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  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
  • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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Definitions

• the present disclosure relates to a non-fluorine block copolymer containing no fluorine atom.
• a fluorine-containing water- and oil-repellent containing a fluorine compound has been known.
• This water / oil repellent exhibits good water / oil repellency when applied to a substrate such as a fiber product.
• a fluorinated block polymer improves liquid repellency.
• an acrylic block copolymer containing no fluorine has been reported.
• block copolymers having a block of a hydrophilic monomer there is no description that the block copolymer improves the liquid repellency.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2004-124088 discloses a hydrophilic polymer component (for example, poly (ethylene oxide)) and a hydrophobic polymer component (for example, poly (methacrylate) having a mesogen side chain or a long alkyl side chain).
• An object of the present disclosure is to provide a fluorine-free block copolymer that gives excellent liquid repellency.
• the block segment (A) provides a non-fluorine block copolymer having a repeating unit formed from an acrylic monomer having a long chain hydrocarbon group having 7 to 40 carbon atoms.
• the present invention provides a method for producing a non-fluorine block copolymer in which a non-fluorine block copolymer is produced by a second polymerization step of polymerizing the other of a monomer or an acrylic monomer having no long-chain hydrocarbon group.
• the present disclosure provides: (1) a surface treatment comprising the above-mentioned non-fluorinated block copolymer, and (2) a liquid medium which is an organic solvent or a liquid medium which is water, an organic solvent or a mixture of water and an organic solvent. Provide the agent.
• the block segment (A) is a non-fluorine block copolymer having a repeating unit formed of one or more acrylic monomers having a long-chain hydrocarbon group having 7 to 40 carbon atoms.
• the non-fluorine block copolymer has a segment (B) different from the block segment (A), and the segment (B) is (B1) a block segment having a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the segment (A); (B2) a block segment having a repeating unit formed from an acrylic monomer having no long-chain hydrocarbon group, (B3) a random segment formed from at least two kinds of acrylic monomers,
• the non-fluorine block copolymer according to [1] which has at least one of the following.
• R 11 is a hydrocarbon group having 7 to 40 carbon atoms
• R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom
• k is 1-3.
• R 22 is a hydrogen atom, a methyl group or a chlorine atom
• R 32 is a hydrogen atom, a methyl group or a chlorine atom
• An acrylic monomer having no long-chain hydrocarbon group has an acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, an acrylic monomer having a dimethylsiloxane moiety in a side chain, or having a hydrophilic group.
• An acrylic monomer an acrylic monomer having a cyclic hydrocarbon group, an acrylic monomer having a crosslinking site, or a halogenated olefin, wherein the hydrophilic group is an OH group, an NH 2 group, a COOH group, a sulfone group or
• the non-fluorinated block copolymer according to any one of [1] to [8], which is an alkali metal or alkaline earth metal base of a phosphate group or a carboxylic acid.
• R 61 is a hydrocarbon group having 1 to 6 carbon atoms or a single bond (direct bond);
• R 62 is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom;
• Y 61 is —O— or —NH—;
• Y 62 is a hydrophilic group, q is a number from 1 to 3.
• the non-fluorine block copolymer according to [9] which is a compound represented by the formula:
• a first polymerization step of polymerizing either an acrylic monomer having a long-chain hydrocarbon group or an acrylic monomer having no long-chain hydrocarbon group, and then an acrylic monomer having a long-chain hydrocarbon group The non-fluorinated block copolymer according to any one of [1] to [11], wherein the non-fluorinated block copolymer is produced by a second polymerization step of polymerizing the other of a monomer or an acrylic monomer having no long-chain hydrocarbon group.
• the block copolymer of the present disclosure is excellent in liquid repellency, that is, excellent in water repellency and oil repellency, particularly excellent in water repellency.
• the block copolymer has a high degree of crystallinity and a melting point of 25 ° C. or higher.
• the block copolymer has good film forming properties. Block copolymers exhibit better performance, such as liquid repellency, than random copolymers formed from the same monomers.
