JP2014122152A - Treatment agent for an inkjet base - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base treatment agent for inkjet printing, which enables formation of a specified pattern based on an inkjet printing method with precision equivalent to that of photolithography.SOLUTION: Provided is a treatment agent for providing an inkjet base with surface-treatment in advance, comprising at least a binder resin (A), a fluorine-containing oligomer (B), an optical acid generator (C), and a solvent (D), wherein the fluorine-containing oligomer (B) comprises a copolymer including, as an indispensable component, a fluorine-containing monomer expressed by the general formula (1), and a resin layer formed by the base treatment agent enables liquid-affinitive/repellent patterning either by light irradiation via a pattern mask or by light irradiation via by a pattern mask and heating.

Description

  TECHNICAL FIELD The present invention relates to an ink jet base treatment agent, and more particularly to a base treatment agent capable of performing lyophobic patterning as a base for ink jet printing.

  As a manufacturing method of a fine device such as a semiconductor element, an integrated circuit, and an organic EL display device, a method is generally used in which a thin film of a functional material is formed on a substrate by vacuum deposition, sputtering or the like, and the thin film is patterned by photolithography. Is used. In general, in photolithography, first, a thin film of a material to be patterned is formed on a substrate, then a photoresist film is formed on the thin film, exposed through a photomask having a predetermined pattern, and an alkaline developer. Development is performed to form a photoresist pattern. Then, etching is performed using the photoresist pattern as a mask, and unnecessary portions are removed to obtain a thin film having a desired pattern shape. Photolithography is complicated and needs to be carried out in a clean room, so the problem is that the utilization efficiency of energy and materials is low and the equipment is expensive. Pattern formation can be carried out at low cost and low energy. As a method, introduction of a printing method is being studied. Among the printing methods, the inkjet printing method is superior to other printing methods in controlling the amount of droplets ejected from the nozzle and the ejection position, and its use will expand in various fields in the future. It is expected that.

  However, the printing accuracy of the ink jet apparatus is currently about ± 10 μm, and the accuracy required for fine devices such as semiconductor elements, integrated circuits, and devices for organic EL displays, that is, the photolithography method used exclusively for manufacturing these devices (± 2 μm) ) Is not accurate. In addition, the area where the ink applied from the ink jet apparatus is printed varies depending on the properties of the substrate to which the ink is applied, for example, wettability with the ink. On the other hand, for example, there is a method disclosed in Patent Document 1 as a method of obtaining a higher-definition printed matter while maintaining the printing accuracy of the ink jet apparatus by making the printed substrate (base) uniform. In this method, a receiving layer having a high affinity with the ink-jet ink (which easily absorbs or absorbs the ink-jet ink) is formed in advance on the surface of the base, and printing is performed on the receiving layer, thereby producing a clear printed matter with less blur. Can be created. However, it is not possible to obtain a printed matter with the accuracy required for a fine device simply by printing on the receiving layer.

  In order to solve the above problem, there has been proposed a method of obtaining a printed matter with improved printing accuracy by controlling the affinity with the inkjet ink by irradiating the receiving layer with light through a photomask. For example, in Patent Document 2, a resin layer that is made more lyophilic with an inkjet ink by light irradiation or light irradiation and heating is provided, and light irradiation (and further heating) is performed through a photomask to thereby improve the affinity with the inkjet ink. By forming a highly liquid portion and performing inkjet printing on this portion, it is possible to obtain a printed matter with higher accuracy (a color filter in the literature). In this case, a lyophilic residue such as a hydroxy group is formed in the exposed portion, and an alkyl group or a silicon-containing group is formed in the unexposed portion. In particular, for organic solvent-based inkjet inks, the lyophilic portion and the liquid-repellent portion are not sufficiently separated, and the difference in organic solvent-based ink acceptance amount cannot be clarified. In addition, the amount of ink that can be applied with liquid is limited, and it is difficult to produce a device that exhibits sufficient performance.

  As another method, high-definition can be achieved by creating in advance the ink-jet ink wetted part (lyophilic part) and hard-to-spread part (liquid repellent part) on the base surface, and printing only on the lyophilic part. There is a way to perform simple printing. In this case, the ink jet ink that is accidentally ejected to the liquid repellent part is repelled on the base surface, and printing is not performed on this part.

  Specific examples thereof include Patent Document 3 and Non-Patent Document 1. Patent Document 3 proposes a method for producing a color filter by ink jet printing using a photocatalyst containing layer whose surface wettability changes by energy irradiation. This method forms a lyophilic pattern by pattern exposure of a photocatalyst-containing layer, and forms a color filter by forming pixels and the like by applying ink on the lyophilic pattern. It is. However, this method has a problem in long-term reliability because a highly active photocatalyst remains in the device.

  On the other hand, Non-Patent Document 1 describes a method for selectively forming a polymer thin film on a pattern substrate using a fluoroalkylsilane monomolecular film by ink jet printing. According to this method, printing that is substantially finer than the landing diameter of the inkjet ink ejected from the inkjet head can be performed. However, the preparation of the monomolecular film is as complicated as the above-described photolithography, and the light source used is deep ultraviolet rays, so that the substrate is damaged by deep ultraviolet rays.

JP 11-216945 A Japanese Patent No. 2872596 JP 11-337726 A

Surface Science Vol. 27, no. 2, pp. 108-115, 2006

  Accordingly, an object of the present invention is to easily create a wettability-spreading portion (lyophilic portion) and a hard-to-spread portion (liquid-repellent portion) of the ink-jet ink, and to achieve high-definition ink-jet printing. An object of the present invention is to provide a treatment agent for an ink-jet substrate that can be used.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that according to a ground treatment agent containing a predetermined component, each component is combined by applying light irradiation (or light irradiation and heating), and an inkjet It was found that the lyophilic part and the liquid repellent part of the ink can be easily patterned, and ink jet printing can be performed with an accuracy equivalent to photolithography, and the present invention has been completed.

