JPH10230154A - Fluorine-based surfactant and composition using thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve defoaming property, recoating property, and post- processing property of such as development by adding a fluorine-based surfactant, which consists of a copolymer of an ethylenically unsaturated monomer containing fluorinated alkyl group and an ethylenically unsaturated monomer containing specified silicone chain to various kinds of coating compositions. SOLUTION: A fluorine-containing surfactant consisting of a copolymer of an ethylenically unsaturated monomer A containing fluorinated alkyl group and an ethylenically unsaturated monomer B containing specified silicone chain having a formula I is produced. In the formula I, R2, R3 stands for 1-20C alkyl group, phenyl group, or a functional group having a formula II, R4-R6 for 1-20C alkyl group and phenyl group, p for 1-3 integer, and in the formula II, R7-R9 stands for 1-20C alkyl group and phenyl group. As the constituent unit of the copolymer, polyoxyalkylene-containing ethylenically unsaturated monomer C and an ethylenically unsaturated monomer containing 2 or more unsaturated bonds in one molecule are included.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating field in which a high degree of homogeneity is required, for example, various coating fields in which the surface smoothness of a multi-layered coating film is required, precision coating is required, Coating fields requiring high-speed, high-shearing coating methods such as coating and spray coating, for example, using a photoresist that is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, excimer laser light, and X-rays. Fluorinated surfactants that can be suitably used in photolithography processes, in particular, semiconductor manufacturing processes such as LSIs and ICs, substrates such as liquid crystals and thermal heads, PS plates, and other photofabrication processes And compositions thereof.

[0002]

2. Description of the Related Art Conventionally, in the field of various coatings, various leveling agents such as hydrocarbons, silicones and fluorines have been used for the purpose of improving the uniformity and smoothness of a coating film.

[0003] Among them, fluorine-based surfactants are widely used because of their high surface tension lowering ability and little contamination after coating. However, since the coating film after coating lacks a practical level of recoatability, it can be used only in a process without post-processing such as one-layer coating, top coating or development, and its use has been limited. . In addition, high-speed coating for improving production efficiency or coating methods that apply high shearing force such as spin coating and spray coating require a long time to defoam before coating because the foaming property becomes intense. Not only efficiency is deteriorated, but also defects such as craters, pinholes, fish eyes, etc., which significantly impair product value due to bubbles are generated on the surface after coating.

[0004] Further, there is a problem that excellent leveling property cannot be obtained only by having high surface tension lowering ability. A typical example is spin coating of a photoresist on a substrate in a semiconductor manufacturing process, and a conventional leveling agent has a fatal defect in the field of fine processing in which uneven coating called striation occurs.

[0005] In order to solve such problems, surfactants such as those disclosed in JP-A-3-30825 and JP-A-8-62834 and compositions using the same have been proposed. Although the effect is recognized, there are many points that are insufficient in a practical processing method and process.

[0006]

SUMMARY OF THE INVENTION The present invention raises the post-processability such as defoaming property, recoating property and development, which have been conventionally regarded as disadvantages of fluorine-based surfactants, to a practical level, and further increases the speed and speed. An object of the present invention is to provide a fluorine-based surfactant having excellent leveling properties even under a severe coating method involving a shearing force, and a composition thereof.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the ethylenically unsaturated monomer (A) containing a fluorinated alkyl group and the ethylenic unsaturated monomer containing a specific silicone chain have been used. By using a fluorine-based surfactant composed of a copolymer obtained by polymerizing an unsaturated monomer (B) as an essential constituent unit in various coating compositions such as paints and resists, coating with high speed and high shear force can be achieved. Even with the construction method, it has been found that the composition has excellent defoaming properties and exhibits a high leveling property, and that the coated film has recoatability and suitability for post-processing, and has completed the present invention.

That is, the present invention comprises a fluorinated alkyl group-containing ethylenically unsaturated monomer (A) and a silicone chain-containing ethylenically unsaturated monomer (B) represented by the formula (1). Wherein R ₂ and R ₃ in the general formula (1) are functional groups represented by the formula (2), and more preferably R ₂ and R ₃ in the formula (1) _4, R _5,
R ₆ , R ₇ , R ₈ and R ₉ in the formula (2) are methyl groups, p is 0, and preferably a polyoxyalkylene group-containing ethylenically unsaturated monomer as a structural unit of the copolymer. More preferably, the present invention provides a fluorine-containing surfactant containing the monomer (C), and more preferably, the polyoxyalkylene group is constituted by repeating units of oxyethylene and oxypropylene.

Preferably, the copolymer further comprises an ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule as a constitutional unit of the copolymer,
Preferably, the weight ratio of the monomers (A), (B), (C) and (D) is 10 to 40/5 to 30/30 to 70.
/ 1 to 10, preferably a copolymer having a number average molecular weight of 1,000 to 200,000.

The present invention further provides a coating composition, a coating composition and a resist composition comprising the above-mentioned surfactant.

[0011]

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[Wherein R ₂ and R ₃ represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a functional group represented by the formula (2);

[0013]

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Wherein R ₇ , R ₈ and R _{9 each} have 1 to 20 carbon atoms.
R ₄ , R ₅ , R ₆
Represents an alkyl group having 1 to 20 carbon atoms or a phenyl group,
p shows the integer of 0-3. ]

[0015]

DETAILED DESCRIPTION OF THE INVENTION First, in the present invention, the fluorinated alkyl group-containing ethylenically unsaturated monomer (A) includes:
There is no particular limitation as long as the compound has an ethylenically unsaturated group and a fluorinated alkyl group in the molecule.
Compatibility with compounds in various coating compositions, ease of controlling such compatibility, or those containing an acrylic ester group and its analogous group from the viewpoint of polymerization reactivity are suitable. Include a fluorinated (meth) acrylate represented by the following formula (3).

In the present invention, the components in the various coating compositions mean all the components from the matrix resin, the solvent or the solvent to the various additives in the intended use. Also, (meth) acrylates are methacrylates, acrylates, fluoroacrylates,
Chlorinated acrylate is a generic term.

That is,

[0018]

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Wherein R _f is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group;
It may be linear, branched, or one in which an oxygen atom is interposed in the main chain, such as-(OCFCF ₂ ) ₂ CF (CF ₃ ) ₂ , wherein R ₁ is H, CH ₃ , Cl, or F. , X is a divalent linking group, specifically-(CH ₂ ) _n- ,

[0020]

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[0021]

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[0022]

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[0023] (however, n is an integer from 1 to 10, R ₂
Is H or an alkyl group having 1 to 6 carbon atoms. ),

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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Or

[0030]

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And a is 0 or 1. And a compound represented by the general formula

[0032]

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Compounds having a plurality of perfluoroalkyl groups in the molecule as described above, wherein l is an integer of 1 to 14. ]. Specific examples of the fluorinated alkyl group-containing (meth) acrylate include the following.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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It is needless to say that the present invention is not limited by the above specific examples. As the fluorinated alkyl group-containing ethylenically unsaturated monomer (A), only one kind may be used, or two or more kinds may be used at the same time.

In the present invention, the fluorinated alkyl group-containing ethylenically unsaturated monomer (A) lowers the static surface tension of the composition to which the fluorine-containing surfactant according to the present invention is added, and reduces the static surface tension. In order to improve the wettability, that is, the leveling property, and further, at a high speed, an essential monomer component for reducing the dynamic surface tension which is an index of the leveling property for a coating method involving high shearing force. is there. Absence of this component results in poor performance, resulting in a lack of uniformity and smoothness of the film.

