KR100955977B1 - Surface Treating Agent for Pattern Formation - Google Patents

Abstract

This invention relates to the surface treating agent for photolithography containing one or more of the following fluorine-type monomers (A) and the fluorine-type polymer (B) containing this fluorine-containing monomer.

That is, (A-1) α-substituted acrylate having a fluoroalkyl group having 1 to 6 carbon atoms, (A-2) a fluorine-containing silsesquioxane monomer containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group, (A-3) a polymerizable monomer having a perfluoropolyether group, (A-4) a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group is -SO ₂ (CH ₂ ) _n- , wherein n is 1 to 10 1) selected from the group consisting of a macromonomer having a (meth) acryloyl group at a terminal of a polymer having at least one of (A-5) monomers (A-1) to (A-4) as a repeating unit The above fluorine monomer is provided.

The surface treating agent provides a sufficiently high water and oil repellency in the liquid repellent region even if it has a short-chain Rf group having 6 or less carbon atoms.

Surface treatment agent for photolithography, fluorine monomer, color filter for display

Description

Surface Treating Agent for Pattern Formation

The present invention relates to a surface treating agent for producing a patterned surface including a lyophilic region and a liquid repellent region by a photolithography method.

Fluoroalkyl group (hereinafter abbreviated as Rf group) containing monomer [J. Poly. Sci. Part A, 37, 77 (1999)], or a technique of blending a copolymer of an Rf group-containing monomer crosslinkable functional group-containing monomer (JP-A-2003-300323) with a crosslinkable monomer and a photopolymerization initiator to photopolymerize Is disclosed. These techniques can be applied as a surface treating agent for producing a patterned surface composed of liquid repellency and lyophilic regions having different wettability by the photolithography method. In the prior art, an Rf group-containing monomer having a long-chain Rf group having 8 or more carbon atoms that is advantageous in liquid repellency has been used.

However, there existed a problem that Rf group containing monomer which has a C8 or more long-chain Rf group, or the copolymer of Rf group containing monomer is incompatible with the crosslinkable monomer, photoinitiator, solvent, etc. which comprise a surface treating agent.

On the other hand, when a C8- or higher-chain Rf group is used for the Rf group-containing monomer, there is a concern about an accumulation problem in the environment and a living body. Conventionally, the Rf group-containing compound having a long chain Rf group having 8 to 12 carbon atoms, which has been widely used as a surface treatment agent in order to impart high water and oil repellency to the substrate, has recently been pointed out a problem of accumulation in the environment and a living body. Recent research results [EPA report "Draft Risk Assessment of the Potential Human Health Effects Associated With Exposure to Perfluorooctanoic Acid and Its Salts (PFOA)" (http://www.epa.gov/opptintr/pfoa/pfoarisk.pdf) From these, the accumulation of human concern about perfluorooctanoic acid (PFOA), a long-chain Rf group-containing compound, has been revealed. On April 14, 2003, the US Environmental Protection Agency (EPA) strengthened the scientific investigation of PFOA. It is announced.

Meanwhile, the Federal Register (FR Vol. 68, No. 73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pdf) or EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) or EPA OPPT FACT SHEET April 14, 2003 (http: //www.epa. gov / opptintr / pfoa / pfoafacts.pdf) declares that telomers are likely to produce PFOA by degradation or metabolism (which is synonymous with the long chain Rf group). It also discloses that telomers are used in many products such as foam extinguishing agents, care products, cleaning products, carpets, textiles, papers, leathers, and the like which have water and oil repellency and antifouling properties.

Because of these environmental problems, there is a need to use an Rf group-containing compound having a short chain Rf group having 1 to 6 carbon atoms as a water / oil repellent agent as a substitute for the long-chain Rf group-containing compound. However, even if the conventional skeleton was replaced with a short-chain Rf group as it is, the water / oil repellency of the liquid repellent region was insufficient.

The objective which concerns on the 1st summary of this invention is providing the surface treatment agent for pattern formation which provides sufficiently high water- and oil-repellent oil repellency to a liquid repellent area, even if it has a C6 or less short-chain Rf group.

An object of the second aspect of the present invention is to provide a liquid-repellent region that is minutely formed on a substrate by a non-contact trace droplet discharging method, and the liquid-repellent region has a high liquid repellency even without using a long-chain Rf group-containing compound. It is to provide a method for producing a substrate.

According to a first aspect, the present invention provides a surface treating agent for photolithography comprising a specific fluorine monomer and / or a specific fluorine polymer.

As a fluorine-type monomer, for example

? -Substituted acrylate monomer having Rf group having 1 to 6 carbon atoms (substituent at? -Position is F, Cl, for example)

Polymerizable silsesquioxane monomers having Rf groups having 1 to 6 carbon atoms,

Polymerizable monomers having a perfluoropolyether group,

Polymerizable monomers in which a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group are linked by -SO ₂ (CH ₂ ) _n- (n is 1 to 10, in particular 3 to 6)

Macromonomer having a (meth) acryloyl group at the terminal of a polymer having at least one of these monomers as a repeating unit

Apply.

The present invention provides a surface treatment agent for photolithography comprising at least one fluorine-containing compound selected from the group consisting of the following fluorine-based monomers (A) and fluorine-based polymers (B).

● fluorine monomer (A)

(A-1) α-substituted acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms (substituent at α-position: fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a straight or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or 1 to 20 carbon atoms Linear or branched alkyl groups),

(A-2) a fluorine-containing silsesquioxane monomer containing a fluoroalkyl group and a polymerizable group having 1 to 6 carbon atoms,

(A-3) a polymerizable monomer having a perfluoropolyether group,

(A-4) a polymerizable monomer in which a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group are linked by -SO ₂ (CH ₂ ) _n- (n is 1 to 10, especially 3 to 6),

(A-5) Macromonomer which has a (meth) acryloyl group in the terminal of the polymer which makes 1 or more types of monomers (A-1)-(A-4) a repeating unit

At least one monomer selected from the group consisting of.

The fluorine monomer may be a mixture of the two kinds (for example, a combination of monomer (A-1) and monomer (A-4)).

● Fluoropolymer (B)

It is a fluorine-type polymer which has a repeating unit derived from the same repeating unit (B-1) as a fluorine-type monomer (A), and may be a homopolymer or a copolymer. In the case of the copolymer, it may be any one of random, alternating, block, and graft.

According to a second aspect, the present invention describes an electromagnetic wave curing composition comprising a fluorine-based monomer (A) containing a fluoroalkyl group, a crosslinking agent (B), and a photocrosslinking catalyst (C) by a noncontact trace droplet ejection method. The present invention also provides a method for producing a patterned substrate, in which a pattern composed of two or more regions having different surface free energies is formed on a substrate by ejecting the film and irradiating and curing the fine coating film.

Effect of the Invention

The surface treatment agent of this invention forms the film which expresses the patterned high water / oil repellency on the board | substrate.

<Mode for carrying out the invention>

Α-position substituted acrylate (A-1) having a fluoroalkyl group having 1 to 6 carbon atoms, a polymerizable monomer (A-3) having a perfluoropolyether group, a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group- The polymerizable monomer (A-4) linked by SO ₂ (CH ₂ ) _n − (n is 1 to 10, especially 3 to 6),

(A) It may be a fluorine-containing monomer which has a fluorine-containing group represented by following formula (I).

Wherein X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), 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 linear or branched alkyl group having 1 to 20 carbon atoms,

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 aliphatic group, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (wherein Y ¹ is a hydrogen atom or an acetyl group), or-(CH ₂ ) _n SO ₂ -group (n is 1 to 10),

Rf is one or more linear or branched fluoroalkyl groups having 1 to 6 carbon atoms, or at least one repeat selected from the group consisting of repeat units -C ₃ F ₆ O-, -C ₂ F ₄ O-, and -CF ₂ O- It is a fluoroether group whose total number of units is 1-200.

[여기서, Y¹은 직접 결합, 산소 원자를 가질 수도 있는 탄소수 1 내지 10의 지방족기, 산소 원자를 가질 수도 있는 탄소수 6 내지 10의 방향족기 또는 환상 지방족기 또는 방향 지방족기, -CH₂CH₂N(R¹)SO₂-(CH₂CH₂)_a-기(단, R¹은 탄소수 1 내지 4의 알킬기이고, a는 0 또는 1임), -CH₂CH(OR¹¹)CH₂-기(단, R¹¹은 수소 원자 또는 아세틸기임) 또는 -(CH₂)_nSO₂-기(n은 1 내지 10임)임], 또는

[여기서, Y²는 -O- 또는 -NH-이고, Z는 -S- 또는 -SO₂-이고, m은 1 내지 10이고, n은 0 내지 10이고, p는 0 또는 1임]를 가질 수도 있다.In the above formula, between the polymerizable group (eg, carbon carbon double bond group) and the fluoroalkyl group (ie, instead of -OY-)

[Wherein, Y ¹ 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 or a cyclic aliphatic group or an aromatic aliphatic group, -CH ₂ CH ₂ N (R ¹ ) SO ₂ — (CH ₂ CH ₂ ) _a —group, wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, a is 0 or 1, and —CH ₂ CH (OR ¹¹ ) CH ₂ − Where R ¹¹ is a hydrogen atom or an acetyl group or a-(CH ₂ ) _n SO ₂ -group (n is 1 to 10); or

Wherein Y ² is —O— or —NH—, Z is —S— or —SO ₂ —, m is 1 to 10, n is 0 to 10, and p is 0 or 1 It may be.

[식 중, B는 -O-Y¹- 또는 -Y²-[-(CH₂)_m-Z-]_p-(CH₂)_n-(여기서, Y¹, Y², Z, m, n 및 p는 상기와 동일함)이고, X 및 Rf는 상기와 동일함]로 표시되는 화합물일 수 있다.Therefore, monomer (A-1), (A-3), (A-4) is a chemical formula

[Wherein B is -OY ¹ -or -Y ² -[-(CH ₂ ) _m -Z-] _p- (CH ₂ ) _n- , where Y ¹ , Y ² , Z, m, n and p Is the same as above), and X and Rf are the same as described above.

Polymerizable monomer (A-3) having a perfluoropolyether group, and a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group is -SO ₂ (CH ₂ ) _n- (n is 1 to 10, especially 3 to 6 In the polymerizable monomer (A-4) linked by), examples of X are hydrogen and methyl group in addition to the above atoms and groups.

The polymerizable monomer (A-3) and the polymerizable monomer (A-4) are monomers having a polymerizable group. The polymerizable group may be a carbon-carbon group (eg, an ethenyl group) bonded by a double bond. The polymerizable monomers (A-2) to (A-4) may be acrylates in which the α position is substituted [as in the monomer (A-1)] (that is, the α position is not hydrogen or an alkyl group). Or the acrylate which has a hydrogen atom or a methyl group in (alpha) position may be sufficient.

In the general formula (I), the carbon number of the Rf group is 1 to 6, for example, 1 to 5, preferably 4. In general, the longer the Rf group is, the better the liquid repellency is, and the shorter the tendency is, the better the compatibility is. 4 is preferable than carbon number 6 also from a bioaccumulation viewpoint.

등이다.An example of the Rf group

And so on.

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 aliphatic group, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (wherein Y ¹ is a hydrogen atom or an acetyl group), or-(CH ₂ ) _n SO ₂ -group (n is 1 to 10). The aliphatic group is preferably an alkylene group (particularly 1 to 4 carbon atoms, for example 1 or 2). The aromatic group and the cyclic aliphatic group may be substituted or may not be substituted. The atom bonded to Rf in the —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group and the — (CH ₂ ) _n SO ₂ — group may be either a carbon atom in the methylene group or a sulfur atom in the sulfone group And may generally be a sulfur atom in a sulfone group.

Examples of the fluorine-containing monomer are as follows.

[Wherein Rf is selected from the group consisting of a linear or branched fluoroalkyl group having 1 to 6 carbon atoms or a repeating unit -C ₃ F ₆ O-, -C ₂ F ₄ O- and -CF ₂ O- A perfluoropolyether group having a total number of one or more repeating units from 1 to 200;

The fluorine-containing silsesquioxane monomer (A-2) containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group is a reactive silane having (i) fluorine-containing incompletely condensed silsesquioxane and (ii) a polymerizable functional group. It is obtained by reacting.

Fluorine-containing incompletely condensed silsesquioxane (i) is incompletely condensed silsesquioxane having a fluoroalkyl group.