That is, the gist of the present invention is as follows.
(1) In an inkjet base treating agent that performs a surface treatment on a substrate used in inkjet printing in advance,
The base treatment agent contains at least a binder resin (A), a fluorine-containing oligomer (B), a photoacid generator (C), and a solvent (D).
The resin layer formed with the surface treatment agent can be formed into a lyophilic / liquid repellent pattern having a lyophilic portion and a lyophobic portion by light irradiation through a pattern mask or light irradiation through a pattern mask and heating. Because
The contact angle with respect to diethylene glycol monoethyl ether acetate before light irradiation or light irradiation and heating of the resin layer is 40 ° or more, and the portion with respect to diethylene glycol monoethyl ether acetate subjected to light irradiation or light irradiation and heating. The contact angle is 15 ° or less,
A treating agent for an ink jet base comprising a copolymer that is polymerized with a fluorine-containing monomer represented by the following general formula (1) as an essential component as the fluorine-containing oligomer (B).
[R1 in General Formula (1) is a hydrogen atom or a methyl group. X is a direct bond, -C (= O) O - , - OC (= O) -, - CH 2 OC (= O) - is either. Y is a direct bond or a divalent organic group (having 1 to 10 carbon atoms and may contain an oxygen atom or a nitrogen atom). Ar is any one of the structures described in the general formula group (2). ]
[R2 to R57 are each independently a hydrogen atom, alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, Alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, amino group which may be substituted, cyano A nitro group or a halogen atom, one of R2 to R7, one of R8 to R15, one of R16 to R25, one of R26 to R31, or R32 to R39 One of them, one of R40 to R47, and One of R48 to R57 is X in the general formula (1), and at least one of R2 to R7, at least one of R8 to R15, and at least one of R16 to R25. At least one of R26 to R31, at least one of R32 to R39, at least one of R40 to R47, and at least one of R48 to R57 are each Rf-O- (Rf represents any one of the following general formula group (3)). M is any one of an oxygen atom, a sulfur atom, and> N-R58, and R58 is a monovalent organic group having 1 to 10 carbon atoms and may contain an oxygen atom or a nitrogen atom. ]

(2) The ink jet primer treatment agent according to (1), wherein the binder resin (A) is an epoxy resin (A1).
(3) The mass ratio of the epoxy resin (A1), the fluorine-containing oligomer (B), and the photoacid generator (C) in the base treatment agent is (A) / (B) / (C) = 100/2. The ink-jet base treatment agent as described in (2), which is in a range of 0.1 / 10 to 0.5.
(4) The epoxy base treatment agent according to (2) or (3), wherein at least 50% by mass of the epoxy resin (A1) is solid at normal temperature (23 ° C.).
(5) The photoacid generator (C) is diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, CF ₃ SO ₃ salt, p-CH ₃ PhSO ₃ salt, p-NO ₂ PhSO ₃ salt (however, , Ph represents a phenyl group), any one of (1) to (4), characterized in that it is at least one selected from the group consisting of organic halogen compounds, orthoquinone-diazidosulfonyl chloride, and sulfonate esters The processing agent for inkjet bases as described in 2.

  According to the present invention, it becomes possible to easily perform lyophilic / repellent patterning on a base, and a higher-definition inkjet printed matter can be obtained.

FIG. 1 is a photomicrograph showing the evaluation of lyophilic / liquid repellent patterning by discharging the inkjet ink for evaluation onto the resin layer obtained in Example 1.

  Hereinafter, the present invention will be described in detail. First, the material which comprises the processing agent of this invention is demonstrated.

<Binder resin (A)>
There is no restriction | limiting in particular as binder resin used for the base-treatment agent of this invention, A generally well-known material can be used. Examples thereof include polyethylene, polyester, acrylic resin, epoxy resin, polyurethane, polyimide, polyamide, melamine resin, and polycarbonate. Among these, it is particularly preferable to use an epoxy resin (A1). By using an epoxy resin, the part irradiated with light (or the part irradiated with light and heated) reacts and cures with the acid generated by the photoacid generator, so that the ink is not soluble in ink and the ink spreads out. Will improve.

  The binder resin can also be selected according to the properties required for the printed material. For example, in applications where insulation and heat resistance are required, polyimide may be selected as the binder resin. The polyimide used as the binder resin is preferably a soluble polyimide that dissolves in a solvent, but it can also be blended as a precursor polyamic acid and then converted into a polyimide by thermosetting. Examples of the soluble polyimide include aliphatic acid dianhydride / diamine, fluorine-containing dianhydride / diamine, silicone-containing dianhydride / diamine, and a bent structure in the molecule (for example, etheric oxygen atom). Examples thereof include polyimides containing repeating units composed of acid dianhydride / diamine and the like.

<Epoxy resin (A1)>
Examples of the epoxy resin (A1) used in the treatment agent of the present invention include a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, and water. Bisphenol F type epoxy resin, bisphenol S type epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin epoxy resin, silicone modified epoxy resin, ε-caprolactone modified epoxy Examples thereof include resins, alicyclic or heterocyclic epoxy resins, and epoxy resins having a dicyclopentadiene type or naphthalene type structure.

  Examples of commercially available epoxy resins include Mitsubishi Chemical's jER series, Nippon Steel & Sumikin Chemical's YD / YDF / ZX / PG / YDPN / YDCN / YDB / FX / YH / ST / YDS / YSLV / YC / YPB / PB / YP. Series, DIC's EPICLON series, Daicel Chemical's Celoxide / EHPE / Epolide / Epofriend series, Nippon Kayaku's ECON / EPPN / NC / BREN / GAN / GOT / AK / RE / CER / XD series, Dow Chemical's D . E. R. / D. E. N. Series. These epoxy resins may be used alone or in combination of two or more.

  Regarding the epoxy resin (A1), when used alone, or when used in combination of two or more, it is desirable that at least 50% by mass of the epoxy resin (A1) is solid at normal temperature (23 ° C.). Solid epoxy resins include jER1001, jER1002, jER1003, jER1055, jER1004, jER1004AF, jER1007, jER1009, jER1010, jER1003F, jER1004F, jER1005FS, jER1007FS, jER1007FS, 400ER JER4250, jER4275, jER5050, jER5051, jER154, jER157S70, jER1031S, jER1032H60, jER545, jER YL6810, jER YX8800, jER YX4000, jER YX4000H, jER YL6121X, jER YL6121X 99, YDF-2001, YDF-2004, YDF-2005RL, YDB-400, YDB-405, ST-4000D, YP-50, YP-50S, YP-70, ZX-1356-2, FX manufactured by Nippon Steel & Sumikin Chemical -316, YPB-43C, YPB-43M, Daicel Chemical EHPE3150, Epofriend AT501, Epofriend CT310, Nippon Kayaku NC-3000, NC-3000-L, NC-3000-H, CER-3000- L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, ECON-1020, ECON-102S, ECON-103S, ECON-104S, CER- 1020, EPPN-201L, BR N-S, and the like BREN-105.

  Further, the epoxy resin (A1) preferably has an epoxy equivalent of 1000 or less, and more preferably 500 or less. When the epoxy equivalent exceeds 1000, the reaction efficiency due to the acid generated by the photoacid generator is lowered, and the exposed portion is easily absorbed and swollen by the ink-jet ink, so that the wetting and spreading of the ink does not improve.

<Fluorine-containing oligomer (B)>
The fluorine-containing oligomer (B) used in the surface treatment agent of the present invention includes a copolymer that is polymerized using the fluorine-containing monomer of the general formula (1) as an essential component.

  R1 in the general formula (1) is a hydrogen atom or a methyl group.

The X in the general formula (1) a direct bond, -C (= O) O - , - OC (= O) -, - CH 2 OC (= O) - is either.

