[go: up one dir, main page]

WO2004018535A1 - Fluorosurfactants - Google Patents

Fluorosurfactants Download PDF

Info

Publication number
WO2004018535A1
WO2004018535A1 PCT/JP2003/010509 JP0310509W WO2004018535A1 WO 2004018535 A1 WO2004018535 A1 WO 2004018535A1 JP 0310509 W JP0310509 W JP 0310509W WO 2004018535 A1 WO2004018535 A1 WO 2004018535A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer
mass
surfactant according
surface tension
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2003/010509
Other languages
French (fr)
Japanese (ja)
Inventor
Shunji Odaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Seimi Chemical Co Ltd
Original Assignee
Seimi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Seimi Chemical Co Ltd filed Critical Seimi Chemical Co Ltd
Priority to JP2004530578A priority Critical patent/JP4544996B2/en
Priority to AU2003257623A priority patent/AU2003257623A1/en
Publication of WO2004018535A1 publication Critical patent/WO2004018535A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers

Definitions

  • the present invention relates to a novel fluorinated surfactant.
  • Fluorosurfactants which have a high surface tension lowering ability, are widely used in coatings and other coatings for the purpose of improving the uniformity and smoothness of coating films.
  • To reduce the accumulation in the human body it is necessary to improve the solubility in water.However, in this case, there is a problem that the ability to lower the surface tension is reduced, and the surface tension reduction ability is high.
  • An object of the present invention is to provide a fluorine-based surfactant having excellent solubility in water and excellent surface tension lowering ability.
  • the present invention is a fluorosurfactant comprising a copolymer obtained by copolymerizing the following monomers A, B and C as a polymerization component.
  • n an integer of 1 to 3.
  • Ri hydrogen atom or methyl group
  • R f a fluoroalkyl group having 1 to 20 carbon atoms.
  • the fluorine-based surfactant of the present invention has low solubility in water due to its high solubility in water, has a high ability to lower surface tension, and has excellent properties such as leveling properties.
  • R f in monomer A which is a raw material of the copolymer of the present invention, is a fluoroalkyl group
  • R f is a fluoroalkyl group
  • R f preferably has 4 to 18 carbon atoms, particularly preferably 4 to 12 carbon atoms.
  • monomer A having a perfluoroalkyl group having 42 ash atoms include the following.
  • A— 14: C 4 F 9 CH 2 CH 2 OCOC (CH 3 ) CH:
  • the present invention is, of course, not limited by the specific examples.
  • the monomers B and C which are the raw materials of the copolymer of the present invention, are composed of only a polyoxypropylene group.
  • the solubility of the copolymer is significantly reduced, and on the other hand, if it is composed of only polyoxyethylene groups and does not contain, for example, polyoxypropylene groups, there is a problem with the compatibility of the copolymer with other polymers or pigments There is.
  • Both the monomers B and C need to have different types of polyoxyalkylene bonds, that is, need to have two or more types of polyoxyalkylene bonds.
  • 1 i,,, 12 , m 2 , and n 2 are preferably 5 to 60, and particularly preferably 10 to 40. They need not be equal.
  • the monomer B include (meth) acrylates in which 1 i,, and are 4 to 10, 8 to 20, and 4 to 10, respectively.
  • the monomer C which is a raw material of the copolymer of the present invention include di (meth) acrylates in which 12 rrl 2 n 2 is 4 20 840 420.
  • the monomers AB and C having the above structure Any structure such as block, random, alternating, or graft may be used as long as the copolymer is copolymerized within the range of the mixing ratio.
  • the graft ratio of the graft copolymer, the random copolymer There is no particular concern for randomness.
  • the monomers A, B and C can be used alone or in a mixture of two or more as long as they are within the range represented by the structural formulas described above.
  • Preferred combinations of monomers A, B and C are A-1, B-4 and C-4; A-7, B-4 and C-14; A-7, B-5 and C-15; A-1, A-3, A-5, A-7, B-4 and C-14. Particularly preferred combinations are A-1, B-4 and C-4.
  • the copolymerization ratio (mass ratio) of the monomers A, B, and C constituting the copolymer of the present invention may be determined by, for example, the blend in the composition in which the copolymer is blended, the level of the desired physical properties, and the like.
  • AZ (B + C) preferably in the range of 5/95 to 70/30, and more preferably in the range of 10Z90 to 50Z50.
  • the molecular weight of the copolymer according to the present invention is preferably such that the weight average molecular weight Mw in terms of polymethyl methacrylate is 1,000 to 100,000, and 3,000. It is particularly preferable that the number is 100,000. When the Mw is less than 1,000, it is difficult to obtain a sufficient surface tension lowering ability. Conversely, when the Mw exceeds 100,000, the compatibility with the compound in the composition becomes poor. descend.
  • the method for producing the copolymer of the present invention is not limited at all, and is based on known methods, that is, a solution polymerization method, a bulk polymerization method, and an emulsification method based on polymerization mechanisms such as a radical polymerization method, a cationic polymerization method, and an anion polymerization method.
  • a radical polymerization method is particularly simple and industrially preferable.
  • polymerization initiators can be used, for example, peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyl nitrile, and transition metal catalysts that cause living radical polymerization And the like.
  • a chain transfer agent such as octyl mercaptan and 2-mercaptoethanol can be used.
  • the polymerization can be carried out in the presence of a solvent or water, or in the absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of workability.
  • the solvent include alcohols such as ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, methyl lactate, and butyl lactate; dimethylformamide, dimethyl sulfoxide; Polar solvents such as methylpyrrolidone; ethers such as methylcellulose solvent, butylcellulose solvent, and butylcarbyl; propylene glycols and esters such as propylene glycol, propylene glycol monoethyl ether acetate; Octalogen compounds such as trichlorene, aromatic hydrocarbons such as benzene, toluene, and xylene, and fluorinated initiators
  • the fluorine-based surfactant according to the present invention may be prepared by using only one type of the copolymer, or may be prepared by using two or more types of the copolymer simultaneously.
  • various surfactants such as hydrocarbon-based, fluorine-based, and silicone-based surfactants can be used in combination for the purpose of improving the compatibility with each component in the fluorine-based surfactant.
  • the solubility of the fluorinated surfactant of the present invention in water at room temperature (at 250 is preferably 1% by mass or more.
  • solubility is in the above range, accumulation in the human body is reduced and safety is reduced. Excellent.
  • the fluorine-based surfactant of the present invention preferably has a surface tension of a 1% by mass aqueous solution at room temperature (25 ° C.) of 25 mNZm or less.
  • a surface tension of a 1% by mass aqueous solution at room temperature (25 ° C.) of 25 mNZm or less.
  • the fluorosurfactant of the present invention is used for its excellent surface active effects, such as a leveling agent for inks, paints, resists, curable resins, etc., a dispersant for pigments, a fire extinguisher for agriculture, Examples include an antifog agent for a film, and a dispersant for a medium-viscosity aqueous pole pen pigment ink.
  • Monomer A-1 in a glass flask equipped with a stirrer, condenser and thermometer 20 parts by mass, 60 parts by mass of monomer B-4, 20 parts by mass of monomer C-4, and 200 parts by mass of ethyl acetate, and polymerized at 70 ° C in a nitrogen gas stream.
  • V_65 azopisdimethylpareronitrile
  • octyl mercaptan as a chain transfer agent
  • the weight average molecular weight Mw of the copolymer as determined by gel permeation chromatography (GPC) was 30,000 in terms of methyl methyl acrylate.
  • Table 1 shows the solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass) and the static surface tension. Indicated. Table 1 also shows the static surface tension when no copolymer was added (control example).
  • the sample prepared so that the concentration of the aqueous solution becomes 0.01%, 0.1%, 1%, and 5% by mass is sufficiently stirred, and left at 25 ° C for 1 hour. After this, the presence or absence of insoluble components was visually checked.
  • the static surface tension was measured by a Wilhelmy method using a ground glass plate at 25 ° C using a surface tension meter CBVB-A3 (manufactured by Kyowa Kagaku Co., Ltd.).
  • Example 1 A-7 was used in place of monomer A-1, Under the same conditions, copolymerization of monomer B-4 and monomer C-14 was performed.
  • the weight average molecular weight Mw in terms of polymethyl methacrylate of this copolymer was 20,000.
  • the solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass), and the static surface tension were determined in Example 1. The results were shown in Table 1.
  • Example 1 a mixture of monomer A instead of monomer A-1 (A-7: 2%, A-1: 77%, A-3: 18%, A-5: 3% However, the above-mentioned% represents gas chromatography purity), and the monomers B-4 and C-4 were copolymerized under exactly the same conditions as in Example 1.
  • the weight average molecular weight Mw in terms of polymethyl methacrylate of this copolymer was 22,000.
  • the solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass), and the static surface tension were determined as in Example 1. The measurement was performed similarly, and the results are shown in Table 1.
  • Example 1 copolymerization of monomer B_4 and monomer C-14 was performed under the same conditions as in Example 1 without adding monomer A-1.
  • the weight average molecular weight Mw in terms of polymethyl methacrylate of this copolymer was 50,000.
  • the solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass) and the static surface tension were measured in Example 1. The measurement was carried out in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 was repeated without adding monomer B-4 and monomer C-14. Polymerization of monomer A-1 was carried out under exactly the same conditions as in 1. The weight average molecular weight Mw in terms of polymethyl methacrylate of this polymer was 20,000. The solubility of the obtained polymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass) and the static surface tension were the same as in Example 1. The results are shown in Table 1. Table 1: Solubility of surfactant in water and amount added to water