• Non-fluorine block copolymer The block copolymer of the present disclosure has a block segment (A) and another segment (B).
• the block copolymer is a non-fluorine block copolymer having no fluorine atom.
• a copolymer having the block segment (A) is referred to as a “block copolymer”.
• “non-fluorine” means “does not contain a fluorine atom”.
• the block segment (A) has a repeating unit formed from an acrylic monomer (a) having a long-chain hydrocarbon group having 7 to 40 carbon atoms.
• the block segment (A) is preferably composed of a repeating unit formed from one type of acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms. It may have a repeating unit formed from two or more (for example, two or three) acrylic monomers having a long-chain hydrocarbon group of from 40 to 40.
• the block segment (A) is preferably formed of one type of acrylic monomer having a long chain hydrocarbon group having 7 to 40 carbon atoms.
• the long-chain hydrocarbon group having 7 to 40 carbon atoms is preferably a linear or branched hydrocarbon group having 7 to 40 carbon atoms.
• the carbon number of the long-chain hydrocarbon group is preferably 10 to 40, for example, 12 to 30, particularly preferably 16 to 26.
• the long chain hydrocarbon group is particularly preferably a stearyl group, an icosyl group or a behenyl group.
• R 11 is independently a hydrocarbon group having 7 to 40 carbon atoms
• R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom
• —, —S ( O) 2 — or —NH—, which is a group composed of at least one or more (excluding the case of only a divalent hydrocarbon group), k is 1-3.
• R 12 may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
• R 12 are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom and a cyano group.
• R 12 is preferably a hydrogen atom, a methyl group, or a chlorine atom, and more preferably a hydrogen atom, a methyl group, and a hydrogen atom, since the main chain of the obtained polymer is not so rigid that the crystallinity of the side chain is not impaired. Is more preferred.
• Y 11 is preferably a divalent group.
• R 11 is preferably a linear or branched hydrocarbon group.
• the hydrocarbon group may in particular be a linear hydrocarbon group.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. If the hydrocarbon group is short, the crystallinity between the side chains is reduced, and the water repellency is also reduced. On the other hand, if the length is too long, the melting point of the corresponding monomer having a hydrocarbon group becomes high, so that problems such as a decrease in the solubility of the monomer and instability of emulsification may occur during polymerization. For these reasons, the hydrocarbon group preferably has 12 to 30, for example, 16 to 26, and particularly preferably 18 to 22, carbon atoms.
• an acrylic monomer represented by the following formula (a2): CH 2 CC (—R 32 ) —C ( O) —Y 31 —Z 31 (—Y 32 —R 31 ) n
• R 31 is independently a hydrocarbon group having 7 to 40 carbon atoms
• R 32 is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom
• Y 31 is —O— or —NH—
• Z 31 is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms
• n is 1 or 2.
• the acrylic monomer (a1) is a long-chain acrylate ester monomer in which Y 21 is —O— or a long-chain acrylamide monomer in which Y 21 is —NH—.
• R 21 is preferably a linear or branched hydrocarbon group.
• the hydrocarbon group may in particular be a linear hydrocarbon group.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. If the hydrocarbon group is short, the crystallinity between the side chains is reduced, and the water repellency is also reduced. On the other hand, if the length is too long, the melting point of the corresponding monomer having a hydrocarbon group becomes high, so that problems such as a decrease in the solubility of the monomer and instability of emulsification may occur during polymerization. From these facts, it is preferable that the number of carbon atoms is 12 to 30, 16 to 26, particularly 18 to 22.
• R 22 may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
• R 22 include hydrogen, a methyl group, a Cl, Br, I, CN.
• R 22 is hydrogen, methyl, Cl is preferably hydrogen, preferably a methyl group, hydrogen is more preferable.
• Preferred specific examples of the long-chain acrylate ester monomer are stearyl (meth) acrylate, icosyl (meth) acrylate, behenyl (meth) acrylate, stearyl ⁇ -chloroacrylate, icosyl ⁇ -chloroacrylate, and behenyl ⁇ -chloroacrylate.
