JP2017088786A - Fluorine surfactant and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To be suitably used as a leveling agent for various coating materials, resist materials, etc. in various coating fields where surface smoothness is required or in the coating field where precise coating is required, and also used for manufacturing semiconductors by photolithography. A fluorosurfactant that can be suitably added to an aqueous solution such as a cleaning liquid (rinsing liquid). A structural unit derived from a fluorine atom-containing allyl ether compound (A) having a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded, and a hydrophilic unit. A fluorine-containing surfactant comprising a structural unit derived from an allyl ether compound (B). [Selection figure] None

Description

  INDUSTRIAL APPLICABILITY The present invention is suitably used as a leveling agent for various coating materials, resist materials, etc. in various coating fields where surface smoothness is required, or in the coating field where precise coating is required, and for manufacturing semiconductors by photolithography. The present invention relates to a fluorosurfactant that can be suitably added to an aqueous solution such as a cleaning liquid (rinsing liquid) used.

  Conventionally, surfactants have been used in various coating fields for the purpose of improving the homogeneity and smoothness of the resulting coating film. Specifically, for example, a surfactant is added as a leveling agent to a resist material used for forming a semiconductor circuit. In addition, for example, a cleaning agent (rinse solution) used when forming a semiconductor circuit is required to have a low surface tension in order to clean the formed circuit satisfactorily. A surfactant is added to the agent (rinsing liquid).

  There are various types of surfactants such as fluorine-based, hydrocarbon-based, and silicon-based surfactants. Among these, a fluorosurfactant is excellent in surface tension reduction characteristics, and is therefore preferably added to the resist material and the rinse solution.

  Examples of the fluorosurfactant that has an excellent ability to reduce surface tension and is suitable for use as a leveling agent or addition to a rinsing liquid include, for example, fluorinated alkyl groups or fluorinated alkylene ethers having 4 to 6 carbon atoms. A fluorine-based surfactant obtained by copolymerizing a monomer (A) having a group and a monomer (B) having a polyoxyalkylene chain is disclosed (for example, see Patent Document 1). ). Specifically, in Patent Document 1, the fluorinated alkyl group or fluorinated alkylene ether group is used as a monomer (A) having a fluorinated alkyl group or fluorinated alkylene ether group having 4 to 6 carbon atoms. A fluorine-containing surfactant obtained by copolymerizing a (meth) acrylic acid ester having a polyoxyalkylene chain and a (meth) acrylic acid ester having a polyoxyalkylene chain as a monomer (B) having It is disclosed.

  In recent years, in consideration of the use environment and the natural environment, various coating materials are being made water-based, and accordingly, the demand for surfactants that can be used for both surfactants and aqueous compositions is increasing. In response to such demand, the fluorosurfactant disclosed in Patent Document 1 is obtained by using the fluorosurfactant disclosed in Patent Document 1 because an ester bond in the structure is hydrolyzed. It has been difficult to maintain the surface tension of a water-based coating material and a cleaning agent (rinse liquid) obtained.

JP 2012-062433 A

  The problem to be solved by the present invention is that it can be used for an aqueous composition, is not easily hydrolyzed in water, and has an aqueous composition such as an aqueous coating material or a cleaning agent (rinsing liquid). The object is to provide a fluorosurfactant that can be maintained in a low state and a composition containing the fluorosurfactant.

  As a result of intensive studies, the present inventors have found that a structural unit derived from a fluorine atom-containing allyl ether compound (A) having a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms, and hydrophilicity The polymer having a structural unit derived from the allyl ether compound (B) has a function of lowering the surface tension of the aqueous composition and can be used as a surfactant (fluorine surfactant). Since surfactants do not contain an ester bond, the bond cannot be hydrolyzed, and when added to an aqueous composition such as an aqueous coating material or a cleaning agent (rinse solution), the surface of these surfactants The inventors have found that the tension can be maintained in a low state over a long period of time, and have completed the present invention.

  That is, the present invention relates to a structural unit derived from a fluorine atom-containing allyl ether compound (A) having a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded, and a hydrophilic unit. And a structural unit derived from a functional allyl ether compound (B).

  Moreover, this invention provides the composition characterized by containing the said fluorosurfactant.