Y in the general formula (1) is a direct bond or a divalent organic group (having 1 to 10 carbon atoms and may contain an oxygen atom or a nitrogen atom). For example, —CH ₂ —, —CH (OH) —, —CH (OCH ₃ ) —, —CH (NH ₂ ) —, —CH (NH (CH ₃ )) —, —CH (N (CH ₃ ) _{2 ) -, - (CH 2)} 2 -, - CH (OH) CH 2 -, - CH 2 CH (OH) -, - CH (OCH 3) CH 2 -, - CH 2 CH (OCH 3) -, - _{CH (N (CH 3) 2} ) CH 2 -, - CH 2 CH (N (CH 3) 2) -, - CH 2 OCH 2 -, - (CH 2) 2 O (CH 2) 2 -, - CH (CH ₃ ) OCH (CH ₃ ) —, —CH ₂ N (CH ₃ ) CH ₂ , — (CH ₂ ) ₃ —, — (CH ₂ O) ₂ CH ₂ — and the like can be mentioned.

Ar in the general formula (1) is one of the structures described in the general formula group (2).
The fluorine-containing oligomer has an aromatic structure as in the general formula group (2), so that the sensitivity of the fluorine-containing oligomer to ultraviolet rays is improved, and the contact angle can be reduced by light irradiation or light irradiation and heating. .

  R2 to R57 in the general formula group (2) are each independently a hydrogen atom, alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group. , Acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, substituted An amino group, a cyano group, a nitro group or a halogen atom which may be present. M is an oxygen atom, a sulfur atom, or> N—R58 (where R58 is a monovalent organic group having 1 to 10 carbon atoms and may contain an oxygen atom or a nitrogen atom). .

However, among R2 to R7, one is surely X bonded to Y in the general formula (1), and at least one other is Rf-O-, and Rf is the following general formula group (3). Any group of

  However, among R8 to R15, one must be X bonded to Y in the general formula (1), and at least one other is Rf-O-, and Rf is the above general formula group (3). Any group of

  However, among R16 to R25, one is surely X bonded to Y in the general formula (1), and at least one other is Rf—O—, and Rf is the above general formula group (3). Any group of

  However, among R26 to R31, one must be X bonded to Y in the general formula (1), and at least one other is Rf-O-, and Rf is the above general formula group (3). Any group of

  However, among R32 to R39, one must be X bonded to Y in the general formula (1), and at least one other is Rf—O—, and Rf is the above general formula group (3). Any group of

  However, among R40 to R47, one must be X bonded to Y in the general formula (1), and at least one other is Rf-O-, and Rf is the above general formula group (3). Any group of

  However, out of R48 to R57, one is surely X bonded to Y in the general formula (1), and at least one other is Rf-O-, and Rf is the above general formula group (3). Any group of

Here, the groups represented by the general formula group (3) are in the relationship of the structural isomers of the perfluoroalkenyl group represented by the composition formula of C ₉ F ₁₇ —, and are obtained as a mixture thereof at the time of synthesis. However, the mixture can be used as it is.

  Moreover, as an alkyl group in R2-R57 in General formula group (2), a C1-C18 linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), a branched alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-decylcyclohexyl).

  Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy And octadecyloxy).

  Examples of the alkylcarbonyl group include linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl. , Dodecanoyl and octadecanoyl).

  Examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

  Examples of the alkoxycarbonyl group include straight-chain or branched-chain alkoxycarbonyl groups having 2 to 18 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec- Butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.).

  Examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

  Examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

  As the acyloxy group, a linear or branched acyloxy group having 2 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert- Butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy and the like).

  As the arylthio group, an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2 -Bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxy Phenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl ] Phenylthio, 4- Phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p-isopropylbenzoyl) phenylthio and 4- ( p-tert-butylbenzoyl) phenylthio and the like.

  Examples of the alkylthio group include linear or branched alkylthio groups having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentyl Luthio, tert-pentylthio, octylthio, decylthio, dodecylthio, isooctadecylthio and the like.

  Examples of the aryl group include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl and naphthyl).

  As the heterocyclic hydrocarbon group, a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl Quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl and the like.

  Examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

  Examples of the alkylsulfinyl group include linear or branched sulfinyl groups having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentyl). Sulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl, etc.).

  Examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl and naphthylsulfinyl).

  As the alkylsulfonyl group, a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, Pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl, etc.).

  Examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc.) and the like.

Examples of the hydroxy (poly) alkyleneoxy group include a hydroxy (poly) alkyleneoxy group represented by the general formula (4).
HO (-AO) q- (4)
[AO represents an ethyleneoxy group and / or a propyleneoxy group, and q represents an integer of 1 to 5. ]

The amino group which may be substituted includes an amino group (—NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl- n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino And isopropylphenylamino) and the like.

The R58, for example methyl, ethyl, propyl, and alkyl groups such as _{isopropyl, -CH 2 OCH 3, - (} CH 2) 2 OCH 3, -CH 2 OCH 2 CH 3, - (CH 2 CH (CH 3) ) OCH _{3 and the} like.

Hereinafter, general formula group (4a) and general formula group (4b) are illustrated as specific examples of the fluorine-containing monomer. In the general formula group (4a) and the general formula group (4b), Rf is any functional group having the structure described in the general formula group (3).

  The other monomer component constituting the fluorine-containing oligomer is not particularly limited as long as it is copolymerizable with the fluorine-containing monomer represented by the general formula (1), and generally known materials can be used.

  Other commercially available monomers include, for example, NOF's Blemmer series, Shin-Nakamura Chemical's NK ester series, Hitachi Chemical's funkrill series, Osaka Organic Chemical's biscoat series, and Kyoeisha Chemical's light ester / light acrylate series. And Toa Gosei's Aronix series.

  As for the mass ratio of the fluorine-containing monomer represented by General formula (1) with respect to the sum of the mass of all the monomers which comprise a fluorine-containing oligomer, it is desirable that it is 40-80 mass%. More desirably, it is the range of 50-70 mass%. If the amount is less than 40% by mass, the contact angle with light-irradiated or diethylene glycol monoethyl ether acetate in a portion where light irradiation and heating are not performed becomes low. If the amount exceeds 80% by mass, the compatibility with the epoxy resin and the solvent is deteriorated and clean. A resin layer cannot be formed.

  There is no restriction | limiting in particular in manufacture of a fluorine-containing oligomer, A well-known method can be used. For example, the method described in “4th edition, Laboratory Science Course 28 Polymer Synthesis (Edited by Chemical Society of Japan), 2.2.4 Acrylic Polymer” published by Maruzen Co., Ltd. can be used.

  The weight average molecular weight of the fluorine-containing oligomer is desirably 2000 to 20000. More desirably, it is in the range of 4000 to 10,000. If the weight average molecular weight is outside this range, the resin layer prepared with the treatment agent may not have the desired performance.

