KR20090097120A - Liquid-repellent resin composition - Google Patents

Abstract

(Problem) The liquid repellent resin composition which shows the liquid repellency which was excellent in stability stably regardless of film production conditions is provided.

(Solution means) The liquid-repellent resin composition containing a cyclic structure containing alkali-soluble resin (A1) and a fluorine-containing polyether compound (B) obtained by making a specific epoxy ester compound, polybasic carboxylic acid, or its anhydride react.

Description

Liquid-repellent resin composition {LIQUID―REPELLENT RESIN COMPOSITION}

The present invention relates to an alkali-soluble liquid-repellent resin composition excellent in liquid repellency, sensitivity, and developability. Moreover, this invention is a negative or positive radiation sensitive resin composition containing this resin composition, Comprising: The protective film and interlayer insulation film in a color filter, a liquid crystal display element, an integrated circuit element, a solid-state image sensor, etc. are prepared. It relates to a composition useful for the purpose of.

Generally, permanent films such as resist materials for forming ITO electrodes such as liquid crystal displays (LCDs) and organic EL displays, interlayer insulating films, circuit protective films, colored pigment dispersion resists for manufacturing color filters of liquid crystal displays, and barrier ribs for organic EL displays. As a forming material, a radiation sensitive resin composition is used widely.

Among these, in recent years, the demand for a liquid crystal display is high for television use etc., and the radiation sensitive resin composition is used abundantly in the manufacturing process. In manufacture of a liquid crystal color filter, the demand of cost reduction is strong with the increase of the demand, and the inkjet method which can manufacture at low cost is proposed. In the manufacture of a color filter by the inkjet method, after forming a partition (bulk wall) defining a pixel by a photolithography method or the like in advance, the pixel is formed by applying ink of red, green, and blue to the pixel portion, respectively, by inkjet. As a method of forming, it is known that the process is simpler and the waste of ink is smaller than that of the conventional production method using the pigment dispersion resist.

In this inkjet method, when dropping an ink drop onto a pixel portion, the substrate and the side walls of the substrate need adhesion to the ink so that the ink ink is required, but it is possible to prevent an ink drop from overflowing the partition to a nearby pixel. In order to prevent mixing of ink between neighboring pixel areas, it is required to make liquid repellency on the partition wall surface.

Patent Document 1 discloses a fluorinated copolymer of hexafluoropropylene, an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, and an unsaturated compound copolymerizable with these components as a radiation-sensitive resin composition having liquid repellency. A radiation sensitive resin composition for forming a color filter partition wall comprising an acid generating compound, a crosslinkable compound, an fluorine-containing organic compound other than the fluorine-containing copolymer, and an organic solvent that is irradiated to generate an acid is disclosed. Perfluoroalkyl groups as organic compounds. Hydrophilic or lipophilic group containing oligomers are illustrated.

Further, Patent Document 2 includes an alkali-soluble radiation-sensitive resin having three or more ethylenic double bonds in an acidic group and a molecule, and an alkyl group having 20 or less carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (wherein the alkyl group A negative radiation-sensitive agent comprising a photoinitiator comprising a polymerized unit having an ether oxygen) and a polymer having a polymerized unit having an ethylenic double bond, and a photopolymerization initiator. A resin composition is disclosed.

In addition, Patent Document 3 has a perfluoroalkyl group having 4 to 6 carbon atoms, and contains a fluorine-containing resin having a fluorine atom content of 7 to 35% by mass and a radiation-sensitive component reacting to light having a wavelength of 100 to 600 nm. As a composition, the resist composition characterized by the ratio of the fluorine-containing resin with respect to the total solid of a composition is 0.1-30 mass%.

In the resin composition containing these fluorine-containing compounds, since the fluorine-containing compound imparts liquid repellency and the fluorine-containing compound has surface transferability, the fluorine-containing compound migrates near the coating film surface at the time of film production, Liquid repellency is provided to the coating film surface. However, in these resin compositions, since it takes time to transfer a liquid repellent agent to the coating film surface, there exists a problem that the liquid repellency of a coating film surface arises according to film manufacturing conditions. Therefore, there is a demand for a resin composition capable of stably obtaining a high level of liquid repellency without depending on film production conditions.

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-281815 (claim 1)

[Patent Document 2] International Publication No. 2004/042474 Pamphlet (Claim 1)

[Patent Document 3] Japanese Unexamined Patent Publication No. 2005-315984 (claim 1)

An object of the present invention is to solve the above-mentioned conventional problems, and an object thereof is to provide a liquid-repellent resin composition which exhibits excellent liquid-repellency stably without depending on the film production conditions. Another object of the present invention is to provide a radiation-sensitive resin composition containing the liquid-repellent resin composition. Another object of the present invention is to provide a cured product obtained by curing such radiation-sensitive resin composition.

As a result of earnestly examining in order to solve the said subject, this invention shows an epoxy ester compound represented by following General formula (1) as a condensed ring structure containing alkali-soluble resin (A):

[Formula 1]

(Wherein D ₁ to ₄ are each independently a group selected from the following General Formula (2) or the following General Formula (3), and p ₁ to 4 each independently represent an integer of 0 to 4;

[Formula 2]

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

[Formula 3]

Here, A <_0> of the said General formula (1), (2) is a 5-membered ring or 6-membered alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of one or more aromatic rings It is a divalent group containing, and R <_1-6> respectively independently has a C1-C10 linear, branched or cyclic alkyl group or an alkenyl group, a C1-C5 alkoxy group, and a substituent Or a halogen atom, q ₁ to ₆ each independently represent an integer of 0 to 4; In addition, R <_7> of the said General formula (1), (2), (3) represents group containing the site | part derived from monobasic carboxylic acid, R <_8-15> respectively independently represents a hydrogen atom or a methyl group, m _{1 to 8} and s _{1 to 2} are each independently an integer of 0 to 10, and the structural formula may be symmetrical or asymmetrical. Moreover, some R <_1-15> , D <_1-6> may be same or different), and polycyclic carboxylic acid or its anhydride is obtained by condensation structure containing alkali-soluble resin (A1), or general formula By the combination of the cyclic structure containing alkali-soluble resin (A2) obtained by making the epoxy ester compound represented by (1), a polyhydric alcohol, polybasic carboxylic acid, or its anhydride react with, and a fluorine-containing polyether compound (B), It was found that the fluorine-containing polyether compound (B) quickly migrated to the coating film surface, and was able to stably provide excellent liquid repellency only to the coating film surface without depending on the film production conditions. This invention is completed based on this knowledge.

In this way, the liquid-repellent resin composition (1) of this invention is condensed structure-containing alkali-soluble resin (A1) obtained by making the epoxy ester compound represented by General formula (1), polybasic carboxylic acid, or its anhydride react with it. And a fluorine-containing polyether compound (B).

Moreover, the liquid-repellent resin composition (2) of this invention is ring-containing structure-containing alkali-soluble resin (A2) obtained by making the epoxy ester compound represented by General formula (1), polyhydric alcohol, and polybasic carboxylic acid or its anhydride react. ) And a fluorine-containing polyether compound (B).

In preferable embodiment, the condensed ring structure containing alkali-soluble resin (A1) in the liquid-repellent resin composition (1) of this invention is an epoxy ester compound which has a bifunctional and linear structure represented by following General formula (4), It is a condensed ring structure containing alkali-soluble resin (A1-1) obtained by making polybasic carboxylic acid or its anhydride react.

[Formula 4]

Where _{A 0, R 1~4, R 7} , R 8~11, q 1~4, m 1~4, s 1 is as defined above, and the following structural formula may be a symmetrical, but may be asymmetrical. In addition, some R <_{1> -4} and R <_{7> -11} may be the same and may differ.

In addition, the liquid-repellent resin composition (2) of the present invention is a cyclic structure-containing alkali-soluble resin (A2-) obtained by reacting the epoxy ester compound represented by the general formula (4), a polyhydric alcohol, a polybasic carboxylic acid or an anhydride thereof. It is preferable to contain 1) and a fluorine-containing polyether compound (B).

In addition, A <_0> of General formula (1), (2), (4) is a 6-membered alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of one or more aromatic rings, Or it is preferable that it is bivalent group containing the alicyclic compound of 5-membered ring (you may contain atoms other than carbon on a ring), and the condensed structure of one aromatic ring.

In addition, A <_0> of General formula (1), (2), (4) has a 5-membered ring alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of two or more aromatic rings It is preferable that bivalent containing is group.

In addition, A <_0> of General formula (1), (2), (4) has a 6-membered alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of two or more aromatic rings It is preferable that bivalent containing is group.

Further, formula (1), (2), it is preferred that the A ₀ (4) and (5) to a divalent group containing chukhwan structure selected from the group consisting of (7).

[Formula 5]

Further, formula (1), (2), it is preferred that the A ₀ (4), (8) and a divalent group containing chukhwan structure selected from the group consisting of (9).

[Formula 6]

Further, formula (1), (2), it is preferred that the A ₀ (4), equation (17) is a divalent group containing chukhwan structure.

[Formula 7]

In a preferred embodiment, the fluorinated polyether compound (B) in the liquid-repellent resin composition (1), (2) is a compound containing a structure selected from the group consisting of formulas (18) to (20) Is preferably.

[Formula 8]

Wherein 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. Is a fluorine-containing alkyl group, x, y, z are each independently an integer of 0 or more, and x + y + z contained in (B) is an integer of 2 or more. Provided that at least one of R ₁₉ and R ₂₀ is F or a C 20 or less fluorine-containing alkyl group, at least one of R ₂₁ to R ₂₄ is an F or a C 20 or less fluorine-containing alkyl group, and in R ₂₅ to R ₃₀ At least one is F or a C20 or less fluorine-containing alkyl group.

In preferable embodiment, the ratio of the fluorine-containing polyether compound (B) in the said liquid repellent resin composition (1), (2) is 0.01-10 with respect to 100 weight part of condensed ring structure containing alkali-soluble resin (A). 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 composition (1), (2) can be polymerized by light or heat. It contains a group.

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

Furthermore, it is preferable that the radiation sensitive resin composition of this invention contains at least 1 sort (s) chosen from the group which consists of carbon black, titanium black, a black metal oxide pigment, and an organic pigment.

This invention contains hardened | cured material formed by hardening | curing the liquid repellent resin composition (1), (2), and the radiation sensitive resin composition, respectively.

EMBODIMENT OF THE INVENTION Below, formation of the thin film using the liquid-sensitive resin composition (1) and (2) of this invention, the radiation-sensitive resin composition containing this liquid-repellent resin composition, and this radiation-sensitive resin composition is demonstrated one by one. .

(I) liquid-repellent resin composition (1), (2)

Cyclocyclic structure-containing alkali-soluble resin (A)

The cyclic 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, may be referred to as an "epoxy ester compound (a1)"):

[Formula 9]

(Wherein D ₁ to ₄ are each independently a group selected from the following General Formula (2) or the following General Formula (3), and p ₁ to 4 each independently represent an integer of 0 to 4;

[Formula 10]

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

[Formula 11]

Here, A <_0> of the said General formula (1), (2) is a 5-membered ring or 6-membered alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of one or more aromatic rings Is a divalent group containing, R ₁ to ₆ are each independently a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group which may have a substituent, Or a halogen atom, q ₁ to ₆ are each independently an integer of 0 to 4; In addition, R <_7> of the said General formula (1), (2), (3) represents group containing the site | part derived from monobasic carboxylic acid, R <_8-15> respectively independently represents a hydrogen atom or a methyl group, m _{1 to 8} and s _{1 to 2} are each independently an integer of 0 to 10, and the structural formula may be symmetrical or asymmetrical. In addition, a plurality of R _{1 to 15} and D ₁ to ₆ may be the same as or different from each other), and are obtained by reacting a polybasic carboxylic acid or an anhydride thereof (a3). In this specification, this cyclic structure containing alkali-soluble unsaturated resin may be called "a cyclic structure containing alkali-soluble resin (A1)""alkali-soluble resin (A1)".

