JP2015196709A - Novolac type phenolic resin and production method thereof, photoresist composition, epoxidized novolac type phenolic resin, epoxy resin composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novolac type phenolic resin that is excellent in flexibility, heat resistance, solubility and the like, and can be suitably used for various uses, and a production method thereof.SOLUTION: A novolac type phenolic resin comprises a compound represented by formula (1), A comprises a functional group represented by the formula (2-1) or a specific formula, and B comprises a functional group represented by another specific formula.

Description

  INDUSTRIAL APPLICABILITY The present invention has a good flexibility, heat resistance, solubility, etc., and can be suitably used for various applications, a novolac type phenol resin, a method for producing the same, a photoresist composition using the same, and an epoxy The present invention relates to a modified novolac type phenol resin, an epoxy resin composition, and a cured product.

  The novolak type phenol resin is used in various applications such as a curing agent for an epoxy resin, a raw material for obtaining an epoxidized novolac type phenol resin by epoxidation, and an alkali-soluble resin for a positive photoresist composition.

  For example, an epoxy resin composition using a novolac-type phenolic resin as a curing agent has good workability, and the cured product has excellent characteristics, so electrical / electronic parts, structural materials, adhesives, paints, etc. Used in the field.

  However, in the electrical / electronic field such as semiconductor encapsulants and laminates, the reflow temperature has become higher due to the use of lead-free solder, so semiconductor packages such as laminates, interlayer insulation materials, and encapsulating materials are used. Higher heat resistance is required for the epoxy resin composition used in the present invention compared to conventional products. In addition, as a countermeasure to environmental problems, flame resistance (flame resistance) is improved without using halogens that may generate dioxins during combustion or antimony or other flame retardants that are suspected of causing carcinogenicity. It is demanded. Furthermore, when the epoxy resin composition is used as a matrix material or an interlayer insulating material for a laminate, the epoxy resin composition is required to be soluble in a solvent in order to use the epoxy resin composition as a varnish uniformly dissolved in a solvent. Yes.

  In addition, positive photoresist compositions in which novolac type phenolic resins are used as alkali-soluble resins have a wide variety of patterns ranging from fine line widths of about 0.3 μm to large line widths of about several tens to several hundreds of μm, for example. It can be formed on the surface of a simple substrate.

  However, in the fields of semiconductor manufacturing and LCDs where positive photoresist compositions are used, the line widths of patterns to be formed are becoming increasingly finer as technology such as TFT and STN advances, In a fine TFT display element, a design dimension of a line width is being requested to a level of several μm.

  Incidentally, in the field of flexible printed wiring boards such as cellular phones, negative dry film photoresists are widely used. The resolution of this dry film photoresist is low, and the line width is about 30 to 300 μm. On the other hand, the positive photoresist composition has high resolution, but when it is going to be made into a dry film, it is difficult to make it into a roll product because the film quality is brittle and lacks flexibility. Is not easy. For this reason, a positive dry film photoresist has not been put into practical use. That is, in the positive photoresist, improvement in flexibility is required.

  In order to solve the above various problems, a phenol novolac resin (Patent Document 1) having a chemical structure obtained by crosslinking (bonding) phenols with a biphenyldiyldimethylene group and a methylene group, or methylphenols, glutaraldehyde and A phenol resin for a photoresist composition that exhibits high flexibility and enables high sensitivity and high resolution by condensation polymerization with dialdehydes containing at least one of adipaldehyde (patented) Document 2) has been proposed.

International Publication No. 2007/026553 International Publication No. 2010/050592

  However, the novolac type phenol resin described in Patent Document 1 has not sufficiently obtained higher heat resistance, solubility and flexibility, and the novolac type phenol resin described in Patent Document 2 is flexible. Although improvement is observed, the flexibility as a photoresist composition is not necessarily improved sufficiently, and there is a need for further improvement in flexibility for practical use.

  The present invention has been made in view of the above problems, and has a good flexibility, heat resistance, solubility, etc., and can be used suitably for various applications, and a method for producing the same. An object of the present invention is to provide a photoresist composition, an epoxidized novolac-type phenol resin, an epoxy resin composition, and a cured product.

  In order to achieve the above-mentioned object, the present inventors have conducted extensive research, and as a result, the novolac-type phenol resin is characterized by containing a compound represented by the formula (1), flexibility, heat resistance and dissolution. I found that the sex was good.