In the present invention, the static surface tension refers to a surface tension measured by a Wilhelmy plate method using a platinum plate, and the dynamic surface tension refers to moving two movable barriers left and right. The surface tension means the surface tension by a surface area change method using a platinum plate and a method similar to the Wilhelmy plate method. In the measurement of the dynamic surface tension, a surface tension-area hysteresis curve is drawn by changing the surface area at a constant cycle.
It is possible to analyze the performance of various surfactants by comparing the obtained surface loss energies.

The present inventors have found that in various coating methods, especially in coating methods involving high speed and high shearing force such as spin coating and spray coating, the static surface tension of the composition may be reduced to some extent. Although it is necessary, it has been found that reducing dynamic surface tension is a more important factor. That is, although having a very low static surface tension lowering ability, the dynamic surface tension lowering ability is excellent even if the static surface tension lowering ability is low, rather than using a surfactant having a low dynamic surface tension lowering ability. It has been found that the use of such a surfactant has a high leveling property capable of coping with various coating methods.

In order to reduce the static surface tension and the dynamic surface tension of the coating composition according to the present invention and, consequently, to exhibit a high leveling property, the fluorinated alkyl group-containing ethylenically unsaturated monomer ( The number of carbon atoms of the perfluoroalkyl group or partially fluorinated alkyl group in A) is preferably 3 or more, more preferably 6 or more.

Next, the silicone chain of the ethylenically unsaturated monomer (B) having a specific silicone chain, which is another essential component according to the present invention, is represented by the general formula (1): is there.

[0046]

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[Wherein R ₂ and R ₃ represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a functional group represented by the formula (2);

[0048]

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(Wherein R ₇ , R ₈ and R _{9 each} have 1 to 20 carbon atoms)
R ₄ , R ₅ , R ₆
Represents an alkyl group having 1 to 20 carbon atoms or a phenyl group,
p shows the integer of 0-3. The silicone chain-containing ethylenically unsaturated monomer (B) is not particularly limited as long as it has a silicone chain and an ethylenically unsaturated group represented by the above formula (1) in the molecule. From the viewpoints of availability, compatibility with compounds in various coating compositions, ease of controlling such compatibility, or polymerization reactivity, acrylic ester groups and their analogous groups as ethylenically unsaturated groups Are preferred, and compounds having the following structure are preferred.

[0050]

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[Wherein R ₁ represents H, Cl, F, CH ₃ , and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ are the same as those described above. , X is -CH ₂ CH (OH) CH ₂ OCO-,-(CH ₂ ) _n NHCH ₂ CH
_{(OH) CH 2 0CO -,} - (CH 2) n OCO -, - (CH 2) n -O- (CH 2) m OCO -, - O
_{CH 2 CH (OH) CH 2} OCO -, - (CH 2) nC (CF 3) 2 selected from ₂ OCO-
P represents an integer of 0 to 3; m and n represent 2 to 6;
And q represents 0 or 1. Specific examples of the silicone chain-containing ethylenically unsaturated monomer (B) include the following compounds.

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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Here, Me and Ph represent a methyl group and a phenyl group, respectively. Incidentally, the present invention, by the above specific example,
Of course, it is not limited at all.

As the silicone chain-containing ethylenically unsaturated monomer (B), only one kind may be used, or two or more kinds may be used simultaneously. In the present invention, the silicone chain-containing ethylenically unsaturated monomer (B) improves the workability during coating by suppressing the foaming property of the compound according to the present invention, and achieves high speed and high shear. It is an important component to be able to cope with a coating method involving force.
Furthermore, similarly to the fluorinated alkyl group-containing ethylenically unsaturated monomer (A), by lowering the static and dynamic surface tension of the compound according to the present invention, the leveling property to the substrate is improved. And contributes to the formation of a uniform and smooth film. Further, from the viewpoint of suppressing the foaming property and forming a uniform and smooth film by improving the leveling property, R ₂ and R ₃ in the formula (1) are functional groups represented by the formula (2). It is preferred to use branched compounds.

On the other hand, generally, the surface of a film after coating with a composition containing a silicone chain-containing compound is improved in water repellency as compared with a film made of the composition containing no compound. Therefore, when post-processing such as recoating property or development is performed, the wettability of the post-processing liquid is reduced, which causes a significant decrease in post-processing efficiency.

The present inventors have found that silicone chains have a short length,
Specifically, it has been found that the above problem can be solved by using a compound of p = 0 to 3 in the formula (1). That is, when a compound having p = 4 or more is used, the dynamic surface tension increases, not only having a large adverse effect on the leveling property of the coating film, but also increasing the water repellency of the coating film after coating, The recoating property and the post-treatment process are hindered and cannot be used for applications involving such a process. a compound having p = 3 or less,
Preferably, when a compound having p = 0 is used, excellent defoaming property and leveling property can be obtained without impairing the recoating property and the post-processing property.

Further, in order to achieve both defoaming and leveling properties and recoating or post-processing properties, R ₂ and R ₃ in the formula (1) are functional groups represented by the formula (2): And R ₄ , R ₅ and R _{6 in} the formula (1) and R ₇ and R in the formula (2)
It is more preferable to use a compound in which ₈ and R ₉ are all methyl groups and p = 0.

It contains the fluorinated alkyl group-containing ethylenically unsaturated monomer (A), which is an essential constituent unit of the copolymer according to the present invention described above, and a silicone chain represented by the formula (1). The effect of the ethylenically unsaturated monomer (B) cannot be distinguished from each other, and the effects of the fluorinated alkyl group-containing ethylenically unsaturated monomer (A) and the silicone chain-containing ethylenically unsaturated monomer By copolymerizing the compound (B) and simultaneously containing the fluorinated alkyl group and the silicone chain represented by the formula (1) in one molecule, the defoaming property which has been difficult by the conventional method In addition, high leveling property, recoating property or post-processing property can be achieved by reducing static surface tension and dynamic surface tension.

Accordingly, in the copolymer of the present invention, either the fluorinated alkyl group-containing ethylenically unsaturated monomer (A) or the specific silicone chain-containing ethylenically unsaturated monomer (B) is used. The present invention refers to the present invention even when a copolymer having only the monomer (A) as an essential component and a copolymer having only the monomer (B) as an essential component are simply mixed and used. It is not possible to achieve both defoaming property and high leveling property with recoating property or post-processing property.

The copolymer according to the present invention is further provided as a structural unit for the purpose of improving the compatibility with the components in the various coating compositions, the recoating property of the coated film or the post-processing property such as development. It is also possible to contain a polyoxyalkylene group-containing ethylenically unsaturated monomer (C).

The polyoxyalkylene group-containing ethylenically unsaturated monomer (C) is not particularly limited as long as it is a compound containing an ethylenically unsaturated group and a polyoxyalkylene group in the molecule. As the ethylenically unsaturated group, the availability of raw materials, compatibility with compounds in various coating compositions, ease of controlling such compatibility, or acrylic ester group and the like from the viewpoint of polymerization reactivity Those containing an analogous group are suitable.