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Fluorosurfactants having low static surface tension and high water solubility, which each consist of a copolymer obtained by copolymerizing the following monomers (A), (B) and (C): monomer (A): Rf-Q-OCOC(R1)=CH2 [wherein Q is -(CH2)n- or -CH2CH2CH(CH3)- (wherein n is an integer of 1 to 3); R1 is hydrogen or methyl; and Rf is fluoroalkyl having 1 to 20carbon atoms], monomer (B): HO(C2H4O)l1(C3H6O)m1(C2H4O)n1COC(R2)=CH2, and monomer (C): CH2=C(R3)COO(C2H4O)l2(C3H6O)m2(C2H4O)n2COC(R4)=CH2 [wherein R2, R3, and R4 are each hydrogen or methyl; and l1, m1, n1, l2, m2, and n2 are each an integer of 1 to 100].

Description

明 フッ素系界面活性剤  Akira Fluorinated surfactant

技術分野 Technical field

本発明は、 新規なフッ素系界面活性剤に関する。  The present invention relates to a novel fluorinated surfactant.

糸田  Itoda

背景技術 Background art

フッ素系界面活性剤は、 表面張力低下能力が高いため、 塗膜の均一性および平 滑性を向上させる目的で、 塗料などコーティング分野で広く使用されている。 し かし、 フッ素系界面活性剤の人体への蓄積性が懸念されているのも事実である。 人体への蓄積性を低下させるには水への溶解性を向上させることが必要であ るが、 その際には肝心な表面張力低下能力が低下するという問題があり、 高い表 面張力低下能力と水への高い溶解性の双方を満足するフッ素系界面活性剤が望ま れていた。  Fluorosurfactants, which have a high surface tension lowering ability, are widely used in coatings and other coatings for the purpose of improving the uniformity and smoothness of coating films. However, it is a fact that there is concern about the accumulation of fluorosurfactants in the human body. To reduce the accumulation in the human body, it is necessary to improve the solubility in water.However, in this case, there is a problem that the ability to lower the surface tension is reduced, and the surface tension reduction ability is high. There has been a demand for a fluorosurfactant that satisfies both of high solubility in water and water.

本発明は、 水への溶解性に優れ、 かつ表面張力低下能力に優れるフッ素系界面 活性剤を提供することを目的とするものである。  An object of the present invention is to provide a fluorine-based surfactant having excellent solubility in water and excellent surface tension lowering ability.

発明の開示 Disclosure of the invention

本発明者は、 上記問題点を解決すべく鋭意検討した結果、 フルォロアルキル基 を有する一群の （メタ） アクリルエステル 1種と、 ポリオキシアルキレン結合を 有する一群の （メタ） アクリルエステル 2種の共重合体が、 水への溶解性に 優れ、 かつ界面活性剤として非常に優れた表面張力低下能力を有することを見出 し、 本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that one group of (meth) acrylic esters having a fluoroalkyl group and two groups of (meth) acrylic esters having a polyoxyalkylene bond are co-polymerized. Coalescence increases solubility in water The present inventors have found that they have excellent surface tension lowering ability as a surfactant, and have completed the present invention.

本発明は、 下記単量体 A、 Bおよび Cを重合成分として共重合せしめた共重合 体からなるフッ素系界面活性剤である。  The present invention is a fluorosurfactant comprising a copolymer obtained by copolymerizing the following monomers A, B and C as a polymerization component.

単量体 A： Rf -Q-OCOC ( ) =CH2 Monomer A: R f -Q-OCOC () = CH 2

[ただし、 単量体 Aにおいて、 Q、 R1 および Rf は以下の意味を示す。[However, in the monomer A, Q, R 1 and R f have the following meanings.

Q： (CH2 ) n 一もしくは一 CH2 CH2 C (CH3 ) Η· Q: (CH 2 ) n One or one CH 2 CH 2 C (CH 3 )

ただし nは 1〜 3の整数を表す。  Here, n represents an integer of 1 to 3.