Silsesquioxane is also called Polyhedral Oligomeric Silsesquioxane (POSS).

The silanol groups of incompletely condensed silsesquioxane (i) are highly reactive and generally present in the molecule in the range of 1 to 3.

Specific examples of the incompletely condensed silsesquioxane (i) are the following (formula I) and the like, for example.

The reactive silane (ii) having a polymerizable functional group has a polymerizable functional group and a reactive group. In the reactive silane (ii), examples of the polymerizable functional group are a (meth) acryl group, an α-substituted acrylic group, an epoxy group, a vinyl group and the like. In the reactive silane (ii), examples of the reactive group are trichlorosilyl group and trialkoxysilyl group (the alkoxy group has 1 to 5 carbon atoms).

[식 중, A¹¹은 중합성 관능기이고, A²¹은 직접 결합 또는 탄소수 1 내지 20(예를 들면, 1 내지 10임)의 알킬기이고, A³¹은 할로겐 원자(예를 들면, 염소 원자 및 브롬 원자임) 또는 알콕시기(알콕시기의 탄소수는 1 내지 5임)임]로 표시되는 화합물이다.Reactive silane (ii) is, for example, a chemical formula

[Wherein, A ¹¹ is a polymerizable functional group, A ²¹ is a direct bond or an alkyl group having 1 to 20 carbon atoms (for example, 1 to 10), and A ³¹ is a halogen atom (for example, a chlorine atom and bromine Atom) or an alkoxy group (wherein the alkoxy group has 1 to 5 carbon atoms).

Examples of the fluorine-containing silsesquioxane monomer (a) are as follows.

When the fluorine-based polymer (B) is a copolymer, an unsaturated organic acid (B-2) and a high softening point monomer (B) are copolymerized monomers for copolymerizing with the fluorine-based monomer (B-1) (that is, the same as the fluorine-based monomer (A)). -3).

The fluoropolymer (B) is, for example

(B1) homopolymer of fluorine monomer (B-1),

(B2) a copolymer of a fluorine monomer (B-1) and an unsaturated organic acid (B-2), or

(B3) It may be a copolymer of a fluorine monomer (B-1), an unsaturated organic acid (B-2), and a high softening point monomer (B-3).

An unsaturated organic acid (B-2) is a monomer which has one or more carbon-carbon double bonds and one or more acid groups (for example, a carboxyl group (COOH®)). Particularly preferred examples of unsaturated organic acids are unsaturated carboxylic acids such as free unsaturated carboxylic acids and unsaturated carboxylic anhydrides. Examples of the unsaturated organic acid (B-2) are (meth) acrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, and cinnamic acid. An unsaturated organic acid (B-2) gives a fluorine-type polymer (B) the crosslinkability with the crosslinking agent in an electromagnetic wave irradiation area | region, and the solubility with the alkali developing solution in an electromagnetic wave non-irradiation area | region.

The high softening point monomer (B-3) is

Monomers having a glass transition point or melting point of at least 100 ° C, in particular at least 120 ° C, in the homopolymer state,

or,

CH ₂ = C (R ¹ ) COOR ² , wherein R ¹ is H or CH ₃ , R ² is a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more.

Examples of R ² are isobornyl, bornyl, penyl (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), nord And crosslinked hydrocarbon rings such as bornyl (C ₇ H ₁₂ , carbon atom / hydrogen atom = 0.58). A hydroxyl group or an alkyl group may be attached to these crosslinked hydrocarbon rings.

Examples of high softening point monomers (B-3) include methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, and adamantyl ( Meth) acrylate. Examples of norbornyl (meth) acrylates include 3-methyl-norbornylmethyl (meth) acrylate, norbornylmethyl (meth) acrylate, norbornyl (meth) acrylate, 1,3,3- Trimethyl-norbornyl (meth) acrylate, Miltanylmethyl (meth) acrylate, isofinocamponyl (meth) acrylate, 2-{[5- (1 ', 1', 1'-trifluoro- 2'-trifluoromethyl-2'-hydroxy) propyl] norbornyl} (meth) acrylate. Examples of adamantyl (meth) acrylates are 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamant Methyl (meth) acrylate and 1-adamantyl-α-trifluoromethyl (meth) acrylate.

And a glass transition point, melting point, extrapolated glass transition ending temperature _(eg T), peak melting temperature (T _pm) each of which is defined in the "method of measuring transition temperature of plastics" of JIS K7121-1987. When the high softening point monomer (B-3) having a glass transition point or melting point of 100 ° C. or higher in the homopolymer state is used for the repeating unit of the fluoropolymer (B), in addition to the effect of excellent dimensional stability when the substrate is heat treated. There is also an effect of improving the liquid repellency of the fluorine-based monomer (B-1).

When the macromonomer (A-5) is copolymerized with the unsaturated organic acid monomer (B-2) and the high softening point monomer (B-3) as the fluorine monomer (B-1), the fluorine monomer (B-1) and the unsaturated organic acid (B- 2), the effect of each high softening point monomer (B-3) increases.

As examples of macromonomers,

Is illustrated. The degree of polymerization n of the fluorinated monomers in the macromonomer is preferably 5 to 20, particularly preferably 5 to 10.

It is especially preferable that the fluorine-based polymer (B) which is said binary or terpolymer is a composition containing a crosslinking agent (C), a photocrosslinking catalyst (D), and a diluent (J).

In the copolymer, the weight ratio of the fluorine monomer (B-1) and the unsaturated organic acid (B-2) may be 60:40 to 98: 2, in particular 80:20 to 95: 5.

In the copolymer, the amount of the high softening point monomer (B-3) may be 0 to 90% by weight, for example 1 to 80% by weight, in particular 10 to 70% by weight, based on the copolymer.

The fluoropolymer (B) is, for example

20 to 80% by weight of a fluorine monomer (B-1),

5 to 30% by weight of unsaturated organic acid (B-2), and

It may comprise 10 to 70% by weight of the high softening point monomer (B-3).

If the fluorine-based monomer (B-1) is 20 to 80% by weight, the liquid repellency is high, and compatibility with other components constituting the surface treatment agent for photolithography is good. When the unsaturated organic acid monomer (B-2) is 5 to 30% by weight, the crosslinkability with the crosslinking agent in the electromagnetic wave irradiation region is good, the solubility with the alkali developer in the electromagnetic non-irradiation region is good, and the liquid repellency is good. Do. If the high softening point monomer (B-3) is 10 to 70 wt. *, The dimensional stability effect is good and the liquid repellency is good.

In addition to the unsaturated organic acid monomer (B-2), a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (for example, 0.1 to 30% by weight, Particularly in the range of 0.5 to 25% by weight), the crosslinkability of the monomer (B-2) with the crosslinking agent in the electromagnetic wave irradiation region and the solubility with the alkali developer in the electromagnetic wave non-irradiation region are enhanced.

The copolymer of a fluoropolymer (B) can also copolymerize the silane group containing monomer (for example, 0.1-30 weight%) represented by (gamma)-methacryloxypropyl trimethoxysilane as needed. By copolymerizing a silane group containing monomer, adhesiveness with a board | substrate improves, for example.

● Manufacturing method of pattern board

According to the first aspect, in the present invention, using a fluorine monomer (A) or a fluorine polymer (B), for example, a patterned substrate composed of a plurality of regions having different surface free energies by the following method, again In other words, a patterned substrate (hereinafter, simply referred to as a "pattern substrate") containing a plurality of patterned liquid repellent regions and a lyophilic region is produced.

Method (1): The fluoropolymer (B) is dissolved in the diluent (J). The fluorine-based polymer solution is applied onto a substrate to form a uniform liquid repellent film, and irradiation of electromagnetic waves (for example, vacuum ultraviolet light having a wavelength of 172 nm) through a photomask causes oxidation of ozone generated by electromagnetic energy and electromagnetic waves. By the action, only the irradiation region is photolyzed to become lyophilic, and a pattern substrate is obtained. Photocatalyst technology may be used in combination to promote photolysis of the liquid repellent film.

Method (2): A composition containing a fluorine monomer (A), a crosslinking agent (C), and a photocrosslinking catalyst (D) (which may optionally add a diluent (J)) is applied onto a substrate to form a film. When electromagnetic waves are irradiated through the photomask, only the irradiated area is cured to form a liquid repellent film. The pattern substrate is obtained by removing (developing) the film of a non-irradiation area | region by using the diluent (J) which is insoluble in a irradiation area and dissolves only a non-irradiation area | region.

Method (3): The fluorine-based polymer (B) having a crosslinkable functional group (E) and the photocrosslinking catalyst (D) are dissolved in the diluent (J). This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when irradiated with electromagnetic waves through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only a non-irradiation area | region.

Method (4): A fluorine-based polymer (B) having a crosslinkable functional group (E), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent (J). This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when irradiated with electromagnetic waves through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only a non-irradiation area | region.

Method (5): A fluorine-based polymer (B) having an acidic group (F) and a crosslinkable functional group (E), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent (J). This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when irradiated with electromagnetic waves through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only a non-irradiation area | region.

Method (6): A fluorine-based polymer (B) having an acidic group (F), a crosslinkable functional group (E) and a silicone chain (G), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent (J). . This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when the electromagnetic wave is irradiated through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only a non-irradiation area | region.

Method (7): A fluorine-based polymer (B) having an acidic group (F), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent (J). This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when irradiated with electromagnetic waves through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only a non-irradiation area | region.

Method (8): A fluorine-based polymer (B) having an acidic group (F) and a silicone chain (G), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent (J). This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when irradiated with electromagnetic waves through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only a non-irradiation area | region.

Method (9): The fluoropolymer (B) and the photocrosslinking catalyst (D) having an acidic group (F) and a crosslinkable functional group (E) are dissolved in a diluent (J). This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when irradiated with electromagnetic waves through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only an unirradiated area | region.

Method (10): The fluorine-based polymer (B) and the photocrosslinking catalyst (D) having an acidic group (F), a crosslinkable functional group (E) and a silicone chain (G) are dissolved in a diluent (J). This fluoropolymer solution is applied onto a substrate to form a liquid repellent film, and when irradiated with electromagnetic waves through a photomask, only the irradiated region is cured. The pattern substrate is obtained by developing with the solvent which melt | dissolves only a non-irradiation area | region.

Method (11): A fluorine-based polymer (B) and a photoacid generator (I) having an acid dissociating group (H) which is converted into an acidic group by the action of an acid are dissolved in a diluent (J). When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region dissociates with acid to become lyophilic, thereby obtaining a pattern substrate.

Method (12): A fluorine-based polymer (B) and a photoacid generator (I) having an acid dissociation group (H), a silicon chain (G), which are converted into an acid group by the action of an acid, are dissolved in a diluent (J). When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region dissociates with acid to become lyophilic, thereby obtaining a pattern substrate.

Method (13): A fluorine-based polymer (B) and a photoacid generator (I) having an acid dissociating group (H) which is converted into an acidic group by the action of an acid are dissolved in a diluent (J). When the fluorine-based polymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region dissociates to an acid and is soluble in an aqueous alkali solution. The pattern substrate is obtained by developing in aqueous alkali solution.

Method (14): A fluorine-based polymer (B) and a photoacid generator (I) having an acid dissociation group (H) and a silicone chain (G) which are converted into an acid group by the action of an acid are dissolved in a diluent (J). When the fluorine-based polymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region dissociates to an acid and is soluble in an aqueous alkali solution. The pattern substrate is obtained by developing in aqueous alkali solution.

In any of the methods (1) to (14), a heat treatment of about 50 to 250 ° C. may be performed before (prebaking) or after (postbaking) irradiation of electromagnetic waves. When using a photoacid generator, it can also perform a PEB (Post Exposure Bake) process in the same temperature range.

● Crosslinking agent  (C)

The crosslinking agent is a monofunctional or preferably a compound having two or more functional groups, and may be in the form of curing by radical polymerization or in the form of curing by cationic polymerization. The former becomes a functional group of an acryloyl group and a vinyl group which are unsaturated double bond groups, and the latter becomes a functional group of an epoxy group, a vinyl ether group, and an oxetane group,

(a) urethane (meth) acrylate

(b) epoxy (meth) acrylate

(c) polyester (meth) acrylate

(d) polyether (meth) acrylate

(e) Silicone (meth) acrylate

(f) (meth) acrylate monomers

(g) epoxy monomers

(h) vinyl ether monomers

(i) oxetane-based monomers. (a)-(f) is a form hardened | cured by a radical polymerization reaction, (g)-(i) is a form hardened | cured by a cationic polymerization reaction.