• Preferred specific examples of the long-chain acrylamide monomer are stearyl (meth) acrylamide, icosyl (meth) acrylamide, and behenyl (meth) acrylamide.
• Z 31 is a direct bond or a
• R 31 is preferably a linear or branched hydrocarbon group.
• the hydrocarbon group may in particular be a linear hydrocarbon group.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. If the hydrocarbon group is short, the crystallinity between the side chains is reduced, and the water repellency is also reduced. On the other hand, if the length is too long, the melting point of the corresponding monomer having a hydrocarbon group becomes high, so that problems such as a decrease in the solubility of the monomer and instability of emulsification may occur during polymerization. From these facts, it is preferable that the number of carbon atoms is 12 to 30, 16 to 26, particularly 18 to 22.
• R 32 may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
• R 32 include hydrogen, a methyl group, a Cl, Br, I, CN.
• R 32 is hydrogen, methyl, Cl is preferably hydrogen, preferably a methyl group, hydrogen is more preferable.
• Z 31 is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, which may have a straight-chain structure or a branched structure.
• the number of carbon atoms of Z 31 is preferably 2 to 4, particularly preferably 2.
• Z 31 is not a direct bond, and Y 32 and Z 31 are not simultaneously a direct bond.
• the acrylic monomer (a2) can be produced by reacting hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with a long-chain alkyl isocyanate.
• the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.
• the acrylic monomer (a2) can also be produced by reacting a (meth) acrylate having an isocyanate group in the side chain, for example, 2-methacryloyloxyethyl methacrylate with a long-chain alkylamine or a long-chain alkyl alcohol.
• a long-chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine.
• the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.
• the compound of the following chemical formula is an acrylic compound in which the ⁇ -position is a hydrogen atom, and specific examples may be a methacle compound in which the ⁇ -position is a methyl group and an ⁇ -chloroacryl compound in which the ⁇ -position is a chlorine atom.
• n is an integer of 7 to 40.
• Acrylic monomer (a) are those R 31 is independently (e.g., a compound R 31 is 17 carbon atoms only) or those R 31 is a plurality of combinations (e.g., number of carbon atoms in R 31 is 17 and a compound having 15 carbon atoms of R 31 ).
• an example of the amide group-containing monomer is a carboxamide alkyl (meth) acrylate.
• Specific examples of the amide group-containing monomer include amide ethyl palmitate (meth) acrylate, amide ethyl stearate (meth) acrylate, amide ethyl behenate (meth) acrylate, amide ethyl myristate (meth) acrylate, and amide laurate (meth) ethyl Acrylate, isostearic acid ethylamide (meth) acrylate, oleic acid ethylamide (meth) acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth) acrylate, adamantanecarboxylic acid ethylamide (meth) acrylate, naphthalenecarboxylic acid amideethyl
• the amide group-containing monomer is preferably amide ethyl stearate (meth) acrylate.
• the amide group-containing monomer may be a mixture containing amide ethyl stearate (meth) acrylate.
• the amount of amide ethyl stearate (meth) acrylate is preferably 55 to 99% by weight based on the total weight of the amide group-containing monomer.
• the remaining monomer may be, for example, amidoethyl palmitate (meth) acrylate.
• Another segment block copolymer has another segment (B) in addition to the block segment (A).
• the block copolymer is an AB block polymer having one block segment (A) and one other segment (B), an A-B block polymer having two block segments (A) and one other segment (B). It may be a -BA block polymer or a BAB block polymer having one block segment (A) and two other segments (B).
• the block copolymer may have an additional segment (C) other than the block segment (A) and another segment (B).
• the block copolymer may be, for example, an ABC block copolymer or a BAC block polymer.
• Examples of other segments (B) are: (B1) a block segment having a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the segment (A); (B2) a block segment having a repeating unit formed from an acrylic monomer having no long-chain hydrocarbon group, (B3) a random segment formed from at least two kinds of acrylic monomers, At least one segment.
