JP5246369B2 - Liquid repellent curable ink composition - Google Patents

Abstract

Disclosed is a liquid-repellent agent for a curable ink composition containing a fluorine-based polymer (A) having as repeating units 100 parts by weight of an a-substituted acrylate (a1) having a C1-8 fluoroalkyl group (which may have an etheric oxygen atom between carbon atoms), 5-60 parts by weight of an epoxy-group-containing monomers (a2), and 10-100 parts by weight of monomers (a3) containing an alkylene oxide group represented by the formula -(R1O)nR2. Through this liquid-repellent agent, a cured film having high liquid repellency can be formed on a base material using only a micro-discharge method, and mixture-free pattern formation is maintained even when contact with an adjacent pattern occurs prior to curing.

Description

  The present invention relates to a liquid repellent agent for a liquid repellent curable ink in which a liquid repellent agent having a specific structure is internally added to a curable (particularly photocuring or thermosetting) composition. The present invention also provides a liquid repellent curable ink composition containing the liquid repellent, which is ejected in a pattern on a substrate by a micro discharge method (such as an ink jet method) and cured to a fine coating (particularly photocuring or heat curing). To a pattern substrate comprising a plurality of regions having different surface free energies to form a pattern substrate on the substrate. Furthermore, the present invention relates to a display color filter in which a cured film obtained from a liquid repellent curable ink is formed on a substrate.

  The following atmospheric pressure plasma method (Patent Document 1) and liquid repellent internal addition method (Patent Documents 2 to 3) are proposed as methods for manufacturing devices such as display pixels and circuits by printing techniques represented by inkjet. Has been.

In the atmospheric pressure plasma method, after partition walls are formed by a photolithography method, the partition walls are made liquid-repellent by treating the partition walls with fluorine gas typified by CF ₄ by the atmospheric pressure plasma method, and the liquid-repellent partition walls are repelled. This is a method for producing a color filter by using a liquid bank and driving a color ink into an opening by an ink jet method. However, the use of fluorine gas with a high global warming potential, the preparation of an atmospheric pressure plasma device, the need for a liquid repellency process, and the liquid repellency to the side walls of the partition walls make it possible to repel the color ink. There were drawbacks such as causing it.

  As a method for improving the problem of the atmospheric pressure plasma method, a liquid repellent internal addition method has been proposed. In the liquid repellent internal addition method, a barrier rib resist material internally added with a liquid repellent agent is uniformly coated on the substrate, and the barrier ribs are patterned by a photolithography method to form barrier ribs whose top surface is liquid repellent in one step. It is possible. However, even in this method, it is necessary to perform a photolithography process at least once for forming the barrier ribs.

  In the patent document 4, the applicant of the present application proposed a method capable of manufacturing a color filter only by an ink jet method without a photolithography process. That is, a liquid repellent bank is formed without a photolithography process by patterning a photocurable ink containing a fluorine-based monomer by an ink jet method and then irradiating it with light. However, the liquid repellent bank formed by this method has insufficient liquid repellency, and there is a problem that color ink discharged by the ink jet method breaks the liquid repellent bank and mixes colors.

International Publication No.99 / 048339 JP 2005-315984 A JP 2008-287251 A International Publication 2006/129800

The object of the present invention is to achieve the following two problems. First, a method of forming a photocured or thermoset film having high liquid repellency on a substrate only by a micro-discharge method (such as an ink jet method) without a photolithography process, and a fluorine-based polymer having a specific structure It is intended to provide a photocurable or thermosetting ink composition internally containing a liquid repellent. At that time,
-The liquid repellent having a specific structure has good compatibility with a photocuring or thermosetting composition (including a solventless photocuring or thermosetting composition)-A liquid repellent photocurable or thermosetting ink composition Two important points are that the liquid repellency of the product after photocuring or heat curing is excellent.

  The second object of the present invention is that when patterning a liquid repellent photocurable or thermosetting ink composition by a micro discharge method, even if adjacent patterns come into contact before photocuring or thermosetting, they are mixed. It is to provide a liquid repellent capable of maintaining the pattern shape without being damaged. Therefore, by using this feature, 3 colors (red, green, blue) or 4 colors (red, green, blue, yellow), or 4 colors (black, red, green) are added to each of them for black matrix. , Blue, black) or five colors (red, green, blue, yellow, black) of liquid-repellent photocurable or thermosetting inks are simultaneously patterned on the substrate and then photocured or thermoset together, An object of the present invention is to provide a method for manufacturing a color filter that does not require a liquid repellent bank and has a small number of steps.

The present invention relates to the following repeating units (a1), (a2) and (a3):
(A1) 100 parts by weight of a repeating unit derived from an α-substituted acrylate having a fluoroalkyl group having 1 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms)
[Substituent at α-position is fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are hydrogen atom, fluorine atom or chlorine atom), cyano group, carbon number A linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms. ],
(A2) 5 to 60 parts by weight of repeating units derived from an epoxy group-containing monomer, and (a3) 10 to 100 parts by weight of repeating units derived from a monomer containing an alkylene oxide group
A liquid repellent agent for a liquid repellent curable ink containing the fluorine-based polymer (A) having the above is provided, thereby achieving the object of the present invention.
Hereinafter, the “ink composition” may be referred to as “ink” or “composition”. “Curable” means in particular photocurable and / or thermosetting.

The fluorine concentration of the fluorine-based polymer (A) (the weight ratio of fluorine atoms to the fluorine-containing polymer) is preferably 10 to 40% by weight.
Moreover, the weight average molecular weight of the fluoropolymer (A) is preferably 3,000 to 20,000. The weight average molecular weight is determined by GPC (gel permeation chromatography) (standard polystyrene conversion).

  The fluorine-based polymer (A) may further contain 5 to 110 parts by weight of repeating units derived from (a4) a high softening point monomer.

  The fluorine-based polymer (A) may be a liquid repellent having a form dissolved in a solvent, if necessary. That is, the liquid repellent may be a solution in which the fluoropolymer (A) is dissolved in a solvent. From the viewpoint of ejection stability, the solvent is preferably a solvent having a boiling point of 100 ° C. or higher, and more preferably a solvent having a boiling point of 200 ° C. or higher. The solvent may be a single compound or a mixture of two or more different compounds.

