Novolac resin, epoxy resin, photosensitive resin composition, curable resin composition, cured product, electronic device, method for producing novolac resin, method for producing epoxy resin, and method for producing active ester resin

Abstract

This novolac resin has a partial structure represented by -C(CF3)H-. This photosensitive resin composition contains the novolac resin and a photosensitizer. This epoxy resin has a partial structure represented by -C(CF3)H-. This curable resin composition contains the novolac resin or the epoxy resin. This cured product is obtained by curing the composition. In this method for producing a novolac resin, a novolac resin having a partial structure represented by -C(CF3)H- is produced by reacting an aromatic compound and fluoral in the presence of an acid catalyst. This method for producing an epoxy resin includes an epoxidation step in which a novolac resin having a partial structure represented by -C(CF3)H- is reacted in the presence of an epihalohydrin and a base.

Description

[Technical field]

[0001] The present invention relates to a novolac resin, an epoxy resin, a photosensitive resin composition, a curable resin composition, a cured product, an electronic device, a method for producing a novolac resin, and a method for producing an epoxy resin. [Background technology]

[0002] Fluorine-based resins are sometimes used for the manufacture of electronic devices. As an example, Patent Document 1 describes a composition for forming a resist upper layer film for lithography, which contains a fluorine-containing resin. As another example, Patent Document 2 describes a resin substrate for circuit boards that contains a polymer having fluorine atoms. As yet another example, Patent Document 3 describes a resist underlayer film material containing a fluorine-containing novolak resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6319582 [Patent Document 2] Patent No. 6206445 [Patent Document 3] Patent No. 6502885 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have carried out investigations with the aim of providing a fluorine-containing resin that can be preferably used in the production of electronic devices. [Means for solving the problem]

[0005] As a result of investigations, the present inventors have completed the following first and second inventions.

[0006] The first invention is as follows.

[0007] A novolac resin having a partial structure represented by --C(CF3)H--.

[0008] Further, according to the present invention, A photosensitive resin composition comprising the novolac resin and a photosensitizer. is provided.

[0009] The second invention is as follows.

[0010] An epoxy resin having a partial structure represented by --C(CF3)H--.

[0011] Further, according to the present invention, A curable resin composition containing at least one of the novolac resin of the first invention and the epoxy resin of the second invention. is provided.

[0012] Further, according to the present invention, A cured product obtained by curing the above curable resin composition. is provided.

[0013] Further, according to the present invention, Electronic device comprising the above cured product is provided.

[0014] Further, according to the present invention, A method for producing a novolak resin, comprising reacting an aromatic compound with fluoral in the presence of an acid catalyst to produce a novolak resin having a partial structure represented by --C(CF3)H--. is provided.

[0015] Further, according to the present invention, A method for producing an epoxy resin is provided, which includes an epoxidation step of reacting a novolak resin having a partial structure represented by —C(CF3)H— with epihalohydrin in the presence of a base.

[0016] According to the present invention, there is provided a fluorine-containing resin that can be preferably used in the production of electronic devices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Hereinafter, an embodiment of the present invention will be described in detail.

[0018] In this specification, unless otherwise specified, the expression "X to Y" in the explanation of a numerical range means from X to Y. For example, "1 to 5% by mass" means "from 1% by mass to 5% by mass".

[0019] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In this specification, the term "organic group" means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound. In the chemical formulas herein, the designation "Me" represents a methyl group (CH3). As used herein, the term "fluoral" means trifluoroacetaldehyde. The term "novolac resin" in this specification includes not only those made from phenolic compounds in which a hydroxyl group is substituted on a monocyclic aromatic ring such as phenol or cresol, but also those made from phenolic compounds in which a hydroxyl group is substituted on a polycyclic aromatic ring such as hydroxynaphthalene. In addition, the term "novolac resin" in this specification includes not only those made from a reaction between a phenolic compound and formaldehyde, but also those made from a reaction between a phenolic compound and various aldehydes (specifically, fluoral, etc.). In addition, in this specification, some or all of the hydrogen atoms of the phenolic hydroxyl groups in the novolac resin may be substituted with groups other than hydrogen atoms. That is, in this specification, the term "novolac resin" may include those that do not have a phenolic hydroxyl group. The term "electronic device" in this specification is used to encompass elements, devices, final products, etc. to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuits, display devices, information and communication terminals, light-emitting diodes, physical batteries, and chemical batteries.

[0020] In this specification, an embodiment of the first invention may be referred to as the first embodiment, and an embodiment of the second invention may be referred to as the second embodiment.

[0021] The novolac resin of the first invention and the epoxy resin of the second invention have in common the fact that they have a partial structure represented by aromatic ring-C(CF3)H-aromatic ring. The presence of such a partial structure improves the transparency of light (g-ray, i-ray, h-ray, etc.) that is often used in the manufacture of electronic devices, and improves solubility in alkaline developing solutions.

[0022] <<First embodiment>> <Novolac resin> The novolac resin of the first embodiment has a partial structure represented by —C(CF3)H—.

[0023] The novolac resin of the first embodiment, for example, has good transmittance to light (g-ray, i-ray, h-ray, etc.) that is often used in the manufacture of electronic devices. This is believed to be because the novolac resin of the first embodiment contains fluorine atoms that are electron-withdrawing (it is believed to be because the C-F bond is less likely to absorb light such as g-ray, i-ray, and h-ray than the C-H bond).

[0024] As another example, the novolac resin of the first embodiment has good solubility in an alkaline developer that is often used in the manufacture of electronic devices, even though it contains fluorine atoms that generally exhibit hydrophobicity (hereinafter, solubility in an alkaline developer will also be referred to simply as "alkali solubility"). Although the mechanism is unclear, it is believed that the novolac resin of the first embodiment has an asymmetric structure of -C(CF3)H-, and therefore the high electron-withdrawing properties of the fluorine atoms and the bent polymer structure contribute greatly. It is presumed that this is related to the good alkaline solubility.

[0025] Furthermore, having fluorine atoms in the structural unit also brings about an advantage in imprinting applications. A property required of a general imprinting resin is expected to be low adhesion to a metal mold. In the first embodiment, having fluorine atoms in the structural unit can reduce adhesion to the mold.

[0026] The novolac resin of the first embodiment will be described below.

[0027] The novolac resin of the first embodiment preferably has a structural unit represented by the following general formula (1): In particular, when n=0 in general formula (1), the above-mentioned light transmittance is excellent.

[0028] [ka]

[0029] In general formula (1), R 1represents a hydrogen atom or a monovalent organic group, R 1 When multiple are present, they may be the same or different, R 2 represents a monovalent substituent, R 2 When multiple are present, they may be the same or different, n is 0 to 2; p is 1 or more, and q is 0 or more, with the proviso that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8.

[0030] (Description of General Formula (1)) R 1 When is a monovalent organic group, examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cyano group, etc. Any carbon atom of these groups may be substituted with any number and combination of substituents such as halogen atoms, alkoxy groups, and haloalkoxy groups. R 1 When is a monovalent organic group, the monovalent organic group has, for example, 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. R 1 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, among which n-butyl, s-butyl, isobutyl, t-butyl, n-propyl, i-propyl, ethyl and methyl groups are preferred, and ethyl and methyl groups are particularly preferred. From the viewpoint of alkali solubility, R 1 is preferably a hydrogen atom (when p is 2 or more, at least one R 1 is preferably a hydrogen atom).

[0031] R 2Examples of the monovalent substituent include an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, an aryloxy group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a silyl group, and a halogeno group (e.g., a fluoro group), etc. These groups may further have a substituent such as a fluorine atom or a carboxyl group. R 2 As R, an alkyl group, an alkoxy group, a fluorinated alkyl group (e.g., a trifluoromethyl group), a halogeno group (e.g., a fluoro group) and a nitro group are preferred. 2 As the alkyl group, an alkyl group is preferable. Specific examples of the alkyl group include R 1 Examples of the alkyl group in the above formula include the same alkyl groups as those mentioned above.

[0032] n may be any value from 0 to 2, but is preferably n = 0. For example, from the viewpoint of the transparency of light (g-line, i-line, h-line, etc.) that is often used in the manufacture of electronic devices, n = 0 to 1 is preferable. When considering electronic devices in a broad sense, for example, in the case of an underlayer film, n = 1 may be preferable from the viewpoint of heat resistance.

[0033] p is 1 or more, and q is 0 or more, except that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8. As stated above, n is preferably 0. From the viewpoint of ease of preparation of raw materials and cost, p is preferably 1. From the viewpoint of ease of preparation of raw materials and costs, q is preferably 0 to 2, more preferably 0 to 1, and further preferably 0.

[0034] Preferred embodiments of the structural unit of the novolak resin having a partial structure represented by —C(CF3)H— include structural units represented by the following general formulas (8) to (11).

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] In the above general formulas (8) to (11), R 1 represents a hydrogen atom or a monovalent organic group, R 1 When multiple are present, they may be the same or different, R 2 represents a monovalent substituent, R 2 When multiple are present, they may be the same or different, R 1 and R 2 Examples of the formula include R 1 and R 2 This is similar to the example in l and m each independently represent 0 to 3; R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, which may be further substituted with a fluorine atom; R 3 may be linked to form a saturated or unsaturated, monocyclic or polycyclic cyclic group having 3 to 10 carbon atoms, R 3 When multiple are present, they may be the same or different.

[0040] In addition, the above R 1It is preferable that the polymerizable carbon-carbon double bond contains a polymerizable carbon-carbon double bond, because the polymerizable carbon-carbon double bonds are bonded to each other by radical polymerization to form a crosslinked structure between molecular chains, thereby increasing the curability by light or heat.

[0041] In addition, the above R 1 is more preferably a partial structure represented by the following general formula (12).

[0042] [ka] In the above general formula (12), R 4 represents a hydrogen atom or a monovalent organic group, R 5 represents a hydrogen atom, a methyl group, or a fluorine atom. Having this partial structure is preferable from the viewpoint of synthesis.

[0043] In addition, the above R 1 is R in the partial structure represented by the above general formula (12). 4 It is more preferable that the monomer unit is a group having a carboxyl group at its terminal. The presence of a carboxyl group at the terminal has the effect of increasing developability.

[0044] Preferred embodiments of the partial structure represented by -C(CF3)H- include structural units represented by the following general formulas (13) to (15) and other structural units listed below. 1 ~R 5 The definitions of are the same as those of general formulas (8) to (12). Just to be clear, the novolac resin of the first embodiment may have two or more partial structures that are different from each other. For example, the novolac resin of the first embodiment may have two or more structural units selected from the structural units of the general formulae (13) to (15) shown below and other listed structural units. Of course, the novolac resin of the first embodiment may be composed of only one structural unit. Furthermore, the novolac resin of the first embodiment may contain a partial structure represented by —C(CF3)H— and a partial structure not represented by —C(CF3)H—.

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] Preferred embodiments of the structural unit represented by general formula (1) include structural units represented by the following formulae (2) to (6) and other listed structural units. In the listed structural units, the definitions of p and q are the same as those in general formula (1). Just to be clear, the novolac resin of the first embodiment corresponds to the general formula (1), but may have two or more structural units with different structures. For example, the novolac resin of the first embodiment may have two or more structural units selected from the structural units of the formulae (2) to (6) shown below and other listed structural units. Of course, the novolac resin of the first embodiment may be composed of only one structural unit. Moreover, the novolac resin of the first embodiment may contain a structural unit that fits the general formula (1) and a structural unit that does not fit the general formula (1).

[0049] [ka]

[0050] [ka]

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[0059] (molecular weight, dispersity) The weight-average molecular weight of the novolac resin of the first embodiment is preferably 300 to 200,000, more preferably 300 to 150,000, and further preferably 300 to 100,000. By adjusting the weight-average molecular weight, it is possible to adjust the alkali solubility, solvent solubility, and physical properties when formed into a film. In other words, by adjusting the weight-average molecular weight, it is possible to further increase the applicability of the novolac resin of the first embodiment to the manufacture of electronic devices. The polydispersity (weight average molecular weight / number average molecular weight) of the novolac resin of the first embodiment is preferably 1 to 20, more preferably 1 to 10. By setting the polydispersity within an appropriate numerical range, for example, a uniform film can be easily obtained, and the mechanical properties of the film can be improved. In addition, improvement in patterning performance using an alkaline developer can be expected. The weight average molecular weight and polydispersity can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0060] <Novolac resin manufacturing method (synthesis method)> The novolac resin of the first embodiment can typically be produced (synthesized) by reacting a phenolic compound with fluoral in the presence of an acid catalyst. The raw materials and reaction conditions are described below.

[0061] (Phenol compounds) Examples of the phenol-based compound include cresols such as phenol, o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; isopropylphenols such as o-isopropylphenol, m-isopropylphenol, and p-isopropylphenol; butylphenols such as o-butylphenol, m-butylphenol, p-butylphenol, p-isobutylphenol, and p-tert-butylphenol; alkylphenols such as p-tert-amylphenol, p-octylphenol, p-nonylphenol, and p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol; and monohydric phenol substituted compounds such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, and trinitrophenol. Further examples include polycyclic phenols such as 1-naphthol, 2-naphthol, and 2-hydroxyanthracene, and dihydroxybenzenes such as hydroquinone, resorcinol, and catechol. Further examples include bisphenols such as bisphenol A, bisphenol F, bisphenol E, bisphenol S, bisphenol AF, hydrogenated bisphenol A, bisphenol M, bisphenol P, and bisphenol Z.

[0062] (Fluoral) For the preparation of fluoral, a hydrate or a hemiacetal of fluoral, which is a commercially available product (Tokyo Chemical Industry Co., Ltd.), can be used as an equivalent. In addition, a hydrate or a hemiacetal of fluoral can be prepared by a method described in a document such as JP-A-5-97757.

[0063] In addition, as described in JP-A-3-184933, it is possible to convert chloral to fluoral almost quantitatively by catalytic gas-phase fluorination reaction of inexpensive chloral (trichloroethanal). By utilizing this, it is also possible to prepare anhydrous fluoral. In the examples described later, fluoral is obtained in this manner.

[0064] Fluoral is a low boiling point compound, and generally has high self-reactivity and is difficult to handle. However, according to the findings of the present inventors, fluoral can be handled very stably in hydrogen fluoride solution. When fluoral is handled in hydrogen fluoride, 1,2,2,2-tetrafluoroethanol, an adduct of fluoral and hydrogen fluoride, is produced as shown in the following scheme.

[0065] [ka]

[0066] Thus, 1,2,2,2-tetrafluoroethanol is in equilibrium with fluoral and hydrogen fluoride. When hydrogen fluoride is present in excess in the system, the equilibrium shifts toward 1,2,2,2-tetrafluoroethanol, and as a result, it is presumed that the decomposition of fluoral is suppressed. According to the findings of the present inventors, it has been confirmed that fluoral in hydrogen fluoride not only improves the stability of the compound, but also increases the boiling point, and fluoral, which is a low boiling point compound even at around room temperature, can be easily handled as an adduct of hydrogen fluoride.

[0067] When the prepared fluoral is handled as a mixture with hydrogen fluoride, the amount of hydrogen fluoride added is usually 0.1 to 100 mol, preferably 1 to 75 mol, and more preferably 2 to 50 mol, per mol of the prepared fluoral. The amount of hydrogen fluoride added is determined based on a sufficient stabilizing effect and cost. In addition, fluoral / hydrogen fluoride mixtures may contain excess hydrogen fluoride. However, hydrogen fluoride itself has the function of an acidic substance, so hydrogen fluoride may act as an acid catalyst or dehydrating agent, or as an additive to promote reactions. In these respects, it can be said that there are advantages to treating fluoral as a mixture with hydrogen fluoride.

