JPH08165335A - Aromatic hydroxycarboxylic acid resin and its use - Google Patents

Abstract

PURPOSE: To obtain an arom. hydroxycarboxylic acid resin which gives a high- sensitivity high-resolving-degree photoresist compsn. and is useful as a metal chelate resin excellent in flexibility and resistances to oxidation and water. CONSTITUTION: This resin is represented by the formula (wherein each A is independently an optionally substd. phenyl or naphthyl; R1 is Hor 1-4C alkyl; R2 is H, 1-10C alkyl, 1-10C alkoxy, nitro, or hydroxyl; l is an integer of 0-100; m is an integer of 0-20, provided when A is phenyl, m is not O; and n is an integer of 0-3).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel hydroxycarboxylic acid resin, a process for producing the same, and its use. The hydroxycarboxylic acid resin of the present invention is a photoresist resin composition having excellent sensitivity and resolution, a metal chelate resin having excellent performance in flexibility and oxidation resistance and water resistance, and a color developing material for pressure-sensitive paper and the same. It is useful as an intermediate and an epoxy resin curing agent.

[0002]

2. Description of the Related Art Phenol or cresol novolac resins are generally used as photoresist resins. A composition comprising a quinonediazide sulfonic acid ester and a novolac resin is used as a positive resist by utilizing the fact that a quinonediazide group is decomposed by irradiation with light of 300 to 500 nm to generate a carboxyl group, so that an alkali-insoluble state becomes alkali-soluble. Used as. This positive type resist has a feature that the resolution is remarkably superior to that of the negative type resist, and is used for making integrated circuits such as IC and LSI. In recent years, the miniaturization of integrated circuits has advanced along with higher integration, and submicron pattern formation is currently required. As a result, even positive resists are required to have better resolution. However, in a resist material composed of a quinonediazide sulfonic acid ester and a novolac resin, there has been a limit in improving the resolution with a combination of conventional materials. For example, increasing the amount of the quinonediazide compound is considered to improve the resolution. However, increasing the amount of the quinonediazide compound has serious drawbacks such as reduction in sensitivity and increase in development residue. Therefore, there is a limit to the improvement of resolution, and there is a demand for a base resin which can replace the phenol or cresol novolac resin.

It has also been attempted to improve the sensitivity and developability of the resist by adding a specific compound to the resist composition as an additive. For example, JP-A-61-141441 discloses a positive type composition containing trihydroxybenzophenone. Although the positive photoresist containing this trihydroxybenzophenone is improved in sensitivity and developability, there is a problem that the heat resistance is deteriorated by the addition of trihydroxybenzophenone. Further, JP-A 64-44439, JP-A 1-177032, JP-A 1-280748 and JP-A 2
By adding an aromatic polyhydroxy compound other than trihydroxybenzophenone to -10350,
Although measures for increasing the sensitivity without deteriorating the heat resistance have been shown, the improvement of the developability is not always sufficient.

On the other hand, salicylic acid novolac resin has already been known as a metal chelate resin, a cement dispersant, a metal-coated pressure-sensitive adhesive, a fiber treatment agent, a developer for pressure-sensitive paper, and the like.
Resins of this kind are produced by reacting salicylic acid with formaldehyde in the presence of an acid catalyst (see, for example, Journal of Organic Chemistry (J.Org.Chem.) 27 1424 (1962) and these). Literature etc.). Further, JP-A-62-164716, 6
No. 2,176,875 discloses a novel salicylic acid-based Zyloc resin. However, like novolak resins typified by phenol-formaldehyde resins, salicylic acid novolak resins have poor flexibility and are susceptible to oxidative deterioration. It has been recognized that improvement is essential. Further, the salicylic acid-based Zyloc resin has a drawback of poor water resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photoresist composition having high resolution and high sensitivity required in the production of highly integrated circuits. , A novel hydroxycarboxylic acid resin useful as a metal chelate resin, a developer for pressure-sensitive paper and its intermediate, an epoxy resin curing agent, etc. To provide.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the problem, the present inventors have found the aromatic hydroxycarboxylic acid resin of the present invention. That is, the present invention relates to an aromatic hydroxycarboxylic acid resin represented by the general formula (1) (formula 11).

[0007]

[Chemical 11] (In the formula, A represents a phenyl group which may have a substituent or a naphthyl group, which may be the same or different,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group, and l Is 0 to 100, m is 0 to 20, and n is an integer of 0 to 3. However, m is not 0 when A is a phenyl group. ) The bond in the general formula (1) has the following meaning. The same applies to other expressions.

[0008]

[Chemical 12]

In addition, the present invention provides the general formula (2)
An aralkylated salicylic acid resin represented by the general formula (3)
Aralkylated hydroxynaphthoic acid resin represented by Chemical Formula 14, general formula (4), hydroxynaphthoic acid resin represented by Chemical Formula 15, and hydroxynaphthoic acid represented by General Formula (5) Acid, general formula (6)
And a hydroxynaphthoic acid co-condensation resin obtained by reacting a hydroxybenzoic acid represented by the formula (7) with a xylylene compound represented by the formula (16), and a hydroxynaphthoic acid represented by the general formula (5). And general formula (7)
A method for producing a hydroxynaphthoic acid resin by reacting a xylylene compound represented by the following formula, the resin represented by the general formula (8) (Chemical formula 17) or (10) (Chemical formula 17) and the general formula (9)
The present invention relates to a method for producing the aralkylated resin, which is obtained by reacting the aralkyl compound represented by (Chemical Formula 17).

[0010]

[Chemical 13]

[0011]

Embedded image

[0012]

[Chemical 15]

[0013]

Embedded image

[0014]

[Chemical 17] (In the above formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group. Represents a group, R ³ is a hydrogen atom or a carbon number of 1 to
10 represents an alkyl group, X represents a halogen atom, Y
Represents a halogen atom, a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, l is 0 to 100, m is 1 to 20, and n is 0.
Represents the integer of 3)

Furthermore, the present invention provides the general formula (11)
Partial esterification product of the hydroxycarboxylic acid resin represented by Chemical formula 18, a hydroxycarboxylic acid resin represented by the general formula (11) or a photoresist composition containing the partial esterification product thereof, the general formula (1 The present invention relates to a polyvalent metal compound of a hydroxycarboxylic acid resin represented by) and a color developing sheet containing the same.

[0016]

Embedded image (In the formula, A represents a phenyl group which may have a substituent or a naphthyl group, which may be the same or different,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group, and 1 Is 0 to 100, m is 0 to 20, and n is 0.
Represents the integer of 3)

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic hydroxycarboxylic acid resin of the present invention comprises a hydroxycarboxylic acid represented by the general formula (12) (formula 19) and a xylylene derivative represented by the general formula (7). The term refers to a hydroxycarboxylic acid resin obtained by the reaction, and an aralkylated hydroxycarboxylic acid resin obtained by further reacting the resin with an aralkyl compound represented by the general formula (9).