Ri ： 水素原子またはメチル基  Ri: hydrogen atom or methyl group

Rf 炭素数 1〜20のフルォロアルキル基。 ] R f a fluoroalkyl group having 1 to 20 carbon atoms. ]

単量体 B： HO (C2 H4 O) n (C3 H6 O) ml (C2 H4 O) nlC〇C Monomer B: HO (C 2 H 4 O) n (C 3 H 6 O) ml (C 2 H 4 O) nl C〇C

(R2 ) =CH: (R 2 ) = CH :

単量体 C： CH2 =C (R3 ) COO (C2 H4 〇） i 2 (C3 H6 〇） m2 Monomer C: CH 2 = C (R 3 ) COO (C 2 H 4 〇) i 2 (C 3 H 6 〇) m2

(C2 H4 〇） n2COC (R4 ) =CH: (C 2 H 4 〇) n2 COC (R 4 ) = CH :

[ただし、 単量体 Bおよび Cにおいて、  [However, in monomers B and C,

2 、 IV 3 k ' 水素原子またはメチル基、  2, IV 3k 'hydrogen atom or methyl group,

11 、 mi 、 n 1 、 1 n 00の整数。 ] 本発明のフッ素系界面活性剤は、 水に対する溶解度が高いため人体への蓄積性 が低く、 なおかつ表面張力低下能力が高く、 レべリング性等の特性に優れる。 発明を実施するための最良の形態  11, mi, n 1, 1 n 00 Integers. The fluorine-based surfactant of the present invention has low solubility in water due to its high solubility in water, has a high ability to lower surface tension, and has excellent properties such as leveling properties. BEST MODE FOR CARRYING OUT THE INVENTION

本発明の共重合体の原料である単量体 Aにおける Rf は、 フルォロアルキル基 (水素原子の 1個以上がフッ素原子で置換されているアルキル基を示す） であれ ば特に制限はないが、 製造の容易さや表面張力低下能力の優秀性からパーフルォ 口アルキル基 （水素原子の全てがフッ素原子で置換されているアルキル基を 示す） であることが好ましい。 Rf は炭素数 4〜18のものが好ましく、 特に炭 素数 4〜12のものが好ましい。 R f in monomer A, which is a raw material of the copolymer of the present invention, is a fluoroalkyl group There is no particular limitation as long as it is an alkyl group in which one or more of the hydrogen atoms is substituted with a fluorine atom. However, from the viewpoint of ease of production and excellent surface tension lowering ability, a perfluoroalkyl group (all hydrogen atoms) Represents an alkyl group substituted by a fluorine atom). R f preferably has 4 to 18 carbon atoms, particularly preferably 4 to 12 carbon atoms.

灰素数 4 2のパーフルォロアルキル基を有する単量体 Aの具体例とし ては、 以下のものが挙げられる。  Specific examples of the monomer A having a perfluoroalkyl group having 42 ash atoms include the following.

A— 1 ： C8 F17CH2 CH2 OCOCH=CH2 A—1: C 8 F 17 CH 2 CH 2 OCOCH = CH 2

A— 2 ： Cs F17CH2 CH2 〇C〇C (CH3 ) =CH2 A—2: C s F 17 CH 2 CH 2 〇C〇C (CH 3 ) = CH 2

A- 3 ： C10F21CH2 CH2 OCOCH=CH2 A- 3: C 10 F 21 CH 2 CH 2 OCOCH = CH 2

A— 4 ： C10F2iCH2 CH2 OCOC (CH3 ) =CH: A—4: C 10 F 2 iCH 2 CH 2 OCOC (CH 3 ) = CH :

A— 5 ： C12F25CH2 CH2 OC〇CH=CH2 A—5: C 12 F 25 CH 2 CH 2 OC〇CH = CH 2

A— 6 ： C12F25CH2 CH2 OCOC (CH3 ) =CH: A—6: C 12 F 25 CH 2 CH 2 OCOC (CH 3 ) = CH:

A- 7 ： C6 F13CH2 CH2 OCOCH=CH2 A- 7: C 6 F 13 CH 2 CH 2 OCOCH = CH 2

A— 8 ： C6 F13CH2 CH2 OCOC (CH3 ) =CH2 A—8: C 6 F 13 CH 2 CH 2 OCOC (CH 3 ) = CH 2

A- 9 ： C8 Fi7CH2 CH2 CH2 OCOCH = CH2 A- 9: C 8 Fi 7 CH 2 CH 2 CH 2 OCOCH = CH 2

A— 10 : C8 F17CH2 CH2 CH2 OCOC (CH3 ) =CH2 A— 10: C 8 F17 CH2 CH 2 CH 2 OCOC (CH 3 ) = CH 2

A— 1 1 ： Cs F17CH2 CH2 CH (CH3 ) 〇COCH=CH2 A—11: Cs F 17 CH 2 CH 2 CH (CH 3 ) 〇COCH = CH 2

Α· 2 ： C8 F 17CH2 CH2 CH (CH3 ) OCOC (CH3 ) = Α2: C 8 F 17 CH 2 CH 2 CH (CH 3 ) OCOC (CH 3 ) =

CH: CH :

A— 13 : C4 F9 CH2 CH2 OC〇CH=CH: A— 13: C 4 F 9 CH 2 CH 2 OC〇CH = CH :

A— 14 : C4 F9 CH2 CH2 OCOC (CH3 ) =CH: なお、 本発明が前記具体例によって、 何ら限定されるものではないことは勿論 である。 A— 14: C 4 F 9 CH 2 CH 2 OCOC (CH 3 ) = CH: The present invention is, of course, not limited by the specific examples.

本発明の共重合体の原料である単量体 Bおよび単量体 Cがポリオキシプロピレ ン基のみで構成され、 例えば、 ポリオキシエチレン基を含有しない場合には、 共 重合体の水への溶解性が著しく低下し、 他方、 ポリオキシエチレン基のみで構成 され、 例えば、 ポリオキシプロピレン基を含有しない場合には、 共重合体と他の ポリマーや顔料との相溶性に問題が生じる場合がある。 単量体 Bおよび単量体 C はいずれも、 異種のポリオキシアルキレン結合を有する必要、 すなわち、 2種以 上のポリオキシアルキレン結合を有する必要がある。 単量体 Bおよび単量体 Cに おいて、 1 i , ， 、 12 , m2 ， n2 は 5〜60であることが好ま しく、 特に 10〜40であることが好ましい。 これらが同数である必要はな い。 The monomers B and C, which are the raw materials of the copolymer of the present invention, are composed of only a polyoxypropylene group. The solubility of the copolymer is significantly reduced, and on the other hand, if it is composed of only polyoxyethylene groups and does not contain, for example, polyoxypropylene groups, there is a problem with the compatibility of the copolymer with other polymers or pigments There is. Both the monomers B and C need to have different types of polyoxyalkylene bonds, that is, need to have two or more types of polyoxyalkylene bonds. In the monomers B and C, 1 i,,, 12 , m 2 , and n 2 are preferably 5 to 60, and particularly preferably 10 to 40. They need not be equal.

単量体 Bの具体例としては、 1 i 、 、 が、 それぞれ 4〜 1 0、 8〜20、 4〜10である （メタ） ァクリレートが挙げられる。  Specific examples of the monomer B include (meth) acrylates in which 1 i,, and are 4 to 10, 8 to 20, and 4 to 10, respectively.