(a)-(e) adds a (meth) acryloyl group to resin, and are often represented by an oligomer, base resin, a prepolymer, etc.

(a) Urethane (meth) acrylate is a thing which has a urethane bond and a (meth) acryloyl group in a molecule | numerator, tris (2-hydroxyethyl) isocyanurate diacrylate, and tris (2-hydroxyethyl) iso Poly [(meth) acryloyloxyalkyl] isocyanurate etc. which are represented by cyanurate triacrylate are illustrated.

(b) Epoxy (meth) acrylate adds the (meth) acryloyl group to an epoxy group, and it is common to use bisphenol A, bisphenol F, a phenol novolak, and an alicyclic compound as starting materials.

(c) Polyester (meth) acrylate adds (meth) acrylate to the ester resin containing polyhydric alcohol and polybasic acid. The polyhydric alcohols are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, and the like. Phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alkenylsuccinic acid and the like.

(d) The polyether (meth) acrylate is obtained by adding (meth) acrylate to a polyether resin of diol, and polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyethylene glycol-poly Propylene glycol di (meth) acrylate, and the like.

(e) Silicone (meth) acrylate is obtained by modifying one or both ends of a dimethylpolysiloxane having a molecular weight of 1,000 to 10,000 with a (meth) acryloyl group, and the following are exemplified.

(f) The (meth) acrylate monomers are monofunctional or polyfunctional alkyl (meth) acrylates, low viscosity polyether (meth) acrylates of 500 mPas (25 ° C) or less, methyl (meth) acrylates, Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl-n-hexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylic Hite, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro- 2-hydroxypropyl (meth) acrylate, (1,1-dimethyl-3-oxobutyl) (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, 2-methoxyethyl (meth) Acrylate, 2-ethoxyethyl (meth) acrylate, neopentylglycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, ethylene glycol di Acrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetra Acrylate etc. are illustrated.

(g) Epoxy type monomers are glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenol novolac and cresol novolac; Glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; And epoxy monomers such as glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid, and oligomers or alicyclic epoxides thereof. Especially, bisphenol A glycidyl ether monomer or oligomer can be used preferably. Specifically, Epicat 828 (molecular weight 380), Epicoat 834 (molecular weight 470), Epicoat 1001 (molecular weight 900), Epicoat 1002 (molecular weight 1,060), Epicoat 1055 (molecular weight 1,350), Epicoat 1007 (Molecular weight 2,900) etc. are illustrated.

(h) Vinyl ether monomers include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, cis-1,1,3-trimethyl-5-vinyloxycyclohexane, trans- 1,1,3-trimethyl-5-vinyloxycyclohexane, 1-isopropyl-4-methyl-2-vinyloxycyclohexane, 2-vinyloxy-7-oxabicyclo [3.2.1] octane-6- Warm, 2-methyl-2-vinyloxyadamantane, 2-ethyl-2-vinyloxyadamantane, 1,3-bis (vinyloxy) adamantane, 1-vinyloxyadamantanol, 3-vinyl Oxy-1-adamantanol, 1,3,5-tris (vinyloxy) adamantane, 3,5-bis (vinyloxy) -1-adamantanol, 5-vinyloxy-1,3-adamant Tandiol, 1,3,5,7-tetrakis (vinyloxy) adamantane, 3,5,7-tris (vinyloxy) -1-adamantanol, 5,7-bis (vinyloxy) -1 , 3-adamantanediol, 7-vinyloxy-1,3,5-adamantanetriol, 1,3-dimethyl-5-vinyloxyadamantane, 1,3-dimethyl-5,7-bis (Vinyloxy) adamantane, 3,5-dimethyl-7-vinyl Ci-1-adamantanol, 1-carboxy-3-vinyloxyadamantane, 1-amino-3-vinyloxyadamantane, 1-nitro-3-vinyloxyadamantane, 1-sulfo-3- Vinyloxyadamantane, 1-t-butyloxycarbonyl-3-vinyloxyadamantane, 4-oxo-1-vinyloxyadamantane, 1-vinyloxy-3- (1-methyl-1-vinyl Oxyethyl) adamantane, 1- (vinyloxymethyl) adamantane, 1- (1-methyl-1-vinyloxyethyl) adamantane, 1- (1-ethyl-1-vinyloxyethyl) adamant Tan, 1,3-bis (1-methyl-1-vinyloxyethyl) adamantane, 1- (1- (norbornan-2-yl) -1-vinyloxyethyl) adamantane, 2,5 -Bis (vinyloxy) norbornane, 2,3-bis (vinyloxy) norbornane, 5-methoxycarbonyl-2-vinyloxynorbornane, 2- (1- (norbornane-2- Yl) -1-vinyloxyethyl) norbornane, 2- (vinyloxymethyl) norbornane, 2- (1-methyl-1-vinyloxyethyl) norbornane, 2- (1-methyl-1- Vinyloxypentyl) norbornane, 3-hydroxy-4-vinyloxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodecane, 3,4-bis (vinyloxy) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 3-hydroxy-8-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3,8-bis (vinyloxy) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 3-methoxycarbonyl-8-vinyloxytetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 3-methoxycarbonyl-9-vinyloxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 3- (vinyloxymethyl ) Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 3-hydroxymethyl-8-vinyloxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 3-hydrate Oxymethyl-9-vinyloxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 8-hydroxy-3- (vinyloxymethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10} ] dodecane, 9-hydroxy-3- (vinyloxymethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, 8-vinyloxy-4-oxatricyclo [5.2.1.0 ^{2 , 6} ] decane-3,5-dione, 4-vinyloxy-11- ^{oxapentacyclo} [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadecane-10,12 -Dione, α-vinyloxy-γ, γ-dimethyl-γ-butyrolactone, α, γ, γ-trimethyl-α-vinyloxy-γ-butyrolactone, γ, γ-dimethyl-β-methoxycarb Bonyl-α-vinyloxy-γ-butyrolactone, 8-vinyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one, 9-vinyloxy-4-oxatricyclo [5.2. 1.0 ^2,6 ] decane-3-one, 8,9-bis (vinyloxy) -4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3-one, 4-vinyloxy-2,7-di Oxabicyclo [3.3.0] octane-3,6-dione, 5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5-methyl-5-vinyloxy-3 -Oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 9-methyl-5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 6-vinyloxy -3- ^oxatricyclo [4.3.1.1 ^4,8 ] undecane-2-one, 6,8-bis (vinyloxy) -3- ^oxatricyclo [4.3.1.1 ^4,8 ] undecane-2-one , 6-hydroxy-8-vinyloxy-3- ^oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one, 8-hydroxy-6-vinyloxy-3-oxatricyclo [4.3. 1.1 ^4,8] undecane-2- This, and such as isopropenyl ethers corresponding to these can be given.

(i) The oxetane monomers are 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] ethyl} benzene (Alonoxetane OXT-121 manufactured by Toagosei Co., Ltd.), 3-ethyl-3 -Hydroxymethyl oxetane (Alonoxetane OXT-101 by Toagosei Co., etc.) etc. are illustrated.

In addition, when an acid is contained in a fluoropolymer, an acid crosslinking agent can also be used for a crosslinking agent. The acid crosslinking agent is a plurality of reactors (for example, 2 to 10) that crosslink an acidic group in one molecule (for example, carboxylic acid, hydroxyl group, amino group, isocyanate group, N-methylol group, alkyl etherified N-methylol group) , An epoxy group, and the like, or a polyvalent metal salt of acetic acid, and an amino resin, an epoxy compound, an oxazoline compound, aluminum acetate, and the like are exemplified.

As an amino resin, the compound which hydroxymethylated the one part or all part of amino groups, such as a melamine type compound, a guanamine type compound, and a urea type compound, or the hydroxyl group of the said hydroxylated compound part or all part of methanol, ethanol, n-butyl Compounds etherified with alcohols, 2-methyl-1-propanol, and the like, for example, hexamethoxymethylmethylolmelamine, and various amino resins of alkyl, methylol, and imino types manufactured by Nippon Cytec Industries, etc. may be mentioned. have.

Examples of the epoxy compound include glycidyl ethers such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, trisphenol methane type epoxy resins, and brominated epoxy resins. Alicyclic epoxy resins such as, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, diglycidyl hexahydrophthalate, diglycidyl tetra Heterocyclic types, such as glycidyl esters, such as hydrophthalate and diglycidyl phthalate, glycidylamines, such as tetraglycidyl diaminodiphenylmethane and triglycidyl paraaminophenol, and triglycidyl isocyanurate Epoxy resin etc. are mentioned.

Examples of oxazoline compounds include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, And copolymers of polymerizable monomers such as 2-isopropenyl-4-methyl-2-oxazoline.

When a polyfunctional thiol like 1,4-bis (3-mercaptobutyryloxy) butane and pentaerythritol tetrakis (3-mercaptobutyrate) is used in combination with the crosslinking agent of the present invention, the curing rate is improved. The amount of the polyfunctional thiol may be, for example, 0.1 to 20 parts by weight, for example 1 to 10 parts by weight, based on 100 parts by weight of the crosslinking agent.

When using together with a fluorine-type monomer, a crosslinking agent is 1-100,000 weight part, especially 10-100,000 weight part with respect to 100 weight part of fluorine-type monomers. Moreover, when using together with a fluoropolymer, it is 1-100 weight part with respect to 100 weight part of fluoropolymers, especially 1-20 weight part.

● Photocrosslinking Catalyst (D)

Examples of the photocrosslinking catalyst include radical photopolymerization initiators and photoacid generators. A radical photoinitiator is a compound which generate | occur | produces a radical by light, For example, (alpha)-diketones, such as benzyl and diacetyl, acyloins, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin iso Thioxanthones such as acyloin ethers such as propyl ether, thioxanthones, 2,4-diethyl thioxanthone and thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino Benzophenones such as benzophenone and 4,4'-bis (diethylamino) benzophenone, acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2 Acetophenones such as -dimethylamino-1- (4-morpholinophenyl) -butan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, 4- Dimethylaminobenzo Aminobenzoic acids such as ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid isoamyl and 2-dimethylhexyl 4-dimethylaminobenzoic acid, halogens such as phenacyl chloride and trihalomethylphenylsulfone Peroxides, such as a compound, an acyl phosphine oxide, and di-t- butyl peroxide, etc. are mentioned. As a commercial item, IRGACURE-184, copper 261, copper 369, copper 500, copper 651, copper 907 (more than Shiva Gaigi), Darocur-1173, copper 1116, copper 2959, copper 1664, copper 4043 (more than Merck Japan production ), And the like.

Photochemical acid generator (PAG) is a material that generates acid by reacting with light. PAG is composed of a chromophore that absorbs light and an acid precursor which becomes an acid after decomposition, and PAG is excited by irradiating light of a specific wavelength to PAG having such a structure to generate acid from an acid precursor portion. PAG is, for example, salts such as diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, CF ₃ SO ₃ , p-CH ₃ PhSO ₃ , p-NO ₂ PhSO ₃ (where ph is a phenyl group) And organic halogen compounds, orthoquinone-diazidesulfonyl chlorides, or sulfonic acid esters.

The organic halogen compound is a compound that forms a hydrohalide acid, and such compounds include those disclosed in US Pat. No. 3,515,551, US Pat. No. 3,536,489, US Pat. No. 3,779,778, and German Patent Publication No. 2,243,621. As part of the present specification).

Compounds which generate an acid by irradiation with other light described above include Japanese Patent Application Laid-Open No. 54-74728, Japanese Patent Application Laid-Open No. 55-24113, Japanese Patent Application Laid-Open No. 55-77742, and Japanese Patent Publication 60-3626, Japanese Patent Laid-Open No. 60-138539, Japanese Patent Laid-Open No. 56-17345 and Japanese Patent Laid-Open No. 56-36209 (these disclosures are disclosed herein) As part of).

WPAG-145 [bis (cyclohexylsulfonyl) diazomethane], WPAG-170 [bis (t-butylsulfonyl) diazomethane], WPAG-199 [bis (p) -Toluenesulfonyl) diazomethane], WPAG-281 [triphenylsulfonium trifluoromethanesulfonate], WPAG-336 [diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate], WPAG-367 [ Diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate], CGI-1397 [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene, manufactured by Ciba Specialty Chemicals Co., Ltd.] )-(2-methylphenyl) acetonitrile], TFE-triazine [2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-tri Azine], TME-triazine [2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine], MP-triazine [2 -(Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine], to dimethoxytriazine [2- [2- (3,4-dimethoxyphenyl) Carbonyl] -4,6-bis (trichloromethyl) -s- triazine may be used; or the like.