<Photoacid generator (C)>
A photoacid generator is a material that reacts with light to generate an acid. The acid generated here acts on the fluorine-containing monomer constituting the fluorine-containing oligomer, thereby accelerating the elimination of the structural unit containing Rf from the mother skeleton of the fluorine-containing oligomer, and the portion irradiated with light (or light irradiation and heating) The contact angle of diethylene glycol monoethyl ether acetate to the portion subjected to (ii) is promoted.

Such materials include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, CF ₃ SO ₃ salts, p-CH ₃ PhSO ₃ salts, p-NO ₂ PhSO ₃ salts (where Ph is a phenyl group) ) And the like, organic halogen compounds, orthoquinone-diazide sulfonyl chloride, and sulfonic acid esters.

  Commercially available photoacid generators include WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367, WPI-113 manufactured by Wako Pure Chemical Industries, and CPI-100P manufactured by San Apro. CPI-101A, CPI-200K, CPI-210S, Sanwa Chemical TS-01, TS-91, TFE-triazine, TME-triazine, MP-triazine, dimethoxytriazine, BASF Irgacure PAG103, Irgacure PAG 121, Irgacure PAG 203, CGI725, CGI1907, Irgacure250, IrgacurePAG290, GSID26-1, Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer made by ADEKA SP-170, Adekaoptomer SP-172, and the like Adekaoptomer SP-300. These photoacid generators may be used alone or in combination of two or more. Among these, WPAG-281, WPAG-336, WPAG-367, CPI-100P, CPI-101A, CPI-200K, CPI-210S, TS-01, TS-91, Irgacure PAG290, which are sulfonium salt photoacid generators. GSID26-1, Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172, Adekaoptomer SP-300 are desirable.

<Solvent (D)>
Examples of the solvent used in the treatment agent of the present invention include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, Ketones such as cyclohexanone and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbi Tall, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethyleneglycol Glycol ethers such as dimethyl monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether Examples include acetates such as acetate and propylene glycol monoethyl ether acetate. These solvents may be used alone or in combination of two or more.

<Ingredients other than (A) to (D)>
Components other than the above (A) to (D) (other components) may be added to the treatment agent of the present invention as necessary. Other components include coloring materials such as dyes and pigments, cross-linking agents such as polyfunctional epoxy compounds and polyfunctional oxetane compounds, fillers such as alumina, mica and silica, leveling agents and antifoaming agents, plasticizers, and couplings. You may contain additives, such as an agent, a hardening | curing agent, a ultraviolet absorber, a light stabilizer, antioxidant, and a fluorescent whitening agent suitably.

<Mass ratio of each component in treatment agent>
The mass ratio of the epoxy resin (A1), the fluorine-containing oligomer (B), and the photoacid generator (C) in the base treatment agent is (A1) / (B) / (C) = 100/2 to 0.1 / A range of 10 to 0.5 is desirable. If the amount of the fluorine-containing oligomer exceeds 2 in the above ratio, the contact angle with diethylene glycol monoethyl ether acetate after light irradiation (or light irradiation and heating) is increased, which is unsuitable. If it is lower, the contact angle with respect to diethylene glycol monoethyl ether acetate in the resin layer before light irradiation (or light irradiation and heating) is lowered, which is not appropriate. In addition, if the photoacid generator is less than 0.5 in the above ratio, the epoxy resin is insufficiently cured and is not suitable, and even if added in a large amount, there is no change in performance, so it is not necessary to add more than 10 . Moreover, it is preferable that the mass ratio in the case of adding another component is a range which does not exceed 100 mass parts, when the sum total of (A)-(C) component is 100 mass parts. When other components exceed 100 parts by mass, the original performance is not exhibited. The mass ratio of the solvent (D) is preferably in the range of 150 to 900 parts by mass, where the total of the components (A) to (C) and other components is 100 parts by mass. More preferably, it is the range of 300-700 mass parts. When the solvent (D) is less than 150 parts by mass or more than 900 parts by mass, it becomes difficult to apply the base treatment agent to the substrate.

  Next, a method for using the surface treatment agent of the present invention will be described. First, this treatment agent is applied to the surface of a substrate on which ink jet printing is performed, and prebaked to form a resin layer made of a base treatment agent on the substrate surface. Next, the resin layer is subjected to light lyophobic patterning having a lyophilic portion and a lyophobic portion for the ink-jet ink by performing light irradiation or light irradiation through a pattern mask and heating. Here, a fine device can be created by printing functional ink on the obtained lyophilic portion with an ink jet apparatus.

<Coating>
There is no particular limitation on the coating method of the ground treatment agent of the present invention, and known methods such as spin coating method, dip coating method, bar coating method, slit coating method, blade coating method, air knife coating method, roll coating method. Any method such as a screen printing method can be adopted, and it is appropriately selected according to the base material to be coated and the coating thickness. The coating thickness is preferably 0.5 to 20 μm in terms of dry film thickness. More preferably, it is 1.0-10 micrometers. When the coating thickness is less than 0.5 μm in terms of dry film thickness, the prepared resin layer may not exhibit desired performance. In addition, in terms of the performance of the resin layer, it is not required to have a thickness exceeding 20 μm in terms of a dry film thickness.

  In addition, there is no restriction | limiting in particular in the base material which coat | covers the base-treatment agent of this invention, It is like board | plates and films, such as inorganic base materials, such as stainless steel, copper foil, glass, a silicon wafer, a polyethylene terephthalate, and a polycarbonate. Any base material such as an organic base material can be adopted, and it is appropriately selected according to the characteristics of the device to be produced.

<Pre-bake>
Pre-baking is performed by heating with an oven, a hot plate or the like, vacuum drying, or a combination thereof, and is appropriately selected depending on the type of the solvent (D) in the base treatment agent and the type of the substrate. However, the drying temperature is preferably 45 to 120 ° C. When the temperature is lower than 45 ° C., the solvent may remain in the resin layer. When the temperature is higher than 120 ° C., the active group in the composition may be deactivated. What is necessary is just to perform about 1 to 10 minutes as drying time, for example. At this time, the contact angle of the resin layer surface with diethylene glycol monoethyl ether acetate is 40 ° or more.

<Light irradiation or light irradiation and heating>
The light irradiation in the present invention is to mainly irradiate ultraviolet rays having a wavelength of 250 nm to 400 nm. Examples of the ultraviolet light source used include a high-pressure mercury lamp and a metal halide lamp, but there is no particular limitation. The resin layer is irradiated with light through a photomask such as a patterned quartz chromium deposition mask. The exposure amount is desirably 1000 to 10,000 mJ / cm ² . More desirably, 3000 to 7000 mJ / cm ² is preferable. If it is less than 1000 mJ / cm ² , the contact angle to the diethylene glycol monoethyl ether acetate of the light irradiated portion does not decrease to 15 ° or less, and even if the exposure dose exceeds 10,000 mJ / cm ² , the performance is not affected. No amount is needed. Furthermore, it is more desirable to perform heating after exposure. The portion irradiated with light is cured by heating, and the contact angle is further reduced. This heating is performed by an oven, a hot plate, or the like. As heating temperature, 50-150 degreeC is desirable. When the temperature is less than 50 ° C., the effect of heating is insufficient, and a temperature exceeding 150 ° C. is not required for curing.