As specific compounds of the polyoxyalkylene group-containing ethylenically unsaturated monomer (C),
100 mono (meth) acrylates of polyalkylene glycols, such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide (hereinafter referred to as alkyl acrylate and methacrylic acid). Alkyl ester), or a polymerization degree of 1 to which the terminal is capped by an alkyl group having 1 to 6 carbon atoms.
And 100 mono (meth) acrylates of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide. Commercially available polyoxyalkylene group-containing ethylenically unsaturated monomers include NK Ester M manufactured by Shin-Nakamura Chemical Co., Ltd.
-20G, M-40G, M-90G, M-230G, A
M-90G, AMP-10G, AMP-20G, AMP
-60G, Blenmer PE-90 manufactured by NOF Corporation,
PE-200, PE-350, PME-100, PME
-200, PME-400, PME-4000, PP-
1000, PP-500, PP-800, 70PEP-
350B, 55PET-800, 50POEP-800
B, NKH-5050, AP-400, AE-350 and the like.

It is needless to say that the present invention is not limited at all by the above specific examples. As the polyoxyalkylene group-containing monomer (C), only one kind may be used, or two or more kinds may be used at the same time.

Such a polyoxyalkylene group-containing monomer (C) is effective in improving the compatibility with the components in various coating compositions, the recoating property of the film after coating or the post-processing property such as development. Although effective, it is a negative factor in the copolymer composition of the present invention from the viewpoint of surface tension lowering ability. According to the findings of the present inventors, compatibility with the compound in the composition, recoating or post-processing,
In consideration of the balance of the surface tension lowering ability, the oxyalkylene group is more preferably a compound composed of oxyethylene and oxypropylene repeating units.

The number of repetitions of the oxyethylene and oxypropylene units depends on the system to which the surfactant of the present invention is applied,
That is, although it depends on the type of other compound, the intended coating method, the post-processability, etc., each repeating unit is 1
-100 is preferable, 2-50 are more preferable, and 5-3
0 is particularly preferred.

The copolymer according to the present invention contains an ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule, mainly from the viewpoint of improving defoaming properties. It is also possible to make it. As described above, regarding the defoaming property, the silicone chain-containing ethylenically unsaturated monomer (B)
Is highly effective when it is copolymerized with the fluorinated alkyl group-containing monomer (A), but when the coating method involving high speed and high shearing force is insufficient, or when the copolymer contains silicone chain-containing ethylene. When the amount of the unsaturated monomer (B) introduced is large, the water repellency of the film surface is improved, which may adversely affect the recoating property or the post-processing property. In such a case, it is effective to introduce an ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule into the copolymer.

The ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule is not particularly limited. As the ethylenically unsaturated group, an acrylic ester group and its analogs from the viewpoints of availability of raw materials, compatibility with compounds in various coating compositions, ease of controlling such compatibility, and polymerization reactivity. Those containing groups are suitable.

Specific examples of the ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule include polyethylene glycol, polypropylene glycol having a polymerization degree of 1 to 100, And a di (meth) acrylate ester of a polyalkylene glycol such as a copolymer of ethylene oxide and propylene oxide, or a polyethylene glycol having a degree of polymerization of 1 to 100 whose terminal is capped by an alkyl group having 1 to 6 carbon atoms. Di (meth) acrylates of polyalkylene glycols such as ethylene glycol and propylene oxide, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, Methylolpropane tri (meth) acrylate and its EO Sex product, tetra trimethylol propane tri (meth) acrylate and EO-modified product, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate and the like. In addition, commercially available products include NK esters 1G, 2G, 3G, 4G, 9G manufactured by Shin-Nakamura Chemical Co., Ltd.
G, 14G, 23G, BG, HD, NPG, A-20
0, A-400, A-600, A-HD, A-NPG,
APG-200, APG-400, APG-700, A
-BPE-4, 701A, Blemmer PDE-50, PDE-100, PDE-150, PD manufactured by NOF Corporation
E-200, PDE-400, PDE-600, ADE
-200, ADE-400 and the like.

The present invention is, of course, not limited to the above specific examples. By introducing such an ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule into the copolymer, a remarkable defoaming effect can be obtained. From the viewpoint of compatibility with the compound in the composition and controllability of the polymerization reaction, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and copolymers of ethylene oxide and propylene oxide having a degree of polymerization of 1 to 100 are used. Di (meth) acrylic acid ester or a terminal having 1 carbon atom
Degree of polymerization 1-1 capped with alkyl groups of
Particularly preferred are poly (alkylene glycol) di (meth) acrylates, such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide.

As the ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule, only one kind may be used, or two or more kinds may be used at the same time.
The proportion of the monomers (A), (B), (C) and (D) constituting the copolymer according to the present invention described above depends on the composition in the composition in which the copolymer is blended. , High leveling properties, defoaming properties, recoating that can be applied to the high-speed, high-shearing coating methods, which are the above-mentioned target physical properties, depending on the target physical property level, coating method, etc. (A) / (B) / (C) / (D) = 5 to 50/3 to 40 in terms of weight ratio in order to satisfy all the post-processability such as performance and development.
/ 0 to 90/0 to 30, preferably (A) / (B) / (C) /
(D) = 10-40 / 5-30 / 30-70 / 1-10
And a particularly preferred range is (A) / (B) /
(C) / (D) = 15 to 25/5 to 20/50 to 70 /
2 to 7.

If the proportion of the copolymer according to the present invention is within the above range, the desired physical properties can be achieved. However, if the proportion is out of this range, a high leveling property, defoaming property, recoating property, after development, etc. All the processability cannot be satisfied, and the practicality as a surfactant meeting the purpose is lost.

The copolymers according to the present invention include, in addition to the monomers (A), (B), (C) and (D), other ethylenically unsaturated monomers (E). Can be introduced as a copolymerization component.

The ethylenically unsaturated monomer (E) is appropriately introduced according to the purpose in consideration of compatibility with the components in various coating compositions, polymerization reactivity, cost, and the like. Such an ethylenically unsaturated monomer (E) is not particularly limited, and any known and used compound can be used. Specifically, styrene, nuclear-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride,
Fatty acid vinyls such as vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid and vinyl acetate, and monovalent α, β-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid Or a derivative of a divalent carboxylic acid or an α, β-ethylenically unsaturated carboxylic acid, wherein the alkyl group has 1 to 1 carbon atoms.
(Meth) acrylic acid alkyl ester (hereinafter, this expression is a generic term for both acrylic acid alkyl ester and methacrylic acid alkyl ester), namely, methyl, ethyl, propyl, butyl (meth) acrylic acid;
Octyl, 2-ethylhexyl, decyl, dodecyl, stearyl ester and the like, and hydroxyalkyl esters of (meth) acrylic acid having 1 to 18 carbon atoms, that is, 2-hydroxyethyl esters, hydroxypropyl esters,
Hydroxybutyl ester and the like.

The (meth) acrylic acid has 1 to 18 carbon atoms.
Aminoalkyl esters of, for example, dimethylaminoethyl ester, diethylaminoethyl ester, diethylaminopropyl ester, etc., and (meth) acrylic acid,
Ether oxygen-containing alkyl esters having 3 to 18 carbon atoms, such as methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester, ethylcarbyl ester, butylcarbyl ester and the like. Cyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth)
Acrylates, dicyclopentanyl (meth) acrylates, dicyclopentenyl (meth) acrylates, and the like, and alkyl vinyl ethers having 1 to 18 alkyl carbon atoms;
Glycidyl esters of (meth) acrylic acid, for example, methyl vinyl ether, propyl vinyl ether, dodecyl vinyl ether, etc., ie, glycidyl methacrylate,
Glycidyl acrylate, etc., and Sartomer's styrene macromonomer 4500, Toa Gosei Co., Ltd.'s AA-6,
Various macromonomers such as AN-6 are exemplified.