（式（１）において、Ａはそれぞれ独立に下記一般式（２−１）又は一般式（２−２）で表される官能基からなり、Ｂは下記一般式（３）で表される官能基からなり、ｎは０〜１００の整数である。）

(In the formula (1), A is independently composed of a functional group represented by the following general formula (2-1) or general formula (2-2), and B is a functional group represented by the following general formula (3). And n is an integer of 0 to 100.)

（式（２−１）において、置換基Ｒ１は、それぞれ独立に、炭素数が１〜６の直鎖のアルキル基、炭素数が１〜６の分岐を持つアルキル基、シクロヘキシル基、又はフェニル基である。また、Ｘは、２価の基であって、それぞれ独立に、アルキレン基、エーテル基、チオエーテル基、およびカルボニル基からなる群より選ばれる２価の基である。）

(In the formula (2-1), each of the substituents R1 is independently a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, or a phenyl group. X is a divalent group, each of which is independently a divalent group selected from the group consisting of an alkylene group, an ether group, a thioether group, and a carbonyl group.

（式（３）において、Ｙはハロゲン原子、アルコキシ基、又は水酸基を表す。）

(In Formula (3), Y represents a halogen atom, an alkoxy group, or a hydroxyl group.)

  In the present invention, the mass ratio [(2-1) / (2-2)] of the formula (2-1) and the formula (2-2) contained in the compound represented by the formula (1) is It is the said novolak-type phenol resin which is the range of 95 / 5-5 / 95.

  Moreover, this invention is a manufacturing method of the novolak type phenol resin characterized by carrying out the condensation reaction of the phenols represented by Formula (4) and (5), and the compound represented by Formula (6). .

（式（４）において、置換基Ｒ^１は、それぞれ独立に、炭素数が１〜６の直鎖のアルキル基、炭素数が１〜６の分岐を持つアルキル基、シクロヘキシル基、又はフェニル基である。また、Ｘは、２価の基であって、それぞれ独立に、アルキレン基、エーテル基、チオエーテル基、およびカルボニル基からなる群より選ばれる２価の基である。）

(In Formula (4), each of the substituents R ¹ is independently a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, or a phenyl group. X is a divalent group, each of which is independently a divalent group selected from the group consisting of an alkylene group, an ether group, a thioether group, and a carbonyl group.)

（式（６）において、Ｙはハロゲン原子、アルコキシ基、又は水酸基を表す。）

(In Formula (6), Y represents a halogen atom, an alkoxy group, or a hydroxyl group.)

  Moreover, this invention is a photoresist composition containing the said novolak-type phenol resin.

  Furthermore, the present invention is an epoxy resin obtained by epoxidizing the novolac type phenol resin, and an epoxy resin composition comprising the epoxy resin and the phenol resin.

  Moreover, this invention is an epoxy resin composition comprised containing the said novolak-type phenol resin and an epoxy resin.

  Furthermore, the present invention is a cured product obtained by curing the epoxy resin composition.

  As described above, according to the present invention, the novolac-type phenolic resin that has good flexibility, heat resistance, solubility, and the like and can be suitably used for various applications, a method for producing the same, and a photoresist composition An epoxidized novolac-type phenol resin, an epoxy resin composition, and a cured product can be provided.

  That is, according to the present invention, a novolac type phenol resin having good flexibility, heat resistance, solubility, and the like can be obtained. This novolac-type phenol resin can be suitably used as a raw material for the epoxidized novolac-type phenol resin by utilizing its characteristics. Moreover, the epoxy resin composition excellent in heat resistance and solubility, and the hardened | cured material which consists of this composition can be obtained suitably using this novolak-type phenol resin or an epoxidized novolak-type phenol resin. Furthermore, a photoresist composition with improved flexibility can be suitably obtained by adopting it as an alkali-soluble resin.

  The novolak-type phenol resin according to the present invention is represented by the formula (1). That is, it consists of a chemical structure in which bisphenols (structure) and trivalent phenols (structure) having no substituent are crosslinked (bonded) with a biphenyldiyldimethylene group. The mass ratio [bisphenol structure (2-1) / trivalent phenol structure (2-2)] to trivalent phenols (structure) not having is preferably in the range of 95/5 to 5/95. Preferably it is the range of 90/10-10/90, More preferably, it is the range of 80/20-20/80, More preferably, it is the range of 70/30-70/30. When the content of the bisphenol structure is reduced, the flexibility of the resulting novolak type phenol resin is lowered. Said (2-1) / (2-2) can be adjusted with ratio of the compounding quantity of phenols represented by postscript Formula (4) and Formula (5). Almost all the phenols represented by the formulas (4) and (5) are incorporated into the novolac type phenol resin as a raw material.