  By printing the functional ink on the lyophilic portion of the lyophilic pattern thus obtained with an ink jet printer, a fine device can be created.

  The evaluation of the prepared lyophilic pattern is by measuring the contact angle of diethylene glycol monoethyl ether acetate between the unexposed part (corresponding to the lyophobic part) and the exposed part (corresponding to the lyophilic part). Do. Ink-jet ink generally uses a high-boiling solvent having a boiling point of 200 ° C. or higher at atmospheric pressure (760 mmHg). As a result, it is possible to suppress drying of the ink in the ink jet head and reduce ink ejection defects. Therefore, in the present invention, diethylene glycol monoethyl ether acetate, which has a high boiling point (at 217 ° C. at atmospheric pressure (760 mmHg)) and is often used for inkjet ink, is used in place of expensive inkjet ink to measure the contact angle. In addition, the lyophobic property is evaluated.

  Embodiments of the present invention will be specifically described below based on examples and comparative examples. In addition, this invention is not limited only to these Examples.

<Synthesis Example 1> Synthesis of fluorinated oligomer B1 In a three-necked flask equipped with a cooling tube, the following general formula (b1, λmax (ε) = 232.5 (10390), 257 (5940) (in acetonitrile)) 16.67 g of a fluorinated monomer represented by the formula: 6.67 g of 4-hydroxybutyl acrylate, 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.56 g of propylene glycol monoethyl ether acetate, 2,2′-azo Bisisobutyronitrile (0.26 g) and lauryl mercaptan (0.78 g) were added to prepare a reaction solution.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B1. The weight average molecular weight (in terms of polystyrene) determined by GPC using tetrahydrofuran as a developing solvent was 8000.

<Synthesis Example 2> Synthesis of fluorinated oligomer B2 In an eggplant flask subjected to nitrogen substitution, 10 g of fluorinated oligomer solution B1, 0.20 g of 2-isocyanatoethyl acrylate, and 1,4-diazabicyclo [2.2. 2] 0.003 g of octane was added. Then, it stirred at 50 degreeC for 12 hours, and cooled to room temperature. The completion of the reaction was confirmed using FT-IR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B2.

<Synthesis Example 3> Synthesis of fluorinated oligomer B3 In a three-necked flask equipped with a cooling tube, 16.67 g of a fluorinated monomer represented by the following general formula (b2), 6.67 g of 4-hydroxybutyl acrylate, 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.56 g of propylene glycol monoethyl ether acetate, 0.26 g of 2,2′-azobisisobutyronitrile and 0.78 g of lauryl mercaptan were added to the reaction solution. did.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B3. The weight average molecular weight (polystyrene equivalent) determined by GPC using tetrahydrofuran as a developing solvent was 8200.

<Synthesis Example 4> Synthesis of fluorinated oligomer B4 In a three-necked flask equipped with a cooling tube, 16.67 g of a fluorinated monomer represented by the following general formula (b3), 6.67 g of 4-hydroxybutyl acrylate, 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.56 g of propylene glycol monoethyl ether acetate, 0.26 g of 2,2′-azobisisobutyronitrile, and 0.78 g of lauryl mercaptan were added to the reaction solution. did.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B4. When the weight average molecular weight (polystyrene conversion) was determined by GPC using tetrahydrofuran as a developing solvent, it was 7500.

<Synthesis Example 5> Synthesis of fluorinated oligomer B5 In a three-necked flask equipped with a cooling tube, 16.67 g of a fluorinated monomer represented by the following general formula (b4), 6.67 g of 4-hydroxybutyl acrylate, 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.56 g of propylene glycol monoethyl ether acetate, 0.26 g of 2,2′-azobisisobutyronitrile, and 0.78 g of lauryl mercaptan were added to the reaction solution. did.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B5. The weight average molecular weight (in terms of polystyrene) determined by GPC using tetrahydrofuran as a developing solvent was 8000.

<Synthesis Example 6> Synthesis of fluorinated oligomer B6 In a three-necked flask equipped with a cooling tube, the following general formula (b5, λmax (ε) = 234 (65000), 268.5 (12500), 332 (2390) (In acetonitrile) 16.67 g of fluorine-containing monomer, 6.67 g of 4-hydroxybutyl acrylate, 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.56 g of propylene glycol monoethyl ether acetate, 2 , 2′-azobisisobutyronitrile (0.26 g) and lauryl mercaptan (0.78 g) were added to prepare a reaction solution.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B6. When the weight average molecular weight (polystyrene conversion) was determined by GPC using tetrahydrofuran as a developing solvent, it was 8500.

<Synthesis Example 7> Synthesis of fluorinated oligomer B7 In a three-necked flask equipped with a cooling tube, 16.67 g of a fluorinated monomer represented by the following general formula (b6), 6.67 g of 4-hydroxybutyl acrylate, A reaction solution was prepared by adding 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.56 g of propylene glycol monomethyl ether acetate, 0.26 g of 2,2′-azobisisobutyronitrile, and 0.78 g of lauryl mercaptan. .
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B7. The weight average molecular weight (polystyrene conversion) determined by GPC using tetrahydrofuran as a developing solvent was 8800.

<Synthesis Example 8> Synthesis of fluorinated oligomer B8 Fluorinated monomer represented by the following general formula (b7, λmax (ε) = 279 (29420) (in acetonitrile)) in a three-necked flask equipped with a cooling tube. 16.67 g, 6.67 g of 4-hydroxybutyl acrylate, 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.56 g of propylene glycol monomethyl ether acetate, 0.26 g of 2,2′-azobisisobutyronitrile , And 0.78 g of lauryl mercaptan was added to prepare a reaction solution.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B8. The weight average molecular weight (polystyrene conversion) determined by GPC using tetrahydrofuran as a developing solvent was 8600.

<Synthesis Example 9> Synthesis of fluorinated oligomer B9 A fluorinated monomer represented by the following general formula (b8, λmax (ε) = 227 (1030) (in acetonitrile)) in a three-necked flask equipped with a cooling tube. 16.67 g, 6.67 g of 4-hydroxybutyl acrylate, 10 g of 2- (2-methoxyethoxy) ethyl methacrylate, 51.24 g of propylene glycol monomethyl ether acetate, 0.30 g of 2,2′-azobisisobutyronitrile And 0.80 g of lauryl mercaptan.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass. The weight average molecular weight (in terms of polystyrene) determined by GPC using tetrahydrofuran as a developing solvent was 6200. 10 g of the obtained fluorine-containing oligomer solution, 0.20 g of 2-isocyanatoethyl acrylate, and 0.003 g of 1,4-diazabicyclo [2.2.2] octane were placed in an eggplant flask subjected to nitrogen substitution. Then, it stirred at 50 degreeC for 12 hours, and cooled to room temperature. The completion of the reaction was confirmed using FT-IR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B9.