Further, γ-methacryloxypropylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, vinyl Monomers containing a silane coupling group such as trimethoxysilane and a polar group in the molecule, especially monomers containing an anionic group or a hydroxyl group, acrylic acid,
Methacrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, partially sulfonated styrene, mono (acryloyloxyethyl) acid phosphate, mono (methacryloxyethyl) acid Examples include phosphate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

The present invention is, of course, not limited to the above specific examples. The ethylenically unsaturated monomer (E) other than the monomers (A), (B), (C) and (D) according to the present invention may be used alone or in combination of two or more. They may be used at the same time.

The copolymerization ratio of the monomers (A), (B), (C), (D) and the other ethylenically unsaturated monomers (E) is such that the copolymer is blended. Depending on the composition in the composition, the level of the desired physical properties, the coating method, etc.,
[(A) + (B) + (C) + (D)] /
(E) = 20/80 to 100/0 is preferable, and a more preferable range is [(A) + (B)
+ (C) + (D)] / (E) = 50/50 to 97/3,
A particularly preferred range is [(A) + (B) + (C) +
(D)] / (E) = 70/30 to 95/5.

When the ratio of the monomers (A), (B), (C) and (D) and the other ethylenically unsaturated monomer (E) deviates from the above range, the desired high degree of Any of the physical properties such as leveling property, defoaming property, recoating property and post-processing property cannot be satisfied, and practicality is lost.

The method for producing the copolymer according to the present invention is not limited at all, and is based on known methods, that is, solution polymerization, bulk polymerization and the like based on polymerization mechanisms such as radical polymerization, cationic polymerization and anionic polymerization. , And further can be produced by an emulsion polymerization method or the like, but a radical polymerization method is particularly convenient,
Industrially preferred.

In this case, as the polymerization initiator, those known in the art can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azobisisobutyronitrile, phenylazotriphenylmethane and the like. Azo compounds, metal chelate compounds such as Mn (acac) 3, and transition metal catalysts that cause living radical polymerization.

If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, and a cupper such as γ-mercaptopropyltrimethoxysilane. An additive such as a chain transfer agent can be used for the ring-group-containing thiol compound.

The fluorine-based random or block copolymer according to the present invention can also be obtained by photopolymerization in the presence of a photosensitizer or a photoinitiator or polymerization using radiation or heat as an energy source.

The polymerization can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of workability. Solvents include ethanol, isopropyl alcohol, n-butanol, iso-butanol.
And alcohols such as tert-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone, and esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and butyl lactate. , Methyl 2-oxypropionate, 2-
Monocarboxylic acids such as ethyl oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate and butyl 2-methoxypropionate Polar solvents such as acid esters, dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone; ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol and ethyl cellosolve acetate; propylene glycol; propylene glycol monomethyl ether;
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
Propylene glycols such as propylene glycol monobutyl ether acetate and esters thereof, 1,1,1
-Trichloroethane, halogen solvents such as chloroform, tetrahydrofuran, ethers such as dioxane,
Aromatics such as benzene, toluene and xylene;
Examples include fluorinated inert liquids such as fluorooctane and perfluorotri-n-butylamine, and any of these can be used.

It is needless to say that the present invention is not limited at all by the above specific examples. The molecular weight of the copolymer according to the present invention is preferably Mn = 1,000 to 200,000 in terms of polystyrene equivalent number average molecular weight,
In order to maintain good compatibility with the compound in the composition and to exhibit high leveling properties, defoaming properties, recoating properties, and post-processing properties such as development, 1,000 to 100,000 is more preferable. And further preferably 2,500 to 50,000.
When the molecular weight of the copolymer is less than 1,000, the compatibility with other components in the composition is good, but the post-processability such as high leveling property, defoaming property, recoating property and development is high. Is difficult to satisfy all of the above, and conversely, the molecular weight is 200,0.
Above 00, compatibility with the formulation in the composition is lacking.

The fluorine-based surfactant according to the present invention comprises 1
Only the types may be used, or two or more types may be used simultaneously. Further, for the purpose of improving the compatibility with the compound in the composition, known and used hydrocarbons, fluorines,
It is also possible to use a silicone-based surfactant or the like in combination.

By using the fluorine-based surfactant according to the present invention, foaming is suppressed, a high leveling property is exhibited, and the coating surface after coating is applied even in a coating method involving high speed and high shearing force. Since the water repellency is also suppressed, it is possible to provide a coating composition that enables reworkability or post-processing such as development. Such coating compositions are not particularly limited, but useful coating compositions include, for example, various coating compositions and photoresist compositions.

First, with respect to the coating composition, various leveling agents have been used in the coating composition in order to improve the leveling property at the time of coating. Fluorosurfactants having a high level are used as leveling agents. However, when a fluorine-based surfactant is used, the water repellency and oil repellency of the film surface after coating are improved, so that recoating becomes difficult, and the usable applications have been limited. From such a viewpoint, it is effective to incorporate the fluorine-based surfactant according to the present invention, which has a high leveling property, defoaming property and recoating property, into the coating composition.

The proportion of the fluorine-based surfactant according to the present invention added to the coating composition depends on the system to be applied, the desired physical properties, the coating method, the cost, and the like. From 0.0001 to 20%, more preferably from 0.001 to 10%, even more preferably from 0.01 to 20%.
~ 7%.

The paint to be applied is not particularly limited, and paints using natural resins, for example, petroleum resin paints, shellac paints, rosin paints, cellulose paints, rubber paints, lacquer, cashew resin paints, oil-based vehicles Paints and other paints using synthetic resins, such as phenolic resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, and silicone resin paints And fluororesin paints, but are not particularly limited thereto.

These paints can be applied in any form such as water-based, solvent-based, non-aqueous dispersion-based, and powder-based paints, and there is no particular limitation on the solvent or dispersion medium. Specific examples of the solvent and the dispersion medium include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl ketone. Ketones, esters such as methyl acetate, ethyl acetate, butyl acetate, etc., polar solvents such as dimethylformamide, dimethyl sulfoxide, ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, 1,1,1-trichloride Halogen solvents such as ethane and chloroform, tetrahydrofuran,
Examples thereof include ethers such as dioxane, aromatics such as benzene, toluene, and xylene, and fluorinated initiators such as perfluorooctane and perfluorotri-n-butylamine.

The present invention is, of course, not limited to the above specific examples. In these paints, if necessary, pigments, dyes, colorants such as carbon, inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide and calcium carbonate, higher fatty acids Organic fine powders such as poly (vinylidene fluoride), poly (tetrafluoroethylene), polyethylene, etc., as well as light resistance improver, weather resistance improver, heat resistance improver, antioxidant, thickener, anti-settling agent, etc. Can be added as appropriate.

Further, any coating method can be used as long as it is a known and publicly used coating method. For example, a method such as a roll coater, an electrostatic coating, a bar coater, a gravure coater, a knife coater, a dipping coating, a spray coating and the like can be used. No.