  In the method for producing a novolak type phenolic resin according to the present invention, the bisphenol represented by the formula (4) is a compound having at least two hydroxyphenyl groups, particularly an alkylene group, an ether group, or a thioether group. Means a compound in which two hydroxyphenyl group (s) are bonded by a divalent group consisting of a carbonyl group. Specifically, bisphenol A; (2,2-bis (4-hydroxyphenyl) propane), bisphenol C; (2,2-bis (3-methyl-4-hydroxyphenyl) propane), bisphenol F; (bis (4-hydroxyphenyl) methane), bisphenol E; (1,1-bis (4-hydroxyphenyl) ethane), bisphenol S; (bis (4-hydroxyphenyl) sulfone), bisphenol B; (2,2-bis (4-hydroxyphenyl) butane), bisphenol Z; (1,1-bis (4-hydroxyphenyl) cyclohexane), 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, etc. Bisphenol C, bisphenol Z and the like are preferable. Bisphenols may be used alone or as a mixture of two or more.

  The phenol represented by the formula (5) is a trivalent polyhydric phenol compound having no substituent, and examples of the trivalent phenol compound include pyrogallol and phloroglucinol. Of these polyhydric phenol compounds not having a substituent, pyrogallol is preferred from the viewpoint of easy availability and high reactivity. These trivalent polyhydric phenol compounds may be used alone or in combination of two or more.

  Examples of the compound containing a biphenyldiyldimethylene structure represented by the formula (6) include 4,4′-bis (halogenomethyl) biphenyl, 2,4′-bis (halogenomethyl) biphenyl, and 2,2′-bis. (Halogenomethyl) biphenyl, 4,4′-bis (alkoxymethyl) biphenyl, 2,4′-bis (alkoxymethyl) biphenyl, 2,2′-bis (alkoxymethyl) biphenyl, and the like can be preferably exemplified. . Furthermore, as a compound containing the biphenyldiyldimethylene structure represented by the general formula (6), 4,4′-bis (hydroxymethyl) biphenyl, 2,4′-bis (hydroxymethyl) biphenyl, 2,2 ′ -Bis (hydroxymethyl) biphenyl etc. can be mentioned suitably. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Further, the alkoxy group is not particularly limited, but an aliphatic alkoxy group having 1 to 6 carbon atoms is preferable. Specific examples include a methoxy group and an ethoxy group. Preferred specific compounds include 4,4'-bis (chloromethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, and 4,4'-bis (ethoxymethyl) biphenyl. These compounds containing a biphenyldiyldimethylene structure represented by the formula (6) may be used alone or in a mixture of plural kinds.

  In the condensation reaction for producing the novolak-type phenolic resin according to the present invention, the resulting novolak-type phenolic resin satisfies the structure of A and B defined by the general formula (1) and the target weight average molecular weight. In addition, the use ratio of reaction raw materials and reaction conditions are adjusted.

  The use molar ratio [phenols / crosslinking component] of the phenols represented by the formula (4) and the formula (5) and the crosslinking component comprising the compound represented by the formula (6) is preferably 0. 0.5 or more, more preferably 0.5 to 3.0, still more preferably 0.7 to 2.8, particularly preferably 0.9 to 2.5, and most preferably 0.9 to 2.4. However, it is preferable because a novolac type phenol resin having sufficiently improved flexibility can be obtained. When the molar ratio [phenols / crosslinking component] exceeds 3.0, the flexibility of the novolak type phenolic resin cannot be improved sufficiently, and the dissolution rate is increased, making it difficult to control alkali dissolution. Since it becomes difficult to achieve resolution and a high residual film ratio, it is not preferable. On the other hand, if it is less than 0.5, it may become insoluble in an alkaline solution, resulting in a decrease in sensitivity and lack of practicality. When the alkali dissolution rate of the novolak type phenol resin is 30 to 8000 kg / s, preferably 50 to 3000 kg / s, a novolak type phenol resin that exhibits high flexibility and has high resolution and a high residual film ratio is obtained. This is preferable. Further, by adjusting [phenols / crosslinking component], the content of the biphenyldiyldimethylene structure, which is a crosslinking group for the phenols, can be defined, and as a result, the molecular weight of the novolak type phenolic resin can be controlled.

  The novolak-type phenolic resin according to the present invention includes a polycondensation reaction between the phenols represented by the formula (4) and the formula (5) and a crosslinking component composed of the compound represented by the formula (6). Can be easily obtained.

