar ratio (F / P) of the said phenols (P) and aldehydes (F) is 0.5-1.0. The manufacturing method of the phenol resin for photoresists of Claim 1 or 2 whose said aldehydes are formaldehyde. The manufacturing method of the phenol resin for photoresists of Claim 1 or 2 in which the obtained phenol resin has the following characteristics. (I) Content of binary nucleus component is 5% or less of the whole resin (II) The weight average molecular weight measured by gel permeation chromatography is 1000-20000. The resin composition for photoresists containing the resin for photoresists obtained by the manufacturing method of Claim 1, or the photosensitive agent, and a solvent.