[0018]

[Chemical 19] (In the formula, A represents a phenyl group or a naphthyl group which may have a substituent)

As examples of the hydroxycarboxylic acid represented by the general formula (12), when A is a phenyl group, optionally substituted 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4 -Hydroxybenzoic acid and the like can be mentioned. When A is a naphthyl group, optionally substituted 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy- Examples thereof include 6-naphthoic acid, 1-hydroxy-4-naphthoic acid, 1-hydroxy-5-naphthoic acid, 2-hydroxy-7-naphthoic acid and 1-hydroxy-8-naphthoic acid. As the substituent, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an octyl group, a trifluoromethyl group, a trifluoroethyl group, a hexafluorobutyl group, and a hexafluoro group. Halogenated alkyl group such as nonyl group, methoxy group,
Examples thereof include an alkoxy group such as an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group, a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, a hydroxy group, a nitro group and a cyano group. In the present invention, esters thereof may be used instead of the hydroxycarboxylic acid represented by the general formula (12).

Examples of the xylylene derivative represented by the general formula (7) include α, α'-dihydroxy-o-xylene, α, α'-dihydroxy-m-xylene, α, α '.
-Dihydroxy-p-xylene, α, α'-dimethoxy-m-xylene, α, α'-dimethoxy-p-xylene, α, α'-diethoxy-o-xylene, α, α'-
Diethoxy-p-xylene, α, α′-diethoxy-m
-Xylene, α, α'-diisopropoxy-o-xylene, α, α'-diisopropoxy-m-xylene, α,
α'-diisopropoxy-p-xylene, α, α'-di-n-propoxy-p-xylene, α, α'-di-n-
Butoxy-m-xylene, α, α'-di-n-butoxy-p-xylene, α, α'-di-sec-butoxy-p-
Xylene, α, α′-diisobutyl-p-xylene,
α, α'-dichloro-o-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-p-xylene, α, α'-dibromo-o-xylene, α, α'-dibromo -M-xylene, α, α′-dibromo-p-xylene, α, α′-difluoro-o-xylene, α, α ′
-Difluoro-m-xylene, α, α'-difluoro-
p-xylene, α, α′-diiodo-o-xylene,
Examples include α, α′-diiodo-m-xylene and α, α′-diiodo-p-xylene. Preferred compounds include α, α′-dihydroxy-p-xylene, α,
α'-dichloro-p-xylene, α, α'-dimethoxy-p-xylene, α, α'-dihydroxy-m-xylene, α, α'-dichloro-m-xylene, α, α'-dimethoxy-m -Such as xylene.

Examples of the aralkyl compound represented by the general formula (9) include benzyl chloride, benzyl bromide, 3-methylbenzyl chloride, 4-methylbenzyl bromide, 4-methoxybenzyl bromide, 2-methoxybenzyl chloride, 3 -Ethoxybenzyl chloride,
2-nitrobenzyl bromide, 4-nitrobenzyl bromide, 3-hydroxybenzyl bromide, α-chloroethylbenzene, α-bromoethylbenzene and the like can be mentioned.

Among the aromatic hydroxycarboxylic acid resins represented by the general formula (1) of the present invention, in the production of the hydroxycarboxylic acid resin in which m = 0, the reaction between the hydroxycarboxylic acid and the xylylene derivative is carried out by the hydroxycarboxylic acid. The xylylene derivative is used in an amount of 0.1 to 1.0 mol, preferably 0.3 to 0.8 mol, per 1 mol of the acid, and the reaction is carried out without a catalyst or in the presence of an acid catalyst. Reaction temperature is 50-250 ℃
The reaction time is 1 to 20 hours.

Examples of the acid catalyst include inorganic and organic acids. As the inorganic acid, mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid,
Friedel-Crafts type catalysts such as zinc chloride, stannic chloride and ferric chloride, and organic acids include organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid. These catalysts may be used alone or in combination. The amount of the catalyst used is about 0.01 to 15% by weight based on the total weight of the hydroxycarboxylic acid of the general formula (12) and the xylylene derivative of the general formula (7).
Is. A solvent may be used in the reaction of the present invention. Examples of the solvent include halogenated hydrocarbons such as dichloroethane, trichloroethane, chlorobenzene and dichlorobenzene, ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether and tetrahydrofuran, and sulfur-containing solvents such as sulfolane and dimethyl sulfoxide.

Among the aromatic hydroxycarboxylic acid resins represented by the general formula (1) of the present invention, the aralkylated hydroxycarboxylic acid resin in which m is not 0 is the same as the hydroxycarboxylic acid resin obtained above. It is obtained by reacting an aralkyl compound represented by (9). The aralkyl compound represented by the general formula (9) is used in an amount of 0.01 to 10 weight ratio, preferably 0.1 to 1 weight ratio, based on the previously obtained hydroxycarboxylic acid resin. This reaction is carried out at a temperature of 50 to 250 ° C for 1 to 20 in the presence of an uncatalyzed or acid catalyst.
Done on time. The above-mentioned is used as the acid catalyst,
The amount thereof used is about 0.01 to 15 parts by weight per 100 parts by weight of the total weight of the hydroxycarboxylic acid of the general formula (1) and the aralkyl compound of the general formula (9). In addition, a solvent may be used in this reaction, and as the solvent, not only the above-mentioned solvents but also dimethylformamide, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylimidazo can be used. Nitrogen-containing solvents such as ridinone are also used. When the reaction is carried out using a hydroxycarboxylic acid ester instead of the hydroxycarboxylic acid, the carboxylic acid resin is treated with sodium hydroxide, potassium hydroxide or the like after the condensation reaction or the aralkylation reaction. It needs to be hydrolyzed with an alkali to give a carboxylic acid.

The partially esterified hydroxycarboxylic acid resin in which a part of the carboxylic acid group represented by the general formula (11) is esterified is obtained by partially esterifying the hydroxycarboxylic acid obtained by the above method with a known esterifying agent. It is obtained by doing. In the partial esterification reaction, the esterifying agent is used in an amount of 0.1 to 70 mol%, preferably 1 to 1 mol of the carboxylic acid group.
˜50 mol% and react in the presence of alkali in an organic solvent at a temperature of 50 to 150 ° C. for 1 to 20 hours. Examples of the esterifying agent used include alkyl halides such as methyl iodide, ethyl iodide, butyl iodide, methyl bromide, ethyl bromide, methyl chloride and butyl chloride, sulfuric acid esters such as dimethylsulfate and diethylsulfate, p -Toluenesulfonic acid ester and the like can be mentioned. Examples of the alkali used include carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, oxides such as magnesium oxide and silver oxide, sodium hydroxide, and the like.
Examples thereof include hydroxides such as potassium hydroxide. In addition, examples of the solvent used in the reaction include the above-mentioned various solvents including a nitrogen-containing solvent.