  In the condensation polymerization reaction, an acid catalyst can be preferably used. Any acid catalyst can be used without particular limitation as long as it has the ability to react a phenol component and a crosslinking component. For example, organic sulfonic acids such as oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid can be used. The usage-amount of an acid catalyst is 0.01 to 5 weight% with respect to phenols. When used for a photoresist composition, it is preferable that the amount is as small as possible in order to improve its properties. This is because the acid catalyst remaining in the resin may adversely affect the characteristics of the photoresist composition. For this reason, after completion of the condensation polymerization reaction, it is preferable to neutralize the acid catalyst in the reaction mixture using an amine or an inorganic alkali.

  The reaction temperature of the condensation polymerization reaction is not particularly limited, but is preferably 60 to 160 ° C, more preferably 80 to 140 ° C. When the temperature is lower than 60 ° C., the polymerization is difficult to proceed, and when the temperature is higher than 160 ° C., it may be difficult to control the reaction, and it becomes difficult to stably obtain the desired novolak type phenol resin.

  In the condensation polymerization reaction, a reaction solvent can be used as necessary. As the reaction solvent, water that easily dissolves the phenol component and the crosslinking component is preferably used, but an organic solvent that does not adversely influence the reaction may be used in some cases. Examples of such organic solvents include ethers such as diethylene glycol dimethyl ether, 1,2-dimethoxyethane, and 1,2-diethoxyethane; esters such as propylene glycol monomethyl ether acetate; and cyclic ethers such as tetrahydrofuran and dioxane. Can be mentioned. The usage-amount of these reaction solvents is a ratio of 20-1000 mass parts normally with respect to 100 mass parts of reaction raw materials.

  The reaction time of the condensation polymerization reaction is usually within 20 hours, although it depends on the reaction temperature. The reaction pressure for the polycondensation reaction is usually carried out under normal pressure, but can also be carried out under slight pressure or reduced pressure.

  In the post-treatment after completion of the polycondensation reaction, it is preferable to add a base to the reaction mixture to neutralize the acid catalyst, and then add water to remove the acid catalyst and perform washing with water.

  The base for neutralizing the acid catalyst is not particularly limited, and any base that neutralizes the acid catalyst and forms a salt that is soluble in water can be used. Examples of the base include inorganic bases such as metal hydroxides and metal carbonates, and organic bases such as amines and organic amines. Specific examples of the inorganic base include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, and calcium carbonate. Specific examples of organic base amines or organic amines include ammonia, trimethylamine, triethylamine, diethylamine, and tributylamine. Preferably organic amines are used. It is preferable to use the base in such an amount that the acid catalyst is neutralized and the pH in the reaction system is in the range of 4-8.

  The amount of washing water and the number of washings are not particularly limited. In order to remove the acid catalyst to an amount that does not affect the actual use as a resist composition, the number of washings is about 1 to 5 times.

  The temperature of washing with water is not particularly limited, but it is preferably 40 to 95 ° C. from the viewpoint of catalyst removal efficiency and workability. When the resin and the washing water are poorly separated during washing with water, it is effective to add a solvent that lowers the viscosity of the resin and raise the washing temperature. Such a solvent can be used without particular limitation as long as it dissolves the phenol resin and lowers the viscosity.

  After removing the acidic catalyst by neutralization and washing with water, for example, the temperature of the reaction system is raised to 130 to 230 ° C., and the volatilization of unreacted raw materials, organic solvents, etc. present in the reaction system under a reduced pressure of 20 to 50 torr. The novolak type phenol resin according to the present invention can be obtained by distilling off the fraction.

  The weight average molecular weight of the novolak type phenol resin according to the present invention is not particularly limited. Usually, it is about 300 to 100,000. When using it for a photoresist composition, 1000-100,000 are preferable, 3000-50000 are more preferable, and 5000-10000 are still more preferable from the performance and handling property of a photoresist composition. When the weight average molecular weight is less than 1000, the sensitivity may be too high, and when it is greater than 100,000, the sensitivity may be low.

  The novolak-type phenol resin according to the present invention can be used in various fields in the same manner as ordinary novolak-type phenol resins.

  For example, when used as a curing agent for an epoxy resin, it can be mixed with an epoxy resin according to a known method to obtain an epoxy resin composition. This epoxy resin composition can be suitably used as an insulating protective film for electronic parts, an interlayer insulating material, a sealing material, a conductive paste, an adhesive, a binder for composite materials, and the like.