[0068] (Novolac resin synthesis conditions) The synthesis may be carried out by referring to a conventional method for synthesizing novolak resins, using an acid catalyst, etc. The synthesis may be carried out, for example, under conditions of -20 to 150°C for 2 to 30 hours. The synthesis can be carried out under an absolute pressure of 0.1 to 10 MPa. The pressure is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa. Since a high pressure reaction vessel is required for the reaction at a high pressure, which increases the equipment cost, it is preferable to carry out the reaction at as low a pressure as possible. In the synthesis, a solvent may be used. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, alcohols such as ethanol and butanol, esters such as ethyl acetate and butyl acetate, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, diisopropyl ether, and tert-butyl methyl ether, ether alcohols such as ethoxyethyl alcohol, ether esters such as propylene glycol monomethyl ether acetate, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N,N-dimethylimidazolidinone, nitriles such as acetonitrile, propionitrile, and benzonitrile, sulfoxides such as dimethyl sulfoxide, cyclic sulfones such as sulfolane, nitro-based hydrocarbons such as nitromethane and nitroethane, and nitro-based aromatic hydrocarbons such as nitrobenzene. In particular, when fluoral is used as in the first embodiment, halogen-based solvents such as 1,2-dichloroethane, chloroform, methylene chloride, carbon tetrachloride, and trichloroethane are also preferably used.

[0069] The mixing ratio of phenolic compound:fluoral during synthesis is preferably 2:1 to 1:1, more preferably 1.8:1, and further preferably 1.5:1. By having the mixing ratio within the above range, fluorine atoms are efficiently introduced into the novolac resin, and alkali solubility and adhesion to a mold when used for imprinting can be made more suitable.

[0070] Catalysts that can be used in the synthesis include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid, and phosphoric acid, organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid, and p-toluenesulfonic acid, and divalent metal salts such as zinc acetate, zinc chloride, and magnesium acetate. These may be used alone or in combination of two or more. Incidentally, as mentioned above, when a mixture of fluoral / hydrogen fluoride is used, it is considered that hydrogen fluoride acts as an acid catalyst.

[0071] When an acid catalyst is used in the synthesis, the amount of the acid catalyst is preferably 0.01 to 100 mol, more preferably 0.1 to 30 mol, and further preferably 0.5 to 25 mol, per mol of fluoral. By setting the amount of the acid catalyst within the above range, fluorine atoms are efficiently introduced into the novolak resin, and the alkali solubility and adhesion to a mold when used for imprinting can be made more suitable.

[0072] (Other notes) It is preferable to remove unreacted substances and impurities from the obtained novolak resin by combining a precipitation treatment in which the resin is poured into a poor solvent (typically water), a washing treatment with water or sodium bicarbonate water, a liquid separation operation, etc. As for the specific method of these treatments, known methods in polymer synthesis can be appropriately referred to. The obtained novolac resin can be used as an epoxy resin by reacting it with epichlorohydrin, etc. The obtained epoxy resin can be used as an epoxy (meth)acrylate resin by reacting it with a carboxylic acid such as (meth)acrylic acid. Furthermore, the obtained epoxy (meth)acrylate resin can be used as an acid-modified epoxy (meth)acrylate resin by reacting it with an acid anhydride, etc. In this case, the acid anhydride to be reacted may be a compound having a polymerizable carbon-carbon bond.

[0073] The novolac resin of the present embodiment may be in a powder form. Also, the powder may be dissolved in any solvent to prepare a novolac resin solution.

[0074] <<Second embodiment>> <Epoxy resin> The epoxy resin of the second embodiment has a partial structure represented by —C(CF3)H—.

[0075] The epoxy resin of the second embodiment has, for example, good light transmittance. In particular, it has good transmittance for visible light and near ultraviolet light. This is believed to be because the epoxy resin structure contains fluorine atoms with high electronegativity, which shifts the absorption wavelength compared to normal fluorine-free epoxy resins. The fact that the visible light transmittance is good means that the epoxy resin of the second embodiment is preferably used, for example, as a raw material for optical members that require a high degree of transparency. The fact that the near-ultraviolet light transmittance is good means that, for example, the epoxy resin of the second embodiment can be preferably applied to a photosensitive resin composition used in the manufacture of an electronic device, because in the manufacture of an electronic device, the photosensitive resin composition is often cured or patterned by irradiating the photosensitive resin composition with near-ultraviolet light.

[0076] Moreover, it can be said that the epoxy resin of the second embodiment is prevented from being excessively rigidified, despite containing fluorine atoms. Generally, when fluorine is introduced into a resin, the resin tends to become rigid. Although the rigidification of the resin is desirable from the viewpoint of improving heat resistance, for example, excessive rigidification can lead to deterioration of other properties, such as deterioration of the mechanical properties of the resin and the cured film (tending to become brittle). However, the epoxy resin of the second embodiment is presumably due to the fact that it has a structure having only one CF3 group (-C(CF3)H-), rather than the structure having two CF3 groups (-C(CF3)2-) described in Patent Document 1, and therefore it is presumed that excessive rigidification of the resin can be suppressed while obtaining the effects of introducing fluorine atoms (good transparency, etc.). The degree of rigidification of the resin can be indicated, for example, by the glass transition temperature of the cured resin.

[0077] In addition, the epoxy resin of the second embodiment tends to have good solubility in various solvents (organic solvents). The reason for this is not necessarily clear, but it is presumed that the inclusion of fluorine atoms in the resin probably results in good affinity with various organic solvents. And / or, as described above, excessive rigidification of the resin is suppressed, which makes the resin more mobile, resulting in good solvent solubility.

[0078] Moreover, the epoxy resin of the second embodiment preferably has a structural unit represented by the following general formula (A): By having the structural unit, the above-mentioned light transmittance, suppression of excessive rigidification of the resin, and solubility can be made more suitable.

[0079] [ka]

[0080] In general formula (A), R1 represents a monovalent substituent, and when a plurality of R1 are present, they may be the same or different. n is 0 to 2; p is 1 or more, and q is 0 or more, with the proviso that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8.

[0081] The epoxy resin of the second embodiment will be described further.

[0082] (Explanation of General Formula (A)) Examples of the monovalent substituent of R1 include an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, an aryloxy group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a silyl group, and a halogeno group (e.g., a fluoro group), etc. These groups may further have a substituent such as a fluorine atom or a carboxyl group. As R1, an alkyl group, an alkoxy group, a fluorinated alkyl group (e.g., a trifluoromethyl group), a halogeno group (e.g., a fluoro group) and a nitro group are preferable. Among them, an alkyl group is preferable as R1. As a specific example of the alkyl group, the alkyl group is preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, among which n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-propyl group, i-propyl group, ethyl group and methyl group are preferable, and particularly ethyl group and methyl group are preferable.

[0083] n may be any value from 0 to 2, but is preferably n = 0. From the viewpoint of visible light transmittance as an optical member and transmittance of light (g-line, i-line, h-line, etc.) often used in the manufacture of electronic devices, n = 0 to 1 is preferred. When considering electronic devices in a broad sense, for example, in the case of an underlayer film, n = 1 may be preferable from the viewpoint of heat resistance.

[0084] p is 1 or more, and q is 0 or more, except that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8. As stated above, n is preferably 0. From the viewpoint of ease of preparation of raw materials and cost, p is preferably 1. From the viewpoint of ease of preparation of raw materials and costs, q is preferably 0 to 2, more preferably 0 to 1, and further preferably 0.

[0085] Preferred embodiments of the structural unit represented by formula (A) include the structural units represented by formulas (B) to (D) below and other listed structural units. In the listed structural units, the definitions of p and q are the same as those in formula (A). Just to be clear, the epoxy resin of the second embodiment corresponds to the general formula (A), but may have two or more structural units that are different from each other. For example, the epoxy resin of the second embodiment may have two or more structural units selected from the structural units of the formulae (B) to (D) shown below and other listed structural units. Of course, the epoxy resin of the second embodiment may be composed of only one structural unit. Moreover, the epoxy resin of the second embodiment may contain a structural unit that fits the general formula (A) and a structural unit that does not fit the general formula (A).

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[0090] (molecular weight, dispersity) The weight average molecular weight of the epoxy resin of the second embodiment is preferably 300 to 200,000, more preferably 300 to 150,000, and further preferably 300 to 100,000. By adjusting the weight average molecular weight, it is possible to adjust the solvent solubility and the physical properties when formed into a film. In other words, by adjusting the weight average molecular weight, it is possible to further increase the applicability of the epoxy resin of the second embodiment to the manufacture of optical materials and electronic devices. The polydispersity (weight average molecular weight / number average molecular weight) of the epoxy resin of the second embodiment is preferably 1 to 20, and more preferably 1 to 10. By setting the polydispersity within an appropriate numerical range, for example, a uniform film tends to be easily obtained, and the mechanical properties of the film tend to be improved. The weight average molecular weight and polydispersity can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0091] (Total chlorine content) The total chlorine content of the epoxy resin of the second embodiment is preferably 0 to 4,000 ppm, more preferably 0 to 2,000 ppm. When the total chlorine content is not too large, for example, corrosion problems can be reduced when the epoxy resin is applied to various applications. The "total chlorine content" can be measured based on JIS K 7243-3:2005.

[0092] (epoxy equivalent) The epoxy equivalent of the epoxy resin of the second embodiment is preferably 150 to 100,000 g / eq, more preferably 150 to 10,000 g / eq, and further preferably 150 to 2,000 g / eq. When the epoxy equivalent is within the preferred range, appropriate curability can be exhibited.

[0093] <Epoxy resin manufacturing method (synthesis method)> The epoxy resin of the second embodiment can be typically produced through a step (epoxidation step) of reacting a novolac resin having a partial structure represented by —C(CF3)H— with epihalohydrin in the presence of a base. An example of a novolac resin having a partial structure represented by —C(CF3)H— is a novolac resin having a structural unit represented by the following general formula (E).

[0094] [ka]

[0095] In general formula (E), R1 represents a monovalent substituent, and when a plurality of R1 are present, they may be the same or different. n is 0 to 2; p is 1 or more, and q is 0 or more, with the proviso that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8.

[0096] In the following, first, (i) the raw material / production method of the novolac resin having the structural unit represented by the general formula (E) will be described, followed by (ii) the epoxidation step of the novolac resin.

[0097] (i) Raw materials and manufacturing method of novolak resin having a structural unit represented by general formula (E) The novolac resin having a structural unit represented by general formula (E) can be prepared by the same method as the method described above in <Production method (synthesis method) of novolac resin> in <<First embodiment>>, and can typically be produced (synthesized) by reacting a phenolic compound with fluoral in the presence of an acid catalyst.

[0098] It is preferable to remove unreacted substances and impurities from the obtained novolak resin by combining a precipitation treatment in which the resin is poured into a poor solvent (typically water), a washing treatment with water or sodium bicarbonate water, a liquid separation operation, etc. As for the specific method of these treatments, known methods in polymer synthesis can be appropriately referred to.

[0099] (ii) Epoxidation process of novolac resin In the epoxidation process of the novolac resin, the novolac resin having the structural unit represented by the general formula (E) is reacted with epihalohydrin in the presence of a base, thereby converting the hydrogen atom of the phenolic hydroxy group in the general formula (E) to a glycidyl group, to obtain an epoxy resin having the structural unit represented by the general formula (A).

[0100] The amount of epihalohydrin (typically epichlorohydrin or epibromohydrin) used in the reaction is preferably 0.1 to 100 mol, more preferably 1.0 to 50 mol, per 1 mol of hydroxy groups in the novolak resin having a structural unit represented by general formula (E).

[0101] The base used in the reaction usually includes an alkali metal hydroxide, an alkali metal alkoxide, an alkali metal carbonate, etc. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium butoxide, potassium butoxide, lithium butoxide, sodium carbonate, potassium carbonate, lithium carbonate, etc. Only one of these bases may be used, or two or more may be used in combination.

[0102] In a preferred embodiment of the reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is usually added as a base to the reaction system in the form of a solid or an aqueous solution to bring the reaction system into "alkaline conditions." The amount of the base added is preferably 0.1 to 50 mol, and more preferably 1 to 10 mol, per 1 mol of the hydroxy group of the novolak resin having the structural unit represented by general formula (E).

[0103] The reaction can be carried out under normal pressure (0.1 MPa; absolute pressure) or under reduced pressure. The reaction temperature is usually 20 to 150°C for the reaction under normal pressure and 30 to 80°C for the reaction under reduced pressure. During the reaction, the reaction liquid is azeotroped while maintaining a specified temperature as necessary, the volatile vapor is cooled, and the resulting condensate is separated into oil and water, and the oil with the water removed is returned to the reaction system for dehydration. Regarding the addition of the alkali metal hydroxide, in order to suppress a rapid reaction, the alkali metal hydroxide is usually added to the reaction system in small amounts intermittently or continuously over a period of 0.1 to 10 hours. The total reaction time is usually 1 to 15 hours. It is preferable to use an analytical instrument such as a nuclear magnetic resonance (NMR) spectrometer or liquid chromatography (LC) to determine the end point of the reaction when it is confirmed that the reaction conversion rate reaches a predetermined value.

[0104] After the reaction is completed, it is preferable to remove the insoluble by-product salt by filtration or by washing with water. Then, it is preferable to remove the unreacted epihalohydrin by distillation under reduced pressure. In this way, the desired epoxy resin is obtained.

[0105] In the reaction, a catalyst such as a quaternary ammonium salt such as tetramethylammonium chloride or tetraethylammonium bromide; a tertiary amine such as benzyldimethylamine or 2,4,6-tris(dimethylaminomethyl)phenol; an imidazole such as 2-ethyl-4-methylimidazole or 2-phenylimidazole; a phosphonium salt such as ethyltriphenylphosphonium iodide; or a phosphine such as triphenylphosphine may be used.

[0106] In the reaction, inert organic solvents such as alcohols such as ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and ethylene glycol dimethyl ether, glycol ethers such as methoxypropanol, and aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide may be used. These organic solvents may be used alone or in combination of two or more.

[0107] If the amount of saponifiable halogen in the obtained epoxy resin is too large, it is sufficient to reprocess it to obtain a purified epoxy resin with a sufficiently reduced amount of saponifiable halogen. The specific procedure is as follows: (i) the crude epoxy resin is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, or dimethyl sulfoxide to obtain a solution, (ii) an alkali metal hydroxide is added to the solution in the form of a solid or aqueous solution, (iii) a ring-closing reaction is then carried out at a temperature of about 20 to 120°C for 0.5 to 8 hours, and (iv) excess alkali metal hydroxide and by-product salts are removed by washing with water or other methods, and the organic solvent is further removed by distillation under reduced pressure. In this manner, a purified epoxy resin having a structural unit represented by the general formula (A) can be obtained.

[0108] <<Resin composition>> The novolac resin of the first embodiment and the epoxy resin of the second embodiment can be used as a resin composition containing the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment by mixing with components different from the novolac resin of the first embodiment and the epoxy resin of the second embodiment.

[0109] <Photosensitive resin composition> A photosensitive resin composition can be preferably cited as an application of the novolac resin of the first embodiment and the epoxy resin of the second embodiment. Specifically, a photosensitive resin composition can be prepared by mixing the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment with at least a photosensitizer. As already mentioned, the novolac resin of the first embodiment and the epoxy resin of the second embodiment tend to have good transmittance of specific light and / or good alkali solubility. By using the novolac resin of the first embodiment and the epoxy resin of the second embodiment having such good properties, a photosensitive resin composition having good performance can be prepared. In particular, the photosensitive resin composition in this specification is useful as a photoresist composition, that is, a composition that can be patterned by exposure using a photomask and subsequent development, and can selectively protect the substrate surface from treatments such as etching in the manufacture of electronic devices. This is due to the specific transmittance of light, the alkali solubility, and the etching resistance of the aromatic ring contained in the novolac resin of the first embodiment and the epoxy resin of the second embodiment.