  The present invention also provides a liquid repellent curable ink (or ink composition) comprising the liquid repellent. The liquid repellent photocurable ink composition provided by the present invention comprises a polyfunctional monomer (B) and a photopolymerization initiator (C) in addition to the fluorine-based polymer (A). Furthermore, if necessary, as other components, a monofunctional monomer (D), an epoxy resin (E), a polymerization inhibitor (F), a colorant (G), and a surfactant (H) may be included. Further, the liquid repellent thermosetting ink composition provided by the present invention comprises a polyfunctional monomer (B), a melamine resin, a urea resin, an alkyd resin, an epoxy resin (E ), At least one resin selected from the group consisting of phenolic resins and cyclopentadiene resins, and a coloring agent (G).

  The present invention also provides a method for forming a liquid repellent cured film using a liquid repellent curable ink (ink composition), a method for forming a pattern substrate using the method, and a color filter using a liquid repellent curable ink. Provide a method. The photocuring referred to in the present invention includes UV curing.

By using the curable ink composition of the present invention, a cured film having high liquid repellency can be formed on a substrate only by a micro discharge method (such as an ink jet method) without a photolithography process. The liquid repellency can be improved and the number of processes can be reduced.
Furthermore, when the liquid repellent curable ink composition of the present invention is patterned by a micro discharge method, even if the adjacent pattern contacts before curing, the pattern shape is maintained without being mixed. 3 colors (red, green, blue) or 4 colors (red, green, blue, yellow), or 4 colors (red, green, blue, black) or 5 colors with black matrix black added to each. By patterning the liquid-repellent curable inks (red, green, blue, yellow, black) on the substrate at the same time and then curing them together, it is possible to provide a method for manufacturing a color filter with fewer steps.

"Monomers used for production of fluoropolymer (A)"
In the fluorine-based polymer (A) used in the liquid repellent for the liquid repellent curable ink composition of the present invention, the fluorine monomer (a1) is a fluoroalkyl group having 1 to 8 carbon atoms (preferably 4 to 8 carbon atoms) (carbon atoms). An α-substituted acrylate having an etheric oxygen atom in between. The α-position substituent is fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are hydrogen atom, fluorine atom or chlorine atom), cyano group, carbon number 1 A -20 linear or branched fluoroalkyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms.
The fluorine-based polymer (A) may further contain an epoxy group-containing monomer (a2) and / or a monomer (a3) containing an alkylene oxide group as a structural unit.
The fluorine-based polymer (A) may preferably further contain a high softening point monomer (a4).

The amounts of the constituent components (a1), (a2) and (a3) of the fluoropolymer (A) are respectively
Α-substituted acrylate (a1) 100 parts by weight Epoxy group-containing monomer (a2) 5 to 60 parts by weight Monomer (a3) containing alkylene oxide group 10 to 100 parts by weight, preferably 40 to 100 parts by weight Preferably it is 70-90 weight part.
When the fluorine-based polymer (A) further contains a high softening point monomer (a4),
-The quantity of a high softening point monomer (a4) is 5-110 weight part, Preferably it is 10-40 weight part, More preferably, it is 10-25 weight part.
The α-substituted acrylate (a1) is preferably 15 to 70% by weight, more preferably 30 to 60% by weight, for example 40 to 50% by weight, based on the fluoropolymer (A).

In the fluorine-based polymer (A), the fluorine concentration (weight ratio of fluorine atoms to the fluorine-containing polymer) may be preferably 10 to 40% by weight, more preferably 15 to 30% by weight. When the fluorine concentration is within these ranges, preferable liquid repellency is exhibited and preferable compatibility is obtained.
In the fluoropolymer (A), the weight average molecular weight may be preferably 3,000 to 20,000, more preferably 5,000 to 15,000. When the weight average molecular weight is within these ranges, preferable liquid repellency is exhibited and preferable compatibility is obtained.

  When the α-substituted acrylate (a1) is 40 to 50% by weight with respect to the fluorine-based polymer (A) and the fluorine concentration of the fluorine-based polymer (A) is 15 to 25% by weight, the curable composition And the liquid repellency after curing of the liquid repellent curable ink composition is further enhanced. Further, when the weight average molecular weight of the fluoropolymer (A) is from 3,000 to 20,000, the surface segregation property of the fluoropolymer (A) in the liquid repellent resist film is excellent, and a small amount is sufficient. Liquidity can be imparted.

［式中、Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ¹Ｘ²基（但し、Ｘ¹およびＸ²は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状もしくは分岐状のフルオロアルキル基、置換もしくは非置換のベンジル基、置換もしくは非置換のフェニル基、または炭素数１〜２０の直鎖状もしくは分岐状アルキル基、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１〜１０の脂肪族基、酸素原子を有していてもよい炭素数６〜１０の芳香族基、環状脂肪族基もしくは芳香脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）、−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、または、−（ＣＨ_２）_ｎＳＯ_２−基（ｎは１〜１０）である。
Ｒｆは炭素数１〜８の直鎖状または分岐状のフルオロアルキル基（炭素原子間にエーテル性酸素原子を有していてもよい）である。］
であることが好ましい。 α-substituted acrylate (a1) is
formula:

[Wherein X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom) ), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms or A branched alkyl group,
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms), a —CH ₂ CH (OY ¹ ) CH ₂ — group ( However, Y ¹ is a hydrogen atom or an acetyl group), or, -. a group (n is _{1~10) - (CH 2) n} SO 2.
Rf is a linear or branched fluoroalkyl group having 1 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms). ]
It is preferable that

Rf is preferably a linear or branched fluoroalkyl group having 4 to 8 carbon atoms. Rf is preferably a perfluoroalkyl group.
When Rf has an etheric oxygen atom between carbon atoms, Rf is a fluoropolyether group having a fluoroalkyl group (more precisely, an oxyfluoroalkylene group) as a repeating unit, particularly a perfluoroalkyl group. A perfluoropolyether group having a group (exactly, an oxyperfluoroalkylene group) as a structural unit is preferable.