It is needless to say that the present invention is not limited at all by the above specific examples. Next, with regard to the composition for photoresist, usually in photolithography of a semiconductor device, the composition for photoresist is coated on a silicon wafer by spin coating with high shearing force so that the thickness becomes about 1 to 2 μm. It is generally applied to the negative electrode. At this time, if the coating film thickness fluctuates or coating unevenness generally called striation occurs,
The problem is that the linearity and reproducibility of the pattern are reduced, and a resist pattern having the desired accuracy cannot be obtained. At the present, resist patterns are becoming finer as semiconductor devices become more highly integrated, and it has become an important issue to suppress fluctuations in coating film thickness and generation of striations. In recent years, from the viewpoint of improving the productivity of semiconductor devices, etc., silicon wafers have been increasing in diameter from 6 inches to 8 inches or larger, but with this increase in diameter. In addition, suppression of the fluctuation of the coating film thickness and the occurrence of striation has become an extremely important issue. Furthermore,
After the application of the photoresist composition, a development step is involved, and the wettability of the developer at that time is also an important factor.

In view of these problems, from the viewpoint of high leveling properties, defoaming properties and improvement of post-processing properties such as development,
The fluorine-based surfactant according to the present invention is also useful as various photoresist compositions.

The photoresist composition according to the present invention comprises the above-mentioned fluorine-based surfactant and a publicly-known photoresist agent. As the photoresist agent which can be combined with the fluorine-based surfactant according to the present invention, any known and publicly available photoresist agent can be used without any limitation.

Usually, the photoresist agent comprises (1) an alkali-soluble resin, (2) a radiation-sensitive substance (photosensitive substance), (3) a solvent, and if necessary, (4) other additives.

As the (1) alkali-soluble resin used in the present invention, any resin can be used without any limitation as long as it is a resin which is soluble in an alkaline solution constituting a developer used for patterning a resist. Possible, for example, phenol, cresol, xylenol, resorcinol,
Fluoroglycinol, aromatic hydroxy compounds such as hydroquinone and at least one of these alkyl-substituted or halogen-substituted aromatic compounds and formaldehyde, acetaldehyde, a novolak resin obtained by condensation with an aldehyde compound such as benzaldehyde,
vinylphenol compounds such as o-vinylphenol, m-vinylphenol, p-vinylphenol, α-methylvinylphenol, and polymers or copolymers of these halogen-substituted compounds, acrylic acid, methacrylic acid Acrylic or methacrylic acid polymers or copolymers such as hydroxyethyl (meth) acrylate, polyvinyl alcohol, and quinonediazide and naphthoquinone azide groups through a part of the hydroxyl groups of the various resins; Modified resins into which a radiation-sensitive group such as an aromatic azide group or an aromatic cinnamoyl group has been introduced can be mentioned, and these resins can be used in combination.

Other examples of the alkali-soluble resin include JP-A-58-105143 and JP-A-58-20343.
4, JP-A-59-231534, JP-A-59-231534
JP-A No. 24545, JP-A-60-121445, JP-A-61-226745, JP-A-61-2
No. 60239, JP-A-62-36657, JP-A-62-123444, JP-A-62-1785.
No. 62, JP-A-62-284354, JP-A-63-24244, JP-A-63-113451, JP-A-63-220139, JP-A-63-214139
98652, JP-A-2-125260, JP-A-3-144648, JP-A-2-247563
JP, JP-A-4-291258, JP-A-4-3258
40549, JP-A-4-368864, JP-A-5-113666, JP-A-6-186735
Gazette, USP 3,666,473, USP
No. 4,115,128, USP 4,173,
No. 470, US Pat. No. 4,526,856, etc., and furthermore, a well-known book, publicly known and publicly described in Teruhiko Yonezawa, "PS Plate Overview", Printing Society Press (1993). Yes, they can be used.

Further, as the alkali-soluble resin, a urethane resin containing an acidic group such as carboxylic acid or sulfonic acid in the molecule can be used, and these urethane resins can be used in combination with the above alkali-soluble resin. Is also possible. Further, as the alkali-soluble resin, two or more different kinds of resins may be mixed and used.

It is needless to say that the present invention is not limited by the above specific examples. As the (2) radiation-sensitive substance (photosensitive substance) according to the present invention, any known and commonly used substance can be used without any limitation. Excimer laser light, X-ray, electron beam, ion beam,
Irradiation with a molecular beam, γ-ray, or the like can be used without any limitation as long as it changes the solubility of the alkali-soluble resin in a developer.

Preferred radiation-sensitive substances include quinonediazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds / organometallic compounds, organic acid ester compounds, and organic acid compounds. Examples include amide compounds, organic acid imide compounds, and poly (olefin sulfone) compounds described in JP-A-59-152.

Specific examples of the quinonediazide compound include, for example, 1,2-benzoquinoneazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-5-sulfonic acid ester.
Sulfonate, 2,1-naphthoquinonediazide-
4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2
-Naphthoquinonediazide-5-sulfonic acid chloride,
Examples thereof include sulfonic acid chlorides of quinonediazide derivatives such as 2,1-naphthoquinonediazide-4-sulfonic acid chloride and 2,1-naphthoquinonediazide-5-sulfonic acid chloride.

Examples of the diazo compound include salts of a condensate of p-diazodiphenylamine with formaldehyde or acetaldehyde, for example, hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the condensate. Diazo resin inorganic salt, which is a reaction product with US, US
As described in P 3,300,309,
An organic salt of a diazo resin, which is a reaction product of the condensate and a sulfonic acid, is exemplified.

Specific examples of the azide compound and the diazide compound include azidochalconic acid, diazidobenzalmethylcyclohexanone and azidocinnamylidenacetophenone as described in JP-A-58-203438, and Nippon Kagaku Journal No. 12, p1708-1
714 (1983), aromatic azide compounds and aromatic diazide compounds.

The halogenated organic compound is not particularly limited as long as it is a halide of an organic compound, and various known compounds can be used. Specific examples thereof include a halogen-containing oxadiazole compound and a halogen-containing triazine. Compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds,
Halogen-containing thiazole-based compounds, halogen-containing oxazole-based compounds, halogen-containing trizol-based compounds, halogen-containing 2-pyrone-based compounds, halogen-containing aliphatic hydrocarbon-based compounds, halogen-containing aromatic hydrocarbon-based compounds, Various compounds such as other halogen-containing heterocyclic compounds and sulfenyl halide compounds, for example, tris (2,3-dibromopropyl) phosphate and tris (2,3-dibromo-3-chloropropyl) phosphate
Chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenylallyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (bromoethyl ether) -Tel)
Tetrabromobisphenol A, bis (chloroethyl ether) tetrachlorobisphenol A, tris (2,
3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyethoxy-3,5
Compounds used as halogen-based flame retardants such as (-dibromophenyl) propane and compounds used as organic chloro-based pesticides such as dichlorophenyltrichloroethane are also included.

Specific examples of the organic acid ester include a carboxylic acid ester and a sulfonic acid ester. Specific examples of the organic acid amide include carboxylic acid amide and sulfonic acid amide. Further, specific examples of the organic acid imide include carboxylic imide, sulfonic imide and the like.

