JP4929733B2 - Method for producing novolac type phenolic resin - Google Patents

Description

The present invention relates to the production how novolak type phenolic resin.

Phenolic resins are used in many fields such as the semiconductor industry, electrical and electronic materials, molding materials, laminates, refractories, paints, and binders for various substrates. Examples of the type of phenol resin include novolak type phenol resins and resol type phenol resins, and various forms suitable for use such as solid and liquid are synthesized and used.
The phenol resin is usually obtained by reacting phenols and aldehydes in the presence of an acidic or basic catalyst. However, the phenols obtained by the usual synthesis method contain many low-nuclear components such as unreacted phenols and dinuclear components in the resin, and depending on the use, there are various types due to the presence of these low-nuclear components. Problems can occur.

For example, one of the uses of phenol resin is a positive photoresist composition.
In general, a positive photoresist uses a photosensitizer having a quinonediazide group such as a naphthoquinonediazide compound and an alkali-soluble resin such as a novolac-type phenolic resin. A positive photoresist having such a composition exhibits a high resolving power by developing with an alkaline solution after exposure, and manufactures semiconductors such as IC and LSI, manufacture of display screen devices such as LCD (liquid crystal display), and manufacture of printing original plates. Has been used. In addition, novolac-type phenolic resin has high dry-etching resistance due to the structure having many aromatic rings against plasma dry etching. So far, novolac-type phenolic resin and naphthoquinone diazide photosensitizers are used. Numerous positive photoresists have been developed and put into practical use and have achieved great results.

As the positive photoresist, a novolak type phenol resin obtained by reacting phenols such as m / p-cresol and formaldehyde in the presence of an acid catalyst is generally used. In order to adjust or improve the characteristics of the photoresist, studies have been made on the ratio of the raw material phenols, the molecular weight of the phenol resin, the molecular weight distribution, and the like.
However, in a photoresist using a resin obtained by a general method from these raw materials, for example, in the LCD manufacturing process, the low-nuclear component (mainly binuclear component) of the phenolic resin in the photoresist is sublimated. As a result, the sublimate accumulates and contaminates the production line, causing a reduction in product yield. For this reason, the reduction | decrease request | requirement of the binuclear component of a phenol resin has become very high.

Such a phenolic resin with a low content of the binuclear component is obtained by removing the binuclear component by a solvent fractionation method (see, for example, Patent Document 1) or a steam distillation method in which the resin is brought into contact with water vapor (for example, patents). There is an example synthesized by reference 2).
The solvent fractionation method is a method that uses the difference in solubility of each component in the phenolic resin in the solvent, but since there is no clear solubility difference between the low-nuclear components of the phenolic resin, the binuclear component is selected. Is difficult to remove. For this reason, excess resin was removed, resulting in a disadvantage that the batch yield was reduced and the production was not possible at a low cost. Further, since the removal efficiency of the dinuclear component is low, it is necessary to repeat the operation, and a large amount of waste liquid containing the removed component is generated, so that the production method has a high environmental load.

In contrast, the steam distillation method has a high boiling point and cannot be distilled off by ordinary vacuum distillation.
This is a technique for distilling off the nuclear component within the normal operating temperature range by azeotropic action with water. Specifically, for example, a resin melted at high temperature is sucked out by a pump from a pipe provided at the bottom of the reaction vessel, mixed with high-temperature steam at about 180 ° C., the generated volatile components are distilled off, and the resin content is removed from the reaction vessel. It is performed by a method of repeating the operation of returning to.
In this method, since the boiling point difference of each component in the phenol resin is used, the resin component of the trinuclear body or more is hardly removed, and the resin can be obtained without significantly reducing the yield.
However, in the case of a resin having a weight average molecular weight exceeding 3000, there is a problem that it becomes difficult to carry out because the melt viscosity is high and the capacity of the pump is exceeded. In addition, it is necessary to have robust equipment that can withstand bumping and explosion phenomena caused by forced mixing of high-temperature resin and steam, and energy costs to generate a large amount of high-temperature steam. However, in the implementation on an industrial scale, it was a technology with problems such as restrictions on characteristics, production technology barriers, and economic burden.

Special table 2001-506294 Japanese Patent Application Laid-Open No. 11-246643

The present invention provides a method capable of efficiently and easily producing a novolak-type phenol resin having a low content of low-nuclear components such as unreacted phenols and dinuclear components.
In addition, by using the novolac type phenol resin obtained by the production method of the present invention, the production of the phenol resin composition for photoresist can reduce the contamination of the production line by the sublimate of the low-nuclear component and improve the productivity. It provides things.