When the fluoroalkyl group of the α-substituted acrylate (a1) is a perfluoroalkyl group that does not contain an etheric oxygen atom, the perfluoroalkyl group may be linear or branched. The carbon number of the perfluoroalkyl group is C1 to C6, more preferably C4 to C6, for example, C6. Specifically, the following are exemplified.
(Linear structure) CF _3- , CF ₃ CF _2- , CF ₃ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- ,
(Branch structure) (CF ₃ ) ₂ CF-, (CF ₃ ) ₃ C-, (CF ₃ ) ₂ CFCF _2- , (CF ₃ ) ₂ CFCF ₂ CF _2- , (CF ₃ ) ₃ CCF _2- , ( CF ₃ ) ₂ CF CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ C (CF ₃ ) CF-

When the fluoroalkyl group of the α-substituted acrylate (a1) is a perfluoropolyether group containing an etheric oxygen atom between carbon atoms, the perfluoroalkyl group constituting the perfluoropolyether group may be linear The carbon number of the perfluoroalkyl group may be C1 to C8, preferably C6 to C8. In addition to the C1 to C6 perfluoroalkyl group, the following C7 to C8 perfluoroalkyl groups are exemplified. Is:
(Linear structure) CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- ,
(Branch structure) (CF ₃ ) ₂ CFCF ₂ CF ₂ CF ₂ CF _2- , (CF ₃ ) ₂ CFCF ₂ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ C (CF ₃ ) CF -, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ C (CF ₃ ) CF-

In the perfluoropolyether group, the number of perfluoroalkyl groups (or oxyperfluoroalkylene groups) may be 2 to 200, for example 3 to 100, in particular 4 to 50.
Specific examples of the oxyperfluoroalkylene group (that is, the perfluoropolyether segment) constituting the perfluoropolyether group are as follows.
- (OCF ₂₎ -,
-(OCF ₂ CF ₂ )-,
-(OCF ₂ CF ₂ CF ₂ )-,
-(OCF (CF ₃ ) CF ₂ )-,
-(OCF (CF ₃ ) CF ₂ CF ₂ )-,
-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,
-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ )-,
-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-,
− (OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-.

Perfluoropolyether groups containing perfluoroalkyl groups:
- (OCF ₂₎ a-,
-(OCF ₂ CF ₂ ) b-,
-(OCF ₂ CF ₂ CF ₂ ) c-,
-(OCF (CF ₃ ) CF ₂ ) d-,
-(OCF (CF ₃ ) CF ₂ CF ₂ ) e-,
-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ ) f-,
-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ ) g-,
-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) h- and-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) i-
[Wherein, a, b, c, d, e, f, g, h and i are each 0 or a positive integer, and 2 ≦ a + b + c + d ≦ 200, preferably 2 ≦ a + The number satisfies b + c + d ≦ 100, more preferably 2 ≦ a + b + c + d ≦ 50. ]
It preferably contains a perfluoropolyether segment composed of

The end of the perfluoropolyether group is preferably capped with C _m F _{2m + 1} − (m = 0 to 5, particularly 1 to 3).

As a specific example of the α-substituted acrylate containing a perfluoropolyether group, the formula (II):
C _m F _{2m + 1-} [OCF (CF ₃ ) CF ₂ ] -OCF (CF ₃ ) CH ₂ O (C = O) C (X) = CH ₂ (m = 1 to 3) (Formula II)
[In the formula, the substituent X at the α-position is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom or a chlorine atom) ), A cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched group having 1 to 20 carbon atoms Alkyl group. ]
And the like.

When Rf is a fluoroalkyl group that does not contain an etheric oxygen atom (between carbon atoms), it is particularly preferably a fluoroalkyl group having 4 to 6 carbon atoms (particularly a perfluoroalkyl group).
When Rf is a perfluoropolyether group containing an etheric oxygen atom between carbon atoms, it is particularly preferably a perfluoropolyether group having a perfluoroalkyl group having 6 to 8 carbon atoms as a structural unit.

Specific examples of the α-substituted acrylate (a1) are as follows.
Rf—CH ₂ —O— (O═C) C (CH ₃ ) ═CH _{2
Rf-CH 2 CH 2 -O- (} O = C) C (CH 3) = CH 2

CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −Rf
[Wherein, Rf represents a linear or branched fluoroalkyl group having 1 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms). ]

  The epoxy group-containing monomer (a2) is preferably a monomer that does not contain a fluorine atom. The epoxy group-containing monomer (a2) is preferably a (meth) acrylate containing an epoxy group. Examples of the epoxy group-containing monomer (a2) include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. Can do. Among them, glycidyl (meth) acrylate can be preferably used in the present invention.

The monomer (a3) containing an alkylene oxide group is preferably a monomer containing no fluorine atom. The monomer (a3) containing an alkylene oxide group is preferably (meth) acrylate. The monomer (a3) containing an alkylene oxide group is an example of the alkylene oxide group of the monomer (a3) containing an alkylene oxide group:
-(R ¹ O) _n R ²
[Wherein, R ¹ represents — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ —,
R ² is hydrogen or a methyl group,
n is 1-10. ].

As the monomer (a3) containing an alkylene oxide group,
_{^{CH 2 = CR 3 COO (R}} 1 O) n R 2
[R ¹ is — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ —, R ² and R ³ are hydrogen or a methyl group, and n is 1 to 10. ]
May be used.
Specifically, the monomer (a3) is hydroxyethyl (meth) acrylate, Nippon Oil & Fats Bremer AP series (polypropylene glycol monoacrylate) AP-400: n≈6, AP-550: n≈9, AP- 800: n ≒ 13, Blemmer PE series (polyethylene glycol monomethacrylate) PE-90: n ≒ 2, PE-200: n ≒ 4.5, PE-350: n ≒ 8, Blemmer PP series (polypropylene glycol monomethacrylate) PP-1OOO: n≈4-6, PP-500: n≈9, PP-800: n≈13, Bremer PME series (methoxy polyethylene glycol monomethacrylate) PME-1OO: n≈2, PME- Examples include 200: n≈4, PME-400: n≈9, PME-1OOO: n≈23, PME-4000: n≈90, and the like.

  An isocyanate group-containing unsaturated compound may be reacted with the hydroxyl group at the terminal of the alkyleneoxy group of (a3) of the fluorine-based polymer (A). Thereby, it is possible to introduce an unsaturated group capable of radical polymerization into the fluorine-based polymer (A).

The high softening point monomer (a4) copolymerized for the preparation of the fluoropolymer (A) is:
A monomer having a glass transition point or a melting point of 100 ° C. or higher, particularly 120 ° C. or higher in a homopolymer state.
The high softening point monomer (a4)
CH ₂ = C (R ¹ ) COOR ²
[R ¹ is H or CH ₃ , and R ² is a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more. ]
It is preferable that Examples of R ² are isobornyl, bornyl, phensil (all of which are C ₁₀ H ₁₇ , carbon atom / hydrogen atom = 0.58), adamantyl (C ₁₀ H ₁₅ , carbon atom / hydrogen atom = 0.66), Examples thereof include a bridged hydrocarbon ring such as norbornyl (C ₇ H ₁₂ , carbon atom / hydrogen atom = 0.58). These crosslinked hydrocarbon rings may have a hydroxyl group or an alkyl group (carbon number is, for example, 1 to 5).