  The fluorosurfactant of the present invention is not affected by hydrolysis. Therefore, the surface tension can be kept low for a long time by adding to an aqueous solution. Therefore, the fluorosurfactant of the present invention can be suitably used as an aqueous coating material or an additive to a rinsing liquid. Further, by adding the fluorinated surfactant of the present invention to a water-based ink using a pigment, the handwriting fixability can be improved on an ink non-penetrating surface such as a resin film.

FIG. 1 is a chart of the ¹ H-NMR spectrum of the fluorosurfactant (1) obtained in Example 1. FIG. 2 is a chart of ¹³ C-NMR spectrum of the fluorosurfactant (1) obtained in Example 1. FIG. 3 is an IR spectrum chart of the fluorosurfactant (1) obtained in Example 1. 4 is a chart of ¹ H-NMR spectrum of the fluorosurfactant (2) obtained in Example 2. FIG. FIG. 5 is a chart of ¹³ C-NMR spectrum of the fluorosurfactant (2) obtained in Example 2. 6 is an IR spectrum chart of the fluorosurfactant (2) obtained in Example 2. FIG.

  The fluorosurfactant of the present invention comprises a structural unit derived from a fluorine atom-containing allyl ether compound (A) having a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms, and a hydrophilic unit. And a structural unit derived from an allyl ether compound (B).

  Specific examples of the structural unit derived from the fluorine atom-containing allyl ether compound (A) include, for example, the following general formula (A-1):

（式中、Ｒｆはフッ素化アルキレンエーテル基またはフッ素原子が直接結合した炭素原子の数が１〜６であるフッ素化アルキル基である。はＲ^１は直接結合または炭素原子数１〜６のアルキレン基である。）
で表される構成単位を具体的に例示することができる。

(Wherein Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. R ¹ is a direct bond or alkylene having 1 to 6 carbon atoms. Group.)
The structural unit represented by can be specifically illustrated.

  As for Rf in the said general formula (A-1), the following structure can be illustrated preferably, for example.

  [N in the above formulas (Rf-1) and (Rf-4) represents an integer of 1-6. N in the above formula (Rf-5) represents an integer of 2 to 6. N in the above formula (Rf-6) represents an integer of 4 to 6. M in said formula (Rf-7) is an integer of 1-5, n is an integer of 0-4, and the sum total of m and n is 1-5. M in the above formula (Rf-8) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 0 to 4, and the sum of m, n and p is 1 to 4. 5. M in the above formula (Rf-9) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 1 to 4, and the sum of m, n, and p is 2 to 4. 5. ]

  As the fluorinated alkyl group possessed by the allyl ether compound (A), a fluorinated surfactant having a low risk of bioaccumulation by selecting a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. An agent is obtained. Among the fluorinated alkyl groups, a fluorinated alkyl group having 4 to 6 carbon atoms to which fluorine atoms are directly bonded is preferable because of excellent surface tension reduction characteristics, and the number of carbon atoms to which fluorine atoms are directly bonded is preferable. More preferred is a fluorinated alkyl group of 6.

  The fluorinated alkyl group may be a partially fluorinated alkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, or a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms. The fluorine atom-containing allyl ether compound (A) may have a fluorinated alkylene ether group as described above. Furthermore, carbon atoms in the fluorinated alkyl group may be bonded by an unsaturated bond.

  The fluorinated alkyl group or fluorinated alkylene ether group may be linear or branched. Among these, a linear fluorinated alkyl group is preferable because of its excellent surface tension reducing ability and easy availability.

  Among the fluorinated alkyl groups, a perfluoroalkyl group is preferable because it is a fluorosurfactant having excellent surface tension reducing properties.

R ¹ is a direct bond or an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include linear alkylene groups such as methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group and n-hexylene group; isopropylene group , Isobutylene group, t-butylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2 -Dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl- n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2 − Methyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1 , 2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, etc. Examples include a branched alkylene group. Among R ¹ , a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms is preferable because a fluorine-based surfactant having excellent water solubility can be obtained. A linear alkylene group having 1 to 3 or a branched alkylene group having 2 to 3 carbon atoms is more preferable.

  Among the structural units represented by (A-1), the following (A-2)

（式中、Ｒｆはフッ素化アルキレンエーテル基またはフッ素原子が直接結合した炭素原子の数が１〜６であるフッ素化アルキル基である。）
で表される構成単位を好ましく例示することができる。

(In the formula, Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded.)
The structural unit represented by can be illustrated preferably.