[0110] The above-mentioned photosensitive resin composition is also useful as a solder resist composition or an imprint composition, i.e., a composition that can be patterned by light and can selectively protect a substrate surface from treatments such as etching in the manufacture of electronic devices. This is due to the above-mentioned specific light transmittance and the etching resistance of the aromatic ring contained in the novolac resin of the first embodiment and the epoxy resin of the second embodiment.

[0111] The amount of the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment is, for example, 20 to 99 mass %, preferably 50 to 98 mass %, of the total non-volatile components of the photosensitive resin composition.

[0112] When the novolac resin of the first embodiment is used in the photosensitive resin composition, a quinone diazide compound is typically used as the photosensitizer. The quinone diazide compound is preferably used, particularly, when preparing a positive-type photosensitive resin composition. There is no particular limitation on the quinone diazide compound that can be used. Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via ester, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via sulfonamide, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via ester and / or sulfonamide. It is preferable that 50 mol % or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide.

[0113] As the structural unit of quinone diazide, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used. A 4-naphthoquinone diazide sulfonyl ester compound has an absorption in the i-line region and is suitable for i-line exposure. A 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region and is suitable for g-line exposure. It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. In addition, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or both a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.

[0114] The quinone diazide compound can be purchased from, for example, Tokyo Chemical Industry Co., Ltd.

[0115] In addition, a photopolymerization initiator may be used as the photosensitizer. The polymerization initiator is preferably used to prepare a negative-type photosensitive resin composition, particularly when the novolac resin contains a polymerizable carbon-carbon double bond.

[0116] The photopolymerization initiator is not particularly limited as long as it can generate active species such as radicals and polymerize polymerizable carbon-carbon double bonds by irradiation with high-energy light such as ultraviolet light. Specific examples include photoradical polymerization initiators.

[0117] Photoradical polymerization initiators include an intramolecular cleavage type that generates radicals by cleaving bonds within a molecule, and a hydrogen abstraction type that generates radicals by using a hydrogen donor such as a tertiary amine or ether in combination. Either type can be used in the first embodiment. For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, which is an intramolecular cleavage type, generates radicals by cleaving a carbon-carbon bond upon irradiation with light. Examples of hydrogen abstraction types include benzophenone, orthobenzoin methyl benzoate, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0118] The photoradical polymerization generator is not particularly limited as long as it is a compound that generates radicals by absorbing light, and a commercially available photoradical polymerization initiator can be used. The photoradical polymerization initiator can be purchased from, for example, BASF.

[0119] The amount of the photosensitizer is typically from 1 to 90% by mass, and preferably from 1 to 50% by mass, of all non-volatile components in the photosensitive resin composition. In particular, when the photosensitizer is a photopolymerization initiator, the proportion thereof is preferably within the range of 0.1 to 7 mass % based on the total mass of the non-volatile components of the photosensitive resin composition.

[0120] The photosensitive resin composition preferably contains a solvent. In other words, the photosensitive resin composition is preferably a composition in which components such as the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment and a photosensitizer are dissolved or dispersed in a solvent. Examples of the solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide, ethers such as tetrahydrofuran, dioxane, and propylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. The solvent may be a single solvent or a mixed solvent.

[0121] The amount of the solvent used may be appropriately adjusted depending on the thickness of the film to be formed using the photosensitive resin composition, etc. Typically, the amount of the solvent used is an amount that allows the non-volatile component concentration of the photosensitive resin composition to be 1 to 95 mass %.

[0122] The photosensitive resin composition may contain optional components for adjusting performance, in addition to the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment, a photosensitizer, and a solvent. Examples of the optional components include a surfactant, an antioxidant, a sensitizer, a resin different from the novolac resin of the first embodiment and the epoxy resin of the second embodiment, a filler, a colorant, a curable monomer, an oligomer, and the like.

[0123] A good pattern can be formed by using the photosensitive resin composition, for example, according to the following procedure. (1) A film-forming step of applying a photosensitive resin composition onto a substrate to form a photosensitive film. (2) Exposure process for exposing a photosensitive film (3) A development process in which the exposed photosensitive film is developed to form a pattern.

[0124] Below, an explanation will be given for each of the above steps.

[0125] ·Film formation process The substrate to which the photosensitive resin composition is applied is not particularly limited. Examples of the substrate include a silicon wafer, a metal, a glass, a ceramic, and a plastic substrate. The photosensitive resin composition may be applied onto a substrate to which another polymer has been applied in advance. As the coating method, a known coating method such as spin coating, dip coating, spray coating, bar coating, applicator, inkjet, roll coater, etc. can be used without any particular limitation.

[0126] The substrate coated with the photosensitive resin composition is heated, for example, at 80 to 120° C. for about 30 seconds to 30 minutes to dry off the solvent, thereby obtaining a photosensitive film.

[0127] Exposure process The photosensitive film obtained in the film formation step is usually irradiated with light through a photomask to form a desired pattern. For the exposure, known methods and devices can be used. As the light source, a light source having a wavelength in the range of 100 to 600 nm can be used. Specific examples that can be used include a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, and a KrF excimer laser (wavelength 248 nm). The exposure dose is usually 1 to 10,000 mJ / cm. 2 Approximately, preferably 10 to 5,000 mJ / cm 2 That's about it.

[0128] After exposure, post-exposure baking can be carried out before or after the development step, if necessary. The post-exposure baking temperature is 60 to 180° C., and the post-exposure baking time is usually 0.1 to 60 minutes, preferably 0.5 to 10 minutes.

[0129] ·Development process The photosensitive film obtained in the exposure process is developed to produce a film having a pattern shape. By using an alkaline aqueous solution as a developer, the exposed areas are dissolved and a pattern is formed.

[0130] The developer is not particularly limited as long as it can remove the photosensitive film in the exposed area. Specific examples include aqueous alkali solutions in which inorganic alkali, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, and mixtures thereof are dissolved. More specifically, examples of the aqueous alkali solution include aqueous solutions of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (abbreviation: TMAH), etc. Among these, it is preferable to use an aqueous solution of TMAH, and it is particularly preferable to use an aqueous solution of 0.1 to 5 mass % of TMAH.

[0131] As the development method, a known method such as a dipping method, a paddle method, a spray method, etc. can be used. The development time is usually 0.1 to 120 minutes, preferably 0.5 to 60 minutes. After that, washing, rinsing, drying, etc. are performed as necessary. In this way, a pattern can be formed on the substrate.

[0132] <Curable resin composition in the first embodiment> In addition to photosensitive resin compositions, the novolac resin of the first embodiment can also be used in curable resin compositions. For example, a curable resin composition can be produced by using the novolac resin of the first embodiment in combination with an epoxy resin (in this case, the novolac resin of the first embodiment acts as a curing agent for the epoxy resin). The novolac resin of the first embodiment contains fluorine atoms, and therefore, a cured product formed from the curable resin composition containing the novolac resin of the first embodiment is expected to have a dielectric constant and / or a dielectric loss tangent suitable for the manufacture of electronic devices.

[0133] In particular, the curable resin composition containing the novolac resin of the first embodiment is useful as a solder resist composition or an imprint composition, that is, a composition that can be pattern-printed by a known method such as a screen printing method and cured by heat or the like, and can selectively protect a substrate surface from treatments such as etching in the manufacture of electronic devices, due to the etching resistance of the aromatic ring contained in the novolac resin.

[0134] (Epoxy resin) There is no particular limitation on the epoxy resin to be combined with the novolac resin of the first embodiment. The epoxy resin of the second embodiment described below may be used, or other known epoxy resins may be used. Examples of known epoxy resins include bifunctional epoxy resins, such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, bisphenol AD ​​type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, diglycidyl ethers of bisphenol A-alkylene oxide adducts, diglycidyl ethers of alkylene oxide adducts of bisphenol F, bisphenol S type epoxy resins, tetramethyl bisphenol A type epoxy resins, tetramethyl bisphenol F type epoxy resins, thiodiphenol type epoxy resins, dihydroxydiphenyl ether type epoxy resins, terpene diphenol type epoxy resins, biphenol type epoxy resins, tetramethyl biphenol type epoxy resins, hydroquinone type epoxy resins, methyl hydroquinone type epoxy resins, dibutyl hydroquinone type epoxy resins, resorcin type epoxy resins, methyl resorcin type epoxy resins, and dihydroxy naphthalene type epoxy resins.

[0135] Examples of polyfunctional epoxy resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol AF novolac type epoxy resins, dicyclopentadiene phenol type epoxy resins, terpene phenol type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthol novolac type epoxy resins, polyhydric phenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., epoxy resins produced from various phenol compounds such as modified phenolic resins obtained by polycondensation of petroleum heavy oils or pitches, formaldehyde polymers, and phenols in the presence of an acid catalyst, and epihalohydrin, and triglycidyl isocyanurate.

[0136] Further examples of the epoxy resin that can be used in combination include epoxy resins produced from various amine compounds such as diaminodiphenylmethane, aminophenol, and xylylenediamine, and epihalohydrin; epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid, and epihalohydrin; epoxy resin diluents such as glycidyl ether of aliphatic alcohol; and alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0137] When the curable resin composition in the second embodiment contains a concomitant epoxy resin, it may contain only one concomitant epoxy resin, or may contain two or more concomitant epoxy resins having different chemical structures.

[0138] The ratio of the amounts of the novolac resin and the epoxy resin in the first embodiment may be appropriately designed in consideration of the epoxy equivalent of the epoxy resin, etc. Typically, the mass ratio of the novolac resin in the first embodiment: the epoxy resin is about 1:10 to 10:1.

[0139] (hardening agent) The curable resin composition in the first embodiment may contain a curing agent other than the novolac resin in the first embodiment. When the curable resin composition in the first embodiment contains a curing agent, the type of the curing agent is not particularly limited. Examples of the curing agent include an amine-based curing agent, an acid anhydride-based curing agent, and a phenol-based curing agent.

[0140] More specific examples of the amine curing agent include aliphatic and alicyclic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, isophoronediamine, bis(4-aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, m-xylylenediamine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5,5]undecane; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo-(5,4,0)-undecene-7, and 1,5-diazabicyclo-(4,3,0)-nonene-7, and salts thereof.

[0141] More specific examples of the acid anhydride curing agent include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride, and alicyclic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl-end-methylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.

[0142] More specific examples of the phenol-based curing agent include dihydric phenols such as catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol AF, bisphenol S, and biphenol, phenol novolaks, cresol novolaks, bisphenol A novolaks, bisphenol AF novolaks, trishydroxyphenylmethanes, and aralkyl polyphenols. Polyhydric phenols such as dicyclopentadiene polyphenols can also be included as phenolic curing agents.

[0143] Other examples of the curing agent include imidazole compounds and their salts, BF3 complex compounds of amines, Bronsted acid salts such as aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, and phosphonium salts, organic acid hydrazides such as dicyandiamide, adipic acid dihydrazide, and phthalic acid dihydrazide, and polycarboxylic acids such as adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyesters.

[0144] When the curable resin composition in the first embodiment contains a curing agent, it may contain only one curing agent, or may contain two or more curing agents having different chemical structures. When the curable resin composition in the first embodiment contains a curing agent, the amount of the curing agent may be appropriately adjusted based on the epoxy equivalent of the epoxy resin, etc. Typically, when a curing agent is used, the amount of the curing agent is about 0.1 to 1,000 parts by mass relative to 100 parts by mass of the epoxy resin.

[0145] (Cure accelerator) From the viewpoint of accelerating the curing rate and / or making the curing more complete, the curable resin composition in the first embodiment may contain a curing accelerator. As the curing accelerator, a curing accelerator for general epoxy resins, such as tertiary amines, imidazoles, organic phosphine compounds or their salts, and metal soaps such as zinc octylate and tin octylate, can be used.

[0146] When the curable resin composition in the first embodiment contains a curing accelerator, it may contain only one curing accelerator, or may contain two or more curing accelerators having different chemical structures. When the curable resin composition in the first embodiment contains a curing accelerator, the amount of the curing accelerator may be appropriately adjusted. Typically, when a curing accelerator is used, the amount is about 0.001 to 10 parts by mass relative to 100 parts by mass of the epoxy resin.

[0147] (Other ingredients) The curable resin composition in the first embodiment may contain one or more optional components in addition to the above components, such as an antioxidant, a filler, a colorant, a resin other than a novolac resin, a curable monomer, an oligomer, and an organic solvent.

[0148] The antioxidant may be a phenol-based, sulfur-based, phosphorus-based antioxidant, etc. When an antioxidant is used, the amount thereof is usually 0.005 to 5 parts by mass, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the novolac resin.

[0149] Examples of the filler include metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as finely powdered silica, fused silica and crystalline silica, glass beads, metal hydroxides such as aluminum hydroxide, metals such as gold, silver, copper and aluminum, fluororesin powders such as polytetrafluoroethylene particles, carbon, rubbers, kaolin, mica, quartz powder, graphite, molybdenum disulfide, boron nitride, and the like. When a filler is used, the amount thereof is, for example, 1,500 parts by mass or less, and preferably 0.1 to 1,500 parts by mass, relative to 100 parts by mass of the novolac resin.

[0150] Examples of colorants include inorganic pigments such as titanium dioxide, molybdenum red, Prussian blue, ultramarine blue, cadmium yellow, and cadmium red, organic pigments, carbon black, and phosphors. When a colorant is used, the amount thereof is usually 0.01 to 30 parts by mass based on 100 parts by mass of the novolak resin.

[0151] Examples of the flame retardant include antimony trioxide, bromine compounds, phosphorus compounds, etc. When a flame retardant is used, the amount thereof is usually 0.01 to 30 parts by mass based on 100 parts by mass of the novolac resin.

[0152] The properties of the curable resin composition in the first embodiment are not particularly limited. The curable resin composition in the first embodiment may be in a solid form (powder, granules, tablet, etc.) or in a liquid form containing a solvent. Specific examples of the solvent include those exemplified in the photosensitive resin composition section.

[0153] <Curable resin composition in the second embodiment> The curable resin composition in the second embodiment contains at least an epoxy resin having a partial structure represented by —C(CF3)H—. As an example, the curable resin composition in the second embodiment contains an epoxy resin having a partial structure represented by —C(CF3)H— and a curing agent. In this case, the composition is cured by the reaction between the epoxy resin and the curing agent. As another example, the curable resin composition in the second embodiment does not necessarily contain a curing agent. In this case, the epoxy resin is polymerized by a cationic polymerization reaction of the epoxy group, and the composition is cured.

[0154] Hereinafter, components preferably contained in the curable resin composition in the second embodiment other than the epoxy resin having a partial structure represented by —C(CF3)H— will be described.

[0155] (hardening agent) When the curable resin composition in the second embodiment contains a curing agent, the type of the curing agent is not particularly limited. As the curing agent, the curing agents exemplified in the above-mentioned <Curable resin composition in the first embodiment> can be used.

[0156] In addition to the curing agents exemplified in the above-mentioned <Curable resin composition in the first embodiment>, active ester curing agents can be used as the curing agent. More specifically, the active ester curing agent can be catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol AF, bisphenol S, biphenol, and other dihydric phenols, phenol novolacs, cresol novolacs, bisphenol A novolacs, bisphenol AF novolacs, trishydroxyphenylmethanes, aralkyl polyphenols, and other active esters. In addition, the active esters of the novolac resin in the first embodiment can also be used.