  Examples of the high softening point monomer (a4) include methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, and adamantyl (meth) acrylate. Examples of norbornyl (meth) acrylate are 3-methyl-norbornylmethyl (meth) acrylate, norbornylmethyl (meth) acrylate, norbornyl (meth) acrylate, 1,3,3-trimethyl-norbornyl (meth) acrylate , Miltanylmethyl (meth) acrylate, isopinocamphanyl (meth) acrylate, 2-{[5- (1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] norbornyl } (Meth) acrylate and the like. Examples of adamantyl (meth) acrylate are 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 1-adamantyl-α -Trifluoromethyl (meth) acrylate and the like.

  The glass transition point and the melting point are the extrapolated glass transition end temperature (Teg) and the melting peak temperature (Tpm) respectively defined by JIS K7121-1987 “Method for measuring plastic transition temperature”. When a high softening point monomer (a4) having a glass transition point or a melting point of 100 ° C. or higher in the homopolymer state is used as the repeating unit of the fluoropolymer (A), in addition to the effect of excellent compatibility with the curable composition There is also an effect of further improving the liquid repellency of the liquid repellent curable ink composition.

"Manufacture of fluoropolymer (A)"
The fluorine-based polymer (A) can be produced as follows. A method in which a monomer and necessary components are dissolved in a solvent, and after substitution with nitrogen, a polymerization catalyst is added and stirred at 20 to 120 ° C., preferably 50 to 90 ° C. for 1 to 20 hours, preferably 3 to 8 hours. Is adopted.
There is no restriction | limiting in particular as a polymerization catalyst, For example, a normal radical polymerization initiator can be used. Examples of the radical polymerization initiator include azo radical polymerization initiators such as azobisisobutyronitrile (AIBN) and peroxide radical polymerization initiators such as benzoyl peroxide (BPO).
There is no restriction | limiting in particular as a polymerization reaction form, For example, emulsion polymerization, solution polymerization, bulk polymerization, etc. are mentioned.
The polymerization reaction may be solventless (bulk) polymerization, but is usually carried out in the presence of a solvent. As the polymerization solvent, an organic solvent and a water-soluble organic solvent can be used. The solvent is used in the polymerization composition in the range of 40 to 80% by weight.

  In order to adjust the molecular weight of the fluoropolymer (A), a chain transfer agent such as mercaptans or alkyl halides may be added. As mercaptans, n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, isooctyl mercaptoate, thioglycolic acid, 3-mercaptopropionic acid , Methoxybutyl thioglycolate, silicone mercaptan (KF-2001 manufactured by Shin-Etsu Chemical Co., Ltd.), and alkyl halides include chloroform, carbon tetrachloride, carbon tetrabromide and the like. These may be used alone or in combination of two or more. When a hydroxyl group-containing monomer simple substance and a mercaptan simple substance as in (a3) are in direct contact with each other, a solvent insoluble matter may be formed. Therefore, when polymerizing using both of them in combination, it is desirable to dilute either one with a solvent in advance. .

  The weight average molecular weight of the fluoropolymer (A) is preferably 3,000 to 20,000, more preferably 5,000 to 15,000. The weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (in terms of standard polystyrene).

  The present invention also provides a liquid repellent curable ink comprising the liquid repellent of the present invention. That is, the present invention provides a liquid repellent curable ink comprising a liquid repellent (or fluorine polymer (A)), a polyfunctional monomer (B), and a colorant (G). The present invention provides a liquid repellent photocurable ink comprising a fluorine-based polymer (A), a polyfunctional monomer (B), a photopolymerization initiator (C), and a colorant (G). At least one non-fluorinated resin (E) selected from the group consisting of a polymer (A), a polyfunctional monomer (B), a melamine resin, a urea resin, an alkyd resin, an epoxy resin, a phenol resin, and a cyclopentadiene resin, and A liquid repellent thermosetting ink comprising a colorant (G) is provided. If necessary, the curable ink (particularly the liquid repellent photocurable ink and the liquid repellent thermosetting ink) may be a monofunctional monomer (D), a polymerization inhibitor (F), and / or a surfactant (H). May be included.

In the ink, with respect to 100 parts by weight of the fluoropolymer (A),
The amount of the polyfunctional monomer (B) is 100 to 400 parts by weight, for example 150 to 300 parts by weight,
The amount of the photopolymerization initiator (C) is 50 parts by weight or less, for example, 10 to 40 parts by weight,
The amount of the monofunctional monomer (D) is 800 parts by weight or less, for example, 100 to 700 parts by weight,
The amount of the non-fluorine resin (E) is 500 parts by weight or less, for example, 30 to 400 parts by weight,
The amount of the polymerization inhibitor (F) is 0.4 parts by weight or less, such as 0.01 to 0.3 parts by weight,
The amount of the colorant (G) is 0.001 to 20 parts by weight, for example 0.01 to 10 parts by weight,
The amount of the surfactant (H) may be 2 parts by weight or less, for example, 0.01 to 1 part by weight.

"Liquid repellent photocuring (including UV curing) ink composition"
The liquid-repellent photocurable ink of the present invention is characterized by containing the above-mentioned fluorine-based polymer (A), polyfunctional monomer (B) and photopolymerization initiator (C), and further if necessary. As other components, a monofunctional monomer (D), an epoxy resin (E), a polymerization inhibitor (F), a colorant (G), and a surfactant (H) may be included.

<Polyfunctional monomer (B)>
The polyfunctional monomer of the component (B) in the present invention is not particularly limited as long as it is polymerized by radicals or ions generated by a photoinitiator or a thermal initiator. The polyfunctional monomer (B) is preferably a (meth) acrylic acid ester having 2 or more, for example, 2 to 6 (meth) acrylic groups, which does not contain a fluorine atom.

  Specific examples of the polyfunctional monomer (B) are ethylene glycol di (meth) acrylate, diethylene glycol di (meth) arylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di ( Such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. Meth) and acrylic acid esters. These may be used alone or in combination of two or more.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) is not particularly limited as long as it has a property of generating radicals upon irradiation with light.