The manner in which the resin of the present invention is used for a photoresist will be described below. The photoresist composition is composed of an aromatic hydroxycarboxylic acid resin represented by the general formula (11) of the present invention and / or its partially esterified resin, other alkali-soluble resin, quinonediazide sulfonic acid ester and a solvent, If necessary, a small amount of resin, dye, sensitivity adjusting agent or the like may be added as an additive. The proportion of the resin of the present invention in the total alkali-soluble resin is 0.1 to 100% by weight, preferably 0.5.
˜50% by weight, more preferably 1 to 30% by weight.

Among the resins of the present invention, preferred compounds include a number average molecular weight of 450 to 20000 represented by the general formula (2).
, And more preferably 500 to 7,000, and the carboxylic acid equivalent is 2
An aralkylated salicylic acid resin of 45 to 440 g / eq, a number average molecular weight represented by the general formula (3) of 510 to 20000, more preferably 520 to 7000 and a carboxylic acid equivalent of 232 to 400.
g / eq aralkylated hydroxynaphthoic acid resin,
Number average molecular weight represented by the general formula (4) 500 to 50,000,
More preferably, it is 550 to 7,000 and the carboxylic acid equivalent is 240.
~ 288 g / eq hydroxynaphthoic acid resin, a co-condensation resin of hydroxynaphthoic acid and hydroxybenzoic acid, having a number average molecular weight of 370-50000, preferably 400-7000, and the carboxylic acid of those resins. Base 1
Examples include esterified products in which ˜50 mol% is esterified. Most preferably, it is an aralkylated salicylic acid resin represented by the general formula (2), and 1 is 0 to 10 and m is 1
-10, n is a resin of 0 to 3, a hydroxynaphthoic acid resin represented by the general formula (4), and a hydroxy group and a carboxyl group are in the ortho position, and 1 is a resin of 0 to 10; It is a resin in which 1 to 50 mol% of carboxylic acid groups are esterified.

When these compounds are used as a photoresist composition, it is preferable that they have a high solubility in a solvent, and a solubility of 2% or more, more preferably 10% or more, in the solvent is required. In that respect, the partially esterified product is preferable because it has higher solubility than the resin before esterification.
The other properties are the same as when using the resin before esterification. Other alkali-soluble resins include
For example, so-called novolac resins obtained by condensing phenols and / or naphthols with aldehydes such as novolac, cresol novolac, and naphthol novolac, copolymer resins of phenols or / and naphthols and dicyclopentadiene, polyhydroxystyrene. And hydrides thereof, styrene-maleic anhydride copolymers, polymethylmethacrylate and the like.

The quinonediazide sulfonic acid ester used in the present invention may be any one derived from a phenol compound. For example, hydroquinone, resorcin, phloroglucin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,3 ', 4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone Hydroxy such as 2,2 ', 3,3'-tetrahydroxybenzophenone, 2,2', 3,3 ', 4'-pentahydroxybenzophenone, 2,3,3', 4,5'-pentahydroxybenzophenone Benzophenones, gallic acid alkyl esters, 2,2-bis ((poly) hydroxyphenyl) alkanes, 2- (3-hydroxyphenyl)
Bis ((poly) hydroxyphenyl) alkanes such as 2- (2,5-dihydroxyphenyl) propane, 1,2-naphthoquinonediazide-4-sulfonic acid esters such as oxyflavans or 1,2-naphthoquinonediazide- Five
-Sulfonic acid esters are exemplified. The amount of the quinonediazide sulfonic acid ester component added is preferably in the range of 10 to 50% by weight based on the total solids in the composition.

It is preferable that the solvent has an appropriate drying rate and that the solvent evaporates to give a uniform and smooth coating film. As such a solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, toluene,
Xylene, propylene glycol, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutanoate, methyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, butyl acetate, ethyl lactate, methyl isobutyl ketone, Cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone and the like can be mentioned. The solvent may be used alone or in combination.

In the photoresist composition of the present invention, the solid concentration is preferably 20 to 40% by weight. It is preferable to remove the insoluble matter by filtering the prepared composition with a filter. This is coated on a substrate such as a silicon wafer using a spin coater.
This silicon wafer is then heated at 50-150 ° C for 30-180 ° C.
Bake for a second. Then, a pattern can be obtained by exposing the wafer through a photomask using an exposure machine and developing with an alkaline aqueous solution. As the alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, aqueous ammonia, ethylamine, n-
Propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, tetramethylammonium hydroxide, choline, piperidine, 1,8-diazabicyclo-
An alkaline aqueous solution is used in which an alkaline compound such as (5,4,0) -7-undecene is dissolved to a concentration of usually 1 to 10% by weight, preferably 2 to 5% by weight.

The radiation used for the exposure is i
Ultraviolet rays such as rays are preferable, but depending on the characteristics of the composition,
Various types of radiation can be selected and used. The reason why the photoresist composition containing the hydroxycarboxylic acid resin of the present invention has high sensitivity and high resolution is that naphthoquinonediazide, which is a photosensitizer, and a hydroxycarboxylic acid are hydrogen-bonded to each other, and It is presumed that this is because the difference in solubility in the alkaline solution is large.

Next, the production of a polyvalent metal compound of the aromatic hydroxycarboxylic acid resin represented by the general formula (1) of the present invention,
And, a mode of using it as a developer for pressure-sensitive paper will be described. Several known methods can be applied to produce a polyvalent metal compound from the resin of the present invention. For example,
It can be produced by reacting the alkali metal salt of the present resin and a water-soluble polyvalent metal salt in water or a solvent in which both are soluble. That is, the resin is reacted with an alkali metal hydroxide, carbonate, alkoxide, or the like to obtain an alkali metal salt of the resin or an aqueous solution, alcohol solution, or water-alcohol mixed solution thereof, which is then dissolved in water. It is a method of producing a valent metal salt by reacting it. It is desirable to react about 0.5 to 1 gram equivalent of water-soluble polyvalent metal salt to 1 mol of carboxylic acid in the resin.