The amount of the photocrosslinking catalyst is 0.1 to 20 parts by weight, in particular 1 to 10 parts by weight, based on 100 parts by weight of the total of the fluorine monomer and the crosslinking agent or the fluorine polymer or the fluorine polymer and the crosslinking agent.

The fluorine-based polymer (B) when used in combination with the photocrosslinking catalyst is at least one selected from the group consisting of a crosslinkable functional group (E), an acidic group (F), and an acid dissociable functional group (H) converted to an acidic group by the action of an acid. It is preferable to have a group. The fluorine-based polymer (B) may further have a silicone chain (G).

● Crosslinkable Functional group  (E)

As a form which hardens | cures by a radical polymerization reaction, the crosslinkable functional group provided to a fluoropolymer is unsaturated double bond groups, such as an acryloyl group and a vinyl group, and an epoxy group, an oxetane group, etc. are illustrated as a form which hardens by a cation polymerization reaction. . Moreover, the reactor which bridge | crosslinks an acidic group, for example, carboxylic acid, a hydroxyl group, an amino group, an isocyanate group, N-methylol group, the alkyl etherified N-methylol group, etc. may be sufficient.

The method of providing a crosslinkable functional group to a fluorine-type polymer is

(1) A method of synthesizing a monomer having a crosslinkable functional group in advance and copolymerizing it with a fluorine monomer

(2) Once synthesize | combining the fluoropolymer which has another functional group, it may be any of the method of converting the functional group into a crosslinkable functional group.

The amount of the crosslinkable functional group in the fluorine-based polymer is generally 0.1 to 20 mol%, particularly 1 to 10 mol%, based on the total of the repeating units in the polymer.

● Acid group  (F)

Examples of acidic groups are carboxyl groups, hydroxyl groups (particularly phenolic hydroxyl groups), sulfonic acid groups and the like.

The method of giving an acidic group to a fluoropolymer is

(1) A method of synthesizing a monomer having an acidic group in advance and copolymerizing it with a fluorine monomer

(2) Once synthesize | combining the fluoropolymer which has another functional group, it may be any method of converting the functional group to an acidic group.

In the case of (1), the following are illustrated as a monomer which has an acidic group. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. As a monomer which has a hydroxyl group, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. are mentioned. In addition, one or more hydrogen atoms of these benzene rings are substituted by one or more hydrogen atoms of an alkyl group such as methyl, ethyl and n-butyl, an alkoxy group such as methoxy, ethoxy and n-butoxy, a halogen atom and an alkyl group by a halogen atom And a compound substituted with a substituted haloalkyl group, nitro group, cyano group, and amide group. Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl, and (meth) acrylic acid-2-sulfo Propyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, and salts thereof. These may be used independently and may use 2 or more types together.

In the case of (1), a composition distribution may arise in a copolymer from the difference of the reactivity of the fluorine-type monomer and the monomer which has an acidic group, and it may adversely affect patterning. When this becomes a problem, it is preferable to use the same thing as the vinyl group structure of the fluorine-type monomer, and the vinyl group structure of the monomer which has an acidic group. For example, when using alpha-Cl acrylate containing an Rf group for a fluorine monomer, it is preferable to use alpha-Cl acrylic acid as a monomer which has an acidic group.

The amount of the acidic group in the fluorine-based polymer is generally 0.1 to 20 mol%, particularly 1 to 10 mol%, based on the total amount of the repeating units in the polymer.

● Silicon chain  (G)

Silicone chain (G) is dimethylpolysiloxane having a molecular weight of 1,000 to 10,000.

The method of giving a silicone chain to a fluoropolymer is

(1) A method of synthesizing a monomer having a silicone chain or a polymerization initiator in advance and copolymerizing it with a fluorine monomer

(2) Once synthesize | combining the fluoropolymer which has another functional group, it may be any of the method of couple | bonding a silicone chain with this functional group. In the case of the method (1), the silicone (meth) acrylate described in the crosslinking agent (C) can also be used.

The amount of the silicone chain in the fluorine-based polymer is generally 0.1 to 50 mol%, particularly 1 to 10 mol%, based on the total amount of the repeating units in the polymer.

● by the action of acid Acidic  Converting Acid dissociation Functional group  (H)

The acid dissociable functional group converted into an acidic group by the action of an acid is a t-butoxycarbonyl group (t-BOC), isopropoxycarbonyl group, tetrahydropyranyl group, trimethylsilyl group, t-butoxycarbonylmethyl group, or these acid dissociation. Illustrative phenolic hydroxyl groups protected by functional groups are exemplified.

The method of providing an acid dissociable functional group to a fluoropolymer is

(1) A method of synthesizing a monomer having an acid dissociable functional group in advance and copolymerizing it with a fluorine monomer

(2) First, any one of the methods of synthesizing a fluorine-based polymer having another functional group and converting the functional group into an acid dissociable functional group may be used. In the case of method (1), t-butyl (meth) acrylate can also be used.

The amount of the acid dissociable functional group in the fluorine-based polymer is generally 0.1 to 50 mol%, particularly 1 to 10 mol%, based on the total of the repeating units in the polymer.

● Photoacid generator  (I)

It is the same as the photoacid generator described in the photocrosslinking catalyst (D). When the film of the fluorine-based polymer (B) having an acid dissociable functional group (H) is irradiated with electromagnetic waves in the presence of a photoacid generator, an acidic group is generated and the irradiated region of the film becomes lyophilic. Moreover, since this acidic group is soluble in aqueous alkali solution, it becomes possible to develop the irradiation area of a film | membrane in aqueous alkali solution.

● thinner (J)

To the surface treatment agent for photolithography of the present invention, a solvent (especially a water-soluble organic solvent, an organic solvent (especially an oil-soluble organic solvent) and water) may be added as the diluent (J) as necessary. Diluents are the same as those used to prepare the fluoropolymer. The diluent is inert to the fluorine monomer (A) or the fluorine polymer (B) and dissolves them. Examples of the diluent 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, and dipropylene glycol monomethyl as water-soluble organic solvents. Ether acetate, dipropylene glycol, tripropylene glycol, 3-methoxybutyl acetate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, iso Propyl alcohol, methanol, ethanol and the like as chloroform, HFC141b, HCHC225, hydrofluoroether, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4 Dioxane, methyl isobutyl ketone, butyl acetate, 1,1,2,2-tetrachlor Of ethane, 1,1,1-trichloro ethane, trichloro there may be mentioned ethylene, perchlorethylene, tetrachloroethane difluoro ethane, trichloro-fluoro roteuri like. These solvents may be used alone or in combination of two or more thereof. A diluent is used in 50-2000 weight part, for example, 50-1000 weight part with respect to a total of 100 weight part of a fluorine-type monomer (A) or a fluoropolymer (B).

● Production of fluorine-based polymer

A fluoropolymer can be manufactured as follows. After dissolving the monomer and the necessary components in a solvent to replace the nitrogen, a method of adding a polymerization catalyst and stirring for 1 to 20 hours in the range of 20 to 120 ° C is employed.

The solvent may be an organic solvent, a water-soluble organic solvent, water, or the like, which is the same as the diluent (J). A solvent is used in 50-2000 weight part, for example, 50-1000 weight part with respect to a total of 100 weight part of monomers.

In order to adjust the molecular weight of a fluoropolymer, chain transfer agents, such as mercaptans and a halogenated alkyl, can also be added. As mercaptans, n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolic acid, 2-ethylhexyl 2-thiohexyl, 2-mercaptoethanol, mercapto acid isooctyl, thioglycolic acid, 3 -Mercaptopropionic acid, thioglycolic acid methoxybutyl, silicone mercaptan (manufactured by Shin-Etsu Chemical Co., Ltd., KF-2001) and the like, and halogenated alkyls include chloroform, carbon tetrachloride, carbon tetrabromide and the like. These may be used independently and may use 2 or more types together.

The weight average molecular weight of the fluoropolymer may be, for example, 1,000 to 500,000, in particular 2,000 to 100,000, in particular 3,000 to 20,000. The weight average molecular weight of a fluoropolymer is calculated | required by GPC (gel permeation chromatography) (standard polystyrene conversion).

● Carbon number  8 to 12 Fluoroalkyl groups  Monomers and Polymers Having

The surface treating agent for photolithography of the present invention may be blended with a monomer having a fluoroalkyl group having 8 to 12 carbon atoms (for example, perfluorooctylethyl acrylate) and a polymer having the monomer as a repeating unit, as necessary. It may be.

● Non-fluorine  polymer

A non-fluorine-type polymer can also be used together with the surface treating agent for photolithography of this invention as needed. Non-fluorine-based polymers are, for example, alkali-soluble resins, the novolac-type phenol resins of Japanese Patent No. 2505033, Japanese Patent Application Laid-Open No. Hei 3-170554, Japanese Patent Application Laid-Open No. Hei 6-118646, and Japanese Patent Laid-Open For the hydrogenation of the polyvinyl phenol resin which narrowed the molecular weight distribution of 7-311463, Unexamined-Japanese-Patent No. 8-292559, Unexamined-Japanese-Patent No. 3-87746, and Unexamined-Japanese-Patent No. 8-44061 Phenol resin converted to a partial cyclic alcohol structure by the above, a resin in which a part of the OH groups of polyvinylphenols of Japanese Patent Application Laid-Open No. Hei 7-295200 and Japanese Patent Application Laid-Open No. Hei 8-152717 are protected by an alkyl group, and Japanese Patent Laid-Open Polyvinylphenol resin having a protecting group inert to acids such as acyl groups of Japanese Patent No. 8-339086, polyvinyl copolymerized with styrene of Japanese Patent Application Laid-Open No. 6-67431, Japanese Patent Application Laid-open No. Hei 10-10733 Phenolic resin, (meth) acrylate short-term retention of Japanese Patent Laid-Open No. 9-166870 Polyvinyl phenol resin copolymerized, resin which has a carboxyl group of Unexamined-Japanese-Patent No. 8-240911, etc. (The indication of these publication is made a part of this specification).

● pigment

Various pigments can also be added to the surface treating agent for photolithography of this invention as needed. For example, black pigments are carbon black, graphite, titanium black, iron oxide, bismuth sulfide, perylene black and the like.

● acid Capture agent

The diffusion of the acid generated from the acid generator in the film can be controlled by adding an acid trapping agent to the surface treating agent for photolithography of the present invention as needed. As the acid trapping agent, organic amines, basic ammonium salts, basic sulfonium salts and the like are used, and those which do not deteriorate sublimation or resist performance are preferable. Among these acid scavengers, organic amines are preferred in terms of excellent image performance. For example, Japanese Patent Laid-Open No. 63-149640, Japanese Patent Laid-Open No. 5-249662, Japanese Patent Laid-Open No. 5-127369, Japanese Patent Laid-Open No. 5-289322, and Japanese Patent Publication No. 5-249683, Japanese Patent Publication No. 5-289340, Japanese Patent Publication No. 5-232706, Japanese Patent Publication No. 5-257282, Japanese Patent Publication No. 242605, Japanese Patent Laid-Open No. 6-242606, Japanese Patent Laid-Open 6-266100, Japanese Patent Laid-Open 6-266110, Japanese Patent Laid-Open 6-317902, Japanese Patent Laid-Open Japanese Patent Publication No. 7-120929, Japanese Patent Publication No. 7-146558 Japanese Patent Publication No. 7-319163 Japanese Patent Publication No. 7-508840 Japanese Patent Publication No. 7-333844 Japanese Patent Laid-Open No. 7-219217, Japanese Patent Laid-Open No. 7-92678, Japanese Patent Laid-Open No. 7-28247, Japanese Patent Laid-Open No. 8-22120, Japan Patent Laid-Open Pyeong) 8-110638, Japanese Patent Publication (Pyeong) 8-123030, Japanese Patent Publication (Pyeong) 9-274312, Japan Patent Japanese Patent Laid-Open No. 9-166871, Japanese Patent Laid-Open No. 9-292708, Japanese Patent Laid-Open No. 9-325496, Japanese Patent Laid-Open No. 7-508840, USP5525453, USP5629134, USP5667938 And basic compounds described in, etc. may be used (these disclosures are part of this specification). As the acid trapping agent, preferably 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether , Pyridinium p-toluenesulfonate, 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine and the like Can be. Among them, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane , 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, triethylamine, tri Organic amines, such as butylamine, are preferable.