Such an object is achieved by the following present inventions (1) to ( 9 ).
(1)
(A) a step of subjecting phenols and aldehydes to a condensation reaction;
(C) while maintaining the reaction system temperature after step (a) to 170 to 250 ° C., a boiling point of 50 ° C. or higher, and a low-boiling compounds having a boiling point not lower than the temperature of the reaction system was added in liquid form Removing the low-nuclear component of the novolac-type phenolic resin,
A process for producing a novolac-type phenolic resin, comprising:
(2)
Even after the step (a) prior to step (c) further comprises (b) the (a) from the reaction system after step, a step of divided the water or water and the reaction solvent The method for producing a novolac type phenol resin according to the above (1), wherein
(3)
(A) a step of subjecting phenols and aldehydes to a condensation reaction;
(B) from the reaction system after step (a), a step of divided the water or water and reaction solvent,
While the reaction system temperature after (c) above (b) step was maintained at 170 to 250 ° C., a boiling point of 50 ° C. or higher, and a low-boiling compounds having a boiling point not lower than the temperature of the reaction system was added in liquid form Removing the low-nuclear component of the novolac-type phenolic resin,
The method for producing a novolac type phenol resin according to (1) above, characterized by comprising:
(4) The method for producing a novolac type phenol resin according to any one of the above (1) to (3), which comprises a step of maintaining the reaction system temperature at 210 to 240 ° C. in the step (c).
( 5 ) The method for producing a novolac type phenol resin according to any one of (1) to ( 4 ), wherein a low-boiling compound containing water is used in the step (c).
( 6 ) A method for producing a novolac type phenol resin, wherein in the step (c), a low-boiling compound containing a compound capable of dissolving a low-nuclear component of a novolac type phenol resin is used. The compound capable of dissolving the low-nuclear component is selected from propylene glycol monomethyl ether acetate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and methyl isobutyl ketone (1) to ( 5 ). The method for producing a novolac type phenol resin according to any one of the above.
( 7 ) The novolac phenol resin according to ( 6 ), wherein the compound capable of dissolving the low-nuclear component of the novolak phenol resin is selected from propylene glycol monomethyl ether acetate, 1-butanol, and methyl isobutyl ketone. Manufacturing method.
( 8 ) The novolak according to any one of (1) to ( 7 ), wherein the amount of the low boiling point compound added in the step (c) is 1 to 10% by weight / hour with respect to the entire reaction system. Type phenolic resin production method.
( 9 ) The method for producing a novolac type phenol resin according to any one of (1) to ( 8 ), wherein the step (c) is performed under a reduced pressure of 80 Torr or less.

According to the present invention, a novolac type phenol resin having a low content of low-nuclear components such as unreacted phenols and binuclear components can be produced efficiently and easily.
The photoresist resin composition using the novolak-type phenolic resin produced by the production method of the present invention reduces the contamination of the production line due to sublimates of low-nuclear components, for example, in the LCD production process, etc. Can be improved.

Hereinafter, the method for producing the novolak type phenolic resin, the novolac type phenolic resin, and the photoresist resin composition of the present invention will be described.
The method for producing the novolac-type phenolic resin of the present invention includes:
(A) a step of subjecting phenols and aldehydes to a condensation reaction;
(C) While maintaining the reaction system temperature after the step (a) at 170 to 250 ° C., a low-boiling compound having a boiling point lower than the reaction system temperature is added, and the low-nuclear component of the novolak-type phenol resin is added. Removing, and
It is characterized by having.
In addition, after the step (a) and before the step (c), (b) water or water and the reaction solvent are substantially removed from the reaction system after the step (a). You may make it provide the process to do.
In addition, the method for producing the novolak type phenolic resin of the present invention includes:
(A) a step of subjecting phenols and aldehydes to a condensation reaction;
(B) a step of substantially removing water or water and the reaction solvent from the reaction system after the step (a);
(C) adding a low-boiling compound having a boiling point lower than the reaction system temperature while removing the low-nuclear component while maintaining the reaction system temperature after the step (b) at 170 to 250 ° C .;
It is characterized by having.

The novolak type phenolic resin of the present invention is obtained by the method for producing the novolac type phenolic resin of the present invention.
And the resin composition for photoresists of the present invention comprises:
(A) the novolak-type phenolic resin of the present invention,
(A) photosensitizer and
(C) Solvent,
It is characterized by containing.
First, a method for producing the novolak type phenolic resin of the present invention (hereinafter sometimes simply referred to as “manufacturing method”) will be described.

  In the production method of the present invention, first, (a) a phenol and an aldehyde are subjected to a condensation reaction.

  Although it does not specifically limit as phenols used at the said (a) process, For example, cresols, such as a phenol, o-cresol, m-cresol, and p-cresol, 2,3-xylenol, 2,4-xylenol, 2 , 5-xylenol, 2,6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol, ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, isopropylphenol, In addition to alkylphenols such as butylphenol and p-tert-butylphenol, polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol, and phloroglucin, and alkyl polyvalent phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone. Lumpur compounds (any alkyl group, carbon number of 1-4) can be mentioned. These can be used alone or in combination of two or more.

Among the phenols described above, when the novolak type phenol resin obtained by the production method of the present invention is applied to a resin composition for photoresist, it is particularly preferable to use m-cresol and p-cresol. By using these phenols and adjusting the blending ratio of the two, various characteristics such as sensitivity and heat resistance as a photoresist can be adjusted.
In this case, the ratio of m-cresol and p-cresol is not particularly limited, but is preferably a weight ratio (m-cresol / p-cresol) = 9/1 to 1/9. More preferably, it is 8/2 to 2/8. When the ratio of m-cresol is less than the lower limit, the sensitivity may decrease, and when the ratio exceeds the upper limit, the heat resistance may decrease.

The aldehydes used in the step (a) are not particularly limited. For example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, Examples include caproaldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, and salicylaldehyde.
Among these, it is preferable in terms of characteristics to use formaldehyde and paraformaldehyde.

It does not specifically limit as reaction molar ratio (F / P) of the said phenols (P) and aldehydes (F), It can implement by well-known reaction molar ratio in manufacture of a novolak-type phenol resin.
In particular, when the obtained novolac type phenol resin is applied to a photoresist, the reaction molar ratio is preferably 0.5 to 1.0. Thereby, it can have a molecular weight suitable for a photoresist.
When the reaction molar ratio exceeds the upper limit, it may be excessively high in molecular weight for use in a photoresist or gelled depending on the reaction conditions. In addition, if the content is less than the lower limit, the content of the low-nuclear component is relatively increased, and thus the efficiency in removing this may be reduced.