By mixing the resin of the present invention with a polyvalent metal salt of an organic carboxylic acid such as formic acid, acetic acid, propionic acid, valeric acid, caproic acid, stearic acid or benzoic acid, and heating and melting the mixture. Can also be manufactured. Depending on the case, a basic substance such as ammonium carbonate, ammonium bicarbonate, ammonium acetate, or ammonium benzoate may be further added, and the mixture may be melted by heating. further,
Using a resin of the present invention and a polyvalent metal carbonate, oxide or hydroxide, ammonium formate, ammonium acetate,
Ammonium caproate, ammonium stearate,
It can be produced by heating and melting reaction with a basic substance such as organic ammonium carboxylate such as ammonium benzoate and then cooling. When producing the metal salt of the resin of the present invention by heating and melting, the melting temperature is usually 100 to 180 ° C., and the reaction time depends on the resin composition, the melting temperature, the type of the polyvalent metal salt, and the amount used. It takes about several hours. The polyvalent metal salt is an organic carboxylate, carbonate or oxide of polyvalent metal such that the metal is present in an amount of 1 wt% to about 20 wt% with respect to the total weight of the resin.
It is desirable to use hydroxide. The amount of the basic substance used is not particularly limited, but is usually 1 to 15% by weight based on the total amount of the resin. When using a basic substance, it is more preferable to use it in advance by mixing with a polyvalent metal salt. The metal of the polyvalent metal compound of the resin of the present invention includes metals other than alkyl metals such as lithium, sodium and potassium, but preferable polyvalent metals include calcium, magnesium, aluminum, copper, zinc and tin. , Barium, cobalt and nickel,
More preferably, zinc is mentioned.

The color-developing sheet of the present invention comprises a method of applying an aqueous coating material using an aqueous suspension of the metallized material to a support such as paper, a method of scraping the metallized material during papermaking, and a method of organically treating the metallized material. It is produced by any method such as a method of applying an oil-based paint dissolved or suspended in a solvent to a support. In producing these paints, kaolin clays, calcium carbonate, starch, synthetic and natural latex, etc. are blended to obtain a paint having an appropriate viscosity and coating suitability. In the paint, the ratio of the metal compound is 10 in the total solids.
A content of less than 70% by weight is desirable. If the content is less than 10% by weight, sufficient color development cannot be achieved, and if it exceeds 70% by weight, the surface properties of the color-developing sheet tend to deteriorate. The coating amount of the coating, dry weight 0.5 g / m ² or more, preferably from 1 to 10 g / m ^2.

[0036]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Synthesis Example 1 A reaction apparatus equipped with a thermometer and a stirrer was charged with 913 parts of methyl salicylate and 0.2 part of trifluoromethanesulfonic acid, and the temperature was raised to 140 to 150 ° C. to obtain α, α′-dimethoxy-p-xylene 498. Parts were added dropwise at the same temperature over 5 hours. Furthermore, 15
Aged at 0 ° C. for 2 hours. Next, the pressure was reduced to 10 mmHg by a pump, and unreacted methyl salicylate was recovered at 150 to 180 ° C. After cooling to 100 ° C., 350 ml of toluene was added to obtain a toluene solution of salicylic acid ester resin. A reactor equipped with a thermometer and a stirrer was charged with 160 parts of potable soda and 907 parts of water, and the toluene solution obtained above was added dropwise at 85 to 90 ° C. over 4 hours. Furthermore, the temperature was raised to 100 ° C. and toluene was distilled off. After removing the insoluble matter, the mixture was neutralized with 2250 parts of an 8% aqueous hydrochloric acid solution, and the precipitated solid was separated by filtration, washed with water and dried. Yield 720
It was a department. Next, in a reactor equipped with a thermometer and a stirrer, the salicylic acid resin obtained earlier [composition ratio by GPC analysis
(Area%) is l = 0; 50.4%, l = 1; 23.6%, l = 2; 1.5%,
l ≧ 3; 4.0%, other; 0.5%, number average molecular weight = 533] 100
Parts, benzyl chloride 33.5 parts, 1,1,2-trichloroethane 400 parts, and zinc chloride 0.4 parts, and charged at 110 ° C for 3
The reaction was carried out over time. After the reaction was completed, 1000 parts of water was added, and 1,1,2-trichloroethane was distilled off by azeotropic distillation, and the precipitated solid was separated by filtration and dried to obtain 121 parts of aralkylated salicylic acid resin. The number average molecular weight was 632, and the carboxylic acid equivalent was 249 g / eq. The DTA analysis data of this product is shown in Fig. 1, and the IR (KBr tablet method) measurement results are shown in Fig. 2. The carboxylic acid equivalent was determined by titration with 0.1N potassium hydroxide methanol solution at room temperature using cresol red as an indicator.

Synthesis Example 2 2-Hydroxy-3 was added to a reactor equipped with a thermometer and a stirrer.
-Add 200 parts of naphthoic acid, 200 parts of sulfolane, and 0.06 part of trifluoromethanesulfonic acid as a catalyst,
At 150 ° C, 58.9 parts of α, α'-dimethoxy-p-xylene was added dropwise over 5 hours, and the reaction was further performed at 150 ° C for 2 hours. The reaction mixture was discharged into 1000 parts of water, the precipitated solid was filtered off and dried. The obtained solid was put in 1500 parts of toluene, heated and stirred, and then hot filtered was repeated 3 times to remove unreacted raw materials and obtain 154 parts of a purified product. The composition ratio (Area%) by GPC analysis is l = 0; 53.2%, l = 1; 31.
2%, l ≧ 2; 13.5%, others; 2.1% with carboxylic acid equivalent 25
It was 0 g / eq and the number average molecular weight was 673. The DTA analysis result of this resin is shown in Fig. 3, and the IR analysis result (KBr tablet method) is shown in Fig. 4.

Synthesis Example 3 A reaction apparatus equipped with a thermometer and a stirrer was charged with 100 parts of the hydroxynaphthoic acid resin obtained in Synthesis Example 2, 0.4 parts of zinc chloride and 300 parts of sulfolane, and the temperature was raised to 100 ° C. Then, 40.8 parts of benzyl chloride was added dropwise at the same temperature over 1 hour. 120
The mixture was heated with stirring at 5 ° C for 5 hours, at 130 ° C for 2 hours, and at 140 ° C for 3 hours. After cooling, the mixture was discharged into 1500 parts of water, and the precipitated solid was taken out by decanting. The obtained solid was added to 1500 parts of water and sludged to remove residual sulfolane. The solid was filtered off, washed with water and dried to obtain 90 parts of aralkylated hydroxynaphthoic acid resin. The number average molecular weight is 870 and the carboxylic acid equivalent is
It was 307 g / eq. The DTA analysis data and the GPC analysis data of this product are shown in FIG. 5 and FIG. 6, respectively.

