JP5224130B2 - Liquid repellent resin composition - Google Patents

Description

The present invention relates to an alkali-soluble liquid-repellent resin composition excellent in liquid repellency, sensitivity, and developability. Furthermore, the present invention is a negative or positive radiation-sensitive resin composition containing the resin composition, and includes a protective film and an interlayer insulating film in a color filter, a liquid crystal display element, an integrated circuit element, a solid-state imaging element, etc. Relates to a composition useful for preparing

In general, resist materials for forming ITO electrodes such as liquid crystal displays (LCDs) and organic EL displays, interlayer insulating films, circuit protective films, color pigment dispersion resists for liquid crystal display color filter manufacturing, partition materials for organic EL displays, etc. As a permanent film forming material, a radiation sensitive resin composition is widely used.
Among these, in recent years, the demand for liquid crystal displays is increasing for television applications and the like, and radiation-sensitive resin compositions are frequently used in the manufacturing process. In the production of liquid crystal color filters, there is a strong demand for cost reduction due to the increasing demand, and an ink jet method that can be produced at low cost has been proposed. In the manufacture of color filters by the ink jet method, a pixel (partition) that defines pixels is formed in advance by a photolithographic method or the like, and then inks of red, green, and blue are respectively applied to the pixel portions by ink jet. Compared with the conventional manufacturing method using a pigment dispersion resist, it is said that the process is simple and the waste of ink is small.
In this ink jet method, when ink droplets are dropped on the pixel portion, the substrate and the side wall of the partition need to have close contact with the ink, and ink-philicity is required. In order to prevent a situation where the ink overflows and to prevent color mixing of ink between adjacent pixel regions, it is required that the partition wall surface has liquid repellency.

Patent Document 1 discloses, as a radiation-sensitive resin composition having liquid repellency, hexafluoropropylene, an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, and an unsaturated compound copolymerizable with these components. Fluorine-containing copolymer, an acid generating compound that generates an acid upon irradiation, a crosslinkable compound, a fluorine-containing organic compound other than the above-mentioned fluorine-containing copolymer, and an organic solvent. A radiation resin composition is disclosed, and examples of the fluorine-containing organic compound include a perfluoroalkyl group and a hydrophilic group or lipophilic group-containing oligomer.

Further, Patent Document 2 discloses an alkali-soluble radiation-sensitive resin having an acidic group and three or more ethylenic double bonds in the molecule, and a carbon number of 20 in which at least one hydrogen atom is substituted with a fluorine atom. An ink repellent agent comprising a polymer unit having the following alkyl group (wherein the alkyl group includes those having ether oxygen), and a polymer unit having an ethylenic double bond, and a photopolymerization initiator A negative-type radiation-sensitive resin composition characterized by containing

Further, Patent Document 3 discloses a fluororesin having a C 4-6 perfluoroalkyl group and a fluorine atom content of 7-35% by mass, and a radiation-sensitive component that reacts with light having a wavelength of 100-600 nm. And a ratio of the fluorine-containing resin to the total solid content of the composition is 0.1 to 30% by mass.

In the resin composition containing these fluorine-containing compounds, the fluorine-containing compound imparts liquid repellency, and since this fluorine-containing compound has surface migration properties, the fluorine-containing compound is applied to the coating film during film formation. It moves to the vicinity of the surface, and liquid repellency is imparted to the surface of the coating film. However, in these resin compositions, since it takes time for the liquid repellent agent to move to the surface of the coating film, there is a problem in that the liquid repellency of the coating film surface varies depending on the film forming conditions. Therefore, there is a demand for a resin composition that can stably obtain a high level of liquid repellency regardless of the film forming conditions.

JP-A-11-281815 (Claim 1) International Publication No. 2004/042474 (Claim 1) JP-A-2005-315984 (Claim 1)

The object of the present invention is to solve the above-mentioned conventional problems, and the object of the present invention is to provide a liquid-repellent resin composition that stably exhibits excellent liquid repellency regardless of the film forming conditions. There is. Another object of the present invention is to provide a radiation sensitive resin composition containing the liquid repellent resin composition. Still another object of the present invention is to provide a cured product obtained by curing such a radiation sensitive resin composition.

As a result of intensive studies in order to solve the above-mentioned problems, the present invention provides, as a condensed ring structure-containing alkali-soluble resin (A), an epoxy ester compound represented by the following general formula (1):

(Here, _D1-4 are each independently a group selected from the following general formula (2) or the following general formula (3), and _p1-4 are each independently an integer of 0-4).

Here, D _5-6 are each independently a group selected from General Formula (2) or the following General Formula (3), and p _5-6 are each independently an integer of 0-4.

Here, A ₀ in the above general formulas (1) and (2) is a 5-membered or 6-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings. R _1-6 each independently represents a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms. It is an alkoxy group, a phenyl group which may have a substituent, or a halogen atom, and q _{1 to 6} are each independently an integer of 0 to 4. Further, R ₇ in the above general formulas (1), (2) and (3) represents a group containing a site derived from a monobasic carboxylic acid, and R _{8 to 15} each independently represents a hydrogen atom or a methyl group. _{M 1-8} and s _1-2 are each independently an integer of 0 to 10, and the structural formula may be bilaterally symmetric or asymmetrical. A plurality of R _1-15 and D _1-6 may be the same or different. ) And a polybasic carboxylic acid or an anhydride thereof, a condensed ring structure-containing alkali-soluble resin (A1) or an epoxy ester compound represented by the general formula (1), A fluorine-containing polyether is obtained by combining a condensed ring-containing alkali-soluble resin (A2) obtained by reacting a polyhydric alcohol with a polybasic carboxylic acid or an anhydride thereof and a fluorine-containing polyether compound (B). It has been found that the compound (B) rapidly moves to the coating surface and can stably impart excellent liquid repellency only to the coating surface regardless of the film forming conditions. The present invention has been completed based on this finding.

Thus, the liquid repellent resin composition (1) of the present invention is obtained by reacting the epoxy ester compound represented by the general formula (1) with a polybasic carboxylic acid or an anhydride thereof. A structure-containing alkali-soluble resin (A1) and a fluorine-containing polyether compound (B) are included.

Moreover, the liquid repellent resin composition (2) of the present invention is obtained by reacting the epoxy ester compound represented by the general formula (1), a polyhydric alcohol, and a polybasic carboxylic acid or an anhydride thereof. The obtained condensed ring-containing alkali-soluble resin (A2) and the fluorine-containing polyether compound (B) are included.

In a preferred embodiment, the condensed ring-containing alkali-soluble resin (A1) in the liquid repellent resin composition (1) of the present invention is an epoxy having a bifunctional and linear structure represented by the following general formula (4). It is a condensed ring structure-containing alkali-soluble resin (A1-1) obtained by reacting an ester compound with a polybasic carboxylic acid or an anhydride thereof.

Here, A ₀ , R _1-4 , R ₇ , R _8-11 , q _1-4 , m _1-4 , s ₁ are the same as described above, and they are asymmetric even if the structural formula is symmetrical. May be. Moreover, several R _{< 1 > -4} , R _{<7> -11} may be the same, and may differ.

Moreover, the liquid repellent resin composition (2) of the present invention is obtained by reacting the epoxy ester compound represented by the general formula (4), a polyhydric alcohol, and a polybasic carboxylic acid or an anhydride thereof. It is preferable that the condensed ring-containing alkali-soluble resin (A2-1) and the fluorinated polyether compound (B) obtained by

In addition, A ₀ in the general formulas (1), (2), and (4) represents a six-membered alicyclic compound (which may contain an atom other than carbon on the ring) and one or more aromatic rings. It is preferably a condensed ring structure or a divalent group containing a condensed structure of a five-membered alicyclic compound (which may contain an atom other than carbon on the ring) and one aromatic ring.

In addition, A ₀ in the general formulas (1), (2), and (4) is a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and two or more aromatic rings. A divalent group containing a condensed ring structure is preferred.

In addition, A ₀ in the general formulas (1), (2), and (4) represents a six-membered alicyclic compound (which may contain an atom other than carbon on the ring) and two or more aromatic rings. A divalent group containing a condensed ring structure is preferred.

In general formula (1), (2), (4) _{A 0} in is preferably a divalent group containing a condensed ring structure selected from the group consisting of the formulas (5) to (7).

In general formula (1), (2), (4) _{A 0} in is preferably a divalent group containing a condensed ring structure selected from the group consisting of the formulas (8) and (9).

In general formula (1), (2), the _{A 0} (4) is preferably a divalent group containing a condensed ring structure is an expression (17).

In a preferred embodiment, the fluorinated polyether compound (B) in the liquid repellent resin compositions (1) and (2) comprises a compound selected from the group consisting of formulas (18) to (20). It is preferable that

Here, in the formula, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are each independently hydrogen, F or carbon It is a fluorine-containing alkyl group having a number of 20 or less, x, y, and z are each independently an integer of 0 or more, and x + y + z contained in (B) is an integer of 2 or more. However, at least one of R ₁₉ and R ₂₀ is F or a fluorine-containing alkyl group having 20 or less carbon atoms, and at least one of R _{21 to} R ₂₄ is F or a fluorine-containing alkyl group having 20 or less carbon atoms. And at least one of R _{25 to} R ₃₀ is F or a fluorine-containing alkyl group having 20 or less carbon atoms.

In a preferred embodiment, the ratio of the fluorinated polyether compound (B) in the liquid repellent resin compositions (1) and (2) is based on 100 parts by weight of the condensed ring structure-containing alkali-soluble resin (A). 0.01 to 10 parts by weight.

In a preferred embodiment, at least one of the condensed ring-containing alkali-soluble resin (A) and the fluorinated polyether compound (B) in the liquid repellent resin compositions (1) and (2) is light or heat. Contains unsaturated groups polymerizable with

The radiation sensitive resin composition of this invention contains this liquid repellent resin composition (1), (2) and a photoinitiator (C).

Furthermore, it is preferable that the radiation sensitive resin composition of the present invention contains at least one selected from the group consisting of carbon black, titanium black, black metal oxide pigments, and organic pigments.

The present invention includes the liquid-repellent resin compositions (1) and (2) and a cured product obtained by curing the radiation-sensitive resin composition.

The liquid repellent resin compositions (1) and (2) of the present invention, a radiation sensitive resin composition containing the liquid repellent resin composition, and a thin film using the radiation sensitive resin composition are described below. The formation will be described sequentially.
(I) Liquid repellent resin composition (1), (2)
Condensed ring structure-containing alkali-soluble resin (A)
The condensed ring structure-containing alkali-soluble resin (A) contained in the liquid repellent resin composition of the present invention is an epoxy ester compound represented by the following general formula (1) (hereinafter referred to as “epoxy ester compound (a1)”). Is):

(Here, _D1-4 are each independently a group selected from the following general formula (2) or the following general formula (3), and _p1-4 are each independently an integer of 0-4).

Here, D _5-6 are each independently a group selected from General Formula (2) or the following General Formula (3), and p _5-6 are each independently an integer of 0-4.

Here, A ₀ in the above general formulas (1) and (2) is a 5-membered or 6-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings. R _1-6 each independently represents a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms. It is an alkoxy group, a phenyl group which may have a substituent, or a halogen atom, and q _{1 to 6} are each independently an integer of 0 to 4. Further, R ₇ in the above general formulas (1), (2) and (3) represents a group containing a site derived from a monobasic carboxylic acid, and R _{8 to 15} each independently represents a hydrogen atom or a methyl group. _{M 1-8} and s _1-2 are each independently an integer of 0 to 10, and the structural formula may be bilaterally symmetric or asymmetrical. A plurality of R _1-15 and D _1-6 may be the same or different. ) And a polybasic carboxylic acid or its anhydride (a3). In the present specification, this condensed ring structure-containing alkali-soluble unsaturated resin may be referred to as “condensed ring structure-containing alkali-soluble resin (A1)” or “alkali-soluble resin (A1)”.