Moreover, the cyclic structure containing alkali-soluble resin (A) of this invention reacts the epoxy ester compound (a1) represented by the said General formula (1), polyhydric alcohol (a2), polybasic carboxylic acid, or its anhydride (a3). It is also obtained by making. In this specification, this cyclic structure containing alkali-soluble resin may be called "a cyclic structure containing alkali-soluble resin (A2)" "alkali-soluble resin (A2)".

As a bivalent group containing the 5-membered ring or 6-membered alicyclic compound in A <_0> and the condensed ring structure of 1 or more aromatic rings, it is a 5-membered ring or a 6-membered ring alicyclic compound, and 1-, for example. And divalent groups containing a condensed structure of three aromatic rings. The alicyclic compound of a 6-membered ring and the alicyclic compound of a 5-membered ring may contain atoms other than carbon on a ring, and the thing containing an oxygen atom, a sulfur atom, and a nitrogen atom is mentioned, for example.

As A ₀ , the divalent group containing the condensed structure chosen from the group which consists of following formula (5)-(9) and (17) is mentioned, for example.

[Formula 12]

When A ₀ is a divalent group containing a condensed structure selected from the group consisting of formulas (5) to (9) and (17), high heat resistance, high refractive index and electrical properties derived from a condensed skeleton containing an aromatic It can provide, and the dispersion stability derived from a large surface structure is obtained. In addition, A ₀ is the equation (5) to (7), (17) the heat resistance, refractive index, electrical properties, dispersion stability in the case 2 is a group containing chukhwan structure selected from a group, a higher level is obtained consisting of a. In addition, when A <_0> is a bivalent group containing the condensed structure of Formula (8), (9), such a condensed structure containing alkali-soluble resin (A) has high solubility to a solvent, it is easy to handle, and manufacturing cost In terms of advantages.

As a C1-C10 linear, branched or cyclic alkyl group in R <_1> -R <_6> , a methyl group, an ethyl group, a propyl group, isopropyl group, a cyclohexyl group, etc. are mentioned, for example. As a C1-C10 linear, branched or cyclic alkenyl group, an ethenyl group, a propenyl group, a cyclohexenyl group, etc. are mentioned, for example. As a C1-C5 alkoxy group, a methoxy group, an ethoxy group, an isopropoxy group, etc. are mentioned, for example. As a phenyl group which may have a substituent, a phenyl group, a tolyl group, a biphenyl group, a cyclohexyl phenyl group, a naphthyl group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. The R ₁ ~ R ₆ is a methyl group, a phenyl group is preferred. If R <_1> -R <_6> is a methyl group and a phenyl group, since a raw material is easy to obtain, it is advantageous in manufacture, and the balance of the heat resistance and handling property of resin obtained is favorable. As for q _1-6 , 0-2 are preferable and it is preferable also when there is no R <_1> -R <_6> .

As for the epoxy ester compound (a1) represented by the said General formula (1), it is preferable that all _p1-4 are zero. That is, the liquid-repellent resin composition of this invention is an epoxy ester compound in which a cyclic structure containing alkali-soluble resin (A1) has a bifunctional and linear structure represented by following General formula (4), polybasic carboxylic acid, or its anhydride. It is preferable that it is a condensed ring structure containing alkali-soluble resin (A1-1) obtained by making it react.

[Formula 13]

Where _{A 0, R 1~4, R 7} , R 8~11, q 1~4, m 1~4, s 1 is as defined above, and the following structural formula may be a symmetrical, but may be asymmetrical. In addition, some R <_{1> -4} and R <_{7> -11} may be the same and may differ.

Moreover, the liquid-repellent resin composition of this invention is a condensation obtained by making a condensed ring structure containing alkali-soluble resin (A2) react with the epoxy ester compound represented by the said General formula (4), polyhydric alcohol, polybasic carboxylic acid, or its anhydride. It is preferable that it is structure containing alkali-soluble resin (A2-1).

The condensed structure-containing alkali-soluble resin (A) of the present invention is preferably a divalent group containing a condensed structure selected from the group consisting of A ₀ is formula (5) to (9) and (17), more preferably. A ₀ is a divalent group containing a condensed structure selected from the group consisting of the formulas (5) to (7) and (17), q ₁ to ₄ are each independently an integer of 0 to 2, m _{1 to 4} Are each independently an integer of 0 to 2, and s ₁ is an integer of 0 to 10. In addition, in formula, it is more preferable that R <_7> is an acryl group.

If the formula (1) of the p _1~4 which is an integer of 1 or more of the epoxy ester compounds are polyfunctional, having a branch structure, and chukhwan structure-containing alkali-soluble resin (A) is obtained there is a branch structure. Moreover, when any one of p <_5-6> is one or more, an epoxy ester compound will have an additional branched structure, and the cyclic structure containing alkali-soluble resin (A) obtained there also has an additional branched structure.

When all p <_1> -4 of the said General formula (1) is 0, an epoxy ester compound has a bifunctional and linear structure, and the cyclic structure containing alkali-soluble resin (A) obtained therein is a structure mainly consisting of a linear structure Becomes Here, polyfunctional and bifunctional show 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 express excellent liquid-repellent properties. In the case of the epoxy ester compound having a branched structure, a dense crosslinked structure is easy after curing. Since it can be formed in such a way, it can be expected to improve physical properties such as heat resistance of the resin composition of the present invention, but on the other hand, it is synthesized so as not to generate a higher-order crosslinked structure when reacting with a polybasic carboxylic acid or its anhydride. It is necessary to adjust the conditions closely. In the case of the epoxy ester compound having a linear structure, the crosslinked structure hardly occurs in the reaction with the polybasic carboxylic acid or its anhydride, so that the molecular weight adjustment which can have a great influence in preparing the radiation-sensitive resin composition, Since the degree of freedom of various types of resin design, such as acid value adjustment, is high, it is used especially suitably as a cyclic structure containing alkali-soluble resin in the resin composition of this invention.

The epoxy ester compound (a1) used for preparation of the ring-containing structure-containing alkali-soluble resin (A1) and (A2) of the present invention includes (1): a step of reacting monobasic carboxylic acid to the ring-containing structure-containing epoxy resin. It is obtained from the manufacturing method mentioned above, or (2): It is obtained from the manufacturing method containing the process of making monobasic carboxylic acid glycidyl react with the polyfunctional hydroxyl-containing condensed structural compound of General formula (10) mentioned later.

First, the method of said (1) is demonstrated.

The condensed ring structure-containing epoxy resin used for preparation of an epoxy ester compound (a1) is obtained from the manufacturing method including the process of making epihalohydrin react with the polyfunctional hydroxyl group containing condensed structure compound shown by following General formula (10). .

[Formula 14]

Here, A <_0> is the same as the above, R <_17-18> may respectively independently have a C1-C10 linear, branched or cyclic alkyl group or an alkenyl group, a C1-C5 alkoxy group, and a substituent It is a phenyl group or a halogen atom, f < _1-2 is an integer of 0-4 each independently. R _{19 to 20} are each independently a hydrogen atom or a methyl group, m ₉ to 10 are each independently an integer of 0 to 10, and r 1 to ₂ are each independently an integer of 1 to 5, and the structural formula may be symmetrical. It may be asymmetrical.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin and the like, and epichlorohydrin is particularly preferably used in view of ease of handling and low cost.

The polyfunctional hydroxyl group-containing condensed structural compound can be prepared by a method known in the art. For example, it is known to manufacture by condensing phenols and ketones in presence of an acidic catalyst (for example, refer Unexamined-Japanese-Patent No. 7-112949).

The reaction of the polyfunctional hydroxyl group-containing condensed structural compound and epichlorohydrin is usually performed for 1 to 10 hours in a temperature range of 50 to 120 ° C. Preferably it is performed for 3 to 6 hours in the temperature range of 70-110 degreeC.

As for the ratio of the said polyfunctional hydroxyl-containing condensed structural compound and epichlorohydrin, 1-20 mol of epichlorohydrin is preferable with respect to 1 mol of hydroxyl groups of a polyfunctional hydroxyl-containing condensed structural compound. As a catalyst used for reaction of a polyfunctional hydroxyl-containing condensed structural compound and epichlorohydrin, for example, phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds and the like Can be mentioned.

As monobasic carboxylic acid used for preparation of the said epoxy ester compound (a1), although the following compound which has one carboxyl group is mentioned, It is not limited to these: (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-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid 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, sikimic acid, 3-hydroxy-3,3-diphenylpropionic acid, 3- (2-oxooxy Lohexyl) propionic acid, 3-cyclohexene-1-carboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid hydrogen alkyl, cycloheptancarboxylic acid, norbornenecarboxylic acid, tetracyclododecenecarboxyl Acids, 1-adamantanecarboxylic acid, (4-tricyclo [5.2.1.0 ^2.6 ] deca-4-yl) acetic acid, p-methylbenzoic acid, p-ethylbenzoic acid, p-octylbenzoic acid, p-decylbenzoic acid, p-dodecylbenzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-propoxybenzoic acid, p-butoxybenzoic acid, p-pentyloxybenzoic acid, p-hexyloxybenzoic acid, p-fluorobenzoic acid, p- Chlorobenzoic acid, p-chloromethylbenzoic acid, pentafluorobenzoic acid, pentachlorobenzoic acid, 4-acetoxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-di-t-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-iodinephenylacetic acid, methoxyphenylacetic acid, 6-phenylhexanoic acid, Biphenylcarboxylic acid, α-naphthoic acid, β-naphthoic acid, anthracenecarboxylic acid, phenanthrenecarboxylic acid, anthraquinone-2-carboxylic acid, indancarboxylic acid, 1,4-dioxo-1, 4-dihydronaphthalene-2-carboxylic acid, 3,3-diphenylpropionic acid, nicotinic acid, isnicotinic acid, cinnamic acid, 3-methoxy cinnamic acid, 4-methoxy cinnamic acid, quinolinecarboxylic acid, etc., which are used alone You may combine and 2 or more types may be combined. As especially preferable monobasic carboxylic acid, it is preferable to contain the unsaturated group which can introduce | transduce a radiation polymerizable functional group into the said cyclic structure containing alkali-soluble resin (A), For example, (meth) acrylic acid is preferable.

As the polyfunctional hydroxyl group-containing condensed structural compound of the general formula (10) used in the method of the above (2), those mentioned above can be used. Examples of the monobasic carboxylic acid glycidyl used in the above method (2) include, but are not limited to, the following compounds: glycidyl (meth) acrylate, glycidyl acetate, and glycidyl butyrate , Glycidyl benzoate, glycidyl p-ethylbenzoate, and the like, and these may be used alone or in combination of two or more thereof.

Reaction of the cyclic structure containing epoxy resin and monobasic carboxylic acid in the manufacturing method of said (1), and polyfunctional hydroxyl-containing cyclic structural compound (10) and monobasic carboxylic acid in the manufacturing method of said (2) Reaction of glycidyl is performed all 5 to 30 hours in 50-120 degreeC temperature range using an appropriate solvent as needed. Examples of the solvent that may 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 Alkylene monoalkyl ether acetates such as 3-methoxybutyl-1-acetate; Alkylene monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dibutyl ether; Ketones such as methyl ethyl ketone and methyl amyl ketone; Esters such as dimethyl succinate, diethyl succinate, diethyl adipic acid, diethyl malonate and dibutyl oxalate. Among these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferable. Moreover, a catalyst and a polymerization inhibitor can be used as needed. Examples of the catalyst to be used include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds and the like, and are usually contained in an amount of 0.01 to 10% by weight of the entire reactant. It is preferable to use in the range. Moreover, as a polymerization inhibitor to be used, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, etc. are mentioned, for example, Usually, the range of 5 weight% or less of the whole reactant is common. Can be added in.