In addition, as radiation-sensitive substances according to the present invention, JP-A-58-105143 and JP-A-58-2105
03434, JP-A-59-231534,
JP-A-60-24545, JP-A-60-1214
No. 45, JP-A-61-226745, JP-A-61-260239, JP-A-62-36657, JP-A-62-123444, and JP-A-62-263.
178562, JP-A-62-284354, JP-A-63-24244, JP-A-63-11
No. 3451, JP-A-63-220139, JP-A-63-98652, JP-A-2-125260
JP, JP-A-3-144648, JP-A-2-2-2
47653, JP-A-4-291258, JP-A-4-340549, JP-A-4-368864
JP-A-5-113666, JP-A-5-13666
No. 86735, USP 3,666,473, USP 4,115,128, USP 4,173,470, USP 4,526,8
It is possible to use a publicly known and public one described in the specification of No. 56 or the like. Further, two or more different types of radiation-sensitive substances may be used.

The present invention is, of course, not limited to the above specific examples. In the photoresist composition, the mixing ratio of the radiation-sensitive substance is 1 to 100 parts by weight, preferably 3 to 50 parts by weight, per 100 parts by weight of the alkali-soluble resin.

In the present invention, an acid-crosslinkable compound can be used, if necessary, for the purpose of adjusting the solubility of the alkali-soluble resin in a developer. In the present invention, the acid-crosslinkable compound is cross-linked at the time of irradiation in the presence of a compound capable of generating an acid under the irradiation of the radiation, and reduces the solubility of the irradiated portion of the alkali-soluble resin in an alkali developer. It refers to a substance, and any known and commonly used substance having such properties can be used without any limitation. Among them, a compound having a C—O—R group (where R is a hydrogen atom or an alkyl group) in a molecule or a compound having an epoxy group is preferable.

Specific examples of the compound having a C—O—R group include, for example, Japanese Patent Application Laid-Open Nos.
Melamine-formaldehyde resin, alkyl ether melamine resin, benzoguanamine resin, alkyl ether benzoguanamine resin, urea resin, alkyl ether urea resin described in
Examples thereof include urethane-formaldehyde resins and phenolic compounds containing an alkyl ether group. As the acid crosslinkable compound, two or more different types may be mixed and used. In the photoresist composition, the compounding ratio of the acid-crosslinkable compound is preferably from 0.1 to 100 parts by weight, preferably from 1 to 50 parts by weight, per 100 parts by weight of the alkali-soluble resin.
Parts by weight are more preferred. When the amount of the acid-crosslinkable compound is less than 0.1 part by weight, it is difficult to form a resist pattern. On the other hand, when the amount exceeds 100 parts by weight, residual development may occur.

As the solvent (3), known and commonly used solvents can be used without any limitation. That is, conventionally, when a photoresist agent is applied to a silicon wafer, Japanese Patent Application Laid-Open (JP-A) No. 62-36657 and Japanese Patent Application Laid-Open (JP-A) No. 4-340549 have been proposed in order to improve coatability, prevent striation, and improve developability. Gazette, JP-A-5-113666
Various solvent compositions have been proposed as described in Japanese Patent Application Laid-Open Publication No. H10-163, but if the fluorine-based surfactant according to the present invention is used, even without such troublesome solvent adjustment, it is excellent. Coating properties, prevention of striation, prevention of generation of particles in the liquid, reduction of embedment of bubbles, and excellent developability associated with improvement of the wettability of the developer during development. . In recent years, from the viewpoint of safety to the human body, from a solvent such as ethyl cellosolve acetate, which has been conventionally used for a photoresist agent, a highly safe solvent such as ethyl lactate has been used, Although careful attention is required to prevent the occurrence of coating and striation, the use of the fluorine-containing surfactant according to the present invention has the advantage that such problems can be eliminated. Therefore,
In the photoresist composition according to the present invention, a wider range of solvents can be selected than before.

It is needless to say that the present invention is not limited at all by the above specific examples. As the solvent,
For example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone, methanol, ethanol, n-propyl alcohol, and iso-propyl alcohol , N-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol
Alcohols such as toluene, nonanol and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane; ethylene glycol monomethyl ether; ethylene glycol monoethyl ether. Alcohols such as ter, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl formate, propyl formate, butyl formate Esters such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate and butyl lactate , 2- Methyl xypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Monocarboxylic acid esters such as butyl propionate, cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, cellosolve esters such as butyl cellosolve acetate, propylene glycol, propylene Propylene glycos such as glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc. Diethylene glycol monoethyl ether, diethyl alcohol glycol monoethyl ether, diethyl alcohol glycol dimethyl ether, diethyl alcohol glycol diethyl ether, diethyl ethylene glycol such as diethyl glycol methyl ethyl ether, trichloroethylene, Freon solvent, HCFC, HFC and the like. Halogenated hydrocarbons,
Perfluorinated solvents such as fluorooctane, toluene,
Examples include aromatics such as xylene, polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone, and the book “Solvent Pocket Handbook” (edited by The Society of Synthetic Organic Chemistry, Japan).
Solvents described in U.S. Pat.
No. 5143, JP-A-58-203434, JP-A-59-231534, JP-A-60-2454
No. 5, JP-A-60-121445, JP-A-60-121445
1-2226745, JP-A-61-260239, JP-A-62-36657, JP-A-62-1
No. 23444, JP-A-62-178562,
JP-A-62-284354, JP-A-63-242
No. 44, JP-A-63-113451, JP-A-63-220139, JP-A-63-98652, JP-A-2-125260, JP-A-3-14
4648, JP-A-2-247563, JP-A-4-291258, JP-A-4-340549, JP-A-4-368864, JP-A-5-11
3666, JP-A-6-186735, US
P 3,666,473, USP 4,11
Known and publicly known solvents described in US Pat. No. 5,128, US Pat. No. 4,173,470, US Pat. No. 4,526,856 and the like can be used. Is possible. As the solvent of the photoresist agent according to the present invention, two or more different solvents can be mixed and used.

It is needless to say that the present invention is not limited by the above specific examples. In the photoresist composition according to the present invention, the compounding ratio of the solvent can be appropriately adjusted according to the required film thickness and the application conditions when the photoresist composition is applied to the substrate. And the sum of radiation-sensitive substances 10
It is 10 to 10,000 parts by weight, preferably 50 to 2,000 parts by weight, based on 0 parts by weight.

In the present invention, the mixing ratio of the fluorine-based surfactant according to the present invention is appropriately adjusted according to the required film thickness and coating conditions when the photoresist composition is coated on the substrate, and the type of solvent used. However, the amount is usually 0.0001 to 5 parts by weight, preferably 0.0005 to 1 part by weight, based on 100 parts by weight of the alkali-soluble resin.

In the photoresist composition according to the present invention, the presence of a fluorine surfactant is extremely important. If the fluorine surfactant is missing, excellent coating properties, prevention of generation of striation, and improvement of the liquid -Prevention of generation of tickles,
This hinders the development of excellent developability associated with the reduction in the inclusion of bubbles and the improvement in the wettability of the developer during development.

In the photoresist composition according to the present invention, if necessary, a known and commonly used surfactant, storage stabilizer,
Needless to say, pigments, dyes, fluorescent agents, color formers, plasticizers, thickeners, thixo agents, resin dissolution inhibitors, and adhesion enhancers such as silane coupling agents can be added.

The method of applying the photoresist composition according to the present invention includes spin coating, roll coating, dip coating, spray coating, pre-coating, curtain coating, and gravure. It is possible to widely use a commonly used coating method such as coating.

The fluorine-containing surfactant according to the present invention further comprises a halogenated photographic material, a lithographic printing plate, a liquid crystal-related product such as a color filter material, and the like.
It can also be added as a leveling agent to various resins used in single-layer or multi-layer coating compositions for the production of PS plates and other photofabrication processes. When added, it exhibits excellent smoothness without pinholes, yuzu skin, uneven coating, cissing and the like.