  Further, the novolak type phenolic resin according to the present invention is obtained by epoxidizing by a known method to obtain an epoxidized novolac type phenolic resin, and mixing the epoxidized novolac type phenolic resin and the phenolic resin to obtain an epoxy resin. A composition can be obtained.

  As an example of epoxidation, the novolak-type phenol resin according to the present invention is subjected to glycidyl etherification reaction at 10 to 120 ° C. in the presence of epihalohydrin and a known method, for example, epichlorohydrin and an alkali metal hydroxide such as sodium hydroxide. Depending on the method, an epoxidized novolac-type phenol resin can be obtained.

  This epoxidized novolac type phenol resin is also mixed with, for example, an amine-based curing agent, an amide-based curing agent, a dianhydride-based curing agent, or a novolac-type phenol resin-based curing agent according to a known method to obtain an epoxy resin composition. , And can be suitably used for the same applications as described above.

  These epoxy resin compositions contain a curing accelerator such as triphenylphosphine, if necessary, and further, ordinary epoxy resins such as inorganic fillers, mold release agents, colorants, coupling agents, flame retardants, etc. The additive which a composition contains can be contained suitably. Moreover, these epoxy resin compositions can raise | generate a hardening reaction by heat-processing, and can form hardened | cured material.

  The novolak-type phenolic resin according to the present invention can be suitably used for a photoresist composition that exhibits particularly high flexibility and has both high resolution and a high residual film ratio.

  The photoresist composition according to the present invention includes, but is not limited to, the novolac type phenol resin (A) according to the present invention, preferably 5 to 40% by weight, more preferably 10 to 25% by weight. The resist composition according to the present invention further contains a photosensitizer (B). As the photosensitizer (B), known photosensitizers for photoresists containing novolak-type phenolic resins can be used. For example, a quinonediazide compound having a quinonediazide group is preferable, and a 1,2-quinonediazide compound or a derivative thereof is particularly preferable. By using a quinonediazide compound, the exposed portion has a higher alkali dissolution rate due to the dissolution promoting effect, and conversely, the non-exposed portion has a lower alkali dissolution rate due to the dissolution inhibiting effect. Due to the difference, a sharp resist pattern with high contrast can be obtained.

  As the quinonediazide compound, known compounds conventionally used in quinonediazide-novolak photoresist compositions can be used. Examples of the compound containing a quinonediazide group include compounds obtained by reacting naphthoquinonediazidesulfonic acid chloride, benzoquinonediazidesulfonic acid chloride, and the like with a compound having a functional group capable of undergoing a condensation reaction with these acid chlorides. preferable. Here, examples of the functional group capable of condensing with an acid chloride include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferred. Examples of the compound having a hydroxyl group capable of condensing with acid chloride include hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4 '-Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2 ', 3,4,6'-pentahydroxybenzophenone, etc. Hydroxyphenyl alkanes such as hydroxybenzophenones, bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane, 4,4 ′ , 3 ", 4" -tetrahydroxy-3,5,3 ', Hydroxytriphenylmethanes such as' -tetramethyltriphenylmethane, 4,4 ', 2 ", 3", 4 "-pentahydroxy-3,5,3', 5'-tetramethyltriphenylmethane These may be used alone or in combination of two or more.

  Specific examples of naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride that are acid chlorides include, for example, 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, and the like. As mentioned.

  The blending amount of the photosensitive agent (B) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the novolac type phenol resin (A). When the blending amount of the photosensitizer (B) is less than 5 parts by mass, sufficient sensitivity as a photosensitive tree composition may not be obtained, and when it exceeds 50 parts by mass, a problem of precipitation of components occurs. This is not preferable.

  The resist composition according to the present invention includes, in addition to the novolak-type phenol resin (A) and the photosensitive agent (B), a stabilizer such as an antioxidant, a plasticizer, and a surfactant, which are conventional components of a photoresist composition. An adhesion improver, a dissolution accelerator, a dissolution inhibitor and the like can be suitably contained.

  The photoresist composition using the novolac-type phenolic resin according to the present invention can be formed into a dry film, and is a lithography process for producing a highly integrated semiconductor, a thin film transistor (TFT) for liquid crystal, a flexible display, and It can be suitably used in a fine processing step such as a flexible printed wiring board.

  When the novolak type phenolic resin according to the present invention is used in a photoresist composition, the weight average molecular weight of the novolac type phenolic resin is preferably 1000 or more and 100,000 or less, more preferably 3000 or more and 50000 or less, More preferably, it is 5000 or more and 10,000 or less.

Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples.
The analysis method of novolac type phenol resin and the evaluation method of the physical properties are as follows.