In the step (a), a reaction solvent can be used as necessary.
The reaction solvent can be used as long as it dissolves a phenol resin, and is not particularly limited. For example, ethylene glycol alkyl such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. Ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol mono D Propylene glycol alkyl ether acetates such as ruether acetate, propylene glycol monopropyl ether acetate, ketones such as cyclohexanone and methyl amyl ketone, cyclic ethers such as dioxane, methyl 2-hydroxypropionate, 2-hydroxypropionic acid Ethyl, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl acetate, Examples thereof include esters such as methyl acetoacetate and ethyl acetoacetate, and amides such as N, N′-dimethylformamide. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

In the step (a), an acidic catalyst can usually be used.
Although it does not specifically limit as an acidic catalyst, For example, inorganic acids, such as hydrochloric acid, a sulfuric acid, phosphoric acid, phosphorous acid, Organic acids, such as oxalic acid, diethyl sulfuric acid, paratoluenesulfonic acid, and organic phosphonic acid, Metal salts, such as zinc acetate Etc. These can be used alone or in combination of two or more.

In the step (a), a known method can be applied as a condition for the condensation reaction of phenols and aldehydes, and is not particularly limited. For example, the reaction can be performed under reflux conditions.
Specifically, for example, phenols, aldehydes, and an acidic catalyst are charged into a reaction vessel equipped with a stirrer, a thermometer, and a heat exchanger, a reaction solvent is added as necessary, and the mixture is refluxed for 1 to 10 hours. The reaction can be performed. Alternatively, the reaction can be performed for 1 to 10 hours under reflux conditions while adding phenols, an acidic catalyst, and a reaction solvent as necessary, and sequentially adding aldehydes.

  Next, in the production method of the present invention, if necessary, water or water and the reaction solvent are substantially removed from the reaction system after the step (b) (a). Note that “substantially remove” means removing until the weight reaches 5% by weight, preferably 3% by weight, based on the weight of the entire reaction system.

A known technique can be applied to the step (b).
For example, the reaction system after the step (a) is heated from 130 to 220 ° C. under normal pressure, reduced pressure, or normal pressure and reduced pressure, and then treated for 1 to 15 hours. Water can be substantially removed. Also, when a reaction solvent is used in the step (a), it can be substantially removed in the step (b). In addition, when processing under reduced pressure, it can carry out by hold | maintaining a reaction system at 40-100 Torr, for example.
In addition, in this (b) process, by implementing on the said conditions, most unreacted monomers contained in a novolak-type phenol resin other than water and a reaction solvent can also be removed.
As described above, when the step (b) is provided and water, the reaction solvent, and in some cases, unreacted monomers are removed, the subsequent step (c) can be efficiently performed.

Next, in the production method of the present invention, (c) after the step (a), or in some cases, the reaction system temperature after the step (b) is maintained at 170 to 250 ° C. In addition, a low-boiling compound having a low boiling point is added to remove the low-nuclear component of the novolak-type phenol resin.
In the present invention, unless otherwise specified, the “low-nuclear component of the novolak-type phenol resin” refers to “an unreacted phenol and a binuclear component of the novolac-type phenol resin”.

In the production method of the present invention, the low-nuclear component contained in the novolac-type phenol resin can be reduced to a predetermined amount or less by performing the step (c).
When the reaction system temperature in the step (c) is less than the above lower limit value, it may be difficult to remove the dinuclear component, in particular. On the other hand, when the above upper limit is exceeded, depending on the reaction molar ratio of the phenols and aldehydes, the time-dependent change of the phenol resin may easily proceed during the step (c).

The reaction system temperature in this (c) process is maintained at 170-250 degreeC.
Here, step (c) can be carried out at a constant reaction system temperature within the above range, or can be carried out by changing the reaction system temperature stepwise as needed.
The step (c) preferably includes a step of maintaining the reaction system temperature at 210 to 240 ° C. Thereby, the low nucleus component in a novolak-type phenol resin can be made easy to distill off.

In the production method of the present invention, a low boiling point compound having a boiling point lower than the temperature of the reaction system is added to the reaction system maintained at the above temperature. Thereby, the low nucleus component contained in the novolac type phenol resin can be distilled off.
Although this mechanism is not clear, when a low boiling point compound is vaporized in contact with a novolac type phenol resin, the low boiling point compound is low together with the low boiling point compound due to an azeotropic action with a low nucleus component contained in the novolac type phenol resin. It is thought that the nucleus component can be distilled off.

The low boiling point compound can be appropriately selected in consideration of the reaction system temperature in the step (c), for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, methanol, Ethanol glycol ethers such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, etc., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. , Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Ethylene glycol alkyl ether acetates such as noethyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, ethers such as dioxane, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, butyl acetate, In addition to esters such as methyl acetoacetate and ethyl acetoacetate, water and the like can be mentioned.
These may be used alone or in combination of two or more.

  In the step (c), it is preferable to add the low boiling point compound in a liquid form. Thereby, handling workability | operativity can be improved.

Further, as the low-boiling compounds having a boiling point of rather low Ri by reaction temperature, and a boiling point of 50 ° C. or higher, preferably it is used as it is 80 ° C. or higher. Thereby, it can be made easy to maintain a liquid form until the low boiling point compound reaches the surface of the novolac type phenol resin in the reaction system.
If the boiling point is less than the above lower limit, depending on the degree of pressure reduction in the reactor, the low boiling point compound may vaporize before reaching the novolac phenol resin surface, and the removal effect of the low-nuclear component may not be sufficient. is there.