The polyhydric alcohol (a2) used for preparation of the said condensed ring structure containing alkali-soluble resin (A2) refers to the compound containing two or more hydroxyl groups in a molecule | numerator, For example, although the following compound is mentioned, It is not limited to these. : Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimethylol butanoic acid, dimethylolpropanoic acid, tartaric acid, Glycerin, diglycerin, trimethylol ethane, trimethylol propane, isocyanuric tris (2-hydroxyethyl), ditrimethylol propane, ditrimethylol ethane, pentaerythritol, erythritol, xylitol, sorbitol, inositol, di Pentaerythritol, polyglycerol and the like. Among these, when trifunctional or more than trifunctional compounds, such as trimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, and dipentaerythritol, are used, the adhesiveness of the thin film obtained from the composition containing resin obtained and the board | substrate are excellent, Moreover, since the film is excellent in transparency, it is preferable. These polyhydric alcohols (a2) may be used independently and may combine 2 or more types.

Polybasic carboxylic acid or its anhydride (a3) used for preparation of the said condensed ring structure containing alkali-soluble resin (A1) (A2) is carboxylic acid which has several carboxyl groups, such as dicarboxylic acid and tetracarboxylic acid. Or as the anhydride thereof, these polybasic carboxylic acids or their anhydrides include the following compounds: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylene Dicarboxylic acids and their anhydrides such as tetrahydrophthalic acid, chloric acid, methyltetrahydrophthalic acid and glutaric acid; Trimellitic acid or its anhydride, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, biphenylsulfontetracarboxylic acid, 4- (1,2-dicarboxyl Tetracarboxylic acids such as ethyl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, butanetetracarboxylic acid, and acid dianhydrides thereof.

In addition, "polybasic carboxylic acid or its anhydride (a3)" means "at least one of specific polybasic carboxylic acid and the anhydride corresponding to it", For example, if polybasic carboxylic acid is phthalic acid, phthalic acid and It refers to at least one of phthalic anhydride.

By suitably selecting the kind and number of polybasic carboxylic acid or its anhydride, various condensed ring structure containing alkali-soluble resin (A1) from which a structure differs can be manufactured. Specifically, the first to third condensed ring-containing alkali-soluble resins (A1) shown in the following (i) to (iii) are prepared, for example.

(i) 1st ring skeleton containing alkali-soluble resin (A1):

Resin obtained by mixing and reacting an epoxy ester compound (a1) and one type of polybasic carboxylic acid or its anhydride (a3);

(ii) 2nd condensed skeleton containing alkali-soluble resin (A1):

The epoxy ester compound (a1) and a mixture of two or more polybasic carboxylic acids or their anhydrides (for example, a mixture of dicarboxylic anhydrides and tetracarboxylic dianhydrides) (a3) are mixed and reacted. Resin obtained; And,

(iii) Third ring-containing skeleton-alkali-soluble resin (A1):

Resin obtained by making dicarboxylic acid or its anhydride (a3-2) react with the reaction product obtained by making an epoxy ester compound (a1), tetracarboxylic acid, or its dianhydride (a3-1) react.

In addition, a condensed ring structure containing alkali-soluble resin (A2) is obtained by making the said epoxy ester compound (a1), polyhydric alcohol (a2), and polybasic carboxylic acid or its anhydride (a3) react. In this reaction, the addition order of an epoxy ester compound (a1), a polyhydric alcohol (a2), and a polybasic carboxylic acid or its anhydride (a3) does not matter. For example, a method in which some or all of these are mixed and reacted at the same time, specifically, an epoxy ester compound (a1) and a polyhydric alcohol (a2) are mixed, and then a polybasic carboxylic acid or its anhydride (a3) is mixed. There is a method of adding, mixing and reacting. Moreover, you may make it react by adding a polybasic carboxylic acid further to these reaction products. By suitably selecting the kind and number of polybasic carboxylic acid or its anhydride, various cyclic structure containing alkali-soluble resin (A2) from which a structure differs can be manufactured. Specifically, for example, the fourth to sixth condensed ring-containing alkali-soluble resins (A2) shown in the following (iv) to (vi) are prepared.

(iv) Fourth Cyclocyclic Skeleton-Containing Alkali-Soluble Resin (A2):

Resin obtained by mixing and reacting an epoxy ester compound (a1), a polyhydric alcohol (a2), and one type of polybasic carboxylic acid or its anhydride (a3);

(v) Fifth ring-containing skeleton-alkali-soluble resin (A2):

A mixture of an epoxy ester compound (a1), a polyhydric alcohol (a2), and two or more polybasic carboxylic acids or anhydrides thereof (for example, a mixture of dicarboxylic anhydrides and tetracarboxylic dianhydrides) ( resin obtained by mixing and reacting a3); And,

(vi) Sixth Cyclocyclic Skeleton-Containing Alkali-Soluble Resin (A2):

Dicarboxylic acid or its anhydride (a3-2) is further added to the reaction product obtained by making an epoxy ester compound (a1), polyhydric alcohol (a2), and tetracarboxylic acid or its dianhydride (a3-1) react. Resin obtained by making it react.

In addition, "a mixture of 2 or more types of polybasic carboxylic acid or its anhydride" means that at least 2 types of polybasic carboxylic acid or its anhydride exist simultaneously. Therefore, in the method of said (ii) and (v), at least 2 type of polybasic carboxylic acid or its anhydride is involved in reaction.

The condensed ring structure-containing alkali-soluble resins (A1) and (A2) are epoxy ester compounds (a1), polyhydric alcohols (a2), polybasic carboxylic acids or anhydrides thereof (a3) in any of the above-described methods. In the illustrated method (step), for example, it is prepared by dissolving (suspending) in cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, and heating and reacting.

In manufacture of the said cyclic structure containing alkali-soluble resin (A2), the molar ratio of the hydroxyl group of an epoxy ester compound (a1) and the hydroxyl group of a polyhydric alcohol (a2) is 99 in an epoxy ester compound (a1) and a polyhydric alcohol (a2). It is preferable to adjust so that it may be / 1-50 / 50, and it is more preferable that it is 95/5-60/40. When the molar ratio of the hydroxyl group of a polyhydric alcohol (a2) exceeds 50%, the molecular weight of resin obtained will increase rapidly and there exists a possibility of gelatinization. Moreover, when it is less than 1%, the molecular weight of resin obtained does not fully rise and there exists a tendency which is difficult to improve heat resistance.

The polybasic carboxylic acid or its anhydride (a3) is preferably 0.3 to 1 equivalent in terms of acid anhydride group, based on 1 equivalent (mol) of the hydroxyl group of the epoxy ester compound (a1) and the polyhydric alcohol (a2), More preferably, it is provided to reaction in the ratio of 0.4-1 equivalent. When the polybasic carboxylic acid or its anhydride (a3) is converted to an acid anhydride group, the molecular weight of the alkali-soluble resin obtained may not be high at less than 0.3 equivalent. Therefore, when exposure and image development are performed using the radiation sensitive resin composition containing such alkali-soluble resin, the heat resistance of the film obtained may be inadequate, or a film may remain on a board | substrate. When the said polybasic carboxylic acid or its anhydride exceeds 1 equivalent in conversion of an acid anhydride group, the unreacted acid or acid anhydride remain | survives, the molecular weight of the alkali-soluble resin obtained becomes low, and the radiation containing this resin The developability of the resin composition may be inferior.

In addition, an acid anhydride group conversion shows the quantity at the time of converting all the carboxyl groups and acid anhydride groups contained in the polybasic carboxylic acid to be used or its anhydride (a3) into acid anhydrides.

At the time of manufacture of the said 2nd, 3rd, 5th and 6th alkali-soluble resin, 2 or more types of polybasic carboxylic acid or its anhydride is used. Generally, dicarboxylic anhydride and tetracarboxylic dianhydride are used. It is preferable that it is 1/99-90/10 in molar ratio, and, as for the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, it is more preferable that it is 5/95-80/20. If the ratio of dicarboxylic anhydride is less than 1 mol% of all the acid anhydride, resin viscosity may become high and workability may fall. Moreover, since the molecular weight of resin obtained becomes large too much, when the thin film is formed on a board | substrate using the radiation sensitive resin composition containing this resin, and it exposes, the exposure part becomes difficult to melt | dissolve with respect to a developing solution, Tends to be difficult to obtain. When the ratio of dicarboxylic anhydride exceeds 90 mol% of all the acid anhydrides, since the molecular weight of resin obtained becomes too small, when a coating film is formed on a board | substrate using the composition containing this resin, after prebaking Problems such as sticking remaining in the coating film tend to occur.

In any case, the reaction temperature is preferably 50 to 130 ° C, more preferably at the time of the reaction of the epoxy ester compound (a1), the polyhydric alcohol (a2), and the polybasic carboxylic acid or its anhydride (a3). Is 70-120 degreeC. When reaction temperature exceeds 130 degreeC, some condensation of a carboxyl group and a hydroxyl group will arise, and molecular weight will increase rapidly. On the other hand, when it is less than 50 degreeC, reaction does not progress smoothly and an unreacted polybasic carboxylic acid or its anhydride remains.

Alkali-soluble resin (A) contained in the liquid-repellent resin composition of this invention may be any of said 1st, 2nd, 3rd, 4th, 5th, and 6th resin, These may be independent resins, and 2 A mixture of species or more may be used. As for the compounding quantity of alkali-soluble resin (A) in the liquid-repellent resin composition of this invention, 20-95 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. As an example of such a fluorine-containing polyether compound (B), what has a fluorine-containing alkylene ether structure represented by any of the following general formula (18)-(20) is mentioned, C2-C100 ether bonds and containing The compound which has a fluorine alkylene group is mentioned.

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.

[Formula 15]

Wherein 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 It is a fluorine alkyl group, x, y, z are each independently an integer of 0 or more, and x + y + z contained in (B) is an integer of 2 or more. Provided that at least one of R ₁₉ and R ₂₀ is F or a C 20 or less fluorine-containing alkyl group, at least one of R ₂₁ to R ₂₄ is an F or a C 20 or less fluorine-containing alkyl group, and in R ₂₅ to R ₃₀ At least one is F or a C20 or less fluorine-containing alkyl group.

As a C20 or less fluorine-containing alkyl group (b1), a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example.

When x, y, z contain only one of the structural units (18), (19) and (20), the fluorine-containing polyether compound (B) contains x, y or z alone or more than 5 And when two or more types of structural units are contained, it is preferable that the sum total of x, y, z is five or more. Moreover, it is preferable that a fluorine-containing polyether compound (B) has an unsaturated group in a molecule | numerator. By containing an unsaturated group, a fluorine-containing polyether compound (B) is fixed to a coating film, and the liquid repellency persistence can be improved.

In this specification, "liquid repellency" means both water repellency and oil repellency.

A fluorine-containing polyether compound (B) can be represented by following General formula (21), for example.

[Formula 16]

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, i ₂ is an integer of 0 to 20, and n is 1 to 200. Is an integer. More preferably, i ₁ is an integer of 0-3, i ₂ is an integer of 0-3, n is an integer of 5-20. h is an integer of 1-5, More preferably, it is an integer of 1-3. In addition, at least one of _a Rf is F or a fluorinated alkyl group having a carbon number of 20 or less, and at least one of Rf _b is, that the fluorinated alkyl group of a carbon number of 20 F or less.