Synthesis Example 4 2-Hydroxy-3 was added to a reactor equipped with a thermometer and a stirrer.
-Naphthoic acid 133 parts (0.74 mol), Salicylic acid 49 parts (0.35 mol)
5 mol), 200 parts of sulfolane, and 0.06 part of trifluoromethanesulfonic acid as a catalyst, and at 140 to 150 ° C.,
58.9 parts of α, α'-dimethoxy-p-xylene over 5 hours
(0.355 mol) was added dropwise and the reaction was further carried out at 150 ° C for 2 hours. The reaction mixture was discharged into 1000 parts of water, the precipitated solid was filtered off and dried. The obtained solid was put in 1500 parts of toluene, heated and stirred, and then hot filtered was repeated 3 times to remove unreacted raw materials to obtain 148 parts of a purified product of hydroxynaphthoic acid co-condensed resin. It had a number average molecular weight of 678 and a carboxylic acid equivalent of 231 g / eq. The DTA analysis data of this product is shown in FIG. 7, and the IR (KBr tablet method) measurement results are shown in FIG.

Synthesis Example 5 A reactor equipped with a thermometer and a stirrer was charged with 913 parts of methyl salicylate and heated to 100 to 110 ° C., and 525 parts of α, α′-dichloro-p-xylene were kept at the same temperature. Then, it took 5 hours to carry out divided charging. Further, it was aged at 150 ° C. for 2 hours. Next, the pressure was reduced to 10 mmHg by a pump, and unreacted methyl salicylate was recovered at 150 to 180 ° C. After cooling to 100 ° C., 350 ml of toluene was added to obtain a toluene solution of salicylic acid ester resin.
Potential soda 160 in a reaction device equipped with a thermometer and stirrer
Part, and 907 parts of water, and add the toluene solution obtained above to 85-90
It was added dropwise at 4 ° C over 4 hours. Then, raise the temperature to 100 ° C,
The toluene was distilled off. After removing insoluble matter, 8% hydrochloric acid aqueous solution
The mixture was neutralized with 2250 parts, and the precipitated solid was separated by filtration, washed with water and dried. The yield was 705 parts. Next, in a reactor equipped with a thermometer and a stirrer, the salicylic acid resin obtained earlier [the composition ratio (Area%) by GPC analysis was 1 = 0; 51.1%, l = 1; 22.3%,
l = 2; 20.3%, l ≧ 3; 4.3%, other; 1.0%, number average molecular weight = 543] 100 parts, benzyl chloride 33.5 parts, 1,1,2-
400 parts of trichloroethane and 0.4 part of zinc chloride were charged and the reaction was carried out at 110 ° C for 3 hours. After the reaction is complete, water 1000
1,1,2-trichloroethane was distilled off by azeotropic distillation, and the precipitated solid was separated by filtration and dried to obtain 121 parts of an aralkylated salicylic acid resin. The number average molecular weight is 641,
The carboxylic acid equivalent was 251 g / eq.

Synthesis Example 6 2-Hydroxy-3 was added to a reactor equipped with a thermometer and a stirrer.
-200 parts of naphthoic acid and 200 parts of o-dichlorobenzene were added, and 62.1 parts of α, α'-dichloro-p-xylene was charged in portions at 140 to 150 ° C over 5 hours and further reacted at 150 ° C for 2 hours. I went. From the reaction mixture by steam distillation
o-Dichlorobenzene was distilled off, and the precipitated solid was filtered off and dried. Methyl isobutyl ketone 1 was added to the obtained solid.
1 and 2 l of water were added, and the pH was adjusted to 5.9 with aqueous potassium hydrogen carbonate solution.
The unreacted 2-hydroxy-3-naphthoic acid was removed to the aqueous layer. The same operation was performed 3 times in total. Then the organic layer
After washing with 2 l of a 1% aqueous hydrochloric acid solution, the mixture was washed with water and the organic solvent was distilled off under reduced pressure to obtain 142 parts of a purified product. Composition ratio (Are
a%) is l = 0; 53.0%, l = 1; 31.0%, l ≧ 2; 12.1%,
Others: 1.8%, the carboxylic acid equivalent was 243 g / eq, and the number average molecular weight was 685.

Synthesis Example 7 A reactor equipped with a thermometer and a stirrer was charged with 100 parts of the hydroxynaphthoic acid resin obtained in Synthesis Example 6, 0.2 parts of zinc chloride and 300 parts of sulfolane, and the temperature was raised to 100 ° C. 20.4 parts of benzyl chloride were added dropwise at the same temperature over 1 hour. 120
The mixture was heated with stirring at 5 ° C for 5 hours, at 130 ° C for 2 hours, and at 140 ° C for 3 hours. After cooling, the mixture was discharged into 1500 parts of water, and the precipitated solid was taken out by decanting. The obtained solid was added to 1500 parts of water and sludged to remove residual sulfolane. The solid was filtered off, washed with water and dried. 112 parts of aralkylated hydroxynaphthoic acid resin was obtained. The number average molecular weight was 851, and the carboxylic acid equivalent was 291 g / eq.

Synthesis Example 8 2-Hydroxy-3 was added to a reactor equipped with a thermometer and a stirrer.
-Naphthoic acid 133 parts (0.74 mol), salicylic acid 49 parts (0.3
55 mol), 200 parts of sulfolane and 0.1 part of trifluoromethanesulfonic acid as a catalyst were added, and the mixture was added at 140 to 150 ° C for 5
Α, α'-dimethoxy-m-xylene 70.7 parts (0.4
(26 mol) was added dropwise, and the reaction was further carried out at 150 ° C. for 2 hours. The reaction mixture was discharged into 1000 parts of water, the precipitated solid was filtered off and dried. To the obtained solid was added 1.5 liters of methyl isobutyl ketone and 3 liters of water, and an aqueous potassium hydrogen carbonate solution was added.
The pH was adjusted to 5.8 and the unreacted raw materials were removed in the aqueous layer. The same operation was performed 3 times in total. After that, the organic layer is washed with 1% hydrochloric acid aqueous solution 2
After washing with l, it was washed with water, the organic solvent was distilled off under reduced pressure, and the purified product was removed.
I got 138 copies. It has a number average molecular weight of 685 and a carboxylic acid equivalent of 23.
It was 9 g / eq.

Synthesis Example 9 50 parts of the hydroxynaphthoic acid resin obtained in Synthesis Example 2, 22 parts of potassium carbonate and 200 parts of tetrahydrofuran were placed in a reactor equipped with a thermometer and a stirrer, and the temperature was raised to 70 ° C. At the same temperature, 20 parts of methyl iodide was added dropwise over 2 hours, and the mixture was heated with stirring for 5 hours. After completion of the reaction, the product was discharged into 1000 parts of water, and the precipitated solid was separated by filtration, washed with water and dried. Carboxylic acid equivalent is 2
It was 65 g / eq.