B- HO (C2 H4 〇） 4 (C3 H6 O) 8 (C2 H4 O) 4 COCH B- HO (C 2 H 4 〇) 4 (C 3 H 6 O) 8 (C 2 H 4 O) 4 COCH

CH; CH ;

B- 2 ： HO (C2 H4 O) 4 (C3 H6 〇） 8 (C2 H4 O) 4 COC ( し H3 ) = ^ H 2 B-2: HO (C 2 H 4 O) 4 (C 3 H 6 〇) 8 (C 2 H 4 O) 4 COC (Shi H3) = ^ H 2

B- 3 ： HO (C2 H4 O) 。 （C3 H6 O) 2。 （C2 H4 O) 10COCH B-3: HO (C 2 H 4 O). (C 3 H 6 O) 2 . (C 2 H 4 O) 10 COCH

= CH2 = CH 2

B-4 ： HO (C2 H4 O) t。 （C3 H6 〇） 2。 （C2 H4 O) 10COC ( B-4: HO (C 2 H 4 O) t. (C 3 H 6 〇) 2 . (C 2 H 4 O) 10 COC (

CH3 ) =CH2 B— 5 ： HO (C2 H4 O) 2 （C3 H6 O) 4 （C2 H4 〇） 20COCH = CH2 CH 3 ) = CH 2 B—5: HO (C 2 H 4 O) 2 (C 3 H 6 O) 4 (C 2 H 4 〇) 20 COCH = CH 2

B— 6 ： HO (C2 H4 O) 2 （C3 H6 〇） 4 （C2 H4 O) 2 C〇C (

Figure imgf000007_0001
B—6: HO (C 2 H 4 O) 2 (C 3 H 6 〇) 4 (C 2 H 4 O) 2 C〇C (
Figure imgf000007_0001

本発明の共重合体の原料である単量体 Cの具体例としては、 12 rrl2 n2 が、 それぞれ 4 20 8 40 4 20であるジ （メタ） ァクリレートが挙 げられる。 」 Specific examples of the monomer C which is a raw material of the copolymer of the present invention include di (meth) acrylates in which 12 rrl 2 n 2 is 4 20 840 420. "

C一 1 ： CH2 =CHCO〇 (C2 H4 〇） 4 (C3 H6 〇） 8 (C2 H4 C-1: CH 2 = CHCO〇 (C 2 H 4 〇) 4 (C 3 H 6 〇) 8 (C 2 H 4

〇） 4 C〇CH=CH2 〇) 4 C〇CH = CH 2

C一 2 ： CH2 =C (CH3 ) COO (C2 H4 O) 4 (C3 H6 〇） 8 ( C-2: CH 2 = C (CH 3 ) COO (C 2 H 4 O) 4 (C 3 H 6 〇) 8 (

C2 H4 〇） 4 COC (CH3 ) =CH2 C 2 H 4 〇) 4 COC (CH 3 ) = CH 2

C一 3 ： CH2 =CHCOO (C2 H4 〇） 10 (C3 H6 O) 2 （C2 H4 C-1 3: CH 2 = CHCOO (C 2 H 4 〇) 10 (C 3 H 6 O) 2 (C 2 H 4

O) 10COCH=CH2 O) 10 COCH = CH 2

C一 4 ： CH2 =C (CH3 ) COO (C2 H4 O) 10 (C3 H6 O) 2 ( C-4: CH 2 = C (CH 3 ) COO (C 2 H 4 O) 10 (C 3 H 6 O) 2 (

C2 H4 O) ioCOC (CH3 ) =CH2 C 2 H 4 O) ioCOC (CH 3 ) = CH 2

C一 5 ： CH2 =CHCO〇 (C2 H4 O) 2 （C3 H6 O) 4 （C2 H4 C-5: CH 2 = CHCO〇 (C 2 H 4 O) 2 (C 3 H 6 O) 4 (C 2 H 4

O) 20COCH=CH2 O) 20 COCH = CH 2

C一 6 ： CH2 =C (CH3 ) COO (C2 H4 O) 2 （C3 H6 〇） 4 (

Figure imgf000007_0002
C-1 6: CH 2 = C (CH 3 ) COO (C 2 H 4 O) 2 (C 3 H 6 〇) 4 (
Figure imgf000007_0002

なお、 本発明が前記具体例によって、 何ら限定されるものではないことは勿論 である。  The present invention is, of course, not limited by the specific examples.

本発明の共重合体は、 前記した構造の単量体 A Bおよび Cが、 下記した共重 合割合の範囲内で共重合したものであれば、 ブロック、 ランダム、 交互、 グラフ トなどいずれの構造であっても差し支えなく、 また、 例えば、 グラフト共重合体 のグラフト率、 ランダム共重合体のランダム性にも格別拘らない。 さらに、 単量 体 A、 Bおよび Cは、 それぞれ前述した構造式で表される範囲内であれば、 1種 でも、 また 2種以上の混合物であっても使用可能である。 好ましい単量体 A、 B および Cの組合わせは、 A— 1、 B— 4および C— 4 ； A— 7、 B— 4および C 一 4； A— 7、 B— 5および C一 5 ； A— 1、 A— 3、 A— 5、 A— 7、 B— 4 および C一 4などである。 特に好ましい組合わせは A— 1、 B— 4および C— 4 である。 In the copolymer of the present invention, the monomers AB and C having the above structure Any structure such as block, random, alternating, or graft may be used as long as the copolymer is copolymerized within the range of the mixing ratio.For example, the graft ratio of the graft copolymer, the random copolymer There is no particular concern for randomness. Further, the monomers A, B and C can be used alone or in a mixture of two or more as long as they are within the range represented by the structural formulas described above. Preferred combinations of monomers A, B and C are A-1, B-4 and C-4; A-7, B-4 and C-14; A-7, B-5 and C-15; A-1, A-3, A-5, A-7, B-4 and C-14. Particularly preferred combinations are A-1, B-4 and C-4.

本発明の共重合体を構成する単量体 A、 Bおよび Cの共重合割合 （質量 比） は、 該共重合体が配合される組成物中の配合物、 目的とする物性のレベルな どによっても異なるが、 AZ (B + C) = 5/95〜 70/30の範囲であるこ とが好ましく、 10Z90〜50Z50の範囲であることがより好ましい。 前記 割合よりも単量体 Aが多いと共重合体の水への溶解性が低下し、 単量体 Bと単量 体 Cの合計量が前記割合よりも多いと共重合体の表面張力低下能力が低下す る。  The copolymerization ratio (mass ratio) of the monomers A, B, and C constituting the copolymer of the present invention may be determined by, for example, the blend in the composition in which the copolymer is blended, the level of the desired physical properties, and the like. AZ (B + C) = preferably in the range of 5/95 to 70/30, and more preferably in the range of 10Z90 to 50Z50. When the amount of monomer A is higher than the above ratio, the solubility of the copolymer in water decreases, and when the total amount of monomer B and monomer C is higher than the above ratio, the surface tension of the copolymer decreases. Ability decreases.

また、 前記 （B + C) における単量体 Bと Cの共重合割合 （質量比） は、 B/C= 30/70〜 99/1の範囲であることが好ましく、 50/ 50 - 90/10の範囲であることがより好ましい。 前記割合よりも Cが多いと架橋し て共重合体の水への溶解性の低下や重合時にゲル化が生じる。  Further, the copolymerization ratio (mass ratio) of the monomers B and C in (B + C) is preferably in the range of B / C = 30/70 to 99/1, and 50/50-90 / More preferably, it is in the range of 10. If the content of C is larger than the above ratio, the copolymer is cross-linked to lower the solubility of the copolymer in water and to gel during polymerization.

本発明に係わる共重合体の分子量は、 ポリメチルメタクリレート換算の重量平 均分子量 Mwが 1， 000〜100, 000であることが好ましく、 3， 000 〜1 0 0， 0 0 0であることが特に好ましい。 Mwが 1， 0 0 0未満の場合は、 十分な表面張力低下能力が得られにくく、 逆に Mwが 1 0 0 , 0 0 0を超え ると、 組成物中の配合物との相溶性が低下する。 The molecular weight of the copolymer according to the present invention is preferably such that the weight average molecular weight Mw in terms of polymethyl methacrylate is 1,000 to 100,000, and 3,000. It is particularly preferable that the number is 100,000. When the Mw is less than 1,000, it is difficult to obtain a sufficient surface tension lowering ability. Conversely, when the Mw exceeds 100,000, the compatibility with the compound in the composition becomes poor. descend.