  Among the structural units represented by (A-2), the following (A-3)

で表される構成単位を、より好ましく例示することができる。

The structural unit represented by can be illustrated more preferably.

  The fluorosurfactant of the present invention is characterized by having a structural unit derived from a hydrophilic allyl ether compound (B).

  Specific examples of the structural unit derived from the hydrophilic allyl ether compound (B) include, for example, the following general formula (B-1):

（式中、Ｒ^２は親水性基である。）
で表される構成単位を具体的に例示することができる。

(In the formula, R ² is a hydrophilic group.)
The structural unit represented by can be specifically illustrated.

  Specific examples of the structural unit represented by the general formula (B-1) include structural units represented by the following general formula (B-2) and general formula (B-3). .

（式中、Ｒ^３、Ｒ^４はそれぞれ炭素原子数１〜６のアルキレン基である。Ｒ^５は水素原子または炭素原子数１〜３のアルキル基である。ｎは１〜３０である。）

(In the formula, R ³ and R ⁴ are each an alkylene group having 1 to 6 carbon atoms. R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. N is 1 to 30.)

Among the R ³ and R ^4, a fluorine-containing surfactant having high affinity with water and excellent water solubility is obtained, so that a linear alkylene group having 1 to 3 carbon atoms or a carbon atom having 2 to 3 carbon atoms is obtained. A branched alkylene group is preferred, and an ethylene group is more preferred. The n is preferably 3 to 15 because a fluorosurfactant having a high affinity with water can be obtained.

  Among the structural units represented by the general formula (B-2) and the general formula (B-3), structural units represented by the following general formula (B-4) and the general formula (B-5) are used. It can be illustrated preferably.

〔（Ｂ−５）中のｎは１〜３０である。〕

[N in (B-5) is 1-30. ]

  Among the fluorosurfactants of the present invention, the following structure (1)

（式中、Ｒｆはフッ素化アルキレンエーテル基またはフッ素原子が直接結合した炭素原子の数が１〜６であるフッ素化アルキル基である。Ｒ^１は直接結合または炭素原子数１〜６のアルキレン基である。Ｒ^２は親水性基である。ａは１〜２５であり、ｂは１〜１００である。）
で表されるフッ素系界面活性剤が水溶性に優れ、かつ良好なレベリング性を得られる理由により好ましい。

(In the formula, Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. R ¹ is a direct bond or an alkylene group having 1 to 6 carbon atoms. R ² is a hydrophilic group, a is 1 to 25, and b is 1 to 100.)
Is preferable because it has excellent water solubility and good leveling properties.

  In the structure (1), a and b each represent the number of repeating structural units. In addition, the structural unit bundled by a and b may exist in a block shape or may exist in a random shape. When each structural unit exists at random, the total number of repetitions of each structural unit is a and b, respectively.

  The fluorine-based surfactant of the present invention includes, for example, a fluorine atom-containing allyl ether compound (A) having a fluorinated alkyl group or a fluorinated alkylene ether group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. A copolymer with a hydrophilic allyl ether compound (B) can be preferably exemplified. Specifically, the copolymer can be suitably obtained by copolymerizing, for example, free radical polymerization, the fluorine atom-containing allyl ether compound (A) and the hydrophilic allyl ether compound (B). it can.

  Examples of the fluorine atom-containing allyl ether compound (A) include the following general formula (a-1):

（式中、Ｒｆはフッ素化アルキレンエーテル基またはフッ素原子が直接結合した炭素原子の数が１〜６であるフッ素化アルキル基である。Ｒ^１は直接結合または炭素原子数１〜６のアルキレン基である。）
で表される化合物を好ましく例示することができる。

(In the formula, Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. R ¹ is a direct bond or an alkylene group having 1 to 6 carbon atoms. .)
The compound represented by can be illustrated preferably.

The Rf is preferably exemplified by the structures represented by (Rf-1) to (Rf-9). In addition, R ¹ can preferably be exemplified by the alkylene group, for example.