[0157] When the curable resin composition in the second embodiment contains a curing agent, it may contain only one curing agent, or may contain two or more curing agents having different chemical structures. When the curable resin composition in the second embodiment contains a curing agent, the amount of the curing agent may be appropriately adjusted based on the epoxy equivalent of the epoxy resin, etc. Typically, when a curing agent is used, the amount of the curing agent is about 0.1 to 1,000 parts by mass relative to 100 parts by mass of the epoxy resin.

[0158] (Cure accelerator) The curable resin composition in the second embodiment may contain a curing accelerator. In this case, the curable resin composition in the second embodiment may or may not contain a curing agent. In the former case, it is considered that the composition is cured mainly by a bond forming reaction between the epoxy resin and the curing agent. In the latter case, it is considered that the composition is cured mainly by a reaction between epoxy resins (cationic polymerization of epoxy groups).

[0159] As the curing accelerator, the curing accelerators exemplified in the above <Curable resin composition in the first embodiment> can be used.

[0160] When the curable resin composition in the second embodiment contains a curing accelerator, it may contain only one curing accelerator, or may contain two or more curing accelerators having different chemical structures. When the curable resin composition in the second embodiment contains a curing accelerator, the amount of the curing accelerator may be appropriately adjusted. Typically, when a curing accelerator is used, the amount is about 0.001 to 10 parts by mass relative to 100 parts by mass of the epoxy resin.

[0161] (Epoxy resin used in combination) The curable resin composition in the second embodiment may contain an epoxy resin (concomitant epoxy resin) other than the epoxy resin having a partial structure represented by —C(CF3)H—.

[0162] Examples of the epoxy resin to be used in combination include bifunctional epoxy resins, such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, bisphenol AD ​​type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, diglycidyl ether of bisphenol A-alkylene oxide adducts, diglycidyl ether of alkylene oxide adducts of bisphenol F, bisphenol S type epoxy resins, tetramethyl bisphenol A type epoxy resins, tetramethyl bisphenol F type epoxy resins, thiodiphenol type epoxy resins, dihydroxydiphenyl ether type epoxy resins, terpene diphenol type epoxy resins, biphenol type epoxy resins, tetramethyl biphenol type epoxy resins, hydroquinone type epoxy resins, methyl hydroquinone type epoxy resins, dibutyl hydroquinone type epoxy resins, resorcin type epoxy resins, methyl resorcin type epoxy resins, and dihydroxy naphthalene type epoxy resins.

[0163] Examples of polyfunctional epoxy resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol AF novolac type epoxy resins, dicyclopentadiene phenol type epoxy resins, terpene phenol type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthol novolac type epoxy resins, polyhydric phenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., epoxy resins produced from various phenol compounds such as modified phenolic resins obtained by polycondensation of petroleum heavy oils or pitches, formaldehyde polymers, and phenols in the presence of an acid catalyst, and epihalohydrin, and triglycidyl isocyanurate.

[0164] Further examples of the epoxy resin that can be used in combination include epoxy resins produced from various amine compounds such as diaminodiphenylmethane, aminophenol, and xylylenediamine, and epihalohydrin; epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid, and epihalohydrin; epoxy resin diluents such as glycidyl ether of aliphatic alcohol; and alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0165] When the curable resin composition in the second embodiment contains a concomitant epoxy resin, it may contain only one concomitant epoxy resin, or may contain two or more concomitant epoxy resins having different chemical structures. When the curable resin composition in the second embodiment contains a concomitant epoxy resin, the amount thereof is, for example, 1 to 80 parts by mass, and preferably 3 to 50 parts by mass, per 100 parts by mass of the epoxy resin having a partial structure represented by —C(CF3)H—.

[0166] (Other ingredients) The curable resin composition in the second embodiment may contain one or more optional components in addition to the above components. As the optional components, an antioxidant, a filler, a colorant, a resin other than an epoxy resin, a curable monomer, an oligomer, an organic solvent, etc., as exemplified in the above <Curable resin composition in the first embodiment> may be used.

[0167] The properties of the curable resin composition in the second embodiment are not particularly limited, and may have the properties exemplified in the above <Curable resin composition in the first embodiment>.

[0168] <Epoxy (meth)acrylate-based curable resin composition> The novolac resin of the first embodiment and the epoxy resin of the second embodiment can be made into an epoxy (meth)acrylate as shown in the above general formulas (13) to (15). Furthermore, by adding other components, it can be made into a curable resin composition. As an example, the epoxy (meth)acrylate curable resin composition contains the novolac resin of the first embodiment and / or the epoxy (meth)acrylate of the epoxy resin of the second embodiment, and a photopolymerization initiator. In this case, the composition is cured by the reaction of the (meth)acrylate group with the photopolymerization initiator.

[0169] The photopolymerization initiator is not particularly limited as long as it can generate active species such as radicals and polymerize polymerizable carbon-carbon double bonds by irradiation with high-energy light such as ultraviolet light. Specific examples include photoradical polymerization initiators.

[0170] Photoradical polymerization initiators include an intramolecular cleavage type that generates radicals by cleaving bonds within a molecule, and a hydrogen abstraction type that generates radicals by using a hydrogen donor such as a tertiary amine or ether in combination. Either type can be used in the first embodiment. For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, which is an intramolecular cleavage type, generates radicals by cleaving a carbon-carbon bond upon irradiation with light. Examples of hydrogen abstraction types include benzophenone, orthobenzoin methyl benzoate, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0171] The photoradical polymerization generator is not particularly limited as long as it is a compound that generates radicals by absorbing light, and a commercially available photoradical polymerization initiator can be used. The photoradical polymerization initiator can be purchased from, for example, BASF.

[0172] The amount of the photopolymerization initiator is typically 0.1 to 10 mass %, preferably 0.1 to 7 mass %, and more preferably 0.1 to 5 mass %, of all non-volatile components in the epoxy (meth)acrylate curable resin composition.

[0173] Hereinafter, components preferably contained in the curable resin composition in the second embodiment other than the novolac resin in the first embodiment and / or the epoxy (meth)acrylate derivative of the epoxy resin in the second embodiment and the photopolymerization initiator will be described.

[0174] (Epoxy (meth)acrylate used in combination) The curable resin composition of the epoxy (meth)acrylate body may contain an epoxy (meth)acrylate body (concomitant epoxy (meth)acrylate body) other than the epoxy (meth)acrylate body of the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment.

[0175] Examples of the epoxy (meth)acrylate used in combination include bifunctional epoxy resins, such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, bisphenol AD ​​type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, diglycidyl ether of bisphenol A-alkylene oxide adducts, diglycidyl ether of alkylene oxide adducts of bisphenol F, bisphenol S type epoxy resins, tetramethyl bisphenol A type epoxy resins, tetramethyl bisphenol F type epoxy resins, thiodiphenol type epoxy resins, dihydroxydiphenyl ether type epoxy resins, terpene diphenol type epoxy resins, biphenol type epoxy resins, tetramethyl biphenol type epoxy resins, hydroquinone type epoxy resins, methyl hydroquinone type epoxy resins, dibutyl hydroquinone type epoxy resins, resorcin type epoxy resins, methyl resorcin type epoxy resins, and dihydroxynaphthalene type epoxy resins.

[0176] Examples of polyfunctional epoxy resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol AF novolac type epoxy resins, dicyclopentadiene phenol type epoxy resins, terpene phenol type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthol novolac type epoxy resins, polyhydric phenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., epoxy resins produced from various phenol compounds such as modified phenolic resins obtained by polycondensation of petroleum heavy oils or pitches, formaldehyde polymers, and phenols in the presence of an acid catalyst, and epihalohydrin, and epoxy (meth)acrylates such as triglycidyl isocyanurate.

[0177] Further examples of the concomitant epoxy (meth)acrylate include epoxy resins produced from various amine compounds such as diaminodiphenylmethane, aminophenol, and xylylenediamine, and epihalohydrin; epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid, and epihalohydrin; epoxy resin diluents such as glycidyl ether of aliphatic alcohol; and alicyclic epoxy resins typified by 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate; and other epoxy (meth)acrylates.

[0178] The above-mentioned epoxy (meth)acrylate used in combination may be unmodified or may be modified with an acid.

[0179] When the curable resin composition of the epoxy (meth)acrylate body contains a concomitant epoxy (meth)acrylate body, it may contain only one concomitant epoxy (meth)acrylate body, or it may contain two or more concomitant epoxy (meth)acrylate bodies having different chemical structures. When the curable resin composition of the epoxy (meth)acrylate body contains a concomitant epoxy (meth)acrylate body, the amount thereof is, for example, 1 to 80 parts by mass, preferably 3 to 50 parts by mass, per 100 parts by mass of the epoxy (meth)acrylate body of the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment.

[0180] (Epoxy resin used in combination) The epoxy (meth)acrylate curable resin composition may contain, as a concomitant epoxy resin, an epoxy product of the novolac resin of the first embodiment and / or an epoxy resin of the second embodiment, or may contain an epoxy resin other than the epoxy product of the novolac resin of the first embodiment and / or the epoxy resin of the second embodiment.

[0181] Examples of the epoxy resin to be used in combination include bifunctional epoxy resins, such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, bisphenol AD ​​type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, diglycidyl ether of bisphenol A-alkylene oxide adducts, diglycidyl ether of alkylene oxide adducts of bisphenol F, bisphenol S type epoxy resins, tetramethyl bisphenol A type epoxy resins, tetramethyl bisphenol F type epoxy resins, thiodiphenol type epoxy resins, dihydroxydiphenyl ether type epoxy resins, terpene diphenol type epoxy resins, biphenol type epoxy resins, tetramethyl biphenol type epoxy resins, hydroquinone type epoxy resins, methyl hydroquinone type epoxy resins, dibutyl hydroquinone type epoxy resins, resorcin type epoxy resins, methyl resorcin type epoxy resins, and dihydroxy naphthalene type epoxy resins.

[0182] Examples of polyfunctional epoxy resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol AF novolac type epoxy resins, dicyclopentadiene phenol type epoxy resins, terpene phenol type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthol novolac type epoxy resins, polyhydric phenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., epoxy resins produced from various phenol compounds such as modified phenolic resins obtained by polycondensation of petroleum heavy oils or pitches, formaldehyde polymers, and phenols in the presence of an acid catalyst, and epihalohydrin, and triglycidyl isocyanurate.

[0183] Further examples of the epoxy resin that can be used in combination include epoxy resins produced from various amine compounds such as diaminodiphenylmethane, aminophenol, and xylylenediamine, and epihalohydrin; epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid, and epihalohydrin; epoxy resin diluents such as glycidyl ether of aliphatic alcohol; and alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0184] When the epoxy (meth)acrylate curable resin composition contains a concomitant epoxy resin, it may contain only one concomitant epoxy resin, or may contain two or more concomitant epoxy resins having different chemical structures. When the epoxy (meth)acrylate curable resin composition contains a concomitant epoxy resin, the amount thereof is, for example, 1 to 80 parts by mass, and preferably 3 to 50 parts by mass, per 100 parts by mass of the novolac resin of the first embodiment and / or the epoxy (meth)acrylate of the epoxy resin of the second embodiment.

[0185] (hardening agent) When the epoxy (meth)acrylate curable resin composition contains a co-used epoxy resin, it may contain a curing agent, and the type of the curing agent is not particularly limited. As the curing agent, the curing agents exemplified in the above-mentioned <Curable resin composition in the first embodiment> can be used.

[0186] When the epoxy (meth)acrylate curable resin composition contains a curing agent, it may contain only one curing agent, or it may contain two or more curing agents having different chemical structures. When the epoxy (meth)acrylate curable resin composition contains a curing agent, the amount thereof is about 0.1 to 1,000 parts by mass per 100 parts by mass of the combined epoxy resin.

[0187] (Cure accelerator) When the epoxy (meth)acrylate-based curable resin composition contains a co-used epoxy resin, it may contain a curing accelerator. In this case, the epoxy (meth)acrylate-based curable resin composition may or may not contain a curing agent.

[0188] As the curing accelerator, the curing accelerators exemplified in the above <Curable resin composition in the first embodiment> can be used.

[0189] When the epoxy (meth)acrylate curable resin composition contains a curing accelerator, it may contain only one curing accelerator, or may contain two or more curing accelerators having different chemical structures. When the epoxy (meth)acrylate curable resin composition contains a curing accelerator, the amount of the curing accelerator may be appropriately adjusted. Typically, when a curing accelerator is used, the amount is about 0.001 to 10 parts by mass relative to 100 parts by mass of the combined epoxy resin.

[0190] (Other ingredients) The epoxy (meth)acrylate curable resin composition may contain one or more optional components in addition to the above components. The optional components may include antioxidants, fillers, colorants, resins other than epoxy resins, curable monomers, oligomers, organic solvents, etc., as exemplified in the above <Curable resin composition in the first embodiment>.

[0191] The properties of the epoxy (meth)acrylate curable resin composition are not particularly limited, and may be the properties exemplified in the above <Curable resin composition in the first embodiment>.

[0192] <Cured products, optical components and electronic devices> The curable resin composition can be cured to obtain a cured product. The curing can be carried out by using light and / or heat. More specifically, the curable resin composition is usually heated at 100 to 200°C for 0.1 to 20 minutes. This allows a cured product to be obtained. In order to improve the curing performance, "post-curing" may be performed at 70 to 200°C for 0.1 to 10 hours. The form of the cured product may be a molded product, a cast product, a laminate in which a cured film is formed on one or both sides of a substrate, a film, a base resin for biomaterials, or the like.

[0193] The cured product obtained by curing the curable resin composition has good transparency. From the viewpoint of this transparency, it is preferable to manufacture an optical member using the curable resin composition (to manufacture an optical member including a cured product of the curable resin composition). For example, the curable resin composition can be used as a transparent material for sealing optical elements such as optical sensors, image pickup elements, etc. The curable resin composition can also be used for the production of microlenses and as an optical adhesive.

[0194] The curable resin composition may be used to manufacture an electronic device. That is, an electronic device including the cured product may be manufactured. The cured product contains fluorine atoms, and is therefore considered to have good dielectric properties (tending to have a low dielectric constant and a low dielectric loss tangent) as well as transparency. Good dielectric properties are preferable for application to electronic devices.

[0195] As an example, the curable resin composition can be used as a material for sealing electronic components. That is, the curable resin composition is heated to form a melt, and then the melt is used to seal the electronic components, thereby producing an electronic device in which the electronic components are sealed with the cured material. As another example, a curable material for lamination can be produced by coating and / or impregnating a substrate (preferably a fiber substrate) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, paper, etc. with a curable resin composition. This curable material for lamination can be suitably used for producing printed wiring boards such as multilayer electrical laminates, build-up laminates, and flexible laminates. As yet another example, an insulating film can be provided by applying a varnish-like curable resin composition to a substrate on which a circuit has been formed to form a resin film, and curing the film.

[0196] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0197] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It should be noted that the present invention is not limited to the Examples.

[0198] In the following, the weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC, HLC-8320 manufactured by Tosoh Corporation). The mobile phase was tetrahydrofuran (THF), and the column was TSKgel SuperHZ (3000 x 1 + 2000 x 2) / (6.0 mm I.D. x 15 cm x 3). The epoxy equivalent was measured based on JIS K 7236:2009. The hydroxyl equivalent was calculated by measuring the hydroxyl value based on JIS K 0070:1992. The acid value of the solid content was calculated by measuring the acid value of the solution based on JIS K 0070:1992 and calculating the acid value of the solid content from the solid content concentration. The solid concentration was calculated by dividing the mass of the reaction substrate excluding the solvent by the total mass of the solution including the solvent.