本発明の共重合体の製造方法には何ら制限はなく、 公知の方法、 すなわちラジ カル重合法、 カチオン重合法、 ァニオン重合法等の重合機構に基づき、 溶液重合 法、 塊状重合法、 さらに乳化重合法等によって製造できるが、 特にラジカル重合 法が簡便であり、 工業的に好ましい。  The method for producing the copolymer of the present invention is not limited at all, and is based on known methods, that is, a solution polymerization method, a bulk polymerization method, and an emulsification method based on polymerization mechanisms such as a radical polymerization method, a cationic polymerization method, and an anion polymerization method. Although it can be produced by a polymerization method or the like, a radical polymerization method is particularly simple and industrially preferable.

この場合、 重合開始剤としては、 公知のものを使用することができ、 例えば、 過酸化ベンゾィル等の過酸化物、 ァゾビスイソブチル二トリル等のァゾ化合物、 リビングラジカル重合を引き起こす遷移金属触媒等が挙げられる。  In this case, known polymerization initiators can be used, for example, peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyl nitrile, and transition metal catalysts that cause living radical polymerization And the like.

さらに必要に応じて、 ォクチルメルカブタン、 2—メルカプトエタノール等の 連鎖移動剤等を使用することができる。  Further, if necessary, a chain transfer agent such as octyl mercaptan and 2-mercaptoethanol can be used.

重合は、 溶剤もしくは水の存在下、 または無溶媒でも実施できるが、 作業性の 点から溶剤存在下での重合が好ましい。 溶剤としてはエタノール、 イソプロピル アルコール等のアルコール類、 アセトン、 メチルェチルケトン、 メチルイソプチ ルケトン等のケトン類、 酢酸メチル、 酢酸ェチル、 乳酸メチル、 乳酸ブチル等の エステル類、 ジメチルホルムアミド、 ジメチルスルホキシド、 N—メチルピロリ ドン等の極性溶媒、 メチルセ口ソルブ、 ブチルセ口ソルブ、 プチルカルビ 1 ル 等のエーテル類、 プロピレングリコール、 プロピレングリコ一ルモノェチルエー テルアセテート等のプロピレングリコール類及びエステル類、 クロ口ホルム、 1， 1 ,卜トリクロルェ夕ン等の八ロゲン化合物類、 ベンゼン、 トルエン、 キシレン等 の芳香族炭化水素類、 さらにパーフルォロォク夕ン等のフッ素化イナ一トリキッ ド等が挙げられ、 これらのいずれもが使用できる。 The polymerization can be carried out in the presence of a solvent or water, or in the absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of workability. Examples of the solvent include alcohols such as ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, methyl lactate, and butyl lactate; dimethylformamide, dimethyl sulfoxide; Polar solvents such as methylpyrrolidone; ethers such as methylcellulose solvent, butylcellulose solvent, and butylcarbyl; propylene glycols and esters such as propylene glycol, propylene glycol monoethyl ether acetate; Octalogen compounds such as trichlorene, aromatic hydrocarbons such as benzene, toluene, and xylene, and fluorinated initiators such as perfluoroquinone And any of these can be used.

なお、 本発明が前記具体例によって、 何ら限定されるものではないことは勿論 である。  The present invention is, of course, not limited by the specific examples.

本発明に係わるフッ素系界面活性剤は、 前記共重合体を 1種類だけ用いて調製 しても構わないし、 前記共重合体を 2種類以上同時に用いて調製しても構わ ない。 また、 フッ素系界面活性剤中の各成分との相溶性の向上等を目的として、 炭化水素系、 フッ素系、 シリコーン系等の各種界面活性剤を併用することも可能 である。  The fluorine-based surfactant according to the present invention may be prepared by using only one type of the copolymer, or may be prepared by using two or more types of the copolymer simultaneously. In addition, various surfactants such as hydrocarbon-based, fluorine-based, and silicone-based surfactants can be used in combination for the purpose of improving the compatibility with each component in the fluorine-based surfactant.

本発明のフッ素系界面活性剤は、 常温 （2 50 での水に対する溶解度が 1質 量％以上であることが好ましい。 溶解度が前記範囲であると、 人体への蓄積性が 低くなり安全性に優れる。  The solubility of the fluorinated surfactant of the present invention in water at room temperature (at 250 is preferably 1% by mass or more. When the solubility is in the above range, accumulation in the human body is reduced and safety is reduced. Excellent.

また、 本発明のフッ素系界面活性剤は、 常温 （2 5 °C) での 1質量％水溶液の 表面張力が 2 5 mNZm以下であることが好ましい。 表面張力が前記範囲である と、 レベリング性などの特性に優れる。  Further, the fluorine-based surfactant of the present invention preferably has a surface tension of a 1% by mass aqueous solution at room temperature (25 ° C.) of 25 mNZm or less. When the surface tension is in the above range, properties such as leveling properties are excellent.

本発明のフッ素系界面活性剤の用途としては、 その優れた界面活性効果から、 インク、 塗料、 レジスト、 硬化性樹脂等のレべリング剤、 顔料等の分散剤、 泡消 火剤、 農業用フィルムの防霧剤、 中粘度水性ポールペン顔料インク用の分散剤等 が挙げられる。  The fluorosurfactant of the present invention is used for its excellent surface active effects, such as a leveling agent for inks, paints, resists, curable resins, etc., a dispersant for pigments, a fire extinguisher for agriculture, Examples include an antifog agent for a film, and a dispersant for a medium-viscosity aqueous pole pen pigment ink.

以下に本発明の実施例を挙げて具体的に説明するが、 本発明はその要旨を超え ない限り、 以下の実施例に限定されるものではない。  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples as long as it does not exceed the gist.

(実施例 1 )  (Example 1)

攪拌装置、 コンデンサ一、 温度計を備えたガラスフラスコに単量体 A— 1 を 2 0質量部、 単量体 B— 4を 6 0質量部、 単量体 C— 4を 20質量部、 酢酸ェ チルを 2 00質量部仕込み、 窒素ガス気流中、 7 0°Cで重合開始剤として和光純 薬工業株式会社製 V_ 6 5 (ァゾピスジメチルパレロニトリル） 1. 5質量部と 連鎖移動剤としてォクチルメルカブタン 7. 6質量部を添加した後、 7 0°Cにて 1 5時間重合反応を行った。 Monomer A-1 in a glass flask equipped with a stirrer, condenser and thermometer 20 parts by mass, 60 parts by mass of monomer B-4, 20 parts by mass of monomer C-4, and 200 parts by mass of ethyl acetate, and polymerized at 70 ° C in a nitrogen gas stream. After adding 1.5 parts by mass of V_65 (azopisdimethylpareronitrile) manufactured by Wako Pure Chemical Industries, Ltd. as an initiator and 7.6 parts by mass of octyl mercaptan as a chain transfer agent, the mixture was heated at 70 ° C. For 15 hours.