Synthesis Example 10 m-cresol 53.0 parts, 2,3-xylenol 25.4 parts, 37% aqueous formaldehyde solution 51.1 were placed in an autoclave.
Parts, oxalic acid dihydrate 4.41 parts, water 58.5 parts and dioxane 272 parts were charged, and the mixture was heated and stirred at a reaction temperature of 130 ° C. for 8 hours. After the reaction, after cooling to room temperature, the content was concentrated by an evaporator to obtain a novolak resin (Mw = 8200). This resin is called novolac resin (NA).

Synthesis Example 11 m-cresol (108.1 parts), 2,3-xylenol (61.1 parts), 3,4-xylenol (20.5 parts), 37% aqueous formaldehyde solution (100 parts), water (110 parts) and dioxane (700) were placed in an autoclave.
Parts and 8.8 parts of oxalic acid dihydrate were charged and treated in the same manner as in Synthesis Example 9 except that the mixture was heated and stirred at 130 ° C. for 7 hours,
A novolak resin (Mw = 8700) was obtained. This resin is called novolac resin (NB).

Synthesis Example 12 64.1 parts of m-cresol, 9.0 parts of 2,3-xylenol, 9.0 parts of 3,4-xylenol, 50.2 parts of a 40% butanol solution of formaldehyde in a flask equipped with a stirrer, a condenser and a thermometer, shu After charging 0.5 parts of acid dihydrate,
The mixture was heated and stirred at 100 ° C for 2 hours. Then 180 ℃ / 30 ~ 50
The volatile matter was removed with mmHg, and the mixture was cooled to room temperature to obtain a novolak resin (Mw = 9200). This resin is a novolac resin (N
C).

Synthesis Example 13 118.1 parts (0.44 mol) of 1,2-naphthoquinone-diazide-4-sulfonic acid chloride and 4,4'-dihydroxybenzophenone were added to a glass reactor equipped with a stirrer, a thermometer and a reflux condenser. (0.1 mol) was dissolved in 300 parts of dimethylacetamide and 21.2 parts of triethylamine was added to 30 parts with stirring.
The mixture was added dropwise over 1 minute, and stirring was continued for another 2 hours. After separating the precipitate by filtration, 250 parts of a 1% hydrochloric acid aqueous solution was added dropwise to the obtained filtrate to precipitate a reaction product. The precipitate was filtered off, washed with water and dried. The purity by GPC was 99.5%. This photosensitizer is referred to as photosensitizer (A).

Synthesis Example 14 1 mol of 1,3,3-tris (4-hydroxyphenyl) butane
1,2-naphthoquinonediazide-5-sulfonyl chloride 2.5
Synthesis was performed in the same manner as in Synthesis Example 13 using mol. The purity by GPC was 99.8%. This photosensitizer is the photosensitizer (B)
And

Synthesis Example 15 1,1,3-Tris (2,5-dimethyl-4-hydroxyphenyl)
Synthesis was carried out in the same manner as in Synthesis Example 13 using 1 mol of butane and 2.5 mol of 1,2-naphthoquinonediazide-4-sulfonyl chloride. The purity by GPC was 99.3%. This photosensitizer is referred to as photosensitizer (C).

Example 1 17 parts of the resin obtained in Synthesis Example 1 and 5 parts of the photosensitizer (A) were dissolved in 48 parts of ethyl cellosolve acetate. A resist solution was prepared by filtering this solution through a 0.2 μm Teflon filter. This was applied to a silicon wafer that had been washed by a conventional method using a spin coater to 1.2 μm.
Was applied to a film thickness of. Then, this silicon wafer 1
Baking was carried out for 60 seconds on a hot plate at 00 ° C. Then, this wafer was exposed by using a reduction projection exposure machine (DSW4800 NA = 0.28 from GCA, Inc.) having an exposure wavelength of 436 nm (g-line) while changing the exposure amount stepwise. A positive pattern was obtained by developing this with a 2% choline solution for 1 minute. Then, the normalized film thickness (= remaining film thickness / initial film thickness) is plotted against the logarithm of the exposure amount, and the inclination θ is obtained.
θ was defined as a γ value. The γ value was 4.3.

Example 2 A resist pattern was formed in the same manner as in Example 1 except that 17 parts of the resin obtained in Synthesis Example 2 and 5 parts of the photosensitizer (A) were used. The γ value of the obtained resist pattern was 4.1. Example 3 A resist pattern was formed in the same manner as in Example 1 except that 17 parts of the resin obtained in Synthesis Example 3 and 5 parts of the photosensitizer (A) were used. The γ value of the obtained resist pattern was 4.2. Example 4 A resist pattern was formed in the same manner as in Example 1 except that 17 parts of the resin obtained in Synthesis Example 4 and 5 parts of the photosensitizer (A) were used. The γ value of the obtained resist pattern was 4.2. Comparative Example 1 A resist pattern was formed in the same manner as in Example 1 except that 17 parts of novolac resin (NA) and 5 parts of photosensitive agent (A) were used. The γ value of the obtained resist pattern was 2.0.

Examples 5 to 26 A solution prepared by dissolving the alkali-soluble resin and the photosensitizer shown in Table 1 (Table 1 to Table 5) in 48 parts of ethyl cellosolve acetate was filtered with a 0.2 μm Teflon filter. A resist solution was prepared. This was coated on a silicon wafer that had been washed by a conventional method to a film thickness of 1.2 μm using a spin coater. Then, this silicon wafer is heated to 100 ° C.
Baked on a hot plate for 60 seconds. Then, this wafer was exposed using a reduction projection exposure machine (NSR-17551i7A NA = 0.50, Nikon Corporation) having an exposure wavelength of 365 nm (i-line). Then, it was baked for 1 minute on a hot plate kept at 110 ° C. This was developed with a 2.4% by weight tetramethylammonium hydroxide aqueous solution for 1 minute to obtain a positive pattern. The obtained resist pattern was evaluated by the following method. The evaluation results are shown in Table-1. As shown in Table 1, the focus tolerance, sensitivity, resolution, developability, pattern shape, and heat resistance were all good. Comparative Example 2 A resist pattern was formed in the same manner as in Example 5 except that 17 parts of novolac resin (NB) and 5 parts of photosensitive agent (A) were used. The evaluation results of the obtained resist pattern are shown in Table-1.
It was shown to.