Moreover, the condensed ring structure-containing alkali-soluble resin (A) of the present invention comprises an epoxy ester compound (a1) represented by the general formula (1), a polyhydric alcohol (a2), a polybasic carboxylic acid or an anhydride thereof. It can also be obtained by reacting with (a3). In the present specification, this condensed ring structure-containing alkali-soluble resin may be referred to as “condensed ring structure-containing alkali-soluble resin (A2)” or “alkali-soluble resin (A2)”.

Examples of the divalent group containing a condensed ring structure of a 5-membered or 6-membered alicyclic compound and one or more aromatic rings in A ₀ include, for example, a 5-membered or 6-membered alicyclic compound and Examples thereof include a divalent group containing a condensed ring structure with 1 to 3 aromatic rings. The six-membered alicyclic compound and the five-membered alicyclic compound may contain atoms other than carbon on the ring, and examples include those containing an oxygen atom, a sulfur atom, and a nitrogen atom.
Examples of A ₀ include a divalent group including a condensed ring structure selected from the group consisting of the following formulas (5) to (9) and (17).

When A ₀ is a divalent group containing a condensed ring structure selected from the group consisting of formulas (5) to (9) and (17), high heat resistance and high refractive index derived from a condensed ring skeleton containing an aromatic group Electrical properties can be imparted, and dispersion stability derived from a large surface structure can be obtained. Further, when A ₀ is a divalent group containing a condensed ring structure selected from the group consisting of formulas (5) to (7) and (17), heat resistance, refractive index, electrical characteristics, dispersion at a higher level Stability is obtained. Further, when A ₀ is a divalent group containing a condensed ring structure of formulas (8) and (9), such a condensed ring structure-containing alkali-soluble resin (A) has high solubility in a solvent, Handling is simple and advantageous in terms of manufacturing cost.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms in R _{1 to} R ₆ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclohexyl group. Examples of the linear, branched or cyclic alkenyl group having 1 to 10 carbon atoms include ethenyl group, propenyl group, cyclohexenyl group and the like. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the phenyl group that may have a substituent include a phenyl group, a tolyl group, a biphenyl group, a cyclohexylphenyl group, and a naphthyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R _{1 to} R ₆ are preferably a methyl group or a phenyl group. When R _{1 to} R ₆ are a methyl group or a phenyl group, raw materials are easily available, which is advantageous in production, and the resulting resin has a good balance of heat resistance and handling properties, which is preferable. q _{1 to 6} are preferably from 0 to 2, and are also preferred when R _{1 to} R ₆ are not present.

In the epoxy ester compound (a1) represented by the general formula (1), p ₁ to ₄ are preferably all 0. That is, the liquid repellent resin composition of the present invention comprises a polybasic epoxy ester compound in which the condensed ring-containing alkali-soluble resin (A1) has a bifunctional / linear structure represented by the following general formula (4): A condensed ring structure-containing alkali-soluble resin (A1-1) obtained by reacting a carboxylic acid or an anhydride thereof is preferable.

Here, A ₀ , R _1-4 , R ₇ , R _8-11 , q _1-4 , m _1-4 , s ₁ are the same as described above, and they are asymmetric even if the structural formula is symmetrical. May be. Moreover, several R _{< 1 > -4} , R _{<7> -11} may be the same, and may differ.

In addition, the liquid repellent resin composition of the present invention includes a condensed ring structure-containing alkali-soluble resin (A2), an epoxy ester compound represented by the general formula (4), a polyhydric alcohol, and a polybasic carboxylic acid. Or it is preferable that it is a condensed ring structure containing alkali-soluble resin (A2-1) obtained by making it react with the anhydride.

The condensed ring structure-containing alkali-soluble resin (A) of the present invention is preferably a divalent group containing a condensed ring structure in which A ₀ is selected from the group consisting of formulas (5) to (9) and (17), more preferably. is a divalent group containing a condensed ring _{structure a 0} is selected from the group consisting of the formulas (5) to (7) and _{(17), q 1 to 4} are each independently integer of 0 to 2, m _1-4 are each independently an integer of 0 to 2, and s ₁ is an integer of 0 to 10. In the formula, R ₇ is more preferably an acrylic group.

When any one of p1 to _{p4 in} the general formula (1) is an integer of 1 or more, the epoxy ester compound has a polyfunctional / branched structure, and further contains a condensed ring structure-containing alkali-soluble resin (A ) Has a branched structure. Further, if any one of p _{5 to 6} is 1 or more, the epoxy ester compound has a further branched structure, and the condensed ring-containing alkali-soluble resin (A) obtained therefrom also has a further branched structure. .
When a p _{1 to 4} are all 0 in the general formula (1), epoxy ester compound has a bifunctional-linear structure, further condensed ring structure-containing alkali-soluble resin obtained therefrom (A) is linear structure The structure is mainly composed of Here, polyfunctional and bifunctional indicate the number of epoxy ester groups.

Regardless of the presence or absence of the branched structure of the condensed ring-containing alkali-soluble resin, the liquid-repellent resin composition of the present invention can exhibit excellent liquid-repellent properties. In this case, since a dense cross-linked structure can be easily formed after curing, improvement in physical properties such as heat resistance of the resin composition of the present invention can be expected, but on the other hand, in the reaction with a polybasic carboxylic acid or its anhydride. Therefore, it is necessary to strictly adjust the synthesis conditions so as not to form a higher-order crosslinked structure. In the case of an epoxy ester compound having a linear structure, since a cross-linked structure is unlikely to occur in the reaction with a polybasic carboxylic acid or its anhydride, the molecular weight adjustment that can greatly affect the preparation of the radiation-sensitive resin composition, It is particularly preferably used as the alkali-soluble resin containing a condensed ring structure in the resin composition of the present invention in that the degree of freedom in designing various types of resins such as acid value adjustment is high.

The epoxy ester compound (a1) used for the preparation of the condensed ring structure-containing alkali-soluble resin (A1) or (A2) of the present invention is (1): a step of allowing a monobasic carboxylic acid to act on the condensed ring structure-containing epoxy resin. Or (2) obtained from a production method including a step of allowing glycidyl monobasic carboxylate to act on a polyfunctional hydroxyl group-containing condensed ring structure compound represented by the following general formula (10).

First, the method (1) will be described.
The condensed ring structure-containing epoxy resin used for the preparation of the epoxy ester compound (a1) is obtained from a production method including a step of causing an epihalohydrin to act on a polyfunctional hydroxyl group-containing condensed ring structure compound represented by the following general formula (10).

Here, A ₀ is the same as above, and R _{17 to 18} are each independently a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, alkoxy having 1 to 5 carbon atoms. Group, a phenyl group which may have a substituent, or a halogen atom, and f ₁ and ₂ are each independently an integer of 0 to 4. R _19-20 are each independently a hydrogen atom or a methyl group, m _9-10 are each independently an integer from 0 to 10, and r _1-2 are each independently an integer from 1 to 5, The equation may be symmetric or asymmetric.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin and the like, and epichlorohydrin is particularly preferably used because it is easy to handle and inexpensive.

The polyfunctional hydroxyl group-containing condensed ring structure compound can be prepared by a method known in the art. For example, it is known that it is produced by condensing phenols and ketones in the presence of an acidic catalyst (see, for example, JP-A-7-112949).

The reaction between the polyfunctional hydroxyl group-containing condensed ring structure compound and epichlorohydrin is usually performed in a temperature range of 50 to 120 ° C. for 1 to 10 hours. Preferably, it is performed for 3 to 6 hours in a temperature range of 70 to 110 ° C.
The ratio of the polyfunctional hydroxyl group-containing condensed ring structure compound and epichlorohydrin is preferably 1 to 20 mol of epichlorohydrin with respect to 1 mol of hydroxyl group of the polyfunctional hydroxyl group-containing condensed ring structure compound. Examples of the catalyst used for the reaction between the polyfunctional hydroxyl group-containing condensed ring structure compound and epichlorohydrin include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, and imidazole compounds.

The monobasic carboxylic acid used for the preparation of the epoxy ester compound (a1) includes, but is not limited to, the following compounds having one carboxyl group: (meth) acrylic acid, cyclopropanecarboxylic acid, 2,2,3,3-tetramethyl-1-cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 2-cyclopentenylcarboxylic acid, 2-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, cyclohexanecarboxylic acid, 4-propylcyclohexane Carboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid, 4-cyanocyclohexane-1-carboxylic acid, 4-hydroxycyclohexanecarboxylic acid 1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid, 2- (1,2-dihydroxy-4-methylcyclohexyl) propionic acid, shikimic acid, 3-hydroxy-3,3-diphenylpropionic acid, 3- (2-oxocyclohexyl) propionic acid, 3-cyclohexene-1-carboxylic acid, hydrogen alkyl 4-cyclohexene-1,2-dicarboxylate, cycloheptanecarboxylic acid, norbornenecarboxylic acid, tetracyclododecenecarboxylic acid, 1 -Adamantanecarboxylic acid, (4-tricyclo [5.2.1.0 ^2.6 ] dec-4-yl) acetic acid, p-methylbenzoic acid, p-ethylbenzoic acid, p-octylbenzoic acid, p-decyl Benzoic acid, p-dodecylbenzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-propoxyan Benzoic acid, p-butoxybenzoic acid, p-pentyloxybenzoic acid, p-hexyloxybenzoic acid, p-fluorobenzoic acid, p-chlorobenzoic acid, p-chloromethylbenzoic acid, pentafluorobenzoic acid, pentachlorobenzoic acid Acid, 4-acetoxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, o-benzoylbenzoic acid, o-nitrobenzoic acid, o- (acetoxybenzoyloxy) ) Benzoic acid, terephthalic acid monomethyl ester, isophthalic acid monomethyl ester, isophthalic acid monocyclohexyl ester, phenoxyacetic acid, chlorophenoxyacetic acid, phenylthioacetic acid, phenylacetic acid, 2-oxo-3-phenylpropionic acid, o-bromophenylacetic acid, o -Iodophenylacetic acid, methoxyphenyl Acid, 6-phenylhexanoic acid, biphenylcarboxylic acid, α-naphthoic acid, β-naphthoic acid, anthracenecarboxylic acid, phenanthrenecarboxylic acid, anthraquinone-2-carboxylic acid, indanecarboxylic acid, 1,4-dioxo-1,4 -Dihydronaphthalene-2-carboxylic acid, 3,3-diphenylpropionic acid, nicotinic acid, isonicotinic acid, cinnamic acid, 3-methoxycinnamic acid, 4-methoxycinnamic acid, quinolinecarboxylic acid, etc. You may use independently and may combine 2 or more types. Particularly preferred monobasic carboxylic acids are those containing an unsaturated group capable of introducing a radiation-polymerizable functional group into the condensed ring-containing alkali-soluble resin (A). For example, (meth) acrylic acid is preferred. .

As the polyfunctional hydroxyl group-containing condensed ring structure compound of the general formula (10) used in the method (2), those described above can be used. The monobasic glycidyl carboxylate used in the method (2) includes, but is not limited to, the following compounds: glycidyl (meth) acrylate, glycidyl acetate, glycidyl butyrate, glycidyl benzoate, p-ethyl Such as glycidyl benzoate, these may be used alone or in combination of two or more.