As the low boiling point compound, it is preferable to use a compound containing water. Water has a high effect of removing low-nuclear components, and also has an advantage of being inexpensive and highly safe.
Further, as the low boiling point compound, it is preferable to use a compound containing a compound capable of dissolving the low nucleus component of the novolak type phenol resin. Thereby, it can prevent that the binuclear component after distilling off adheres to the inside of piping or a heat exchanger, and solidifies.
As the low-boiling compound, when a compound capable of dissolving the low-nuclear component of the novolak-type phenolic resin is used together with water, the low-nuclear component can be efficiently removed and the low-nuclear compound after being distilled off The handleability of the components can be improved.

As a compound which can melt | dissolve the low nucleus component of the said novolak-type phenol resin, propylene glycol monomethyl ether acetate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, methyl isobutyl ketone etc. are mentioned, for example.
Among these, it is preferable to use one selected from propylene glycol monomethyl ether acetate, 1-butanol, and methyl isobutyl ketone. In particular, it is preferable to use propylene glycol monomethyl ether acetate.
Propylene glycol monomethyl ether acetate is easily available in the high purity (low impurity) grade used as a solvent for photoresist resin compositions. In particular, the resulting novolac phenolic resin is used for photoresists. When used in the above, the low-nuclear component can be removed without increasing the impurities in the novolak-type phenol resin, and a novolak-type phenol resin suitable for photoresist applications can be obtained.

In this step (c), the method for adding the low boiling point compound to the novolak type phenol resin is not particularly limited. For example, the low boiling point compound is added to the reactor used in the above steps (a) and (b). There is a method of adding the tank while adjusting the amount with a valve capable of adjusting the flow rate.
Here, when using 2 or more types of low boiling-point compounds, they can be mixed previously and can be added from one tank, and can also be added separately from each tank.
In the step (c), it is preferable to add the low boiling point compound while keeping the addition amount per unit time constant. As a result, the distillation rate of the low-nuclear component can be kept constant, and the content of the desired low-nuclear component can be easily derived.

The amount of the low boiling point compound added in step (c) (added amount per unit time) is preferably 1 to 10% by weight / hour with respect to the entire reaction system.
If the amount added is too small, it may take a long time to reduce the low-nuclear component. Moreover, when too large, the temperature of a reaction system will fall and it may become difficult to distill off a low-nuclear-body component smoothly. Therefore, by setting the amount of the low-boiling compound added within the above range, the low-nuclear component can be efficiently removed while maintaining the temperature of the reaction system at a suitable level.
The total amount of low-boiling compounds added in step (c) is not particularly limited, and depends on the amount of low-nuclear component distilled off, the temperature of the reaction system, and the type of low-boiling compounds used. Can be set as appropriate.

In the production method of the present invention, the step (c) is preferably carried out under reduced pressure. Thereby, the low boiling point compound vaporized after contacting with the novolac-type phenol resin and the low nuclei component vaporized together with the low boiling point compound can be smoothly distilled out of the reaction system.
For this purpose, the step (c) is preferably performed under a reduced pressure of 80 Torr or less. Thereby, the said effect | action can be expressed effectively.

As described above, the production method of the present invention is characterized in that, in the step (c), a low boiling point compound having a boiling point lower than that of the reaction system is added to the reaction system maintained at a predetermined temperature. .
Thereby, the low nucleus component in a novolak-type phenol resin can be distilled off. And since the method of the present invention utilizes a clear boiling point difference of each component in the novolak-type phenol resin, not only the low-nuclear component can be selectively removed, it is not only excellent in removal efficiency but also novolak. There is also an advantage that the yield of the type phenol resin is high.
In addition, for example, compared with the conventional steam distillation method, there is no problem of handleability due to the use of high-temperature steam, and the investment for equipment can be greatly reduced. It is possible to obtain a novolac type phenol resin with a low content of.

Next, the novolak type phenol resin of the present invention will be described.
The novolak-type phenol resin of the present invention is obtained by the production method of the present invention.

In the novolak-type phenol resin of the present invention, the content of unreacted phenols is not particularly limited, but it is preferably 3% by weight or less, preferably 1% by weight or less.
Similarly, the content of the binuclear component is not particularly limited, but it is preferably 7% or less, preferably 6% or less.
As a result, in particular, when the novolak type phenolic resin of the present invention is applied to a photoresist, it effectively reduces the amount of low-nuclear component sublimates generated in the manufacturing process of LCD and the like, and effectively improves productivity. Can be expressed.

The molecular weight of the novolak-type phenol resin of the present invention is not particularly limited, but the weight average molecular weight measured by GPC method is preferably 1000 to 20000.
In producing a novolac type phenol resin having such a molecular weight, the production method of the present invention can be particularly preferably applied.

Moreover, when applying the novolak-type phenol resin of this invention for photoresists, it is preferable that a weight average molecular weight is 1000-20000, More preferably, it is 1500-15000, Most preferably, it is 2000-7000.
Thereby, it can have a characteristic preferable as resin for photoresists, such as heat resistance and a sensitivity. If the weight average molecular weight is smaller than the lower limit, the heat resistance may be lowered, and if it is larger than the upper limit, the sensitivity may not be sufficient.

Here, the content of unreacted phenols is measured by an internal standard method using 3,5-xylenol as an internal standard substance in accordance with JIS K 0114.
In addition, the weight average molecular weight and the content of the binuclear component are measured by gel permeation chromatography (GPC measurement). The weight average molecular weight is calculated based on a calibration curve prepared using a polystyrene standard. The content of the binuclear component is calculated from the molecular weight distribution curve by the area ratio (%) of the binuclear component to the entire resin. GPC measurement is performed using tetrahydrofuran as an elution solvent under conditions of a flow rate of 1.0 ml / min and a column temperature of 40 ° C.
The apparatus is, for example: Main body: HLC-8020 manufactured by TOSOH
-Detector: UV-8011 manufactured by TOSOH Corporation set at a wavelength of 280 nm
-Column for analysis: Showa Denko Co., Ltd. * 1 SHODEX KF-802, 1 KF-803, 1 KF-805 are used.