• the block segment (B1) contains a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms which forms the segment (A). Having a repeating unit formed from an acrylic monomer having the same. That is, the acrylic monomer having a long chain hydrocarbon group having 7 to 40 carbon atoms forming the block segment (B1) has a long chain hydrocarbon group having 7 to 40 carbon atoms forming the block segment (A). Different from acrylic monomer.
• a preferred embodiment of the acrylic monomer having a long chain hydrocarbon group having 7 to 40 carbon atoms forming the block segment (B1) is a long chain hydrocarbon group having 7 to 40 carbon atoms forming the block segment (A). It is the same as the acrylic monomer.
• (B1) is a monomer wherein Y 11 is —O— (eg, stearyl Acrylate).
• the block segment (B2) has a repeating unit formed from an acrylic monomer having no long-chain hydrocarbon group.
• the acrylic monomer having no long-chain hydrocarbon group include an acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, an acrylic monomer having a hydrophilic group, and a cyclic hydrocarbon group.
• Acrylic monomers and halogenated olefins are examples of the acrylic monomer having no long-chain hydrocarbon group.
• Other examples of the acrylic monomer having no long-chain hydrocarbon group are an acrylic monomer having a dimethylsiloxane moiety in a side chain and a divinyl compound represented by a compound having two acrylic groups.
• the acrylic monomer is an acrylate ester monomer or an acrylamide monomer.
• R 51 is a linear or branched hydrocarbon group.
• the linear or branched hydrocarbon group has 1 to 6 carbon atoms.
• the linear or branched hydrocarbon group preferably has 1 to 4 carbon atoms, and is generally an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. Further, it may contain an oxygen atom.
• An example of a hydrocarbon group containing an oxygen atom is a glycidyl group.
• R 52 may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
• R 52 are hydrogen, methyl, Cl, Br, I, CN.
• R 52 is hydrogen, methyl, Cl is preferably hydrogen, more preferably methyl, hydrogen Is more preferred.
• the short-chain acrylic monomer include methyl (meth) acrylate, methyl ⁇ -chloroacrylate, ethyl (meth) acrylate, ethyl ⁇ -chloroacrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate.
• R 61 is a hydrocarbon group having 1 to 10 carbon atoms
• R 62 is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom
• Y 61 is —O— or —NH—
• X 61 is a hydrophilic group
• p is 0 or 1
• q is a number from 1 to 4.
• hydrophilic groups are OH groups, NH 2 groups, COOH groups, sulphone groups or phosphate groups, alkali metal or alkaline earth metal bases of carboxylic acids.
• a polar group such as a hydrophilic group facilitates formation of a phase-separated structure, and improves the liquid repellency of the obtained copolymer.
• adhesion to a substrate such as cloth or glass is improved, and water repellency and durability of water repellency are improved.
• R 61 is a linear, branched or cyclic hydrocarbon group.
• R 61 may have 1 to 6 carbon atoms.
• R 62 may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
• R 62 are hydrogen, methyl, Cl, Br, I, CN.
• R 62 is, as a main chain is not rigid, because it does not inhibit the crystallinity of the side chains of block segments (A), hydrogen, methyl, Cl is preferably hydrogen, and more preferably a methyl group, hydrogen is more preferable.
• acrylic monomer having a hydrophilic group examples include hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylamide, (meth) acrylic acid, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylamide, and hydroxyethyl (meth) acrylamide.
• R 71 is a hydrocarbon group of a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms
• R 72 is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom
• Y 71 is —O— or —NH—.
• the acrylic monomer having a cyclic hydrocarbon group is preferably a monomer having a glass transition point of a homopolymer thereof which does not inhibit the crystallinity of the block segment (A) (for example, 25 ° C. or lower).
• the cyclic hydrocarbon group-containing acrylic monomer does not have a fluoroalkyl group.
• R 71 is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group).
• the cyclic hydrocarbon group include a saturated or unsaturated monocyclic group, polycyclic group, bridged ring group, and the like.