● Other additives

The other various additive is used for the surface treatment agent for photolithography of this invention as needed. For example, a fluorine-based, silicon-based or hydrocarbon-based surfactant for improving the smoothness of the membrane, a silane coupling agent, a titanate coupling agent for improving the adhesion of the membrane, other thermal polymerization inhibitors, ultraviolet absorbers, or antioxidants for inhibiting cancer reactions. And antifoaming agents.

● mention

The base material used for the board | substrate of this invention is silicon, a synthetic resin, glass, a metal, a ceramic, etc.

The synthetic resin may be any one of a thermoplastic resin and a thermosetting resin, and for example, polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers (EVA), cyclic polyolefins, modified polyolefins, polychlorides Vinyl, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene air Polyesters such as copolymer (AS resin), butadiene-styrene copolymer, polio copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), and polyether , Polyether ketone (PEK), polyether ether ketone (PEEK), polyetherimide, polyacetal (P0M), polyphenylene oxide, modified polype Nylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluorine resin, styrene, polyolefin, polyvinyl chloride, polyurethane, fluororubber, chlorinated polyethylene Various thermoplastic elastomers, such as a system, an epoxy resin, a phenol resin, a urea resin, a melamine resin, unsaturated polyester, a silicone resin, a polyurethane, etc., or a copolymer, a blend body, a polymer alloy mainly containing these, etc. are mentioned, These are mentioned. It can be used in combination of one or two or more of them (for example, as a laminate of two or more layers). When the substrate made of synthetic resin is used, characteristics such as light weight, transparency, low cost, and flexibility can be imparted to the substrate.

As glass, silicate glass (quartz glass), silicate alkali glass, soda-lime glass, kali lime glass, lead (alkali) glass, barium glass, boron silicate glass, etc. are mentioned, for example.

Examples of the metal include gold, silver, copper, iron, nickel, aluminum, platinum and the like.

Examples of ceramics include oxides (e.g., aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (e.g. silicon nitride, boron nitride), sulfides (e.g. cadmium sulfide), carbides ( For example, silicon carbide) etc. can be mentioned, A mixture thereof can be used.

In any case of using a substrate, pretreatment such as plasma treatment or UV ozone treatment may be performed. By these pretreatments, a lyophilic functional group (for example, OH group, COOH group, NH group) can be introduced to the substrate surface.

The shape of the pattern surface is preferably selected according to the purpose of the device to be finally manufactured, and examples include circles, squares, triangles, straight lines, curves, and the like. The patterns of each other may be adjacent or apart. For example, in the case of Line & Space, the line width and line spacing can be 0.5 to 100 μm, for example 1 to 20 μm. The line width may be equally spaced or the width may vary. The shape of the line may be a straight line or a curve.

The surface treatment agent (fluorine-containing compound) is uniformly treated in the liquid phase or the gas phase on the surface of these substrates. As long as the treatment in the liquid phase can control the film thickness, a known coating method can be employed. For example, a roll coating method, a gravure coating method, a micro gravure coating method, a flow coating method, a bar coating method, a spray coating method, a die coating method, a spin coating method, an immersion coating method, or the like can be adopted. Can be selected in consideration of the shape, productivity, controllability of the film thickness, and the like. For example, the substrate is applied to the fluorine-containing compound solution by spin coating, and then heated at 70 to 150 ° C. for 1 second to 10 minutes (for example, at 110 ° C. for 1 minute) to remove the solvent from the film of the fluorine-containing compound. It can carry out by drying. This simple process forms a film of the fluorine-containing compound on the surface of the substrate. The thickness of the film of the fluorine-containing compound may generally be 0.5 nm to 1000 μm, for example 10 nm to 200 μm, in particular 50 nm to 100 μm. In the manufacturing methods (1) and (11) to (14) of the pattern substrate, a uniform liquid-repellent surface of 60 ° or more, particularly 80 ° or more can be obtained with respect to the water contact angle without irradiating light. On the other hand, in the manufacturing method (2)-(10) of a pattern board | substrate, by irradiating light, the liquid-repellent surface of 60 degrees or more, especially 80 degrees or more with respect to a water contact angle is formed in an irradiation area.

Subsequently, by using the photolithography method, patterning is performed so that it may be 50 degrees or less with respect to the water contact angle of a lyophilic region. A plurality of regions having different surface free energies ((1) 60 degrees or more with respect to the water contact angle, in particular 80 degrees or more with respect to the water contact angle, and (2) 50 degrees or less with respect to the water contact angle, particularly with respect to the water contact angle. Region of 30 degrees or less] is manufactured. Region 1 and region 2 are adjacent.

In order to pattern a film of a fluorine-containing compound by photolithography, electromagnetic waves are irradiated.

● electromagnetic waves

The electromagnetic wave irradiated to the film in the present invention is light having a wavelength of 10 to 400 nm, ultraviolet (UV, 200 to 400 nm), vacuum ultraviolet light (VUV, 150 to 200 nm), extreme ultraviolet (EUV, 10 to 120 nm). Etc. are illustrated. When using VUV, the light source may use a commercially available xenon excimer lamp capable of emitting VUV with a wavelength of 172 nm. In addition, when using UV, a light source can use a mercury xenon lamp, a mercury lamp, a xenon lamp, and a xenon excimer lamp. It is also possible to use a 248 nm KrF excimer laser, a 193 nm ArF excimer laser, and a 157 nm F2 excimer laser. The exposure dose can be 1 to 10,000 mJ / cm ² , in particular 1 to 1000 mJ / cm ² .

In addition to the light, an X-ray having a wavelength of 0.1 to 10 nm, an electron beam having a wavelength of 0.001 to 0.01 nm, and an electromagnetic wave of a laser beam having a wavelength of 10 to 300 nm may be used.

In the case of performing photolithography with light or X-rays, light can be irradiated onto the film through a photomask, and without a mask, using a semiconductor such as DMD (Digital Micromirror Device) developed by Texas Instruments, Inc. Light can also be irradiated on a pattern. DMD fills 480,000 to 1.13 million micro-micro mirrors (micromirrors), and reflects the lamp light on the mirror to irradiate light onto the film in a pattern.

On the other hand, in an electron beam and a laser beam, a pattern is drawn on the board | substrate directly surface-treated uniformly without a photomask using a commercially available drawing apparatus. The exposure dose of the electron beam may be 10 to 10,000 μC / cm ² in raster drawing, in particular 100 to 1,000 μC / cm ² , and 100 to 100,000 fC / dot in short drawing, especially 1,000 to 10,000 fC / dot.

● Status

In this invention, what is called "development" which removes the area | region of a solvent soluble using the solubility contrast with respect to a solvent after irradiating said electromagnetic wave can also be performed. The solvent (developer) used for image development uses the thing used for manufacture of a fluoropolymer, or aqueous alkali solution. The aqueous alkali solution is an inorganic alkaline aqueous solution such as sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, aqueous ammonia, 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; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; An aqueous organic alkali solution containing alkalis of cyclic amines such as pyrrole and piperidine is used. These may be used independently and may mix 2 or more types. In addition, a surfactant may be added.

The developing method can be performed in the range of 10 seconds to 10 minutes by the dipping method, the puddle method, or the like.

According to a second aspect, in the present invention, the following method for producing a patterned substrate can be used.

● Manufacturing method of pattern board

In the present invention, an electromagnetic wave curing composition comprising a fluorine-based monomer (A) containing a fluoroalkyl group, a crosslinking agent (B), and a photocrosslinking catalyst (C) is discharged onto a substrate by a noncontact microdroplet ejection method to produce a microstructure. The film | membrane which has is formed, and an electromagnetic wave is irradiated to harden a film | membrane. As an example of a non-contact trace liquid droplet discharge method, the inkjet method, the micro dispenser method, etc. are mentioned, for example.

The piezo system can be used as the inkjet method. The piezo system is also used in inkjet printers because of excellent controllability of droplets and high freedom of ink selection. In addition, the piezo system includes MLP (Multi Layer Piezo) type and MLChip (Multi Layer Ceramic Hyper Integrated Piezo Segments) type. It may be an inkjet method using a thermal method in which a heating element is generated to generate bubbles to extrude ink liquid. The capacity per drop of the droplets ejected by the inkjet method is 0.1 pL to 1 nL. The physical property at 25 degrees C of the electromagnetic wave hardening composition (ink) suitable for the inkjet method in this invention is a viscosity of 1-50 mPa * s, surface tension 19-30 mN / m, and boiling point 100-250 degreeC.

As the micro dispenser method, a tubing method or an air compression method can be used. The capacity per drop of the droplets ejected by the micro dispenser method is generally 1 nL to 1 µL.

The heat-repellent film may be subjected to a heat treatment of about 50 to 250 ° C. before irradiating electromagnetic waves (prebaking) or after (postbaking). When hardening is inhibited by oxygen, electromagnetic waves can also be irradiated in inert gas atmosphere, such as nitrogen and argon.

In this simple process, a liquid repellent film is formed on the surface of the substrate, and a pattern substrate composed of a plurality of (two or more) regions having different surface free energies, that is, a pattern including one or more patterned liquid repellent regions and one or more lyophilic regions A substrate (hereinafter, simply referred to as a "pattern substrate") can be manufactured.

The thickness of the liquid repellent film may generally be 1 nm to 1000 μm, for example 10 nm to 200 μm, in particular 50 nm to 100 μm. The liquid repelling region shows liquid repellency of, for example, 70 ° or more, particularly 80 ° or more, with respect to the water contact angle. It is preferable to select the shape of the pattern of the liquid repellent area according to the purpose of the device finally manufactured, and a straight line, a curve, a circle, a rectangle, a triangle, etc. are illustrated. The patterns of each other may be adjacent or apart. For example, in the case of line & space, the width of the line (liquid repellent region) can be 10 to 1000 mu m, for example 100 to 500 mu m. The ratio of line to space is arbitrary, for example 1/10 to 10/1. The shape of the line may be a straight line or a curve.

Application of a functional compound solution to a substrate having a pattern formed thereon;

In this invention, the solution or dispersion liquid of a functional compound is apply | coated to the board | substrate with which the pattern was formed. The method of applying the functional compound solution is spin coating method, dip coating method, casting method, roll coating method, printing method, transfer method, ink jet method [P. Calvert, Chem. Mater., 13, 3299 (2001)], bar coating method, capillary method, etc. are mentioned.

A functional compound layer is formed on the film of the patterned fluorine-containing compound.

A functional compound layer can be formed by apply | coating the solution which melt | dissolved the functional compound in the solvent on the pattern surface, and removing a solvent. When the functional compound solution is applied to a plurality of regions having different surface free energies, the functional compound solution avoids an area of 60 ° or more, particularly 80 ° or more, with respect to the water contact angle, and thus, 50 ° or less, especially 30 ° or less, with respect to the water contact angle. Is only attached. In this way, the functional compound layer is formed on the lyophilic region patterned on the substrate.

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

As a semiconductor compound, an organic type is preferable and a pentacene derivative, a polythiophene derivative, a phthalocyanine derivative, a polyfluorene derivative, poly p-phenylene vinylene, a layered perovskite compound, etc. are mentioned, for example.

The conductive compound has conductivity of 10 ² S / cm or more at room temperature. For example, in an organic type, a polyacetylene derivative, a polythiophene derivative, polypyrrole, poly p-phenylene vinylene, polyaniline, etc. are mentioned. Doping these compounds can also improve conductivity. In metal system, what disperse | distributed nanoparticles, such as gold, silver, copper, to a liquid is mentioned.

As a photochromic compound, an organic type is preferable, For example, an azobenzene derivative, a spiropyran derivative, a fulgid derivative, a diarylethene derivative, etc. are mentioned.

The thermochromic compound is a generic term for compounds in which the color of a substance is reversibly changed with temperature changes. For example, salicylidene aniline, polythiophene derivative, tetrahalogeno complex, ethylenediamine derivative complex, dinit Rhodiamine copper complex, 1,4-diazacyclooctane (daco) complex, hexamethylenetetramine (hmta) complex, salicylate (salen) complex, etc. are mentioned.

The thickness of the functional compound layer may be 0.1 nm to 100 μm, for example 1 nm to 1 μm.