[Formula 17]

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 of the carbon atoms constituting the alkylene group is one or more fluorine atoms or fluorocarbons having 20 or less carbon atoms. alkyl group (for example CF _3, etc.) means that has a structure which is bonded. At least one of _n fluorine-containing alkylene ether structures FE ₁ to FE _n in General Formula (21) contains a fluorine-containing alkylene ether structure represented by any one of General Formulas (18) to (20). it is preferable, and a fluorinated alkyl ether structure FE ₁ - FE _n is more preferably are each independently also shown that any of the formulas (18) to (20) a fluorine alkyl ether structure. In the case where n is 2 or more, FE ₁ to FE _n may be the same as or different from each other, and the order of bonding does not matter. when n is 1, it is assumed that FE ₁ is present in one same main chain.

L is a single bond,

[Formula 18]

Either of which is represented and K is group containing an unsaturated group, group which has a structure as described in following formula (23)-(33) etc. is mentioned as a specific example.

In addition, the fluorine-containing polyether compound (B) includes what is represented by following General formula (22), for example.

[Formula 19]

J <_1> is an integer of 1-100 here, j <_2> is an integer of 1-50. Rf _c is a fluorine-containing polyether group having two or more etheric oxygen atoms, and preferably contains at least one fluorine-containing alkylene ether structure represented by any one of General Formulas (18) to (20). When j ₂ is 2 or more, a plurality of Rf _c may be the same or different. The meanings of K and L are the same as above. In addition, L 'is a group represented by a single bond or the following general formula.

[Formula 20]

As a fluorine-containing polyether compound (B) described by the said General formula (21), it is a, for example,

[Formula 21]

[Formula 22]

There is. Here, each of Rf _{1 's} independently represents a fluorine-containing alkyl group having 20 or less carbon atoms. y1 is an integer of 0-30, z1 is an integer of 0-20, and at least one of y1 and z1 is an integer of 1 or more. y2 is an integer of 1-30, z2 is an integer of 1-20, and the thing similar to said (b1) etc. are mentioned as a C20 or less fluorine-containing alkyl group. K ₁ is

[Formula 23]

Etc. are mentioned as an example.

As a manufacturing method of the said specific example (FPE2), the method as described in international publication 94/27945 pamphlet, international publication 01/46107 pamphlet, etc. are mentioned, for example.

The manufacturing method of specific examples (FPE1) and (FPE3) is, for example,

[Formula 24]

[Formula 25]

And a method of reacting an acid halide such as? -Fluoroacrylic acid fluoride with a fluorine-containing compound having an OH group (wherein y1, z1 and z2 are the same as above).

In addition, as an example of the fluorine-containing polyether compound (B) described by the said General formula (21),

[Formula 26]

There is this. 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 hydrogen atoms, F, and CF ₃ . At least one of Rf ₆ is a group containing a fluorine atom (F or a C 20 or less fluorine-containing alkyl group), and at least one of Rf ₇ is a group containing a fluorine atom (F or a C 20 or less) Fluorine-containing alkyl group). h is an integer of 1-5, i is an integer of 0-20, j is an integer of 0-20, n is an integer of 1-200. More preferably, h is an integer of 1-3, i is an integer of 0-3, j is an integer of 0-3, n is an integer of 5-20. The meaning of FE ₁ to FE _n is the same as above, and 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, it is assumed that FE ₁ is present in one same main chain. K ₂ is a group containing a (meth) acryloyloxy group. As a specific example of K ₂ ,

[Formula 27]

[Formula 28]

Etc. (In formula, m is an integer of 0-10. * Represents a coupling | bond part). Of these, chukhwan structure containing at friendly viewpoint of the alkali along with soluble resin (A) fluorine-polyether compound (B), K ₂ preferably a structure containing a urethane bond, and also specifically, equation (31) to ( 33) can be mentioned.

As a fluorine-containing polyether compound (B) described by the said General formula (22), for example,

[Formula 29]

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

In addition, when two or more types of structural units exist in FPE1 and FPE4, the order is arbitrary. Moreover, two or more points may exist in the same structural unit in the same main chain. For example, in FPE4

[Formula 30]

(Hereinafter referred to as "y3 '") and

[Formula 31]

(Hereinafter, referred to as "y4") may be any of -y3'-y4'- or -y4'-y3'- and are randomly combined (y3'-y4'-y3 ', etc.). You may be. Moreover, the structural unit (for example, the structural unit represented by Formula (18) or other fluorine-containing alkyl ether other than that represented by Formula (18)) other than the structural unit represented by y3 'and y4' may be contained, and the bonding position of this structural unit is specifically limited. May be coupled to the outside of the structure represented by -y3'-y4'- or -y4'-y3'- or the like, or may be sandwiched between the structural units represented by y3 'and y4'.

As a manufacturing method of a specific example (FPE4), for example, the method of the international publication 03/076484 pamphlet etc., namely, of tetrafluoroethylene and fluorovinyl ethers using the radical initiator which produces hydroxyl radical OH *, There exist a method of making methanol and allylamine react with a radical copolymer.

As a manufacturing method of specific example (FPE5), for example,

[Formula 32]

2-isocyanatoethyl acrylate or 2-isocyanatoethyl to a fluorine-containing polyether compound having an OH group such as wherein Rf ₆ , Rf ₇ , i, j and FE ₁ to FE _n are the same as above. A method of reacting isocyanates such as methacrylate, the fluorine-containing polyether compound having an OH group, 2-hydroxyethyl methacrylate (2-HEMA), 4-hydroxybutyl acrylate (4-HBA), OH group-containing (meth) acrylate compounds such as 1,4-cyclohexanedimethanol monoacrylate (CHDMMA), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4 , 4'-diphenylmethane diisocyanate (MDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethyl-hexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), tetra Methylxylylenediisocyane Bit (TMXDI), naphthalene diisocyanate, and reacting the polyisocyanates, such as those of the multi-core body can be preferably used also. Specific examples of the polyisocyanates include polyisocyanates (eg, Nippon Polyurethane Co., Ltd. coronate L-55E, etc.), TDI, or HDI obtained by reacting polymer MDI, TDI, or MDI with polyhydric alcohols. The polyisocyanate (for example, coronate 2030 by Nippon Polyurethane Industry Co., Ltd., coronate HX, etc.) which has the isocyanurate ring as mentioned above is mentioned. As described above, K ₂ in the (FPE5), in order to manufacture the (FPE5) to have a desirable, and such a structure that contains a urethane bond, is required compound having a plurality of isocyanate, and this From the viewpoint, the polyisocyanates are particularly preferred. In the liquid-repellent resin composition of the present invention, the fluorinated polyether compound (B) needs to be efficiently transferred to the membrane surface during film production. However, in the composition (plating solution) state, the condensed structure-containing alkali-soluble resin (A) And the fluorine-containing polyether compound (B) need to be mixed uniformly and stably. Since the fluorine-containing polyether compound (B) in the present invention has a suitable affinity with the condensed ring-containing alkali-soluble resin (A), this can be made compatible with each other. (FPE5) having a urethane bond, because of having a moderate affinity with the containing alkali-soluble resin (A) and having a very good balance between the stability of the mixture and the surface transferability of the fluorinated polyether compound (B) during film production Particularly preferred. When the (meth) acryloyl group coexists, when the liquid-repellent resin composition of the present invention is cured, the fluorinated polyether (B) also participates in the curing reaction and enters the surface of the coating film, so that the liquid-repellent persistence is maintained. It is preferable at the point which can be raised.

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

In the liquid-repellent resin composition (1), (2) of the present invention, the ratio of the fluorine-containing polyether compound (B) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the condensed ring-containing alkali-soluble resin (A). More preferably, it is the range of 0.05-5 weight part. When the ratio of the fluorine-containing 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 fluorine-containing polyether compound (B) is exquisitely maintained, and the fluorine-containing polyether compound (B ) Is quickly transferred to the coating film surface, liquid repellency is imparted only to the coating film surface, and furthermore, the developability is good, and it is possible to prevent a decrease in substrate adhesion by a fluoroalkyl group. If it 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 composition (1), (2) of the present invention, at least one of the condensed ring-containing alkali-soluble resin (A) and the fluorinated polyether compound (B) contains an unsaturated group which can be polymerized by light or heat. desirable. More preferably, both of (A) and (B) contain the said unsaturated group.

In addition, since a cyclic structure containing alkali-soluble resin (A) and a fluorine-containing polyether compound (B) are mainly solid, it is preferable that the liquid-repellent resin composition (1) and (2) of this invention contain a solvent.

As such a solvent, what is necessary is just an organic solvent which does not react with each component in a composition, for example, can melt | dissolve or disperse them, and there is no restriction | limiting in particular. For example, the following compounds are mentioned: Alcohol, 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 mono Alkylene glycol alkyl ether acetates such as butyl ether acetate and 3-methoxybutyl-1-acetate; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-methylbutanoic acid Esters such as methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate.

Among them, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferable, and ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol methyl ether acetate and ethylene glycol mono Ethyl ether acetate and methyl amyl ketone are preferred. These solvents may be used individually by 1 type, and may mix and use 2 or more types.

As for the compounding quantity of the solvent in the liquid-repellent resin composition of this invention, 5-70 weight% of the whole composition is preferable.

(II) radiation-sensitive resin composition

The radiation sensitive resin composition of this invention contains at least one of the said liquid repellent resin composition (1) or (2). As used herein, the term "radiation" refers to at least one of visible rays, ultraviolet rays, far ultraviolet rays, X rays, electron rays, molecular rays, gamma rays, synchrotron radiation, and proton beam rays.

Usually, this radiation sensitive resin composition contains the liquid repellent resin composition and a radiation reactive compound. In the case where the composition is a positive radiation-sensitive resin composition, the radiation-reactive compound is, for example, a quinone diazide compound (hereinafter may be referred to as a quinone diazide compound (D)). It is preferable to contain 0.5-50 weight part with respect to 100 weight part of resin compositions. In the case of a negative radiation sensitive resin composition, a radiation reactive compound is a photoinitiator (C), for example. It is preferable to contain 0.1-30 weight part with respect to 100 weight part of said liquid repellent resin compositions, More preferably, a photoinitiator (C) is the range of 0.4-10 weight part. The radiation sensitive resin composition of this invention contains another component as needed.

The negative radiation sensitive resin composition is given to the following and the description is given about the radiation sensitive resin composition of this invention.

The negative radiation sensitive resin composition of this invention contains a photoinitiator (C) as said liquid-repellent resin composition and a radiation reactive compound. The photoinitiator of the said (C) means the compound which has a photoinitiator action, and / or a compound which has a sensitization effect. Examples of such a compound include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroaceto Acetophenones such as phenone, p-tert-butylacetophenone and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Sulfur compounds such as benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl thioxanthene, 2-methylthioxanthene, and 2-isopropyl thioxanthene; Anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; Organic peroxides such as azobisisobutyronitrile, benzoyl peroxide and cumene peroxide; And thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.

These compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, although it does not act as a photoinitiator by itself, it can also add the compound which can increase the capability of a photoinitiator by using it in combination with the said compound. As such a compound, tertiary amines, such as triethanolamine which are effective when used in combination with benzophenone, are mentioned, for example.