[0132]

EXAMPLES The present invention will be described in more detail with reference to specific synthesis examples and examples according to the present invention. However, it is needless to say that the present invention is not limited to the specific examples and the like. Example 1 In a glass flask equipped with a stirrer, a condenser and a thermometer, 18 parts by weight of a (meth) acrylate monomer (a-1) containing a fluorinated alkyl group and an ethylenically unsaturated monomer containing a silicone chain were used. Body (b-3-1) 12 parts by weight, molecular weight 400
58 parts by weight of a monoacrylate compound having a copolymer of ethylene oxide and propylene oxide in the side chain, 4 parts by weight of a compound in which both ends of tetraethylene glycol are methacrylated, and 8 parts by weight of methyl methacrylate And 350 parts by weight of isopropyl alcohol (hereinafter abbreviated as IPA), and 1 part by weight of azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator under reflux in a nitrogen gas stream. After adding 10 parts by weight of lauryl mercaptan as a serial transfer agent, the mixture was refluxed at 85 ° C. for 7 hours to complete the polymerization.

The molecular weight of this polymer in terms of polystyrene as determined by gel permeation graph (hereinafter abbreviated as GPC) was Mn = 3,500. This copolymer is referred to as “fluorinated surfactant 1”.

Synthesis Examples 2 to 16 Various fluorinated alkyl group-containing (meth) acrylate monomers (A), silicone chain-containing ethylenically unsaturated monomers (B), polyoxyethylene group-containing ethylenic monomers Unsaturated monomers (C), ethylenically unsaturated monomers (D) having two or more unsaturated bonds in one molecule, and (A), (B),
(C), ethylenically unsaturated monomers other than (D) (E),
A fluorine-based copolymer was obtained in the same manner as in Synthesis Example 1 except that the chain transfer agent was used in the ratio shown in Table 1. Table 1 shows the results of measuring the molecular weights of these polymers. In addition, the charging ratio of each raw material in Table 1 is part by weight, and the symbol of the raw material indicates the compound described in the text.

Synthesis Example 17 As a silicone chain-containing ethylenically unsaturated monomer (B), a silicone monomethacrylate having a molecular weight of 1310 in which p is 4 in the formula (1) described in the text [described in the text] R ₂ , R ₃ , R of the formulas (1) and (2)
₄ , R ₅ and R ₆ are methyl groups, p is 4, R ₄ , R ₅ and R ₆ are methyl groups, and R ₂ and R ₃ are R ₇ , R ₈ and R _{9 in the} formula (2).
Is a methyl group and the linking group X is — (CH ₂ ) ₃ OCO——silicone monomethacrylate).
In the same manner as in the above, a fluorinated copolymer was obtained. Table 1 shows the results of the molecular weight measurement of this polymer.

Synthesis Example 18 A silicone chain-containing ethylenically unsaturated monomer (B) was used.
And silicone monomethacrylate having a molecular weight of about 3800
[R in formulas (1) and (2) described in the text) _Two,
R_Three, R_Four, R_Five, R₆Is a methyl group, p is 50, and
When the linking group X is-(CH_Two)_ThreeOCO- silicone monomethacrylate
Rate] in the same manner as in Synthesis Example 1 except that
A copolymer was obtained. The results of the molecular weight measurement of this polymer are shown in Table 1.
1, Table-2.

[0137]

[Table 1]

[0138]

[Table 2]

Example 1 The fluorine-based copolymer of Synthesis Example 1 was added to the four types of paints shown below in an amount of 0.5% based on the solid content of the resin. The following evaluation was performed on the coating film surface obtained under each condition. The thickness of the coating films obtained under the following conditions was all 30 μm. (Type of paint and method of preparing coating film) Using acrylic dry paint Acridic A-181 (manufactured by Dainippon Ink and Chemicals, Inc.), a steel plate (SPCC-
After coating on SB), it was left at room temperature for 1 week to obtain a coating film for evaluation. Using two-component acrylic urethane paint Acrydic A-801-P and Barnock DN-980 (all manufactured by Dainippon Ink and Chemicals, Inc.) as a curing agent, a steel plate (SPC
After coating on C-SB), a heat treatment was performed at 80 ° C. for 20 minutes to obtain a coating film for evaluation. Acrylic A-465 baked acrylic melamine paint and Super Beckamine
Using L-117-60 (all manufactured by Dainippon Ink and Chemicals, Inc.), a steel plate (SPCC-SB) is coated by spraying and then baked at 150 ° C. for 30 minutes to obtain a coating film for evaluation. Was. Using a baked alkyd melamine paint Veccosol WB-703 and Super Beckamine L-117-60 (both manufactured by Dainippon Ink and Chemicals, Inc.), a steel plate (SPCC-SB) is coated by spraying, and then heated to 150 ° C. 30
Baking was carried out for a minute to obtain a coating film for evaluation.

The surface of the coating film obtained as described above was evaluated for the following items. In addition, the above 4
The following evaluations were also performed for various kinds of coating resin liquids. <Test Method and Evaluation Criteria> (1) Foaming Property 50 cc of the obtained resin liquid for coating was evaluated in a 100 cc sample bottle with a stopper, and penetrated 50 times with an amplitude of 30 cm twice a second, 50 times. The state of air bubbles after standing was confirmed.

A: Bubbles disappear with standing. Δ: One minute after the start of standing, bubbles disappeared. ×: Air bubbles are present even one minute after the start of standing. (2) Leveling Property The leveling property of the obtained coating film surface was visually evaluated from the viewpoint of the smoothness, the presence or absence of cissing, and the like.

：: No uneven coating or cissing was observed. Δ: There is almost no coating unevenness, but repelling is observed on the coating film surface. X: Uneven coating is observed, and cissing is further observed. (3) Recoating property A 100 mm square of 1 mm square was formed on the obtained coating film surface with a cutter knife, and a cellophane tape peeling test was performed.
The evaluation was indicated by the number of cells in 100 cells that did not peel.

Examples 2 to 14 Coatings obtained in exactly the same manner as in Example 1 except that Synthesis Examples 2 to 14 were used as the fluorine-based copolymer, and a resin solution for coating were used. Performed in the same manner as in Example 1.

Comparative Example 1 Example 1 was repeated except that no fluorine-based copolymer was added.
Evaluation was performed in the same manner as in Example 1 using the coating film and the coating resin liquid obtained in exactly the same manner as in Example 1.

Comparative Examples 2 to 9 Fluorinated copolymers of Synthesis Examples 15 to 18, Synthesis Examples 15 and 1
6, a coating film obtained in exactly the same manner as in Example 1 except that a 50/50 (weight ratio) mixture or a commercially available fluorine-based surfactant was used, and a resin solution for coating were used. Performed in the same manner as in Example 1.

Table 3 shows the above evaluation results.

[0147]

[Table 3]

Megafac F-173, F-177,
F-179 is a fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc. Florard FC-430 is a fluorine-based surfactant manufactured by Sumitomo 3M Limited.