<Synthesis Example 10> Synthesis of fluorinated oligomer B10 In a three-necked flask equipped with a cooling tube, the following general formula (b1, λmax (ε) = 232.5 (10390), 257 (5940) (in acetonitrile)) 16.67 g of a fluorine-containing monomer represented by the formula: 6.67 g of 4-hydroxybutyl acrylate, 8 g of 2- (2-methoxyethoxy) ethyl methacrylate, 2 g of methacrylic acid, 51.56 g of propylene glycol monomethyl ether acetate, 2,2 A reaction solution was prepared by adding 0.26 g of '-azobisisobutyronitrile and 0.78 g of lauryl mercaptan.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B10. The weight average molecular weight (in terms of polystyrene) determined by GPC using tetrahydrofuran as a developing solvent was 5000.

<Synthesis Example 11> Synthesis of fluorinated oligomer B11 In a three-necked flask equipped with a cooling tube, the following general formula (b1, λmax (ε) = 232.5 (10390), 257 (5940) (in acetonitrile)) 16.67 g of a fluorine-containing monomer represented by the formula: 6.67 g of 4-hydroxybutyl acrylate, 5 g of 2- (2-methoxyethoxy) ethyl methacrylate, 5 g of 3,4-epoxycyclohexylmethyl methacrylate, propylene glycol monomethyl ether acetate 51.56 g, 2,2′-azobisisobutyronitrile 0.26 g, and lauryl mercaptan 0.78 g were added to prepare a reaction solution.
[Rf is a mixture having the structure shown in the general formula group (3)]

  Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed using 1H-NMR. After cooling, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass to obtain a fluorine-containing oligomer solution B11. The weight average molecular weight (polystyrene conversion) determined by GPC using tetrahydrofuran as a developing solvent was 8800.

<Synthesis Example 12> Synthesis of Binder Resin A-PI (Soluble Polyimide) 27.8 g of dimer amine and 87.5 g of dehydrated and purified xylene in a glass reaction vessel equipped with a heat-dried Dean-Stark trap in a dry nitrogen stream. I put it in. After stirring for a while, 87.5 g of dehydrated and purified N-methylpyrrolidone and 47.2 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride were added, and the temperature increase was started. The polymerization reaction was performed at 170 to 180 ° C. for 4 hours. Meanwhile, water generated by dehydration condensation and xylene as an azeotropic solvent were excluded from the reaction system by a Dean-Stark trap. After the temperature was lowered, the mixture was diluted with N-methylpyrrolidone so that the solid content concentration was 35% by mass to obtain a binder resin A-PI.

<Formulation Example 1> Preparation of Evaluation Inkjet Ink Pigment Red 254 was dispersed in a bead mill using diethylene glycol monoethyl ether acetate as a solvent in the presence of a polymer dispersant to prepare a red dispersion. Based on this dispersion, the composition described below was mixed.
Pigment Red 254: 4.1 parts by mass polymer dispersant: 2.3 parts by mass diethylene glycol monoethyl ether acetate (manufactured by Daicel Chemical Industries): 60.4 parts by mass pentaerythritol triacrylate (manufactured by Nippon Kayaku): 28.4 masses Part 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF Japan): 3.9 parts by mass 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) : 0.6 part by mass surfactant (manufactured by Big Chemie Japan, trade name “BYK-378”): 0.1 part by mass

  The mixed solution obtained above was subjected to pressure filtration with a 1 μm depth filter to produce an inkjet ink for evaluation. The viscosity of the prepared ink-jet ink was 11.3 mPa · sec (measured by 23 ° C., RE type viscometer (Toki Sangyo)), and the surface tension was 22.3 mN / m (23 ° C., CBVP-Z (Kyowa Interface Science)). Measurement).

<Example 1>
Including 10 g of EHPE-3150 (component (A), solid epoxy resin manufactured by Daicel Chemical Industries: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol) Fluorine oligomer solution B1 ((B) component, 20 mass% solution) 0.25 g, CPI-100P ((C) component, San Apro photoacid generator, 50 mass% solution) 0.4 g, propylene glycol monomethyl ether acetate ( (D) 30 g of a component (manufactured by Daicel Chemical Industries) was mixed. Next, the substrate treatment agent for inkjet 1 was prepared by filtering using a 2 μm polypropylene membrane filter.

The obtained surface treatment agent 1 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. The pre-baked resin layer had a contact angle of 49 ° with diethylene glycol monoethyl ether acetate. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 11 ° in the portion subjected to light irradiation and heating.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). A photomicrograph at this time is shown in FIG. As can be seen from this photograph, the ink spreads out in the lyophilic part of the lyophilic part (line / space = 30 μm / 30 μm) having the lyophilic part and the lyophobic part with respect to the inkjet ink for evaluation. A red line of about 30 μm was formed by repelling the ink.

<Example 2>
EHPE-3150 (component (A), Daicel Chemical Solid Epoxy Resin) 10 g, fluorine-containing oligomer solution B2 (component (B), 20% by mass solution) 0.25 g, CPI-100P (component (C), San Apro light 0.4 g of acid generator, 50% by mass solution) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Subsequently, the base-treatment agent 2 for inkjets was adjusted by filtering using a 2 micrometers polypropylene membrane filter.

The obtained surface treatment agent 2 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. About the resin layer after a prebaking, the contact angle with respect to diethylene glycol monoethyl ether acetate was 48 degrees. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 10 ° or less in the portion where light irradiation and heating were performed.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 3>
jER YX-4000HK (component (A), Mitsubishi Chemical solid epoxy resin: biphenyl type epoxy) 10 g, fluorine-containing oligomer solution B3 (component (B), 20% by mass solution) 0.25 g, GSID26-1 ((C) Ingredients, 0.2 g of BASF photoacid generator) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical) were mixed. Next, the substrate treatment agent for inkjet 3 was prepared by filtering using a 2 μm polypropylene membrane filter.

The obtained ground treatment agent 3 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. About the resin layer after a prebaking, the contact angle with respect to diethylene glycol monoethyl ether acetate was 48 degrees. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 10 ° or less in the portion where light irradiation and heating were performed.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 4>
jER YX-4000HK ((A) component, solid epoxy resin manufactured by Mitsubishi Chemical) 10 g, fluorine-containing oligomer solution B4 ((B) component, 20 mass% solution) 0.25 g, GSID26-1 ((C) component, manufactured by BASF) 0.2 g of photoacid generator) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical) were mixed. Subsequently, the base-coat agent 4 for inkjets was adjusted by filtering using a 2 micrometers polypropylene membrane filter.

The obtained ground treatment agent 4 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. About the resin layer after prebaking, the contact angle with respect to diethylene glycol monoethyl ether acetate was 47 °. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 10 ° or less in the portion where light irradiation and heating were performed.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm).