• the cyclic hydrocarbon group is preferably saturated.
• the cyclic hydrocarbon group has 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms.
• Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 30, preferably 4 to 20, particularly 5 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and preferably 6 to 20 carbon atoms, 7 to 30, preferably 7 to 20 araliphatic hydrocarbon groups.
• cyclic hydrocarbon group examples include a saturated or unsaturated monocyclic group, polycyclic group, bridged ring group, and the like.
• the cyclic hydrocarbon group is preferably saturated.
• the number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 10 or less.
• R 72 may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
• R 72 are hydrogen, methyl, Cl, Br, I, CN.
• R 72 is preferably hydrogen, a methyl group, or Cl, more preferably a hydrogen or methyl group, and more preferably hydrogen, as the main chain of the obtained polymer is not so rigid that the crystallinity of the side chain is not impaired.
• cyclic hydrocarbon group examples include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group.
• the acrylate group is preferably an acrylate group or a methacrylate group, but an acrylate group is particularly preferred.
• the monomer having a cyclic hydrocarbon group examples include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-adamantyl (meth) acrylate and the like.
• the halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms.
• the halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms.
• Preferred specific examples of halogenated olefins are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides, such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Halogenated olefins have no fluorine atoms.
• the block segment (B2) may be composed of a silicon-containing monomer (silicon-containing compound).
• silicon-containing monomer examples include a monomer having a dimethylsiloxane group.
• the monomer having a dimethylsiloxane group is preferably a compound having a dimethylsiloxane group and an olefinic carbon-carbon double bond (particularly, a (meth) acryl group or a vinyl group).
• the longer the length (n) of the dimethylsiloxane group the lower the glass transition temperature of the resulting copolymer, and the more the coating film made of the copolymer is improved in flexibility, texture, and water falling property.
• the length (n) of the dimethylsiloxane group is preferably from 1 to 50, more preferably from 3 to 30, and even more preferably from 3 to 20.
• acrylic monomer having two acrylic groups and the divinyl compound examples include tripropylene glycol di (meth) acrylate, divinylbenzene, tetramethylene glycol di (meth) acrylate, and hexamethylene glycol di (meth) acrylate (1, 6-bisacryloylhexane), nonamethylene glycol di (meth) acrylate, decamethylene glycol di (meth) acrylate, glycerol dimethacrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, ethylene glycol Di (meth) acrylate, 1,4-bis [4- (3-acryloyloxypropoxy) benzoyloxy] -2-methylbenzene.
• a trivinyl compound or a tetravinyl compound may also be contained, for example, pentaerythritol tetraacrylate.
• a divinyl compound or a tetravinyl or trivinyl compound
• a structure having a large number of branching sites generally called a star is obtained.
• the “block copolymer” having the block segment (A) includes those having a star structure.
• the random segment (B3) is formed from at least two kinds of acrylic monomers.
• the acrylic monomer includes the above-mentioned acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, the above-described acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, and the above-described hydrophilic monomer. Any of the acrylic monomer having a group, the acrylic monomer having a cyclic hydrocarbon group, the halogenated olefin, and the monomer having a dimethylsiloxane group may be used. Other examples of acrylic monomers are divinyl compounds, silicon-containing compounds.
• divinyl compound examples include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, divinylbenzene, tetramethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, nonamethylene glycol di ( (Meth) acrylate, decamethylene glycol di (meth) acrylate, glycerol dimethacrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, ethylene glycol dimethacrylate, 1,4-bis [4- (3-acryloyloxypropoxy) benzoyloxy] -2-methylbenzene.
• Trivinyl compounds and tetravinyl compounds may also be contained, for example, pentaerythritol tetraacrylate.
• a divinyl compound or a tetravinyl or trivinyl compound
• a structure having a large number of branching sites generally called a star is obtained.
• the “block copolymer” having the block segment (A) includes those having a star structure.