  Specific examples of the photopolymerization initiator (C) include α-diketones such as benzyl (or dibenzoyl) and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenones, benzophenones such as 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, Acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-me Acetophenones such as ru [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, anthraquinone, 1 Quinones such as 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 4-dimethylamino Examples thereof include aminobenzoic acids such as 2-ethylhexyl benzoate, halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone, peroxides such as acylphosphine oxides and di-t-butyl peroxide. When the epoxy group-containing monomer (a2) is contained in the fluoropolymer, a quinonediazide group-containing compound described in JP-A-2003-76012 may be used.

As a commercial item of a photoinitiator (C),
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one,
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone,
IRGACURE 2959: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one,
IRGACURE 127: 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one,
IRGACURE 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one,
IRGACURE 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,
IRGACURE 379: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone,
IRGACURE 819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
IRGACURE 784: bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium,
IRGACURE OXE 01: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)],
IRGACURE OXE 02: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime),
IRGACURE261, IRGACURE369, IRGACURE500,

DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
DAROCUR TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
DAROCUR1116, DAROCUR2959, DAROCUR1664, DAROCUR4043,
IRGACURE 754 Oxyphenylacetic acid: a mixture of 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester,
IRGACURE 500: IRGACURE 184: Benzophenone = 1: 1 mixture,
IRGACURE 1300: IRGACURE 369: IRGACURE 651 = 3: 7 mixture,
IRGACURE 1800: mixture of CGI403: IRGACURE 184 = 1: 3,
IRGACURE 1870: mixture of CGI403: IRGACURE 184 = 7: 3 and
DAROCUR 4265: DAROCUR TPO: DAROCUR 1173 = 1: 1 mixture
Etc. are exemplified. Here, IRGACURE is manufactured by Ciba Specialty Chemicals and DAROCUR is manufactured by Merck Japan.

  In addition, diethylthioxanthone and isopropylthioxanthone are used as sensitizers, and DAROCUR EDB (ethyl-4-dimethylaminobenzoate) and DAROCUR EHA (2-ethylhexyl-4-dimethylaminobenzoate) are used in combination as polymerization accelerators. Also good.

<Monofunctional monomer (D)>
The monofunctional monomer is not particularly limited as long as it is polymerized by radicals or ions generated from the photopolymerization initiator. The monofunctional monomer (D) is preferably (meth) acrylic acid or a (meth) acrylic acid ester that does not contain a fluorine atom and has one (meth) acrylic group.

  Specific examples of the monofunctional monomer (D) include (meth) acrylic acid, methyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethyl carbitol (meth) ) Acrylate, 2-phenoxyethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

Non-fluorine resin (E)
The liquid repellent photocurable ink composition of the present invention may contain a non-fluorine resin (E). The non-fluorine resin (E) is at least one resin selected from the group consisting of melamine resin, urea resin, alkyd resin, epoxy resin, phenol resin, and cyclopentadiene resin.
The non-fluorine resin (E) is preferably an epoxy resin.

<Epoxy resin>
The liquid repellent photocurable ink composition of the present invention may contain an epoxy resin.
Including an epoxy resin is preferable because durability of the obtained cured film is improved.
Specific examples of the epoxy resin include trade names “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828”, “Epicoat 190P”, “Epicoat 191P”, “Epicoat 1004”, “Epicoat 1256” (Mitsubishi Chemical Corporation), trade names “Celoxide 2021P”, “EHPE-3150” (Made by Daicel Chemical Industries), trade name “Techmore VG3101” (Purin Corporation) Bisphenol A type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins and the like. The epoxy resin may be a single compound or a mixture of two or more compounds.

Examples of melamine resins are Mellan 265 and Mellan 2650L (above, manufactured by Hitachi Chemical Co., Ltd.).
An example of the urea resin is ADBLUE (manufactured by Nippon Kasei Co., Ltd.).
Examples of alkyd resins are various alkyd resins manufactured by DIC Corporation.
An example of the phenol resin is a base resin for photoresist manufactured by Meiwa Kasei Co., Ltd.
Examples of the cyclopentadiene resin are various cyclopentadiene manufactured by Hitachi Chemical Co., Ltd.

<Polymerization inhibitor (F)>
The liquid repellent photocurable ink composition of the present invention may contain a polymerization inhibitor.
It is preferable to include a polymerization inhibitor because the storage stability is improved.
Specific examples of the polymerization inhibitor include 4-methoxyphenol, t-butylcatechol, bilgarol, hydroquinone, butylhydroxytoluene, phenothiazine and the like.

<Colorant (G)>
The liquid repellent photocurable ink composition of the present invention may contain a colorant (G) as long as the characteristics of the liquid repellent photocurable ink composition of the present invention are not impaired. By containing the colorant (G) in the ink of the present invention, the cured film obtained from the composition of the present invention can be used for partition walls such as a black matrix used for a color filter for display or for pixel formation. it can.

  The colorant (G) may be a pigment or a dye.

<Surfactant (H)>
The liquid-repellent photocurable ink composition of the present invention has a silicone-based surfactant, an acrylic surfactant, or a fluorine-based surfactant for the purpose of improving wettability, leveling or coating properties to the substrate. An agent or the like may be contained. These surfactants may be used alone or in combination of two or more.

<Other ingredients>
-Solvent A solvent, for example, a water-soluble organic solvent, an organic solvent (particularly an oil-soluble organic solvent), or water) may be added to the liquid-repellent photocurable ink composition of the present invention as necessary. The same type of solvent is also used to produce the fluoropolymer (A). The solvent is inert and dissolves in the fluoropolymer (A).
The solvent contained in the liquid repellent photocurable ink composition is preferably a solvent having a boiling point of 100 ° C. or higher, and more preferably a solvent having a boiling point of 200 ° C. or higher from the viewpoint of ejection stability. The solvent may be a single compound or a mixture of two or more different compounds.

  Specific examples of the solvent having a boiling point of 100 ° C. or higher include water, acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate , Diechi Glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate (= butyl carbitol acetate) (BCA), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1,3-butylene glycol diacetate, cyclohexanol acetate, dimethylformamide, dimethyl sulfoxide, ethyl lactate, isopropyl alcohol , Methanol, ethanol, chloroform, HFC141b, HCHC225, hydrofluoroether, pentane, hexane, heptane, octane, cyclohexane, cyclopentanone, benzene, toluene, xylene, anisole, tetralin, cyclohexylbenzene, mesitylene, petroleum ether, tetrahydrofuran, 1 1,4-dioxane, methyl isobutyl ketone, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane and the like.