The radiation sensitive resin composition of this invention contains a radiation sensitive monomer or oligomer (E) as needed. A radiation sensitive monomer or oligomer (E) is a monomer and oligomer which can superpose | polymerize with a radiation, and can be contained according to the physical property according to the purpose of use of a composition. These monomers or oligomers may act as a viscosity modifier or an optical crosslinking agent, and may be contained in the range which does not impair the property of the liquid-repellent resin composition of this invention. When at least one of a cyclic structure containing alkali-soluble resin (A) and a fluorine-containing polyether compound (B) has radiation reactivity (when an unsaturated group is contained in a molecule), a radiation sensitive monomer or oligomer (E) is further added. Inclusion is not an essential condition. However, when both (A) and (B) do not have radiation reactivity (when no unsaturated group is contained in the molecule), in order to function as a radiation sensitive resin composition, it further contains a radiation sensitive monomer or oligomer (E). I need to.

Usually, the said monomer and oligomer are contained in the composition in 50 weight part or less with respect to 100 weight part of solid content of the liquid-repellent resin composition of this invention in the total amount. When content of this monomer or oligomer exceeds 50 weight part, the sticking property after prebaking may arise.

As a monomer or oligomer which can superpose | polymerize with the radiation of said (E), the following monomer or oligomer is mentioned: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 Monomers having hydroxyl groups such as hydroxypropyl (meth) 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, trimethyl All propane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di (Meth) acrylic acid esters, such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate. These monomers or oligomers may be used individually by 1 type, or may be used in combination of 2 or more type.

The radiation sensitive resin composition of this invention contains the compound which has (a) epoxy group, (b) additive, (c) solvent, etc. further as needed.

As a compound which has an epoxy group of said (a), the polymer or monomer which has at least one epoxy group is used. As a polymer which has at least 1 epoxy group, it is a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, biphenyl type epoxy resin, for example. And epoxy resins such as alicyclic epoxy resins. Examples of the monomer having at least one epoxy group include phenylglycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl. Methacrylate, and the like. These compounds may be used alone or in combination of two or more thereof.

The compound which has these epoxy groups can be contained in the range which does not impair the property of the resin composition of this invention. Usually, the compound which has an epoxy group is contained in the ratio of 50 weight part or less per 100 weight part of solid content of this liquid repellent resin composition. When it exceeds 50 weight part, when hardening the composition containing the component, a crack will occur easily and adhesiveness will also fall easily.

Examples of the additive (b) include a thermal polymerization inhibitor, an adhesion aid, an epoxy group curing accelerator, a surfactant, an antifoaming agent, and the like, which are contained in the composition in an amount within a range not impairing the object of the present invention.

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

The said adhesion | attachment adjuvant is contained in order to improve the adhesiveness of the composition obtained. As an adhesion | attachment adjuvant, the silane compound (functional silane coupling agent) which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanato group, an epoxy group, is preferable. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and γ-isocyanatopropyltriethoxy Silane, (gamma)-glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

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

The said surfactant is contained, for example in order to make it easy to apply | coat a liquid composition on a board | substrate, and also the flatness of the film | membrane obtained by this improves. As surfactant, For example, BM-1000 (made by BM Hemi Corporation), Megapack F142D, Megapack F172, Megapack F173, and Megapack F183 (made by Dainippon Ink Chemical Co., Ltd.), Prodora FC-135 , PRODORA FC-170C, PRODORA FC-430 and PRODORA FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Saffron S-112, Saffron S-113, Saffron S-131, Saffron S-141 And Saffron S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (manufactured by Torre Silicone Co., Ltd.) ), And the like.

As said antifoamer, compounds, such as a silicone type, a fluorine type, and an acryl type, are mentioned, for example.

The solvent of the said (c) which can be contained in the radiation sensitive resin composition of this invention is used in order to melt | dissolve each component in a composition uniformly, for example, to make easy coating on a board | substrate. As such a solvent, what is necessary is just an organic solvent which does not react with each component in a composition, and can melt | dissolve or disperse them, and there is no restriction | limiting in particular. For example, the following compounds are mentioned: Alcohol, 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 mono Alkylene glycol alkyl ether acetates such as butyl ether acetate and 3-methoxybutyl-1-acetate; Diethylene glycol (di) alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether Ryu; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-methylbutanoic acid Esters such as methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate.

Among them, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferable, and ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol methyl ether acetate and ethylene glycol mono Ethyl ether acetate and methyl amyl ketone are preferred. These solvents may be used individually by 1 type, and may mix and use 2 or more types.

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) by light irradiation with a wavelength of 100 to 600 nm, and the unsaturated group crosslinks with each other. In the case where the liquid-repellent resin composition of the present invention is composed of a compound having no unsaturated group, the liquid-repellent property of the liquid-repellent resin in the crosslinked matrix generated by the crosslinking reaction between the radiation-sensitive monomers or oligomers which may be added to the negative radiation-sensitive resin composition The resin composition is immobilized. Moreover, when the condensed ring structure-containing alkali-soluble resin (A) and / or the fluorinated polyether compound (B) of the liquid-repellent resin composition of the present invention contains an unsaturated group, the liquid-repellent resin composition itself is involved in the polymerization reaction, It is inserted into the crosslinked structure and immobilized. As a result, the exposed portion becomes insoluble in alkali, and in the subsequent alkali developing step, since the condensed ring-containing alkali-soluble resin (A) has alkali solubility, the unexposed portion can be removed to form a pattern.

The hardened | cured material obtained by hardening | curing the resin composition which consists of a condensed ring structure containing alkali-soluble resin (A) and a fluorine-containing polyether compound (B) is a coating film, when (A) and (B) itself are inserted in and fixed to the crosslinked structure of hardened | cured material. Since the liquid repellency is excellent in the durability, it is preferable that the condensed ring-containing alkali-soluble resin (A) and the fluorine-containing polyether compound (B) have an unsaturated group.

In the radiation sensitive resin composition of this invention, a coloring agent can be contained as needed. As a coloring agent, dye, an organic pigment, an inorganic pigment, a metallic pigment, etc. are illustrated. As dye, the compound classified as dye in the color index (C.I .; The Society of Dyers and Colourists), such as an azo dye, an azomethine dye, a xanthene dye, and a quinone dye, is mentioned. Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists), and the central metals are Cu, Mg, Al, Si, Ti, V, Mn, And dissimilar metal phthalocyanine pigments such as Fe, Co, Ni, Zn, Ge, and Sn. Examples of the 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 hafnium sulfate; calcium carbonate, gold chloride and gold bromide Metal salts such as silver chloride, silver bromide, silver iodide, palladium chloride, chloroplatinic acid, sodium chloride, silver nitrate, platinum acetylacetonate and palladiumacetylacetonate; precious metals such as gold, silver, platinum, palladium, rhodium, ruthenium, and iridium; Lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium red, ultramarine blue, tap blue, chromium oxide rust, cobalt rust, amber, titanium black, synthetic iron black, carbon black, carbon nanotubes Can be. Examples of the metallic pigments include aluminum flakes and copper bronze flakes.

It is preferable that the radiation sensitive resin composition of this invention contains at least 1 sort (s) chosen from the group which consists of carbon black, titanium black, a black metal oxide pigment, and an organic pigment as a coloring agent. As the black metal oxide pigment, 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.

The negative radiation sensitive resin composition which mixed the black coloring agent can be used as a light-shielding coating film. For example, in the case of a color filter, it can use for forming a black matrix in order to raise the contrast of RGB light emission color. Examples of the black colorant include carbon black, graphite, iron black, aniline black, cyanine black, titanium black, and the like. Moreover, the mixture of a red pigment, a blue pigment, and a green pigment can also be used as a black coloring agent.

As for the compounding quantity of a coloring agent, 1-40 weight% of the whole composition is preferable. When it is less than 1 weight%, coloring may not be enough, and when more than 40 weight%, the fluidity | liquidity of a composition may worsen or adhesiveness may fall.

As a coloring agent, carbon black is preferable from a viewpoint of light shielding property, an image characteristic, etc. As carbon black, furnace black, thermal black, acetylene black, etc. are mentioned, for example. Specifically, Mitsubishi Chemical Corporation make brand names "MA7", "MA8", "MA11", "MA100", "MA220", "MA230", "# 52", "# 50", "# 47", `` # 45 '', `` # 2700 '', `` # 2650 '', `` # 2200 '', `` # 1000 '', `` # 990 '', `` # 900 '', etc. , "Printex 85", "Printex 75", "Printex 55", "Printex 45", "Printex 40", "Printex 30", "Printex 3", "Printex A", "Printex G", "Special Black 550" '', `` Special Black 350 '', `` Special Black 250 '', `` Special Black 100 '', Kabot company brand name `` Monarch 460 '', `` Monarch 430 '', `` Monarch 280 '', `` Monarch 120 '', `` Monarch 800 '' , "Monarch 4630", "REGAL 99", "REGAL 99R", "REGAL 415", "REGAL 415R", "REGAL 250", "REGAL 250R", "REGAL 330", "BLACK PEARLS 480", "BLACK PEARLS" 130 ", such as product made in Colombia carbon company brand names" RAVEN 11, "RAVEN 15", "RAVEN 30", `` RAVEN 35 '', `` RAVEN 40 '', `` RAVEN 410 '', `` RAVEN 420 '', `` RAVEN 450 '', `` RAVEN 500 '', `` RAVEN 780 '', `` RAVEN 850 '', `` RAVEN 890H '', `` RAVEN 1000 '', "RAVEN 1020", "RAVEN 1040" are mentioned. These carbon blacks can be used individually or in mixture of 2 or more types.

A coloring agent is disperse | distributed with dispersing agents, such as a 3 roll mill, a ball mill, and a sand mill, with a dispersing agent (for example, a polycaprolactone type compound, a long chain alkyl polyaminoamide type compound, etc.), and after that, it is radiation sensitive You may add to a resin composition. As for a particle diameter, 1 micrometer or less is preferable. The developability of a negative radiation sensitive resin composition becomes it favorable that it is the said range.

The radiation sensitive resin composition of this invention is soluble in alkali, and can be hardened by radiation irradiation. The radiation sensitive resin composition containing alkali-soluble resin (A) of this invention is shape | molded in a desired shape, hardened by radiation, and is used for various objectives. In particular, it is used for the purpose of forming the thin film which has a predetermined | prescribed pattern by forming a thin film on the board | substrate with this composition, irradiating, and developing.

For example, as mentioned above, when forming a thin film on a board | substrate, and performing radiation hardening and image development, each component of the said composition containing a solvent is mixed first, and a liquid composition is obtained. It is more preferable to filter this, for example with a millipore filter of about 1.0-0.2 micrometer of pore diameters, and to make it a uniform liquid substance. Subsequently, this liquid composition is apply | coated on a board | substrate and a coating film is obtained. As a coating method, there are a dipping method, a spraying method, a roller coating method, a slit coating method, a bar coating method, a spin coating method and the like. In particular, the spin coat method is widely used. By these methods, after apply | coating a liquid resin composition to the thickness of about 1-30 micrometers, a thin film is formed when a solvent is removed. Usually, a prebaking process is performed in order to fully remove a solvent.

After mounting the mask which has a desired pattern on the thin film of this board | substrate, irradiation with radiation is performed. As radiation used, visible light, an ultraviolet-ray, an electron beam, an X ray, (alpha) ray, (beta) ray, and (gamma) ray are mentioned in order from a long wavelength. Among them, in terms of economy and efficiency, ultraviolet rays are the most preferable radiations in practical use. Ultraviolet light emitted from lamps such as a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, an arc lamp, and a xenon lamp can be preferably used for the ultraviolet rays used in the present invention. Radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and, in theory, is superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

By the said irradiation, an exposure part is hardened by a polymerization reaction. The unexposed parts are developed with a developer. Thereby, the unirradiated part of radiation is removed, and the thin film which has a desired pattern is obtained. Examples of the developing method include a liquid mounting method, a dipping method, a rocking dipping method, and the like.