• acrylic monomers include: Stearyl (meth) acrylate / hydroxyethyl (meth) acrylate, t-butyl (meth) acrylate / hydroxyethyl (meth) acrylate, Stearyl (meth) acrylate / hydroxybutyl (meth) acrylate, t-butyl (meth) acrylate / hydroxybutyl (meth) acrylate, Stearyl (meth) acrylate / t-butyl (meth) acrylate hydroxyethyl (meth) acrylate / hydroxybutyl methacrylate glycidyl ether; Hydroxybutyl (meth) acrylate / hydroxybutyl methacrylate glycidyl ether, Hydroxyethyl (meth) acrylate / glycidyl (meth) acrylate, Hydroxybutyl (meth) acrylate / glycidyl ether
• Silicon-containing compounds can be used as monomers or chain transfer agents.
• One or both of a silicon-containing monomer and a silicon-containing chain transfer agent may be used.
• the silicon-containing monomer include a monomer having a silane group.
• the monomer having a silane group is preferably a compound having a silane group (particularly, a terminal silane group) and an olefinic carbon-carbon double bond (particularly, a (meth) acryl group or a vinyl group).
• the monomer having a silane group may be a terminal silane coupling group or a monomer having a silane coupling group in a side chain.
• the silicon-containing monomer may be a monomer having one (meth) acryl group or vinyl group and one silane group.
• One (meth) acrylic group or vinyl group is preferably bonded to one silane group by a direct bond, a C1-C10 alkylene group, or a (divalent) bonding group such as a siloxane group.
• the bonding group is preferably an alkylene group having 1 to 10 carbon atoms or a siloxane group.
• the linking group is preferably a direct bond.
• Silicon-containing compounds can be used as chain transfer agents.
• the silicon-containing chain transfer agent may be a mercapto-functional organopolysiloxane. By polymerizing the monomer in the presence of a silicon-containing chain transfer agent, a block copolymer having a siloxane group can be obtained.
• the mercapto-functional organopolysiloxane has siloxy units having the following average formula: (R 2 SiO) a (RR N SiO) b (RR S SiO) c
• a is 0 to 4000, 0 to 1000, or 0 to 400
• b is 1 to 1000, or 1 to 100, or 1 to 50
• c is from 1 to 1000, alternatively from 1 to 100, alternatively from 1 to 50
• R is independently a monovalent organic group, Alternatively, R is a hydrocarbon having 1 to 30 carbons, Alternatively, R is a monovalent alkyl group having 1 to 12 carbon atoms; Alternatively, R is a methyl group
• R N is a monovalent amino-functional organic group
• R S is a monovalent mercapto-functional organic group.
• R N is the formula: -R 1 NHR 2, wherein: -R 1 NR 2 2 or formula: -R 1 NHR 1 NHR 2 (wherein each of R 1 Is independently a divalent hydrocarbon group having 2 or more carbon atoms, and R 2 is hydrogen or an alkyl group having 1 to 20 carbon atoms.) Each R 1 is typically an alkylene group having 2 to 20 carbon atoms.
• Suitable amino-functional hydrocarbon groups include: —CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 NH 2 , —CH 2 CHCH 3 NH 2 , —CH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 NHCH 3 , —CH 2 CH 2 CH 2 NHCH 3 , —CH 2 (CH 3 ) CHCH 2 NHCH 3 , —CH 2 CH 2 CH 2 CH 2 NHCH 3 , —CH 2 CH 2 NHCH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 CH 2 NH 2 , —CH 2 CH 2 NHCH 2 CH
• R S has the formula: —R 1 SR 2 (wherein each R 1 is independently a divalent hydrocarbon group having 2 or more carbon atoms, and R 2 is hydrogen or alkyl having 1 to 20 carbon atoms. Wherein each of R 1 and R 2 is as described above.) Each R 1 is typically an alkylene group having 2 to 20 carbon atoms.
• Examples of mercapto functional groups are: -CH 2 CH 2 CH 2 SH, -CH 2 CHCH 3 SH, -CH 2 CH 2 CH 2 CH 2 SH, -CH 2 CH 2 CH 2 CH 2 SH, -CH 2 CH 2 CH 2 CH 2 CH 2 SH and —CH 2 CH 2 SCH 3 .