<Example 5>
ST-4000D (component (A), Nippon Steel & Sumikin Chemical solid epoxy resin: hydrogenated BPA type special epoxy) 10 g, fluorine-containing oligomer solution B5 (component (B), 20 mass% solution) 0.25 g, CPI-100P ( Component (C), San Apro-made photoacid generator, 50% by mass solution) 0.4 g, and propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical) 30 g were mixed. Subsequently, the base-coat agent 5 for inkjet was adjusted by filtering using a 2 micrometers polypropylene membrane filter.

The obtained surface treatment agent 2 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. About the resin layer after prebaking, the contact angle with respect to diethylene glycol monoethyl ether acetate was 47 °. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 10 ° or less in the portion where light irradiation and heating were performed.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 6>
ST-4000D (component (A), Nippon Steel & Sumikin Chemical solid epoxy resin) 10 g, fluorine-containing oligomer solution B6 (component (B), 20% by mass solution) 0.25 g, CPI-100P (component (C), San Apro) 0.4 g of a photoacid generator, 50% by mass solution) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Subsequently, the base-coat agent 6 for inkjets was adjusted by filtering using a 2 micrometers polypropylene membrane filter.

The obtained ground treatment agent 6 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. About the resin layer after a prebaking, the contact angle with respect to diethylene glycol monoethyl ether acetate was 44 degrees. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 10 ° or less in the portion where light irradiation and heating were performed.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 7>
ST-4000D (component (A), Nippon Steel & Sumikin Chemical solid epoxy resin) 10 g, fluorine-containing oligomer solution B6 (component (B), 20% by mass solution) 0.25 g, CPI-100P (component (C), San Apro) 0.4 g of a photoacid generator, 50% by mass solution) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Next, the substrate treatment agent for inkjet 7 was prepared by filtering using a 2 μm polypropylene membrane filter.

The obtained surface treatment agent 7 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. About the resin layer after a prebaking, the contact angle with respect to diethylene glycol monoethyl ether acetate was 44 degrees. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 10 ° or less in the portion where light irradiation and heating were performed.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 8>
ST-4000D (component (A), Nippon Steel & Sumikin Chemical solid epoxy resin) 10 g, fluorine-containing oligomer solution B8 (component (B), 20% by mass solution) 0.25 g, CPI-100P (component (C), San Apro) 0.4 g of a photoacid generator, 50% by mass solution) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Subsequently, the base-treatment agent 8 for inkjets was adjusted by filtering using a 2 μm polypropylene membrane filter.

The obtained surface treatment agent 8 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. About the resin layer after a prebaking, the contact angle with respect to diethylene glycol monoethyl ether acetate was 44 degrees. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. In the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate was lowered to 10 ° or less in the portion where light irradiation and heating were performed.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 9>
EHPE-3150 ((A) component, solid epoxy resin made by Daicel Chemical Industries) 10 g, fluorinated oligomer solution B10 ((B) component, 20 mass% solution) 0.25 g, CPI-100P ((C) component, San Apro light) 0.4 g of acid generator, 50% by mass solution) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Subsequently, the base-coat agent 9 for inkjet was adjusted by filtering using a 2 micrometers polypropylene membrane filter.

The obtained surface treatment agent 9 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. went. The contact angle on the substrate with respect to diethylene glycol monoethyl ether acetate after pre-baking was 48 °. When this substrate was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line standard) and then heated at 70 ° C. for 5 minutes, the contact angle on the substrate to diethylene glycol monoethyl ether acetate was 12 °. Declined.

At the time of exposure, a quartz photomask (line / space = 30 μm / 30 μm) is applied for exposure (5000 mJ / cm ² , based on i-line), and this substrate is heated at 70 ° C. for 5 minutes to form a line / space. = Lipophilic patterning of 30 μm / 30 μm was performed. 14 pl of the inkjet ink for evaluation was ejected onto this substrate using an inkjet head manufactured by Konica Minolta IJ (piezo element drive type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 10>
EHPE-3150 ((A) component, solid epoxy resin made by Daicel Chemical Industries) 10 g, fluorinated oligomer solution B11 ((B) component, 20 mass% solution) 0.25 g, CPI-100P ((C) component, San Apro light) 0.4 g of acid generator, 50% by mass solution) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Next, the substrate treatment agent for inkjet 10 was prepared by filtering using a 2 μm polypropylene membrane filter.

The obtained ground treatment agent 10 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. went. The contact angle on the substrate with respect to diethylene glycol monoethyl ether acetate after pre-baking was 48 °. When this substrate was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line standard) and then heated at 70 ° C. for 5 minutes, the contact angle on the substrate to diethylene glycol monoethyl ether acetate was 11 °. Declined.

At the time of exposure, a quartz photomask (line / space = 30 μm / 30 μm) is applied for exposure (5000 mJ / cm ² , based on i-line), and this substrate is heated at 70 ° C. for 5 minutes to form a line / space. = Lipophilic patterning of 30 μm / 30 μm was performed. 14 pl of the inkjet ink for evaluation was ejected onto this substrate using an inkjet head manufactured by Konica Minolta IJ (piezo element drive type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 11>
28.57 g of soluble polyimide A-PI ((A) component, 35 mass% solution) synthesized in Synthesis Example 12, 0.5 g of fluorine-containing oligomer solution B1 ((B) component, 20 mass% solution), CPI-100P ( Component (C), San Apro photoacid generator, 50% by mass solution) 0.4 g, and N-methylpyrrolidone (component (D)) 11.43 g were mixed. Subsequently, the ink-jet base treatment agent 11 was prepared by filtering using a 2 μm polypropylene membrane filter.

The obtained surface treatment agent 11 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. went. The contact angle on the substrate to diethylene glycol monoethyl ether acetate after pre-baking was 44 °. When this substrate was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line standard) and then heated at 70 ° C. for 5 minutes, the contact angle on the substrate to diethylene glycol monoethyl ether acetate was 12 °. Declined.

At the time of exposure, a quartz photomask (line / space = 30 μm / 30 μm) is applied for exposure (5000 mJ / cm ² , based on i-line), and this substrate is heated at 70 ° C. for 5 minutes to form a line / space. = Lipophilic patterning of 30 μm / 30 μm was performed. 14 pl of the inkjet ink for evaluation was ejected onto this substrate using an inkjet head manufactured by Konica Minolta IJ (piezo element drive type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Example 12>
V-259ME (component (A), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 56 mass% solution of radical reactive solid resin) 12.5 g, fluorine-containing oligomer solution B2 (component (B), 20 mass% solution) 0.5 g, CPI- 100 P (component (C), San Apro photoacid generator, 50 mass% solution) 0.4 g, propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical) 24.5 g, light acrylate BP-4EA (others 3 g of components, manufactured by Kyoeisha Chemical Co., Ltd.) and 0.2 g of Irgacure OXE01 (other components, manufactured by BASF Japan) were mixed. Next, the substrate treatment agent for inkjet 12 was prepared by filtering using a 2 μm polypropylene membrane filter.