[0199] [Preparation of catalyst for fluoral synthesis] 896g of special grade reagent CrCl3·6H2O was dissolved in pure water to make 3.0L of solution. 400g of granular alumina was immersed in this solution and left for a day and night. After leaving it, the solution was filtered to remove the alumina, which was then kept at 100℃ in a hot air circulating dryer and dried for another day and night. In this way, chromium-loaded alumina was obtained. The obtained chromium-supported alumina was packed into a cylindrical SUS316L reaction tube (diameter 4.2 cm, length 60 cm) equipped with an electric furnace. The chromium-supported alumina was heated to 300°C while flowing nitrogen gas at a flow rate of about 20 mL / min into the reaction tube. When water was no longer seen flowing out of the reaction tube, hydrogen fluoride was added to the nitrogen gas and its concentration was gradually increased. When the hot spot caused by the fluorination of the packed chromium-supported alumina reached the outlet end of the reaction tube, the reactor temperature was raised to 350°C and kept at that state for 5 hours. In this way, a catalyst for fluoral synthesis was obtained. Hereinafter, this catalyst is referred to as "Catalyst A".

[0200] [Preparation example of Fluoral] 125 mL of catalyst A was packed into a gas phase reaction apparatus (made of SUS316L, diameter 2.5 cm, length 40 cm) having a cylindrical reaction tube equipped with an electric furnace. While air was flowing through the gas phase reactor at a flow rate of about 100 mL / min, the temperature of the reaction tube was raised to 280° C., and hydrogen fluoride was introduced at a rate of about 0.32 g / min over 1 hour. Next, chloral (trichloroethanal) was started to be fed into the reaction tube at a rate of about 0.38 g / min (contact time 15 seconds). The reaction stabilized one hour after the start of the reaction. After the reaction stabilized, the gas flowing out of the reactor was collected in a SUS304 cylinder equipped with an inlet tube cooled with a refrigerant at -15°C for 18 hours. The hydrogen fluoride content, hydrogen chloride content, and organic matter content of the 484.8 g of fluoral-containing collected liquid thus obtained were calculated by titration. The calculation results showed that the hydrogen fluoride content was 40 mass %, hydrogen chloride content was 11 mass %, and the organic matter content was 49 mass %, and the recovery rate of the organic matter was 88% (based on the number of moles of chloral in the feedstock material). In addition, a portion of the recovered organic matter was collected in a resin NMR tube, 19When the degree of fluorination was confirmed by F-NMR, almost no low-order fluorinated products were detected, confirming that the fluorination had progressed quantitatively. Next, 150 g of the collected mixture containing fluoral (hydrogen fluoride: 40% by mass, hydrogen chloride: 11% by mass, organic matter: 49% by mass) was charged into a 500 ml SUS reactor equipped with a cooling tube through which a -15°C refrigerant was passed, a thermometer, and a stirrer, and the reactor was heated to 25°C. While refluxing hydrogen fluoride through the cooling tube under normal pressure, hydrogen chloride that slipped through the top tower of the cooling tube was absorbed in water and removed. After refluxing for 5 hours, a sample was taken from the reactor, and the hydrogen fluoride content, hydrogen chloride content, and organic matter content were calculated by titrating the obtained sample. The calculated results were hydrogen fluoride: 44% by mass, hydrogen chloride: 1% by mass, and organic matter: 55% by mass. In this sample (mixture), 1,2,2,2-tetrafluoroethanol, hydrogen fluoride, and fluoral coexist in equilibrium. [Physical property data] 1,2,2,2-Tetrafluoroethanol: 19 F-NMR(400MHz,CFCl3)δ(ppm):-85.82(3F,s),-137.95(1F,d,J=54.9Hz) Hydrogen fluoride: 19 F-NMR(400MHz,CFCl3)δ(ppm):-193.37(1F,s)

[0201] <Synthesis of Novolac Resin> (Synthesis Example 1: Synthesis of novolac resin having the following structural units)

[0202] [ka]

[0203] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 29.6 g (fluoral: 0.167 mol, hydrogen fluoride: 0.651 mol) of the fluoral-containing mixture (hydrogen fluoride: 44 mass%, hydrogen chloride: 1 mass%, organic matter: 55 mass%) obtained in the above [Preparation Example of Fluoral], 20.3 g (1.02 mol) of hydrogen fluoride, 15.7 g (0.167 mol) of phenol, and 39.2 g of 1,2-dichloroethane were placed. Then, the mixture was reacted at 25°C and an absolute pressure of 0.2 MPa for 24 hours. The reaction solution was then poured into 200g of ice water, and the organic matter was extracted with 200g of ethyl acetate. The organic layer recovered from the extraction operation was washed twice with 200g of water, and then with 50g of saturated sodium bicarbonate water. The organic layer was then recovered by a separation operation. The organic layer was concentrated using an evaporator to obtain 31.0g of crude novolac resin. The obtained crude novolac resin was dissolved in 30g of methanol and gradually poured into a large beaker containing 300g of vigorously stirred water to precipitate the novolac resin. The solid was collected by filtration and dried in a vacuum dryer at 80°C under reduced pressure for 5 hours. As a result, 26.3g of the desired novolac resin was obtained. [Physical property data] Number average molecular weight (Mn) = 1184, weight average molecular weight (Mw) = 3182, polydispersity (Mw / Mn) = 2.688

[0204] (Synthesis Example 2: Synthesis of novolac resin having the following structural units)

[0205] [ka]

[0206] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 24.8 g (fluoral: 0.139 mol, hydrogen fluoride: 0.55 mol) of the fluoral-containing mixture (hydrogen fluoride: 44 mass%, hydrogen chloride: 1 mass%, organic matter: 55 mass%) obtained in the above [Preparation Example of Fluoral], 16.9 g (0.85 mol) of hydrogen fluoride, 15.0 g (0.139 mol) of 2-cresol, and 37.6 g of 1,2-dichloroethane were placed. Then, the mixture was heated to an internal temperature of 80° C. using a water bath, and reacted for 1 hour at an absolute pressure of 0.4 MPa. The subsequent reaction termination and purification were performed in the same manner as in Synthesis Example 1. As a result of the above, 24.1 g of the target novolak resin was obtained. [Physical property data] Number average molecular weight (Mn)=2882, weight average molecular weight (Mw)=9304, polydispersity (Mw / Mn)=3.228.

[0207] (Synthesis Example 3: Synthesis of novolac resin having the following structural units)

[0208] [ka]

[0209] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 29.8g (fluoral: 0.167mol, hydrogen fluoride: 0.656mol) of the fluoral-containing mixture (hydrogen fluoride: 44% by mass, hydrogen chloride: 1% by mass, organic matter: 55% by mass) obtained in the above [Preparation Example of Fluoral], 53.6g (26.8mol) of hydrogen fluoride, and 18.0g (0.167mol) of 2-cresol were placed. Then, the reaction was carried out for 3 hours at 25°C and an absolute pressure of 0.2MPa. The reaction product was dissolved in 300g of ethyl acetate and poured into 200g of ice water. The subsequent purification was carried out in the same manner as in Synthesis Example 1. As a result of the above, 25.2g of the target novolak resin was obtained. [Physical property data] Number average molecular weight (Mn) = 729, weight average molecular weight (Mw) = 2252, polydispersity (Mw / Mn) = 3.091.

[0210] (Synthesis Example 4: Synthesis of novolak resin having the following structural units)

[0211] [ka]

[0212] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 23.8g (fluoral: 0.133mol, hydrogen fluoride: 0.524mol) of the fluoral-containing mixture (hydrogen fluoride: 44% by mass, hydrogen chloride: 1% by mass, organic matter: 55% by mass) obtained in the above [Preparation Example of Fluoral], 16.2g (0.81mol) of hydrogen fluoride, 19.2g (0.133mol) of 2-naphthol, and 38.4g of 1,2-dichloroethane were placed. Then, the reaction was carried out for 24 hours at 25°C and an absolute pressure of 0.2MPa. The subsequent reaction termination and purification were carried out in the same manner as in Synthesis Example 1. As a result of the above, 22.4g of the target novolak resin was obtained. [Physical property data] Number average molecular weight (Mn)=598, weight average molecular weight (Mw)=1182, polydispersity (Mw / Mn)=1.975.

[0213] (Synthesis Example 5: Synthesis of novolak resin having the following structural units)

[0214] [ka]

[0215] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 29.6g (fluoral: 0.166mol, hydrogen fluoride: 0.65mol) of the fluoral-containing mixture (hydrogen fluoride: 44% by mass, hydrogen chloride: 1% by mass, organic matter: 55% by mass) obtained in the above [Preparation Example of Fluoral], 20.0g (1.0mol) of hydrogen fluoride, 18.0g (0.166mol) of anisole, and 39.2g of 1,2-dichloroethane were placed. Then, the reaction was carried out for 5 hours at 25°C and an absolute pressure of 0.2MPa. The subsequent reaction termination and purification were carried out in the same manner as in Synthesis Example 1. As a result of the above, 30.0g of the target novolak resin was obtained. [Physical property data] Number average molecular weight (Mn)=1326, weight average molecular weight (Mw)=3627, polydispersity (Mw / Mn)=2.735.

[0216] (Synthesis Example 6: Synthesis of novolak resin having the following structural units (two types))

[0217] [ka]

[0218] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 29.6g (fluoral: 0.166mol, hydrogen fluoride: 0.65mol) of the mixture containing fluoral obtained in the above [Preparation Example of Fluoral] (hydrogen fluoride: 44% by mass, hydrogen chloride: 1% by mass, organic matter: 55% by mass), 20.0g (1.0mol) of hydrogen fluoride, 7.8g (83mmol) of phenol, 9.0g (83mmol) of 2-cresol, and 39.2g of 1,2-dichloroethane were placed. Then, the reaction was carried out for 18 hours at 25°C and an absolute pressure of 0.2MPa. The subsequent reaction termination and purification were carried out in the same manner as in Synthesis Example 1. As a result of the above, 29.2g of the target novolak resin was obtained. [Physical property data] Number average molecular weight (Mn) = 1600, weight average molecular weight (Mw) = 4380, polydispersity (Mw / Mn) = 2.737

[0219] (Synthesis Example G: Synthesis of novolac resin having the following structural units)

[0220] [ka]

[0221] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 37.1 g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.205 mol, hydrogen fluoride: 0.816 mol), 33.0 g (1.69 mol) of hydrogen fluoride and 30.6 g (0.273 mol) of 2-fluorophenol were placed. Then, the internal temperature was set to 60°C in a water bath and the reaction was carried out for 20 hours at an absolute pressure of 0.3 MPa. After the reaction was completed, the reaction liquid was poured into 200 g of ice water and the organic matter was extracted with 200 g of diisopropyl ether. The organic layer recovered by the extraction operation was washed with 200 g of water, and further 200 g of water and potassium hydrogen carbonate were added for neutralization and washing. After that, it was washed with 200 g of water, and the organic layer was recovered by a liquid separation operation. The organic layer was concentrated with an evaporator to obtain 42.8 g of novolac resin. [Physical property data] Number average molecular weight (Mn) = 960, weight average molecular weight (Mw) = 1254, polydispersity (Mw / Mn) = 1.3

[0222] (Synthesis Example H: Synthesis of novolac resin having the following structural units)

[0223] [ka]

[0224] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 38.5 g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.216 mol, hydrogen fluoride: 0.847 mol), 35.1 g (1.76 mol) of hydrogen fluoride, and 39.0 g (0.241 mol) of 3-hydroxybenzotrifluoride were placed. Then, the internal temperature was set to 60°C in a water bath, and the reaction was carried out for 20 hours at an absolute pressure of 0.4 MPa. After the reaction was completed, the reaction liquid was poured into 200 g of ice water, and the organic matter was extracted with 200 g of diisopropyl ether. The organic layer recovered by the extraction operation was washed with 200 g of water, and further 200 g of water and potassium hydrogen carbonate were added for neutralization and washing. After that, it was washed with 200 g of water, and the organic layer was recovered by a liquid separation operation. The organic layer was concentrated using an evaporator to obtain 44.8 g of a novolak resin. [Physical property data] Number average molecular weight (Mn) = 702, weight average molecular weight (Mw) = 951, polydispersity (Mw / Mn) = 1.3

[0225] (Synthesis Example I: Synthesis of novolak resin having the following structural units)

[0226] [ka]

[0227] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 30.4 g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.170 mol, hydrogen fluoride: 0.668 mol), 17.2 g (0.862 mol) of hydrogen fluoride and 25.0 g (0.227 mol) of hydroquinone were placed. Then, the mixture was reacted for 24 hours at 25°C and absolute pressure of 0.2 MPa. After the reaction was completed, the reaction liquid was poured into 200 g of ice water, and organic matter was extracted with 200 g of methyl isobutyl ketone. The organic layer recovered by the extraction operation was washed with 200 g of water, and further neutralized and washed by adding 200 g of water and potassium hydrogen carbonate. After that, the organic layer was washed with 200 g of water, and the organic layer was recovered by a liquid separation operation. The organic layer was concentrated with an evaporator to obtain 37.5 g of novolac resin. [Physical property data] Number average molecular weight (Mn) = 850, weight average molecular weight (Mw) = 983, polydispersity (Mw / Mn) = 1.2

[0228] (Comparative Synthesis Example 1: Synthesis of novolak resin having the following structural units)

[0229] [ka]

[0230] A 100 mL glass flask equipped with a stirrer, reflux device, vacuum distillation device, and thermometer was charged with 32.4 g (0.30 mol) of 3-cresol, 21.6 g (0.20 mol) of 4-cresol, 0.13 g (1.4 mmol) of oxalic acid, 11.5 g (0.38 mol) of paraformaldehyde (purity 90%), and 14.3 g of water. The mixture was then heated to an internal temperature of 100° C. in a water bath and reacted for 2 hours. After the reaction was completed, the reaction solution was heated to an internal temperature of 200°C in an oil bath under normal pressure, and water was distilled off for 2 hours to remove water. It was then heated to 230°C and subjected to reduced pressure distillation at an absolute pressure of 0.1 kPa for 6 hours to remove low boiling point components. After cooling, 40.0 g of the desired novolac resin was obtained. [Physical property data] Number average molecular weight (Mn) = 1681, weight average molecular weight (Mw) = 8310, polydispersity (Mw / Mn) = 4.943.

[0231] (Synthesis Example 11: Synthesis of novolak resin having the following structural units)

[0232] [ka]

[0233] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 24.8 g (fluoral: 0.139 mol, hydrogen fluoride: 0.55 mol) of the fluoral-containing mixture (hydrogen fluoride: 44 mass%, hydrogen chloride: 1 mass%, organic matter: 55 mass%) obtained in the above [Preparation Example of Fluoral], 16.9 g (0.85 mol) of hydrogen fluoride, and 40.9 g (0.204 mol) of 4,4'-dihydroxyphenylmethane (bisphenol F) were placed. Then, the reaction was carried out for 24 hours at an internal temperature of 25°C and an absolute pressure of 0.2 MPa. The subsequent reaction termination and purification were carried out in the same manner as in Synthesis Example 1. As a result of the above, 41.2 g of the target novolac resin was obtained. The hydroxyl group equivalent of this novolac resin was 161 g / equivalent. [Physical property data] Number average molecular weight (Mn) = 819, weight average molecular weight (Mw) = 1612, polydispersity (Mw / Mn) = 1.969

[0234] (Synthesis Example 12: Synthesis of novolak resin having the following structural units)

[0235] [ka]

[0236] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 24.8 g (fluoral: 0.139 mol, hydrogen fluoride: 0.55 mol) of the fluoral-containing mixture (hydrogen fluoride: 44 mass%, hydrogen chloride: 1 mass%, organic matter: 55 mass%) obtained in the above [Preparation Example of Fluoral], 16.9 g (0.85 mol) of hydrogen fluoride, and 53.8 g (0.160 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF) were placed. Then, the reaction was carried out for 4 hours at an internal temperature of 60°C and an absolute pressure of 0.4 MPa. The subsequent reaction termination and purification were carried out in the same manner as in Synthesis Example 1. As a result of the above, 57.2 g of the target novolac resin was obtained. The hydroxyl group equivalent of this novolac resin was 253 g / equivalent. [Physical property data] Number average molecular weight (Mn) = 954, weight average molecular weight (Mw) = 2093, polydispersity (Mw / Mn) = 2.194

[0237] <Synthesis of epoxy resin> (Synthesis Example A: Production of epoxy resin having the following structural units)

[0238] [ka]

[0239] Novolac resin synthesis In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 38.5 g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.216 mol, hydrogen fluoride: 0.847 mol), 35.1 g (1.76 mol) of hydrogen fluoride, and 27.0 g (0.287 mol) of phenol were placed. Then, the mixture was reacted at 25°C and an absolute pressure of 0.2 MPa for 24 hours. After the reaction was completed, the reaction solution was poured into 500g of ice water, and the organic matter was extracted with 500g of ethyl acetate. The organic layer recovered from the extraction was washed with 500g of water, and then neutralized and washed by adding 500g of water and 20g of potassium bicarbonate. After that, it was washed with 500g of water, and the organic layer was recovered by a separation operation. The organic layer was concentrated with an evaporator to obtain 42.1g of novolac resin. The hydroxyl equivalent of this novolac resin was 170g / equivalent.