As said developing solution, the alkaline aqueous solution, the liquid mixture of this alkaline aqueous solution and water-soluble organic solvent, and / or surfactant, and the organic solvent which can melt | dissolve the composition of this invention are mentioned, Preferably the liquid mixture of alkaline aqueous solution and surfactant is preferable. to be.

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, piperi Dine, 1,8-diazabicyclo (5.4.0) -7-undecene, 1,5-diazabicyclo (4.3.0) -5-nonane, and preferably sodium carbonate and tetramethylammonium hydroxide. Lockseed and the like are used.

A suitable amount of water-soluble organic solvents, such as methanol, ethanol, acetone, propanol, ethylene glycol, surfactant, etc. are added to this alkaline aqueous solution as needed.

The image development of the resin composition of this invention can be normally performed at 10-50 degreeC, Preferably it is 20-40 degreeC using a commercially available developer and an ultrasonic cleaner. The developing time can be appropriately adjusted by the developing method, the developing solution, the temperature, the film thickness of the coating film, and the like.

After alkali development, in order to improve alkali resistance, it is preferable to heat and harden | cure (post-baking process). In the resin composition of the present invention, not only the durability against strong alkaline water is remarkably improved by heat treatment, but also all the properties such as adhesion to metal or glass such as copper, heat resistance and surface hardness are also improved. Preferable heating temperature and heating time are 80-250 degreeC and 10-120 minutes. In this way, a cured thin film having a desired pattern can be obtained.

Since the cured film obtained by hardening | curing the liquid repellent composition of this invention shows high ink repellency on the film surface, it is used suitably as a partition material (black matrix) required for manufacture of the color filter by the inkjet method. That is, the liquid-repellent composition of this invention can easily form the partition which the surface part has liquid repellency, and the side surface has lipophilic. This is because the fluorine-containing polyether compound (B) giving liquid repellency has surface transferability, and the fluorine-containing polyether compound (B) migrates near the coating film surface at the time of film production.

In addition, due to the exquisite balance of compatibility between the condensed ring-containing alkali-soluble resin (A) and the fluorine-containing polyether compound (B), the fluorine-containing polyether compound (B) is quickly transferred to the coating film surface, and the film production conditions It was found that it was possible to provide excellent liquid repellency only to the coating film surface stably without depending. As in the prior art, when the fluorine-containing compound does not move quickly to the coating film surface, it is necessary to set the film production conditions in consideration of the time for the fluorine component to migrate to the coating film surface. The fluorine-containing compound may remain inside the coating film, resulting in the liquid repellency of the side surface of the film.

By using the liquid repellent composition of the present invention, since the fluorine component is quickly transferred to the coating film surface, it is possible to stably form a pattern having excellent liquid repellency only on the coating film surface without setting special film production conditions.

The said liquid repellency can be evaluated by the contact angle of water and an organic solvent (for example, n-hexane). 90 degree or more is preferable and, as for the contact angle of water, 100 degree or more is more preferable. As the contact angle of the organic solvent, for example, the contact angle of n-hexane is preferably 30 degrees or more, more preferably 40 degrees or more.

Moreover, since the negative radiation sensitive resin composition of this invention has the outstanding alkali solubility and developability, a fine pattern can be formed. It is specifically used for pattern formation of 100 micrometers or less, and it is used more preferably for pattern formation of 50 micrometers or less.

Moreover, the cured film obtained by hardening the liquid-repellent resin composition or radiation sensitive resin composition of this invention is excellent in heat resistance, transparency, adhesiveness with a base material, acid resistance, alkali resistance, chemical resistance, solvent resistance, surface hardness, etc. Therefore, the liquid repellent composition of this invention is used suitably as a formation material of the color filter of a liquid crystal display, the radiation sensitive resin composition for bank materials of organic EL, etc., for example.

By using the liquid-repellent resin composition of this invention, the fluorine-containing polyether compound (B) is quickly made to a coating film surface by the exquisite balance of compatibility of a cyclic structure containing alkali-soluble resin (A) and a fluorine-containing polyether compound (B). It transfers and liquid repellency is provided only to the coating film surface. After film production, the fluorine-containing polyether compound (B) is quickly transferred to the surface of the coating film, so that it is not influenced by the difference in film production conditions and is suitable for ink jet partitions simply by utilizing existing film production techniques. It can give performance.

Mode for carrying out the invention

Although an Example demonstrates this invention in detail below, this invention is not limited to these Examples.

Synthesis Example 1 Synthesis of Cyclocyclic Structure-Containing Epoxy Resin

230 g of bisphenol xanthene represented by Formula (11) was dissolved in 800 g of epichlorohydrin, 1.8 g of benzyltriethylammonium chloride was further added, and it stirred at 100 degreeC for 5 hours. Next, 165g of 40% sodium hydroxide aqueous solution was dripped at 70 degreeC under reduced pressure (150 mmHg) for 3 hours. In the meantime, the produced water was taken out of the system by azeotroping with epichlorohydrin, and the effluent epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for 30 minutes. Then, after removing the salt produced | generated by filtration and also washing with water, epichlorohydrin was distilled off and methanol was added, and 230 g of bisphenol xanthene type epoxy resins represented by Formula (12) were obtained. The epoxy equivalent of this resin was 270g / eq.

[Formula 33]

Synthesis Example 2 Synthesis of Bisphenol Xanthene Epoxy Ester Compound

In a 300 ml four-necked flask, 210 g (epoxy equivalent 270 g / eq) of bisphenol xanthene type epoxy resin obtained in Synthesis Example 1, 600 mg of triethylbenzyl ammonium chloride as a catalyst, and 56 mg of 2,6-diisobutylphenol as a polymerization inhibitor And 71 g of acrylic acid were injected and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 10 ml / min. Next, this was gradually heated up to 120 degreeC. The solution became clear and viscous but continued to stir. In the meantime, the acid value was measured and heating and stirring were continued until it became less than 1.0 mgKOH / g. It took 15 hours to reach the goal. The bisphenol xanthene type epoxy ester compound (1 * a) which is pale yellow transparent and represented by a following formula was obtained (In general formula (1), A <_0> is a divalent group whose said formula (5), and R < ₇ > is eth. Nyl group (CH ₂ = CH), p _1-2 = 0, q _1-2 = 0, m ₁ = 0, m ₄ = 0, S ₁ = 0).

[Formula 34]

Synthesis Example 3 Synthesis of Cyclocyclic Structure-Containing Epoxy Resin

Polyfunctional hydroxyl group containing condensed structural compound represented by the following Formula (13) (In the said General formula (10), A <_0> is a divalent group whose formula (5) and R <_17> , R <_18> = CH <_3> , _{f1-- 2} = 2, r _1-2 = 1, m _9-10 = 0) 250 g of epichlorohydrin was dissolved in 800 g of benzyltriethylammonium chloride, and further stirred at 100 ° C for 5 hours. Next, 165g of 40% sodium hydroxide aqueous solution was dripped at 70 degreeC under reduced pressure (150 mmHg) for 3 hours. In the meantime, the produced water was taken out of the system by azeotroping with epichlorohydrin, and the leaked epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for 30 minutes. Then, after removing the salt produced | generated by filtration, and also washing with water, epichlorohydrin was distilled off and methanol was added and 250 g of condensed structure containing epoxy resins represented by Formula (14) were obtained. The epoxy equivalent of this resin was 270g / eq.

[Formula 35]

[Formula 36]

Synthesis Example 4 Synthesis of Biszylenol Xanthene Epoxy Ester Compound

In a 300 ml four-necked flask, 230 g of the condensed ring-containing epoxy resin obtained in Synthesis Example 3 (epoxy equivalent 270 g / eq), 600 mg of triethylbenzyl ammonium chloride as a catalyst and 56 mg of 2,6-diisobutylphenol as a polymerization inhibitor And 71 g of acrylic acid were injected and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 10 ml / min. Next, this was gradually heated up to 120 degreeC. The solution became clear and viscous but continued to stir. In the meantime, the acid value was measured and heating and stirring were continued until it became less than 1.0 mgKOH / g. It took 15 hours to reach the goal. A pale yellow transparent, solid, bisxyllenol xanthene type epoxy ester compound (1.b) was obtained (In general formula (1), A ₀ is a divalent group of the formula (5), and R 1 to 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).

[Formula 37]

Synthesis Example 5 Synthesis of Cyclocyclic Structure-Containing Epoxy Resin

240 g of bisphenol anthrones represented by the formula (15) were dissolved in 800 g of epichlorohydrin, 1.8 g of benzyltriethylammonium chloride was further added, and the mixture was stirred at 100 ° C for 5 hours. Next, 165g of 40% sodium hydroxide aqueous solution was dripped at 70 degreeC under reduced pressure (150 mmHg) for 3 hours. In the meantime, the produced water was taken out of the system by azeotroping with epichlorohydrin, and the leaked epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for 30 minutes. Then, after removing the salt produced | generated by filtration and also washing with water, epichlorohydrin was distilled off and methanol was added, and 240 g of bisphenol anthron-type epoxy resins represented by Formula (16) were obtained. The epoxy equivalent of this resin was 270g / eq.

[Formula 38]

Synthesis Example 6 Synthesis of Bisphenol Antrone-type Epoxy Ester Compound

In a 300 ml four-necked flask, 220 g of bisphenol anthrone-type epoxy resin (Epoxy equivalent 270 g / eq) obtained in Synthesis Example 5, 600 mg of triethylbenzyl ammonium chloride as a catalyst, and 2,6-diisobutylphenol 56 as a polymerization inhibitor MG and 71 g of acrylic acid were injected and heated and dissolved at 90 to 100 ° C while blowing air at a rate of 10 ml / min. Next, this was gradually heated up to 120 degreeC. The solution became clear and viscous but continued to stir. In the meantime, the acid value was measured and heating and stirring were continued until it became less than 1.0 mgKOH / g. It took 15 hours to reach the goal. A pale yellow transparent, solid, bisphenolanthrone type epoxy ester compound (1 · c) was obtained. (In the general formula (1), A ₀ is a divalent group wherein the 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).

[Formula 39]

Synthesis Example 7 Synthesis of Condensed Ring-Containing Epoxy Resin

350 g of biscresolfluorene represented by the formula (34) was dissolved in 257 g of epichlorohydrin, and 243 g of an aqueous 40% sodium hydroxide solution was added dropwise at 80 ° C for 10 hours. After completion of the dropwise addition, the reaction was continued for 1 hour. Thereafter, 1500 g of toluene and 300 g of water were added to the reaction solution, the resulting salt was dissolved in water, and after separation, the lower aqueous layer was removed. Furthermore, after wash | cleaning the upper layer of toluene layer, the solvent was distilled off under reduced pressure and 420 g of biscresol fluorene type epoxy resins represented by Formula (35) were obtained. The epoxy equivalent of this resin is 320g / eq, and p = 0 is 50%, p = 1 is 30%, p = 2 is 15% and p = 3 is 3% with respect to p in following formula (35). , p = 4 was a mixture of 2%.

[Formula 40]

Synthesis Example 8 Synthesis of Biscresol Fluorene Epoxy Ester Compound

In a 300 ml four-necked flask, 200 g (epoxy equivalent 320 g / eq) of biscresol fluorene type epoxy resin obtained in Synthesis Example 7, 600 mg of triethylbenzyl ammonium chloride as a catalyst, and 2,6-diisobutylphenol as a polymerization inhibitor 56 mg and 45 g of acrylic acid were injected and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 10 ml / min. Next, this was gradually heated up to 120 degreeC. The solution became clear and viscous but continued to stir. In the meantime, the acid value was measured and heating and stirring were continued until it became less than 1.0 mgKOH / g. It took 20 hours for the mountain to reach its goal. To represented by the following formula, a pale yellow transparent, and the solid phase of biscresol fluorene type epoxy ester compound (1 · d) were obtained (in the formula (1), A ₀ is a divalent group of the formula (17), R _{1 4} = CH ₃ , R ₇ = ethenyl group (CH ₂ = CH), p _1-4 = 0, q _1-4 = 1, m _1-4 = 0, and for s ₁ , s ₁ = 0 50%, s ₁ = 1 was 30%, s ₁ = 2 was 15%, s ₁ = 3 was 3%, and s ₁ = 4 was 2%).