Next, the photoresist resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) will be described.
The resin composition of the present invention is
(A) the novolak-type phenolic resin of the present invention,
(A) photosensitizer and
(C) Solvent,
It is characterized by containing.

In the resin composition of the present invention, (a) the novolac type phenol resin of the present invention can be used as the resin component.
The (a) photosensitizer can contain, for example, a quinonediazide group-containing compound.
And (c) As a solvent, what melt | dissolves said (a) and (b) component can be used.

The (a) photosensitive agent will be described.
As the photosensitizer, for example, a quinonediazide group-containing compound can be used.
Examples of the quinonediazide group-containing compound include (1) 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-tri Hydroxybenzophenone, 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-pentahydroxybenzophenone, 2,3 ′, 4,4 Polyhydroxybenzenes such as ', 5', 6-hexahydroxybenzophenone, 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone Nzophenones,

(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′-tri Hydroxyphenyl) propane, 4,4 ′-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, 3,3′-dimethyl- {1- [4- [ Bis [(poly) hydroxyphenyl] such as 2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol
Alkanes,

(3) Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenyl Methane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2, Tris (hydroxyphenyl) methane such as 5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, or a methyl-substituted product thereof,

(4) Bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-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-Me Tilphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxy Phenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4) -Methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane and the like, bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes Is a complete ester compound of a quinonediazide group-containing sulfonic acid such as naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinonediazidesulfonic acid, etc. , Partial ester compounds, amidated products or partially amidated products.

  Here, the quinonediazide group-containing compound component may be contained singly or in combination of two or more.

In the resin composition of the present invention, (a) the amount of the photosensitizer is not particularly limited, but (a) 5 to 100 parts by weight, preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the novolak type phenol resin. It can mix | blend in the range of.
(A) When the blending amount of the photosensitizer is less than the lower limit, it is difficult to obtain an image faithful to the pattern, and transferability may be deteriorated. On the other hand, when the upper limit is exceeded, the sensitivity of the photoresist may be reduced.

The (c) solvent will be described.
Examples of the solvent used in the resin composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol alkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene 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, propylene glycol monoethyl ether acetate, propylene glycol Propylene glycol alkyl ether acetates such as monopropyl ether acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone, cyclic ethers such as dioxane, and methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate , Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, acetic acid Examples include esters such as ethyl, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Although the usage-amount of the said solvent is not specifically limited, It is preferable that the solid content concentration in a resin composition shall be 30 to 65 weight%. When the solid content concentration is less than the above lower limit value, the fluidity of the composition is lowered, so that it becomes difficult to handle and it is difficult to obtain a uniform resist film by the spin coating method.

  In addition to the above-described components, the resin composition of the present invention may contain various additives such as a filler, a pigment, a surfactant, an adhesion improver, and a dissolution accelerator, as necessary. Agents can be used.

The method for preparing the resin composition of the present invention is not particularly limited. However, when no filler or pigment is added to the resin composition, the components (a) to (c) are mixed and stirred by a usual method. Can be prepared.
Moreover, when adding a filler and a pigment, it can disperse | distribute and mix using dispersers, such as a dissolver, a homogenizer, and a 3 roll mill. Further, if necessary, the resin composition can be filtered using a mesh filter, a membrane filter or the like.

  By exposing the resin composition thus obtained through a mask, a structural change occurs in the resin composition in the exposed portion, and the solubility in an alkali developer is promoted. . On the other hand, low solubility in an alkaline developer is maintained in the non-exposed area. A resist function can be provided by the difference in solubility generated in this way.

As described above, the method for producing a novolak type phenolic resin of the present invention can efficiently and easily produce a novolak type phenolic resin having a low content of low-nuclear component.
The novolak-type phenolic resin produced by the production method of the present invention can be applied to various uses. For example, by applying it to a photoresist, for example, in the LCD production process, the subnucleate of a low-nuclear component is used. It is possible to reduce the contamination of the production line and improve the productivity.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples. In the examples and comparative examples, “part” means “part by weight”, and “%” means “% by weight” except for the content of the binuclear component.

1. Synthesis of phenolic resin for photoresist (1) Example 1
Phenol in which m-cresol and p-cresol are mixed in a molar ratio (m-cresol: p-cresol) = 40: 60 in a 3 L four-necked flask equipped with a stirrer, a thermometer, and a heat exchanger. 1000 parts, a 37% aqueous formaldehyde solution (450 parts) (F / P = 0.60), and 6 parts of oxalic acid were charged, and the reaction was performed under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure, and further, the temperature was raised to 220 ° C. under a reduced pressure of 60 Torr, followed by dehydration under reduced pressure.
Thereafter, the reaction system was maintained at 220 ° C., and water (boiling point: 100 ° C.) was added for 4 hours under a reduced pressure of 60 torr at a rate of 7 (% / hour) with respect to the entire reaction system. Thus, 710 parts of a novolak type phenol resin having a weight average molecular weight of 4000, a dinuclear component of 6.4%, and an unreacted phenol (monomer) of 0.1% or less was obtained.

(2) Example 2
1000 parts of phenols and 473 parts of 37% formaldehyde aqueous solution prepared by mixing m-cresol and p-cresol in a molar ratio (m-cresol: p-cresol) = 50: 50 in the same apparatus as in Example 1. (F / P = 0.63), 12 parts of oxalic acid was charged, and the reaction was performed under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 230 ° C. under a reduced pressure of 50 Torr, and dehydration was performed under reduced pressure.
Thereafter, the reaction system was maintained at 230 ° C., and a process of adding water at a rate of 5 (% / hour) with respect to the entire reaction system was performed for 7 hours under a reduced pressure of 50 torr. As a result, 740 parts of a novolak-type phenol resin having 3.2% dinuclear component and 0.1% or less of unreacted phenols was obtained.

