JP5516484B2 - Positive-type liquid repellent resist composition - Google Patents

Description

  The present invention relates to a liquid repellent resist composition (LYOPHOBIC RESIST COMPOSITION) for producing a pattern surface comprising a liquid repellent region and a lyophilic region by a photolithography method.

  In order to manufacture display pixels, wiring, thin film transistors (TFTs), biochips, and other devices using printing techniques such as inkjet, the substrate is lyophobic and lyophilic on the micrometer scale in advance by photolithography. Must be patterned. Liquid repellent-a resist having both liquid repellency (water-insoluble) and developability (solubility in an aqueous alkali solution) which are considered to be contradictory properties for forming a lyophilic pattern (hereinafter referred to as "liquid repellent resist") Nomenclature) A composition is required, and the following two technologies are disclosed as fluorine-based polymers to be blended therein.

  Patent Publication No. 2008-287251 includes (i) an α-substituted acrylate containing a fluoroalkyl group having 4 to 6 carbon atoms (hereinafter abbreviated as Rf group), (ii) an unsaturated organic acid, A copolymer-based fluoropolymer comprising (iii) an epoxy group-containing monomer and (iv) an alkyleneoxy group-containing monomer is disclosed, and Japanese Patent No. 4370843 discloses a perfluoropolyether group and an acidic group. A liquid repellent resist composition obtained from a fluorine-based polymer having a group as an essential component is disclosed.

  However, such a conventional liquid repellent resist composition is a negative resist in which the ultraviolet irradiation part is cured, and does not correspond to a positive resist in which the ultraviolet irradiation part becomes alkali-soluble and can be developed. A positive resist is more suitable for fine processing than a negative resist. In addition, after applying the functional material ink in a pattern after forming the liquid repellent pattern, if the liquid repellent pattern becomes unnecessary, the liquid repellent pattern can be removed by exposing the substrate to the whole surface and treating with an alkali developer. There are features. When a fluorine-based polymer designed for a negative resist is used for a positive resist, there is a problem that a residue remains during development.

  On the other hand, International Publication No. WO2008 / 090828 (Nissan Chemical) has a total of four types of functional groups: two functional groups having thermal crosslinkability, a functional group having a fluoroalkyl group, and a functional group containing a silicon atom. A positive photosensitive resin composition containing an alkali-soluble resin as a main component is disclosed. However, the photosensitive properties of this composition are not necessarily sufficient for oil repellency, and since it has a functional group having a silicon atom, the storage stability is not necessarily sufficient, and further improvement is required. .

Patent Publication No. 2008-287251 Japanese Patent No. 4370843 International Publication No. WO2008 / 090828

  Therefore, a positive resist composition containing a fluorine polymer in which the upper surface of the resist film after development is liquid repellent is desired. An object of the present invention is to provide a positive type liquid repellent resist composition containing a fluoroacrylate copolymer having a specific structure and capable of achieving both liquid repellency and developability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a positive resist composition containing a specific fluorine-based polymer. Reached. That is, the present invention provides a positive resist composition containing a fluorine-based polymer and having both good liquid repellency and developability.

The present invention is a liquid repellent resist composition,
(A1) α-substituted acrylate having a fluoroalkyl group having 4 to 8 carbon atoms [which may have an etheric oxygen atom between carbon atoms] [the substituent at the α-position is a fluorine atom, a chlorine atom, bromine; Atom, iodine atom, 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 alkyl group having 1 to 20 carbon atoms] 100 parts by weight,
(A2) Unsaturated organic acid [the acidic group may be protected with an acid ester-forming group] 30 to 60 parts by weight,
(A3) 10-25 parts by weight of an epoxy group-containing monomer, and (a4) (R ¹ O) _n R ² [R ¹ is — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ —, R ² is hydrogen or Containing a fluorine-based polymer (A) having a repeating unit of 40 to 80 parts by weight of a monomer containing an alkyleneoxy group represented by a methyl group, n is 1 to 10,
Provided is a positive-type liquid repellent resist composition having a fluorine concentration of 15 to 40% by weight and a weight average molecular weight of 3,000 to 20,000 of the fluorine-based polymer (A).

  The present invention also provides a method for producing a thin film transistor (TFT) substrate using the positive-type liquid repellent resist composition, a TFT substrate obtained by the production method, a method for producing an organic EL pixel, and an organic EL pixel obtained by the production method. Provided is an organic EL device containing the same.

  The lyophobic resist composition of the present invention can form a lyophobic-lyophilic pattern having a clear wetting contrast on a substrate. That is, by using the lyophobic resist composition of the present invention, a pattern comprising a lyophilic region and a lyophobic region can be formed on a substrate by, for example, a photolithography method. Sufficient liquid repellency is imparted to the liquid region, (2) there is little residue after development, and (3) the fluoropolymer is less likely to be eluted into the lyophilic region during development [(1) to (3) are so-called “ This means that the pattern is cut off.] (4) The fluorine-based polymer exhibits high compatibility with the resist constituents, and (5) the coating property to the substrate is good.

Hereinafter, the present invention will be described in detail.
<Monomers used for fluoropolymer production>
In the fluorine-based polymer (A) used in the liquid repellent resist composition of the present invention, the component (a1) is a fluoroalkyl group having 4 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms). Α-substituted acrylate having 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) further contains an unsaturated organic acid (a2), an epoxy group-containing monomer (a3), and a monomer (a4) containing an alkyleneoxy group.

The composition ratio of the components (a1), (a2), (a3) and (a4) of the fluoropolymer (A) is as follows:
The unsaturated organic acid (a2) may be 30 to 60 parts by weight, preferably 35 to 55 parts by weight, based on 100 parts by weight of the α-substituted acrylate (a1).
The epoxy group-containing monomer (a3) may be 10 to 25 parts by weight, preferably 10 to 20 parts by weight,
The monomer (a4) containing an alkyleneoxy group may be 40 to 80 parts by weight, preferably 50 to 70 parts by weight, for example, 50 to 65 parts by weight.
The α-substituted acrylate (a1) is preferably 20 to 70% by weight, more preferably 30 to 65% by weight, for example 40 to 55% by weight, based on the fluoropolymer (A).

In the fluoropolymer (A), the fluorine concentration may be 10 to 40% by weight, preferably 15 to 35% by weight, more preferably 15 to 25% by weight, and the weight average molecular weight is 3,000 to 20,000. , Preferably 5,000 to 15,000.
By reducing the α-substituted acrylate (a1) and increasing the amount of the (a2) epoxy group-containing monomer, (i) compatibility of the fluorinated polymer in the liquid repellent resist composition, (ii) cross-linking with other raw materials And (iii) alkali solubility can be improved.

  When the α-substituted acrylate (a1) constituting the fluorine-based polymer (A) is 40 to 55% by weight and the fluorine concentration of the fluorine-based polymer (A) is 15 to 25% by weight, the liquid repellency is It is high and has good compatibility with other components constituting the liquid repellent resist composition. When the weight average molecular weight of the fluorinated polymer (A) is from 5,000 to 15,000, the surface segregation of the fluorinated polymer (A) in the liquid repellent resist film is excellent, and a small amount is sufficient for liquid repellency. Can be granted.

When a hydroxyl group-containing monomer is used as the alkyleneoxy group-containing monomer (a4) of the fluorine-based polymer (A), an isocyanate group-containing (meth) acrylate may be further reacted with the hydroxyl group in the polymer.
The fluoropolymer (A) may be random, alternating, block, or graft copolymer.

［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であり、
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、−（ＣＨ２）_ｎＳＯ_２−基（ｎは１〜１０）である。Ｒｆは炭素数４〜８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) - (CH2) n SO} 2. Rf is a linear or branched fluoroalkyl group having 4 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms)]
It is preferable that

When Rf is a perfluoroalkyl group not containing an etheric oxygen atom between carbon atoms, a perfluoroalkyl group having 4 to 6 carbon atoms is particularly preferable.
When Rf is a perfluoropolyether group containing an etheric oxygen atom between carbon atoms, it is particularly preferred that it has 6 to 8 carbon atoms.
Examples of the α-substituted acrylate (a1) are as follows.

Rf-SO₂(CH₂)₃-OCO-CH=CH₂

Rf-SO ₂ (CH ₂ ) ₃ -OCO-CH = CH ₂

CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ N (-CH ₃ ) SO ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ N (-C ₂ H ₅ ) SO ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O-CH ₂ CH (-OH) CH ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O-CH ₂ CH (-OCOCH ₃ ) CH ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O)-NH- (CH ₂ ) ₂ -Rf
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 is a linear or branched fluoroalkyl group having 4 to 8 carbon atoms (which may have an etheric oxygen atom between carbon atoms)]

The unsaturated organic acid (a2) is a monomer having at least one carbon-carbon double bond and at least one acid group [for example, a carboxyl group (COOH group)], and the acid value of the fluoropolymer (A). Is 10 to 200 mgKOH / g. Here, when the acidic group is protected with an acid ester-forming group, for example, the acid value of the fluoropolymer (A) after being deprotected by hydrolysis with an acid from a photoacid generator is 10 It is preferable to carry out the copolymerization so that it becomes -200 mgKOH / g. Therefore, the acid value of the fluoropolymer (A) before deprotection may be less than 10.
The acid value is defined in JIS0070.2.1, and means the number of mg of potassium hydroxide required to neutralize free fatty acid, resin acid, etc. contained in 1 g of a sample. Particularly preferred examples of unsaturated organic acids are unsaturated carboxylic acids, such as free unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. Examples of unsaturated organic acids (a4) are (meth) acrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, phthalic anhydride, tetrahydrophthalic anhydride and silicic acid. For example, cinnamate. The unsaturated organic acid (a2) imparts solubility with an alkali developer in the electromagnetic wave irradiation region to the fluorine-based polymer (A).

  Here, the acid ester forming group which is an acidic group protecting agent is a group that is hydrolyzed and deprotected by the acid generated from the photoacid generator. Conventionally, in resist materials, particularly chemically amplified resist materials. Any known acid ester forming group used may be used. For example, groups represented by the following general formulas (L1) to (L4), tertiary alkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms (for example, t-butyl group, t-amyl group, etc.), each alkyl Examples thereof include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

  Here, a broken line shows a bond. In the formula (L1), RL01 and RL02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10, specifically hydrogen atom, methyl group, ethyl Group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, adamantyl group and the like. RL03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, In which a part of the hydrogen atom is substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, etc., specifically, as a linear, branched or cyclic alkyl group Can be the same as those described above for RL01 and RL02, and examples of the substituted alkyl group include the following groups.

  Here, RL01 and RL02, RL01 and RL03, RL02 and RL03 may be bonded to each other to form a ring together with the carbon atom or oxygen atom to which they are bonded. Each represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

  In the formula (L2), RL04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and oxo having 4 to 20 carbon atoms. An alkyl group or a group represented by the above general formula (L1) is shown. Specific examples of the tertiary alkyl group include tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 2-cyclopentylpropane- 2-yl group, 2-cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propane- 2-yl group, 2- (tricyclo [5.2.1.02,6] decan-8-yl) propan-2-yl group, 2- (tetracyclo [4.4.0.12,5.17, 10] Dodecan-3-yl) propa N-2-yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 8-methyl-8-tricyclo [5.2.1.02,6] decyl, 8-ethyl-8-tricyclo [5.2 1.02,6] decyl, 3-methyl-3-tetracyclo [4.4.0.12,5.17,10] dodecyl, 3-ethyl-3-tetracyclo [4.4.0.12,5 .17,10] dodecyl and the like, and specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like, and examples of the oxoalkyl group include Specifically oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-2-oxooxolan-5-yl group can be exemplified. y is an integer of 0-6.

  In the formula (L3), RL05 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted or an aryl group having 6 to 20 carbon atoms which may be substituted. Specific examples of the alkyl group which may be used include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, and n-pentyl. , N-hexyl group, cyclopentyl group, cyclohexyl group, linear, branched or cyclic alkyl groups such as bicyclo [2.2.1] heptyl group, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy Group, alkoxycarbonyl group, oxo group, amino group, alkylamino group, cyano group, mercapto group, alkylthio group, sulfo group, etc., or these Examples of the aryl group that may be substituted include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, and a phenanthryl. Examples thereof include a group and a pyrenyl group. In the formula (L3), m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

  In the formula (L4), RL06 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may be substituted; Specifically, the same as RL05 can be exemplified. RL07 to RL16 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, specifically a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec -Butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentyl Linear, branched or cyclic alkyl groups such as ethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, and cyclohexylbutyl group, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, alkoxycarbonyls Group, oxo group, amino group, alkylamino group, cyano group, mercapto group, alkyl O group, such as those substituted with a sulfo group and the like. RL07 to RL16 may be bonded to each other to form a ring together with the carbon atom to which they are bonded (for example, RL07 and RL08, RL07 and RL09, RL08 and RL10, RL09 and RL10, RL11 and RL12, RL13 and RL14, etc.), in which case the group involved in the ring formation is a divalent hydrocarbon group having 1 to 15 carbon atoms, specifically hydrogen from those exemplified for the monovalent hydrocarbon group above. The thing except one atom etc. can be illustrated. RL07 to RL16 may be bonded to each other adjacent to each other to form a double bond (for example, RL07 and RL09, RL09 and RL15, RL13 and RL15, etc.).

Of the acid ester-forming groups represented by the formula (L1), specific examples of the linear or branched ones include the following groups.

  Among the acid ester-forming groups represented by the above formula (L1), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated.

  Specific examples of the acid ester-forming group of the above formula (L2) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group, and 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Specific examples of the acid ester-forming group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec- Butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxybutyl) cyclopentyl, 1- (bicyclo [2.2.1] heptan-2-yl) cyclopentyl, 1- (7-oxabicyclo [2.2.1] ] Heptan-2-yl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methyl-2-cyclopentenyl, 1-ethyl-2-cyclopentenyl, 1-methyl-2-cyclohexenyl, 1-ethyl- Examples include 2-cyclohexenyl.

As the acid ester-forming group of the above formula (L4), groups represented by the following formulas (L4-1) to (L4-4) are particularly preferable.

  In the general formulas (L4-1) to (L4-4), a broken line indicates a coupling position and a coupling direction. RL41 independently represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Examples include butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

  In the general formulas (L4-1) to (L4-4), enantiomers and diastereomers may exist, but the general formulas (L4-1) to (L4-4) may exist. ) Represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

For example, the general formula (L4-3) represents one or a mixture of two selected from the groups represented by the following general formulas (L4-3-1) and (L4-3-2). To do.

The general formula (L4-4) represents one or a mixture of two or more selected from groups represented by the following general formulas (L4-4-1) to (L4-4-4). And

The general formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2), and formulas (L4-4-1) to (L4-4-4) are Their enantiomers and enantiomeric mixtures are also shown representatively.
In addition, the coupling | bonding of Formula (L4-1)-(L4-4), (L4-3-1), (L4-3-2), and Formula (L4-4-1)-(L4-4-4) The high reactivity in the acid-catalyzed elimination reaction is realized by the fact that each direction is on the exo side with respect to the bicyclo [2.2.1] heptane ring. In the production of a monomer having a tertiary exo-alkyl group having a bicyclo [2.2.1] heptane skeleton as a substituent, the following general formulas (L4-1-endo) to (L4-4-endo) are used. In some cases, a monomer substituted with the indicated endo-alkyl group may be included, but in order to achieve good reactivity, the exo ratio is preferably 50 mol% or more, and the exo ratio is 80 mol% or more. More preferably.

Specific examples of the acid ester-forming group of the above formula (L4) include the following groups.

  Further, tertiary alkyl groups having 4 to 20 carbon atoms, trialkylsilyl groups each having 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms, specifically, those exemplified in RL04 And the like.

  The introduction amount of the repeating unit containing an acid ester-forming group in the fluorine-based polymer (A) that is soluble in an alkali developer by the action of an acid is when all the unsaturated fatty acids (a2) amount is 100 mol%, It is desirable to substitute 5 to 80 mol%, preferably 10 to 70 mol%, more preferably 15 to 65 mol% from a2. Although the case outside the above range is not positively excluded, in this case, the balance of various performances required for the resist material may be lost.

  Examples of the epoxy group-containing monomer (a3) copolymerized for the preparation of the fluoropolymer (A) are epoxy group-containing (meth) acrylates, particularly preferably glycidyl (meth) acrylate.

An example of the monomer (a4) containing an alkyleneoxy group copolymerized for the preparation of the fluoropolymer (A) is an alkyleneoxy group-containing (meth) acrylate.
Examples of alkyleneoxy groups have the formula:
-(R ¹ O) _n R ²
[R ¹ is — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ —, R ² is hydrogen or a methyl group, and n is 1 to 10].
The monomer (a4) containing an alkyleneoxy group has the formula:
_{^{CH 2 = CR 3 COO (R}} 1 O) n R 2
A group represented by [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, (a4) 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-1000: n≈4-6, PP-500: n≈9, PP-800: n≈13, PME-100 in the Bremer PME series (methoxypolyethylene glycol monomethacrylate): n≈2, PME-200 : N≈4, PME-400: n≈9, PME-1000: n≈23, PME-4000: n≈90, etc.

  An isocyanate group-containing unsaturated compound may be reacted with the hydroxyl group at the terminal of the alkyleneoxy group in (a4) of the fluorine-based polymer (A).

  In the fluoropolymer (A) of the present invention, it is particularly preferable to use glycidyl (meth) acrylate as (a3) and hydroxyethyl (meth) acrylate as (a4) at the same time. Glycidyl (meth) acrylate has the effect of improving compatibility in the liquid repellent resist composition, crosslinkability with other raw materials, and alkali solubility. Hydroxyethyl (meth) acrylate is alkali-soluble and has the effect of improving coating properties. Here, the coating property is a function of forming a smooth coating film on the substrate. By simultaneously containing an epoxy group and a hydroxyl group in the fluoropolymer, alkali solubility becomes extremely good.

The fluorine-based polymer (A) of the present invention may be copolymerized with a high softening point monomer (a5) in the range of 5 to 20% by weight as necessary. This has the effect of maintaining the liquid repellency of the liquid repellent area when dry cleaning is performed to increase the wetting contrast of the liquid repellent-lyophilic pattern (liquid repellent dry cleaning resistance).
The high softening point monomer (a5)
CH ₂ = C (R ¹ ) COOR ²
[R ¹ is H or CH ₃ , R ² : 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 bridged hydrocarbon rings 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, for example, 1 to 5).

  Examples of the high softening point monomer (a5) are 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. 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.

The glass transition point and melting point are the extrapolated glass transition end temperature (T _eg ) and melting peak temperature (T _pm ) respectively defined by JIS K7121-1987 “Method for Measuring Plastic Transition Temperature”. When the high-softening point monomer (a3) having a glass transition point or a melting point of 100 ° C. or higher is used in the homopolymer state as the repeating unit of the fluoropolymer (A), the dimensional stability when the substrate is heat-treated is excellent. In addition, there is an effect of improving the liquid repellency of the fluorine-based monomer (A).

<Manufacture of fluoropolymers>
A fluorine-type polymer can be manufactured as follows. A monomer and necessary components are dissolved in a solvent, and after substitution with nitrogen, a polymerization initiator is added and stirred at 20 to 120 ° C., preferably 50 to 90 ° C., for 1 to 20 hours, preferably 3 to 8 hours. The method is adopted.

  As the solvent, an organic solvent, a water-soluble organic solvent, water and the like can be used (details are described later in paragraph 0075). The solvent is used in the polymerization composition in the range of 50 to 90% by weight.

  A chain transfer agent such as mercaptans or alkyl halides may be added to adjust the molecular weight of the fluorine-based polymer. 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 (a4) are in direct contact with each other, a solvent insoluble matter may be generated. Therefore, when polymerizing using both in combination, it is desirable to dilute one of them with a solvent in advance. .

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

<Ingredients in liquid repellent resist composition>
One of the liquid repellent resist compositions provided by the present invention includes an alkali-soluble resin (B), a naphthoquinonediazide group-containing compound (C), and a sensitizer (D) in addition to the fluorine-based polymer (A). And a solvent (E). A liquid repellent resist composition characterized by comprising:

The components in the liquid repellent resist composition may be the following combinations.
Fluorine-based polymer (A), alkali-soluble resin (B), naphthoquinonediazide group-containing compound (C) and solvent (E);
Fluoropolymer (A), alkali-soluble resin (B), naphthoquinonediazide group-containing compound (C), sensitizer (D) and solvent (E).

<Pattern substrate manufacturing method>
In the present invention, a substrate composed of a plurality of lyophobic regions and lyophilic regions patterned using the fluoropolymer (A), for example, by the following method (hereinafter simply referred to as “pattern substrate”). There is).

  Method (1): A novolak resin and a naphthoquinonediazide group-containing compound (hereinafter abbreviated as DNQ) (C) are dissolved in a solvent (E) as a fluorine-based polymer (A) and an alkali-soluble resin (B). Below, the principle by which this resist composition acts as a positive type will be described. Hydrophobic DNQ acts as a dissolution inhibitor and prevents the novolak resin from dissolving in the alkaline developer. When irradiated with light, DNQ releases nitrogen to form carbene, which is transferred to ketene (Wolf transition). Highly reactive ketene reacts with water in the system and changes to indenecarboxylic acid. This product is hydrophilic, has no dissolution inhibiting power, and the novolak resin becomes soluble in an alkaline developer. In the presence of indenecarboxylic acid, the dissolution rate is faster than the novolac resin itself. In this way, a large solubility contrast is generated between the light-irradiated region and the non-irradiated region, so that a positive image can be obtained by alkali development. When this positive resist composition is applied onto a substrate to form a photosensitive liquid repellent film and irradiated with electromagnetic waves through a photomask, DNQ becomes indenecarboxylic acid and the novolac resin is alkali-soluble in the light irradiated portion. Become. For this reason, only the light-irradiated portion is removed with an alkali developer, and a positive pattern substrate is obtained.

Method (2): A novolak resin, DNQ (C), and a sensitizer (D) are dissolved in the solvent (E) as the fluorine-based polymer (A) and the alkali-soluble resin (B). When this resist composition is coated on a substrate to form a photosensitive liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area becomes alkali-soluble as in the case of method (1), and alkali development is performed. By developing with a liquid, a positive pattern substrate can be obtained.
In any of the methods (1) and (2), heat treatment at about 50 to 250 ° C. may be performed before irradiation with electromagnetic waves (pre-baking) or after development (post-baking).

<Alkali-soluble resin (B)>
A representative example of the alkali-soluble resin (B) used in the present invention is an alkali-soluble novolak resin. The alkali-soluble novolak resin is not particularly limited as long as it is a resin obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.

  The phenols used in the above novolak resin are, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4 -Dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4- Examples include methyl-catechol, pyrogallol, phloroglucinol, thymol, and isothymol. These phenols can be used alone or in combination of two or more.

Examples of aldehydes to be condensed include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxy. Examples include benzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde.

Examples of the acid catalyst used for the condensation of phenols and aldehydes include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, p-toluenesulfonic acid, etc. Can do. These acid catalysts can be used alone or in combination of two or more.

The weight average molecular weight of the component (B) is preferably 1,000 to 50,000 from the viewpoints of developability and resolution of the positive resist composition.

<Naphthoquinonediazide group-containing compound (C)>
The naphthoquinonediazide group-containing compound that can be used in the present invention is not particularly limited, and examples thereof include those conventionally used as the photosensitive component of i-type positive resist compositions. Examples include naphthoquinone-1,2-diazide sulfonic acid ester compounds, orthobenzoquinone diazide sulfonic acid esters, ortho anthraquinone diazide sulfonic acid esters, etc., and these are arbitrarily selected from those usually used without limitation. Preferred are naphthoquinones such as naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-6-sulfonyl chloride, etc. An esterified product of a -1,2-diazide sulfonyl halide and a hydroxy compound is exemplified.

Examples of the hydroxy compounds include phenol, hydroquinone, resorcinol, catechol, phloroglucinol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2 ′, 4′-dihydroxyacetophenone, 2 ′, 5′-dihydroxyacetophenone, 2 ′ , 6′-dihydroxyacetophenone, 3 ′, 5′-dihydroxyacetophenone, 2 ′, 3 ′, 4′-trihydroxyacetophenone, 2 ′, 4 ′, 6′-trihydroxyacetophenone, 2,2-bis (4- Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hex Safluoropropane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, 4,4′-biphenyldiol, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 4, Phenol compounds such as 4′-dihydroxyphenyl sulfone can be mentioned.

  In particular, from the viewpoint of solubility, the naphthoquinone diazide compound is preferably naphthoquinone diazide-4-sulfonic acid ester, naphthoquinone diazide-5-sulfonic acid ester, or naphthoquinone diazide-6-sulfonic acid ester. These compounds may be used alone or in combination of two or more.

The blending amount of the naphthoquinonediazide group-containing compound (C) is within the range of 10 to 60% by weight based on the total amount of the alkali-soluble resin (B) and the following sensitizer (D) added as desired. In particular, the range of 20 to 50% by weight is preferable, and if it exceeds 60% by weight, the sensitivity is inferior, and if it is less than 10% by weight, the film is reduced in the unexposed area and the resolution is deteriorated. A faithful image cannot be obtained, which is not preferable.

<Sensitizer (D)>
The sensitizer is not particularly limited, and those conventionally known as sensitizers for i-line positive resist compositions can be used. For example, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, 1,4-bis [1- (3,5-dimethyl-4-hydroxyphenyl) isopropyl] benzene, 2, 4-bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) Nyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2,6-bis [1- (2,4-dihydroxyphenyl) isopropyl] -4-methylphenol 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcin, 4,6-bis (3,5-dimethoxy-4-hydroxyphenylmethyl) pyrogallol, 4,6-bis (3,5-dimethyl) -4-hydroxyphenylmethyl) pyrogallol, 2,6-bis (3-methyl-4,6-dihydroxyphenylmethyl) -4-methylphenol, 2,6-bis (2,3,4-trihydroxyphenylmethyl) -4-methylphenol, 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) -4-methylphenol, 1,1-biphenol (4-hydroxyphenyl) cyclohexane. In addition, 6-hydroxy-4a- (2,4-dihydroxyphenyl) -9-1'-spirocyclohexyl-1,2,3,4,4a, 9a-hexahydroxanthene, 6-hydroxy-5-methyl- 4a- (2,4-dihydroxy-3-methylphenyl) -9-1'-spirocyclohexyl-1,2,3,4,4a, 9a-hexahydroxanthene and the like can also be used. Among them, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, 2,6-bis (3,5-dimethyl-4-) Hydroxybenzyl) -4-methylphenol, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and the like are preferable.

  When mix | blending these sensitizers, the content is 5-50 weight% with respect to a phenol novolak resin, Preferably it is chosen in 10-35 weight%.

<Solvent (E)>
If necessary, a solvent such as a water-soluble organic solvent, an organic solvent (particularly an oil-soluble organic solvent) or water may be added to the liquid repellent resist composition of the present invention. The same type of solvent is also used to produce the fluoropolymer (paragraph 0065). As the solvent, a solvent which is inactive with respect to the resist constituents including the fluorine-based polymer (A) is selected, and is blended for dissolving them. Examples of solvents include water-soluble organic solvents such as acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monomethyl ether, Dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1,3-butylene glycol diacetate, cyclohexanol acetate, dimethylformamide, dimethyl sulfoxide, Methyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, Examples include rubitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol, and oil-soluble organic solvents such as chloroform, HFC141b, HCHC225, hydrofluoroether, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene. , Anisole, tetralin, cyclohexylbenzene, mesitylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, par Examples include chloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane and the like. These solvents may be used alone or in combination of two or more. As the solvent, PGMEA and MBA are particularly preferable from the viewpoints of solubility and safety of the fluorine-based polymer and the resist constituting raw material.

The solvent is preferably used in the liquid repellent resist composition in the range of 30 to 95% by weight (solid content 70 to 5% by weight), for example 50 to 90% by weight (solid content 50 to 10% by weight).
For example, as one of preferred embodiments, the present invention provides a liquid repellent in which the fluoropolymer (A) is dissolved in a glycol solvent at a concentration of 10 to 30% by weight.

In addition to the fluorine-based polymer (A), the liquid repellent resist composition of the present invention includes a compound (Q) having two or more vinyl ether groups in one molecule, and two or more blocked isocyanate groups in one molecule. A positive-type liquid repellent resist composition comprising a compound (R) having a photoacid generator (S) and a solvent (E).
The content ratio of these components is, for example, 1 to 80 parts by mass of component (Q), 1 to 80 parts by mass of component (R), and 0.5 to Contains 80 parts by weight of component (S). These components are, for example, 1 to 80% by mass, for example 5 to 60% by mass, or 10 to 50% by mass as a solid content. Here, solid content means what remove | excluded the solvent (E) from all the components of the positive photosensitive resin composition.

<Compound having two or more vinyl ether groups in one molecule: Component (Q)>
Component (Q) is a compound having two or more vinyl ether groups in one molecule, and can be thermally crosslinked with the fluoropolymer (A) at a conventional pre-baking temperature (for example, 80 ° C. to 150 ° C.). Any compound having two or more vinyl ether groups in one molecule may be used, and the type and structure are not particularly limited.

The compound of component (Q) is separated (decrosslinked) from the fluorine polymer (A) by an acid generated by exposure in the presence of a photoacid generator after thermal crosslinking with the fluorine polymer (A). Then, it is removed together with the fluorine-based polymer (A) by development using an alkaline developer. Accordingly, as this type of compound, a vinyl ether compound generally used as a component of a vinyl ether type chemically amplified resist can be applied. The use of such a compound has the advantage that the shape of the formed film can be controlled by adjusting the thermal crosslinking density by changing the compounding amount of the compound.
In addition, the compound of component (Q) is used in a proportion of 1 to 80 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of the fluoropolymer (A). When the amount of the component (Q) compound used is an excessive amount less than the lower limit of the above range, the film reduction in the unexposed area becomes remarkable and the pattern shape becomes poor. On the other hand, when the amount of the component (Q) compound used exceeds the upper limit of the above range, the sensitivity of the film is greatly lowered, and residues between patterns are generated after development.

（式中、ｎは２乃至１０の整数、ｋは１乃至１０の整数であり、Ｒ1はｎ価の有機基を表
す。）
および式（４）：

（式中、ｍは２乃至１０の整数を表す。）
で表される化合物が、露光部において残膜や残渣なく現像される点で、好ましい。 And as a compound of a component (Q), especially among the said vinyl ether type compounds, Formula (3):

(In the formula, n is an integer of 2 to 10, k is an integer of 1 to 10, and R1 represents an n-valent organic group.)
And formula (4):

(In the formula, m represents an integer of 2 to 10.)
Is preferable in that it is developed without residual film or residue in the exposed area.

  N in the formula (3) represents the number of vinyl ether groups in one molecule, and n is more preferably an integer of 2 to 4. In the formula (4), m also represents the number of vinyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.

  Specific examples of the compounds represented by formulas (3) and (4) include bis (4- (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether. , Tris (4-vinyloxy) butyl trimellrate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butyl isophthalate, and cyclohexanedimethanol divinyl ether.

<Compound having two or more blocked isocyanate groups in one molecule: Component (R)>
Component (R) is a compound having two or more blocked isocyanate groups in one molecule. This is thermosetting at a conventional post-bake temperature, for example, for a film made of a fluoropolymer (A) that has been thermally crosslinked with the compound of component (R) or further decrosslinked with it. As long as it is a compound having two or more blocked isocyanate groups in one molecule, the type and structure thereof are not particularly limited.

The compound of component (R) has two or more blocked isocyanate groups in one molecule whose isocyanate groups (—NCO) are blocked by appropriate protective groups, and is exposed to a high temperature during thermosetting. The protective group (block portion) is dissociated by thermal dissociation, and the crosslinking reaction proceeds between the functional groups for thermal curing in the fluoropolymer (A) via the generated isocyanate group.
Further, the compound of component (R) is used in a proportion of 1 to 80 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of the fluoropolymer (A). When the amount of the component (R) compound used is an excessive amount less than the lower limit of the above range, the thermosetting is insufficient and a satisfactory cured film cannot be obtained, while the amount of the component (R) compound used. If the amount exceeds the upper limit of the above range, the development is insufficient and a development residue is generated.

  Examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, etc., or dimers thereof. Trimers, or reaction products of these with diols, triols, diamines, and triamines can be used.

  Examples of the blocking agent include methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol, and other alcohols, phenol, o-nitrophenol. , P-chlorophenol, phenols such as o-, m- or p-cresol, lactams such as ε-caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime And pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole, and thiols such as dodecanethiol and benzenethiol.

式中、イソシアネート化合物がイソホロンジイソシアネートから誘導されるものである成分（Ｒ）の化合物が、耐熱性、塗膜性の点からより好ましく、斯様な化合物としては、以下のものが挙げられる。下記式中のＲは有機基を表す。 Examples of the compound of component (R) include the following specific examples.

In the formula, the compound of component (R) in which the isocyanate compound is derived from isophorone diisocyanate is more preferable from the viewpoint of heat resistance and coating properties, and examples of such a compound include the following. R in the following formula represents an organic group.

<Photoacid generator (PAG): Component (S)>
The photoacid generator (PAG) component (S) used in the present invention is a substance that generates an acid (sulfonic acid, carboxylic acid, etc.) directly or indirectly by irradiation of light used for exposure. As long as it has such properties, its type and structure are not particularly limited.

  Examples of the photoacid generator of component (S) include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazines. Examples thereof include compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation. The photoacid generator of component (S) may be used alone or in combination of two or more.

  The photoacid generator component (S) is used in a proportion of 0.5 to 80 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the fluoropolymer (A). When the amount of the photoacid generator component (S) used is an excessive amount less than the lower limit of the above range, the compound of the (Q) component that has been thermally cross-linked during the exposure may be dissociated from the fluoropolymer (A). If the amount of the photoacid generator component (S) used exceeds the upper limit of the above range, it is difficult to obtain a desired pattern-like relief. It becomes inferior in the storage stability of things.

  Specific examples of the photoacid generator component (S) include the following. However, these compounds are examples of a very large number of applicable photoacid generators, and are not limited thereto.

  Diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert- Butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis ( p-tert-butylphenyl) iodoniumtetraf Oroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium trifluoromethanesulfonate , Tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p -Methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phospho Phosphonium hexafluorophosphonate, tri (p- ethoxyphenyl) phosphonium tetrafluoroborate,

<Pattern substrate manufacturing method>
In the present invention, a substrate composed of a plurality of lyophobic regions and lyophilic regions patterned using the fluoropolymer (A), for example, by the following method (hereinafter simply referred to as “pattern substrate”). There is).

  Method (3): Fluoropolymer (A), compound (Q) containing two or more vinyl ether groups in one molecule, compound (R) containing two or more blocked isocyanate groups in one molecule, and light The acid generator (S) is dissolved in the solvent (E). A coating film can be formed by applying this resist composition onto a substrate and then pre-drying it with a hot plate or oven. Then, a positive photosensitive resin film is formed by heat-treating this coating film. As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes. The positive photosensitive resin film formed in this way is difficult for an alkali developer because the compound (Q) having a vinyl ether group is crosslinked with the resin (A) by heat treatment during formation. It becomes a soluble film. In this case, when the temperature of the heat treatment is lower than the lower limit of the above temperature range, the thermal crosslinking is insufficient, and the film may be reduced in the unexposed area. In addition, when the temperature of the heat treatment exceeds the upper limit of the above temperature range and is too high, the once formed thermal bridge portion may be cut again to cause film reduction in the unexposed portion. When a positive photosensitive resin film formed from this positive photosensitive resin composition is exposed to light such as ultraviolet rays, ArF, KrF, and F2 laser light using a mask having a predetermined pattern, positive photosensitive properties are obtained. Due to the action of the acid generated from the photoacid generator (PAG) of the (S) component contained in the resin film, the exposed portion of the film becomes soluble in an alkaline developer as described above. Subsequently, if necessary, post-exposure heating (PEB) is performed on the positive photosensitive resin film. As heating conditions in this case, a heating temperature and a heating time appropriately selected from the range of a temperature of 80 ° C. to 150 ° C. and a time of 0.3 to 60 minutes are employed. Thereafter, development is performed using an alkaline developer. As a result, the exposed portion of the positive photosensitive resin film is removed, and a pattern is formed.

  The liquid repellent resist composition of the present invention may be one obtained by blending the fluorine-based polymer (A) described in the present invention with a commercially available positive resist. For example, those in the “Sumiresin Excel CRC-8000” series of semiconductor coating materials manufactured by Sumitomo Bakelite, specifically, for example, CRC-8200 and CRC-8300 can be used. Also, OFPR-800, TSMR-V90, TMMR S2000, PMER-900 manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used. Those in the “ELPAC WPR series” manufactured by JSR, specifically, for example, WPR-1020 can be used. Zeon's positive insulation film “ZEOCOAT series” and TFT production positive photoresist “ZEONREX” “ZPP2400, ZPP2500, ZPP2600, ZPP2700 series” can be used. "NPR9000, 7800, 8000 series" manufactured by Nagase ChemteX can be used. `` TFP600 series '' manufactured by AZ Electronic Materials, specifically TFP-650F5, TFP-650H2, for example `` AZ SR series '', specifically AZ SR-100, AZ SR-110 AZ SR-210 can be used from the “AZ SFP series”, specifically, for example, AZ SFP-1400 and AZ SFP-1500.

<Pattern substrate manufacturing method>
In the present invention, using a liquid repellent resist composition in which a fluorine-based polymer (A) is blended with a commercially available positive resist, for example, from the plurality of patterned liquid repellent areas and lyophilic areas by the following method: A substrate is produced.

  Method (4): A liquid-repellent resist composition in which a fluorine-based polymer (A) is blended with a commercially available positive resist is applied on a substrate, and then pre-dried in a hot plate or oven to form a coating film. can do. Then, a positive photosensitive resin film is formed by heat-treating this coating film. As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes. The positive photosensitive resin film thus formed becomes a film that is hardly soluble in an alkaline developer by the heat treatment during the formation. When the positive photosensitive resin film formed from this positive photosensitive resin composition is exposed to light such as ultraviolet rays, ArF, KrF, and F2 laser light using a mask having a predetermined pattern, the exposed portion becomes alkaline. It becomes soluble in the developer. Subsequently, if necessary, post-exposure heating (PEB) is performed on the positive photosensitive resin film. As heating conditions in this case, a heating temperature and a heating time appropriately selected from the range of a temperature of 80 ° C. to 150 ° C. and a time of 0.3 to 60 minutes are employed. Thereafter, development is performed using an alkaline developer. As a result, the exposed portion of the positive photosensitive resin film is removed, and a pattern is formed.

<Substrate, application to substrate and patterning method>
The present invention includes a thin film transistor (TFT) comprising a step of forming a lyophobic partition wall in a pattern on a lyophilic transparent substrate by photolithography using the positive type liquid repellent resist composition. ) A method for manufacturing a substrate is provided.
The present invention also includes a step of applying a functional material ink such as a nanometal ink, an oxide semiconductor ink, and an organic semiconductor ink on a lyophilic transparent substrate having a liquid-repellent patterned partition wall, and a step of removing the solvent. A method of manufacturing a thin film transistor substrate, comprising: The present invention also provides a thin film transistor substrate manufactured by the manufacturing method.
These will be described in detail below.

The base material used for the TFT substrate of the present invention is a silicon wafer, synthetic resin, glass, metal, ceramic or the like.
The synthetic resin may be either a thermoplastic resin or a thermosetting resin. For example, polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified Polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer (AS Resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), etc. Polyester, polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoro Various thermoplastic elastomers such as ethylene, polyvinylidene fluoride, other fluorine resins, styrene, polyolefin, polyvinyl chloride, polyurethane, fluororubber, chlorinated polyethylene, ethoxy resin, phenol resin, urea resin, melamine Resins, unsaturated polyesters, silicone resins, polyurethanes, etc., and copolymers, blends, polymer alloys, etc. mainly composed of these, and one or more of these are combined. Can be used Align Te (for example, as a laminate of two or more layers). If a synthetic resin substrate is used, the substrate can be provided with features such as light weight, transparency, low cost, and bending.

Examples of the glass include silicate glass (quartz glass), alkali silicate glass, soda lime glass, potassium lime glass, lead (alkali) glass, barium glass, and borosilicate glass.
Examples of the metal include gold, silver, copper, iron, nickel, aluminum, and platinum.
Ceramics include oxides (eg, aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (eg, silicon nitride, boron nitride), sulfides (eg, cadmium sulfide), carbides (For example, silicon carbide) and the like, and a mixture thereof may be used.

Even when a substrate made of any base material is used, pre-treatment such as O ₂ plasma treatment, UV ozone treatment, corona treatment, etc. may be performed. By these pretreatments, hydrophilic functional groups (for example, OH, COOH, ═NH, —NH _2, etc.) can be introduced into the substrate surface.

  The shape of the pattern surface may be selected appropriately depending on the purpose of the element to be finally produced, and examples thereof include a circle, a square, a triangle, a straight line, and a curve. Mutual patterns may be in contact or separated. For example, in the case of a line and space, the line width and the line interval may be 0.5 to 100 μm, for example, 1 to 20 μm. The line widths may be equally spaced or the widths may vary. The shape of the line may be a straight line or a curved line.

  The liquid repellent resist composition is uniformly applied in a liquid phase to the surfaces of these substrates. As the treatment method, a known coating method can be adopted as long as the film thickness can be controlled. For example, roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted. Can be selected in consideration of the controllability and controllability of the film thickness. For example, after a liquid repellent resist composition is applied to a substrate by spin coating, the solvent is dried from the film of the liquid repellent resist composition by heating at 70 to 150 ° C. for 1 second to 10 minutes (eg, 110 ° C. for 1 minute). You can do that. With this simple process, the fluoropolymer (A) layer is formed on the surface of the film. The thickness of the liquid-repellent resist composition film after solvent drying is generally 50 nm to 100 μm, for example 100 nm to 10 μm, in particular 500 nm to 5 μm.

Next, patterning is performed using a photolithography method so that the contact angle with water in the lyophilic region is 50 ° or less. A plurality of regions having different surface free energies [(1) a region with a water contact angle of 80 ° or more, especially a region with a water contact angle of 100 ° or more, and (2) a region with a water contact angle of 50 ° or less, particularly water A pattern substrate composed of a region having a contact angle of 30 ° or less] is prepared. Region (1) and region (2) are adjacent.
In order to pattern the film of the liquid repellent resist composition by photolithography, an electromagnetic wave is irradiated.

<Electromagnetic wave>
The electromagnetic wave irradiated to the film in the present invention is light having a wavelength of 10 to 400 nm, such as ultraviolet light (UV, 200 to 400 nm), vacuum ultraviolet light (VUV, 150 to 200 nm), extreme ultraviolet light (EUV, 10 to 120 nm), etc. Illustrated. When VUV is used, a commercially available xenon excimer lamp capable of emitting VUV having a wavelength of 172 nm can be used as the light source. When UV is used, a mercury xenon lamp, mercury lamp, xenon lamp, or xenon excimer lamp can be used as the light source. Further, a 248 nm KrF excimer laser, a 193 nm ArF excimer laser, and a 157 nm F ₂ excimer laser may be used. Exposure amount 1~10,000mJ / cm ^2, may be a particularly 1~1,000mJ / cm ^2.
In addition to light, electromagnetic waves such as X-rays having a wavelength of 0.1 to 10 nm, electron beams having a wavelength of 0.001 to 0.01 nm, and laser beams having a wavelength of 10 to 300 nm may be used.

  When photolithography is performed using light or X-rays, the film may be irradiated with light through a photomask, or a Micro Electro such as DMD (digital micromirror device) developed by Texas Instruments, USA Mechanics (MEMS) may be used to irradiate light in a pattern without a mask. The DMD is a device in which 480,000 to 1.31 million movable mirrors (micromirrors) of 10 μm scale are arranged in a lattice shape, and the lamp light is reflected on the mirror to irradiate the film with light in a pattern.

On the other hand, with an electron beam or a laser beam, a pattern is drawn on a substrate that has been uniformly surface-treated directly without a photomask using a commercially available drawing apparatus. Exposure of the electron beam 10~10,000μC / cm ² in raster drawing, especially 100~1,000μC / cm ^2, a shot draw 100~100,000fC / dot, may in particular 1,000~10,000fC / dot.

<Development>
In the present invention, after the irradiation with the above-mentioned electromagnetic wave, a step of removing a soluble region by so-called “development” is performed using the solubility contrast with respect to the solvent. An alkaline aqueous solution is used as a solvent (developer) used for development. Examples of the alkaline aqueous solution include inorganic alkaline aqueous solutions such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine, methyldiethylamine and N-methylpyrrolidone; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium A quaternary ammonium salt such as hydroxide, tetraethylammonium hydroxide (TMAH), choline, or the like; an organic alkali aqueous solution comprising alkalis of cyclic amines such as pyrrole and piperidine is used. In the production of a TFT substrate, an organic alkali is preferable to an inorganic alkali, and TMAH which is widely used in a semiconductor photolithography process is particularly preferable. These may be used alone or in combination of two or more. A surfactant may be added.
The developing method may be performed in the range of 10 seconds to 10 minutes by an immersion method, a liquid filling method, a shower method, a paddle method, an ultrasonic method, or the like.

In the present invention, in order to enhance the wetting contrast of the lyophobic / lyophilic pattern, a treatment such as O ₂ plasma treatment, UV ozone treatment, or corona treatment may be performed after pattern formation. Moreover, you may heat-process after these processes. The contact angle of the lyophobic region of the lyophobic-lyophilic pattern formed using the lyophobic resist composition of the present invention is a contact angle with water of 80 ° or more, particularly 100 ° or more, with respect to n-hexadecane or butyl carbitol acetate. (BCA) The contact angle is 50 ° or more, particularly 55 ° or more. On the other hand, the contact angle of the lyophilic region is 50 ° or less, particularly 30 ° or less, and the contact angle to n-hexadecane or BCA is 20 ° or less, particularly 10 ° or less.

<Liquid repellent-application of functional compound solution to substrate on which lyophilic pattern is formed>
In the present invention, a functional compound solution or dispersion is applied to a substrate on which a pattern is formed. The functional compound solution can be applied by spin coating, dip coating, casting, roll coating, printing, transfer, ink jet [P. Calvert, Chem. Mater., 13, 3299 (2001)]. , Barcode method, capillary method and the like.

  The functional compound layer can be formed by applying a solution obtained by dissolving the functional compound in a solvent on the pattern surface and removing the solvent. When the functional compound solution is applied to a plurality of regions having different surface free energies, the functional compound solution is repelled in the liquid repellent region and is applied only to the lyophilic surface. Thus, a layer of functional compound is formed on the lyophilic region patterned on the substrate.

  Examples of functional compounds are semiconductor compounds, conductive compounds, dyes or pigments for forming display pixels, photochromic compounds, thermochromic compounds, lens materials, life science drugs, and the like.

As the semiconductor compound, an oxide semiconductor or an organic semiconductor is preferable. Oxide semiconductors are coating-type transparent amorphous oxide semiconductors described in, for example, Monthly Display, January 2011, p-4-13 (Recent Trends and Prospects of Oxide TFTs). In-Ga-Zn-O (a-IGZO) is preferred. Examples of the organic semiconductor include a pentacene derivative, a polythiophene derivative, a phthalocyanine derivative, a polyfluorene derivative, poly p-phenylene vinylene, and a layered herbskite compound.
The conductive compound has a conductivity of 10 ² S / cm 2 or more at room temperature. For example, in an organic system, polyacetylene derivatives, polythiophene derivatives, polypyrrole, poly p-phenylene vinylene, polyaniline and the like can be mentioned. Conductivity may be improved by doping these compounds. In the metal system, a material in which nanoparticles such as gold, silver and copper are dispersed in a liquid can be used.

The photochromic compound is preferably an organic compound, and examples thereof include azobenzene derivatives, spiropyran derivatives, fulgide derivatives, and diarylethene derivatives.
A thermochromic compound is a general term for compounds whose color changes reversibly with changes in temperature. For example, salicylideneanilines, polythiophene derivatives, tetrahalogeno complexes, ethylenediamine derivative complexes, dinitrodiammine copper complexes, Examples include 1,4-diazacyclooctane (daco) complex, hexamethylenetetramine (hmta) complex, and saltylaldehyde (salen) complex.

  The thickness of the functional compound layer after solvent drying may be 0.1 nm to 100 μm, preferably 0.5 nm to 10 μm, for example 1 nm to 1 μm.

Examples of the solvent that dissolves the functional compound are an organic solvent (particularly an oil-soluble organic solvent), a water-soluble organic solvent, and water. When the functional compound is sparingly soluble in water, it must be dissolved in an organic solvent (particularly an oil-soluble organic solvent) or a water-soluble organic solvent.
In the present invention, the solvent for dissolving the functional compound is preferably an organic solvent having a surface tension of 40 mN / m or less, for example, 30 mN / m or less. When the surface tension is 40 mN / m or less, the solution can easily spread out along the pattern shape.

Examples of the organic solvent include alcohols, esters, ketones, ethers, hydrocarbons (eg, aliphatic hydrocarbons and aromatic hydrocarbons), and the organic solvent may or may not be fluorinated. . Specific examples of organic solvents are perfluorodecalin, hydrofluoroether, HCFC225, chloroform, 1,1,2,2-tetrachloroethane, tetrachloroethylene, chlorobenzene, butyl acetate, hexane, isopentane, toluene, xylene, anisole, tetralin, cyclohexyl Examples include benzene, mesitylene, and tetrahydrofuran. Specific examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene Examples include propylene glycol, tripropylene glycol, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, and ethanol.
When water is used, the surface tension may be lowered by adding a surfactant, the above water-soluble organic solvent, or the like.

The concentration of the functional compound in the functional compound solution may be 0.1 to 30% by weight, for example 1 to 20% by weight.
The solvent can be removed by evaporation or the like. The removal of the solvent can be performed by heating the substrate (for example, 60 to 200 ° C.). The solvent removal may be performed under reduced pressure (for example, 0.01 to 100 Pa).

  The liquid repellent resist composition of the present invention can be used in devices for a wide range of applications such as production of electronic, optical, medical and chemical analyses. For example, the electronic device can be used for an integrated circuit such as a transistor, a memory, a light emitting diode (EL), a laser, or a solar cell. TVs, flexible displays, wireless tags, wearable computers, and the like are manufactured from these devices. Optical devices include display pixels such as color filters for liquid crystal displays, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photonic crystals, lens arrays, and other medical devices. The device can be used for biochips such as DNA arrays and protein arrays. The chemical analysis device can be used for a microchemical chip such as a microchemical plant or a microchemical analysis system.

  The present invention also provides a method for producing an organic EL pixel using the positive-type liquid-repellent resist composition of the present invention and an organic EL device containing the organic EL pixel obtained by the production method. That is, the present invention includes (i) an organic process comprising a step of forming a lyophobic partition wall in a pattern on a lyophilic transparent substrate by photolithography using the positive-type liquid-repellent resist composition of the present invention. (I) including a method for manufacturing an EL pixel, and (ii) a step of applying an organic EL light-emitting material and a step of removing a solvent on a lyophilic transparent substrate having a liquid-repellent patterned partition wall The organic EL device containing the organic EL pixel manufactured by the manufacturing method of the described organic EL pixel, and the manufacturing method as described in said (i) or (ii) is provided.

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

<Evaluation of compatibility of resist composition>
The appearance of the composition in which only the solvent was removed from the resist composition was evaluated in five stages. ◎>○>△>×> XX in order of good compatibility
It was evaluated.

<Development evaluation>
The developability was evaluated in five stages by observing a pattern developed after exposure with a mask aligner ES20d [manufactured by Mitsunaga Electric Co., Ltd., manufactured by Nanotech Co., Ltd.] with an optical microscope. The term “developability” as used herein refers to a comprehensive evaluation of the pattern shape of the UV exposed area remaining after development and the film removability of the UV unexposed area. >×> ××
It was evaluated.

<Evaluation of splitting property of nanometal ink>
By observing the shape of the metal pattern after the nanometal ink Ag (manufactured by ULVAC Material Co., Ltd.) is formed on the formed lyophilic-liquid-repellent pattern by the ink jet method with an optical microscope, Rated by stage. ◎ ＞ ○ ＞ △ ＞ × ＞ XX in order of good splitting
It was evaluated.

The static contact angle was measured by the following method using a fully automatic contact angle meter DropMaster701 (manufactured by Kyowa Interface Science Co., Ltd.).
<Measurement of static contact angle>
The static contact angle is obtained by dropping 2 μL of water, n-hexadecane, or butyl carbitol (BCA) from a microsyringe onto a horizontally placed substrate, and taking a still image one second after dropping with a video microscope. It was.

Production Example 1
<Rf (C4) α-Cl acrylate / MAA / GMA / HEMA = 45 / 20.6 / 6.9 / 27.5 (weight ratio) copolymer>
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, CH ₂ ═C (Cl) COO—CH ₂ CH ₂ C ₄ F ₉ (abbreviation: FA) as fluoroacrylate (abbreviation: FA). Rf (C4) α-Cl acrylate) 22.5 g, methacrylic acid (abbreviation: MAA) 10.3 g, glycidyl methacrylate (abbreviation: GMA) 3.4 g, 2-hydroxyethyl methacrylate (abbreviation: HEMA) 13.7 g, chain 6.3 g of lauryl mercaptan (abbreviation: LSH) as a transfer agent and 104 g of propylene glycol methyl ether acetate (abbreviation: PGMEA) as a solvent were added, heated to 70 ° C., and stirred for 30 minutes under a nitrogen stream. To this was added 0.5 g of a polymerization initiator azobisisobutyronitrile (abbreviation: AIBN), and polymerization was carried out for 18 hours. By analyzing the Rf (C4) α-Cl acrylate monomer remaining in the reaction solution by gas chromatography, it was confirmed that the conversion rate was 95% or more. As a result of measuring the solid content concentration of the reaction solution obtained by evaporation residue when heated at 130 ° C. for 2 hours, it was 33% by weight. This reaction solution was diluted with PGMEA to obtain a liquid repellent with a solid content concentration of 20% by weight. The liquid repellent was diluted with THF to a solid content concentration of 0.5% by weight, and the molecular weight of the fluoropolymer was measured by GPC. As a result, the weight average molecular weight was 6,400.

Production Example 2
<Rf (C4) α-F acrylate / MAA / GMA / HEMA = 45 / 20.6 / 6.9 / 27.5 (weight ratio) copolymer>
Manufactured except that Rf (C4) α-Cl acrylate of Production Example 1 is replaced with CH ₂ ═C (F) COO—CH ₂ CH ₂ C ₄ F ₉ (abbreviation: Rf (C4) α-F acrylate) as FA. A polymerization reaction was performed in the same manner as in Example 1 to obtain a fluoropolymer. As a result of measuring the molecular weight of the obtained fluoropolymer by GPC, the weight average molecular weight was 5,000.

Production Example 3
<PFPE (C8) methacrylate / MAA / GMA / HEMA = 45 / 20.6 / 6.9 / 27.5 (weight ratio) copolymer>
As FA, Preparation 1 Rf (C4) α-Cl acrylate _{C 3 F 9 - [OCF (} CF 3) CF 2] -OCF (CF 3) CH 2 OCOC (CH 3) = CH 2 ( abbreviation: PFPE A polymerization reaction was carried out in the same manner as in Production Example 1 except that (C8) methacrylate) was substituted to obtain a fluoropolymer. As a result of measuring the molecular weight of the obtained fluoropolymer by GPC, the weight average molecular weight was 5,200.

Production Example 4
<Rf (C4) α-Cl acrylate / MAA / GMA / HEMA / tBMA = 45 / 7.8 / 6.9 / 27.5 / 12.8 (weight ratio) copolymer>
Rf (C4) α-Cl acrylate 22.5 g, MAA 3.9 g, GMA 3.4 g, HEMA 13.8 g, methacrylic acid as FA in a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer 6.4 g of tert-butyl (abbreviation: tBMA) 5.7 g of lauryl mercaptan (abbreviation: LSH) as a chain transfer agent and 104 g of propylene glycol methyl ether acetate (abbreviation: PGMEA) as a solvent are added and heated to 70 ° C. for 30 minutes Stirring was performed under a nitrogen stream. To this was added 0.5 g of a polymerization initiator azobisisobutyronitrile (abbreviation: AIBN), and polymerization was carried out for 18 hours. By analyzing the Rf (C4) α-Cl acrylate monomer remaining in the reaction solution by gas chromatography, it was confirmed that the conversion rate was 95% or more. The solid content was measured and found to be 33% by weight. The obtained reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer. As a result of measuring the molecular weight of the obtained fluoropolymer by GPC, the weight average molecular weight was 4,600.

Production Example 5
<Rf (C4) α-Cl acrylate / tBMA / GMA / HEMA = 45 / 20.6 / 6.9 / 27.5 (weight ratio) copolymer>
A polymerization reaction was performed in the same manner as in Production Example 1 except that MAA in Production Example 1 was replaced with tet-butyl methacrylate (abbreviation: tBMA) to obtain a fluoropolymer. As a result of measuring the molecular weight of the obtained fluoropolymer by GPC, the weight average molecular weight was 4,900.

Production Example 6
<Rf (C4) α-Cl acrylate / MAA / GMA / HEMA = 55 / 16.9 / 5.6 / 22.5 (weight ratio) copolymer>
The polymer composition of Production Example 1 was changed as shown in Table 1, and a polymerization reaction was performed in the same manner as in Production Example 1 to obtain a fluoropolymer. As a result of measuring the molecular weight of the obtained fluoropolymer by GPC, the weight average molecular weight was 6,800.

Production Example 7
<Rf (C4) α-Cl acrylate / MAA / GMA / HEMA = 50 / 18.8 / 6.3 / 25 (weight ratio) copolymer>
The polymer composition of Production Example 1 was changed as shown in Table 1, and a polymerization reaction was performed in the same manner as in Production Example 1 to obtain a fluoropolymer. As a result of measuring the molecular weight of the obtained fluoropolymer by GPC, the weight average molecular weight was 6,400.

Production Example 8
<Rf (C4) α-Cl acrylate / MAA / GMA / HEMA = 40 / 22.5 / 7.5 / 30 (weight ratio) copolymer>
The polymer composition of Production Example 1 was changed as shown in Table 1, and a polymerization reaction was performed in the same manner as in Production Example 1 to obtain a fluoropolymer. As a result of measuring the molecular weight of the obtained fluoropolymer by GPC, the weight average molecular weight was 6,400.

Comparative production example 1
<Rf (C4) α-Cl acrylate / MAA / GMA / HEMA = 60/15/5/20 (weight ratio) copolymer>
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer, and a stirrer, 30.0 g of Rf (C4) α-Cl acrylate, 7.5 g of MAA, 2.5 g of GMA, 10 g of HEMA, LSH5. 4 g and 105 g of PGMEA as a solvent were added, heated to 70 ° C., and stirred for 30 minutes under a nitrogen stream. To this was added 0.4 g of polymerization initiator AIBN, and polymerization was carried out for 18 hours. By analyzing the Rf (C4) α-Cl acrylate monomer remaining in the reaction solution by gas chromatography, it was confirmed that the conversion rate was 95% or more. It was 33 weight% as a result of measuring solid content concentration of the obtained reaction liquid. This reaction solution was diluted with PGMEA to obtain a liquid repellent with a solid content concentration of 20% by weight. The liquid repellent was diluted with THF to a solid content concentration of 0.5% by weight, and the molecular weight of the fluoropolymer was measured by GPC. As a result, the weight average molecular weight was 6,800.

The production conditions for the fluoropolymers of Production Examples 1 to 4 and Comparative Production Example 1 are summarized in Table 1. Table 2 shows the fluorine concentration (% by weight), acid value, and weight average molecular weight of the obtained fluoropolymer.

FA：フルオロアクリレート
GMA：グリシジルメタクリレート
HEMA：２−ヒドロキシメタクリレート
MAA：メタクリル酸
ｔＢＭＡ：メタクリル酸ｔｅｒｔ-ブチル
LSH：ラウリルメルカプタン

FA: Fluoroacrylate
GMA: Glycidyl methacrylate
HEMA: 2-hydroxymethacrylate
MAA: methacrylic acid tBMA: tert-butyl methacrylate
LSH: Lauryl mercaptan

Examples 1-8 and Comparative Example 1
Fluoropolymer (A), alkali-soluble resin (B), naphthoquinone diazide, using the fluorinated polymer obtained in Production Examples 1 to 8 or the fluorinated polymer obtained in Comparative Production Example 1 as the fluoropolymer (A), respectively. A positive resist composition was prepared from a solution comprising a group-containing compound (C), a sensitizer (D) and a solvent (E) (the formulation is shown in the next paragraph). This solution was spin-coated on a glass substrate made hydrophilic by immersing it in a concentrated sulfuric acid / hydrogen peroxide (= 3/7 volume ratio) mixed solution for 1 hour, and the film thickness (after the solvent was removed by drying) The film thickness was 2 μm. After preheating and heating at 90 ° C. for 3 minutes, this film was irradiated with ultraviolet rays having a wavelength of 365 nm from a UV exposure apparatus mask aligner ES20d through a photomask of line / space = 1 μm / 1 μm under the condition of an integrated light quantity of 200 mJ / cm ² . . Next, it was developed by heating at 90 ° C. for 3 minutes as a post-exposure bake and then immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute. Thereafter, it was washed with water and dried to prepare a pattern substrate composed of a liquid repellent region and a lyophilic region.

The resist compositions used in Examples 1-8 and Comparative Example 1 are as follows:
・ Fluoropolymer (A)
As the component (A), the polymer synthesized in Production Examples 1 to 8 or Comparative Production Example 1 contains 0.8% by weight in terms of solid content.
・ Alkali-soluble resin (B)
As component (B), 17.2% by weight of (b1) shown in the following synthesis example is included.
(B1): A cresol novolak resin having a mass average molecular weight of 4500, obtained by mixing m-cresol and p-cresol = 35/65 (molar ratio), adding formalin thereto, and subjecting it to a condensation reaction with an oxalic acid catalyst. .
・ Naphthoquinonediazide group-containing compound (C)
As the component (C), 2,5,4,4'-tetrahydroxybenzophenone 1,2-naphthoquinodiazide-5-sulfonic acid ester is contained in an amount of 5% by weight.
・ Sensitizer (D)
As component (D), 2% by weight of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene is contained.
・ Solvent (E)
As component (E), 75% by weight of propylene glycol methyl ether acetate (abbreviation: PGMEA) is included.

  A uniform liquid repellent film was prepared without irradiating the film on which the resist composition was spin-coated with ultraviolet rays. Table 2 shows the result of measuring the contact angle of the obtained uniform liquid repellent region.

HD：ｎ−ヘキサデカン
BCA：ブチルカルビトールアセテート

表２中、製造例３および４は、不飽和酸モノマーとして酸エステル形成基であるｔＢｕ基でカルボン酸基が保護されたｔＢＭＡを用いている。表中、製造例４および５の酸価４７および０の数値は、酸エステル形成基を加水分解によって脱保護した後のフッ素系ポリマー（Ａ）の酸価、１３０および１３１に対応していた。

HD: n-hexadecane
BCA: Butyl carbitol acetate

In Table 2, Production Examples 3 and 4 use tBMA in which a carboxylic acid group is protected with a tBu group that is an acid ester forming group as an unsaturated acid monomer. In the table, the numerical values of acid numbers 47 and 0 in Production Examples 4 and 5 corresponded to the acid values 130 and 131 of the fluoropolymer (A) after the acid ester forming group was deprotected by hydrolysis.

  As is clear from Table 2, in Examples 1 to 8 using the polymers shown in Synthesis Examples 1 to 8, the compatibility is good, and it can be confirmed that the development is excellent without any residue remaining during development. It was. On the other hand, Comparative Example 1 using a polymer whose synthesis example was shown in Comparative Production Example 1 was poor in compatibility and remarkably poor in developability.

  The liquid repellent resist composition of the present invention forms a pattern surface comprising a lyophilic region and a liquid repellent region on a substrate by a photolithography method. For example, as an electronic device, a transistor, a memory, a light emitting diode (EL), a laser Can be used in integrated circuits such as solar cells, and optical devices include color filters for liquid crystal displays, display pixels such as organic EL, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarization It can be used for elements, photonic crystals, lens arrays, and the like, and as a medical device, it can be used for biochips such as DNA arrays and protein arrays. In particular, it is advantageously used for making the partition walls for wiring of the TFT substrate for display and the partition walls for thin film transistors lyophobic.

Claims (13)

A liquid repellent resist composition comprising:
(A1) α-substituted acrylate having a fluoroalkyl group having 4 to 8 carbon atoms [which may have an etheric oxygen atom between carbon atoms] [the substituent at the α-position is a fluorine atom, a chlorine atom, bromine; Atom, iodine atom, 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 alkyl group having 1 to 20 carbon atoms] 100 parts by weight,
(A2) Unsaturated organic acid [the acidic group may be protected with an acid ester-forming group] 30 to 60 parts by weight,
(A3) 10-25 parts by weight of an epoxy group-containing monomer, and (a4) (R ¹ O) _n R ² [R ¹ is — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ —, R ² is hydrogen or Containing a fluorine-based polymer (A) having a repeating unit of 40 to 80 parts by weight of a monomer containing an alkyleneoxy group represented by a methyl group, n is 1 to 10,
A positive-type liquid-repellent resist composition having a fluorine concentration of 15 to 40% by weight and a weight average molecular weight of 3,000 to 20,000 in the fluorine-based polymer (A).   The acid value (the acid value after deprotection by hydrolysis when the acidic group is protected with an acid ester-forming group) of the fluoropolymer (A) is 10 to 200 mgKOH / g. A positive-type liquid-repellent resist composition.   The positive-type liquid-repellent resist composition according to any one of claims 1 and 2, wherein the fluoroalkyl group (a1) is a perfluoroalkyl group having 4 to 6 carbon atoms.   The positive-type liquid-repellent resist composition according to any one of claims 1 and 2, wherein the fluoroalkyl group (a1) is a perfluoropolyether group having 6 to 8 carbon atoms.   5. The composition according to claim 1, comprising an alkali-soluble resin (B), a naphthoquinonediazide group-containing compound (C), a sensitizer (D), and a solvent (E) in addition to the fluorine-based polymer (A). The positive-type liquid-repellent resist composition according to one.   In addition to fluorine-based polymer (A), compound (Q) containing two or more vinyl ether groups in one molecule, compound (R) containing two or more blocked isocyanate groups in one molecule, photoacid generation The positive-type liquid-repellent resist composition according to any one of claims 1 to 4, comprising an agent (S) and a solvent (E). A liquid repellent in which the fluoropolymer (A) according to any one of claims 1 to 4 is dissolved in a glycol solvent at a concentration of 10 to 30% by weight.   Using the positive-type liquid-repellent resist composition according to any one of claims 1 to 6, including a step of forming a liquid-repellent partition wall in a pattern on a lyophilic transparent substrate by a photolithography method. A method for manufacturing a thin film transistor substrate.   9. The method according to claim 8, comprising a step of applying any one of the nanometal ink, the oxide semiconductor ink, and the organic semiconductor ink on the lyophilic transparent substrate having the liquid-repellent patterned partition walls, and the step of removing the solvent. A method for manufacturing a thin film transistor substrate. A thin film transistor substrate manufactured by the manufacturing method according to claim 8.
  Using the positive-type liquid-repellent resist composition according to any one of claims 1 to 6, including a step of forming a liquid-repellent partition wall in a pattern on a lyophilic transparent substrate by a photolithography method. Manufacturing method of organic EL pixel.   The manufacturing method of the organic EL pixel of Claim 11 including the process of apply | coating an organic electroluminescent light emitting material, and the process of removing a solvent on the lyophilic transparent substrate which has the liquid-repellent patterned partition.   The organic EL device containing the organic EL pixel manufactured with the manufacturing method of Claim 11 or 12.