A— 1 ： C8 F17CH2 CH2 〇C〇CH=CH2 A—1: C 8 F 17 CH 2 CH 2 〇C〇CH = CH 2

B-4 ： HO (C2 H4 〇） 10 (C3 H6 〇） 2。 （C2 H4 O) 10C〇C ( B-4: HO (C 2 H 4 〇) 10 (C 3 H 6 〇) 2 . (C 2 H 4 O) 10 C〇C (

CH3 ) =CH2 CH 3 ) = CH 2

C-4 ： CH2 =C (CH3 ) COO (C2 H4 〇） 10 (C3 H6 〇） 2。 （ C-4: CH 2 = C (CH 3 ) COO (C 2 H 4 10) 10 (C 3 H 6 〇) 2 . (

C2 H4 〇） IOCOC (CH3 ) =CH2 C 2 H 4 〇) IOCOC (CH 3 ) = CH 2

この共重合体のゲルパーミエーションクロマトグラフ （GPC) によるポリメ チルメ夕クリレート換算重量平均分子量 Mwは 30, 000であった。  The weight average molecular weight Mw of the copolymer as determined by gel permeation chromatography (GPC) was 30,000 in terms of methyl methyl acrylate.

得られた共重合体の水への溶解性と、 共重合体の水に対する添加量 （1質 量％、 0. 1質量％、 0. 0 1質量％) と静的表面張力を表 1に示した。 共重合 体未添加の場合の静的表面張力も合わせて表 1に示した （対照例） 。  Table 1 shows the solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass) and the static surface tension. Indicated. Table 1 also shows the static surface tension when no copolymer was added (control example).

水への溶解性は、 水溶液濃度が 0. 0 1質量％、 0. 1質量％、 1質量％、 5 質量％になるように調合した試料を充分攪拌し、 2 5 °Cで 1時間放置した後の不 溶解分の有無を目視で確認した。  For solubility in water, the sample prepared so that the concentration of the aqueous solution becomes 0.01%, 0.1%, 1%, and 5% by mass is sufficiently stirred, and left at 25 ° C for 1 hour. After this, the presence or absence of insoluble components was visually checked.

静的表面張力は表面張力計 C BVB— A 3 (協和科学株式会社製） を用い て 2 5°Cにて、 すりガラス板を用いたウィルヘルミ一法にて測定した。  The static surface tension was measured by a Wilhelmy method using a ground glass plate at 25 ° C using a surface tension meter CBVB-A3 (manufactured by Kyowa Kagaku Co., Ltd.).

(実施例 2)  (Example 2)

実施例 1において、 単量体 A— 1の代わりに A— 7を用いて、 実施例 1と全く 同じ条件で単量体 B— 4と単量体 C一 4との共重合を行った。 この共重合体のポ リメチルメタクリレート換算重量平均分子量 Mwは 2 0， 0 0 0であった。 得ら れた共重合体の水への溶解性と、 共重合体の水に対する添加量 （1質量％、 0 . 1質量％、 0 . 0 1質量％) と静的表面張力を実施例 1と同様に測定し、 そ の結果を表 1に示した。 In Example 1, A-7 was used in place of monomer A-1, Under the same conditions, copolymerization of monomer B-4 and monomer C-14 was performed. The weight average molecular weight Mw in terms of polymethyl methacrylate of this copolymer was 20,000. The solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass), and the static surface tension were determined in Example 1. The results were shown in Table 1.

(実施例 3 )  (Example 3)

実施例 1において、 単量体 A— 1の代わりに単量体 Aの混合物 （A— 7 ： 2 %、 A— 1 ： 7 7 %、 A- 3 ： 1 8 %、 A— 5 ： 3 %。 ただし前述の％はガス クロ純度を表す。 ） を用いて、 実施例 1と全く同じ条件で単量体 B— 4と単量体 C— 4との共重合を行った。 この共重合体のポリメチルメタクリレート換算重量 平均分子量 Mwは 2 2， 0 0 0であった。 得られた共重合体の水への溶解性と、 共重合体の水に対する添加量 （1質量％、 0 . 1質量％、 0 . 0 1質量％) と静 的表面張力を実施例 1と同様に測定し、 その結果を表 1に示した。  In Example 1, a mixture of monomer A instead of monomer A-1 (A-7: 2%, A-1: 77%, A-3: 18%, A-5: 3% However, the above-mentioned% represents gas chromatography purity), and the monomers B-4 and C-4 were copolymerized under exactly the same conditions as in Example 1. The weight average molecular weight Mw in terms of polymethyl methacrylate of this copolymer was 22,000. The solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass), and the static surface tension were determined as in Example 1. The measurement was performed similarly, and the results are shown in Table 1.

(比較例 1 )  (Comparative Example 1)

実施例 1において、 単量体 A— 1を添加することなく、 実施例 1と全く同じ条 件で単量体 B _ 4と単量体 C一 4の共重合を行った。 この共重合体のポリメチル メタクリレート換算重量平均分子量 Mwは 5 0， 0 0 0であった。 得られた共重 合体の水への溶解性と、 共重合体の水に対する添加量 （1質量％、 0 . 1質 量％、 0 . 0 1質量％) と静的表面張力を実施例 1と同様に測定し、 その結果を 表 1に示した。  In Example 1, copolymerization of monomer B_4 and monomer C-14 was performed under the same conditions as in Example 1 without adding monomer A-1. The weight average molecular weight Mw in terms of polymethyl methacrylate of this copolymer was 50,000. The solubility of the obtained copolymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass) and the static surface tension were measured in Example 1. The measurement was carried out in the same manner as in Example 1. The results are shown in Table 1.

(比較例 2 )  (Comparative Example 2)

実施例 1において、 単量体 B— 4と単量体 C一 4を添加することなく、 実施例 1と全く同じ条件で単量体 A— 1の重合を行った。 この重合体のポリメチルメタ クリレ一ト換算重量平均分子量 Mwは 2 0， 0 0 0であった。 得られた重合体の 水への溶解性と、 共重合体の水に対する添加量 （1質量％、 0 . 1質量％、 0 . 0 1質量％) と静的表面張力を実施例 1と同様に測定し、 その結果を表 1に 示した。 表 1 ： 界面活性剤の水に対する溶解度と、 水に対する添加量と Example 1 was repeated without adding monomer B-4 and monomer C-14. Polymerization of monomer A-1 was carried out under exactly the same conditions as in 1. The weight average molecular weight Mw in terms of polymethyl methacrylate of this polymer was 20,000. The solubility of the obtained polymer in water, the amount of the copolymer added to water (1% by mass, 0.1% by mass, 0.01% by mass) and the static surface tension were the same as in Example 1. The results are shown in Table 1. Table 1: Solubility of surfactant in water and amount added to water

静的表面張力の関係 （液温 2 5 °C)  Relation of static surface tension (liquid temperature 25 ° C)

Figure imgf000013_0001
Figure imgf000013_0001

実施例と比較例、 対照例との対比から単量体 A、 Bおよび Cを重合成分とする 共重合体の場合に限り、 静的表面張力が小さく、 水に対する溶解度が大きいこと がわかる。  From the comparison of the examples with the comparative examples and the control examples, it can be seen that only in the case of the copolymer containing monomers A, B and C as the polymerization components, the static surface tension is small and the solubility in water is large.