(3) Example 3
1000 parts of phenols and 653 parts of 37% formaldehyde aqueous solution prepared by mixing m-cresol and p-cresol in a molar ratio (m-cresol: p-cresol) = 70: 30 in the same apparatus as in Example 1. (F / P = 0.87) and 0.4 part of oxalic acid were charged, and the reaction was performed under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 150 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 240 ° C. under a reduced pressure of 40 Torr, and dehydration was performed.
Thereafter, the reaction system was maintained at 240 ° C., and 1-butanol (boiling point 118 ° C.) was added at a rate of 10 (% / hour) to the entire reaction system under a reduced pressure of 40 torr for 8 hours. As a result, 720 parts of a novolak type phenol resin having a weight average molecular weight of 6000, a dinuclear component of 2.3%, and an unreacted phenol of 0.1% or less was obtained.

(4) Example 4
1000 parts of phenols and 473 parts of 37% formaldehyde aqueous solution prepared by mixing m-cresol and p-cresol in a molar ratio (m-cresol: p-cresol) = 50: 50 in the same apparatus as in Example 1. (F / P = 0.63) and 7.5 parts of oxalic acid were charged, and the reaction was performed under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure, and further, the temperature was raised to 220 ° C. under a reduced pressure of 60 Torr, followed by dehydration under reduced pressure.
Thereafter, a process of adding propylene glycol monomethyl ether acetate (boiling point 146 ° C.) at a rate of 10 (% / hour) to the whole reaction system under a reduced pressure of 60 torr while maintaining the reaction system at 220 ° C. 3 After a period of time, 700 parts of a novolak type phenol resin having a weight average molecular weight of 4,500, a binuclear component of 6.9%, and an unreacted phenol of 0.1% or less was obtained.

(5) Example 5
In the same apparatus as in Example 1, m-cresol and p-cresol were mixed at a molar ratio (m-cresol: p-cresol) = 45: 55, 1000 parts of phenol, 480 parts of 37% aqueous formaldehyde solution. (F / P = 0.64), 3.5 parts of oxalic acid were charged, and the reaction was performed for 4 hours under reflux conditions.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 210 ° C. under a reduced pressure of 30 Torr, and dehydration was performed under reduced pressure.
Thereafter, the reaction system was maintained at 210 ° C., and a process of adding methyl isobutyl ketone (boiling point 116 ° C.) at a rate of 8 (% / hour) to the entire reaction system was performed for 5 hours under a reduced pressure of 30 torr. As a result, 700 parts of a novolak type phenol resin having a weight average molecular weight of 4900, a binuclear component of 4.8%, and a monomer component of 0.1% or less was obtained.

(6) Example 6
In the same apparatus as in Example 1, m-cresol and p-cresol were mixed in a molar ratio (m-cresol: p-cresol) = 50: 50: 1000 parts of phenol, 488 parts of 37% aqueous formaldehyde solution (F / P = 0.65) and 10.5 parts of oxalic acid were charged and reacted under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 230 ° C. under a reduced pressure of 50 Torr, and dehydration was performed under reduced pressure.
Thereafter, the reaction system was maintained at 230 ° C., and a mixed solution of water and propylene glycol monomethyl ether acetate (85:15) at a rate of 6 (% / hour) with respect to the whole reaction system under a reduced pressure of 50 torr. Was added for 8 hours to obtain 740 parts of a novolak-type phenol resin having a weight average molecular weight of 3,200, a dinuclear component of 3.4%, and unreacted phenols of 0.1% or less.

(7) Example 7
In the same apparatus as in Example 1, m-cresol and p-cresol were mixed in a molar ratio (m-cresol: p-cresol) = 45: 55. (F / P = 0.60), 11 parts of oxalic acid were charged, and the reaction was performed under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure, and further, the temperature was raised to 220 ° C. under a reduced pressure of 60 Torr, followed by dehydration under reduced pressure.
Thereafter, the reaction system was maintained at 220 ° C., and a mixed solution of water and propylene glycol monomethyl ether acetate (90:10) at a rate of 4 (% / hour) with respect to the whole reaction system under a reduced pressure of 60 torr. Was added for 2 hours to obtain 710 parts of a novolak type phenol resin having a weight average molecular weight of 3700, a binuclear component of 6.4%, and unreacted phenols of 0.1% or less.

(8) Example 8
In the same apparatus as in Example 1, m-cresol and p-cresol were mixed at a molar ratio (m-cresol: p-cresol) = 40: 60, 1000 parts of phenols, 458 parts of 37% formaldehyde aqueous solution. (F / P = 0.61), 0.4 part of oxalic acid was charged, and the reaction was performed under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 150 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 210 ° C. under a reduced pressure of 30 Torr, and dehydration was performed under reduced pressure.
Thereafter, the reaction system was maintained at 210 ° C., and a mixed solution of water and methyl ethyl ketone (boiling point 80 ° C.) at a rate of 8 (% / hour) with respect to the whole reaction system under a reduced pressure of 30 torr (95: 5) Was added for 8 hours to obtain 690 parts of a novolak-type phenol resin having a weight average molecular weight of 4700, a binuclear component of 4.0%, and unreacted phenols of 0.1% or less.