[Formula 41]

Synthesis Example 9 Synthesis of Cyclocyclic Structure-Containing Alkali-Soluble Resin (A1-a)

Biphenyltetracarboxylic acid (s-BPDA) to 1230.8 g of 3-methoxybutyl acetate solution (56.2% of solid content) of the bisphenol xanthene type | mold epoxy ester compound (1 * a) obtained by the synthesis example 2 in a 2 L separable flask. 170.8g was mixed, this was heated up gradually and made it react at 110-115 degreeC for 14 hours. Subsequently, 87.2 g of tetrahydro phthalic anhydride (THPA) was added to the said reaction material, and it was made to react at 90-95 degreeC for 4 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring-containing alkali-soluble resin was obtained (A1-a).

Synthesis Example 10 Synthesis of Condensed Ring-Containing Alkali-Soluble Resin (A1-b)

Biphenyltetracarboxylic acid (s) in a 300 ml separable flask to 103.6 g of a 3-methoxybutyl acetate solution (solid content 56.2%) of the bisxylenoxanthene type epoxy ester compound (1 · b) obtained in Synthesis Example 4 -BPDA) 24.4g and 1.7 g of tetraethylammonium bromide were mixed, it was heated up gradually, and it was made to react at 110-115 degreeC for 12 hours. Subsequently, 13.6 g of tetrahydro phthalic anhydride (THPA) was added to the said reaction material, and it was made to react at 90-95 degreeC for 4 hours. Thus, 3-methoxybutyl acetate solution of alkali-soluble resin was obtained (A1-b).

Synthesis Example 11 Synthesis of Cyclocyclic Structure-Containing Alkali-Soluble Resin (A1-c)

Biphenyltetracarboxylic acid (s-BPDA) to 1240.7 g of the 3-methoxybutyl acetate solution (55.4% of solid content) of the bisphenol-anthrone type epoxy ester compound (1 * c) obtained by the synthesis example 6 in the 2 L separable flask. ) 174.0 g were mixed, and this was gradually heated to react at 110 to 115 ° C for 14 hours. Subsequently, 89.9 g of tetrahydro phthalic anhydride (THPA) was added to the said reaction material, and it was made to react at 90-95 degreeC for 4 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring-containing alkali-soluble resin was obtained (A1-c).

Synthesis Example 12 Synthesis of Cyclocyclic Structure-Containing Alkali-Soluble Resin (A2-a)

Into a 300 ml separable flask, 70 g of 3-methoxybutyl acetate solution (solid content 58.3%) of the bisxyllenoxanthene type epoxy ester compound (1 · b) obtained in Synthesis Example 4, 8.0 g of ditrimethylolpropane and biphenyl 14.1 g of tetracarboxylic acid (s-BPDA) and 0.1 g of tetraethylammonium bromide were mixed, this was gradually heated up and reacted at 110-115 degreeC for 12 hours. Next, 7.5 g of tetrahydro phthalic anhydride (THPA) was added to the said reaction material, and it was made to react at 90-95 degreeC for 4 hours. Thus, 3-methoxybutyl acetate solution of alkali-soluble radiation polymerizable unsaturated resin was obtained (A2-a).

Synthesis Example 13 Synthesis of Cyclocyclic Structure-Containing Alkali-Soluble Resin (A1-d)

43.3 g of pyromellitic anhydride (PMDA) to 500 g of a 3-methoxybutyl acetate solution (solid content 50.0%) of the biscresol fluorene type epoxy ester compound (1 · d) obtained in Synthesis Example 8 in a 2 L separable flask; 33.4 g of hexahydro phthalic anhydride (HHPA) was mixed, and the temperature was gradually raised to react at 110 to 115 ° C for 14 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring-containing alkali-soluble resin was obtained (A1-d).

Synthesis Example 14 Synthesis of Condensed Ring-Containing Alkali-Soluble Resin (A2-b)

5.0 g of trimethylol ethane and benzophenone tetracarb in 500 g of 3-methoxybutyl acetate solution (50.0% of solid content) of the biscresol fluorene type epoxy ester compound (1 * d) obtained by the synthesis example 8 in the 2 L separable flask. 71.8 g of acid dianhydrides (BTDA) were mixed, and this was gradually heated to react at 110 to 115 ° C for 14 hours. In this way, a 3-methoxybutyl acetate solution of a condensed ring-containing alkali-soluble resin was obtained (A2-b).

Synthesis Example 15 Synthesis of Fluorinated Polyether Compound (B1)

In a 500 ml four-necked flask under nitrogen atmosphere, perfluoropolyether alcohol represented by the formula (b-1):

[Formula 42]

To 20.2 g, 1.1 g of pyridine, 50 ml of perfluoromethylcyclohexane, 10 ml of methyl ethyl ketone (MEK) were charged, and the mixture was ice-cooled to 5 ° C or lower, and the system was nitrogen-substituted. Next, it was added dropwise by dissolving the acid chloride (CH ₂ = CHCOCl) 1.2g into the dropping funnel in MEK 10㎖ for about 10 minutes. After completion of the dropwise addition, the temperature was raised to room temperature and further 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 aqueous sodium chloride solution, and dried over anhydrous sodium sulfate. Furthermore, after distilling off under reduced pressure, the organic phase was dried overnight under reduced pressure and 70 degreeC, and 19.3 g of colorless transparent syrup liquid (B1) were obtained.

[Formula 43]

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):

[Formula 44]

To 20.2 g, 50 ml of perfluoromethylcyclohexane, 10 ml of methyl ethyl ketone (MEK), and 0.01 g of dibutyltin dilaurate were injected, and 2-isocyanatoethyl acrylate (Karens manufactured by Showa Denko) What dissolved 1.5 g of (R) AOI) in 10 ml of MEK was dripped at 50-60 degreeC for about 10 minutes. After completion of the dropwise addition, the temperature was raised to room temperature and further stirring was continued for 2 hours. After completion | finish of reaction, it confirmed that the absorption derived from the isocyanate bond observed in 2300 cm <^-1> vicinity was lost by the infrared spectrophotometer, and 80g of colorless transparent syrup solutions (B2) of 25% of solid content were obtained.

[Formula 45]

Synthesis Example 17 Synthesis of Fluorinated Polyether Compound (B3)

Perfluoropolyether alcohol represented by Formula (b-3) in a 500 ml four-necked flask under nitrogen atmosphere:

[Formula 46]

21.1 g of 2-hydroxyethyl methacrylate, 4.9 g of perfluoromethylcyclohexane, 10 ml of methyl ethyl ketone (MEK), and 0.01 g of dibutyltin dilaurate were injected, followed by polymer MDI (Mitsui). What dissolved 10.1 g of Chemical Polyurethane Co., Ltd. Cosmonate M-200) in 10 ml of MEK was dripped at 50-60 degreeC for about 10 minutes. After completion of the dropwise addition, the temperature was raised to room temperature and further stirring was continued for 2 hours. After the completion of the reaction, it was confirmed by an infrared spectrophotometer that absorption due to the isocyanate bond observed in the vicinity of 2300 cm ^-1 was lost, and 80 g of a pale brown transparent syrup solution (B3) having a solid content of 35% was obtained.

[Formula 47]

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

(Comparative Synthesis Example) Synthesis of Bisphenol A Alkali-Soluble Resin (RF1)

1100.9 g of 3-methoxybutyl acetate solution and 145.6 g of biphenyltetracarboxylic acid (s-BPDA) of EB3700 (bisphenol A type basic epoxy acrylate, manufactured by Daicel Ushibi Co., Ltd.) were injected into a 2 L separable flask. This was gradually heated up and reacted at 110-115 degreeC for 12 hours. Subsequently, 79.6 g of tetrahydro phthalic anhydride (THPA) was added to the said reactant, and it was made to react at 90-95 degreeC for 4 hours. Thus, the solution (RF1) of alkali-soluble radiation polymerizable unsaturated resin was obtained.

[Preparation 1 of a radiation sensitive resin composition and a radiation sensitive resin composition containing the resin composition]

It mix | blended according to the ratio shown in Table 1, and prepared the liquid repellent resin composition.

TABLE 1

* 1 HEMA: 2-hydroxyethyl methacrylate

* 2 3-MBA: 3-methoxybutyl acetate

* 3 Irgacure 907: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one (made by Chiba Specialty Chemicals)

* 4 BR: 2- (perfluorodecyl) ethylacrylate (fluorine compound other than fluorine-containing polyether)

[Preparation 2 of the radiation sensitive resin composition containing liquid-repellent resin composition and this resin composition]

200 parts by weight of an alkali-soluble resin solution (A1-a), 10 parts by weight of a fluorine-containing polyether compound (B2), Irgacure OXE-02 (manufactured by Chiba Specialty Chemicals Co., Ltd. 1- [9-ethyl-6- (2) -Methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetate) 5 parts by weight, dipentaerythritol hexaacrylate 30 parts by weight, 3-methoxybutyl acetate The resin solution which mixed 385 weight part was obtained. Next, 125 parts by weight of carbon black MA100 (manufactured by Mitsubishi Chemical Corporation), 85 parts by weight of the pigment dispersant Azisper PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.), 260 parts by weight of methyl isobutyl ketone, and 50 parts by weight of p-xylene were used as a paint shaker. The mixture was mixed to obtain a carbon black dispersion solution. Furthermore, the said resin solution and the carbon black dispersion solution were mixed, it disperse | distributed with a bead mill for about 1 hour using 0.5 mm zirconia beads (70% of filling rate) as a media, and the carbon black dispersion type radiation sensitive resin composition (Formulation No. 19 )

In the preparation of the compounding number 19, 200 parts by weight of the alkali-soluble resin solution (A1-a) 225 parts by weight (A1-d), 10 parts by weight of the fluorinated polyether compound (B2) 8 parts by weight (B3), 3- Except having made 385 weight part of methoxybutyl acetate 410 weight part, the carbon black dispersion type radiation sensitive resin composition (formulation number 20) was obtained by the same method as the preparation method of compound number 19.

[Membrane Preparation]

Film preparation uses each composition shown in Table 1, (i) the application | coating process apply | coated on a glass substrate using a spinner, (ii) the prebaking process which removes a solvent from a coating film, and (iii) hardens a coating film. 5 steps of an exposure step, (iv) a developing step of removing the uncured coating film, and (v) a drying step of drying the substrate after development (FIG. 1), and having a coating film having a film thickness of about 1 μm. The substrate was prepared and used for liquid repellency evaluation.

In order to grasp the influence according to the conditions of each process, according to the conditions shown in Table 2, after apply | coating with a spinner, time to prebaking (WT1), prebaking time (PBTi), prebaking temperature ( PBTm) and film production were performed by changing the conditions of the waiting time (WT2) to exposure after prebaking, and the coating film obtained was evaluated.

TABLE 2

[Evaluation of liquid repellency]

In order to confirm that only the film surface has liquid repellency with respect to the coating film hardened | cured using the liquid-repellent resin composition of this invention, in the said film | membrane manufacturing process, the irradiation amount of the ultraviolet-ray at the time of exposure is reduced, and also the back side of a board | substrate is By performing from (backside exposure), only the inside of a coating film was hardened, the board | substrate which removed the coating film surface by the development process was manufactured, and the contact angle was measured similarly.