Among these solvents, PGMEA, BCA, or MBA is particularly preferable from the viewpoints of solubility and ejection stability of the fluorine-based polymer and the liquid repellent photocurable ink composition.
The solvent is preferably used in the range of 0 to 80% by weight in the liquid repellent photocurable ink composition, more preferably 0 to 70% by weight, for example 5 to 60% by weight.

  The liquid repellent thermosetting ink composition of the present invention may be obtained by adding a fluorine-based polymer (A) to a thermosetting ink composition for color filters. Specifically, a thermosetting ink for a color filter containing a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent (International Publication WO / 2010/137702, WO / 2010/137702 and JP-A-9-21910) and the fluorine polymer (A) of the present invention may be added. Also, thermosetting ink compositions for color filters containing at least one of red, green, blue, each color pigment, surfactant, melamine resin, urea resin, alkyd resin, phenol resin, cyclopentadiene resin, etc. No. 9-21910) to which the fluoropolymer (A) of the present invention is added. For example, at least one resin such as melamine resin, urea resin, alkyd resin, phenol resin, cyclopentadiene resin is added to the above-described photocurable ink composition from which the photopolymerization initiator (C) has been removed, The fluoropolymer (A) of the present invention is added.

In the present invention, the liquid-repellent photocurable ink is ejected onto the substrate by a micro-ejection method to form a coating film of the photocurable composition on the substrate, and then the coating film is irradiated with light and cured. There is provided a method for forming a cured film including a step of forming a cured film.
In the present invention, the liquid-repellent thermosetting ink of the present invention is discharged onto a substrate by a micro-discharge method to form a coating film of the thermosetting composition on the substrate, and then the coating film is heat-treated and cured. There is provided a method for forming a cured film, including a step of forming a cured film by causing the film to form a cured film.

In the present invention, when a liquid repellent photocurable ink or a thermosetting ink is ejected onto a substrate by a small amount ejection method to form a coating film of the cured composition on the substrate, light irradiation and heat treatment are used in combination. May be. The order may be light irradiation → heat treatment or heat treatment → light irradiation.
The present invention also provides a method for forming a cured film, which is any one of an inkjet method, a nozzle printing method, and a microdispenser method as the above-described micro discharge method.
The present invention also provides a method for forming a patterned substrate, wherein at least one lyophobic region and at least one lyophilic region are obtained using the method for forming a cured film.

As described above, the liquid repellent curable ink of the present invention is desirably applied to the substrate by a micro discharge method. The micro discharge method is not particularly limited, but any one of an ink jet method (for example, JP-A-10-153967), a nozzle printing method (for example, JP-A-2002-75640), and a dispenser method is preferable. Nozzle printing is a method in which a head provided with several tens of fine nozzles is multiplexed and a small amount of ink is ejected with a single stroke.
The dispenser method is a method that uses a liquid dispensing device, and the material dispensing system is a flow rate control system, pressurization ON / OFF type, flow channel ON / OFF type, volumetric metering system, fixed measuring chamber type It is classified as a measuring chamber change type.

  The present invention also provides a photo-curing or thermosetting composition on a substrate by ejecting three kinds of inks of the present invention, which are each independently colored in three colors of red, green and blue, onto the substrate by a micro ejection method. Manufacturing a color filter for a display, comprising a step of forming a cured film by forming a coated film, and then curing the coated film by light irradiation or heat treatment according to photocuring or thermal effects, respectively. Provide a method. This method is characterized in that the step of forming a cured film forms a pattern substrate comprising at least one liquid repellent region and at least one lyophilic region.

The present invention also provides a method for producing a color filter for a display using four types of inks, each of which is an ink of three colors, red, green and blue, and an ink colored yellow.
The present invention further provides a method for producing a color filter for display, wherein four or five types of ink added with black colored ink for a black matrix are used.
The present invention also provides a display color filter manufactured by the above-described manufacturing method.
The use of the color filter for display produced in the present invention is particularly preferably an electronic signboard (digital signage). Since the color filter for electronic signboards is coarser than the high-definition color filter for television, it can be easily manufactured by a micro discharge method.

Furthermore, when patterning the liquid repellent curable ink composition of the present invention by a micro discharge method, even if the adjacent pattern contacts before curing, the pattern shape is maintained without being mixed, 3 colors (red, green, blue) or 4 colors (red, green, blue, yellow), or 4 colors (red, green, blue, black) or 5 colors (black, black matrix) Red, green, blue, yellow, black) liquid repellent curable inks are simultaneously patterned on a substrate and then cured together to provide a method for manufacturing a color filter that requires fewer liquid repellent banks and requires fewer steps can do. At this time, a liquid repellent may be added to all colors of ink used, or a liquid repellent may be added only to a specific color. For example, when three colors of red, green, and blue are used, a liquid repellent may be added to all three colors, or a liquid repellent is added to two colors of red / green, red / blue, and green / blue. Alternatively, a liquid repellent may be added to any one of the three colors.
In the case of producing a color filter without forming a liquid repellent bank in the present invention, an image receiving layer may be provided on the substrate in order to prevent ink from spreading on the substrate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. In the following, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

“Composition of liquid repellent containing fluoropolymer (A)”
The composition of the liquid repellent containing the fluoropolymer (A) used in the following examples and comparative examples is shown below:
<Liquid repellent A-1>:
Polymer: Rf (C4) α-Cl acrylate / GMA / HEMA / iBMA = copolymer consisting of 45/10/35/10 (weight ratio) 50% by weight
・ Solvent: 50% by weight of BCA
<Liquid repellent A-2>:
Polymer: Rf (C4) α-Cl acrylate / GMA / HEMA / iBMA = 45/10/30/15 (weight ratio) copolymer 50% by weight
・ Solvent: 50% by weight of BCA
<Liquid repellent A-3>:
Polymer: Rf (C4) α-Cl acrylate / GMA / HEMA / iBMA = 45/10/20/25 (weight ratio) copolymer 50% by weight
・ Solvent: 50% by weight of BCA
<Liquid repellent A-4>:
Polymer: PFPE (C8) methacrylate / GMA / HEMA / iBMA = copolymer consisting of 45/10/20/25 (weight ratio) 50% by weight
・ Solvent: 50% by weight of BCA
<Liquid repellent A-5>:
Polymer: Rf (C4) α-Cl acrylate / GMA / HEMA / iBMA = 60/10/20/10 (weight ratio) copolymer 50% by weight
・ Solvent: 50% by weight of BCA