Reaction of the condensed ring structure-containing epoxy resin and monobasic carboxylic acid in the production method of (1) above, and polyfunctional hydroxyl group-containing condensed ring structure compound (10) and monobasic glycidyl carboxylate in the production method of (2) above These reactions are carried out in a temperature range of 50 to 120 ° C. for 5 to 30 hours using an appropriate solvent as necessary. Examples of the solvent that can be used include methyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and 3-methoxybutyl-1-acetate. Alkylene monoalkyl ether acetates; alkylene monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether; ketones such as methyl ethyl ketone and methyl amyl ketone; dimethyl succinate, diethyl succinate, diethyl adipate, Malonic acid die Le, and the like esters such as dibutyl oxalate. Of these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferred. Furthermore, a catalyst and a polymerization inhibitor can be used as necessary. Examples of the catalyst used include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds, and the like, and usually used in a range of 0.01 to 10% by weight of the total reaction product. It is preferred that Examples of the polymerization inhibitor to be used include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine and the like, and can be usually added in the following range of 5% by weight of the whole reaction product.

The polyhydric alcohol (a2) used for the preparation of the condensed ring structure-containing alkali-soluble resin (A2) refers to a compound containing two or more hydroxyl groups in the molecule, and examples thereof include the following compounds: Not limited to: ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimethylolbutanoic acid, dimethylolpropanoic acid, tartaric acid, Glycerin, diglycerin, trimethylolethane, trimethylolpropane, isocyanuric acid tris (2-hydroxyethyl), ditrimethylolpropane, ditrimethylolethane, pentaerythritol, erythritol, xylitol, sorbitol, i Shitoru, dipentaerythritol, poly glycerin. Among these, when a trifunctional or higher functional compound such as trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol is used, the adhesion between the thin film obtained from the composition containing the resin and the substrate Is preferable, and the transparency of the film is excellent. These polyhydric alcohols (a2) may be used alone or in combination of two or more.

The polybasic carboxylic acid or its anhydride (a3) used for the preparation of the condensed ring structure-containing alkali-soluble resin (A1) or (A2) is a carboxylic acid having a plurality of carboxyl groups such as dicarboxylic acid and tetracarboxylic acid. Or their anhydrides, and these polybasic carboxylic acids, or their anhydrides, include the following compounds: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Dicarboxylic acids such as methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, glutaric acid and their anhydrides; trimellitic acid or its anhydride, pyromellitic acid, benzophenone tetracarboxylic acid, Biphenyl tetracarboxylic acid, biphenyl A Tetracarboxylic acid, biphenylsulfonetetracarboxylic acid, 4- (1,2-dicarboxyethyl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, butanetetracarboxylic acid, etc. Acids and their acid dianhydrides and the like.

The “polybasic carboxylic acid or its anhydride (a3)” means “at least one of a specific polybasic carboxylic acid and its corresponding anhydride”. If the acid is phthalic acid, it refers to at least one of phthalic acid and phthalic anhydride.

By appropriately selecting the type and number of polybasic carboxylic acid or its anhydride, various condensed ring structure-containing alkali-soluble resins (A1) having different structures can be produced. Specifically, for example, the first to third condensed ring structure-containing alkali-soluble resins (A1) shown in the following (i) to (iii) are prepared, but these are exemplifications.
(I) First condensed ring skeleton-containing alkali-soluble resin (A1):
A resin obtained by mixing and reacting an epoxy ester compound (a1) with one kind of polybasic carboxylic acid or its anhydride (a3);
(Ii) Second condensed ring skeleton-containing alkali-soluble resin (A1):
Mixing the epoxy ester compound (a1) with two or more polybasic carboxylic acids or a mixture of anhydrides thereof (for example, a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride) (a3); A resin obtained by reaction; and
(Iii) Third condensed ring skeleton-containing alkali-soluble resin (A1):
Obtained by further reacting the reaction product obtained by reacting the epoxy ester compound (a1) with tetracarboxylic acid or its dianhydride (a3-1) with dicarboxylic acid or its anhydride (a3-2). Resin.

The condensed ring-containing alkali-soluble resin (A2) is obtained by reacting the epoxy ester compound (a1), the polyhydric alcohol (a2), and the polybasic carboxylic acid or its anhydride (a3). . In this reaction, the addition order of the epoxy ester compound (a1), the polyhydric alcohol (a2), and the polybasic carboxylic acid or its anhydride (a3) is not particularly limited. For example, a method in which a part or all of these are mixed and reacted at the same time, specifically, the epoxy ester compound (a1) and the polyhydric alcohol (a2) are mixed, and then the polybasic carboxylic acid or its anhydride is mixed. There is a method of adding and mixing the product (a3) and reacting. Further, a polybasic carboxylic acid may be further added to these reaction products for reaction. By appropriately selecting the type and number of the polybasic carboxylic acid or its anhydride, various condensed ring structure-containing alkali-soluble resins (A2) having different structures can be produced. Specifically, for example, the fourth to sixth condensed ring-containing alkali-soluble resins (A2) shown in the following (iv) to (vi) are prepared, but these are exemplifications.
(Iv) Fourth condensed ring skeleton-containing alkali-soluble resin (A2):
A resin obtained by mixing and reacting an epoxy ester compound (a1), a polyhydric alcohol (a2), and one kind of polybasic carboxylic acid or its anhydride (a3);
(V) Fifth condensed ring skeleton-containing alkali-soluble resin (A2):
Epoxy ester compound (a1), polyhydric alcohol (a2), and a mixture of two or more polybasic carboxylic acids or anhydrides thereof (for example, a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride) A resin obtained by mixing and reacting with (a3); and
(Vi) Sixth condensed ring skeleton-containing alkali-soluble resin (A2):
The reaction product obtained by reacting the epoxy ester compound (a1), the polyhydric alcohol (a2), and the tetracarboxylic acid or its dianhydride (a3-1) is further added to a dicarboxylic acid or its anhydride (a3). -2) and a resin obtained.

Further, “a mixture of two or more polybasic carboxylic acids or anhydrides thereof” means that at least two types of polybasic carboxylic acids or anhydrides thereof are simultaneously present. Therefore, in the methods (ii) and (v), at least two types of polybasic carboxylic acids or their anhydrides are involved in the reaction.

The fused ring structure-containing alkali-soluble resin (A1) or (A2) is an epoxy ester compound (a1), a polyhydric alcohol (a2), a polybasic carboxylic acid or an anhydride thereof (a3) in any of the methods exemplified above. ) Are dissolved (suspended) in a cellosolve-based solvent such as ethyl cellosolve acetate and butyl cellosolve acetate, and heated to react in the above exemplified method (order).

In the production of the condensed ring-structure-containing alkali-soluble resin (A2), the epoxy ester compound (a1) and the polyhydric alcohol (a2) are the hydroxyl group of the epoxy ester compound (a1) and the hydroxyl group of the polyhydric alcohol (a2). The molar ratio is preferably adjusted to be 99/1 to 50/50, more preferably 95/5 to 60/40. When the molar ratio of the hydroxyl groups of the polyhydric alcohol (a2) exceeds 50%, the molecular weight of the resulting resin increases rapidly and there is a risk of gelation. On the other hand, if it is less than 1%, the molecular weight of the resulting resin does not increase sufficiently, and the heat resistance tends to be difficult to improve.

The polybasic carboxylic acid or anhydride (a3) thereof is preferably 0.000 in terms of acid anhydride group with respect to 1 equivalent (mole) of the total hydroxyl groups of the epoxy ester compound (a1) and the polyhydric alcohol (a2). It is subjected to the reaction at a ratio of 3 to 1 equivalent, more preferably 0.4 to 1 equivalent. If polybasic carboxylic acid or its anhydride (a3) is less than 0.3 equivalent in terms of acid anhydride group, the molecular weight of the resulting alkali-soluble resin may not be high. Therefore, when exposure and development are performed using such a radiation-sensitive resin composition containing an alkali-soluble resin, the resulting film may have insufficient heat resistance or the film may remain on the substrate. is there. When the polybasic carboxylic acid or its anhydride exceeds 1 equivalent in terms of acid anhydride group, unreacted acid or acid anhydride remains, and the molecular weight of the resulting alkali-soluble resin becomes low, and the resin In some cases, the developability of the radiation-sensitive resin composition containing is poor.

In addition, acid anhydride group conversion shows the quantity when all the carboxyl groups and acid anhydride groups contained in the polybasic carboxylic acid to be used or its anhydride (a3) are converted into acid anhydride.

In the production of the second, third, fifth, and sixth alkali-soluble resins, two or more polybasic carboxylic acids or anhydrides thereof are used. Generally, dicarboxylic anhydride and tetracarboxylic dianhydride are used. The ratio between the dicarboxylic acid anhydride and the tetracarboxylic dianhydride is preferably 1/99 to 90/10, and more preferably 5/95 to 80/20, as a molar ratio. If the ratio of the dicarboxylic acid anhydride is less than 1 mol% of the total acid anhydride, the resin viscosity becomes high and workability may be lowered. Furthermore, since the molecular weight of the obtained resin becomes too large, when the thin film is formed on the substrate using the radiation-sensitive resin composition containing the resin and the exposure is performed, the exposed portion is in contact with the developer. It tends to be difficult to dissolve and difficult to obtain the desired pattern. When the proportion of dicarboxylic acid anhydride exceeds 90 mol% of the total acid anhydride, the molecular weight of the resulting resin becomes too small, so when a coating film is formed on the substrate using the composition containing the resin, Problems such as sticking remaining in the coating film after pre-baking tend to occur.

In any of the above cases, during the reaction of the epoxy ester compound (a1), the polyhydric alcohol (a2), and the polybasic carboxylic acid or its anhydride (a3), the reaction temperature is preferably 50 to 130 ° C. Preferably it is 70-120 degreeC. When the reaction temperature exceeds 130 ° C., some condensation of carboxyl groups and hydroxyl groups occurs, and the molecular weight increases rapidly. On the other hand, if it is less than 50 ° C., the reaction does not proceed smoothly, and unreacted polybasic carboxylic acid or its anhydride remains.

The alkali-soluble resin (A) contained in the liquid-repellent resin composition of the present invention may be any of the first, second, third, fourth, fifth and sixth resins. May be a single resin or a mixture of two or more. As for the compounding quantity of alkali-soluble resin (A) in the liquid repellent resin composition of this invention, 20 to 95 weight% is preferable with respect to the whole liquid repellent resin composition.

Fluorine-containing polyether compound (B)
The fluorine-containing polyether compound (B) of the present invention refers to a fluorine compound having two or more etheric oxygen atoms. Examples of such a fluorine-containing polyether compound (B) include those having a fluorine-containing alkylene ether structure represented by any of the following general formulas (18) to (20), and having 2 to 100 carbon atoms. Examples thereof include compounds having an ether bond and a fluorine-containing alkylene group.
Since the fluorine-containing polyether compound (B) of the present invention has two or more etheric oxygen atoms, the liquid repellency of the coating film surface can be improved.

In the formula, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are each independently hydrogen, F or 20 or less carbon atoms. X, y and z are each independently an integer of 0 or more, and x + y + z contained in (B) is an integer of 2 or more. However, at least one of R ₁₉ and R ₂₀ is F or a fluorine-containing alkyl group having 20 or less carbon atoms, and at least one of R _{21 to} R ₂₄ is F or a fluorine-containing alkyl group having 20 or less carbon atoms. And at least one of R _{25 to} R ₃₀ is F or a fluorine-containing alkyl group having 20 or less carbon atoms.