The obtained ground treatment agent 12 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. went. The contact angle on the substrate with respect to diethylene glycol monoethyl ether acetate after pre-baking was 48 °. When this substrate was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line standard) and then heated at 70 ° C. for 5 minutes, the contact angle on the substrate to diethylene glycol monoethyl ether acetate was 11 °. Declined.

At the time of exposure, a quartz photomask (line / space = 30 μm / 30 μm) is applied for exposure (5000 mJ / cm ² , based on i-line), and this substrate is heated at 70 ° C. for 5 minutes to form a line / space. = Lipophilic patterning of 30 μm / 30 μm was performed. 14 pl of the inkjet ink for evaluation was ejected onto this substrate using an inkjet head manufactured by Konica Minolta IJ (piezo element drive type, KM512M). In the same manner as in Example 1, the ink spreads out in the lyophilic portion of the lyophilic and liquid repellent patterning (line / space = 30 μm / 30 μm), and the red line of about 30 μm was formed by repelling the ink in the lyophobic portion.

<Comparative Example 1>
EHPE-3150 ((A) component, solid epoxy resin made by Daicel Chemical Industries) 10 g, fluorinated oligomer solution B9 ((B) component, 20 mass% solution) 0.25 g, CPI-100P ((C) component, San Apro light) 0.4 g of acid generator, 50% by mass solution) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Subsequently, the base-coat agent 9 for inkjet was adjusted by filtering using a 2 micrometers polypropylene membrane filter.

The obtained surface treatment agent 9 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. The pre-baked resin layer had a contact angle of 49 ° with diethylene glycol monoethyl ether acetate. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. As for the resin layer after heating, the contact angle with respect to diethylene glycol monoethyl ether acetate in the portion subjected to light irradiation and heating hardly decreased to 46 °.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). Unlike the case of the example, the ink was only spread in a circular shape without distinguishing between the lyophilic portion and the lyophobic portion of the lyophilic / repellent patterning.

<Comparative example 2>
YX-4000HK (component (A), Mitsubishi Chemical solid epoxy resin) 10 g, fluorine-containing oligomer solution B9 (component (B), 20% by mass solution) 0.25 g, GSID26-1 (component (C), light produced by BASF 0.2 g of acid generator) and 30 g of propylene glycol monomethyl ether acetate (component (D), manufactured by Daicel Chemical Industries) were mixed. Next, the substrate treatment agent for inkjet 10 was prepared by filtering using a 2 μm polypropylene membrane filter.

The obtained ground treatment agent 10 was applied onto a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after prebaking was 2 μm, and prebaked at 70 ° C. for 3 minutes using a hot plate. The resin layer was formed on the glass substrate. The pre-baked resin layer had a contact angle of 49 ° with diethylene glycol monoethyl ether acetate. Next, the substrate provided with the resin layer was exposed to an ultra-high pressure mercury lamp (5000 mJ / cm ² , i-line reference), and then heated at 70 ° C. for 5 minutes. Regarding the heated resin layer, the contact angle with respect to diethylene glycol monoethyl ether acetate in the portion subjected to light irradiation and heating hardly decreased to 44 °.

In the case of the above exposure, a quartz photomask (line / space = 30 μm / 30 μm) is placed on the resin layer for exposure (5000 mJ / cm ² , based on the i-line), and the whole substrate is heated at 70 ° C. for 5 minutes. Thus, lyophilic / liquid repellent patterning of line / space = 30 μm / 30 μm was performed. Then, 14 pl of the inkjet ink for evaluation was ejected onto the substrate provided with the resin layer by using an inkjet head manufactured by Konica Minolta IJ (piezo element driving type, KM512M). Unlike the case of the example, the ink was only spread in a circular shape without distinguishing between the lyophilic portion and the lyophobic portion of the lyophilic / repellent patterning.

Claims (5)

In an inkjet base treatment agent that performs a surface treatment on a substrate used for inkjet printing in advance,
The base treatment agent contains at least a binder resin (A), a fluorine-containing oligomer (B), a photoacid generator (C), and a solvent (D).
The resin layer formed with the surface treatment agent can be formed into a lyophilic / liquid repellent pattern having a lyophilic portion and a lyophobic portion by light irradiation through a pattern mask or light irradiation through a pattern mask and heating. Because
The contact angle with respect to diethylene glycol monoethyl ether acetate before light irradiation or light irradiation and heating of the resin layer is 40 ° or more, and the portion with respect to diethylene glycol monoethyl ether acetate subjected to light irradiation or light irradiation and heating. The contact angle is 15 ° or less,
A treating agent for an ink jet base comprising a copolymer that is polymerized with a fluorine-containing monomer represented by the following general formula (1) as an essential component as the fluorine-containing oligomer (B).
[R1 in General Formula (1) is a hydrogen atom or a methyl group. X is a direct bond, -C (= O) O - , - OC (= O) -, - CH 2 OC (= O) - is either. Y is a direct bond or a divalent organic group (having 1 to 10 carbon atoms and may contain an oxygen atom or a nitrogen atom). Ar is any one of the structures described in the general formula group (2). ]
[R2 to R57 are each independently a hydrogen atom, alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, Alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, amino group which may be substituted, cyano A nitro group or a halogen atom, one of R2 to R7, one of R8 to R15, one of R16 to R25, one of R26 to R31, or R32 to R39 One of them, one of R40 to R47, and One of R48 to R57 is X in the general formula (1), and at least one of R2 to R7, at least one of R8 to R15, and at least one of R16 to R25. At least one of R26 to R31, at least one of R32 to R39, at least one of R40 to R47, and at least one of R48 to R57 are each Rf-O- (Rf represents any one of the following general formula group (3)). M is any one of an oxygen atom, a sulfur atom, and> N-R58, and R58 is a monovalent organic group having 1 to 10 carbon atoms and may contain an oxygen atom or a nitrogen atom. ]
  The binder resin (A) is an epoxy resin (A1), and the ink jet primer treatment agent according to claim 1.   The mass ratio of the epoxy resin (A1), the fluorine-containing oligomer (B), and the photoacid generator (C) in the base treatment agent is (A) / (B) / (C) = 100/2 to 0.1. It is the range of /10-0.5, The processing agent for inkjet base materials of Claim 2 characterized by the above-mentioned.   4. The inkjet base treatment agent according to claim 2, wherein at least 50 mass% of the epoxy resin (A1) is solid at normal temperature (23 ° C.). 5. Photoacid generator (C) is diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, CF ₃ SO ₃ salt, p-CH ₃ PhSO ₃ salt, p-NO ₂ PhSO ₃ salt (where Ph is The inkjet base material according to claim 1, wherein the inkjet base material is at least one selected from the group consisting of an organic halogen compound, orthoquinone-diazide sulfonyl chloride, and a sulfonic acid ester. Treatment agent.