Claims

請求の範囲 The scope of the claims 1. 下記単量体 A、 Bおよび Cを重合成分として共重合せしめた共重合体から なるフッ素系界面活性剤。 1. A fluorosurfactant consisting of a copolymer obtained by copolymerizing the following monomers A, B and C as polymerization components. 単量体 A： Rf -Q-OCOC (Ri ) =CH2 Monomer A: R f -Q-OCOC (Ri) = CH 2 [ただし、 単量体 Aにおいて、 Q、 Ri および Rf は以下の意味を示す。 Q： 一 (CH2 ) π 一もしくは一 CH2 CH2 CH (CH3 ) 一。 [However, in the monomer A, Q, Ri and Rf have the following meanings. Q: One (CH 2 ) π One or one CH 2 CH 2 CH (CH 3 ) One. ただし n: ：!〜 3の整数。  Where n: is an integer from! To 3. R! ： 水素原子またはメチル基、  R !: hydrogen atom or methyl group, Rf ： 炭素数 1〜20のフルォロアルキル基。 ] R f : a fluoroalkyl group having 1 to 20 carbon atoms. ] 単量体 B ： HO (C2 H4 O) n (C3 H6 O) ml (C2 H4 O) n,CO Monomer B: HO (C 2 H 4 O) n (C 3 H 6 O) ml (C 2 H 4 O) n , CO C 2 ) ~ ^ ri 2  C 2) ~ ^ ri 2 単量体 C： CH2 =C (R3 ) COO (C2 H4 O) 12 (C3 H6 O) m2 Monomer C: CH 2 = C (R 3 ) COO (C 2 H 4 O) 12 (C 3 H 6 O) m2 (C2 H4 O) n2COC (R4 ) =CH2 (C 2 H 4 O) n2 COC (R 4 ) = CH 2 [ただし、 単量体 Bおよび。において、  [However, monomer B and. At R2 、 R3 、 R4 ： 水素原子またはメチル基、 R 2 , R 3 , R 4 : hydrogen atom or methyl group, 1 ^ mi > Π . 12 , m2 , n2 ： 1 ~ 100の整数。 ]1 ^ mi> Π. 12, m 2 , n 2 : An integer from 1 to 100. ] 2. 単量体 A、 単量体 Bまたは単量体 Cが、 それぞれ、 前記構造式で表される 化合物の 1種または 2種以上の混合物である請求項 1に記載のフッ素系界面活性 剤。 2. The fluorinated surfactant according to claim 1, wherein the monomer A, the monomer B, or the monomer C is one or a mixture of two or more of the compounds represented by the structural formulas. . 3. 単量体 Aにおける Rf が炭素数 1〜20のパーフルォロアルキル基である 請求項 1または請求項 2に記載のフッ素系界面活性剤。 3. The fluorine-based surfactant according to claim 1, wherein R f in the monomer A is a perfluoroalkyl group having 1 to 20 carbon atoms. 4. 単量体 Aにおける Rf が炭素数 4〜18のパ一フルォロアルキル基である 請求項 1または請求項 2に記載のフッ素系界面活性剤。 4. The fluorine-based surfactant according to claim 1, wherein R f in the monomer A is a perfluoroalkyl group having 4 to 18 carbon atoms. 5. 単量体 Aにおける Rf が炭素数 4〜18のパーフルォロアルキル基である 請求項 3に記載のフッ素系界面活性剤。 5. The fluorinated surfactant according to claim 3, wherein R f in the monomer A is a perfluoroalkyl group having 4 to 18 carbon atoms. 6. 常温における水に対する溶解度が 1質量％以上である請求項 1または請求 項 2に記載のフッ素系界面活性剤。  6. The fluorinated surfactant according to claim 1, having a solubility in water at room temperature of 1% by mass or more. 7. 常温における水に対する溶解度が 1質量％以上である請求項 3に記載 のフッ素系界面活性剤。  7. The fluorinated surfactant according to claim 3, which has a solubility in water at room temperature of 1% by mass or more. 8. 常温における水に対する溶解度が 1質量％以上である請求項 4に記載 のフッ素系界面活性剤。  8. The fluorinated surfactant according to claim 4, which has a solubility in water at room temperature of 1% by mass or more. 9. 常温における 1質量％水溶液の表面張力が 25mNZm以下である請求項 1または請求項 2に記載のフッ素系界面活性剤。  9. The fluorinated surfactant according to claim 1, wherein the 1% by mass aqueous solution at room temperature has a surface tension of 25 mNZm or less. 10. 常温における 1質量％水溶液の表面張力が 25mNZm以下である請求 項 3に記載のフッ素系界面活性剤。  10. The fluorinated surfactant according to claim 3, wherein the surface tension of the 1% by mass aqueous solution at room temperature is 25 mNZm or less. 11. 常温における 1質量％水溶液の表面張力が 25 mNZm以下である請求 項 4に記載のフッ素系界面活性剤。  11. The fluorinated surfactant according to claim 4, wherein the 1% by mass aqueous solution at room temperature has a surface tension of 25 mNZm or less. 12. 常温における水に対する溶解度が 1質量％以上であり、 1質量％水溶液 の表面張力が 25mN/m以下である請求項 1または請求項 2に記載のフッ素系 界面活性剤。  12. The fluorine-containing surfactant according to claim 1, wherein the solubility in water at room temperature is 1% by mass or more, and the surface tension of the 1% by mass aqueous solution is 25 mN / m or less. 13. 常温における水に対する溶解度が 1質量％以上であり、 1質量％水溶液 の表面張力が 25 mNZm以下である請求項 3に記載のフッ素系界面活性剤。  13. The fluorinated surfactant according to claim 3, wherein the solubility in water at room temperature is 1% by mass or more, and the surface tension of the 1% by mass aqueous solution is 25 mNZm or less. 14. 常温における水に対する溶解度が 1質量％以上であり、 1質量％水溶液 の表面張力が 2 5 mN/m以下である請求項 4に記載のフッ素系界面活性剤。 14. The solubility in water at room temperature is 1% by mass or more, and 1% by mass aqueous solution 5. The fluorinated surfactant according to claim 4, wherein the surface tension of the fluorinated surfactant is 25 mN / m or less.
PCT/JP2003/010509 2002-08-22 2003-08-20 Fluorosurfactants Ceased WO2004018535A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2004530578A JP4544996B2 (en) 2002-08-22 2003-08-20 Fluorosurfactant
AU2003257623A AU2003257623A1 (en) 2002-08-22 2003-08-20 Fluorosurfactants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002241434 2002-08-22
JP2002/241434 2002-08-22

Publications (1)

Publication Number Publication Date
WO2004018535A1 true WO2004018535A1 (en) 2004-03-04

Family

ID=31943993

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/010509 Ceased WO2004018535A1 (en) 2002-08-22 2003-08-20 Fluorosurfactants

Country Status (4)