Examples of the fluorine-containing alkyl group (b1) having 20 or less carbon atoms include a trifluoromethyl group and a pentafluoroethyl group.
For x, y, and z, when the fluorine-containing polyether compound (B) contains only one of the structural units (18), (19), and (20), x, y, or z is independently 5 or more. Yes, when two or more types of structural units are included, it is preferable that the total of x, y, and z is 5 or more.
Further, the fluorine-containing polyether compound (B) preferably has an unsaturated group in the molecule. By containing an unsaturated group, a fluorine-containing polyether compound (B) is fixed to a coating film, and liquid-repellent durability can be improved.
In this specification, “liquid repellency” indicates both water repellency and oil repellency.

The fluorine-containing polyether compound (B) can be represented, for example, by the following general formula (21).

Here, Rf _{a and} Rf _b each independently represent hydrogen, F, or a fluorine-containing alkyl group having 20 or less carbon atoms, i ₁ is an integer of 0 to 20, and i ₂ is an integer of 0 to 20. , N is an integer from 1 to 200. More preferably, i ₁ is an integer of 0 to 3, i ₂ is an integer of 0 to 3, and n is an integer of 5 to 20. h is an integer of 1 to 5, more preferably an integer of 1 to 3. Further, at least one of Rf _a is preferably F or a fluorine-containing alkyl group having 20 or less carbon atoms, and at least one of Rf _b is preferably F or a fluorine-containing alkyl group having 20 or less carbon atoms. .

Represents a structure composed of n fluorine-containing alkylene ether structures FE _{1 to} FE _n . Here, the fluorine-containing alkylene ether structure is one in which an alkylene group is bonded to one oxygen atom, and at least one carbon atom constituting the alkylene group has one or more fluorine atoms. An atom or a structure having a fluoroalkyl group having 20 or less carbon atoms (for example, CF ₃ etc.) is bonded. At least one of the _n fluorine-containing alkylene ether structures FE _{1 to} FE n in the general formula (21) is a structure including the fluorine-containing alkylene ether structure represented by any of the general formulas (18) to (20). It is preferable that the fluorine-containing alkylene ether structures FE _{1 to} FE _n are each independently a fluorine-containing alkylene ether structure represented by any one of the general formulas (18) to (20). When n is 2 or more, FE _{1 to} FE _n may be the same or different, and the order of bonding is not particularly limited. When n is 1, one FE ₁ is present in the same main chain.
L is a single bond,

And K is a group containing an unsaturated group, and specific examples include groups having structures described in the following formulas (23) to (33).

The fluorine-containing polyether compound (B) includes, for example, those represented by the following general formula (22).

Wherein _{j 1} is an integer of 1 to 100, _{j 2} is an integer of 1 to 50. Rf _c is a fluorinated polyether group having two or more etheric oxygen atoms, the general formula (18) to preferably contains at least one fluorine-containing alkylene ether structure represented by any one of (20). If j ₂ is 2 or more, the plurality of Rf _c may be the same or different. The meanings of K and L are the same as above. L ′ is a single bond or a group represented by the following general formula.

As the fluorine-containing polyether compound (B) described in the general formula (21), for example,

There is. Here, Rf ₁ is each independently a fluorine-containing alkyl group having 20 or less carbon atoms. y1 is an integer of 0 to 30, z1 is an integer of 0 to 20, and at least one of y1 and z1 is an integer of 1 or more. y2 is an integer of 1 to 30, z2 is an integer of 1 to 20, and examples of the fluorine-containing alkyl group having 20 or less carbon atoms include the same as the above (b1). K ₁ is

Etc. are mentioned as specific examples.
Examples of the production method of the above specific example (FPE2) include the methods described in International Publication No. 94/27945 pamphlet and International Publication No. 01/46107 pamphlet.
Specific examples (FPE1) and (FPE3) are produced by, for example,

(Wherein y1, z1, and z2 are the same as above), there is a method of reacting a fluorine-containing compound having an OH group with an acid halide such as α-fluoroacrylic acid fluoride.

Furthermore, as an example of the fluorine-containing polyether compound (B) described in the general formula (21),

There is. Rf ₆ and Rf ₇ each independently represent hydrogen, F, or a fluorine-containing alkyl group having 20 or less carbon atoms, and more preferably a hydrogen atom, F, or CF ₃ . At least one of Rf ₆ is a group containing a fluorine atom (F or a fluorine-containing alkyl group having 20 or less carbon atoms), and at least one Rf ₇ is a group containing a fluorine atom (F or A fluorine-containing alkyl group having 20 or less carbon atoms is desirable. h is an integer of 1 to 5, i is an integer of 0 to 20, j is an integer of 0 to 20, and n is an integer of 1 to 200. More desirably, h is an integer of 1 to 3, i is an integer of 0 to 3, j is an integer of 0 to 3, and n is an integer of 5 to 20. Meaning of FE ₁ ~FE _n is as defined above, n may be 2 or _more, FE 1 ~FE _n may be different even in the same order of binding is not particularly limited. When n is 1, one FE ₁ is present in the same main chain. K ₂ is a group containing a (meth) acryloyloxy group. Examples of K _2,

(In the formula, m is an integer of 0 to 10. * represents a bonding part). Among these, from the viewpoint of the affinity between the condensed ring-containing alkali-soluble resin (A) and the fluorine-containing polyether compound (B), a structure having a urethane bond also in K ₂ is preferable. The thing as shown by Formula (31)-(33) is mentioned.

As the fluorine-containing polyether compound (B) described in the general formula (22), for example,

There is. Here, Rf ₅ is a fluorine-based polyether group containing at least one of the above (19) or (20). y3 is 1-100, and y4 is 1-50.

Moreover, when two or more types of structural units exist in FPE1 and FPE4, the order is arbitrary. Two or more identical structural units may be present in the same main chain. For example, in FPE4

(Hereinafter referred to as “y3 ′”) and

The order (hereinafter referred to as “y4 ′”) may be either −y3′-y4′- or -y4′-y3′-, and may be combined at random (y3′-y4′-y3 ′, etc.). May be. Furthermore, structural units other than the structural units represented by y3 ′ and y4 ′ (for example, structural units represented by the formula (18) and other fluorine-containing alkyl ethers) may be contained. The bonding position is not particularly limited, and may be bonded to the outside of the structure represented by -y3'-y4'- or -y4'-y3'-, and is represented by y3 'and y4'. It may be sandwiched between structural units.

As a manufacturing method of the specific example (FPE4), for example, a method described in International Publication No. 03/076484 pamphlet or the like, that is, a radical of tetrafluoroethylene and fluorovinylethers using a radical initiator that generates a hydroxyl radical OH. There is a method of reacting methanol and allylamine with a copolymer.
As a manufacturing method of a specific example (FPE5), for example,

(Wherein Rf ₆ , Rf ₇ , i, j, and FE _{1 to} FE _n are the same as above) fluorinated polyether compounds having an OH group such as 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate Of the above-mentioned isocyanates, the above fluorinated polyether compound having an OH group, 2-hydroxyethyl methacrylate (2-HEMA), 4-hydroxybutyl acrylate (4-HBA), 1,4-cyclohexanedimethanol OH group-containing (meth) acrylate compounds such as monoacrylate (CHDMMA) and tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′-diphenylmethane diisocyanate (MDI), 2 , 2,4 Reacts with polyisocyanates such as trimethylhexamethylene diisocyanate / 2,4,4-trimethyl-hexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate and their polynuclear compounds. The method of making it etc. can also be used suitably. Specific examples of the above polyisocyanates include polyisocyanates obtained by reacting polymeric MDI, TDI, and MDI with polyhydric alcohols (for example, Coronate L-55E manufactured by Nippon Polyurethane Industry Co., Ltd.), TDI, and HDI. And polyisocyanates having an isocyanurate ring (for example, Coronate 2030 or Coronate HX manufactured by Nippon Polyurethane Industry Co., Ltd.). As described above, K ₂ in (FPE5) preferably contains a urethane bond, and in order to produce (FPE5) having such a structure, a compound having a plurality of isocyanate groups is required. From this viewpoint, the above polyisocyanates are particularly preferable. In the liquid repellent resin composition of the present invention, the fluorine-containing polyether compound (B) needs to efficiently migrate to the film surface during film formation, but in the state of the composition (coating liquid), it contains a condensed ring structure. It is necessary that the alkali-soluble resin (A) and the fluorine-containing polyether compound (B) are mixed uniformly and stably. The fluorine-containing polyether compound (B) in the present invention has an appropriate affinity with the condensed ring structure-containing alkali-soluble resin (A). Therefore, it has moderate affinity with the condensed ring structure-containing alkali-soluble resin (A), and the balance between the stability of the blended liquid and the surface migration of the fluorinated polyether compound (B) during film formation is extremely excellent. Therefore, (FPE5) having a urethane bond is particularly preferable. In addition, when the (meth) acryloyl group coexists, when the liquid repellent resin composition of the present invention is cured, the fluorinated polyether (B) is also involved in the curing reaction and incorporated into the coating surface. Therefore, it is preferable in terms of enhancing the liquid repellency.

The fluorine-containing polyether compound (B) contained in the liquid repellent resin compositions (1) and (2) of the present invention is not limited to the above compounds, but these are single resins. It may also be a mixture of two or more.

In the liquid repellent resin compositions (1) and (2) of the present invention, the ratio of the fluorine-containing polyether compound (B) is 0.01 to 100 parts by weight of the condensed ring structure-containing alkali-soluble resin (A). Is preferably in the range of 0.05 to 5 parts by weight. When the ratio of the fluorinated polyether compound (B) is in the range of 0.01 to 10 parts by weight, the compatibility between the alkali-soluble resin (A) and the fluorinated polyether compound (B) is kept exquisitely. The fluorine-containing polyether compound (B) quickly migrates to the coating surface, imparts liquid repellency only to the coating surface, has good developability, and lowers substrate adhesion due to the fluoroalkyl group. Can be prevented. When the amount is more than 10 parts by weight, the fluorine component is widely distributed inside the film, and it becomes difficult to impart liquid repellency only to the coating film surface.

In the liquid repellent resin compositions (1) and (2) of the present invention, at least one of the condensed ring-containing alkali-soluble resin (A) and the fluorine-containing polyether compound (B) can be polymerized by light or heat. It preferably contains an unsaturated group. More preferably, both (A) and (B) contain the unsaturated group.

Moreover, since the condensed ring-containing alkali-soluble resin (A) and the fluorinated polyether compound (B) are mainly solid, the liquid repellent resin compositions (1) and (2) of the present invention contain a solvent. It is preferable to make it.
Such a solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the composition and can dissolve or disperse them. Examples include the following compounds: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl Cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methoxybutyl-1- acetate Any alkylene glycol alkyl ether acetates; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol alkyl ethers; aromatic hydrocarbons such as toluene and xylene Ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methyl propionate, ethyl ethoxy acetate, hydroxyacetate , Methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, lactic acid Esters such as ethyl.

Of these, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, and in particular ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol methyl ether acetate, ethylene glycol monoethyl ether Acetate and methyl amyl ketone are preferred. These solvents may be used alone or in a combination of two or more.
The blending amount of the solvent in the liquid repellent resin composition of the present invention is preferably 5 to 70% by weight of the whole composition.