  Among the Rf, a fluorinated alkyl group having 4 to 6 carbon atoms to which fluorine atoms are directly bonded is preferable because a fluorine-based surfactant having excellent surface tension reducing properties is obtained, and fluorine atoms are directly bonded. More preferred are fluorinated alkyl groups having 6 carbon atoms.

  The fluorinated alkyl group may be a partially fluorinated alkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, or a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms. The fluorine atom-containing allyl ether compound (A) may have a fluorinated alkylene ether group as described above. Furthermore, carbon atoms in the fluorinated alkyl group may be bonded by an unsaturated bond.

  The fluorinated alkyl group or fluorinated alkylene ether group may be linear or branched. Among them, a linear fluorinated alkyl group is preferable because of its high affinity with water.

In the general formula (a-1), R ¹ is preferably an alkylene group having 1 to 3 carbon atoms because it is an easily available compound.

  Examples of the fluorine atom-containing allyl ether compound represented by the general formula (a-1) include perfluorohexyl alkyl allyl ethers such as 2- (perfluorohexyl) ethyl allyl ether, perfluoro (methyl allyl ether), Examples include perfluoro (ethyl allyl ether), perfluoro (propyl allyl ether), perfluoro (butyl allyl ether), perfluoro (isobutyl allyl ether), perfluoro (propoxypropyl allyl ether), and the like. Of these, 2- (perfluorohexyl) ethyl allyl ether is preferred because a fluorosurfactant having an excellent ability to reduce the surface tension can be obtained and is easily available.

  The allyl ether compound (A) used in the present invention may be used alone or in combination of two or more.

  The allyl ether compound (B) used in the present invention is hydrophilic. In the present invention, whether or not the allyl ether compound is hydrophilic is determined based on the solubility in water. Specifically, an allyl ether compound that can be dissolved in an amount of 5 g or more in 100 g of water at 25 ° C. can be used as the hydrophilic allyl ether compound (B) in the present invention.

  The allyl ether compound (B) used in the present invention is, for example, the following general formula (b-1) or (b-2)

（式中、Ｒ^３、Ｒ^４はそれぞれ炭素原子数１〜６のアルキレン基である。Ｒ^５は水素原子または炭素原子数１〜３のアルキル基である。ｎは１〜３０である。）
で表される化合物を好ましく例示することができる。

(In the formula, R ³ and R ⁴ are each an alkylene group having 1 to 6 carbon atoms. R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. N is 1 to 30.)
The compound represented by can be illustrated preferably.

Among the R ³ and R ^4, a fluorine-containing surfactant having high affinity with water and excellent water solubility is obtained, so that a linear alkylene group having 1 to 3 carbon atoms or a carbon atom having 2 to 3 carbon atoms is obtained. A branched alkylene group is preferable, a linear alkylene group having 1 to 3 carbon atoms is more preferable, and an ethylene group is further preferable. The n is preferably 3 to 15 because a fluorosurfactant having a high affinity with water can be obtained.

  In the allyl ether compound represented by (b-1), examples of the allyl ether compound having a linear alkylene group include 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl. Examples include ether, 5-hydroxypentyl allyl ether, and 6-hydroxyhexyl allyl ether. Examples of the allyl ether compound having a branched alkylene group include 1-hydroxypropyl allyl ether, 2-hydroxypropyl allyl ether, 1-hydroxybutyl allyl ether, 2-hydroxybutyl allyl ether, 3-hydroxybutyl allyl ether, Examples include 3-hydroxy-2-methylpropyl allyl ether and 4-hydroxy-2-methylbutyl allyl ether.

  Examples of the allyl ether compound represented by (b-2) include methoxy-polyethyleneoxyallyl ether, methoxy-polypropyleneoxyallyl ether, methoxy-polybutyleneoxyallyl ether, hydroxy-polyethyleneoxyallyl ether, and hydroxy-polypropylene. Examples include oxyallyl ether and hydroxy-polybutylene oxyallyl ether.

  Among allyl ether compounds (B) used in the present invention, hydroxyethyl allyl ether and methoxy-polyethyleneoxy allyl ether are obtained because a fluorosurfactant having excellent ability to reduce surface tension and water solubility is obtained. Is preferred. The number of ethyleneoxy repeats of methoxy-polyethyleneoxyallyl ether is preferably 1 to 30 because a fluorine-based surfactant having high affinity with water is obtained, and has high affinity with water and exhibits good leveling properties. 3 to 15 is preferable because a fluorinated surfactant that can be obtained is easily obtained.