<Liquid repellent A-6>:
Polymer: Rf (C4) α-Cl acrylate / MAA / GMA / HEMA = copolymer consisting of 45/15/25/15 (weight ratio) 50% by weight
・ Solvent: 50% by weight of MBA
<Liquid repellent A-7>:
Polymer: Rf (C4) α-Cl acrylate / MAA / GMA / HEMA = copolymer comprising 60/15/5/20 (weight ratio) 50% by weight
・ Solvent: 50% by weight of MBA
<Liquid repellent A-8>:
Fluorine monomer: Rf (C4) α-Cl acrylate <Liquid repellent A-9>:
Fluorine monomer: Rf (C6) α-Cl acrylate <Liquid repellent A-10>:
Polymer: Rf (C4) α-Cl acrylate / GMA / HEMA / iBMA = copolymer composed of 45/10/35/10 (weight ratio) 30% by weight
・ Solvent: PGMEA 70% by weight

The fluorine concentration of the liquid repellent polymer of each liquid repellent is shown in Table 2 below.
The fluorine concentration of the fluorine-containing polymer was measured with an F ion meter by a combustion method. The F ion meter used is ORION 720A manufactured by Thermo Electron Corporation.

Abbreviations in the above formula are as follows:
Rf (C4) α-Cl acrylate: C ₄ F ₉ -CH ₂ CH ₂ -O (C = O) C (Cl) = CH ₂
Rf (C6) α-Cl acrylate: C ₆ F ₁₃ -CH ₂ CH ₂ -O (C = O) C (Cl) = CH ₂
PFPE (C8) _{methacrylate: C 3 F 9 - [OCF} (CF 3) CF 2] -OCF (CF 3) -CH 2 -O (C = O) C (CH 3) = CH 2
MAA: Methacrylic acid
GMA: Glycidyl methacrylate
HEMA: 2-hydroxyethyl methacrylate
iBMA: Isobornyl methacrylate
BCA: Diethylene glycol monobutyl ether acetate (= butyl carbitol acetate)
MBA: 3-methoxybutyl acetate
PGMEA: Propylene glycol monomethyl ether acetate

"Components of UV curable composition"
<Polyfunctional monomer (B)>
B-1: Pentaerythritol tetraacrylate B-2: 1,6-hexanediol diacrylate B-3: Dipentaerythritol hexaacrylate

<Photopolymerization initiator (C)>
C-1: Irgacure 907 [Product name: Ciba Specialty Chemicals Co., Ltd.]
<Thermal polymerization initiator (C)>
C-2: AIBN (azobisisobutyronitrile)

<Monofunctional monomer (D)>
D-1: 2-hydroxyethyl methacrylate D-2: Methyl methacrylate

<Epoxy resin (E)>
E-1: Techmore VG3101
<Melamine resin>
E-2: Sumitec Resin M-3
E-3: Accelerator ACX (melamine resin curing agent)

<Polymerization inhibitor (F)>
F-1: Phenothiazine

Examples 1-10 and Comparative Examples 1-3
Each blending component was mixed and dissolved at the blending ratio shown in Table 1 to prepare a liquid repellent UV curable and thermosetting ink composition (the numerical values in Table 1 represent “% by weight”). Examples 1 to 9 and Comparative Examples 1 to 3 are liquid-repellent UV curable ink compositions, and Example 10 is a liquid-repellent thermosetting ink composition. In addition, in this example, in order to simplify experiment, although the coloring agent is not mix | blended, even if it mix | blends a coloring agent, there is no difference in an essential effect.

  The liquid repellent UV curable and thermosetting ink compositions obtained in Examples 1 to 10 or Comparative Examples 1 to 3, and the evaluation method of the cured film are as follows.

“Liquid repellency of a liquid repellent single film containing a fluoropolymer (A)”
The static contact angle of the liquid repellent was measured by the following method using a fully automatic contact angle meter DropMaster701 (manufactured by Kyowa Interface Science). The liquid repellent of the present invention was uniformly applied on a silicon wafer (3 cm × 3 cm) by a spin coating method (2000 rpm, 30 seconds), and heated on a hot plate at 110 ° C. for 3 minutes to prepare a measurement sample. 2 μL each of water, n-hexadecane, or butyl carbitol acetate (BCA) was dropped from a microsyringe onto the sample, and a still image one second after the dropping was photographed with a video microscope.

"Compatibility of liquid repellent with UV curable or thermosetting ink composition"
The appearance of the liquid repellent UV curable or thermosetting ink prepared by blending the liquid repellent with the ink composition was observed, and the compatibility of the liquid repellent with the ink composition was observed.
◎ ＞ ○ ＞ △ ＞ × in order from good compatibility
It was evaluated.

"Liquid repellency of UV-cured or thermoset film (after UV or heat irradiation)"
Since the liquid repellent region of the present invention has a very small area, the contact angle cannot be measured as it is. Therefore, in order to measure the contact angle, a large-area liquid repellent region was prepared by the following method. The liquid repellent UV curable or thermosetting ink composition of the present invention is uniformly applied on a silicon wafer (3 cm × 3 cm) by a spin coating method (2000 rpm, 30 seconds), and the liquid repellent UV curable ink composition ( In the case of Examples 1 to 9 and Comparative Examples 1 to 3), the coating film was cured by irradiating ultraviolet rays (mixed spectrum consisting of g-line, h-line and i-line) with an integrated illuminance of 1000 mJ / cm ² under a nitrogen atmosphere. I let you. In the case of the liquid repellent thermosetting ink composition (Example 10), the coating film was cured by heat treatment on a hot plate at 80 ° C. for 3 minutes. As for the contact angle, 2 μL of BCA was dropped from a microsyringe onto a horizontally placed substrate, the contact angle after 5 minutes of dropping was measured with a fully automatic contact angle meter, and the results were evaluated as follows.
○: The contact angle is maintained at 30 ° or more, Δ: 20 ° or more is maintained, and X: is decreased to 20 ° or less.