[Evaluation method of resist] -Sensitivity A reduction projection exposure machine [NSR-17551i7A NA = 0.50 manufactured by Nikon Corp.] was exposed to i-line having a wavelength of 365 nm while changing the exposure time, and then 2.4% by weight of tetramethylammonium hydroxide was used. It was developed at 25 ° C. for 60 seconds with an aqueous solution to form a positive resist on the wafer. The optimum exposure time (line width 0.
35μm line and space pattern (1L1S) 1
The exposure time generated in a width of 1] was defined as the sensitivity. -Resolution The dimension of the smallest resist pattern resolved when exposed at the optimum exposure time was defined as resolution, and the dimension equivalent to the comparative example was B, and the dimension smaller than that was A.・ Focus tolerance The 1L1S with a line width of 0.35 μm is observed using a scanning electron microscope, and the resolved pattern size is ± 10 of the mask design size.
Focus allowance was evaluated from the range of focus deviation when the ratio of the thickness of the resist pattern after development to the thickness of the resist pattern before development (residual film rate) was 90% or more, and 90% or more. The one equivalent to the comparative example was designated as B, and the one having a larger swing width was designated as A. -Developability Using a scanning electron microscope, the one having less scum and less development residue than the comparative example was designated as A, and the one equivalent to the comparative example was designated as B.・ Pattern shape 1L1S with a line width of 0.35 μm The lower side dimension L1 and the upper side dimension L2 of a rectangular cross section are measured using a scanning electron microscope, and 0.85 ≦
The case where L2 / L1 ≦ 1 and the pattern shape was vertical was defined as A.・ Heat resistance A wafer with a resist pattern formed is heated in an oven for 130
The sample was heated at 2 ° C. for 2 minutes, and the case where the pattern shape did not collapse was designated as A.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

Example 27 10 g of the resin obtained in Synthesis Example 1 was crushed and dispersed in 100 g of a 0.8% aqueous caustic soda solution. This dispersion was heated and dissolved at 70 ° C. with stirring. Next, while maintaining this solution at 30 to 35 ° C., a solution in which 2.0 g of anhydrous zinc chloride was previously dissolved in 30 ml of water was added dropwise under stirring for 30 minutes. A white precipitate was deposited and after stirring at the same temperature for 2 hours, filtration,
It was washed with water and dried to obtain 9.8 g of a white powder. This was the zinc salt of the resin and had a zinc content of 7.0%. Using the metal salt of the resin obtained above as a suspending agent, the suspension was prepared by dispersing it with a sand grinding mill in the following composition. Hanging color agent 6 parts by weight 10% aqueous polyvinyl alcohol solution (Kuraray # 117) 3 parts by weight water 22.5 parts by weight Next, a coating composition having the following composition was prepared using the suspension. Suspension 10 parts by weight Light calcium carbonate 10 parts by weight Starch 0.8 parts by weight Synthetic rubber latex 0.8 parts by weight Water 32.5 parts by weight Dry coating amount of these coatings on high-quality paper is 5.0 to 5.5 g / m.
^The coated sheet was dried so as to be ^2, and a color developing sheet was obtained. The developer sheet was evaluated by the following methods, and the evaluation results are shown in Table-2 (Table 6).

[Performance Evaluation Method for Hanging Paper of Pressure-Sensitive Copy Paper] 1. Color development speed and density (conducted in a constant temperature and humidity room at 20 ° C and 65% RH) In the case of blue color, crystal violet lactone (C
Using a commercially available blue coloring top paper (NW-40T made by Jujo Paper Co., Ltd.) containing VL) as the main pressure-sensitive dye, and overlaying it with a developer sheet (bottom paper) coated with a water-based paint so that both coating surfaces face each other. , Press and color with an electronic typewriter. The reflectance is Σ for two points, 30 seconds after stamping and 24 hours after stamping.
The color is measured with a -80 color difference meter (manufactured by Tokyo Denshoku Industries Co., Ltd.) and displayed as Y value. 2. Light fastness of color image 1. The hanging color sheet developed by the method of 2 is exposed to a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 2 hours (and 4 hours), and the density after irradiation is measured using a Σ-80 color difference meter. displayed. The lower the Y value and the smaller the difference from the value before the test, the less fading due to light is preferable. 3. Plasticizer resistance Dioctyl phthalalate (DOP) is used as a core substance and melamine-formaldehyde resin film microcapsules with an average particle size of 5.0 μm are prepared, and a coating liquid containing a small amount of starch-based binder is applied on a fine paper with an air knife coater. A DOP microcapsule-coated paper is prepared by coating and drying so that the dry coating amount becomes 5 g / m ² . The DOP microcapsule coated paper and 1. After facing the color development surface of the color development sheet
Pass through a super calender roll having a linear pressure of 100 kg / cm to allow DOP to uniformly permeate the color development surface. After 1 hour from the test, the density was measured using a Σ-80 color difference meter, and Y
Display by value. The lower the Y value and the smaller the difference from the value before the test, the better the plasticizer resistance of the color image. 4. Water resistance of color image 1. The color-developing sheet colored by the above method was immersed in water for 2 hours, and the density change of the color image was visually observed.

5. Yellowing of color developing sheet (5-1) Yellowing due to NO _{X Based on} JIS L-0855 (Testing method for nitric oxide gas fastness of dyes and dyes), the color developing sheet was changed to NaNO ₂ (sodium nitrite). ) and it was stored for 1 hour in a closed container of the NO _X gas atmosphere produced by reaction with phosphoric acid, to examine the extent of yellowing.
At the first hour after the end of the test, the color is measured using a Σ-80 color difference meter and displayed as a WB value. The larger the WB value and the smaller the difference from the WB value of the untested sheet, the less the yellowing under NO _X atmosphere. (5-2) Yellowing by light A carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.) is irradiated with the color-developing sheet for 4 hours, and after the test, the color is measured using a Σ-80 color difference meter and displayed as a WB value. A larger WB value and a smaller difference from the WB value of the untested sheet means less yellowing due to light irradiation.

Comparative Example 3 Example 27 using Zn 3,5-di-tert-butylsalicylate
A color developing sheet was prepared and evaluated in the same manner as in. The evaluation results are shown in Table-2.

[0064]

[Table 6] Examples 28 to 30 The metal salts of the resins shown in Table 3 (Table 7) were synthesized in the same manner as in Example 27 to obtain color developing sheets. A performance test was performed on the obtained color developing sheet in the same manner as in Example 27. The test results are shown in Table 3.

[0065]

[Table 7] Examples 31 to 40 The metal salts of the resins shown in Table 4 (Table 8 and Table 9) were used in Example 27.
Synthesis was carried out in the same manner as above to obtain a color developing sheet. A performance test was performed on the obtained color developing sheet in the same manner as in Example 27. The test results are shown in Table-5 (Table 10 and Table 11).