  The allyl ether compound (B) used in the present invention may be used alone or in combination of two or more.

  In addition to the structural unit derived from the fluorine atom-containing allyl ether compound (A) and the structural unit derived from the hydrophilic allyl ether compound (B), the fluorosurfactant of the present invention is within a range that does not impair the effects of the present invention. You may have the structural unit derived from another polymeric compound (C). As other structural units derived from the polymerizable compound (C), for example, structural units derived from the allyl ether compound (C1) other than the allyl ether compound (A) and the allyl ether compound (B), derived from the vinyl ether compound (C2). And the like.

  Examples of the allyl ether compound (C1) include hydroxyl group-containing allyl ethers such as 4-hydroxycyclohexyl allyl ether; methyl allyl ether, ethyl allyl ether, n-propyl allyl ether, isopropyl allyl ether, n-butyl allyl ether, Alkyl allyl ethers such as isobutyl allyl ether, tert-butyl allyl ether, n-pentyl allyl ether, n-hexyl allyl ether, n-octyl allyl ether, n-dodecyl allyl ether, 2-ethylhexyl allyl ether or cyclohexyl allyl ether And cyclic allyl ethers.

  Examples of the vinyl ether compound (C2) include (perfluorohexyl) methyl vinyl ether, 2- (perfluorohexyl) ethyl vinyl ether, 3- (perfluorohexyl) propyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether. 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 1-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 1-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 3-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 4-hydroxycyclohexane Sil vinyl ether, cyclohexane-1,4-dimethanol mono vinyl ether, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether , N-octyl vinyl ether, n-dodecyl vinyl ether, alkyl vinyl ethers such as 2-ethylhexyl vinyl ether, and cyclic allyl ethers such as cyclohexyl vinyl ether.

  In order to obtain the fluorosurfactant of the present invention, various polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037, JP-A-2003-313397, etc.) may be used. The synthesis method described can be used. Among these, a radical polymerization method using a radical polymerization reaction is preferable, and a free radical polymerization method is preferable.

  When obtaining the fluorosurfactant of the present invention by the free radical polymerization method, for example, allyl ether compound (A), allyl ether compound (B) and optionally polymerizable compound (C) in an organic solvent, The method of polymerizing using an initiator is mentioned. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability.

  Examples of the initiator include azo initiators, peroxide initiators, ionic initiators, and redox initiators.

  Since the fluorine-based surfactant of the present invention becomes a water-soluble surfactant, the use ratio of the fluorine atom-containing allyl ether compound (A) and the hydrophilic allyl ether compound (B) is a mass ratio. [(A) / (B)] is preferably a copolymer of 10/90 to 60/40, more preferably a copolymer of 20/80 to 50/50.

  The number average molecular weight (Mn) of the fluorosurfactant of the present invention is 500 to 30,000 because it is excellent in solubility in an aqueous solution such as a coating material or a rinsing liquid, and an aqueous solution having a low surface tension can be obtained. Is preferable, and 500 to 10,000 are more preferable. Further, the weight average molecular weight (Mw) is preferably 500 to 100,000, more preferably 1,000 to 30,000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + “TSK− manufactured by Tosoh Corporation” GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement condition:
Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  The composition of the present invention contains the fluorosurfactant of the present invention. Specific examples of the composition of the present invention include an aqueous coating material, a rinsing liquid for photolithography, and a rinsing liquid for producing a color filter. Especially, the composition of this invention can be used especially suitably as a rinse liquid for photolithography manufacture.

  Further, since the fluorosurfactant of the present invention can also be expected to have an effect of dispersing the pigment in an aqueous medium, the effect of improving the dispersibility of the pigment by adding the fluorosurfactant of the present invention to the aqueous ink. Can be expected. In addition, the water-based ink using the fluorosurfactant of the present invention can be expected to improve the fixability of handwriting on an ink non-penetrating surface such as a resin film.

  Hereinafter, the present invention will be described more specifically based on examples. Unless otherwise specified,% in the examples is based on mass.