[0240] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 35 g of the novolak resin obtained above (hydroxyl equivalent: 170 g / equivalent), 189.7 g (2.05 mol) of epichlorohydrin and 19 g of 1-butanol were charged and heated to an internal temperature of 50°C in a water bath. Then, 45.1 g (0.226 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. After that, the flask was kept at 50°C for 1 hour to complete the reaction. After the reaction was completed, the organic layer was collected by a separation operation and washed with 100 g of water three times.Then, the organic layer was collected by a separation operation and concentrated with an evaporator to obtain a crude epoxy resin. The above crude epoxy resin, 150g of methyl isobutyl ketone, 25g of 1-butanol, and 38g of 20% by mass aqueous sodium hydroxide solution were charged into a 300mL glass flask equipped with a stirrer and a thermometer, and the mixture was heated to an internal temperature of 80°C in a water bath for 2 hours to perform an alkali treatment. The organic layer was then recovered by a separation operation and washed three times with 100g of water. The organic layer was then recovered by a separation operation and concentrated with an evaporator to obtain 49.5g of the desired epoxy resin. The epoxy equivalent was 310g / equivalent.

[0241] [Physical property data] Number average molecular weight (Mn) = 809, weight average molecular weight (Mw) = 1308, polydispersity (Mw / Mn) = 1.62

[0242] (Synthesis Example B: Production of epoxy resin having the following structural units)

[0243] [ka]

[0244] Novolac resin synthesis In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 36.9g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.207mol, hydrogen fluoride: 0.812mol), 33.68g (1.68mol) of hydrogen fluoride and 29.7g (0.275mol) of 2-cresol were placed. Then, the mixture was reacted for 24 hours at 25°C and absolute pressure of 0.2MPa. After the reaction was completed, the same operation as in Synthesis Example A was performed to obtain 42.1g of novolak resin. The hydroxyl group equivalent was 183g / equivalent.

[0245] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 35 g of the novolak resin obtained above (hydroxyl equivalent: 183 g / equivalent), 177.0 g (1.91 mol) of epichlorohydrin and 17.7 g of 1-butanol were charged and heated to an internal temperature of 50°C in a water bath. Then, 42.1 g (0.211 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. Then, the same operation as in Synthesis Example A was performed to obtain 46.8 g of the desired epoxy resin. The epoxy equivalent was 391 g / equivalent.

[0246] [Physical property data] Number average molecular weight (Mn) = 849, weight average molecular weight (Mw) = 1090, polydispersity (Mw / Mn) = 1.28

[0247] (Synthesis Example C: Preparation of epoxy resin having the following structural units)

[0248] [ka]

[0249] Novolac resin synthesis In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 37.8g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.212mol, hydrogen fluoride: 0.65mol), 34.2g (1.7mol) of hydrogen fluoride, 13.3g (0.141mol) of phenol and 15.2g (0.141mol) of 2-cresol were placed. Then, the reaction was carried out for 18 hours at 25°C and an absolute pressure of 0.2MPa. After the reaction was completed, the same operation as in Synthesis Example A was carried out to obtain 40.2g of the desired novolak resin. The hydroxyl group equivalent was 169g / equivalent.

[0250] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 30 g of the obtained novolak resin (hydroxyl equivalent: 169 g / equivalent), 164.7 g (1.78 mol) of epichlorohydrin and 16.5 g of 1-butanol were charged and heated to an internal temperature of 50°C in a water bath. Then, 39.2 g (0.196 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. Then, the same operation as in Synthesis Example A was performed to obtain 40.8 g of the desired epoxy resin. The epoxy equivalent was 326 g / equivalent.

[0251] [Physical property data] Number average molecular weight (Mn) = 891, weight average molecular weight (Mw) = 1238, polydispersity (Mw / Mn) = 1.39

[0252] (Synthesis Example D: Preparation of epoxy resin having the following structural units)

[0253] [ka]

[0254] Novolac resin synthesis In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 34.0 g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.191 mol, hydrogen fluoride: 0.748 mol), 30.7 g (1.54 mol) of hydrogen fluoride and 36.5 g (0.253 mol) of 1-naphthol were placed. Then, the mixture was reacted for 24 hours at 25°C and absolute pressure of 0.2 MPa. After the reaction was completed, the same operation as in Synthesis Example A was performed to obtain 51.1 g of novolac resin. Then, the obtained novolac resin was dissolved in 50 g of ethyl acetate and dropped into 1.5 kg of heptane that was strongly stirred to precipitate a solid. The solid was filtered and the solvent was distilled off with an evaporator to obtain 28.4 g of the target novolac resin. The hydroxyl group equivalent was 329 g / equivalent.

[0255] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 24 g of the obtained novolak resin (hydroxyl equivalent: 329 g / equivalent), 67.5 g (0.730 mol) of epichlorohydrin and 6.7 g of 1-butanol were charged and heated to an internal temperature of 50°C in a water bath. Then, 16.0 g (80 mmol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. Then, the same operation as in Synthesis Example A was performed to obtain 27.9 g of the desired epoxy resin. The epoxy equivalent was 803 g / equivalent.

[0256] [Physical property data] Number average molecular weight (Mn) = 951, weight average molecular weight (Mw) = 1412, polydispersity (Mw / Mn) = 1.49

[0257] (Synthesis Example E: Preparation of epoxy resin having the following structural units)

[0258] [ka]

[0259] Novolac resin synthesis In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 36.9g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.207mol, hydrogen fluoride: 0.812mol), 33.68g (1.68mol) of hydrogen fluoride and 29.7g (0.275mol) of 3-cresol were placed. Then, the mixture was reacted for 24 hours at 25°C and absolute pressure of 0.2MPa. After the reaction was completed, the same operation as in Synthesis Example A was performed to obtain 42.1g of novolak resin. The hydroxyl group equivalent was 180g / equivalent.

[0260] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 35 g of the novolak resin obtained above (hydroxyl equivalent: 180 g / equivalent), 177.0 g (1.91 mol) of epichlorohydrin and 17.7 g of 1-butanol were charged and heated to an internal temperature of 50°C in a water bath. Then, 42.1 g (0.211 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. Then, the same operation as in Synthesis Example A was performed to obtain 45.8 g of the desired epoxy resin. The epoxy equivalent was 390 g / equivalent.

[0261] [Physical property data] Number average molecular weight (Mn) = 860, weight average molecular weight (Mw) = 1100, polydispersity (Mw / Mn) = 1.30

[0262] (Synthesis Example F: Preparation of epoxy resin having the following structural units)

[0263] [ka]

[0264] Novolac resin synthesis In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 36.9g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.207mol, hydrogen fluoride: 0.812mol), 33.68g (1.68mol) of hydrogen fluoride and 29.7g (0.275mol) of 4-cresol were placed. Then, the mixture was reacted for 24 hours at 25°C and absolute pressure of 0.2MPa. After the reaction was completed, the same operation as in Synthesis Example A was carried out to obtain 40.1g of novolak resin. The hydroxyl group equivalent was 185g / equivalent.

[0265] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 35 g of the novolak resin obtained above (hydroxyl equivalent: 185 g / equivalent), 177.0 g (1.91 mol) of epichlorohydrin and 17.7 g of 1-butanol were charged and heated to an internal temperature of 50°C in a water bath. Then, 42.1 g (0.211 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. Then, the same operation as in Synthesis Example A was performed to obtain 47.1 g of the desired epoxy resin. The epoxy equivalent was 395 g / equivalent.

[0266] [Physical property data] Number average molecular weight (Mn) = 844, weight average molecular weight (Mw) = 1095, polydispersity (Mw / Mn) = 1.28

[0267] (Synthesis Example J: Synthesis of epoxy resin having the following structural units)

[0268] [ka]

[0269] In a 100 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 20 g of the novolak resin obtained in Synthesis Example 11 (hydroxyl equivalent: 161 g / equivalent), 68.8 g (0.74 mol) of epichlorohydrin and 6.9 g of 1-butanol were charged and heated to an internal temperature of 50°C using a water bath. Then, 27.3 g (0.136 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 2 hours. After that, the flask was kept at 50°C for 1 hour to complete the reaction. After the reaction was completed, the organic layer was collected by a separation operation and concentrated with an evaporator to obtain a crude epoxy resin. The above crude epoxy resin, 40.0 g of methyl isobutyl ketone, 7 g of 1-butanol, and 9.9 g of 20% by mass aqueous sodium hydroxide solution were charged into a 100 mL glass flask equipped with a stirrer and a thermometer, and the mixture was heated to an internal temperature of 80°C in a water bath for 3 hours to perform an alkali treatment. Then, 82 g of methyl isobutyl ketone and 160 g of water were added, and the organic layer was recovered by a separation operation and washed three times with 160 g of water. The recovered organic layer was then concentrated with an evaporator to obtain 40.0 g of the desired epoxy resin. The epoxy equivalent was 209 g / equivalent. [Physical property data] Number average molecular weight (Mn) = 773, weight average molecular weight (Mw) = 6367, polydispersity (Mw / Mn) = 8.2

[0270] (Synthesis Example K: Synthesis of epoxy resin having the following structural units)

[0271] [ka]

[0272] In a 100 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 20 g of the novolak resin obtained in Synthesis Example 12 (hydroxyl equivalent: 253 g / equivalent), 43.9 g (0.47 mol) of epichlorohydrin and 4.4 g of 1-butanol were charged and heated to an internal temperature of 50°C using a water bath. Then, 17.4 g (87 mmol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 2 hours. After that, the flask was kept at 50°C for 1 hour to complete the reaction. After the reaction was completed, the organic layer was collected by a separation operation and concentrated with an evaporator to obtain a crude epoxy resin. The above crude epoxy resin, 40.0 g of methyl isobutyl ketone, 7 g of 1-butanol, and 12.5 g of 20% by mass aqueous sodium hydroxide solution were charged into a 300 mL glass flask equipped with a stirrer and a thermometer, and the mixture was heated to an internal temperature of 80°C in a water bath and alkali-treated for 4 hours. Then, 82 g of methyl isobutyl ketone and 160 g of water were added, and the organic layer was recovered by a separation operation and washed three times with 160 g of water. The recovered organic layer was then concentrated with an evaporator to obtain 49.5 g of the desired epoxy resin. The epoxy equivalent was 300 g / equivalent. [Physical property data] Number average molecular weight (Mn) = 1091, weight average molecular weight (Mw) = 4624, polydispersity (Mw / Mn) = 4.2

[0273] (Preparation of epoxy resin for comparison) A novolac epoxy resin having the following structural units, manufactured by Aldrich, was prepared. The epoxy equivalent was 225. [Physical property data] Number average molecular weight (Mn) = 1014, weight average molecular weight (Mw) = 1967, polydispersity (Mw / Mn) = 2.824

[0274] [ka]

[0275] <Synthesis of epoxy acrylate> (Synthesis Example 7: Synthesis of epoxy acrylate resin solution having the following structural units)

[0276] [ka]

[0277] Novolac resin synthesis In a 500 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 162 g (8.08 mol) of hydrogen fluoride and 125.2 g (1.33 mol) of phenol were placed. Then, while cooling in a 10 ° C. water bath, 178.2 g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 1.00 mol, hydrogen fluoride: 3.92 mol) was introduced over 33 minutes at an internal temperature of 10 to 13 ° C. Then, the temperature was raised to 25 ° C., and the reaction was carried out for 27 hours at an absolute pressure of 0.2 MPa. After the reaction was completed, the reaction liquid was poured into 1.2 kg of ice water, and the organic matter was extracted with 820 g of diisopropyl ether. The organic layer recovered by the extraction operation was washed twice with 1.4 kg of water, and further neutralized and washed by adding 600 g of water and 4 g of 48 mass% potassium hydroxide aqueous solution. After that, the mixture was washed twice with 600 g of water, and the organic layer was collected by a separation operation. The organic layer was concentrated with an evaporator to obtain 178.2 g of novolac resin. The hydroxyl equivalent of this novolac resin was 187 g / equivalent.

[0278] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 50 g of the novolak resin obtained above (hydroxyl equivalent: 187 g / equivalent), 148.2 g (1.60 mol) of epichlorohydrin and 15 g of 1-butanol were charged and heated to an internal temperature of 50° C. in a water bath. Then, 58.7 g (0.291 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. After that, the flask was kept at 50° C. for 3 hours to react. After the reaction was completed, the organic layer was recovered by a separation operation and washed with 148 g of water. Then, the organic layer was recovered by a separation operation and concentrated with an evaporator to obtain a crude epoxy resin. The above crude epoxy resin, 104 g of methyl isobutyl ketone, 17 g of 1-butanol, and 25 g of 20% by mass aqueous sodium hydroxide solution were charged into a 300 mL glass flask equipped with a stirrer and a thermometer, and the mixture was heated to an internal temperature of 80°C in a water bath and alkali-treated for 5 hours. After that, the organic layer was collected by a liquid separation operation, concentrated with an evaporator to remove 1-butanol, and then 350 g of methyl isobutyl ketone was added and washed three times with 200 g of water. Then, the organic layer was collected by a liquid separation operation and concentrated with an evaporator to obtain 56.1 g of epoxy resin. The epoxy equivalent was 254 g / equivalent.

[0279] Epoxy acrylate resin solution synthesis In a 100mL glass flask equipped with a stirrer, reflux condenser and thermometer, 38.8g of the epoxy resin obtained above (epoxy equivalent 254g / equivalent), 11.0g (0.153mol) of acrylic acid, 60mg of hydroquinone and 22.8g of diethylene glycol monoethyl ether acetate were charged, and the mixture was heated to an internal temperature of 100°C using an oil bath and stirred to dissolve uniformly. Next, 170mg of triphenylphosphine was charged, and while introducing dry air, the internal temperature was raised to 110°C and reacted for 2 hours, and then the internal temperature was raised to 120°C and reacted for another 12 hours to complete the reaction. After cooling, the desired epoxy acrylate resin solution (I) was obtained.