(II) Radiation sensitive resin composition The radiation sensitive resin composition of the present invention contains at least one of the liquid repellent resin composition (1) or (2). As used herein, “radiation” refers to at least one of visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, and proton beam rays.
Usually, this radiation-sensitive resin composition contains the liquid-repellent resin composition and a radiation-reactive compound. When this composition is a positive radiation-sensitive resin composition, the radiation-reactive compound is, for example, a quinonediazide compound (hereinafter sometimes referred to as a quinonediazide compound (D)). It is preferable to contain 0.5 to 50 parts by weight with respect to 100 parts by weight of the liquid resin composition. In the case of a negative radiation-sensitive resin composition, the radiation-reactive compound is, for example, a photopolymerization initiator (C). The photopolymerization initiator (C) is preferably contained in an amount of 0.1 to 30 parts by weight, more preferably in the range of 0.4 to 10 parts by weight with respect to 100 parts by weight of the liquid repellent resin composition. is there. The radiation sensitive resin composition of the present invention further contains other components as necessary.
Hereinafter, the radiation-sensitive resin composition of the present invention will be described by taking a negative radiation-sensitive resin composition as an example.

The negative radiation sensitive resin composition of the present invention contains a photopolymerization initiator (C) as a radiation-reactive compound with the liquid repellent resin composition. The photopolymerization initiator (C) refers to a compound having a photopolymerization initiating action and / or a compound having a sensitizing effect. Examples of such compounds include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone. , Acetophenones such as 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p′-bisdimethylaminobenzophenone Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzyl dimethyl ketal, thioxanthene, 2-chlorothioxan Sulfur compounds such as 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone Organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide; and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole.

These compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Furthermore, a compound which does not act as a photopolymerization initiator itself but can increase the ability of the photopolymerization initiator by using it in combination with the above compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

The radiation sensitive resin composition of this invention contains a radiation sensitive monomer or oligomer (E) as needed. The radiation-sensitive monomer or oligomer (E) is a monomer or oligomer that can be polymerized by radiation, and can be contained according to the physical properties according to the intended use of the composition. These monomers or oligomers can be contained as long as they act as a viscosity modifier or a photocrosslinking agent and do not impair the properties of the liquid repellent resin composition of the present invention. When at least one of the condensed ring structure-containing alkali-soluble resin (A) and the fluorine-containing polyether compound (B) has a radiation sensitive reactivity (when it contains an unsaturated group in the molecule), a radiation sensitive monomer or It is not essential to contain the oligomer (E). However, when both (A) and (B) do not have radiation-sensitive reactivity (when no unsaturated group is contained in the molecule), in order to function as a radiation-sensitive resin composition, a further radiation-sensitive monomer Or it is necessary to contain an oligomer (E).
Usually, the monomer and oligomer are contained in the composition in a total amount of 50 parts by weight or less based on 100 parts by weight of the solid content of the liquid repellent resin composition of the present invention. When the content of the monomer or oligomer exceeds 50 parts by weight, there may be a problem in sticking property after pre-baking.

Examples of the monomer or oligomer that can be polymerized by the radiation (E) include the following monomers or oligomers: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth). Monomers having a hydroxyl group such as acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid esters such as glycerol (meth) acrylate. These monomers or oligomers may be used alone or in combination of two or more.

The radiation sensitive resin composition of the present invention further contains (a) a compound having an epoxy group, (b) an additive, (c) a solvent, and the like, as necessary.
As the compound (a) having an epoxy group, a polymer or monomer having at least one epoxy group is used. Examples of the polymer having at least one epoxy group include a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenyl epoxy resin, and an alicyclic ring. There is an epoxy resin such as an epoxy resin. Examples of the monomer having at least one epoxy group include phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate. These compounds may be used alone or in combination of two or more.

The compound which has these epoxy groups may be contained in the range which does not impair the property of the resin composition of this invention. Usually, the compound having an epoxy group is contained in a proportion of 50 parts by weight or less per 100 parts by weight of the solid content of the liquid repellent resin composition. When the amount exceeds 50 parts by weight, cracking is likely to occur when the composition containing the component is cured, and the adhesion tends to be lowered.

Examples of the additive (b) include a thermal polymerization inhibitor, an adhesion assistant, an epoxy group curing accelerator, a surfactant, and an antifoaming agent, and these are in amounts that do not impair the purpose of the present invention. Contained in the composition.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like.

The adhesion aid is contained in order to improve the adhesion of the resulting composition. As the adhesion assistant, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanato group, and an epoxy group is preferable. Specific examples of this functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. By containing a small amount of an epoxy group curing accelerator, various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties and hardness of the cured film obtained by heating are improved.

The surfactant is included, for example, to facilitate application of a liquid composition on a substrate, and the flatness of the resulting film is also improved. Surfactants include, for example, BM-1000 (manufactured by BM Hemy), MegaFuck F142D, MegaFuck F172, MegaFuck F173 and MegaFuck F183 (Dainippon Ink Chemical Co., Ltd.), Florard FC-135, Fluorard FC-170C, Fluorard FC-430 and Fluorard FC-431 (manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141 and Surflon S-145 (Asahi Glass Co., Ltd.) )), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.).

Examples of the antifoaming agent include silicone, fluorine, and acrylic compounds.

The solvent (c) that can be contained in the radiation-sensitive resin composition of the present invention is used to uniformly dissolve each component in the composition, for example, to facilitate coating on a substrate. Such a solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the composition and can dissolve or disperse them. Examples include the following compounds: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl Cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methoxybutyl-1- acetate Any alkylene glycol alkyl ether acetates; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other diethylene glycol (di) alkyl ethers; aromatics such as toluene and xylene Hydrocarbons; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy 2-methyl ethyl propionate, ethyl ethoxy acetate, hydroxy Ethyl acetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, Esters such as ethyl lactate.

Of these, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, and in particular ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol methyl ether acetate, ethylene glycol monoethyl ether Acetate and methyl amyl ketone are preferred. These solvents may be used alone or in a combination of two or more.
As for the compounding quantity of the solvent (c) in the radiation sensitive resin composition of this invention, 5-70 weight% of the whole composition is preferable.

In the negative radiation sensitive resin composition of the present invention, radicals are preferably generated from the photopolymerization initiator (C) upon irradiation with light having a wavelength of 100 to 600 nm, and the unsaturated group undergoes a crosslinking reaction. When the liquid repellent resin composition of the present invention is composed of a compound having no unsaturated group, a crosslinked matrix produced by a crosslinking reaction between radiation-sensitive monomers or oligomers that can be added to the negative radiation-sensitive resin composition The liquid repellent resin composition is immobilized on the surface. In addition, when the alkali-soluble resin (A) and / or the fluorinated polyether compound (B) containing the condensed ring structure of the liquid repellent resin composition of the present invention contains an unsaturated group, the liquid repellent resin composition itself. Participates in the polymerization reaction, is incorporated into the crosslinked structure, and is immobilized. As a result, the exposed portion becomes insoluble in alkali, and in the subsequent alkali development step, since the condensed ring-containing alkali-soluble resin (A) has alkali solubility, the unexposed portion can be removed and a pattern can be formed. .
A cured product obtained by curing a resin composition comprising a condensed ring structure-containing alkali-soluble resin (A) and a fluorine-containing polyether compound (B) has (A) and (B) itself in a crosslinked structure of the cured product. When incorporated and fixed, the liquid-repellent durability of the coating film is excellent, and therefore the condensed ring-containing alkali-soluble resin (A) and the fluorinated polyether compound (B) preferably have an unsaturated group.

In the radiation sensitive resin composition of this invention, a coloring agent can be contained as needed. Examples of the colorant include dyes, organic pigments, inorganic pigments, metallic pigments and the like. Examples of the dye include compounds classified as dyes in color indexes (CI; issued by The Society of Dyers and Colorists) such as azo dyes, azomethine dyes, xanthene dyes, and quinone dyes. Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), and the central metals are Cu, Mg, Al, Si, Ti, V, Examples include dissimilar metal phthalocyanine pigments such as Mn, Fe, Co, Ni, Zn, Ge, and Sn. Inorganic pigments include metal oxides such as titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, cerium oxide, tin oxide, tantalum oxide, indium tin oxide, cobalt oxide, and barium oxide hafnium sulfate; calcium carbonate, gold chloride, odor Metal salts such as gold chloride, silver chloride, silver bromide, silver iodide, palladium chloride, chloroplatinic acid, sodium chloroaurate, silver nitrate, platinum acetylacetonate, palladium acetylacetonate; gold, silver, platinum, palladium, Noble metals such as rhodium, ruthenium, iridium; zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, green chromium oxide, cobalt green, amber, titanium black Synthetic iron black, carbon black, carbon nanotube, and the like. Examples of metallic pigments include aluminum flakes and copper bronze flakes.
The radiation-sensitive resin composition of the present invention preferably contains at least one selected from the group consisting of carbon black, titanium black, black metal oxide pigments, and organic pigments as a colorant. Examples of black metal oxide pigments include iron oxide (Fe ₃ O ₄ ), cobalt oxide (Co ₃ O ₄ ), copper oxide (CuO), chromium oxide (CrO ₂ ), manganese oxide (Mn ₃ O ₄ ), and aluminum oxide. (Al ₂ O ₃ ) and the like.
A negative radiation sensitive resin composition mixed with a black colorant can be used as a light-shielding coating film. For example, in color filters, it can be used to form a black matrix in order to increase the contrast of RGB emission colors. Examples of the black colorant include carbon black, graphite, iron black, aniline black, cyanine black, and titanium black. Moreover, a mixture of a red pigment, a blue pigment, and a green pigment can also be used as the black colorant.
The blending amount of the colorant is preferably 1 to 40% by weight of the entire composition. If it is less than 1% by weight, it may not be sufficiently colored, and if it is more than 40% by weight, the fluidity of the composition may be deteriorated or the adhesion may be lowered.

As the colorant, carbon black is preferable in terms of light shielding properties, image characteristics, and the like. Examples of carbon black include furnace black, thermal black, and acetylene black. Specifically, for example, trade names “MA7”, “MA8”, “MA11”, “MA100”, “MA220”, “MA230”, “# 52”, “# 50”, “# 47” manufactured by Mitsubishi Chemical Corporation ”,“ # 45 ”,“ # 2700 ”,“ # 2650 ”,“ # 2200 ”,“ # 1000 ”,“ # 990 ”,“ # 900 ”, etc., trade names“ Printex95 ”,“ Printex90 ”manufactured by Tegusa , "Printex85", "Printex75", "Printex55", "Printex45", "Printex40", "Printex30", "Printex3", "PrintexA", "PrintexG", "SpecialBlack550c, 250" Special product names “Monarch460”, “Monarch430”, “Monarch280”, “Monarch120”, “Monarch800”, “Monarch4630”, “REGAL99”, “REGAL99R”, “REGAL415R”, “REGAL415R”, etc. “REGAL250”, “REGAL250R”, “REGAL330”, “BLACK PEARLS480”, “BLACK PEARLS130”, etc., product names “Raven11”, “Raven15”, “Raven30”, “Raven35”, “Raven40”, “Raven40”, “Raven40”, “Raven40” “Raven410”, “Raven420”, “Raven450”, “Raven500”, “Raven780” "RAVEN850", "RAVEN890H", "RAVEN1000", "RAVENl020", "RAVEN1040", and the like. These carbon blacks can be used alone or in admixture of two or more.
The colorant is dispersed by a dispersing machine such as a three-roll mill, a ball mill, or a sand mill together with a dispersant (for example, a polycaprolactone compound, a long-chain alkylpolyaminoamide compound, etc.), and then added to the radiation-sensitive resin composition. Also good. The particle size is preferably 1 μm or less. Within this range, the developability of the negative radiation sensitive resin composition will be good.