Example 1
To a glass flask equipped with a stirrer, a condenser, and a thermometer, 6.8 g of toluene was added, and the temperature was raised to 120 ° C. while stirring in a nitrogen stream. Then, 20 g of 2- (perfluorohexyl) ethyl allyl ether, 40 g of hydroxyethyl allyl ether, 10 g of 1,1-di (t-butylperoxy) cyclohexane and 4.8 g of toluene were set in a dropping device. The flask was added dropwise over 2 hours while maintaining the inside of the flask at 120 ° C. After completion of dropping, the mixture was stirred at 120 ° C. for 4 hours. After completion of the reaction, the solvent and unreacted monomer are distilled off under reduced pressure, and the fluorine-based interface of the present invention having a structural unit derived from the allyl ether compound (A) and a structural unit derived from the hydrophilic allyl ether compound (B) Activator (1) was obtained. The number average molecular weight of the fluorosurfactant (1) was 880, and the weight average molecular weight was 2,000. FIG. 1 shows a chart of ¹ H-NMR spectrum of the fluorosurfactant (1), FIG. 2 shows a chart of ¹³ C-NMR spectrum, and FIG. 3 shows a chart of IR spectrum. In addition, as for fluorine-type surfactant (1), the average of a in the said Structural formula (1) was 1, and the average of b was 8.

  The composition of the present invention was obtained using the obtained fluorosurfactant (1). Using the obtained composition, the hydrolytic resistance, surface smoothness (leveling property), and wettability of the fluorosurfactant (1) were evaluated. The preparation method and evaluation method of each composition are shown below.

Evaluation of hydrolysis resistance of fluorosurfactant (1) (1)
The fluorosurfactant (1) was added to water so that the content was 0.01% and 1% to obtain the compositions (1-1) and (1-2) of the present invention. These compositions were allowed to stand in an environment of 65 ° C., and the surface tension of the compositions at the time of standing (0 day), 3 days, 7 days, 10 days and 14 days was measured. The smaller the surface tension, the better the surface active effect (surface tension lowering property), and the smaller the width of the surface tension that increases with time, the less it is hydrolyzed in water. In addition, the measured value of the surface tension of each composition is an average value of two samples. The measurement results are shown in Table 1.

In the present invention, the surface tension was measured according to the following conditions.
<Surface tension measurement conditions>
Measuring instrument: Automatic balance type electro surface tension meter (“ESB-IV type” manufactured by Kyowa Kagaku Co., Ltd.) Measuring method: Static surface tension was measured by an Wilhelmy method using a platinum plate at an environmental temperature of 23 ° C. In addition, the static surface tension of water was 72.3 mN / m ² under the above measurement conditions (reference example).

Evaluation of hydrolysis resistance of fluorinated surfactant (1) (2)
The fluorosurfactant (1) is added to a 0.63% aqueous KOH solution so that the content is 0.01% and 1%, and the compositions (1-3) and (1-4) of the present invention are added. ) Compositions (1-3) and (1-4) were used, and these compositions were allowed to stand in an environment of 65 ° C., and when they were allowed to stand (0 days), 1 day later, 2 days later, 4 days later The surface tension was measured in the same manner as in “Evaluation of Hydrolysis Resistance of Fluorosurfactant (1) (1)” except that the surface tension was measured after 7 days and after 10 days. The measurement results are shown in Table 2.

Evaluation of leveling property of fluorosurfactant (1) 100 parts of aqueous acrylic urethane resin (Bernock WD-551 manufactured by DIC Corporation), 0.2 part of fluorosurfactant (1) and 100 parts of water were mixed, A composition (1-5) of the present invention was obtained. 5 g of the composition (1-5) was dropped onto a 10 cm × 10 cm chromium-plated glass plate, and then formed by spin coating (300 rpm, 10 seconds) to obtain a coating film. After drying at room temperature for 10 minutes, the entire coating film was scanned with a reflective spectral film thickness meter ("FE-3000" manufactured by Otsuka Electronics Co., Ltd.), and the smoothness of the coating film surface was evaluated according to the following criteria. The measurement results are shown in Table 3.

○ Most coating unevenness is not observed.
X Many coating irregularities are observed.

Evaluation of the wettability of the fluorosurfactant (1) The composition (1-6) was obtained by adding it to water so that the solid content of the fluorosurfactant (1) was 0.2%. 3 μL of the composition (1-6) was dropped on a PET plate, and the contact angle after 30 seconds was measured. For the measurement, “DropMaster” manufactured by Kyowa Interface Science was used, and evaluation was performed by the θ / 2 method. The lower the contact angle measurement value, the higher the wettability. The measurement results are shown in Table 4.