(9) Example 9
1000 parts of phenols and 443 parts of 37% aqueous formaldehyde solution prepared by mixing m-cresol and p-cresol in a molar ratio (m-cresol: p-cresol) = 45: 55 in the same apparatus as in Example 1. (F / P = 0.59), 0.6 part of oxalic acid was charged, and the reaction was performed for 4 hours under reflux conditions.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 240 ° C. under a reduced pressure of 30 Torr, followed by dehydration under reduced pressure.
Thereafter, the reaction system is maintained at 240 ° C., and a mixed solution of water and 1-butanol (80:20) is added at a rate of 3 (% / hour) to the whole reaction system under a reduced pressure of 30 torr. The treatment was carried out for 6 hours to obtain 620 parts of a novolak type phenol resin having a weight average molecular weight of 4300, a binuclear component of 2.0%, and unreacted phenols of 0.1% or less.

(10) Example 10
In a 3 L four-necked flask equipped with a stirrer, a thermometer, two dropping funnels, and a heat exchanger, m-cresol and p-cresol were mixed at a molar ratio (m-cresol: p-cresol) = 35: 65. 1000 parts of phenols mixed at a ratio, 420 parts of a 37% formaldehyde aqueous solution (F / P = 0.56), and 6 parts of oxalic acid were charged and reacted under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 170 ° C. and dehydrated under normal pressure, and further, the temperature was raised to 220 ° C. under a reduced pressure of 60 Torr, followed by dehydration under reduced pressure.
Thereafter, the temperature of the reaction system was raised to 230 ° C. and maintained, and under a reduced pressure of 40 torr, 4 (% / hour) of water and 3 (% / hour) of propylene glycol monomethyl ether acetate were added to the entire reaction system. Are added at these ratios simultaneously for 12 hours to obtain 690 parts of a novolak-type phenol resin having a weight average molecular weight of 3800, a binuclear component of 3.4%, and unreacted phenols of 0.1% or less. It was.

(11) Example 11
In the same apparatus as in Example 1, 1000 parts of phenol, 647 parts of 37% formaldehyde aqueous solution (F / P = 0.75), and 10 parts of oxalic acid were charged and reacted under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 140 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 170 ° C. under a reduced pressure of 80 Torr, and dehydration was performed under reduced pressure.
Thereafter, the temperature of the reaction system was raised to 240 ° C. and maintained, and a treatment of adding water at a rate of 4 (% / hour) to the entire reaction system was performed for 6 hours under a reduced pressure of 80 torr. 800 parts of a novolak-type phenol resin having an average molecular weight of 2500, a binuclear component of 2.1%, and unreacted phenols of 0.1% or less was obtained.

(12) Example 12
In the same apparatus as in Example 1, 1000 parts of phenol, 690 parts of a 37% aqueous formaldehyde solution (F / P = 0.80) and 10 parts of oxalic acid were charged and reacted under reflux conditions for 4 hours.
After the reaction, the temperature was raised to an internal temperature of 150 ° C. and dehydrated under normal pressure. Further, the temperature was raised to 200 ° C. under a reduced pressure of 40 Torr, and dehydration was performed.
Thereafter, the temperature of the reaction system was raised to 210 ° C. and maintained, and a process of adding water at a rate of 6 (% / hour) to the entire reaction system was performed for 5 hours under a reduced pressure of 40 torr. 820 parts of a novolak type phenol resin having an average molecular weight of 4500, a dinuclear component of 5.6%, and unreacted phenols of 0.1% or less was obtained.

(13) Comparative Example 1
In the same apparatus as in Example 1, m-cresol and p-cresol were mixed in a molar ratio (m-cresol: p-cresol) = 40: 60: 1000 parts of phenol, 450 parts of 37% aqueous formaldehyde solution (F / P = 0.58), 21 parts of oxalic acid was charged, and the reaction was performed under reflux conditions for 4 hours.
Thereafter, dehydration is carried out under normal pressure up to an internal temperature of 170 ° C., and further, dehydration under reduced pressure is carried out by raising the temperature to 230 ° C. under a reduced pressure of 60 torr, a weight average molecular weight of 2800, a binuclear component of 11.2%, unreacted phenol 730 parts of a 1.1% novolak type phenolic resin was obtained.

(14) Comparative Example 2
In the same apparatus as in Example 1, m-cresol and p-cresol were mixed at a molar ratio (m-cresol: p-cresol) = 60: 40. (F / P = 0.71), 8 parts of oxalic acid were charged, and the reaction was performed for 4 hours under reflux conditions.
Thereafter, dehydration is performed under normal pressure up to an internal temperature of 170 ° C., and further, dehydration under reduced pressure is performed by increasing the temperature to 220 ° C. under a reduced pressure of 50 torr, a weight average molecular weight of 4,500, a binuclear component of 10.0%, unreacted phenol 780 parts of a novolak type phenolic resin of 1.8% was obtained.

  Table 1 shows the novolac type phenol resins obtained in Examples 1 to 12 and Comparative Examples 1 and 2.

2. Preparation of phenolic resin composition for photoresist (1) Example 21
70 parts of the novolak-type phenol resin obtained in Example 1 and 15 parts of 2,3,4-trihydroxybenzophenone ester of naphthoquinone-1,2-diazide-5-sulfonic acid were mixed with PGMEA (propylene glycol monomethyl ether acetate). ) After dissolving in 150 parts, the mixture was filtered using a membrane filter having a pore size of 1.0 μm to obtain a resin composition.

(2) Examples 22-30
In Example 22, a resin composition was obtained in the same manner as in Example 21, except that the novolac type phenol resin obtained in Example 2 was used instead of the novolac type phenol resin obtained in Example 1. .
Similarly to Examples 23 to 30, Example 21 and Example 21 were used except that the novolac type phenol resin obtained in Examples 3 to 10 was used instead of the novolac type phenol resin obtained in Example 1. Similarly, a resin composition was obtained.