≪ (1) Weight average molecular weight (GPC measurement method) ≫
Model: HLC-8220 Tosoh Co., Ltd. column: TSK-GEL H type G2000H × L 4 G3000H × L 1 G4000H × L 1 Measurement condition: Column pressure 13.5 MPa
Eluent: Tetrahydrofuran (THF) flow rate 1 ml / min
Temperature: 40 ° C
Detector: Spectrophotometer (UV-8020) RANGE 2.56
WAVE LENGTH: 254nm and RI
Injection volume: 100 μmL
Sample concentration: 5 mg / mL

≪ (2) Evaluation method of alkali dissolution rate of novolac type phenol resin≫
3 g of novolak type phenol resin was dissolved in 9 g of PGMEA (propylene glycol monomethyl ether acetate) to prepare a resin solution. These were filtered through a 0.2 micron membrane filter. This was coated on a 4 inch silicon wafer with a spin coater to a thickness of about 1.5 μm, and dried on a hot plate at 110 ° C. for 60 seconds. Next, using a developing solution (1.60% tetramethylammonium hydroxide aqueous solution), the time until the film completely disappeared was measured. The value obtained by dividing the initial film thickness by the time until dissolution was taken as the dissolution rate.

  A method for preparing a photoresist composition (photosensitive composition), a method for evaluating the photosensitizer solubility, coatability, flexibility, remaining film ratio (%), and resolution of the obtained composition are as follows.

≪ (3) Preparation of photoresist composition≫
10 g of novolac-type phenol resin and 2.5 g of 2,3,4,4′-tetrahydroxybenzophenone ester of naphthoquinone 1,2-diazide-5-sulfonic acid are dissolved in 37.5 g of PGMEA (propylene glycol monomethyl ether acetate). A photoresist composition was obtained.

≪ (4) Photoresist composition flexibility evaluation≫
The obtained novolac-type phenol resin was dissolved in PGMEA (propylene glycol monomethyl ether acetate) to prepare a resin solution. These were filtered through a 0.2 micron membrane filter. This was applied on a polyimide film having a thickness of 50 μm so as to have a thickness of about 5.0 μm, and dried on a hot plate at 110 ° C. for 90 seconds. After drying, the state of the resist surface was observed, and the applicability was evaluated based on the presence or absence of cissing.
Subsequently, it was immersed for 60 seconds using the developing solution (2.38% tetramethylammonium hydroxide aqueous solution). After rinsing and drying, bending was performed at 180 degrees, and the state of the bent portion was observed and evaluated visually and under a microscope (1000 times) according to the following criteria.
○: There is no crack in the resist film by microscopic observation.
Δ: The resist film is not cracked by visual observation, but the resist film is cracked by microscopic observation (practical use as a flexible photoresist composition is difficult).
X: The resist film is cracked by visual observation.

≪ (5) Evaluation method of remaining film ratio and resolution of photoresist composition≫
The photoresist composition is filtered through a 0.2 micron membrane filter, which is coated on a 4 inch silicon wafer with a spin coater to a thickness of about 1.5 μm, and dried on a hot plate at 110 ° C. for 60 seconds. I let you. Thereafter, exposure was performed using a reduced projection exposure apparatus while changing the exposure time stepwise. Next, using a developer (2.38% tetramethylammonium hydroxide aqueous solution), development was performed for 60 seconds, followed by rinsing and drying. The remaining film ratio is a ratio between the film thickness of the photosensitive resin after development and the film thickness of the photosensitive resin before development, and is a value represented by the following formula.
Residual film ratio (%) = (photosensitive resin film thickness after development / photosensitive resin film thickness before development) × 100
The resolution was evaluated according to the following criteria using a test chart mask.
○: 4.0 μ line & space can be resolved.
X: 4.0 μ line & space cannot be resolved.

[Example 1]
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, 27 g (0.12 mol) of bisphenol A, 3 g (0.02 mol) of pyrogallol, 4,4′-bis (methoxymethyl) biphenyl (hereinafter, (It may be abbreviated as 4,4′-BMMB.) 13.77 g (0.06 mol) and 0.15 g of catalyst paratoluenesulfonic acid were added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.15 g of triethylamine was added, 33 g of ion-exchanged water was added, stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 150 ° C. and dehydrated, followed by distillation under reduced pressure at 30 torr for 1 hour to remove moisture and the like, thereby obtaining 32 g of a novolac type phenol resin.