Example 2
To a glass flask equipped with a stirrer, a condenser, and a thermometer, 6.8 g of toluene was added, and the temperature was raised to 120 ° C. while stirring in a nitrogen stream. Subsequently, 20 g of 2- (perfluorohexyl) ethyl allyl ether, 40 g of methoxy-polyethyleneoxyallyl ether (average number of repetitions of oxyethylene = 9), and 10 g of 1,1-di (t-butylperoxy) cyclohexane were mixed. The solution and 4.8 g of toluene were set in a dropping device, and dropped in 2 hours while keeping the inside of the flask at 120 ° C. After completion of dropping, the mixture was stirred at 120 ° C. for 4 hours. After completion of the reaction, the solvent is distilled off under reduced pressure, and the fluorosurfactant (2) having a structural unit derived from the allyl ether compound (A) and a structural unit derived from the hydrophilic allyl ether compound (B) (2 ) The number average molecular weight of the fluorosurfactant (2) was 2,400, and the weight average molecular weight was 9,300. FIG. 4 shows a chart of ¹ H-NMR spectrum of the fluorosurfactant (2), FIG. 5 shows a chart of ¹³ C-NMR spectrum, and FIG. 6 shows a chart of IR spectrum. In addition, as for fluorine-type surfactant (2), the average of a in the said Structural formula (1) was 8, and the average of b was 25.

  Compositions (2-1) to (2-6) were obtained in the same manner as in Example 1 except that the fluorosurfactant (2) was used. Evaluation similar to Example 1 is performed, and the results are shown in Tables 1 to 4.

Comparative Example 1
To a glass flask equipped with a stirrer, a condenser and a thermometer, 300 g of methyl ethyl ketone (MEK) was added, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. Next, 70 g of 2- (perfluorohexyl) ethyl acrylate and 130 g of methoxypolyethylene glycol acrylate (ethylene glycol average repeat number = 9) were mixed, and 10 g of dimethyl 2,2′-azobisisobutyrate was dissolved in 100 g of MEK. Each dropped liquid was set in a dropping device, and both dropped liquids were dropped over 4 hours while keeping the inside of the flask at 80 ° C. After completion of dropping, the mixture was stirred at 80 ° C. for 16 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a comparative fluorosurfactant (1 ′). The number average molecular weight of the comparative fluorosurfactant (1 ′) was 1,500, and the weight average molecular weight was 4,200.

  Comparative compositions (1′-1) to (1′-6) were obtained in the same manner as in Example 1 except that the comparative fluorosurfactant (1 ′) was used. Evaluation similar to Example 1 is performed, and the results are shown in Tables 1 to 3.

Comparative Example 2
A comparative control composition (2'-5) and a comparative control composition in the same manner as the composition (1-5) and the composition (1-6) obtained in Example 1 except that no surfactant was added. (2′-6) was obtained. In the same manner as in Example 1, leveling property and wettability were evaluated. The results are shown in Table 3.

Footnotes in Tables 1 and 2-: Not evaluated.

  According to the results of (1-1), (2-1) and (1′-1), the fluorine-containing surfactant is contained in the composition at a low content of 0.01% by mass, respectively. In (1-1) and (2-1) containing a surfactant, the surface tension reducing ability is excellent and the surface tension reducing ability can be maintained over a long period of time. It can be seen that (1′-1) containing a system surfactant is inferior in surface tension reducing ability with time.

  In addition, according to the results of (1-2), (2-2) and (1′-2) containing 1% by mass of the fluorosurfactant in the composition, the fluorosurfactant of the present invention is The contained (1-2) and (2-2) are more excellent in surface tension reducing ability than the above (1-1) and (2-1), and can maintain the surface tension reducing ability over a long period of time. I understand that. On the other hand, (1′-2) containing a fluorosurfactant for comparison and control has a surface tension reducing ability as compared with (1-2) containing the surfactant of the present invention at the same concentration. I understand that it is inferior.