The radiation-sensitive resin composition of the present invention is soluble in alkali and can be cured by radiation irradiation. The radiation-sensitive resin composition containing the alkali-soluble resin (A) of the present invention is molded into a desired shape, cured by radiation, and used for various purposes. In particular, it is used for the purpose of forming a thin film having a predetermined pattern by forming a thin film on a substrate with the composition, irradiating with radiation, and developing.

For example, as described above, when a thin film is formed on a substrate and radiation curing and development are performed, usually, the components of the composition containing a solvent are first mixed to obtain a liquid composition. For example, it is more preferable to filter this with a Millipore filter having a pore diameter of about 1.0 to 0.2 μm to obtain a uniform liquid. Next, this liquid composition is applied onto a substrate to obtain a coating film. Examples of the coating method include a dipping method, a spray method, a roller coating method, a slit coating method, a bar coating method, and a spin coating method. In particular, a spin coating method is widely used. By applying the liquid resin composition to a thickness of about 1 to 30 μm by these methods and then removing the solvent, a thin film is formed. Usually, a pre-bake treatment is performed to sufficiently remove the solvent.

After placing a mask having a desired pattern on the thin film of the substrate, irradiation with radiation is performed. Examples of the radiation used include visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, and γ-ray in order from the longest wavelength. Of these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. Ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an arc lamp, or a xenon lamp can be preferably used as the ultraviolet light used in the present invention. Radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

By the irradiation, the exposed part is cured by a polymerization reaction. Unexposed portions are developed with a developer. Thereby, the non-irradiated part of the radiation is removed, and a thin film having a desired pattern is obtained. Examples of the developing method include a liquid piling method, a dipping method, and a rocking dipping method.

Examples of the developer include an alkaline aqueous solution, a mixed solution of the alkaline aqueous solution and a water-soluble organic solvent and / or a surfactant, and an organic solvent in which the composition of the present invention can be dissolved. It is a liquid mixture with an active agent.

Examples of the base used for preparing an alkaline aqueous solution suitable for developing the radiation-sensitive resin composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo (5.4.0) -7-undecene, 1,5-diazabicyclo (4.3.0) -5-nonane, preferably sodium carbonate, tetramethylammonium hydroxide, etc. It is needed.

An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, acetone, propanol, or ethylene glycol, or a surfactant is added to the alkaline aqueous solution as necessary.

The development of the resin composition of the present invention can be usually performed at a temperature of 10 to 50 ° C., preferably 20 to 40 ° C., using a commercially available developing machine or ultrasonic cleaner. The development time can be appropriately adjusted depending on the development method, developer, temperature, coating film thickness, and the like.

After alkali development, in order to improve alkali resistance, it is desirable to perform a curing treatment by heating (post-baking treatment). In the resin composition of the present invention, by performing heat treatment, not only the durability against strong alkaline water is remarkably improved, but also various properties such as adhesion to metals such as copper or glass, heat resistance, surface hardness, etc. improves. A preferable heating temperature and heating time are 80 to 250 ° C. and 10 to 120 minutes. In this way, a cured thin film having a desired pattern can be obtained.

The cured film obtained by curing the liquid repellent composition of the present invention exhibits high ink repellency on the film surface, and is therefore suitably used as a partition wall material (black matrix) required for the production of color filters by the inkjet method. The That is, the liquid repellent composition of the present invention can easily form partition walls having liquid repellency on the surface portion and lipophilicity on the side surfaces. This is because the fluorinated polyether compound (B) that imparts liquid repellency has surface migration, and the fluorinated polyether compound (B) migrates to the vicinity of the coating surface during film formation. is there.
In addition, due to the exquisite balance of compatibility between the condensed ring structure-containing alkali-soluble resin (A) and the fluorine-containing polyether compound (B), the fluorine-containing polyether compound (B) quickly moves to the coating film surface, The present inventors have found that excellent liquid repellency can be stably imparted only to the coating film surface regardless of the film forming conditions. If the fluorine-containing compound does not move quickly to the coating surface as in the prior art, it is necessary to set the film forming conditions considering the time for the fluorine component to move to the coating surface. When the film is formed, the fluorine-containing compound may remain inside the coating film, resulting in liquid repellency at the side surface portion of the film.
When the liquid repellent composition of the present invention is used, the fluorine component rapidly moves to the surface of the coating film, so that a pattern having excellent liquid repellency only on the coating film surface without setting special film forming conditions. Can be formed stably.
The liquid repellency can be evaluated by the contact angle of water and an organic solvent (for example, n-hexane). The contact angle of water is preferably 90 degrees or more, and more preferably 100 degrees or more. As the contact angle of the organic solvent, for example, the contact angle of n-hexane is preferably 30 ° or more, and more preferably 40 ° or more.

Moreover, since the negative radiation sensitive resin composition of this invention has the outstanding alkali solubility and developability, it is possible to form a fine pattern. Specifically, it is preferably used for pattern formation of 100 μm or less, and is preferably used for pattern formation of 50 μm or less.

Furthermore, the cured film obtained by curing the liquid repellent resin composition or the radiation sensitive resin composition of the present invention has heat resistance, transparency, adhesion to a substrate, acid resistance, alkali resistance, chemical resistance. Excellent solvent resistance and surface hardness. Therefore, the liquid repellent composition of the present invention is suitably used as, for example, a color filter forming material for liquid crystal displays, a radiation sensitive resin composition for organic EL bank materials, and the like.

By using the liquid-repellent resin composition of the present invention, the fluorinated polyether compound (B) can be obtained due to an exquisite balance of compatibility between the condensed ring-containing alkali-soluble resin (A) and the fluorinated polyether compound (B). Quickly moves to the surface of the coating film, and liquid repellency is imparted only to the surface of the coating film. After film formation, the fluorine-containing polyether compound (B) quickly moves to the surface of the coating film, so that it is not affected by the difference in film formation conditions, and can be stably ink jetted simply by diverting existing film formation technology. A suitable performance can be imparted to the partition wall.

FIG. 1 is a diagram for explaining five steps necessary for forming a coating film in an example. FIG. 2 is a diagram schematically illustrating a normal exposure method in the embodiment. FIG. 3 is a diagram schematically illustrating backside exposure in the embodiment.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1) Synthesis of condensed ring structure-containing epoxy resin 230 g of bisphenolxanthene represented by the formula (11) was dissolved in 800 g of epichlorohydrin, and 1.8 g of benzyltriethylammonium chloride was added, and the mixture was heated at 100 ° C for 5 hours. Stir. Next, 165 g of 40% aqueous sodium hydroxide solution was added dropwise at 70 ° C. under reduced pressure (150 mmHg) over 3 hours. Meanwhile, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, after removing the salt produced | generated by filtration and washing with water, epichlorohydrin was distilled off and methanol was added, and 230 g of bisphenol xanthene type epoxy resins shown by Formula (12) were obtained. The epoxy equivalent of this resin was 270 g / eq.

(Synthesis Example 2) Synthesis of bisphenolxanthene type epoxy ester compound In a 300 ml four-necked flask, 210 g of bisphenolxanthene type epoxy resin obtained in Synthesis Example 1 (epoxy equivalent: 270 g / eq), 600 mg of triethylbenzylammonium chloride as a catalyst, As a polymerization inhibitor, 56 mg of 2,6-diisobutylphenol and 71 g of acrylic acid were charged, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 15 hours for the acid value to reach the target. A light yellow transparent and solid bisphenolxanthene-type epoxy ester compound (1a) represented by the following formula was obtained (in the general formula (1), A ₀ is a divalent group represented by the above formula (5)). , R ₇ = ethenyl group (CH ₂ ═CH), p _1-2 = 0, q _1-2 = 0, m ₁ = 0, m ₄ = 0, s ₁ = 0).

(Synthesis Example 3) Synthesis of condensed ring structure-containing epoxy resin Polyfunctional hydroxyl group-containing condensed ring structure compound represented by the following formula (13) (in the above general formula (10), A ₀ is the formula (5) R ₁₇ , R ₁₈ = CH ₃ , f _1-2 = 2, r _1-2 = 1, m _9-10 = 0) 250 g is dissolved in epichlorohydrin 800 g, and benzyltriethylammonium chloride 1.8g was added and it stirred at 100 degreeC for 5 hours. Next, 165 g of 40% aqueous sodium hydroxide solution was added dropwise at 70 ° C. under reduced pressure (150 mmHg) over 3 hours. Meanwhile, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, after removing the salt produced | generated by filtration and washing with water, epichlorohydrin was distilled off and methanol was added and 250 g of condensed ring structure containing epoxy resins shown by Formula (14) were obtained. The epoxy equivalent of this resin was 270 g / eq.

(Synthesis Example 4) Synthesis of Bisxylenol-Xanthene Type Epoxy Ester Compound In a 300 ml four-necked flask, 230 g (epoxy equivalent: 270 g / eq) of the condensed ring structure-containing epoxy resin obtained in Synthesis Example 3, and triethylbenzylammonium chloride as a catalyst 600 mg, 2,6-diisobutylphenol 56 mg as a polymerization inhibitor, and 71 g of acrylic acid were charged, and heated and dissolved at 90-100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 15 hours for the acid value to reach the target. A pale yellow transparent and solid bisxylenol xanthene type epoxy ester compound (1.b) was obtained (in the general formula (1), A ₀ is a divalent group represented by the above formula (5), and R _1-2 = _CH 3, _{R 7} = ethenyl group _{(CH 2 = CH), p} 1~2 = 0, q 1~2 = 2, m 1 = 0, m 4 = 0, s 1 = 0).

(Synthesis Example 5) Synthesis of condensed ring structure-containing epoxy resin 240 g of bisphenolanthrone represented by the formula (15) was dissolved in 800 g of epichlorohydrin, and 1.8 g of benzyltriethylammonium chloride was added, and the mixture was heated at 100 ° C for 5 hours. Stir. Next, 165 g of 40% aqueous sodium hydroxide solution was added dropwise at 70 ° C. under reduced pressure (150 mmHg) over 3 hours. Meanwhile, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, the salt produced | generated by filtration was removed, and also after washing with water, epichlorohydrin was distilled off and methanol was added, and 240 g of bisphenol anthrone type epoxy resins shown by Formula (16) were obtained. The epoxy equivalent of this resin was 270 g / eq.

(Synthesis Example 6) Synthesis of bisphenol anthrone type epoxy ester compound In a 300 ml four-necked flask, 220 g of bisphenol anthrone type epoxy resin obtained in Synthesis Example 5 (epoxy equivalent 270 g / eq), 600 mg of triethylbenzylammonium chloride as a catalyst, As a polymerization inhibitor, 56 mg of 2,6-diisobutylphenol and 71 g of acrylic acid were charged, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 15 hours for the acid value to reach the target. A pale yellow transparent and solid bisphenolanthrone-type epoxy ester compound (1 · c) was obtained (in the above general formula (1), A ₀ is a divalent group represented by the above formula (6), and R ₇ = ethenyl. group _{(CH 2 = CH), p} 1~2 = 0, q 1~2 = 0, m 1 = 0, m 4 = 0, s 1 = 0).