If film production is carried out under the conditions of such backside exposure, the surface of the coating film is not cured. Therefore, when the liquid repellent component is present only on the surface of the coating film, liquid repellency is lost. When the liquid repellent component remains inside the coating film, the liquid repellency is maintained even when the coating film surface is lost.

2 is a typical exposure method, and FIG. 3 is a figure which demonstrated back surface exposure typically.

In the exposure step of (iii), a 250 W high-pressure mercury lamp is used, and in the usual exposure method, the remaining film rate after the developing step is 100%. In the back exposure, the remaining film rate after the developing step is about 90%. Ultraviolet rays were irradiated to

In the development step of (iv), the development treatment was performed at 23 ° C. for 60 seconds using 0.4 wt% tetramethylammonium hydroxide aqueous solution, followed by rinsing treatment with ultrapure water. Moreover, in the drying process of (v), the board | substrate which has the obtained thin film was dried on 130 degreeC and the conditions for 2 minutes.

The contact angle with respect to water and an organic solvent was measured as an indicator of the liquid repellency of the liquid repellent resin composition of this invention. Hexane was used as the organic solvent. The contact angle was measured using a contact angle gauge CA-D manufactured by Kyowa Interface Chemical.

TABLE 3

In Examples 1 to 60 (when either composition is exposed from the surface), the contact angle of the coating film is 100 to 109 ° in water and 41 to 51 ° in an organic solvent (hexane), without depending on the film production conditions. All showed high levels of liquid repellent properties. Moreover, when exposing from the back surface, the contact angle was 7-14 degrees with organic solvent (hexane), and 38-48 degrees with water, and the contact angle fell significantly compared with the case of surface exposure in all. In the experiment exposed from the surface, since the whole film is hardened | cured, liquid repellency is shown by the fluorine-containing polyether compound (B) which exists in the coating film surface. On the other hand, when exposed from the back side, since a coating film hardens from the board | substrate side, the film surface remains uncured, and the fluorinated polyether compound (B) which existed on the surface is thought to be removed at the time of image development, and will not show liquid repellency. do.

From these results, it turns out that the resin composition of this invention can liquid-proof only a coating film surface. On the other hand, in Comparative Examples 1 to 15 containing a resin of a Comparative Synthesis Example and a fluorine compound other than a fluorine-containing polyether compound, although the same composition was used, the contact angle value greatly changed due to the difference in process, and the oil repellency was increased. It was found to have a large influence on the manufacturing conditions. In addition, the difference in contact angle between surface exposure and backside exposure is small, which indicates that a fluorine component that imparts liquid repellency is also present inside the film.

Thus, it turns out that the coating film which reliably liquefied only the film surface can be obtained by using the liquid-repellent resin composition of this invention.

According to the present invention, it is possible to obtain a coating film having a high level of liquid repellency stably at all times without being influenced by the film production process conditions, and partition walls such as color filters for liquid crystals or organic EL displays of an inkjet system requiring liquid repellency. It is used suitably for manufacture of the wiring pattern in a semiconductor device or an electric circuit.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure explaining the five process required for formation of a coating film in an Example.

2 is a diagram schematically illustrating a typical exposure method in the embodiment.

3 is a diagram schematically illustrating back exposure in an embodiment.

(Explanation of symbols for the main parts of the drawing)

1: glass substrate

2: resin layer (uncured)

3: resin layer with high content of fluorine component (uncured)

4: resin layer (cured)

5: Resin layer with much content of fluorine component (hardening)

6: exposure light source

Claims (22)

As a condensed ring structure containing alkali-soluble resin (A), the epoxy ester compound represented by following General formula (1): [Formula 1]

(Wherein D ₁ to ₄ are each independently a group selected from the following General Formula (2) or the following General Formula (3), and p ₁ to 4 each independently represent an integer of 0 to 4; [Formula 2]

D _5-6 are each independently group selected from general formula (2) or the following general formula (3), and p _5-6 are each independently an integer of 0-4. [Formula 3]

Here, A <_0> of the said General formula (1), (2) is a 5-membered ring or 6-membered alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of one or more aromatic rings Is a divalent group containing, R ₁ to ₆ are each independently a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group which may have a substituent, Or a halogen atom, q ₁ to ₆ are each independently an integer of 0 to 4; In addition, R <_7> of the said General formula (1), (2), (3) represents group containing the site | part derived from monobasic carboxylic acid, R <_8-15> respectively independently represents a hydrogen atom or a methyl group, m _{1 to 8} and s _{1 to 2} are each independently an integer of 0 to 10, and the structural formula may be symmetrical or asymmetrical. In addition, a plurality of R _{1 to 15} and D ₁ to ₆ may be the same as or different from each other), a polycyclic carboxylic acid or an anhydride thereof, and a cyclic structure-containing alkali-soluble resin (A1) and fluorine-containing Liquid-repellent resin composition containing a polyether compound (B). The method of claim 1, A <_0> of the said General formula (1), (2) is a 6-membered alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of one or more aromatic, or alicyclic of 5-membered ring The liquid-repellent resin composition which is a bivalent group containing a formula compound (you may contain atoms other than carbon on a ring), and the condensed ring structure of one aromatic ring. The method of claim 1, A ₀ of the general formulas (1) and (2) is a divalent group containing a 5-membered ring alicyclic compound (may contain atoms other than carbon on the ring) and a condensed structure of two or more aromatic rings. Liquid-repellent resin composition. The method according to claim 1 or 2, A ₀ of the general formulas (1) and (2) is a divalent group containing a 6-membered alicyclic compound (may contain atoms other than carbon on the ring) and a condensed structure of two or more aromatic rings. Liquid-repellent resin composition. As a condensed ring structure containing alkali-soluble resin (A), the epoxy ester compound represented by following General formula (1): [Formula 4]

(Wherein D ₁ to ₄ are each independently a group selected from the following General Formula (2) or the following General Formula (3), and p ₁ to 4 each independently represent an integer of 0 to 4; [Formula 5]

D _5-6 are each independently group selected from general formula (2) or the following general formula (3), and p _5-6 are each independently an integer of 0-4. [Formula 6]

Here, A <_0> of the said General formula (1), (2) is a 5-membered ring or 6-membered alicyclic compound (you may contain atoms other than carbon on a ring), and the condensed structure of one or more aromatic rings It is a divalent group containing, and R <_1-6> respectively independently has a C1-C10 linear, branched or cyclic alkyl group or an alkenyl group, a C1-C5 alkoxy group, and a substituent Or a halogen atom, q ₁ to ₆ each independently represent an integer of 0 to 4; In addition, R <_7> of the said General formula (1), (2), (3) represents group containing the site | part derived from monobasic carboxylic acid, and R <8> _-15 respectively 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 symmetrical or asymmetrical. In addition, a plurality of R _{1 to 15} and D ₁ to ₆ may be the same as or different from each other), a polyhydric alcohol, and a polybasic carboxylic acid or an anhydride thereof, and a condensed structure-containing alkali-soluble resin (A2) and And liquid repellent resin composition containing a fluorine-containing polyether compound (B). The method of claim 5, wherein A ₀ in the general formulas (1) and (2) is a 6-membered alicyclic compound (may contain atoms other than carbon on the ring) and a condensed structure of one or more aromatic rings, or a 5-membered ring. The liquid-repellent resin composition which is a bivalent group containing an alicyclic compound (you may contain atoms other than carbon on a ring) and the condensed ring structure of one aromatic ring. The method of claim 5, wherein A ₀ of the general formulas (1) and (2) is a divalent group containing a 5-membered ring alicyclic compound (may contain atoms other than carbon on the ring) and a condensed structure of two or more aromatic rings. Liquid-repellent resin composition. The method according to claim 5 or 6, A ₀ of the general formulas (1) and (2) is a divalent group containing a 6-membered alicyclic compound (may contain atoms other than carbon on the ring) and a condensed structure of two or more aromatic rings. Liquid-repellent resin composition. The method according to any one of claims 1 to 4, The condensed ring structure-containing alkali-soluble resin (A1) is a condensed ring structure-containing alkali-soluble resin (A1-1) obtained by reacting an epoxy ester compound represented by the following general formula (4) with a polybasic carboxylic acid or its anhydride. The liquid-repellent resin composition characterized by the above-mentioned. [Formula 7]

Where _{A 0, R 1~4, R 7} , R 8~11, q 1~4, m 1~4, s 1 is as defined above, and the following structural formula may be a symmetrical, but may be asymmetrical. In addition, a plurality of R _1-4 , R _7-11 may be the same and may differ. The method according to any one of claims 5 to 8, Cyclocyclic structure containing alkali-soluble resin (A2-1) obtained by making epoxy-response compound, polyhydric alcohol, and polybasic carboxylic acid or its anhydride represented by following General formula (4) react. ) Liquid-repellent resin composition, characterized in that. [Formula 8]

Where _{A 0, R 1~4, R 7} , R 8~11, q 1~4, m 1~4, s 1 is as defined above, and the following structural formula may be a symmetrical, but may be asymmetrical. In addition, a plurality of R _1-4 , R _7-11 may be the same and may differ. The method according to any one of claims 1, 2, 4, 5, 6 and 8, Formula (1), (2) of the A _0, expression (5) to (7), the second containing chukhwan structure selected from the group group consisting of a liquid-repellent resin composition. [Formula 9]

The method according to claim 9 or 10, The liquid-repellent resin composition which is bivalent group containing the condensed structure selected from the group which A <_0> of General formula (4) consists of Formula (5)-(7). [Formula 10]

The method according to any one of claims 1, 2, 5 and 6, Formula (1), (2) of the A _0, formula (8) and (9) a second containing chukhwan structure selected from the group group consisting of a liquid-repellent resin composition. [Formula 11]

The method according to claim 9 or 10, The liquid-repellent resin composition which is bivalent group containing A condensed structure chosen from the group which A <_0> of General formula (4) consists of Formula (8) and (9). [Formula 12]

The method according to any one of claims 1, 3, 5 and 7, Formula (1), (2) of the A _0, formula (17) in the second containing chukhwan structure group represented liquid-repellent resin composition. [Formula 13]

The method according to claim 9 or 10, A liquid repellent resin composition wherein A _{0 in} General Formula (4) is a divalent group containing a condensed ring structure represented by Formula (17). [Formula 14]

The method according to any one of claims 1 to 16, The liquid-repellent resin composition characterized by the fluorine-containing polyether compound (B) having a structure selected from the group consisting of the following general formulas (18) to (20). [Formula 15]

Wherein 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 It is a fluorine alkyl group, x, y, z are each independently an integer of 0 or more, and x + y + z contained in (B) is an integer of 2 or more. Provided that at least one of R ₁₉ and R ₂₀ is F or a C 20 or less fluorine-containing alkyl group, at least one of R ₂₁ to R ₂₄ is an F or a C 20 or less fluorine-containing alkyl group, and in R ₂₅ to R ₃₀ At least one is F or a C20 or less fluorine-containing alkyl group. The method according to any one of claims 1 to 17, The liquid-repellent resin composition in which at least 1 of a cyclic structure containing alkali-soluble resin (A) and a fluorine-containing polyether compound (B) contains the unsaturated group which can superpose | polymerize with light or heat. The method according to any one of claims 1 to 18, The liquid-repellent resin composition whose content of a fluorine-containing polyether compound (B) is 0.01-10 weight part with respect to 100 weight part of condensed ring structure containing alkali-soluble resin (A). The radiation sensitive resin composition containing the liquid-repellent resin composition as described in any one of Claims 1-19, and a photoinitiator (C). The method of claim 20, Furthermore, the radiation sensitive resin composition containing at least 1 sort (s) chosen 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.

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