  About compositions (1-3), (1-4), (2-3), (2-4), (1′-3) and (1′-4) evaluated with an alkaline solution (KOH solution) The same tendency as described above is observed, and it can be seen that the surfactant of the present invention can be preferably used for a solution in a strongly alkaline environment such as a developer or a rinse solution used for manufacturing a semiconductor or a color filter.

  Furthermore, it can be seen from the results in Tables 3 and 4 that the fluorosurfactant of the present invention has good leveling properties and good wettability. Therefore, it turns out that the surfactant of this invention can be preferably used with respect to the solution in strong alkali environments, such as a developing solution and a rinse solution used for semiconductor manufacture or color filter manufacture.

Claims (17)

  A structural unit derived from a fluorine atom-containing allyl ether compound (A) having a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded, and a hydrophilic allyl ether compound ( B) A fluorosurfactant characterized by having a structural unit derived from. The structural unit derived from the allyl ether compound (A) is represented by the following general formula (A-1)

(In the formula, Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. R ¹ is a direct bond or an alkylene group having 1 to 6 carbon atoms. .)
The structural unit derived from the allyl ether compound (B) is represented by the following general formula (B-1):

(In the formula, R ² is a hydrophilic group.)
The fluorine-based surfactant according to claim 1, which is a structural unit represented by the formula:   The fluorosurfactant according to claim 2, wherein Rf is a linear fluorinated alkyl group. The structural unit derived from the allyl ether compound (A) is represented by the following general formula (A-2)

(In the formula, Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded.)
The fluorine-based surfactant according to claim 1, which is a structural unit represented by the formula: The structural unit derived from the allyl ether compound (A) is represented by the following general formula (A-3)

The structural unit derived from the allyl ether compound (B) is represented by the following general formula (B-2) or (B-3):

(In the formula, R ³ and R ⁴ are each an alkylene group having 1 to 6 carbon atoms. R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. N is 1 to 30.)
The fluorine-based surfactant according to claim 1, which is a structural unit represented by the formula: The structural unit derived from the allyl ether compound (A) is a structural unit represented by the general formula (A-3), and the allyl ether compound (B) is represented by the following general formula (B-4) or (B-5). )

[N in (B-5) is 1-30. ]
The fluorine-based surfactant according to claim 5, which is a structural unit represented by: The following structure (1)

(In the formula, Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. R ¹ is a direct bond or an alkylene group having 1 to 6 carbon atoms. R ² is a hydrophilic group, a is 1 to 25, and b is 1 to 100.)
The fluorine-type surfactant of Claim 1 represented by these.   A fluorine atom-containing allyl ether compound (A) having a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded, and a hydrophilic allyl ether compound (B) The fluorosurfactant according to claim 1, which is a copolymer.   The fluorinated surfactant according to claim 7, wherein the fluorinated alkyl group is a linear fluorinated alkyl group. The fluorine atom-containing allyl ether compound (A) is represented by the following general formula (a-1)

(In the formula, Rf is a fluorinated alkylene ether group or a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded. R ¹ is a direct bond or an alkylene group having 1 to 6 carbon atoms. .)
The fluorine-type surfactant of Claim 8 which is a compound represented by these. The hydrophilic allyl ether compound (B) is represented by the following general formula (b-1) or (b-2)

(In the formula, R ³ and R ⁴ are each an alkylene group having 1 to 6 carbon atoms. R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. N is 1 to 30.)
The fluorine-type surfactant of Claim 8 which is a compound represented by these. The fluorine-based surfactant according to claim 11, wherein each of R ³ and R ⁴ is a linear alkylene group. The fluorosurfactant according to claim 11, wherein each of R ³ and R ⁴ is an ethylene group.   The fluorine-based surfactant according to claim 8, wherein the fluorine atom-containing allyl ether compound (A) is 2- (perfluorohexyl) ethyl allyl ether.   The fluorosurfactant according to claim 8, wherein the hydrophilic allyl ether compound (B) is hydroxyethyl allyl ether or methoxy-polyethyleneoxy allyl ether.   The use ratio of the fluorine atom-containing vinyl ether compound (A) and the hydrophilic vinyl ether compound (B) is a copolymer having a mass ratio [(A) / (B)] of 10/90 to 60/40. Item 9. A fluorosurfactant according to Item 8.   A composition comprising the fluorosurfactant according to any one of claims 1 to 16.

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