Country Link
JP (1) JP4544996B2 (en)
AU (1) AU2003257623A1 (en)
TW (1) TW200404821A (en)
WO (1) WO2004018535A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249130A (en) * 2005-03-08 2006-09-21 Dainippon Ink & Chem Inc Manufacturing method of oligomer containing fluorinated alkyl group
JP2007186671A (en) * 2005-12-13 2007-07-26 Agc Seimi Chemical Co Ltd Surfactant and surface tension reduction method
JP2008222909A (en) * 2007-03-14 2008-09-25 Dic Corp Metallic paint
JP2010055054A (en) * 2008-03-12 2010-03-11 Fujifilm Corp Photosensitive resin composition, photosensitive resin transfer material, photospacer, method of manufacturing the same, substrate for display device and display device
WO2012002361A1 (en) * 2010-07-02 2012-01-05 Dic株式会社 Fluorine-based surfactant, and coating composition and resist composition each using same
JP2012062433A (en) * 2010-09-17 2012-03-29 Dic Corp Fluorine-based surfactant and coating composition and resist composition using the same
WO2012111741A1 (en) * 2011-02-18 2012-08-23 Ａｇｃセイミケミカル株式会社 Surfactant, composition including surfactant, use thereof, and fluorine-containing compound
JP5306815B2 (en) * 2006-09-07 2013-10-02 国立大学法人豊橋技術科学大学 Copolymer and process for producing the same
JP2014051863A (en) * 2012-09-10 2014-03-20 Asahi Glass Co Ltd Method for treating hydrocarbon including stratum, method for recovering hydrocarbon and composition for treating hydrocarbon including stratum

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101774254B1 (en) * 2015-12-16 2017-09-04 주식회사 해림엔지니어링 Selective non-catalytic reduction solution for nitrogen oxides removal

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6236657A (en) * 1985-08-10 1987-02-17 Japan Synthetic Rubber Co Ltd Resist composition
EP0239082A2 (en) * 1986-03-27 1987-09-30 Fuji Photo Film Co., Ltd. Light-sensitive composition
JPH09281636A (en) * 1996-04-15 1997-10-31 Fuji Photo Film Co Ltd Heat-developable photosensitive material
JPH10168140A (en) * 1996-12-10 1998-06-23 Shin Etsu Chem Co Ltd Paint additive
US6156860A (en) * 1997-02-18 2000-12-05 Dainippon Ink And Chemicals, Inc. Surface active agent containing fluorine and coating compositions using the same
EP1246012A2 (en) * 2001-03-30 2002-10-02 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10309455A (en) * 1997-05-13 1998-11-24 Dainippon Ink & Chem Inc Fluorinated surfactant and composition using the same
JPH11209787A (en) * 1998-01-28 1999-08-03 Dainippon Ink & Chem Inc Fluorinated surfactant and composition thereof
JP4055217B2 (en) * 1997-02-18 2008-03-05 大日本インキ化学工業株式会社 Fluorine surfactant and composition using the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6236657A (en) * 1985-08-10 1987-02-17 Japan Synthetic Rubber Co Ltd Resist composition
EP0239082A2 (en) * 1986-03-27 1987-09-30 Fuji Photo Film Co., Ltd. Light-sensitive composition
JPH09281636A (en) * 1996-04-15 1997-10-31 Fuji Photo Film Co Ltd Heat-developable photosensitive material
JPH10168140A (en) * 1996-12-10 1998-06-23 Shin Etsu Chem Co Ltd Paint additive
US6156860A (en) * 1997-02-18 2000-12-05 Dainippon Ink And Chemicals, Inc. Surface active agent containing fluorine and coating compositions using the same
EP1246012A2 (en) * 2001-03-30 2002-10-02 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249130A (en) * 2005-03-08 2006-09-21 Dainippon Ink & Chem Inc Manufacturing method of oligomer containing fluorinated alkyl group
JP2007186671A (en) * 2005-12-13 2007-07-26 Agc Seimi Chemical Co Ltd Surfactant and surface tension reduction method
JP5306815B2 (en) * 2006-09-07 2013-10-02 国立大学法人豊橋技術科学大学 Copolymer and process for producing the same
JP2008222909A (en) * 2007-03-14 2008-09-25 Dic Corp Metallic paint
JP2010055054A (en) * 2008-03-12 2010-03-11 Fujifilm Corp Photosensitive resin composition, photosensitive resin transfer material, photospacer, method of manufacturing the same, substrate for display device and display device
KR101608762B1 (en) 2008-03-12 2016-04-04 후지필름 가부시키가이샤 Photosensitive resin composition, photosensitive resin transfer material, photo spacer, method of manufacturing the same, substrate for display device, and display device
JP4973966B2 (en) * 2010-07-02 2012-07-11 Ｄｉｃ株式会社 Fluorosurfactant, coating composition using the same, and resist composition
CN102971391A (en) * 2010-07-02 2013-03-13 Dic株式会社 Fluorine-based surfactant, and coating composition and resist composition each using same
WO2012002361A1 (en) * 2010-07-02 2012-01-05 Dic株式会社 Fluorine-based surfactant, and coating composition and resist composition each using same
CN102971391B (en) * 2010-07-02 2014-10-22 Dic株式会社 Fluorine-based surfactant, and coating composition and resist composition each using same
JP2012062433A (en) * 2010-09-17 2012-03-29 Dic Corp Fluorine-based surfactant and coating composition and resist composition using the same
WO2012111741A1 (en) * 2011-02-18 2012-08-23 Ａｇｃセイミケミカル株式会社 Surfactant, composition including surfactant, use thereof, and fluorine-containing compound
JP2014051863A (en) * 2012-09-10 2014-03-20 Asahi Glass Co Ltd Method for treating hydrocarbon including stratum, method for recovering hydrocarbon and composition for treating hydrocarbon including stratum

Also Published As

Publication number Publication date
JPWO2004018535A1 (en) 2005-12-08
TW200404821A (en) 2004-04-01
JP4544996B2 (en) 2010-09-15
AU2003257623A1 (en) 2004-03-11

Similar Documents

Publication Publication Date Title
JP2009517528A5 (en)
WO2004018535A1 (en) Fluorosurfactants
JP2011099077A (en) Fluoropolymer and coating agent
CN1281643C (en) Silicofluoride containing acrylic copolyresin emulsion and paint
JP2013185072A (en) Water-slippery surface treating agent
JP7136994B1 (en) Dispersants for fluororesins, compositions, dispersions, articles and copolymers
WO2020195916A1 (en) Composition that contains fluorine-containing copolymer, and defoamer
WO2022019183A1 (en) Dispersant for fluororesins, composition, dispersion liquid, article and copolymer
JP4844097B2 (en) Polyimide coating composition
JP2003192749A5 (en)
CN104364281A (en) Method for producing fluorine polymer-containing aqueous dispersion liquid
JPH04110310A (en) Fluorine-containing copolymer and coating composition containing the polymer
JP2022191185A (en) Fluorine-containing polymer and surfactant
JP7101520B2 (en) Hydrophilic oil repellent
JP2022019568A (en) Fluorine-containing surface modifier composition
JP7289204B2 (en) Composition containing fluorine-containing copolymer
WO2020090749A1 (en) Aqueous coating material and coated article
JP2980999B2 (en) UV absorber, additive for fluororesin, and fluororesin composition
JP2636933B2 (en) Method for producing resin for highly water-repellent paint
JP2009040829A (en) Fluorine surfactant and composition using the same
WO2021090831A1 (en) Dispersant for fluororesins, dispersion liquid, and article
JPH05117546A (en) Fluorine-based ultravilet curing resin coating
JP7634832B2 (en) Vinyl polymer and method for producing same
JP3314437B2 (en) Resin composition for coating
WO2022004641A1 (en) Fluorine-containing copolymer, thermoplastic resin composition, molded product, and production method for molded product

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2004530578

Country of ref document: JP

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase