JP6831708B2 - Phenol resin and its manufacturing method - Google Patents

Description

The present invention relates to a novel phenol resin having a trisphenol skeleton [particularly a tris (hydroxyphenyl) methane skeleton] and having high heat resistance and solubility, and a method for producing the same.

In the field of semiconductors and the like, it is known that trisphenols can be used as modifiers and sensitizers for positive photoresist compositions from the viewpoint of improving the alkali solubility of resins. Such trisphenols can be produced by a condensation reaction between phenols and aldehydes. For example, Japanese Patent Application Laid-Open No. 2005-29504 (Patent Document 1) describes phenols and aromatic aldehydes as phosphorus. A method for producing a phenol derivative by causing a heterogeneous reaction at a predetermined ratio in the presence of acids is disclosed. In the examples of this document, 4,4'-[(2-hydroxyphenyl) methylene] bis [2,6-xylenol], 4,4'-[(2-hydroxyphenyl) methylene] bis [2,5- Xylenol] and other trisphenols have been synthesized. However, Patent Document 1 does not describe the preparation of phenolic resins using trisphenols.

Further, Japanese Patent Application Laid-Open No. 8-211600 (Patent Document 2) describes predetermined alkali-soluble polyphenols, alkali-soluble polyhydroxy compounds represented by the general formula (II), alkali-soluble novolak resins, and 1,2-quinonediazide compounds. A positive resist composition containing the above is disclosed.

(In the formula, R ₈ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R _{9 to} R ₁₁ independently represent an alkyl group having 1 to 6 carbon atoms and carbon. The numbers 1 to 6 represent an alkoxy group, a carboxyl group, or a halogen atom, and a to f each independently represent an integer of 0 to 3, but at least two of b, d, and f represent an integer of 1 to 3. ).

In this document, examples of the alkali-soluble novolak resin include resins using phenol represented by the following general formula as a polymerization component.

(In the formula, R _{13 to} R ₁₈ independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₁₉ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. It represents a group or a phenyl group, and x, y and z each independently represent an integer of 0 to 2, but x + y + z> 2).

In the examples of this document, 4,4'-[(2-hydroxyphenyl) methylene] bis [2,6-xylenol] is used as the alkali-soluble polyhydroxy compound represented by the general formula (II). However, as the alkali-soluble novolak resin, a novolak resin containing m-cresol and p-cresol as a polymerization component is used, and a novolak resin containing trisphenols as a polymerization component is not specifically described.

In WO 2012/14 1 165 No. (Patent Document 3), a positive photoresist composition containing a novolak type phenolic resin (B) at a predetermined ratio with respect to cresol novolak resin (A), the The novolak type phenol resin (B) has the following formula (1).

[In the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and X is the following formula (2).

(In the formula, R ¹ , R ² , and R ³ are independently hydrogen atoms and alkyl groups having 1 to 8 carbon atoms. M and n are independently integers of 1 to 4, and p. Is an integer of 0 to 4. t is 1 or 2), or is an aromatic hydrocarbon group (x2) other than the structure (x1). ]
Disclosed is a positive photoresist composition having a structural unit represented by (x1) as a repeating unit and having a content of the structure (x1) of 85% or more with respect to the total number of the structures (x1) and the structures (x2). There is. In Synthesis Examples 4 and 5 of this document, a novolak resin (B) containing trisphenols represented by the following formulas (2-1) and (3) as phenol components is synthesized, respectively.

However, novolak resins containing trisphenols having an o-phenol skeleton (a phenol skeleton in which an OH group is substituted at the o-position with respect to the bond position with the central carbon atom) as a phenol component have not been synthesized. Further, in the examples, as the sensitivity of the positive photoresist composition, the alkali dissolution rate of the coating film formed of the mixture of the cresol novolak resin (A) and the novolak resin (B) is described, but the novolak resin. (B) The solubility of a single substance in an organic solvent is not described.

Japanese Unexamined Patent Publication No. 2005-29504 (Claim 1, Examples, Paragraphs [0001] to [0003]) Japanese Unexamined Patent Publication No. 8-221600 (Claim 1, Examples, Paragraphs [0029] to [0031]) International Publication No. 2012/141165 (Claim 1, Synthesis Examples 4 and 5, Example 1)

Therefore, an object of the present invention is a novel phenol resin having high heat resistance, a high molecular weight, a large amount of benzene ring skeleton, high solvent solubility, and excellent handleability, and a method for producing the same. Is to provide.

As a result of diligent studies to achieve the above problems, the present inventors are expected to have high heat resistance of a phenol resin having a specific trisphenol skeleton, and further, a decrease in solubility at a high molecular weight. The present invention has been completed by finding that it exhibits surprisingly high solvent solubility despite having many benzene ring skeletons.

That is, the phenol resin of the present invention contains at least a phenol component containing phenols represented by the following formula (1) and an aldehyde component as polymerization components.

(In the formula, R ¹ indicates the same or different hydrocarbon group, n indicates the same or different 0 or 1).

In the formula (1), R ¹ may be an alkyl group. Further, the aldehyde component may be formaldehydes.

The phenol resin may be a novolak resin (or novolak type phenol resin) having a weight average molecular weight Mw of about 5,000 to 15,000. Further, the phenol resin may be soluble in propylene glycol monomethyl ether acetate at a concentration of 45% by weight.

The present invention also includes a method for producing the phenol resin by reacting at least a phenol component containing phenols represented by the formula (1) with an aldehyde component.

The novel phenol resin of the present invention not only exhibits high heat resistance, but also exhibits high solvent solubility even if it has many benzene ring skeletons, so that it is excellent in handleability.

The novel phenol resin of the present invention comprises a phenol component containing at least the phenols represented by the formula (1) (simply referred to as the first phenols) and an aldehyde component as polymerization components.

[Phenol component]
(First phenols)
In the above formula (1), examples of the hydrocarbon group represented by the group R ¹ include an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group and t-butyl group. A linear or branched C _1-10 alkyl group such as a group, preferably a linear or branched C _1-6 alkyl group, more preferably a linear or branched C _1-4 alkyl group or the like. ); Cycloalkyl group (eg, C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group); aryl group [eg, phenyl group, alkylphenyl group (eg, methylphenyl group (trill group), dimethylphenyl group) (Xyryl group), etc.), C _6-12 aryl groups such as biphenylyl group, naphthyl group, etc.]; Aralkyl groups (eg, C _6-10 aryl-C _1-4 alkyl groups such as benzyl group, phenethyl group, etc.), etc. Can be mentioned.

Among these hydrocarbon groups, an alkyl group (for example, a linear or branched C _1-3 alkyl group) is preferable, and a C _1-2 alkyl group such as a methyl group is particularly preferable. The type of a plurality of groups R ¹ may be the same or different from each other.

The number of substitutions n may be either 0 or 1, and is preferably 0. Further, the plurality of substitution numbers n may be the same or different from each other.

Typical first phenols include, for example, bis (4-hydroxy-3,5-diC _1- ) such as bis (4-hydroxy-3,5-dimethylphenyl)-(2-hydroxyphenyl) methane. ₄ Alkyl-phenyl)-(2-Hydroxyphenyl) methane; Bis (4-hydroxy-3,5,5) such as bis (4-hydroxy-3,5-dimethylphenyl)-(2-hydroxy-4-methylphenyl) methane -Di-C _1-4 alkyl-phenyl)-(2-hydroxy-4-C _1-4 alkyl-phenyl) methane and the like can be mentioned.

These first phenols can be used alone or in combination of two or more. Among these first phenols, bis (4-hydroxy-3,5-diC _1-2 alkyl-) such as bis (4-hydroxy-3,5-dimethylphenyl)-(2-hydroxyphenyl) methane Phenyl)-(2-hydroxyphenyl) methane is preferred.

As these first phenols, commercially available products may be used, and conventional methods such as the method described in Patent Document 1 (for example, a method of reacting aromatic aldehydes and phenols under an acid catalyst) are used. It may be synthesized by a method.

(Second phenols)
The phenol component may contain at least the first phenols, and may contain other phenols (second phenols) other than the first phenols. Examples of the second phenols include monophenols {for example, phenol; alkylphenol [cresol (o-cresol, m-cresol, p-cresol), ethylphenol (2-ethylphenol, etc.), butylphenol, octylphenol, nonylphenol). , Xylenol (2,3-dimethylphenol, 2,4-dimethylphenol, etc.), mono or diC _1-6 alkylphenol such as 2-t-butyl-4-methylphenol], cycloalkylphenol (2-cyclohexylphenol, etc.) ), Arylphenol (such as o-phenylphenol), alkoxyphenol (such as anisole such as o-methoxyphenol), phenol having substituents such as aminophenol; naphthols [eg, naphthol (1-naphthol, 2-naphthol) ), Alkyl naphthol (C _1-4 alkyl naphthol such as methyl naphthol, ethyl naphthol, dimethyl naphthol, etc.)] etc.}; Phenols having multiple phenolic hydroxyl groups {for example, dihydroxybenzene (catechol, resorcinol, hydroquinone), Alkyl-dihydroxybenzene (mono such as dihydroxytoluene, dihydroxyxylene or diC _1-6 alkyl-dihydroxybenzene, etc.), aryl-dihydroxybenzene (C _6-8 aryl-dihydroxybenzene, etc. such as 2,3-dihydroxybiphenyl), Polyphenols such as alkoxy-dihydroxybenzene (mono such as 3-methoxycatechol or diC _1-6 alkoxy-dihydroxybenzene), trihydroxybenzenes (pyrogalol, hydroxyhydroquinone, fluoroglusinol, etc.); bisphenols (bisphenols) Bisphenol A, Bisphenol F, Bisphenol S, etc.); Trisphenols other than Trisphenols represented by the above formula (1) [bis (4-hydroxy-3,5-dimethylphenyl)-(4-hydroxyphenyl) methane Etc.] etc.} etc.

These second phenols can also be used alone or in combination of two or more. The proportion of the first phenols in the phenol component is, for example, 50 mol% or more (for example, 70 to 100 mol%), preferably 80 mol% or more (90 to 99 mol%), and more preferably 95 mol%. As mentioned above, in particular, it may be 100 mol% (substantially only the first phenols).

[Aldehyde component]
Examples of the aldehyde component include formaldehydes [for example, formaldehyde; paraformaldehyde, cyclic formal compounds (eg, 1,3,5-trioxane, 1,3,5,7-tetraoxane, 1,3,5,7,9). -Multimers of formaldehyde such as pentaoxane]; aliphatic aldehydes (eg acetaldehyde, propionaldehyde, butylaldehyde, etc.); alicyclic aldehydes (eg cyclohexanecarboxyaldehyde, etc.); aromatic aldehydes (eg, cyclohexanecarboxyaldehyde, etc.) , Benzaldehyde, salicylaldehyde, p-hydroxybenzaldehyde, terephthalaldehyde, naphthoaldehyde, etc.) and the like.

These aldehyde components can be used alone or in combination of two or more. Of these aldehyde components, formaldehydes (eg, formaldehyde, paraformaldehyde, especially paraformaldehyde) are preferable. The aldehyde component may be in the form of an aqueous solution such as formalin.

[Manufacturing method and characteristics]
The phenol resin of the present invention can be produced by reacting (or polymerizing) a phenol component containing at least the first phenols with an aldehyde component in the presence of a catalyst. The phenolic resin of the present invention may be either novolak (novolak resin or novolak-type phenol resin) or resol (resole resin or resol-type phenol resin) depending on the type of catalyst [acid catalyst or base catalyst]. Often, novolak produced using an acid catalyst is preferable.

The ratio of the phenol component and the aldehyde component is not particularly limited, and can be selected from the range of, for example, the former / the latter (molar ratio) = 1 / 0.5 to 1/10, for example, 1 / 0.8 to 1. / 7, preferably about 1 / 0.9 to 1/5, more preferably about 1/1 to 1/3, and usually about 1/2 to 1/4.

The acid catalyst is not particularly limited, and is an inorganic acid [for example, protonic acid (sulfuric acid, hydrogen chloride (or hydrochloric acid), phosphoric acid, etc.); Lewis acid (boron trifluoride, aluminum chloride, zinc chloride, etc.)]; Organic acids {eg, sulfonic acids (alcan sulfonic acids such as methanesulfonic acid, allene sulfonic acids such as p-toluenesulfonic acid); carboxylic acids [eg, aliphatic carboxylic acids (eg, aliphatics such as acetic acid, oxalic acid) Mono or dicarboxylic acid, etc.)] etc.}.

These acid catalysts may be used alone or in combination of two or more. Of these acid catalysts, inorganic acids such as hydrochloric acid are preferable. The amount of the catalyst used is not particularly limited, and may be about 1 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably about 10 to 30 parts by weight with respect to 100 parts by weight of the phenol component.

The reaction may be carried out in the presence or absence of a solvent. When a solvent is used, the type thereof is not particularly limited as long as it is inert to the reaction, and for example, water; alcohols (alkyl alcohols such as methanol, ethanol, isopropanol and butanol; alicyclic alcohols such as cyclohexanol, etc. ); Ethers (dialkyl ethers such as diisopropyl ether; cyclic ethers such as tetrahydrofuran); glycol ethers (cellosolves such as ethylene glycol monomethyl ether); glycol ether acetates (methylcellosolve acetate etc.); ketones (acetones) , Methyl ethyl ketone, methyl isobutyl ketone, chain ketone such as diisopropyl ketone; cyclic ketone such as cyclohexanone; esters (ethyl acetate, etc.); nitriles (acetritale, etc.); amides (dimethylformamide, etc.); sulfoxides (dimethyl, etc.) Sulfoxide, etc.); Hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), etc.] and the like.

These solvents may be used alone or in combination of two or more. Of these solvents, ketones (such as chain ketones such as methyl isobutyl ketone) are often used. The amount of the solvent used is not particularly limited, and usually, an amount that can homogenize the reaction system may be used.

The reaction temperature may be, for example, 0 to 150 ° C., preferably 20 to 120 ° C., more preferably 50 to 110 ° C. (for example, 80 to 100 ° C.). The reaction time is not particularly limited, and may be, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, and more preferably 3 to 12 hours.

The reaction may be carried out with stirring, in air or in an inert atmosphere (nitrogen, rare gas, etc.), or under normal pressure or pressure. Further, the reaction may be carried out under reflux of the solvent.

The reaction mixture after completion of the reaction contains a solvent, a catalyst (acid catalyst, etc.), an unreacted component, and the like, in addition to the phenol resin. Therefore, the phenolic resin may be separated and purified by a conventional method, for example, a separation or purification means such as filtration, concentration, extraction, washing, neutralization, reprecipitation, column chromatography, or a method combining these. ..

The phenolic resin of the present invention (for example, novolak resin) has a relatively high molecular weight, and the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is, for example, 1000 to 50,000 (for example, in terms of standard polystyrene). For example, it may be about 2000 to 30000), preferably 2000 to 20000 (for example, 5000 to 15000), and more preferably about 70000 to 12000. The molecular weight distribution Mw / Mn may be, for example, 1.1 to 10, preferably 1.5 to 5, and more preferably about 2 to 3. The weight average molecular weight Mw and the molecular weight distribution Mw / Mn can be measured by the methods described in Examples described later.

Although it is difficult to analyze the novolak resin, as is clear from the literature "Novolak formation and decomposition reaction polymer Vol.14, No. 161 p.650-658", the o-position of the phenolic hydroxyl group and The polymerization proceeds by the addition reaction of the aldehyde component and the condensation reaction of the functional group (methylol group or the like) derived from the aldehyde component generated by the addition reaction with respect to the substitution position at the p-position and which is not substituted. Therefore, the phenol resin has a structural unit represented by the following formula (2).

(In the formula, R ² is a hydrogen atom or a hydrocarbon group, and R ¹ and n are the same as those in the above formula (1), respectively).

In the formula (2), the group R ² is a hydrogen atom or a hydrocarbon group corresponding to the above-exemplified aldehyde component. Examples of the hydrocarbon group include an alkyl group (linear or branched C _1-6 alkyl group such as methyl group and ethyl group); cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group) and the like. ); Aryl group [eg, phenyl group, alkylphenyl group (eg, methylphenyl group (trill group), dimethylphenyl group (xylyl group), etc.), biphenylyl group, naphthyl group, etc. _C6-12 aryl group, etc.]; Examples thereof include an aralkyl group (for example, a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group). The group R ² is preferably a hydrogen atom.

Further, the phenol resin of the present invention has excellent heat resistance. Further, the phenolic resin of the present invention has a surprisingly high solvent solubility and is easy to handle, even though it has a high molecular weight and contains a large amount of a benzene ring skeleton that is expected to decrease in solubility. Are better. Therefore, the phenol resin of the present invention can be easily dissolved in a general-purpose organic solvent such as glycol ether acetates (propylene glycol monomethyl ether acetate, etc.). Further, the solution (for example, propylene glycol monomethyl ether acetate solution) can be adjusted to a relatively high concentration, for example, 5% by weight or more (10 to 70% by weight), preferably 20% by weight or more (30 to 60% by weight). %), More preferably 35% by weight or more (40 to 50% by weight, particularly 45% by weight).

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The raw materials used and the evaluation method are shown below.

[material]
Bis (4-hydroxy-3,5-dimethylphenyl)-(2-hydroxyphenyl) methane: Synthesized according to Comparative Example 1 of Patent Document 1.

[Evaluation methods]
(Weight average molecular weight Mw, molecular weight distribution Mw / Mn)
Using gel permeation chromatography (GPC) (HLC-8120GPC, manufactured by Toso Co., Ltd.), the sample was dissolved in tetrahydrofuran (THF), and the sample was converted to polystyrene at a temperature of 30 ° C. (flow rate 1.00 mL / min). The weight average molecular weight Mw and its molecular weight distribution Mw / Mn were measured.

(Soluble solubility)
Propylene glycol monomethyl ether acetate (PGMEA) was added to the sample so as to have a concentration of 45% by weight, and the solubility of the sample was visually confirmed and evaluated according to the following criteria.

◯: Completely dissolved ×: Part or all remains without being dissolved.

(Remaining heating)
The mixed solution prepared for the evaluation of solvent solubility was measured by heating with a halogen moisture meter manufactured by METTLER TOLEDO Co., Ltd. at a setting of 200 ° C.

[Example 1]
In a 500 mL three-necked flask, 34.8 g (0.1 mol) of bis (4-hydroxy-3,5-dimethylphenyl)-(2-hydroxyphenyl) methane, 9.0 g of paraformaldehyde (0.3 mol in terms of formaldehyde), 35 7.0 g of mass% hydrochloric acid (0.07 mol in terms of hydrogen chloride) and 108 g of methyl isobutyl ketone (MIBK) were added. After raising the temperature to 90 ° C. and reacting for 6 hours, the obtained reaction solution was neutralized by washing with a 5 mass% aqueous sodium hydrogen carbonate solution three times, and it was confirmed that the pH was 7. Further, it was washed twice with distilled water and removed by concentrating MIBK under reduced pressure. As a result, a reddish brown viscous liquid was obtained with a yield of 82 g. The weight average molecular weight Mw of the obtained phenol resin (novolak resin) was 10327, the molecular weight distribution Mw / Mn was 2.47, the solvent solubility was ◯, and the heating residue was 45.3%.

Although it is difficult to analyze novolak resin, as is clear from the literature "Novolak formation and decomposition reaction polymer Vol.14, No. 161 p.650-658", the o-position or p-position of the phenol nucleus Since formaldehyde is added to the position or the methylol group is condensed to form novolak, the obtained phenol resin has a structural unit represented by the following formula (2a).

[Comparative Example 1]
When the solvent solubility of bis (4-hydroxy-3,5-dimethylphenyl)-(2-hydroxyphenyl) methane alone was confirmed, the evaluation result was x.

As is clear from the results of Examples and Comparative Examples, although the compound obtained in Examples has a large number of benzene ring skeletons, surprisingly, bis which is a polymerization component (monomer). It showed higher solvent solubility than (4-hydroxy-3,5-dimethylphenyl)-(2-hydroxyphenyl) methane. It also had high heat resistance.

Since the phenol resin of the present invention is excellent in solvent solubility and heat resistance, it can be used for various purposes as a form such as a resin composition containing the resin or a cured product obtained by curing the resin with a curing agent. it can. Typical applications include, for example, electrical / electronic parts (electrical parts, laminates for electrical insulation, IC sealants, etc.), mechanical parts (gears, bearings, sliding linings, disc brake pistons, etc.), building materials. (Roofing materials, interior / exterior wall panels, interior materials such as subway premises, interior partitioning materials, ceiling materials, heat insulating materials, air ducts, pipes, doors, etc.), adhesives or adhesives (for wood (plywood, particle board, fiber board, etc.) ), Space aircraft, automobiles, railroad vehicles, shoes, furniture, etc.), binders (molds and cores for metal casting, iron-making furnaces, etc.), paints (undercoat paints, corrosion-resistant paints, marine paints, etc.) , Food can inner paint, printing ink vehicle, etc.), photoresist material (resist resin, positive photoresist modifier (sensitizer, etc.), etc.), carbon material, epoxy resin raw material, resin curing Examples include agents.

Claims (6)

At least the following formula (1)

(In the formula, R ¹ represents the same or different hydrocarbon group, n represents the same or different 0 or 1), and a phenol resin containing a phenol component containing phenols and an aldehyde component as polymerization components. A phenolic resin containing the phenols represented by the formula (1) in a proportion of 50 mol% or more with respect to the phenol component . The phenolic resin according to claim ¹ , wherein in the formula (1), R ¹ is an alkyl group. The phenolic resin according to claim 1 or 2, wherein the aldehyde component is formaldehyde. The phenolic resin according to any one of claims 1 to 3, which is a novolak resin having a weight average molecular weight Mw of 5000 to 15000. Novolac resin comprising 45 wt% concentration in soluble in propylene glycol monomethyl ether acetate for one phenolic resin according to claims 1-4. The method for producing the phenol resin according to any one of claims 1 to 5 by reacting at least a phenol component containing a phenol represented by the formula (1) according to claim 1 or 2 with an aldehyde component.