[0280] [Physical property data] Number average molecular weight (Mn) = 2076, weight average molecular weight (Mw) = 5768, polydispersity (Mw / Mn) = 2.779, solid content concentration 68.7% by mass

[0281] (Synthesis Example 8: Synthesis of an acid-modified epoxy acrylate resin solution having the following structural units)

[0282] [ka]

[0283] In a 100 mL glass flask equipped with a stirrer, reflux condenser, and thermometer, 54.6 g of epoxy acrylate resin solution (I), 10.3 g of orthoxylene, and 10.5 g (69.0 mmol) of 1,2,3,6-tetrahydrophthalic anhydride were placed. Then, while introducing dry air, the mixture was heated to an internal temperature of 110°C using an oil bath and reacted for 5 hours. After cooling, the desired acid-modified epoxy acrylate resin solution was obtained. [Physical property data] Number average molecular weight (Mn) = 2528, weight average molecular weight (Mw) = 7298, polydispersity (Mw / Mn) = 2.887, solid content acid value = 82mgKOH / g, solid content concentration 63.7% by mass

[0284] (Synthesis Example 9: Synthesis of epoxy acrylate resin solution (II) having the following structural units)

[0285] [ka]

[0286] Novolac resin synthesis In a 300 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube and a stirring motor, 119.3 g (5.97 mol) of hydrogen fluoride and 89.7 g (0.829 mol) of 2-cresol were placed. Then, while cooling in a water bath at 2°C, 69.0 g of the fluoral-containing mixture obtained in the above [Preparation Example of Fluoral] (fluoral: 0.623 mol, hydrogen fluoride: 1.52 mol) was introduced over 23 minutes at an internal temperature of 2 to 18°C. The temperature was then raised to 25°C, and the reaction was carried out for 30 hours at an absolute pressure of 0.2 MPa. Thereafter, the same operation as in Synthesis Example 7 was carried out to obtain 120.4 g of novolac resin. The hydroxyl equivalent of this novolac resin was 174 g / equivalent.

[0287] Epoxy resin synthesis In a 300 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 50 g of the novolak resin obtained above (hydroxyl equivalent: 174 g / equivalent), 159.5 g (1.72 mol) of epichlorohydrin and 16 g of 1-butanol were charged and heated to an internal temperature of 50°C using a water bath. Then, 63.2 g (0.318 mol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 3 hours. Then, the same operation as in Synthesis Example 7 was performed to obtain 58.9 g of epoxy resin. The epoxy equivalent was 262 g / equivalent.

[0288] Epoxy acrylate resin synthesis In a 100mL glass flask equipped with a stirrer, reflux condenser and thermometer, 38.8g of the epoxy resin obtained above (epoxy equivalent: 262g / equivalent), 10.7g (0.148mol) of acrylic acid, 60mg of hydroquinone and 22.6g of diethylene glycol monoethyl ether acetate were charged, and the mixture was heated to an internal temperature of 100°C using an oil bath and stirred to dissolve uniformly. Next, 170mg of triphenylphosphine was charged, and while introducing dry air, the internal temperature was raised to 110°C and reacted for 2 hours, and then the internal temperature was raised to 120°C and reacted for another 12 hours to complete the reaction. After cooling, the desired epoxy acrylate resin solution (II) was obtained. [Physical property data] Number average molecular weight (Mn) = 1185, weight average molecular weight (Mw) = 2075, polydispersity (Mw / Mn) = 1.750

[0289] (Synthesis Example 10: Synthesis of an acid-modified epoxy acrylate resin solution having the following structural units)

[0290] [ka]

[0291] Synthesis of acid-modified epoxy acrylate resin In a 100 mL glass flask equipped with a stirrer, reflux condenser and thermometer, 56.0 g of epoxy acrylate resin solution (II), 10.3 g of orthoxylene and 10.4 g (68.4 mmol) of 1,2,3,6-tetrahydrophthalic anhydride were placed. Then, while introducing dry air, the mixture was heated to an internal temperature of 110°C using an oil bath and reacted for 5 hours. After cooling, the target acid-modified epoxy acrylate resin solution was obtained. [Physical property data] Number average molecular weight (Mn) = 1393, weight average molecular weight (Mw) = 2586, polydispersity (Mw / Mn) = 1.856, solid content acid value 84mgKOH / g, solid content concentration 63.7% by mass

[0292] (Comparative Synthesis Example 2: Synthesis of an acid-modified epoxy acrylate solution having the following structure)

[0293] [ka] A resin solution of the compound having the above structure was obtained by the same procedures as in Synthesis Examples 7 and 8, except that 50 g of phenol novolak (HF-1M manufactured by Meiwa Kasei) was used as the novolak resin. [Physical property data] Number average molecular weight (Mn) = 2187, weight average molecular weight (Mw) = 10158, polydispersity (Mw / Mn) = 4.645, solid content acid value = 91mgKOH / g, solid content concentration 63.8% by mass

[0294] (Comparative Synthesis Example 3: Synthesis of an acid-modified epoxy acrylate solution having the following structure)

[0295] [ka] A resin solution of the compound having the above structure was obtained by the same procedures as in Synthesis Examples 9 and 10, except that 50 g of cresol novolak (Phenolite KA-1160 manufactured by DIC) was used as the novolak resin. [Physical property data] Number average molecular weight (Mn) = 1385, weight average molecular weight (Mw) = 2559, polydispersity (Mw / Mn) = 1.848, solid content acid value = 85mgKOH / g, solid content concentration 63.7% by mass

[0296] (Synthesis Example L: Synthesis of epoxy acrylate resin solution having the following structural units)

[0297] [ka]

[0298] In a 100 mL glass flask equipped with a stirrer, reflux condenser and thermometer, 4.0 g of the epoxy resin obtained in Synthesis Example J (epoxy equivalent: 209 g / equivalent), 1.4 g (19 mmol) of acrylic acid, 20 mg of hydroquinone and 2.4 g of diethylene glycol monoethyl ether acetate were charged, and the mixture was heated to an internal temperature of 110°C using an oil bath while stirring and dissolving uniformly. Next, 21 mg of triphenylphosphine was charged, and the mixture was stirred for 2 hours while introducing dry air, and then the internal temperature was raised to 120°C and stirred for another 8 hours to complete the reaction. After cooling, the desired epoxy acrylate resin solution was obtained. [Physical property data] Number average molecular weight (Mn) = 1040, weight average molecular weight (Mw) = 6192, polydispersity (Mw / Mn) = 6.0, solid content concentration 69.1% by mass

[0299] (Synthesis Example M: ​​Synthesis of an acid-modified epoxy acrylate resin solution having the following structural units)

[0300] [ka]

[0301] In a 100 mL glass flask equipped with a stirrer, reflux condenser, and thermometer, 10.0 g of the epoxy acrylate resin solution obtained in Synthesis Example L, 1.5 g of orthoxylene, and 1.5 g (12 mmol) of 1,2,3,6-tetrahydrophthalic anhydride were placed. Then, while introducing dry air, the mixture was heated to an internal temperature of 110°C using an oil bath and reacted for 5 hours. After cooling, the target acid-modified epoxy acrylate resin solution was obtained. [Physical property data] Number average molecular weight (Mn) = 1629, weight average molecular weight (Mw) = 6273, polydispersity (Mw / Mn) = 3.9, solid content acid value 82mgKOH / g, solid content concentration 63.2% by mass

[0302] (Synthesis Example N: Synthesis of epoxy acrylate resin solution having the following structural units)

[0303] [ka]

[0304] In a 100mL glass flask equipped with a stirrer, reflux condenser and thermometer, 5.0g of the epoxy resin obtained in Synthesis Example K (epoxy equivalent: 300g / equivalent), 1.2g (17mmol) of acrylic acid, 31mg of hydroquinone and 3.8g of diethylene glycol monoethyl ether acetate were charged, and the mixture was heated to an internal temperature of 110°C using an oil bath while stirring to dissolve uniformly. Next, 22mg of triphenylphosphine was charged, and the mixture was stirred for 2 hours while introducing dry air, and then the internal temperature was raised to 120°C and stirred for another 8 hours to complete the reaction. After cooling, the desired epoxy acrylate resin solution was obtained. [Physical property data] Number average molecular weight (Mn) = 1650, weight average molecular weight (Mw) = 13263, polydispersity (Mw / Mn) = 8.0, solid content concentration 62.2% by mass

[0305] (Synthesis Example O: Synthesis of an acid-modified epoxy acrylate resin solution having the following structural units)

[0306] [ka]

[0307] In a 100 mL glass flask equipped with a stirrer, reflux condenser, and thermometer, 10.0 g of the epoxy acrylate resin solution obtained in Synthesis Example N, 1.5 g of orthoxylene, and 1.5 g (10 mmol) of 1,2,3,6-tetrahydrophthalic anhydride were placed. Then, while introducing dry air, the mixture was heated to an internal temperature of 110°C using an oil bath and reacted for 8 hours. After cooling, the target acid-modified epoxy acrylate resin solution was obtained. [Physical property data] Number average molecular weight (Mn) = 1725, weight average molecular weight (Mw) = 24333, polydispersity (Mw / Mn) = 14.1, solid content acid value 67mgKOH / g, solid content concentration 59.3% by mass

[0308] <Preparation of active ester resin> (Synthesis Example P: Synthesis of active ester resin having the following structural units)

[0309] [ka]

[0310] In a 100 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 10.0 g of the novolac resin obtained in Synthesis Example 7 (hydroxyl equivalent: 187 g / equivalent), 7.6 g (54.1 mmol) of benzoyl chloride, 40.0 g of methyl isobutyl ketone and 13 mg of tetrabutylammonium bromide were charged, and the internal temperature was adjusted to 20° C. in a water bath. Then, 11.3 g (56.5 mmol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 20 minutes. After that, the flask was kept at 20° C. for 1 hour to complete the reaction. After the reaction was completed, 80g of methyl isobutyl ketone and 80g of water were added, and the organic layer was recovered by separation and washed twice with 80g of water. The recovered organic layer was then concentrated with an evaporator to obtain 15.5g of active ester resin. The active ester equivalent was 291g / equivalent.

[0311] (Synthesis Example Q: Synthesis of active ester resin having the following structural units)

[0312] [ka]

[0313] In a 100 mL glass flask equipped with a stirrer, a dropping funnel and a thermometer, 10.0 g of the novolac resin obtained in Synthesis Example 9 (hydroxyl equivalent: 174 g / equivalent), 8.3 g (59.0 mmol) of benzoyl chloride, 40.0 g of methyl isobutyl ketone and 14 mg of tetrabutylammonium bromide were charged, and the internal temperature was adjusted to 20° C. in a water bath. Then, 11.9 g (59.5 mmol) of a 20% by mass aqueous sodium hydroxide solution was dropped into the flask over 20 minutes. After that, the flask was kept at 20° C. for 1 hour to complete the reaction. After the reaction was completed, 80g of methyl isobutyl ketone and 80g of water were added, and the organic layer was recovered by separation and washed twice with 80g of water. The recovered organic layer was then concentrated with an evaporator to obtain 15.9g of active ester resin. The active ester equivalent was 278g / equivalent.

[0314] <Evaluation of absorbance> Measurements were performed using an ultraviolet-visible near-infrared spectrophotometer (UV-VIS-NIR SPECTROMETER model UV-3150) manufactured by Shimadzu Corporation. Specifically, a 16% by mass propylene glycol monomethyl ether acetate solution of each novolac resin was introduced into a cell with an optical path length of 1 cm, and the absorbance of g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm) was measured. The measurement results are shown in the table below.

[0315] [Table 1]

[0316] From the above table, it is shown that the novolac resin corresponding to the general formula (1) where n = 0 in particular exhibits small absorbance for g-line, h-line and i-line (high transmittance of these rays). In other words, it can be said that the novolac resin of the first embodiment is preferably applicable to photosensitive resin compositions such as photoresists.

[0317] <Evaluation of alkali solubility> The following steps were followed. (1) The novolac resin obtained in Synthesis Example 2 was dissolved in PGMEA (propylene glycol monomethyl ether acetate) and then filtered through a filter with a pore size of 0.2 μm. In this way, a PGMEA solution of the novolac resin was obtained. The amounts of the novolac resin and PGMEA were adjusted so that the ratio of the novolac resin in the solution was 20 mass %. (2) The above PGMEA solution was applied by spin coating to the surface of the HMDS-treated silicon wafer, and the PGMEA was dried using a hot plate. In this way, a resin film was formed on the surface of the silicon wafer. The details of the spin coating and drying conditions are as follows. Spin coating conditions: slope 50s, 1,000rpm, 60s ·Drying conditions: 110℃, 60s ·Dry film thickness: 1μm (3) The resin film formed in (2) above was immersed together with the silicon wafer in an alkaline aqueous solution (a 2.38 mass% aqueous solution of tetramethylammonium hydroxide).Then, the alkaline dissolution rate of the resin film formed of the novolac resin obtained in Synthesis Example 2 was calculated from the relationship between the immersion time and the film thickness. (4) The same procedures as those of (1) to (3) above were carried out, except that the novolak resin obtained in Comparative Synthesis Example 1 was used instead of the novolak resin obtained in Synthesis Example 2. As a result, the alkali dissolution rate of the resin film formed from the novolak resin obtained in Comparative Synthesis Example 1 was calculated.

[0318] As a result of the above evaluation, the alkali dissolution rate of the resin film formed from the novolak resin obtained in Synthesis Example 2 was 0.95 μm / s. On the other hand, the alkali dissolution rate of the resin film formed from the novolak resin obtained in Comparative Synthesis Example 1 was 0.02 μm / s. Comparing the above two results, it is understood that the novolak resin of the first embodiment has good alkali solubility.

[0319] <Preparation and Evaluation of Photosensitive Resin Composition (Photoresist Composition)> Photosensitive resin compositions (photoresist compositions) were prepared and evaluated according to the following procedures. (1) 75 parts by mass of the novolak resin obtained in Synthesis Example 2 and 25 parts by mass of a quinone diazide-based photosensitizer (NT200, manufactured by Toyo Gosei Co., Ltd.) were dissolved in 500 parts by mass of PGMEA (propylene glycol monomethyl ether acetate), and then filtered through a filter with a pore size of 0.2 μm. In this way, a photosensitive resin composition (photoresist composition) was prepared. (2) A photosensitive resin composition (photoresist composition) was applied by spin coating to the surface of the HMDS-treated silicon wafer, and the PGMEA was dried using a hot plate. In this way, a photosensitive resin film (photoresist film) was formed on the surface of the silicon wafer. Spin coating conditions: slope 50s, 1,000rpm, 60s ·Drying conditions: 110℃, 60s ·Dry film thickness: 1μm (3) A photomask with line / space patterns of various widths is placed on the photosensitive resin film (photoresist film) formed in (2) above, and photo-irradiation is performed at 200 mJ / cm using a g·h·i-line lamp (a device that simultaneously emits g, h, and i-line). 2 The specimen was exposed to light of 10 ... (4) The irradiated photosensitive resin film (photoresist film) was developed by immersing the silicon wafer in a developer (1.19% by mass tetramethylammonium hydroxide aqueous solution) for 60 seconds. After immersion, the resin film on the removed silicon wafer was dried by blowing nitrogen gas onto it. In this way, a "pattern" was obtained on the silicon wafer.

[0320] The above-mentioned "pattern" was observed under a microscope. As a result of the observation, it was confirmed that a pattern with a line / space of 5 μm / 5 μm was resolved. From this result, it is understood that the novolac resin of the first embodiment is preferably applied to a photosensitive resin composition such as a photoresist that is used in the manufacture of electronic devices.

[0321] <Evaluation of novolac resin as a "hardening agent"> First, the following components were mixed to prepare a curable resin composition. 100 parts by weight of the novolak resin synthesized in Synthesis Example 1 Bisphenol A epoxy resin (Tokyo Chemical Industry Co., Ltd., epoxy equivalent 189g / eq) Curing accelerator: 1,2-dimethylimidazole 0.096 parts by weight

[0322] 3 g of the curable resin composition was placed in an aluminum cup container with a diameter of 51 mm and placed on a hot plate. Then, the composition was heated at 180°C for 10 minutes and then at 200°C for 1.5 hours. In this manner, a cured product was obtained. In other words, it was confirmed that the novolac resin of the first embodiment can also be used as a curing agent for epoxy resins.