• the mercapto functional group is -CH 2 CH 2 CH 2 SH.
• the acrylic monomer is generally (meth) acrylate or (meth) acrylamide.
• (meth) acrylate means acrylate or methacrylate
• (meth) acrylamide means acrylamide or methacrylamide.
• the amount of the acrylic monomer (a) having a long-chain hydrocarbon group having 7 to 40 carbon atoms may be 30 mol% or more, preferably 35 mol% or more, based on the repeating units of the block copolymer. .
• the amount of the monomer (a) may be 99 mol% or less based on the repeating units of the block copolymer.
• the molar ratio of the repeating unit in the block segment (A) to the other segment (B) is, for example, 30:70 to 99: 1, preferably 35:65 to 90:10, particularly 40:60 to 90:10. Good.
• the amount of the repeating unit in the block segment (C) is from 0.1 to 30 mol%, for example, from 1 to 20 mol%, based on the entire repeating unit of the block copolymer. May be.
• the number average molecular weight (Mn) of the block copolymer may be generally from 1,000 to 1,000,000, for example, from 5,000 to 500,000, preferably from 8,000 to 200,000, more preferably from 8,000 to 100,000.
• the number average molecular weight (Mn) of the block copolymer is generally measured by GPC (gel permeation chromatography).
• GPC gel permeation chromatography
• a copolymer synthesized by a living polymerization method such as ATRP or RAFT shows a monomodal peak, and its molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is narrow, and is generally 3%. 0.0 or less, preferably 2.0 or less.
• Thermophysical properties such as the melting point, glass transition temperature, crystallization temperature, and melting energy of the block copolymer of the present disclosure can be measured by differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• a block copolymer exhibits a melting point and a glass transition temperature equivalent to those of a homopolymer comprising only a monomer which is a constituent unit thereof.
• the block copolymer of the present disclosure also shows the same melting point as the homopolymer of the monomer of the structural unit of the block segment (A), and has no block segment (A) and has only a random structure. Shows a melting point lower than that of the homopolymer of the monomer of the structural unit.
• the melting point is derived from the long-chain hydrocarbon group. It is preferable that the melting point derived from the long-chain hydrocarbon group be high because the liquid repellency of the coating film made of the polymer is improved. Therefore, a block copolymer of the present disclosure showing the same melting point as a homopolymer composed of only an acrylic monomer having a long-chain hydrocarbon group is more preferable than a random copolymer.
• the melting point of the block copolymer is preferably within -15 ° C (for example, lower by 0 to 15 ° C), more preferably within -10 ° C, particularly preferably within -5 ° C. .
• the melting point (Tm) of a homopolymer using stearyl acrylate as an acrylic monomer is 50.3 ° C.
• the block copolymer is used.
• the melting point of the coalesced is preferably 35.3 ° C. or higher, more preferably 40.3 ° C. or higher, and particularly preferably 45.3 ° C. or higher. Is the highest value of the melting point of each homopolymer in the body).
• the melting point of the block copolymer is 78. It is preferably at least 6 ° C, more preferably at least 83.6 ° C, particularly preferably at least 88.6 ° C.
• the lowest melting point of each homopolymer is preferably within 15 ° C. minus 15 ° C.
• the upper limit of the melting point of the copolymer is the highest value of the melting point of each homopolymer of the monomers constituting the block copolymer.) is there).
• the melting point of the block copolymer is preferably from 40 ° C to 200 ° C, more preferably from 45 ° C to 180 ° C, and preferably from 50 ° C to 170 ° C.
• the liquid repellency performance of the copolymer can be evaluated based on the difference in melting point from the homopolymer and the value of the melting point itself.
• the melting point satisfies the above-mentioned temperature range
• it also satisfies the preferable conditions of dynamic and static contact angles of water described later. Is preferred.
• the dynamic and static contact angles of hexadecane described below are also satisfied.