[Example 2]
In a glass three-necked flask equipped with a thermometer, a charging / discharging outlet and a stirrer, 21 g (0.09 mol) of bisphenol A, 9 g (0.07 mol) of pyrogallol, 19.79 g (0.08 mol) of 4,4′-BMMB And 0.15 g of paratoluenesulfonic acid as a catalyst were added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.15 g of triethylamine was added, 33 g of ion-exchanged water was added, stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 150 ° C. and dehydration was performed, followed by distillation under reduced pressure at 30 torr for 1 hour to remove moisture and the like, thereby obtaining 28 g of a novolac type phenol resin.

Example 3
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, bisphenol A 15 g (0.07 mol), pyrogallol 15 g (0.12 mol), 4,4′-BMMB 35.79 g (0.15 mol) And 0.15 g of paratoluenesulfonic acid as a catalyst were added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.15 g of triethylamine was added, 33 g of ion-exchanged water was added, stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Then, after heating up to 150 degreeC and dehydrating, it distilled under reduced pressure at 30 torr for 1 hour, the water | moisture content etc. were removed, and 35g of novolak-type phenol resins were obtained.

Example 4
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet, and a stirrer, bisphenol A 9 g (0.04 mol), pyrogallol 21 g (0.17 mol), 4,4′-BMMB 49.9 g (0.21 mol) And 0.15 g of paratoluenesulfonic acid as a catalyst were added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.15 g of triethylamine was added, 33 g of ion-exchanged water was added, stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 150 ° C. and dehydration was performed, followed by distillation under reduced pressure at 30 torr for 1 hour to remove moisture and the like, and 48 g of a novolac type phenol resin was obtained.

Example 5
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, bisphenol A 3 g (0.01 mol), pyrogallol 27 g (0.21 mol), 4,4′-BMMB 55.06 g (0.23 mol) And 0.15 g of paratoluenesulfonic acid as a catalyst were added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.15 g of triethylamine was added, 33 g of ion-exchanged water was added, stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 150 ° C. and dehydration was performed, followed by distillation under reduced pressure at 30 torr for 1 hour to remove moisture and the like, thereby obtaining 46 g of a novolac type phenol resin.

[Comparative Example 1]
To a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, 80 g (0.740 mol) of m-cresol, 120 g (1.110 mol) of p-cresol, 81.3 g of 42% formalin (1.137) Mol) and 0.8 g of oxalic acid were added and reacted at 100 ° C. for 10 hours. Thereafter, the temperature was raised to 180 ° C. for dehydration, followed by distillation under reduced pressure at 30 torr for 2 hours to obtain 150 g of a novolac type phenol resin.

[Comparative Example 2]
Bisphenol A (217 g, 0.951 mol), 42% formalin (50.6 g, 0.708 mol), and oxalic acid (1.0 g) were placed in a glass three-necked flask equipped with a thermometer, a charging / distilling outlet, and a stirrer. For 10 hours. Thereafter, the temperature was raised to 180 ° C. for dehydration, and then vacuum distillation was performed at 30 torr for 2 hours to obtain 180 g of a novolac type phenol resin.

[Comparative Example 3]
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, 30 g (0.13 mol) of bisphenol A, 12.74 g (0.05 mol) of 4,4′-BMMB, and paratoluenesulfonic acid 0 as a catalyst .15 g was added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.15 g of triethylamine was added, 33 g of ion-exchanged water was added, stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 150 ° C. and dehydrated, followed by distillation under reduced pressure at 30 torr for 1 hour to remove moisture and the like, to obtain 27 g of a novolac type phenol resin.

[Comparative Example 4]
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, pyrogallol 30 g (0.24 mol), 4,4′-BMMB 38.62 g (0.16 mol), and catalyst paratoluenesulfonic acid 0 .15 g was added and reacted at 100 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.15 g of triethylamine was added, 33 g of ion-exchanged water was added, stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 150 ° C. and dehydration was performed, followed by distillation under reduced pressure at 30 torr for 1 hour to remove moisture and the like, thereby obtaining 28 g of a novolac type phenol resin.

[Comparative Example 5]
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, m-cresol 100 g (0.925 mol), 50% glutaraldehyde aqueous solution 42.6 g (0.213 mol), and paratoluenesulfonic acid 0 .2 g was added and reacted at 96 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.2 g of triethylamine was added, 100 g of ion-exchanged water was added, and the mixture was stirred and allowed to stand. The pH of the aqueous layer separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 185 ° C. for dehydration, and then vacuum distillation was performed at 30 torr for 2 hours to obtain 82 g of a novolac type phenol resin.