(Synthesis Example 7) Synthesis of a condensed ring structure-containing epoxy resin 350 g of biscresol fluorene represented by the formula (34) was dissolved in 257 g of epichlorohydrin, and 243 g of 40% aqueous sodium hydroxide solution was added at 80 ° C. over 10 hours. It was dripped. After completion of the dropwise addition, the reaction was continued for another hour. Thereafter, 1500 g of toluene and 300 g of water were added to the reaction solution, and the resulting salt was dissolved in water. After liquid separation, the lower aqueous layer was removed. Further, the upper toluene layer was washed with water, and then the solvent was distilled off under reduced pressure to obtain 420 g of a biscresol fluorene type epoxy resin represented by the formula (35). The epoxy equivalent of this resin is 320 g / eq. For p in the following formula (35), p = 0 is 50%, p = 1 is 30%, p = 2 is 15%, p = 3 is 3%, p = 4 was a 2% mixture.

(Synthesis Example 8) Synthesis of biscresol fluorene type epoxy ester compound In a 300 ml four-necked flask, 200 g of biscresol fluorene type epoxy resin obtained in Synthesis Example 7 (epoxy equivalent 320 g / eq) and triethylbenzylammonium chloride as a catalyst 600 mg, 2,6-diisobutylphenol 56 mg as a polymerization inhibitor, and 45 g of acrylic acid were charged, and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 20 hours for the acid value to reach the target. A light yellow transparent and solid biscresol fluorene type epoxy ester compound (1 · d) represented by the following formula was obtained (in the general formula (1), A ₀ is the above formula (17). in _{and, R 1~4 = CH 3, R} 7 = ethenyl group _{(CH 2} = _CH), a _{p 1~4 = 0, q 1~4 =} 1, m 1~4 = 0, for _{s 1} is S ₁ = 0 was 50%, s ₁ = 1 was 30%, s ₁ = 2 was 15%, s ₁ = 3 was 3%, and s ₁ = 4 was 2%).

(Synthesis Example 9) Synthesis of Condensed Ring Structure-Containing Alkali-Soluble Resin (A1-a) In a 2 L separable flask, 3-methoxybutyl acetate of the bisphenolxanthene-type epoxy ester compound (1 · a) obtained in Synthesis Example 2 170.8 g of biphenyltetracarboxylic acid (s-BPDA) was mixed with 1230.8 g of the solution (solid content: 56.2%), and this was gradually heated and reacted at 110 to 115 ° C. for 14 hours. Next, 87.2 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring structure-containing alkali-soluble resin was obtained (A1-a).

(Synthesis Example 10) Synthesis of condensed ring structure-containing alkali-soluble resin (A1-b) In a 300 mL separable flask, 3-methoxybutyl of the bisxylenol-xanthene-type epoxy ester compound (1 · b) obtained in Synthesis Example 4 23.6 g of biphenyltetracarboxylic acid (s-BPDA) and 1.7 g of tetraethylammonium bromide were mixed with 103.6 g of the acetate solution (solid content 56.2%). The reaction was carried out at 20 ° C. for 12 hours. Next, 13.6 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. In this way, a 3-methoxybutyl acetate solution of an alkali-soluble resin was obtained (A1-b).

(Synthesis Example 11) Synthesis of condensed ring structure-containing alkali-soluble resin (A1-c) 3-methoxybutyl acetate of bisphenol anthrone type epoxy ester compound (1 · c) obtained in Synthesis Example 6 was added to a 2 L separable flask. To 1240.7 g of the solution (solid content 55.4%), 174.0 g of biphenyltetracarboxylic acid (s-BPDA) was mixed, and this was gradually heated and reacted at 110 to 115 ° C. for 14 hours. Next, 89.9 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring structure-containing alkali-soluble resin was obtained (A1-c).

(Synthesis Example 12) Synthesis of condensed ring structure-containing alkali-soluble resin (A2-a) In a 300 mL separable flask, 3-methoxybutyl of the bisxylenol-xanthene-type epoxy ester compound (1 · b) obtained in Synthesis Example 4 70 g of acetate solution (solid content: 58.3%) was mixed with 8.0 g of ditrimethylolpropane, 14.1 g of biphenyltetracarboxylic acid (s-BPDA) and 0.1 g of tetraethylammonium bromide, and the temperature was gradually raised. And reacted at 110 to 115 ° C. for 12 hours. Next, 7.5 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. In this way, a 3-methoxybutyl acetate solution of an alkali-soluble radiation-polymerizable unsaturated resin was obtained (A2-a).

Synthesis Example 13 Synthesis of Condensed Ring Structure-Containing Alkali-Soluble Resin (A1-d) In a 2 L separable flask, 3-methoxybutyl of the biscresol fluorene type epoxy ester compound (1 · d) obtained in Synthesis Example 8 To 500 g of an acetate solution (solid content: 50.0%), 43.3 g of pyromellitic anhydride (PMDA) and 33.4 g of hexahydrophthalic anhydride (HHPA) were mixed, and the temperature was gradually increased. The reaction was carried out at 115 ° C. for 14 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring structure-containing alkali-soluble resin was obtained (A1-d).

Synthesis Example 14 Synthesis of Condensed Ring Structure-Containing Alkali-Soluble Resin (A2-b) In a 2 L separable flask, 3-methoxybutyl of the biscresol fluorene type epoxy ester compound (1 · d) obtained in Synthesis Example 8 To 500 g of an acetate solution (solid content: 50.0%), 5.0 g of trimethylolethane and 71.8 g of benzophenonetetracarboxylic dianhydride (BTDA) were mixed, and the temperature was gradually raised to 110 to 115 ° C. For 14 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring structure-containing alkali-soluble resin was obtained (A2-b).

(Synthesis Example 15) Synthesis of fluorinated polyether compound (B1) A perfluoropolyether alcohol represented by the formula (b-1) in a 500 ml four-necked flask under a nitrogen atmosphere:

20.2 g, 1.1 g of pyridine, 50 ml of perfluoromethylcyclohexane, and 10 ml of methyl ethyl ketone (MEK) were charged with ice and cooled to 5 ° C. or lower, and the system was purged with nitrogen. Was then added dropwise to that dissolved acrylic acid chloride was placed in a dropping funnel _(CH 2 = CHCOCl) 1.2g to MEK10ml over about 10 minutes. After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 2 hours. After completion of the reaction, the reaction solution was placed in a separatory funnel, washed with water, hydrochloric acid and an aqueous sodium chloride solution, and dried over anhydrous sodium sulfate. Further, the organic phase was distilled off under reduced pressure, followed by drying at 70 ° C. overnight under reduced pressure to obtain 19.3 g of a colorless and transparent bowl-like liquid (B1).

(Synthesis Example 16) Synthesis of fluorinated polyether compound (B2) In a 500 ml four-necked flask under a nitrogen atmosphere, perfluoropolyether alcohol represented by the formula (b-2):

20.2 g, 50 ml of perfluoromethylcyclohexane, 10 ml of methyl ethyl ketone (MEK), 0.01 g of dibutyltin dilaurate, and 1.5 g of 2-isocyanatoethyl acrylate (Karenz (R) AOI manufactured by Showa Denko KK) dissolved in 10 ml of MEK The product was added dropwise at 50-60 ° C. over about 10 minutes. After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 2 hours. After completion of the reaction, it was confirmed by an infrared spectrophotometer that absorption due to an isocyanate bond observed in the vicinity of 2300 cm −1 disappeared, and a colorless and transparent bowl-like solution (B2) having a solid content of 25% ) 80 g was obtained.

(Synthesis Example 17) Synthesis of fluorinated polyether compound (B3) In a 500 ml four-necked flask under a nitrogen atmosphere, perfluoropolyether alcohol represented by the formula (b-3):

21.1 g, 2-hydroxyethyl methacrylate 4.9 g, perfluoromethylcyclohexane 50 ml, methyl ethyl ketone (MEK) 10 ml, dibutyltin dilaurate 0.01 g, Polymeric MDI (Cosmonate M-200 manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) What melt | dissolved 10.1g in MEK10ml was dripped over about 10 minutes at 50-60 degreeC. After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 2 hours. After completion of the reaction, it was confirmed by an infrared spectrophotometer that the absorption derived from the isocyanate bond observed in the vicinity of 2300 cm ⁻¹ disappeared, and a light brown transparent bowl-like solution having a solid content of 35% ( B3) 80 g was obtained.

The structural formula (36) is a representative structure of the fluorine-containing polyether compound (B3), and has a plurality of structures in which the bonding position and number of the fluorine polyether-containing group, the methacryloyloxy group-containing group, and the benzene ring are different. It is a mixture of compounds.

(Comparative synthesis example) Synthesis of bisphenol A type alkali-soluble resin (RF1)
A 2 L separable flask was charged with 1100.9 g of 3-methoxybutyl acetate solution of EB3700 (bisphenol A type basic epoxy acrylate manufactured by Daicel UCB Corporation) and 145.6 g of biphenyltetracarboxylic acid (s-BPDA). The temperature was gradually raised and reacted at 110-115 ° C. for 12 hours. Next, 79.6 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. In this way, an alkali-soluble radiation-polymerizable unsaturated resin solution (RF1) was obtained.

[Preparation 1 of liquid-repellent resin composition and radiation-sensitive resin composition containing the resin composition]
According to the ratio shown in Table 1, the liquid repellent resin composition was prepared.

＊１ ＨＥＭＡ：２−ヒドロキシエチルメタアクリレート
＊２ ３−ＭＢＡ：３−メトキシブチルアセテート
＊３ イルガキュア９０７：２−メチル−１−［４−（メチルチオ）フェニル］−２−モリフォリノプロパン−１−オン（チバ・スペシャリティ・ケミカルズ社製）
＊４ ＢＲ：２−（パーフルオロデシル）エチルアクリレート（含フッ素ポリエーテルではないフッ素化合物）

* 1 HEMA: 2-hydroxyethyl methacrylate
* 2 3-MBA: 3-methoxybutyl acetate * 3 Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals)
* 4 BR: 2- (perfluorodecyl) ethyl acrylate (fluorine compound not a fluorine-containing polyether)

[Preparation 2 of liquid-repellent resin composition and radiation-sensitive resin composition containing the resin composition]
200 parts by weight of an alkali-soluble resin solution (A1-a), 10 parts by weight of a fluorinated polyether compound (B2), Irgacure OXE-02 (Ciba Specialty Chemicals 1- [9-ethyl-6- (2-methyl) Benzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate) 5 parts by weight, dipentaerythritol hexaacrylate 30 parts by weight, 3-methoxybutyl acetate 385 parts by weight A solution was obtained. Next, 125 parts by weight of carbon black MA100 (manufactured by Mitsubishi Chemical Corporation), 85 parts by weight of pigment dispersant Ajisper PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.), 260 parts by weight of methyl isobutyl ketone, and 50 parts by weight of p-xylene And mixed to obtain a carbon black dispersion solution. Further, the above resin solution and the carbon black dispersion solution are mixed, 0.5 mm zirconia beads (filling ratio 70%) are used as media, and dispersed for about 1 hour by a bead mill. A resin composition (Formulation No. 19) was obtained.

In the preparation of Formulation No. 19, 200 parts by weight of the alkali-soluble resin solution (A1-a) is 225 parts by weight of (A1-d), 10 parts by weight of the fluorine-containing polyether compound (B2) is 8 parts by weight of (B3), A carbon black-dispersed radiation sensitive resin composition (formulation number 20) was obtained by the same method as the preparation method of composition number 19 except that 385 parts by weight of 3-methoxybutyl acetate was changed to 410 parts by weight.