[0323] <Measurement of transmittance (solution)> Using an ultraviolet-visible-near infrared spectrophotometer (UV-VIS-NIR SPECTROMETER, model name: UV-3150) manufactured by Shimadzu Corporation, a 20 mass% methyl ethyl ketone solution of the epoxy resin of Synthesis Example A was introduced into a cell with an optical path length of 1 cm, and the transmittance of light with a wavelength of 400 nm (visible light) and light with a wavelength of 365 nm (near ultraviolet light) was measured. The transmittance (solution) of the epoxy resin of Synthesis Example B and the comparative epoxy resin was also measured in the same manner. The results are summarized in the table below.

[0324] [Table 2]

[0325] As shown in the above table, the epoxy resin of the second embodiment had good transmittance for visible light and near ultraviolet light.

[0326] <Total chlorine measurement> The total chlorine content of the epoxy resin of Synthesis Example A was measured based on JIS K 7243-3:2005. The measurement result was 533 ppm. In other words, the total chlorine content of the epoxy resin of the second embodiment was sufficiently small.

[0327] <Preparation of curable resin composition, production and evaluation of cured product> Curable resin compositions having the compositions shown in the table below were prepared using the epoxy resin of Synthesis Example A, the epoxy resin of Synthesis Example B, and a comparative epoxy resin. In the table below, the units of values ​​are parts by mass. In the table below, the curing agent is methylhexahydrophthalic anhydride (acid anhydride equivalent: 165 g / mass, liquid at room temperature), and the curing accelerator is tributyl(ethyl)phosphonium diethylphosphate (liquid at room temperature). The curable resin composition obtained by mixing each component while heating was liquid (solvent-free varnish).

[0328] [Table 3]

[0329] 3 g of the prepared curable resin composition was placed in a 51 mmφ aluminum cup container and stirred at 100° C. for about 3 minutes to make it uniform. Then, it was heated at 100° C. for 3 hours using a hot plate, and then further heated at 140° C. for 3 hours. As a result, a cured product with a thickness of 1 mm was obtained for evaluation.

[0330] Glass transition temperature measurement The glass transition temperature of each cured product was measured using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, model name DSC7000) at a heating rate of 10° C. / min.

[0331] Measurement of transmittance (cured product) The transmittance of the cured product for light with a wavelength of 400 nm (visible light) and light with a wavelength of 365 nm (near ultraviolet light) was measured using a UV-VIS-NIR SPECTROMETER (model: UV-3150) manufactured by Shimadzu Corporation.

[0332] The results are summarized in the table below.

[0333] [Table 4]

[0334] From the above table, it can be seen that the glass transition temperatures of the cured products of Examples 1 and 2, which were prepared using a fluorine-containing epoxy resin having a partial structure represented by -C(CF3)H-, were similar to that of the cured product of Comparative Example 1, which was prepared using a comparative epoxy resin containing no fluorine. From this result, it can be said that the epoxy resin of the second embodiment is prevented from becoming excessively rigid, despite containing fluorine atoms. Furthermore, good transparency in visible light and near ultraviolet light was confirmed not only in the resin solution but also in the cured product.

[0335] <Comparison of solubility of epoxy resin in solvents> A 30% by mass solution was prepared for each of the epoxy resin obtained in Synthesis Example 13 and the comparative epoxy resin using the solvents shown in the table below. The solution was then left to stand at room temperature for one day. The state of the solution after being left for one day was visually observed, and a solution that was homogeneous was rated as having good solubility (◯), and a solution in which precipitation or separation occurred was rated as having poor solubility (×).

[0336] [Table 5]

[0337] As shown in the above table, the epoxy resin of Synthesis Example B exhibited good solubility in various organic solvents. On the other hand, in the evaluation using the comparative epoxy resin, the results showed that it had poor solubility in alcohol-based solvents such as methanol and butyl cellosolve.

[0338] <Photosensitive resin composition> Photosensitive resin compositions for solder resists were prepared by mixing the resin solutions of Synthesis Examples 8 and 10 and Comparative Synthesis Examples 2 and 3 in the ratios shown in Table 6 below and stirring until homogeneous. The physical properties of each composition and its cured product are shown in Table 7.

[0339] [Table 6] 1 Epoxy resin: EOCN-1020-55 (manufactured by Nippon Kayaku) 2 Photopolymerization initiator: Irgacure OXE02 (manufactured by BASF Japan)

[0340] [Table 7]

[0341] The sample preparation and test methods for the performance tests in Table 7 above are as follows.

[0342] <Preparation of photosensitive resin film> The photosensitive resin compositions of Examples 3 and 4 and Comparative Examples 2 and 3 were applied using a bar coater onto glass substrates whose surfaces had been treated with ozone for 1 minute, and the substrates were then dried at 80°C for 30 minutes using a hot plate and allowed to cool to room temperature to produce the films.

[0343] <Evaluation of patterning> The above photosensitive resin film was exposed to light at a dose of 2 J / cm2 through a photomask using an exposure machine (manufactured by SUSS MicroTec). 2After i-line exposure under the above conditions, the sample was immersed in a 1% Na2CO3 aqueous solution for 45 minutes. It was then washed with ultrapure water, dried with N2 blow, and heated at 150℃ for 1 hour using a hot plate to obtain an evaluation sample. The obtained sample was observed using an optical microscope to evaluate the collapse of the patterning. The evaluation criteria are as follows: ○: No pattern collapse is observed △: Partial pattern collapse is observed ?: A collapse of the overall pattern is observed

[0344] <Preparation of cured photosensitive resin> The above photosensitive resin film was exposed to 2 J / cm using an LED exposure machine (HOYA H-20AH4-FS1). 2 After exposure under the above conditions, the film was heated on a hot plate at 150°C for 1 hour. The resulting cured product was peeled off from the glass substrate, cut into a predetermined size, and used to evaluate the glass transition temperature, linear thermal expansion coefficient, and mechanical strength.

[0345] <Measurement of glass transition temperature> The measurements were performed using a differential scanning calorimeter (DSC7000 manufactured by Hitachi High-Tech Science) under the conditions of a sample amount of about 10 mg, a heating rate of 5° C. / min, and a nitrogen atmosphere.

[0346] <Measurement of linear thermal expansion coefficient> A sample of 20 mm x 5 mm was cut from the cured product. Using a thermomechanical analyzer (TMA8310 manufactured by Rigaku), measurements were taken twice consecutively using the tensile load method under conditions of a load of 98 mN and a heating rate of 10°C / min. The average linear thermal expansion coefficient from 50 to 150°C in the second measurement was calculated.

[0347] <Mechanical strength measurement> The cured product was cut into a sample measuring 60 mm x 5 mm. The elongation, tensile modulus, and tensile stress were measured in accordance with JIS K7127.

[0348] From the results shown in Table 7, the photosensitive resin composition of Example 3 has better patterning than the photosensitive resin composition of Comparative Example 2. The cured product of the photosensitive resin composition of Example 3 has a smaller linear thermal expansion coefficient than the cured product of the photosensitive resin composition of Comparative Example 2, and is considered to have excellent dimensional stability. In addition, the cured products of the photosensitive resin compositions of Examples 3 and 4 have higher glass transition points, larger elongations, and lower elastic moduli than the cured products of the photosensitive resin compositions of Comparative Examples 2 and 3, respectively, and are therefore considered to have excellent heat resistance and crack resistance, and are understood to be suitable for solder resist applications or imprint applications.

[0349] <Preparation and Evaluation of Curable Resin Compositions Using Active Ester Resins> First, a curable resin composition having the composition shown in Table 8 was prepared.

[0350] [Table 8]

[0351] In the above table, the bisphenol A type epoxy resin, curing accelerator and solvent are as follows. Bisphenol A epoxy resin: Tokyo Kasei Co., Ltd., epoxy equivalent weight 189g / equivalent Curing accelerator: 4-dimethylaminopyridine Solvent: Methyl ethyl ketone

[0352] 1 g of the prepared curable resin composition was placed in an aluminum cup with a diameter of 51 mm, and heated at 120° C. for 1 hour using a hot plate to evaporate the solvent, and then heated at 200° C. for 2 hours. As a result, a cured product was obtained.

[0353] The glass transition temperature of the cured product was measured by a differential scanning calorimeter. The differential scanning calorimeter used was a DSC7000 manufactured by Hitachi High-Tech Science Corporation, and the measurement was performed under the condition of a temperature increase rate of 10°C / min. The glass transition temperature of the cured product of Example 5 was 85°C.

[0354] This application claims priority based on Japanese Patent Application No. 2020-057369, filed on March 27, 2020, Japanese Patent Application No. 2020-078271, filed on April 27, 2020, and Japanese Patent Application No. 2020-164681, filed on September 30, 2020, the disclosures of which are incorporated herein in their entirety.

Claims

1. -C (CF ３ ) H-, A novolak resin having a structural unit represented by the following general formula (1). 【Chemistry 1】 In general formula (1), R 1 represents a hydrogen atom or a monovalent organic group, and when a plurality of R 1 are present, they may be the same or different; R 2 represents a monovalent substituent, and when a plurality of R 2s are present, they may be the same or different; n is 0 to 2; p is 1 or more, and q is 0 or more, provided that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8.

2. 2. The novolak resin of claim 1 , A novolac resin where n=0.

3. 2. The novolak resin of claim 1 , A novolak resin having at least one structural unit selected from the group consisting of the following general formulas (8) to (11): 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 In general formulas (8) to (11), R １ represents a hydrogen atom or a monovalent organic group; R １ When multiple are present, they may be the same or different, R ２ represents a monovalent substituent, R ２ When multiple are present, they may be the same or different, l and m each independently represent 0 to 3; R ３ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, which may be further substituted with a fluorine atom; R ３ may be linked to form a saturated or unsaturated, monocyclic or polycyclic cyclic group having 3 to 10 carbon atoms, R ３ When multiple are present, they may be the same or different.

4. The novolak resin according to any one of claims 1 to 3, The R １ A novolac resin containing a polymerizable carbon-carbon double bond.

5. The novolak resin according to any one of claims 1 to 4, A novolak resin having a partial structure represented by the following general formula (12): 【Chemistry 6】 In general formula (12), R ４ represents a hydrogen atom or a monovalent organic group, R ５ represents a hydrogen atom, a methyl group, or a fluorine atom.

6. 6. The novolak resin according to claim 5, R ４ represents a group having a carboxy group at its terminal;

7. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (2): 【Chemistry 7】

8. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (3): 【Chemistry 8】

9. 2. The novolak resin of claim 1 , A novolak resin having a structural unit represented by the following formula (4): 【Chemistry 9】

10. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (5): 【Chemistry 10】

11. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (6): 【Chemistry 11】

12. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (22): 【Chemistry 12】

13. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (23): 【Chemistry 13】

14. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (24): 【Chemistry 14】

15. 3. The novolak resin according to claim 1 or 2, A novolak resin having a structural unit represented by the following formula (25): 【Chemistry 15】 In general formula (25), R ２ represents a monovalent substituent, R ２ When multiple are present, they may be the same or different, q is 0 to 3.

16. The novolak resin according to any one of claims 1 to 3, A novolak resin having at least one structural unit selected from the group consisting of the following general formulas (13) to (15): 【Chemistry 16】 【Chemistry 17】 【Chemistry 18】 In general formulas (13) to (15), R １ represents a hydrogen atom or a monovalent organic group; R １ When multiple are present, they may be the same or different, R ３ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, which may be further substituted with a fluorine atom; R ３ may be linked to form a saturated or unsaturated, monocyclic or polycyclic cyclic group having 3 to 10 carbon atoms, R ３ When multiple are present, they may be the same or different, R ４ represents a hydrogen atom or a monovalent organic group, R ５ represents a hydrogen atom, a methyl group, or a fluorine atom.

17. The novolak resin according to any one of claims 1 to 16, A novolac resin having a weight average molecular weight of 300 to 200,000.

18. A photosensitive resin composition comprising the novolac resin according to any one of claims 1 to 17 and a photosensitizer.

19. The photosensitive resin composition according to claim 18, A photosensitive resin composition which is a photoresist composition, a solder resist composition or an imprint composition.

20. -C (CF ３ ) An epoxy resin having a partial structure represented by H-.

21. 21. The epoxy resin of claim 20, An epoxy resin having a structural unit represented by the following general formula (A). 【Chemistry 19】 In general formula (A), R １ represents a monovalent substituent, R １ When multiple are present, they may be the same or different, n is 0 to 2; p is 1 or more, and q is 0 or more, provided that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8.

22. 22. The epoxy resin of claim 21, R １ is at least one selected from the group consisting of an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, an aryloxy group, an amino group, an alkylamino group, an arylamino group, a cyano group, a nitro group, a silyl group and a halogeno group.

23. 21. The epoxy resin of claim 20, An epoxy resin having at least one structural unit selected from the group consisting of the following general formulas (8) to (11): 【Chemistry 20】 【Chemistry 21】 【Chemical 22】 【Chemistry 23】 In general formulas (8) to (11), R 1 represents a hydrogen atom or a monovalent organic group; R １ at least one of R 1 is a glycidyl group, and when a plurality of R 1 are present, they may be the same or different; R 2 represents a monovalent substituent, and when a plurality of R 2s are present, they may be the same or different; l and m each independently represent 0 to 3; R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and these groups may be further substituted with a fluorine atom. R 3 may be combined with each other to form a saturated or unsaturated, monocyclic or polycyclic cyclic group having 3 to 10 carbon atoms. When a plurality of R 3 s are present, they may be the same or different.

24. 22. The epoxy resin according to claim 20 or 21, An epoxy resin having a structural unit represented by the following formula (B): 【Chemistry 24】

25. 22. The epoxy resin according to claim 20 or 21, An epoxy resin having a structural unit represented by the following formula (C): 【Chemistry 25】

26. 22. The epoxy resin according to claim 20 or 21, An epoxy resin having a structural unit represented by the following formula (D): 【Chemistry 26】

27. The epoxy resin according to any one of claims 20 to 26, An epoxy resin having a total chlorine content of 0 to 4000 ppm.

28. A hardener comprising the novolac resin according to any one of claims 1 to 17.

29. A curable resin composition comprising at least one of the novolac resin according to any one of claims 1 to 17 or the epoxy resin according to any one of claims 20 to 27.

30. 30. The curable resin composition according to claim 29, A curable resin composition which is a solder resist composition or an imprint composition.

31. A cured product obtained by curing the curable resin composition according to claim 29 or 30.

32. An electronic device comprising the cured product according to claim 31.

33. By reacting an aromatic compound with fluoral in the presence of an acid catalyst, -C(CF ３ )H—, and producing a novolak resin having a structural unit represented by general formula (1) below: 【Chemical 27】 In general formula (1), R 1 represents a hydrogen atom or a monovalent organic group, and when a plurality of R 1 are present, they may be the same or different; R 2 represents a monovalent substituent, and when a plurality of R 2s are present, they may be the same or different; n is 0 to 2; p is 1 or more, and q is 0 or more, provided that when n is 0, p+q≦4, when n is 1, p+q≦6, and when n is 2, p+q≦8.

34. -C (CF ３ 2. A method for producing an epoxy resin, comprising the steps of: reacting a novolak resin having a partial structure represented by the formula:

35. A method for producing an active ester resin, comprising: a synthesis step of synthesizing a novolak resin having a partial structure represented by -C(CF3)H- by reacting an aromatic compound with fluoral in the presence of an acid catalyst; and a reaction step of reacting at least the novolak resin with an aromatic carboxylic acid or an acid halide thereof.

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