"Line pattern shape retention characteristics before UV curing"
Liquid-repellent UV curable or thermosetting ink is ejected onto a glass substrate hydrophobized with a fluorine-based silane coupling agent (perfluorohexylethyltrimethoxysilane) to the substrate at a dot density of 40 μm by an inkjet method. Thus, a plurality of adjacent line patterns (line width 40 μm) were drawn. The inkjet device was Litrex 70 (manufactured by Litrex) and had a capacity of 15 pL per drop. The shape retention of the line pattern 5 minutes after drawing was observed with an optical microscope, and the results were evaluated as follows.
○: Fully maintained △: There is a place that mixes with the adjacent line ×: Fully mixes with the adjacent line

  Table 2 shows the fluorine concentration (% by weight) of the fluorine-based polymer (A) in the liquid repellent, the weight average molecular weight, and the static contact angle of the liquid repellent single film.

  Table 3 shows the evaluation results of the liquid-repellent UV curable and thermosetting ink compositions of Examples 1 to 10 and Comparative Examples 1 to 3 shown in Table 1.

  As shown in Table 3, in Examples 1 to 10, the liquid repellent exhibited good compatibility with the UV or thermosetting composition, and the cured film after UV irradiation or heat treatment exhibited high liquid repellency. On the other hand, in Comparative Example 1, the liquid repellent was not dissolved in the UV curable composition.

  In Comparative Examples 2 and 3 in which the fluoropolymer of Comparative Example 1 was replaced with a fluoromonomer, the compatibility with the UV curable composition was good, but the liquid repellency of the cured film after UV irradiation was low. Indicated.

  A liquid repellent for a liquid repellent curable ink composition comprising a fluorine-containing polymer having a specific structure according to the present invention, and a light or thermosetting ink composition containing the liquid repellent are used for display pixels and circuits. And a color filter for display, etc. are used as a method for producing by a printing technique represented by inkjet.

Claims (22)

The following repeating units (a1), (a2) and (a3):
(A1) Formula:

[Wherein X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom) ), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms or A branched alkyl group,
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms), a —CH ₂ CH (OY ¹ ) CH ₂ — group ( However, Y ¹ is a hydrogen atom or an acetyl group), or, -. a group (n is _{1~10) - (CH 2) n} SO 2.
Rf is a linear or branched fluoroalkyl group having 1 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms). ]
100 parts by weight of a repeating unit derived from an α-substituted acrylate represented by
(A2) 5 to 60 parts by weight of repeating units derived from an epoxy group-containing monomer, and (a3) a fluorine-based polymer having 10 to 100 parts by weight of repeating units derived from a monomer containing an alkylene oxide group ( A liquid repellent agent for liquid repellent curable ink containing A).   The liquid repellent for curable ink according to claim 1, wherein the fluorine concentration of the fluorine-based polymer (A) is 10 to 40% by weight.   The liquid repellent for curable ink according to claim 1 or 2, wherein the fluorine-based polymer (A) has a weight average molecular weight of 3,000 to 20,000. The repeating unit of the fluoropolymer (A) is further
(A4) The curable ink according to any one of claims 1 to 3, comprising 5 to 110 parts by weight of a high softening point monomer which is a monomer having a glass transition point or a melting point of 100 ° C or higher in a homopolymer state. Liquid repellent.   The liquid repellent for curable ink according to any one of claims 1 to 4, wherein the fluoroalkyl group is a perfluoroalkyl group having 4 to 6 carbon atoms.   The liquid repellent for curable ink according to any one of claims 1 to 4, wherein the fluoroalkyl group is a perfluoropolyether group having 6 to 8 carbon atoms.   The liquid repellent for curable ink according to any one of claims 1 to 6, wherein the fluoropolymer (A) has a form dissolved in a glycol solvent at a concentration of 20 to 60% by weight. The liquid repellent for curable ink according to any one of claims 1 to 7 , wherein the epoxy group-containing monomer (a2) is a (meth) acrylate containing an epoxy group. In the monomer (a3) containing an alkylene oxide group, the alkylene oxide group has the formula:
-(R ¹ O) _n R ²
[Wherein, R ¹ represents — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ —,
R ² is hydrogen or a methyl group,
n is 1-10. ]
The liquid repellent for curable ink according to any one of claims 1 to 8 , which is represented by: A curable ink comprising the liquid repellent according to any one of claims 1 to 9 . Polyfunctional monomer (B), comprising the photopolymerization initiator (C) and a coloring agent (G) Further, the liquid repellency photocurable ink according to claim 1 0. At least one non-fluorinated resin (E) selected from the group consisting of a polyfunctional monomer (B), a melamine resin, a urea resin, an alkyd resin, an epoxy resin, a phenol resin, and a cyclopentadiene resin, and a colorant (G) Furthermore comprising liquid repellent thermosetting ink according to claim 1 0. The liquid repellency photocurable ink according to claim 1 0 or 1 1 by discharging a substrate in traces discharge method to form a coating film of the photocurable composition on a substrate, a light coating film A method for forming a cured film, comprising a step of forming a cured film by irradiation and curing. The liquid repellency thermosetting ink according to claim 1 0 or 1 2 is ejected to the substrate in traces discharge method to form a coating film of the thermosetting composition on a substrate, heat-treating the coating film A method for forming a cured film, comprising a step of forming a cured film by curing. Trace ejection method an ink-jet method, either of a nozzle printing method or a micro dispenser method, a method of forming the cured film according to claim 1 3 or 1 4. Claim 1 to obtain 3 or 1 4 using a method for forming a cured film according to at least one liquid-repellent region and at least one lyophilic areas, the method of forming the patterned substrate. Independently red, green and blue inks three according to any one of claims 1 0-1 2 colored in the three colors of, ejected to the substrate in traces discharge method to a substrate material It includes a step of forming a cured film by forming a coating film of a photocuring or thermosetting composition and then curing the coating film by light irradiation or heat treatment according to the photocuring or thermal effect, respectively. A method for producing a color filter for display. The method for producing a color filter for display according to claim 17 , wherein the step of forming a cured film forms a pattern substrate comprising at least one liquid repellent region and at least one lyophilic region. The method for producing a color filter for a display according to claim 17 or 18 , wherein four types of inks, each of which is an ink of three colors of red, green, and blue and further added with a yellow colored ink, are used. . Further, using four kinds or five kinds of ink plus a colored ink on a black for black matrix, according to claim 1 7-19 manufacturing method of a color filter for a display according to any one of. Any one of claims 1 7-2 0 produced by the production method according to the color filter for a display. Claim 1 7-2 0 produced by the production method according to any one of the color filters for displays used in digital signage applications.