Examples 15 to 31, Comparative Examples 9 to 20 27 parts by weight of a condensate of 2,3,4-trihydroxybenzophenone and o-naphthoxydiazide-5-sulfonyl chloride, cresol and formaldehyde Of novolak resin obtained by condensation of
0 parts by weight to prepare a solution.
8, a 50/50 of Synthesis Examples 15 and 16
(Weight ratio) A mixture or a commercially available fluorinated surfactant was added so as to have a predetermined concentration with respect to the solid content in the solution, and the mixture was subjected to microfiltration with a 0.1 μm PTFE filter to form a photoresist composition. Was prepared. The photoresist composition was spin-coated on a silicon wafer having a diameter of 8 inches at a rotation speed of 3,000 rpm, and then heated on a hot plate for 90 seconds to remove the solvent. A wafer having a resist film was obtained. The following items were evaluated for the silicon wafer having the resist film obtained as described above.

The following evaluation was also performed on the photoresist solution. The evaluation results are shown in Table-4 and Table-5.

[0151]

[Table 4]

[0152]

[Table 5]

Mega Fac F-173, F-177,
F-179 is a fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc. Florard FC-430 is a fluorine-based surfactant manufactured by Sumitomo 3M Limited.

In the table, the addition amount (ppm) of the fluoropolymer or the commercially available surfactant is the amount of the solid content of the fluoropolymer with respect to the solid content of the photoresist agent. Example 1
The solvent of the photoresist composition shown in 5 is a mixed solvent of ethyl lactate / propylene glycol monomethyl ether (70/30 by weight) or a mixed solvent of methyl ethyl ketone / 2-heptanone (50/50 by weight) However, for the synthesis examples 1 to 14, which are the fluorine-based polymers according to the present invention, good results were obtained in any of the tests, while the fluorine-based copolymers of Synthesis Examples 15 to 18 and Good results could not be obtained with a 50/50 (weight ratio) mixture of Synthesis Examples 15 and 16 and a commercially available fluorine-based surfactant.

<Test Method and Evaluation Criteria> (1) Bubbling Property Photoresist solution 50 prepared as in Example 12
cc into a 100 cc sealed sample bottle,
Penetrates 50 times with an amplitude of 30 cm twice a second,
The state of air bubbles after standing was confirmed.

A: Bubbles disappear with standing. Δ: One minute after the start of standing, bubbles disappeared. ×: Air bubbles are present even one minute after the start of standing. (2) Striation With respect to the resist composition, the surface of the resist film was magnified 100 times with an optical microscope, and the occurrence of striation was observed.

：: No striation was observed. Δ: Striation is slightly recognized. X: Striation is remarkably recognized. (3) Surface Roughness The surface roughness of the resist film was measured using a surface roughness meter "Taristep" manufactured by Rankteller Hobson. The number of measurements was 21 points / 1 wafer, and the average value of 21 measurement points was determined. (4) Water Repellency As an index of suitability for post-processing such as development, a water contact angle was measured using a resist composition immediately after a droplet was dropped on the film surface after coating. The contact angle was measured by a droplet method using an automatic contact angle meter CA-Z type (manufactured by Kyowa Interface Science Co., Ltd.). (5) Coatability The surface of the resist film was visually observed, and the presence or absence of unpainted portions was observed.

○: No residual paint remaining. Δ: A residue was found on a very small part of the periphery of the wafer. ×: A part of the periphery of the wafer was left uncoated. (6) Leveling Property The static surface tension value according to the Wilhelmy method, which has been conventionally used as an index of the leveling property, and the leveling property for a coating method involving high speed and high shearing force found by the present inventors. The value of dynamic surface tension, which is one of the indices, was measured.

The static surface tension was measured by using an automatic equilibrium electro-surface tensiometer ESB-IV (manufactured by Kyowa Kagaku Co., Ltd.) using a solvent mixture of ethyl lactate and propylene glycol monomethyl ether acetate (weight ratio). The solid content of the fluorinated copolymer or commercially available surfactant is adjusted to 1% with respect to
It measured by the Wilhelmy method using a platinum plate at ° C.

On the other hand, the dynamic surface tension was measured using an automatic dynamic tensiometer DST-A1 (manufactured by Kyowa Interface Science Co., Ltd.) with a surface area of 60 cm ² (maximum surface area 80 cm ² , minimum surface area 20 cm).
cm ² ), a measurement cycle of 10 seconds, and a solution temperature of 25 ° C., a mixed solvent of ethyl lactate and propylene glycol monomethyl ether acetate as a resist solvent (7 by weight).
0/30), using a solution obtained by adjusting the solid content of the fluorine-based copolymer or the commercially available surfactant to a predetermined concentration shown in Table 3, the surface loss energy was measured 10 times, Evaluation was made based on the average value. Incidentally, a decrease in the dynamic surface tension in the present invention is synonymous with a small surface loss energy value in this evaluation.

[0161]

The fluorine surfactant according to the present invention comprises:
Post-processing properties such as defoaming property, recoating property and development, which have been regarded as the fatal drawbacks of fluorine-based surfactants, have been raised to practical levels, and for severe coating methods involving high speed and high shear force. Has an effect of exhibiting excellent leveling properties. Therefore, by applying the fluorine-based surfactant according to the present invention to various coating compositions for paints, resists, and the like, the desired performance can be sufficiently exhibited.

Claims (11)

[Claims] 1. A polymerization wherein a fluorinated alkyl group-containing ethylenically unsaturated monomer (A) and a silicone chain-containing ethylenically unsaturated monomer (B) represented by the formula (1) are essential constituent units. A fluorinated surfactant consisting of a stiffened copolymer. Embedded image [Wherein, R ₂ and R ₃ represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a functional group represented by the formula (2); (Wherein, R ₇ , R ₈ , and R _{9 each} represent an alkyl group having 1 to 20 carbon atoms or a phenyl group), R ₄ , R ₅ , and R _{6 each} have 1 to carbon atoms.
20 represents an alkyl group or a phenyl group, and p represents an integer of 0 to 3. ] 2. The surfactant according to claim 1, wherein R ₂ and R ₃ in the formula (1) are functional groups represented by the formula (2). Embedded image [Wherein, R ₇ , R ₈ and R ₉ represent an alkyl group having 1 to 20 carbon atoms or a phenyl group, and p represents an integer of 0 to 3. ] 3. A method according to claim 1, wherein R ₄ , R ₅ and R _{6 in} the formula (1) and R ₇ , R ₈ and R ₉ in the formula (2) are methyl groups and p is 0. The surfactant according to claim 1 or 2, wherein 4. The interface according to claim 1, further comprising a polyoxyalkylene group-containing ethylenically unsaturated monomer (C) as a constitutional unit of the copolymer. Activator. 5. The surfactant according to claim 4, wherein the polyoxyalkylene group in the monomer (C) is constituted by repeating units of oxyethylene and oxypropylene. 6. The copolymer according to claim 1, further comprising an ethylenically unsaturated monomer (D) having two or more unsaturated bonds in one molecule as a constitutional unit of the copolymer. The surfactant according to any one of the above. 7. A monomer (A) constituting a copolymer,
The weight ratio of each monomer of (B), (C) and (D) is 10
The surfactant according to claim 6, wherein the surfactant is from 40/5 to 30/30 to 70/1 to 10. 8. The copolymer according to claim 1, wherein the number average molecular weight of the copolymer is from 1,000 to 200,000.
The surfactant according to any one of claims 1 to 7. 9. A coating composition comprising the surfactant according to any one of claims 1 to 8. 10. A coating composition comprising the surfactant according to any one of claims 1 to 8. A resist composition comprising the surfactant according to any one of claims 1 to 8.