[Comparative Example 6]
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, 50 g (0.462 mol) of m-cresol, 50 g (0.462 mol) of p-cresol, 37.0 g of 50% aqueous glutaraldehyde solution (0 .185 mol) and 0.2 g of p-toluenesulfonic acid were added and reacted at 96 ° C. for 20 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.2 g of triethylamine was added, 100 g of ion-exchanged water was added, and the mixture was stirred and allowed to stand. The pH of the aqueous layer separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Then, after heating up to 185 degreeC and dehydrating, it distilled under reduced pressure at 30 torr for 2 hours, and obtained 64 g of novolak-type phenol resins which concern on the comparative example 4.

[Comparative Example 7]
In a glass three-necked flask equipped with a thermometer, a charging / distilling outlet and a stirrer, m-cresol 40 g (0.370 mol), p-cresol 60 g (0.555 mol), 50% glutaraldehyde aqueous solution 37.0 g (0 .185 mol) and 0.2 g of p-toluenesulfonic acid were added and reacted at 96 ° C. for 20 hours. Thereafter, 13.2 g (0.185 mol) of 42% aqueous formaldehyde solution was added to the reaction mixture, and further reacted at 96 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.2 g of triethylamine was added, 100 g of ion-exchanged water was added, and the mixture was stirred and allowed to stand. The pH of the aqueous layer separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 185 ° C. to dehydrate, and then vacuum distillation was performed at 30 torr for 2 hours to obtain 94 g of a novolak type phenol resin.

  For the novolak type phenol resins obtained in Examples 1 to 5 and Comparative Examples 1 to 7, the chemical composition, the molar ratio, the analytical evaluation results as the resin, the evaluation results as the photoresist composition are shown in the following table. The results are collectively shown in 1-2.

  The novolac type phenol resins of Examples 1 to 5 had improved flexibility. On the other hand, Comparative Example 1 which is a conventional general novolac type phenol resin was not flexible. Although the novolac type phenol resins of Comparative Examples 5 to 7 corresponding to the novolak type phenol resin of Patent Document 1 have improved flexibility, there is still room for improvement. In the evaluation as a photoresist composition, the novolak type phenol resins of Examples 1 to 5 are more flexible than the photoresist compositions prepared using the novolak type phenol resins obtained in Comparative Examples 1 to 7. In addition, the remaining film rate and resolution performance were well balanced. In particular, the novolac type phenol resin obtained in Example 2 has a weight average molecular weight in the particularly preferred range of 5000 to 10,000, and therefore the flexibility and resolution of the photoresist composition prepared using it are good. In addition, the characteristics as a photoresist were extremely excellent, such as a particularly good residual film ratio.

Claims (9)

A novolac-type phenol resin comprising a compound represented by the formula (1).

(In the formula (1), A is independently composed of a functional group represented by the following general formula (2-1) or general formula (2-2), and B is a functional group represented by the following general formula (3). And n is an integer from 0 to 100)

(In the formula (2-1), each of the substituents R1 is independently a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, or a phenyl group. X is a divalent group, each of which is independently a divalent group selected from the group consisting of an alkylene group, an ether group, a thioether group, and a carbonyl group.

(In Formula (3), Y represents a halogen atom, an alkoxy group, or a hydroxyl group.)   The mass ratio [(2-1) / (2-2)] of the formula (2-1) and the formula (2-2) contained in the compound represented by the formula (1) is 95/5 to 5 / The novolak type phenol resin according to claim 1, which is in the range of 95. A method for producing a novolac type phenol resin, comprising subjecting a phenol represented by formulas (4) and (5) and a compound represented by formula (6) to a condensation reaction.

(In Formula (4), each of the substituents R ¹ is independently a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, or a phenyl group. X is a divalent group, each of which is independently a divalent group selected from the group consisting of an alkylene group, an ether group, a thioether group, and a carbonyl group.)

(In Formula (6), Y represents a halogen atom, an alkoxy group, or a hydroxyl group.)   A photoresist composition comprising the novolak type phenolic resin according to claim 1.   5. The photoresist composition according to claim 4, wherein the novolac type phenol resin has a weight average molecular weight of 1,000 or more and less than 100,000.   An epoxidized novolac type phenolic resin obtained by epoxidizing the novolak type phenolic resin according to claim 1.   An epoxy resin composition comprising the novolac type phenolic resin according to claim 1 and an epoxy resin.   An epoxy resin composition comprising the epoxidized novolac-type phenolic resin according to claim 6 and a phenolic resin. A cured product obtained by curing the epoxy resin composition according to claim 7 or 8.