Examples of the solvent for dissolving the functional compound are organic solvents (particularly oil-soluble organic solvents), water-soluble organic solvents, and water. When the functional compound is poorly soluble in water, it is necessary to dissolve it in an organic solvent (especially 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. As the surface tension is 40 mN / m or less, the solution can easily spread along the pattern shape.

Examples of the organic solvent include alcohols, esters, ketones, ethers, hydrocarbons (for example, aliphatic hydrocarbons and aromatic hydrocarbons), and the organic solvents may or may not be fluorinated. Specific examples of the organic solvent include perfluorodecalin, hydrofluoroether, HCFC225, chloroform, 1,1,2,2-tetrachloroethane, tetrachloroethylene, chlorobenzene, butyl acetate, hexane, isopentane, toluene, x Silane, tetrahydrofuran and the like. 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 glycol, tripropylene glycol, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol, etc. Can be mentioned.

When using water, surface tension can also be reduced by adding surfactant, the above water-soluble organic solvent, etc.

The concentration of the functional compound in the functional compound solution may be 0.1 to 20% by weight, for example 1 to 10% by weight.

The solvent can be removed by evaporation or the like. Removal of a solvent can be performed by heating a base material (for example, 60-200 degreeC). Solvent removal may be performed under reduced pressure (for example, 0.01-100 Pa).

The substrate of the present invention can be used for devices of a wide range of applications such as electronic, optical, medical, and chemical analysis. For example, it can be used for integrated circuits, such as a transistor, a memory, a light emitting diode (EL), a laser, and a solar cell, as an electronic device. Flexible displays, wireless tags, wearable computers and the like are manufactured from these devices. In addition, as an optical device, a pixel for display, an optical memory, an optical modulation element, an optical shutter, a secondary high frequency (SHG) element, a polarizing element, a photonic crystal, a lens array, etc., can be used as a medical device such as a DNA array, a protein array, or the like. Biochip etc. can be used. As a chemical analysis device, it can use for microchemical chips, such as a microchemical plant and a microchemical analysis system.

The surface treatment agent for photolithography of the present invention is very useful for liquid-repellent black matrix required when producing a color filter for display by an inkjet method. The inkjet method is expected as a technique for producing a color filter at low cost, but the inkjet technique alone lacks an impact accuracy enough to accurately print red, green, and blue inks in the black matrix (pixel portion). Therefore, it is necessary to liquefy the upper part of the black matrix to turn the ink droplets which erroneously escape into the pixel. In addition, when red, green, and blue inks are injected to an amount exceeding the height of the black matrix in order to increase the film thickness of the pixel, liquid liquefaction on the black matrix is essential. The liquid repellency of the former is indicated by the drop angle of the ink solution, and the liquid repellency of the latter is indicated by the static contact angle.

Conventionally, in order to liquefy the black matrix, CF ₄ , SF ₆ , CHF ₃ by atmospheric plasma method Fluorine gas, such as the above, was adsorbed onto the black matrix (Japanese Patent Laid-Open No. 2000-353594). However, this method has a problem that a uniform liquid repellent region is not formed due to defects derived from plasma, or liquid repellents are formed on the side as well as the top of the black matrix. In order to improve these drawbacks, fluorinated polymer photosensitive liquid repellent treatment agents have been devised.

For example, Japanese Patent Laid-Open No. 11-281815, Japanese Patent Laid-Open No. 2004-151618, and Japanese Patent Laid-Open No. 2005-315984 can be referred to.

However, the fluorine-based polymer disclosed in these documents was unable to achieve both liquid repellency and compatibility with other materials forming the photosensitive composition. On the other hand, the surface treatment agent for photolithography of this invention is compatible with very high liquid repellency and compatibility.

Hereinafter, two methods for liquid-repelling a black matrix using the surface treatment agent for photolithography of this invention are demonstrated.

The first method is a method of forming a liquid-repellent black matrix on a lyophilic transparent substrate by a photolithography method by using a dispersion of a black pigment in the surface treatment agent for photolithography of the present invention. As an example of the surface treating agent for photolithography at this time, it is, for example

Fluorine-type polymer (B) which has a crosslinkable functional group (E) and an acidic group (F)

5 to 10 wt%

1 to 5% by weight of crosslinking agent (C)

1 to 5% by weight of the photocrosslinking catalyst (D)

20 to 20 weight percent carbon black dispersion

Solvent Residue (Total 100% by Weight)

Can be mentioned.

The second method is to uniformly apply the surface treatment agent for photolithography of the present invention onto the photosensitive resin black layer formed uniformly on the lyophilic transparent substrate, and then liquefy the liquid onto the lyophilic transparent substrate by a photolithography method. It is a method of forming a black matrix. As an example of the surface treating agent for photolithography at this time, it is, for example

5 to 10 wt% of the fluoropolymer (B) having an acidic group (F)

1 to 5% by weight of crosslinking agent (C)

1 to 5% by weight of the photocrosslinking catalyst (D)

Solvent Residue (Total 100% by Weight)

Can be mentioned.

The color filter can be manufactured very cheaply by apply | coating the red, green, and blue pigment dispersion liquid for color filters by the inkjet method, and removing a solvent on the transparent substrate which has the liquid-repellent black matrix by any of these.

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.

Static contact angle and tumble angle were measured by the following method.

silence Contact angle Tumbled  Measure

Static contact angle was calculated | required by dropping 2 microliters of water or n-hexadecane from the micro syringe to the horizontally placed board | substrate, and taking a still image 1 second after dripping by the video microscope.

In addition, the tumble angle was calculated | required by the following method. 20 microliters for water, 5 microliters for n-hexadecane and propylene glycol monomethyl ether acetate (PGMEA) were dripped from the microsyringe to the horizontally placed substrate, and the substrate was inclined at a rate of 2 ° per second to Until the start of tumble was recorded as a moving image with a video microscope. The angle at which the droplet starts to fall by reproducing the moving image is set as the tumble angle.

<Manufacture example 1>

100 g of fluorinated monomers CH ₂ = C (F) COOCH ₂ CH ₂ C ₄ F ₉ (abbreviated α-F) and 400 g of HCFC225 were placed in a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirring device. After heating to 占 폚, the mixture was stirred for 30 minutes under a nitrogen stream. 0.5 g of 2,2'- azobisisobutyronitrile was added here, and it superposed | polymerized for 18 hours. The residual monomer in the reaction solution was analyzed by gas chromatography to confirm that the polymerization rate was 95% or more. The obtained reaction solution was precipitated with methanol and dried in vacuo to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 21,000 (polystyrene conversion).

<Manufacture example 2, 3, Comparative manufacture example 1>

The fluorinated monomers of Preparation Example 1 were each CH ₂ = C (Cl) COOCH ₂ CH ₂ C ₄ F ₉ (abbreviated α-Cl), CH ₂ = C (H) COO (CH ₂ ) ₃ SO ₂ C ₄ F ₉ ( abbreviated _{SO2Pr), CH 2 = CHCOOCH 2} CH 2 C 4 F ₉ was (abbreviated to one substituted with a α-H) prepared in examples 2 and 3 and Comparative Preparation example 1. The weight average molecular weights were 16,000, 9,000 and 15,000, respectively.

<Examples 1-3, Comparative Example 1>

After cleaning the silicon wafer of the substrate with acetone, the surface was made superhydrophilic by irradiating vacuum ultraviolet light. 1 nm by weight solution prepared by diluting the fluorinated polymers of Preparation Examples 1 to 3 and Comparative Preparation Example 1 with HCFC225 on this substrate was subjected to spin coating under conditions of 2000 rpm and 1 minute to obtain a film thickness (film thickness excluding solvent) 100 nm. Was prepared. The static contact angle and tumble angle of this membrane were measured. The results are shown in Table 1 below. Indicated glass transition points are measured for bulk polymers. The static contact angles were hardly different between the examples and the comparative examples, but the tumble angles were much smaller than those of the comparative examples, and liquids were likely to fall.

A photomask of line / space = 10 mu m / 10 mu m was brought into close contact with these films to irradiate vacuum ultraviolet light for 10 minutes to lyze the irradiated region, thereby producing a patterned substrate including the liquid repellent region and the lyophilic region.

A 1 wt% toluene solution of poly (9,9-dioctylfluorene) (ADS129BE manufactured by American Dye Source) was applied to these pattern substrates by the inkjet method. Inkjet was carried out by the on-demand method with a nozzle diameter of 50 micrometers. When the thin film after toluene drying was observed with the optical microscope, in Example 1-3, the clearly thin polymer thin film | membrane was formed along the lyophilic region of the line width of 10 micrometers. On the other hand, in Comparative Example 1, it was only apparently cleaved.

<Examples 4 and 5, Comparative Example 2>

The same substrate as in Example 1 was used. In Example 4, 45 weight% of bisphenol A-dihydroxyethyl ether diacrylate (crosslinking agent), 25 weight% of (alpha) -F (fluorine-type monomer), and the dimethylpolysiloxane (crosslinking agent) of molecular weight 5,000 in which both ends were modified by the methacryloyl group ) 25% by weight, 2-hydroxy-2-methyl-1-phenylpropane (photopolymerization initiator) mixed and dissolved to 5% by weight, and this solution was deposited on a substrate using a doctor blade (film without solvent) Thickness) to 100 μm. In Example 5 and Comparative Example 2, α-F was substituted with α-Cl and α-H, respectively.

Under a nitrogen atmosphere, ultraviolet rays having a wavelength of 365 nm were irradiated to the treated substrate under a condition of cumulative illuminance of 1000 mJ / cm ² through a photomask having a line / space = 10 μm / 10 μm. In this operation, the irradiation region is crosslinked and insoluble in the solvent. Subsequently, a pattern substrate including a liquid repellent region and a lyophilic region was prepared by dissolving and removing the fluorine-based polymer in the unirradiated region by dipping the substrate in methanol.

To these patterned substrates, a 1 wt% toluene solution of poly (9,9-dioctylfluorene) was applied by the inkjet method. When the thin film after toluene drying was observed with the optical microscope, in Example 4, 5, the polymer thin film which was clearly divided along the lyophilic region of 10 micrometers of line widths was formed. On the other hand, in Comparative Example 2, it was only apparently cleaved.

&Lt; Preparation Example 4 &

50 g of α-Cl, 50 g of methacrylic acid, and 400 g of isopropyl alcohol were added to a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirring device, and heated to 70 ° C., followed by stirring under a nitrogen stream for 30 minutes. It was. 1 g of 2,2'-azobisisobutyronitrile was added thereto and polymerized for 18 hours. The residual monomer in the reaction solution was analyzed by gas chromatography to confirm that the polymerization rate was 95% or more. The obtained reaction solution was precipitated with hexane and dried in vacuo to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 35,000 (polystyrene conversion).

<Comparative Production Example 2>

What substituted the fluorine-type monomer of the manufacture example 4 with (alpha) -H was made into the comparative manufacture example 2. The weight average molecular weight was 32,000.

<Example 6, Comparative Example 3>

10 wt% of the fluorine-based polymer of Preparation Example 4 or Comparative Preparation Example 2, 1 wt% of the acid generator WPAG-199 (Wako Pure Chemical Industries), 5 wt% of the acid crosslinking agent Cymel 303 (Nippon Cytec Industries), propylene glycol monomethyl ether A 84 wt% solution was spin-coated on the same substrate as in Example 1 to prepare a 5 탆 film (film thickness except solvent) on the substrate. After heating at 110 ° C. for 3 minutes, the film was irradiated with 365 nm UV light under a condition of cumulative illuminance of 100 mJ / cm ² through a photomask of line / space = 10 μm / 10 μm, and further at 110 ° C. for 3 minutes. Heated. In this operation, the irradiation region is crosslinked and insoluble in the solvent. Subsequently, after developing by immersing in 2.38 weight% of tetramethylammonium hydroxide aqueous solution for 1 minute, it washed with water and manufactured the patterned substrate which contains a liquid repellent region and a lyophilic region.

To these patterned substrates, a 1 wt% toluene solution of poly (9,9-dioctylfluorene) was applied by the inkjet method. When the thin film after toluene drying was observed under the optical microscope, in Example 6, a clearly divided polymer thin film was formed along the lyophilic region having a line width of 10 mu m. On the other hand, in Comparative Example 3, it was only apparently cleaved.

Production Example 5

50 g of α-Cl, 50 g of t-butyl methacrylate and 400 g of butyl acetate were added to a four-necked flask equipped with a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, and heated to 70 ° C., followed by nitrogen gas flow for 30 minutes. Stirred under. 1 g of 2,2'-azobisisobutyronitrile was added thereto and polymerized for 18 hours. The residual monomer in the reaction solution was analyzed by gas chromatography to confirm that the polymerization rate was 95% or more. The obtained reaction solution was precipitated with hexane and dried in vacuo to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 36,000 (polystyrene conversion).

<Comparative Production Example 3>

What substituted the fluorine-type monomer of the manufacture example 5 with (alpha) -H was made into the comparative manufacture example 3. The weight average molecular weight was 33,000.

<Example 7, Comparative Example 4>

A solution of 10% by weight of the fluorinated polymer of Preparation Example 5 or Comparative Preparation Example 3, 1% by weight of the photoacid generator WPAG-199 (Wakko Sanya) and 89% by weight of butyl acetate was spin-coated on the same substrate as in Example 1, onto the substrate A film having a thickness of 3 탆 (film thickness except solvent) was prepared. After heating at 110 ° C. for 3 minutes, the film was irradiated with 365 nm of UV light under a condition of cumulative illuminance of 100 mJ / cm ² through a photomask of line / space = 10 μm / 10 μm, and furthermore, 110 ° C. as a PEB treatment. Heated at for 3 min. By the action of the strong acid generated from the acid generator by this operation, the t-butyl group of t-butyl methacrylate in the irradiation region is released to form a carboxylic acid. Subsequently, after developing by immersing in 2.38 weight% tetramethylammonium hydroxide solution for 1 minute, it washed with water, dried and heat-processed at 200 degreeC for 30 minutes, and produced the pattern substrate which consists of a liquid repellent region and a lyophilic region.

To these patterned substrates, a 1 wt% toluene solution of poly (9,9-dioctylfluorene) was applied by the inkjet method. When the thin film after toluene drying was observed under the optical microscope, in Example 7, a clearly divided polymer thin film was formed along the lyophilic region having a line width of 10 mu m. On the other hand, in Comparative Example 4, it was only apparently cleaved.

<Manufacture example 6>

50 g of fluoroacrylate CH ₂ = C (Cl) COOCH ₂ CH ₂ C ₄ F ₉ (abbreviated α-Cl), methacrylic acid 20 in a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirring device. 30 g of 2-ethyl-2-adamantyl methacrylate (abbreviated AdEMA), 5 g of lauryl mercaptan, 300 g of propylene glycol monomethyl ether acetate were added thereto, and heated to 70 ° C., followed by nitrogen gas flow for 30 minutes. Stirred. 1 g of 2,2'-azobisisobutyronitrile was added thereto and polymerized for 18 hours. The residual monomer in the reaction solution was analyzed by gas chromatography to confirm that the polymerization rate was 95% or more. The obtained reaction solution was precipitated with hexane and dried in vacuo to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 11,000 (polystyrene conversion). In addition, the glass transition point measured by DSC was 135 degreeC. The temperature range and the temperature increase rate of DSC are 1st RUN: -50 to 200 ° C (10 ° C / min), 2nd RUN: -50 to 200 ° C (10 ° C / min), and the glass transition point is the end of extrapolated glass transition of 2nd RUN. It was set as the temperature.

<Manufacture example 7, 8, Comparative manufacture example 3>

The fluoroacrylates of Preparation Example 6 were each CH ₂ = C (H) COO (CH ₂ ) ₃ SO ₂ C ₄ F ₉ (abbreviated SO2Pr), CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₄ F ₉ (abbreviated as α-CH3) was _{a, CH 2 = CHCOOCH 2 CH 2} C 4 F 9 ( abbreviated as α-H) prepared in example 7, 8 and Comparative preparation 3, the substituted. The weight average molecular weights were 9,000, 12,000 and 10,000, respectively. The glass transition points were 115 °, 87 °, and 71 °, respectively.

<Examples 8 to 10, Comparative Example 5>

10 wt% of fluoropolymers of Preparation Example 6 (corresponding to Example 8), Preparation Example 7 (corresponding to Example 9), Preparation Example 8 (corresponding to Example 10), and Comparative Comparative Example 3 (corresponding to Comparative Example 5). 4% by weight of acid crosslinking agent Cymel 300 [hexamethoxymethylmelamine] (manufactured by Nippon Cytec Industries, Inc.), acid generator CGI-1397 [(5-propylsulfonyloxyimino-5H-thiophene-2-ylidene) -(2-methylphenyl) acetonitrile] (Siba Specialty Chemicals Co., Ltd.) 0.5 wt% solution of propylene glycol monomethyl ether acetate 85.5 wt% by spin coating on a superhydrophilic glass substrate in the same manner as in Example 1 A film having a thickness of 3 m (film thickness except solvent) was prepared on the substrate. After heating at 110 ° C. for 3 minutes, the film was subjected to 365 nm UV through a mask aligner PLA-501 manufactured by Canon through a photomask having a line / space = 10 μm / 10 μm of cumulative illuminance of 30 mJ / cm ² . It was irradiated with, and heated at 110 ° C. for 3 minutes as a PEB treatment. In this operation, the irradiation region is crosslinked and insoluble in the solvent. Subsequently, it developed by immersing in 15% aqueous solution of alkaline developing solution P3 disperse M (made by Henkel Japan) for 1 minute, and it washed with water, drying, and it heats at 200 degreeC for 1 hour, and produced the pattern substrate containing a liquid repellent area and a lyophilic area | region. . The pattern was observed with a field effect scanning electron microscope (FE-SEM). In Examples 8 to 10, a clear line pattern having a line width of 10 mu m was formed. On the other hand, in the comparative example 5, the disturbance was observed in the shape of a line.

The coloring agent for liquid crystal display color filters was apply | coated to these pattern substrates by the inkjet method. The inkjet apparatus was discharged to the patterned substrate by the space | interval of dot density of 80 micrometers with the capacity of 15 pL per drop using Litrex 70 (made by Litrex company). In the case of using a uniformly hydrophilized substrate, it was observed with an optical microscope that a thin film having a diameter of about 200 μm was formed after solvent drying. On the other hand, in the case of using a pattern substrate, in Examples 8 to 10, a clearly divided color thin film was formed along the lyophilic region having a line width of 10 µm. In contrast, in Comparative Example 5, the thin film was formed not only in the lyophilic region but also in the liquid repellent region, and the color thin film was incompletely divided.

The falling angle of the uniform liquid-repellent area | region prepared by irradiating the ultraviolet-ray to the whole surface through the film which spin-coated the said electromagnetic wave hardening composition through a photomask was measured. The tumble angles for n-hexadecane of Examples 8 to 10 and Comparative Example 5 were 15 °, 17 °, 20 °, 55 °, and the tumble angles for PGMEA were 17 °, 20 °, 21 °, and 62 °, respectively. The liquid-repellent region of the example was very easy for the liquid to fall down. In the fall angle, a force of mg · sinα (where m is the mass of the drop, g is the acceleration of gravity and α is the fall angle) is applied in the inclined plane with respect to the drop. In other words, the tumble angle represents the minimum force for moving the droplet in the liquid repellent region. The reason why the cleavability of the color filter coloring agent was good in Examples 8 to 10 is presumably because the liquid droplets moved easily in the liquid repellent region.

<Manufacture example 9-20, Comparative manufacture example 4>

The case where the fluoroacrylate and the high softening point monomer of manufacture example 6 were substituted by what was shown in following Table 2 was used as manufacture examples 9-20, and comparative manufacture example 4. The relationship between a compound name and an abbreviation is as follows. CH ₂ = CHCOOCH ₂ CH ₂ C ₈ F ₁₇ (abbreviated C8α-H), 2-methyl-2-adamantyl methacrylate (abbreviated AdMMA), methyl methacrylate (abbreviated MMA), isobornyl methacrylate (Abbreviated iBMA), phenyl methacrylate (abbreviated PhMA), norbornylmethyl methacrylate (abbreviated NBMA), cyclohexyl methacrylate (abbreviated CHMA). The weight average molecular weights were the ranges of 5,000-12,000 in all. The glass transition points are shown in Table 2.

<Examples 11 to 22, Comparative Example 6>

The case where the fluorine-type polymer (Example 6) of Example 8 was substituted by manufacture examples 7-20 and comparative manufacture example 4 was made into Examples 11-22, and comparative example 6. When the pattern was observed by FE-SEM, in Example 11-22, the clear line pattern of 10 micrometers of line widths was formed. On the other hand, in the comparative example 6, the disturbance was observed in the shape of a line. The coloring agent for color filters was apply | coated to these patterned board | substrates by the inkjet method. When the thin film after solvent drying was observed with the optical microscope, in Example 11-22, the clearly divided color thin film was formed along the lyophilic region of 10 micrometers of line widths. On the other hand, in the comparative example 6, the part in which the thin film was formed not only in the lyophilic region but also in the liquid repellent region existed.

On the other hand, Table 2 shows the results of measuring the static contact angle and the fall angle of the uniform liquid-repellent region prepared by irradiating the entire surface of the electromagnetic wave curable composition by spin-coating the film without passing through a photomask.

<Example 23>

8% by weight of the fluoropolymer of Production Example 7, 4% by weight of pentaerythritol tetraacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-monolinopropanone-1 (Ciba specialty) A solution of 1% by weight of Irgacure 907, 82% by weight of propylene glycol monomethyl ether acetate, was spin-coated to a superhydrophilic glass substrate in the same manner as in Example 1 Film thickness excluding solvent) 2 탆 membrane was prepared. A pattern substrate including a liquid repellent region and a lyophilic region was manufactured in the same manner as in Example 8. When the pattern was observed by FE-SEM, a clear line pattern with a line width of 10 mu m was formed.

When the color filter coloring agent was apply | coated to these pattern board | substrates by the method similar to Example 8 by the inkjet method, the color thin film which was clearly divided along the lyophilic region of 10 micrometers of line widths was formed.

Production Example 21

로 치환한 그래프트 공중합체를 제조예 21로 하였다. 중량 평균 분자량은 13,000, 유리 전이점은 125 ℃였다.Fluoroacrylate of Preparation Example 14

The graft copolymer substituted with was obtained as Preparation Example 21. The weight average molecular weight was 13,000 and the glass transition point was 125 degreeC.

<Example 24>

Example 24 replaced the fluorine-type polymer (random copolymer) of Example 16 with the graft copolymer of Production Example 21. When the pattern was observed by FE-SEM, a clear line pattern with a line width of 10 mu m was formed. When the color filter coloring agent was apply | coated to these pattern board | substrates by the method similar to Example 8 by the inkjet method, the color thin film which was clearly divided along the lyophilic region of 10 micrometers of line widths was formed.

As a result of measuring the tumble angle of the uniform liquid-repellent region prepared by irradiating the front surface of the film with the electromagnetic wave curing composition without passing through a photomask, the tumble angle with respect to n-hexadecane was 10 ° and tumbled with respect to PGMEA. The angle was 14 degrees, which improved the performance more than Example 16 using a random copolymer.

-Measuring method of contact angle in liquid repellent area-

Since the liquid-repellent area of this invention is a small area, it is impossible to measure a contact angle in that state. Therefore, a large liquid repellent area was produced by the following method in order to measure the contact angle. The electromagnetic wave hardening composition of this invention is apply | coated uniformly to the base material of 3 cm x 3 cm by spin-coating method (2000 rpm, 30 second), and a coating film is hardened by irradiating the ultraviolet-ray of 1000 mJ / cm <^2> of accumulated illuminance under nitrogen atmosphere. I was. Contact angle was measured by the fully automatic contact angle meter by dropping 2 microliters of water or n-hexadecane from the micro syringe to the horizontally placed board | substrate.

<Example 25>

CH ₂ = C (Cl) COO-CH ₂ CH ₂ C ₄ F ₉ [called Rf (C4) α-Cl acrylate] 90% by weight, 1,6-hexanedioldiacrylate (called HX-2A) 10 weight% is melt | dissolved, and it is marketed from 2-methyl-1- [4- (methylthio) phenyl] -2-monolino propanone- 1 (Ciba specialty chemicals Co., Ltd.) with respect to this mixture. 5% by weight of Irgacure 907) was added and dissolved. The contact angle of this electromagnetic wave hardening composition is shown in Table 1. It showed high liquid repellency in water, n-hexadecane droplets.

The electromagnetic wave hardening composition of Example 25 was discharged from the inkjet apparatus of the nozzle diameter of 50 micrometers, and the liquid-repellent area | region of line / space = 100 micrometers / 100 micrometer was drawn on the silicon wafer of a board | substrate. After the silicon wafer was washed with acetone, a superhydrophilized surface was used by irradiating vacuum ultraviolet light. The film | membrane of the electromagnetic wave hardening composition was hardened by irradiating this board | substrate with the ultraviolet-ray of cumulative roughness 1000mJ / cm <^2> in nitrogen atmosphere.

A 1 wt% toluene solution of poly (9,9-dioctylfluorene) [referred to F8] was applied to this patterned substrate by spin coating (2000 rpm, 30 seconds). When the thin film after toluene drying was observed under the optical microscope, a clearly divided polymer thin film was formed along the lyophilic region having a line width of 100 mu m.

<Example 26, 27>

Example 26 The use of trimethylolpropane triacrylate (referred to as TMP-3A) in place of the HX-2A of Example 25 is followed by the use of pentaerythritol tetraacrylate (referred to as PEN-4A). It was set as. In all cases, it showed high liquid repellency, and the cleavage property of the F8 thin film with respect to the pattern substrate was also favorable.

<Example 28>

CH ₂ = C (H) COO-CH ₂ CH ₂ C ₆ F _{13 in} place of the Rf (C 4) α-Cl acrylate of Example 25 Example 28 was used for making Irgacure 907 1 weight% using [referred to as Rf (C6) acrylate]. In this system, when Irgacure 907 was blended 2% by weight or more, the electromagnetic wave curing composition did not dissolve uniformly. This electromagnetic wave hardening composition showed high liquid repellency, and also the cleavability of the F8 thin film with respect to the pattern board | substrate was also favorable.

<Comparative Example 7, 8>

The case where TMP-3A was used instead of HX-2A of Example 28 was used as the comparative example 7, and the case where PEN-4A was used for the comparative example 8. In this system, when TMP-3A and PEN-4A were blended, the electromagnetic wave curing composition did not dissolve uniformly.

<Comparative Examples 9 to 11>

Using lauryl acrylate in place of Rf (C4) α-Cl acrylate of Example 25 and using HX-2A, TMP-3A, PEN-4A as polyfunctional acrylates, respectively, as Comparative Examples 9, 10, and 11 It was. This electromagnetic wave hardening composition had little liquid repellency with respect to n-hexadecane, and was also poor in the cleavability of the F8 thin film with respect to a pattern substrate.

Claims (39)

A surface treating agent for photolithography comprising at least one fluorine-containing compound selected from the group consisting of fluorine-based monomers (A) and fluorine-based polymers (B), a crosslinking agent (C), and a photocrosslinking catalyst (D). (A) (A-1) α-substituted acrylate monomer having a perfluoroalkyl group having 1 to 6 carbon atoms [substituent at α-position: fluorine atom, 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 perfluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, and a substituted or unsubstituted phenyl group It is selected from the group consisting of; (A-2) a fluorine-containing silsesquioxane monomer containing a perfluoroalkyl group and a polymerizable group having 1 to 6 carbon atoms, (A-4) a polymerizable monomer in which a perfluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group are linked by -SO ₂ (CH ₂ ) _n- , where n is 1 to 10, (A-5) Macromonomer which has a (meth) acryloyl group in the terminal of the polymer which makes one or more types of monomers (A-1), (A-2), and (A-4) a repeating unit At least one fluorine monomer selected from the group consisting of (B) The fluorine-type polymer which has a repeating unit derived from the same fluorine-type monomer (B-1) as a fluorine-type monomer (A). The surface treating agent for photolithography which contains the 1 or more types of fluorine-containing compound chosen from the group which consists of the following fluorine-type monomers (A) and fluorine-type polymer (B). (A) (A-1) α-substituted acrylate monomer having a perfluoroalkyl group having 1 to 6 carbon atoms [substituent at α-position: fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, substituted or unsubstituted Benzyl group, substituted or unsubstituted phenyl group], (A-2) a fluorine-containing silsesquioxane monomer containing a perfluoroalkyl group and a polymerizable group having 1 to 6 carbon atoms, (A-4) a polymerizable monomer in which a perfluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group are linked by -SO ₂ (CH ₂ ) _n- , where n is 1 to 10, (A-5) Macromonomer which has a (meth) acryloyl group in the terminal of the polymer which makes one or more types of monomers (A-1), (A-2), and (A-4) a repeating unit At least one fluorine monomer selected from the group consisting of (B) The fluorine-type polymer which has a repeating unit derived from the same fluorine-type monomer (B-1) as a fluorine-type monomer (A). The surface treating agent for photolithography according to claim 1, wherein the surface treating agent contains a fluorine-based polymer (B), and the fluorine-based polymer (B) has a crosslinkable functional group (E). The photolithography according to claim 2, wherein the surface treating agent contains a fluorine-based polymer (B), a crosslinking agent (C), and a photocrosslinking catalyst (D), and the fluorine-based polymer (B) has a crosslinkable functional group (E). Surface treatment agent. The surface treating agent for photolithography according to claim 1, wherein the surface treating agent contains a fluorine-based polymer (B), and the fluorine-based polymer (B) has a crosslinkable functional group (E) and an acidic group (F). The surface for photolithography according to claim 1, wherein the surface treating agent contains a fluorine-based polymer (B), and the fluorine-based polymer (B) has a crosslinkable functional group (E), an acidic group (F), and a silicon chain (G). Treatment agent. The surface treating agent for photolithography according to claim 1, wherein the surface treating agent contains a fluorine-based polymer (B), and the fluorine-based polymer (B) has an acidic group (F). The surface treating agent for photolithography according to claim 1, wherein the surface treating agent contains a fluorine-based polymer (B), and the fluorine-based polymer (B) has an acidic group (F) and a silicone chain (G). The surface treating agent for photolithography according to claim 1, wherein the surface treating agent contains a fluorine-based polymer (B), and the fluorine-based polymer (B) has a crosslinkable functional group (E) and an acidic group (F). The surface for photolithography according to claim 1, wherein the surface treating agent contains a fluorine-based polymer (B), and the fluorine-based polymer (B) has a crosslinkable functional group (E), an acidic group (F), and a silicon chain (G). Treatment agent. The surface treating agent for photolithography according to any one of claims 1 and 3 to 8, wherein the crosslinking agent (C) has any one of a radical polymerizable functional group, a cationic polymerizable functional group, and a functional group capable of crosslinking with an acid. The surface treating agent for photolithography according to any one of claims 1 and 3 to 8, wherein the crosslinking agent (C) is silicone (meth) acrylate. The surface treating agent for photolithography according to any one of claims 3 to 6, 9 and 10, wherein the crosslinkable functional group (E) is any one of a radical polymerizable group, a cationic polymerizable group and an acid crosslinkable functional group. . The surface treating agent comprises a fluorine-based polymer (B) and a photoacid generator (I), and the fluorine-based polymer (B) has an acid dissociable functional group (H) which is converted into an acidic group by the action of an acid. Surface treatment agent for photolithography. The acid dissociable functional group (H) and silicone according to claim 2, wherein the surface treating agent contains a fluorine-based polymer (B) and a photoacid generator (I), and the fluorine-based polymer (B) is converted into an acidic group by the action of an acid. Surface treatment agent for photolithography which has a chain (G). The method according to any one of claims 3 to 10, 14 and 15, wherein the fluoropolymer (B) is derived from repeating units derived from fluorinated monomers (B-1) and unsaturated organic acids (B-2). Surface treatment agent for photolithography which is a copolymer which has the repeating unit which was carried out. The surface treating agent for photolithography according to claim 16, wherein in the fluorine-based polymer (B), the weight ratio of the fluorine-based monomer (B-1) and the unsaturated organic acid (B-2) is 60:40 to 98: 2. 17. The surface treatment agent for photolithography according to claim 16, wherein the fluorine-based polymer (B) further has repeating units derived from a high softening point monomer (B-3) having a glass transition point or melting point of at least 100 ° C in a homopolymer state. The fluorine-based polymer (B) of claim 18, 20 to 80% by weight of a fluorine monomer (B-1), 5 to 30% by weight of unsaturated organic acid (B-2), Surface treatment agent for photolithography comprised from 10 to 70 weight% of high softening point monomer (B-3). The unsaturated organic acid (B-2) is one selected from the group consisting of (meth) acrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid and cinnamic acid. Surface treatment agent for photolithography which is the above. 19. The method according to claim 18, wherein the high softening point monomer (B-3) is methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate and ars. Surface treatment agent for photolithography which is 1 or more types chosen from the group which consists of a dandelion (meth) acrylate. delete The photolithography according to any one of claims 1 to 10, 14 and 15, wherein _{n in} -SO ₂ (CH ₂ ) _n -in the fluorinated monomer (A-4) is 3 to 6. Surface treatment agent. The fluorine monomers (A-1), (A-2), (A-4) and (A-5) according to any one of claims 1 to 10, Surface treatment agent for photolithography whose carbon number of a perfluoroalkyl group is four. Using the surface treatment agent for photolithography according to any one of claims 1 to 10, 14 and 15, a pattern composed of a plurality of regions having different surface free energies by the photolithography method is formed on a substrate. It is formed in the manufacturing method of the pattern substrate. 27. The method of claim 25, wherein the electromagnetic waves used for photolithography are Light with a wavelength of 10 to 400 nm, X-rays with a wavelength of 0.1 to 10 nm, Electron beams having a wavelength of 0.001 to 0.01 nm, or Any one of laser beams having a wavelength of 10 to 300 nm. The patterned substrate manufactured by the method of Claim 25. A solution of a functional compound selected from a semiconductor compound, a conductive compound, a pigment or pigment for forming a pixel for a display, a photochromic compound, a thermochromic compound, a lens material, or a life science agent on the pattern substrate according to claim 27 Or apply | coating a dispersion liquid and removing a solvent. A device for electronic, optical, medical or analytical chemistry produced by the manufacturing method of claim 28. The device of claim 29, wherein the device is an integrated circuit, a pixel for a display, a lens array, a biochip or a microchemical chip. The liquid repelled on the lyophilic transparent substrate by the photolithography method using the thing which disperse | distributed the black pigment in the surface treatment agent for photolithography in any one of Claims 1-10, 14 and 15 was used. A method of producing a color filter for display, characterized by forming a black matrix. The surface treatment agent for photolithography according to any one of claims 1 to 10, 14 and 15 is further uniformly applied on the photosensitive resin black layer uniformly formed on the lyophilic transparent substrate. And a liquid-repellent black matrix formed on a lyophilic transparent substrate by a photolithography method. The manufacturing method of the color filter for displays of Claim 31 which apply | coats the dispersion liquid which disperse | distributed red, green, and blue pigment on the transparent substrate which has a liquid-repellent black matrix, and removes a solvent. The color filter for display manufactured by the manufacturing method of Claim 33. (A) a fluorine monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms, (B) a crosslinking agent, and (C) photocrosslinking catalyst And discharging the electromagnetic wave curing composition comprising a non-contact trace droplet ejection method to a substrate to form a coating film of the electromagnetic wave curing composition on the substrate, and irradiating and curing the coating film to two or more regions having different surface free energies. The pattern formed is formed on a base material, The manufacturing method of the pattern substrate characterized by the above-mentioned. The fluorine-based monomer (A) of the electromagnetic wave curing composition according to claim 35, (A-1) α-substituted acrylate monomer having a perfluoroalkyl group having 1 to 6 carbon atoms [substituents at α-position: fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ And X ² is a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a straight or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or 1 to C carbon atoms. 20 straight or branched alkyl groups], (A-2) a fluorine-containing silsesquioxane monomer containing a perfluoroalkyl group and a polymerizable group having 1 to 6 carbon atoms, (A-3) a polymerizable monomer having a perfluoropolyether group, (A-4) a polymerizable monomer in which a perfluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group are linked by -SO ₂ (CH ₂ ) _n- , where n is 1 to 10, (A-5) Macromonomer which has a (meth) acryloyl group in the terminal of the polymer which makes one or more types of monomers (A-1)-(A-4) a repeating unit At least one fluorine monomer selected from the group consisting of: 37. The method of claim 35 or 36, wherein the crosslinking agent (B) has a radically polymerizable functional group or a cationically polymerizable functional group. 36. The method of claim 35, wherein the non-contact microdrop ejection method is an inkjet method or a micro dispenser method. 36. The method of claim 35, wherein a liquid repellent film is formed on the substrate, and the patterned one or more liquid repellent regions and one or more lyophilic regions are obtained.