(3) Comparative Example 21
A resin composition was obtained in the same manner as in Example 11 except that the novolak type phenol resin obtained in Comparative Example 1 was used instead of the novolak type phenol resin obtained in Example 1.

(4) Comparative Example 22
A resin composition was obtained in the same manner as in Example 11 except that the novolak type phenol resin obtained in Comparative Example 2 was used instead of the novolak type phenol resin obtained in Example 1.

  The characteristic evaluation shown below was performed using the resin compositions obtained in Examples 21 to 30 and Comparative Examples 21 to 22. The results are shown in Table 2.

3. 3. Evaluation method of characteristics 3.1 Novolak type phenolic resin (1) yield It was calculated by the following formula.
Yield (%) = (weight of resin obtained / weight of charged phenolic monomer) × 100

(2) Content of Unreacted Phenols (Monomer) Based on JIS K 0114, it was measured by an internal standard method using 3,5-xylenol as an internal standard substance.

(3) Weight average molecular weight (Mw) and content of binuclear component Measured by gel permeation chromatography (GPC measurement). The weight average molecular weight was calculated based on a calibration curve prepared using a polystyrene standard. The content of the binuclear component was calculated from the molecular weight distribution curve by the area ratio (%) of the binuclear component to the entire resin. GPC measurement was performed using tetrahydrofuran as an elution solvent under conditions of a flow rate of 1.0 ml / min and a column temperature of 40 ° C.
The device
-Body: manufactured by TOSOH-"HLC-8020"
・ Detector: TOSOH manufactured at a wavelength of 280 nm ・ “UV-8011”
・ Analytical column: Showa Denko Co., Ltd. “SHODEX KF-802 x 1, KF-803 x 1, KF-805 x 1”
It was used.

3.2 Phenolic resin composition for photoresist (1) Sublimation test The resin composition was applied on a 3 inch silicon wafer with a spin coater to a thickness of about 1 μm and dried on a hot plate at 110 ° C. for 100 seconds. I let you. During this drying, the silicon wafer was covered with a petri dish to collect the sublimate. This operation was performed for 10 sheets, and the weight of the substance adhering to the petri dish was measured.

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

Examples 1 to 12 are novolak type phenol resins obtained by the production method of the present invention, and the novolak type phenol resin having a low content of low-nuclear components such as unreacted phenols and binuclear components is efficiently used. I was able to get it.
Examples 21-30 are the phenol resin compositions for photoresists using the novolac type phenol resin obtained in Examples 1-10, and the comparative example using the novolak type phenol resin obtained by the conventional manufacturing method. Compared with 11 and 12, the amount of sublimation was small, and the film reduction rate was excellent.

The production method of the present invention can efficiently produce a novolac-type phenol resin with a low content of low-nuclear components. Since the phenolic resin composition for photoresist using the novolak type phenolic resin obtained by the production method of the present invention can reduce the contamination of the production line by the sublimates of low-nuclear components and improve the productivity. It can be suitably used for the manufacture of semiconductors such as IC and LSI, the manufacture of display screen devices such as LCDs, and the manufacture of printing originals.

Claims (9)

(A) a step of subjecting phenols and aldehydes to a condensation reaction;
(C) while maintaining the reaction system temperature after step (a) to 170 to 250 ° C., a boiling point of 50 ° C. or higher, and a low-boiling compounds having a boiling point not lower than the temperature of the reaction system was added in liquid form Removing the low-nuclear component of the novolac-type phenolic resin,
A process for producing a novolac-type phenolic resin, comprising: Even after the step (a) prior to step (c) further comprises (b) the (a) from the reaction system after step, a step of divided the water or water and the reaction solvent The method for producing a novolac type phenolic resin according to claim 1, wherein: (A) a step of subjecting phenols and aldehydes to a condensation reaction;
(B) from the reaction system after step (a), a step of divided the water or water and reaction solvent,
(C) while maintaining the reaction system temperature after step (b) to 170 to 250 ° C., a boiling point of 50 ° C. or higher, and a low-boiling compounds having a boiling point not lower than the temperature of the reaction system was added in liquid form Removing the low-nuclear component of the novolac-type phenolic resin,
The method for producing a novolac type phenol resin according to claim 1, comprising: The method for producing a novolac type phenolic resin according to any one of claims 1 to 3, further comprising a step of maintaining the reaction system temperature at 210 to 240 ° C in the step (c). The method for producing a novolac type phenol resin according to any one of claims 1 to 4 , wherein a low-boiling compound containing water is used in the step (c). In the step (c), a method for producing a novolac type phenol resin using a low boiling point compound containing a compound capable of dissolving a low nucleus component of a novolac type phenol resin, wherein the low nucleus of the novolac type phenol resin is used compounds capable of dissolving the body component, propylene glycol monomethyl ether acetate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, according to any one of 5 claims 1 are those selected from methyl isobutyl ketone Of producing a novolac-type phenolic resin. The method for producing a novolak type phenol resin according to claim 6 , wherein the compound capable of dissolving the low-nuclear component of the novolak type phenol resin is selected from propylene glycol monomethyl ether acetate, 1-butanol, and methyl isobutyl ketone. The method for producing a novolac type phenol resin according to any one of claims 1 to 7 , wherein the amount of the low boiling point compound added in the step (c) is 1 to 10% by weight / hour with respect to the entire reaction system. . The method for producing a novolac type phenol resin according to any one of claims 1 to 8 , wherein the step (c) is carried out under a reduced pressure of 80 Torr or less.