[0066]

[Table 8]

[0067]

[Table 9]

[0068]

[Table 10]

[0069]

[Table 11]

As is clear from the results shown in Table 1, the photosensitive resin composition containing the hydroxycarboxylic acid resin of the present invention is suitable for forming a high-resolution positive pattern, It is possible to obtain a fine pattern with excellent processing accuracy as compared with a conventional alkali-soluble resin that uses a conventional novolac resin alone. This is in line with the manufacturing of more highly integrated semiconductor devices than required in such industrial fields. Further, as is clear from Tables 3 and 5, the metal salt of the hydroxycarboxylic acid resin of the present invention is useful as a developer and is excellent in NO _X yellowing resistance, light yellowing resistance, plasticity, and water resistance. Provide a color development sheet.

[0071]

Industrial Applicability The resin is a photoresist resin having excellent sensitivity and resolution, a metal chelate resin having excellent performances in flexibility, oxidation resistance and water resistance, a color developing material for pressure sensitive paper and intermediates thereof. However, due to its structure, it can also be used as a curing agent for epoxy resins.

[Brief description of drawings]

FIG. 1 is a DTA chart of the resin obtained in Synthesis Example 1.

FIG. 2 is an IR chart of the resin obtained in Synthesis Example 1.

FIG. 3 is a DTA chart of the resin obtained in Synthesis Example 2.

FIG. 4 is an IR chart of the resin obtained in Synthesis Example 2.

FIG. 5 is a DTA chart of the resin obtained in Synthesis Example 3.

FIG. 6 is a GPC chart of the resin obtained in Synthesis Example 3.

7 is a DTA chart of the resin obtained in Synthesis Example 4. FIG.

FIG. 8 is an IR chart of the resin obtained in Synthesis Example 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical indication location G03F 7/023 511 7/039 H01L 21/027 (31) Priority claim number Japanese Patent Application No. 6-247883 (32) Priority Day Hei 6 (1994) October 13 (33) Priority claiming country Japan (JP) (72) Inventor Yuko Ishihara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (12)

[Claims] 1. An aromatic hydroxycarboxylic acid resin represented by the general formula (1) (formula 1). Embedded image (In the formula, A represents a phenyl group which may have a substituent or a naphthyl group, which may be the same or different,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group, and 1 Is 0 to 100, m is 0 to 20, and n is 0.
Represents an integer of 3. However, when A is a phenyl group, m is 0.
is not) 2. Represented by the general formula (2) (Chemical formula 2), and
The resin according to claim 1, which is an aralkylated salicylic acid resin having a number average molecular weight of 450 to 20,000 and a carboxylic acid equivalent of 245 to 440 g / eq. Embedded image (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group. Represents, 1 is 0 to 100, m is 1 to 20, n
Represents an integer of 0 to 3) 3. Represented by the general formula (3) (Chemical Formula 3), and
The resin according to claim 1, which is an aralkylated hydroxyxynaphthoic acid resin having a number average molecular weight of 510 to 20,000 and a carboxylic acid equivalent of 232 to 400 g / eq. Embedded image (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group. Represents, 1 is 0 to 100, m is 1 to 20, n
Represents an integer of 0 to 3) 4. Represented by the general formula (4) (Chemical formula 4), and
The resin according to claim 1, which is a hydroxynaphthoic acid resin having a number average molecular weight of 500 to 50,000 and a carboxylic acid equivalent of 240 to 288 g / eq. [Chemical 4] (In the formula, l represents an integer of 0 to 100) 5. A hydroxynaphthoic acid represented by the general formula (5) (formula 5), a hydroxybenzoic acid represented by the general formula (6) (formula 5), and a general formula (7) (formula 5). With a xylylene compound represented by the formula: [xylylene compound / (hydroxynaphthoic acid and hydroxybenzoic acid)] molar ratio = 0.1 to 1.0, and (hydroxynaphthoic acid / hydroxybenzoic acid) molar ratio = 0 The resin according to claim 1, which is a hydroxynaphthoic acid co-condensation resin having a number average molecular weight of 370 to 50,000 obtained by reacting 0.01 to 100. Embedded image (In the above formula, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Y is a halogen atom, a hydroxyl group or 1 to 4 carbon atoms.
Represents an alkoxy group of 6. A salicylic acid resin represented by the general formula (8) (Chemical formula 6) and an aralkyl compound represented by the general formula (9) (Chemical formula 6) are added in a weight ratio of aralkyl compound / salicylic acid resin = 0. The method for producing a resin according to claim 2, wherein the reaction is conducted at 0.01 to 10. [Chemical 6] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group. Represents, X represents a halogen atom, and 1 represents 0 to
Represents an integer of 100) 7. A hydroxynaphthoic acid resin represented by the general formula (10) (Chemical formula 7) and an aralkyl compound represented by the general formula (9) (Chemical formula 7) are added by weight of aralkyl compound / hydroxynaphthoic acid resin. The method for producing a resin according to claim 3, wherein the reaction is carried out at a ratio of 0.01 to 10. [Chemical 7] (In the formula, l represents an integer of 0 to 100, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. 10 represents an alkoxy group, a nitro group or a hydroxy group, and X represents a halogen atom) 8. A hydroxynaphthoic acid represented by the general formula (5) (Chemical formula 8) and a xylylene compound represented by the general formula (7) (Chemical formula 8) are mixed with [xylylene compound / hydroxynaphthoic acid] mol. The method for producing a resin according to claim 4, wherein the reaction is carried out at a ratio of 0.1 to 1.0. Embedded image (In the formula, Y is a halogen atom, a hydroxyl group or 1 to 4 carbon atoms.
Represents an alkoxy group of 9. A partially esterified hydroxycarboxylic acid resin in which a part of the carboxylic acid group represented by the general formula (11) (Chemical Formula 9) is esterified. [Chemical 9] (In the formula, A represents a phenyl group which may have a substituent or a naphthyl group, which may be the same or different,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group, and 1 Is 0 to 100, m is 0 to 20, and n is 0.
Represents the integer of 3) 10. A hydroxycarboxylic acid resin represented by the general formula (11) (Chemical Formula 10) or at least one partially esterified hydroxycarboxylic acid resin in which a part of carboxylic acid groups of the resin is esterified. Photoresist composition. [Chemical 10] (In the formula, A represents a phenyl group which may have a substituent or a naphthyl group, which may be the same or different,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a nitro group or a hydroxy group, and Is 0 to 100, m is 0 to 20, n
Represents an integer of 0 to 3) 11. A polyvalent metal compound of a hydroxycarboxylic acid resin obtained by reacting the hydroxycarboxylic acid resin according to claim 1 with a polyvalent metal compound. 12. A color-developing sheet containing the polyvalent metal compound of the resin according to claim 11.