[Film formation]
The film formation uses each composition shown in Table 1, and (i) a coating process for coating on a glass substrate using a spinner, (ii) a pre-baking process for removing the solvent from the coating film, and (iii) a coating film A coating process with a film thickness of about 1 μm is performed through five steps: an exposure process for curing, (iv) a development process for removing an uncured coating film, and (v) a drying process for drying the substrate after development (FIG. 1). The board | substrate which has was produced, and it used for liquid-repellent evaluation.
In order to grasp the influence of the conditions of each process, according to the conditions shown in Table 2, the time from application with a spinner to pre-baking (WT1), pre-baking time (PBTi), pre-baking temperature (PBTm), pre-baking Then, film formation was performed while changing the conditions of the waiting time (WT2) until exposure, and the obtained coating film was evaluated.

[Evaluation of liquid repellency]
In the coating film cured using the liquid-repellent resin composition of the present invention, in order to confirm that only the film surface has liquid-repellent properties, in the above film-forming process, the amount of UV irradiation during exposure is reduced. Furthermore, by performing from the back side of the substrate (backside exposure), a substrate was prepared in which only the inside of the coating film was cured and the coating film surface was removed by development treatment, and the contact angle was similarly measured.
When film formation is performed under such conditions of back exposure, the surface of the coating film is not cured, so that the liquid repellency is lost when the liquid repellent component is present only on the surface of the coating film. When the liquid repellent component remains inside the coating film, the liquid repellency is maintained even if the coating film surface is lost.
FIG. 2 is a diagram schematically illustrating a normal exposure method, and FIG. 3 is a diagram schematically illustrating back surface exposure.

Further, in the exposure step (iii), a 250 W high-pressure mercury lamp is used so that the remaining film rate after the development step is 100% in the normal exposure method, and in the backside exposure, the post-development step is performed. Ultraviolet rays were irradiated so that the remaining film ratio was about 90%.
In the development step (iv), a development process was performed for 60 seconds at 23 ° C. using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, and a rinse process was performed with ultrapure water. Furthermore, in the drying step (v), the obtained substrate having a thin film was dried at 130 ° C. for 2 minutes.

As an index of liquid repellency of the liquid repellent resin composition of the present invention, contact angles with water and organic solvents were measured. Hexane was used as the organic solvent. The contact angle was measured using a contact angle meter CA-D type manufactured by Kyowa Interface Chemical Co., Ltd.

In Examples 1 to 60 (when any composition is exposed from the surface), the contact angle of the coating film is 100 to 109 ° for water and 41 to 51 ° for an organic solvent (hexane). Regardless, all showed a high level of liquid repellency. In addition, when exposed from the back surface, the contact angle is 7 to 14 ° with an organic solvent (hexane), and 38 to 48 ° with water. Declined. In the experiment exposed from the surface, since the entire film is cured, the fluorinated polyether compound (B) present on the coating film surface exhibits liquid repellency. On the other hand, when exposed from the back side, the coating film is cured from the substrate side, so that the film surface remains uncured, and the fluorine-containing polyether compound (B) present on the surface is removed during development, resulting in liquid repellency. Probably not shown.
From these results, it can be seen that the resin composition of the present invention can make the surface of the coating film repellent.
On the other hand, in Comparative Examples 1 to 15 containing a fluorine compound that is not a resin of a comparative synthesis example or a fluorine-containing polyether compound, the contact angle value varies greatly depending on the process even though the same composition is used. It was found that the oil repellency greatly affects the film forming conditions. In addition, there are cases where the difference in contact angle between the front surface exposure and the back surface exposure is small, which indicates that a fluorine component imparting liquid repellency is also present in the film.
Thus, it can be seen that by using the liquid-repellent resin composition of the present invention, it is possible to obtain a coating film in which only the film surface is stably liquid-repellent.

According to the present invention, it is possible to obtain a coating film having a high level of liquid repellency at all times without being affected by the film forming process conditions, and an ink jet type liquid crystal that requires liquid repellency. It is suitably used for manufacturing a wiring pattern in a partition, a semiconductor device or an electric circuit such as a color filter or an organic EL display.

1 Glass substrate 2 Resin layer (uncured)
3 Resin layer with a high content of fluorine component (uncured)
4 Resin layer (cured)
5 Resin layer with a high fluorine content (cured)
6 Exposure machine light source

Claims (22)

As the condensed ring-containing alkali-soluble resin (A), an epoxy ester compound represented by the following general formula (1):

(Here, _D1-4 are each independently a group selected from the following general formula (2) or the following general formula (3), and _p1-4 are each independently an integer of 0-4).

Here, D _5-6 are each independently a group selected from General Formula (2) or the following General Formula (3), and p _5-6 are each independently an integer of 0-4.

Here, A ₀ in the general formulas (1) and (2) is a five-membered or six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings. R _1-6 each independently represents a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms. It is an alkoxy group, a phenyl group which may have a substituent, or a halogen atom, and q _{1 to 6} are each independently an integer of 0 to 4. Further, R _{7 in the} general formulas (1), (2), and (3) represents a group containing a site derived from a monobasic carboxylic acid, and R _{8 to 15} each independently represents a hydrogen atom or a methyl group. _{M 1-8} and s _1-2 are each independently an integer of 0 to 10, and the structural formula may be bilaterally symmetric or asymmetrical. A plurality of R _1-15 and D _1-6 may be the same or different. And a polybasic carboxylic acid or an anhydride thereof, a liquid repellent resin composition comprising a condensed ring structure-containing alkali-soluble resin (A1) and a fluorinated polyether compound (B) object. A ₀ in the general formulas (1) and (2) is a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, or The liquid repellent resin composition according to claim 1, which is a divalent group containing a condensed ring structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring. object. A ₀ in the general formulas (1) and (2) includes a condensed structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and two or more aromatic rings. The liquid repellent resin composition according to claim 1, which is a divalent group. A ₀ in the general formulas (1) and (2) includes a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and two or more aromatic rings. The liquid repellent resin composition according to claim 1, which is a divalent group. As the condensed ring-containing alkali-soluble resin (A), an epoxy ester compound represented by the following general formula (1):

(Here, _D1-4 are each independently a group selected from the following general formula (2) or the following general formula (3), and _p1-4 are each independently an integer of 0-4).

Here, D _5-6 are each independently a group selected from General Formula (2) or the following General Formula (3), and p _5-6 are each independently an integer of 0-4.

Here, A ₀ in the general formulas (1) and (2) is a five-membered or six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings. R _1-6 each independently represents a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms. It is an alkoxy group, a phenyl group which may have a substituent, or a halogen atom, and q _{1 to 6} are each independently an integer of 0 to 4. Furthermore, R _{7 in the} general formulas (1), (2), and (3) represents a group containing a site derived from a monobasic carboxylic acid, and R _{8 to 15} are each independently a hydrogen atom or a methyl group, m _1-8 and s _1-2 are each independently an integer of 0 to 10, and the structural formula may be bilaterally symmetric or asymmetric. A plurality of R _1-15 and D _1-6 may be the same or different. ), A polyhydric alcohol, and a polybasic carboxylic acid or an anhydride thereof, and a liquid repellent containing a condensed ring structure-containing alkali-soluble resin (A2) and a fluorinated polyether compound (B) Resin composition. A ₀ in the general formulas (1) and (2) is a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one or more aromatic rings, or The liquid repellent resin composition according to claim 5, which is a divalent group containing a condensed ring structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and one aromatic ring. object. A ₀ in the general formulas (1) and (2) includes a condensed structure of a five-membered alicyclic compound (which may contain atoms other than carbon on the ring) and two or more aromatic rings. 6. The liquid repellent resin composition according to claim 5, which is a divalent group. A ₀ in the general formulas (1) and (2) includes a condensed ring structure of a six-membered alicyclic compound (which may contain atoms other than carbon on the ring) and two or more aromatic rings. The liquid repellent resin composition according to claim 5, which is a divalent group. A condensed ring structure-containing alkali obtained by reacting a condensed ring structure-containing alkali-soluble resin (A1) with an epoxy ester compound represented by the following general formula (4) and a polybasic carboxylic acid or an anhydride thereof: It is soluble resin (A1-1), The liquid repellent resin composition of any one of Claims 1-4 characterized by the above-mentioned.

Here, A ₀ , R _1-4 , R ₇ , R _8-11 , q _1-4 , m _1-4 , and s ₁ are the same as described above, and they are asymmetric even if the structural formula is symmetrical. May be. Moreover, several R _{< 1 > -4} , R _{<7> -11} may be the same, and may differ. The condensed ring structure-containing alkali-soluble resin (A2) is obtained by reacting an epoxy ester compound represented by the following general formula (4), a polyhydric alcohol, and a polybasic carboxylic acid or anhydride thereof. It is a ring structure containing alkali-soluble resin (A2-1), The liquid repellent resin composition of any one of Claims 5-8 characterized by the above-mentioned.

Here, A ₀ , R _1-4 , R ₇ , R _8-11 , q _1-4 , m _1-4 , and s ₁ are the same as described above, and they are asymmetric even if the structural formula is symmetrical. May be. Moreover, several R _{< 1 > -4} , R _{<7> -11} may be the same, and may differ. A _{0 in the} general formulas (1) and (2) is a divalent group containing a condensed ring structure selected from the group consisting of the formulas (5) to (7). 9. The liquid repellent resin composition according to any one of 8 above.

The liquid repellent resin composition according to claim 9 or 10, wherein A _{0 in the} general formula (4) is a divalent group containing a condensed ring structure selected from the group consisting of the formulas (5) to (7).

The A _{0 in the} general formulas (1) and (2) is a divalent group containing a condensed ring structure selected from the group consisting of the formulas (8) and (9). 2. The liquid repellent resin composition according to item 1.

The liquid repellent resin composition according to claim 9 or 10, wherein A _{0 in the} general formula (4) is a divalent group containing a condensed ring structure selected from the group consisting of the formulas (8) and (9).

The repellent according to any one of claims 1, 3, 5, and 7, wherein A _{0 in the} general formulas (1) and (2) is a divalent group including a condensed ring structure represented by the formula (17). Liquid resin composition.

The liquid repellent resin composition according to claim 9 or 10, wherein A _{0 in the} general formula (4) is a divalent group including a condensed ring structure represented by the formula (17).

The liquid-repellent resin according to any one of claims 1 to 16, wherein the fluorine-containing polyether compound (B) has a structure selected from the group consisting of the following general formulas (18) to (20). Composition.

In the formula, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are each independently hydrogen, F or 20 or less carbon atoms. X, y and z are each independently an integer of 0 or more, and x + y + z contained in (B) is an integer of 2 or more. However, at least one of R ₁₉ and R ₂₀ is F or a fluorine-containing alkyl group having 20 or less carbon atoms, and at least one of R _{21 to} R ₂₄ is F or a fluorine-containing alkyl group having 20 or less carbon atoms. And at least one of R _{25 to} R ₃₀ is F or a fluorine-containing alkyl group having 20 or less carbon atoms. The condensed ring structure-containing alkali-soluble resin (A) and at least one of the fluorine-containing polyether compound (B) contain an unsaturated group that can be polymerized by light or heat. Liquid repellent resin composition. The content of the fluorine-containing polyether compound (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the condensed ring-containing alkali-soluble resin (A). The liquid repellent resin composition as described. The radiation sensitive resin composition containing the liquid repellent resin composition of any one of Claims 1-19, and a photoinitiator (C). Furthermore, the radiation sensitive resin composition of Claim 20 containing at least 1 sort (s) selected from the group which consists of carbon black, titanium black, a black metal oxide pigment, and an organic pigment. Hardened | cured material formed by hardening | curing the resin composition of any one of Claims 1-21.

Images