• a smooth coating film is created, and the static and dynamic contact angles of the coating film are measured to obtain the polymer.
• a static contact angle of water it is preferably at least 107 °, more preferably at least 108 °, particularly preferably at least 110 °.
• the falling angle is preferably 20 ° or less, more preferably 18 ° or less, and particularly preferably 15 ° or less.
• both the static and dynamic contact angles of water satisfy the above ranges.
• the falling angle of water is very high, such as 8 ° or less
• the static contact angle is 103 ° or more
• the falling angle is preferably 9 ° or less, more preferably 7 ° or less, and particularly preferably 5 ° or less.
• the static and dynamic contact angles of hexadecane both satisfy the above.
• the water repellency of the cloth coated with the block copolymer of the present disclosure can be evaluated by a shower water repellency test (JIS-L-1092 (AATCC-22): described later).
• the water repellency is 0, 50, 70, 80, 90 and 100 points in the order from poor to excellent, and preferably 70 points or more.
• the strong water repellency of the cloth coated with the block copolymer of the present disclosure can be determined by visual inspection based on the repellency of water in contact with the cloth and the speed of falling off the cloth when tested by the spray method of JIS-L-1092 (AATCC-22). You can also evaluate. 1, 2, 3, 4, and 5 points in the order of poor to strong water repellency, and preferably 2 or more points.
• shower water repellency test and strong water repellency test are indicators of the water repellency of the cloth, and are preferred forms of the present disclosure.
• a monomer is copolymerized to obtain a composition in which the copolymer is dispersed or dissolved in a medium.
• the liquid medium is at least one selected from water and an organic solvent.
• the liquid medium may be an organic solvent alone.
• the liquid medium may be an aqueous medium.
• the aqueous medium can be, for example, water alone or a mixture of water and a (water-miscible) organic solvent.
• the amount of water-miscible organic solvent may be up to 30% by weight, for example up to 10% by weight, based on the liquid medium.
• the amount of liquid medium may be from 30 to 99.5% by weight, in particular from 50 to 99.3% by weight, based on the surface treatment agent.
• the surface treating agent may contain other components.
• the surface treatment agent preferably contains an emulsifier.
• the emulsifier may be at least one selected from a nonionic emulsifier, a cationic emulsifier, an anionic emulsifier and an amphoteric emulsifier.
• Nonionic surfactants examples include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.
• examples of the ether are compounds having an oxyalkylene group (preferably, a polyoxyethylene group).
• examples of esters are esters of alcohols and fatty acids.
• examples of alcohols are monovalent to hexavalent (particularly divalent to pentavalent) alcohols having 1 to 50 (particularly 3 to 30 carbon atoms) (eg, aliphatic alcohols).
• Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms.
• ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid.
• alcohols are monovalent to hexavalent (particularly divalent to pentavalent) alcohols having 1 to 50 (particularly 3 to 30 carbon atoms) (eg, aliphatic alcohols).
• fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms.
• alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamino.
• fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms.
• the alkanolamine may be an alkanol having 2 to 50, especially 5 to 30 carbon atoms having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
• the polyhydric alcohol may be a divalent to pentavalent alcohol having 10 to 30 carbon atoms.
• the amine oxide may be an amine (secondary or preferably tertiary amine) oxide (eg, having 5 to 50 carbon atoms).
• the nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group).
• the alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms. Generally, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.
• the nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.
• Nonionic surfactants include alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated). , A polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like.
• POE polyoxyethylene
• POP polyoxypropylene
• the structure of the alkylene oxide-added portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (even if it is a random copolymer or a block copolymer). May be preferable).
• the nonionic surfactant preferably has a structure containing no aromatic group due to environmental problems (biodegradability, environmental hormones, etc.).
• the nonionic surfactant has the formula: R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3 [Wherein, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or an acyl group having 2 to 22 carbon atoms, R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (eg, 3 to 10); R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number greater than or equal to 2; q is 0 or a number of 1 or more.
• R 1 preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms.
• Preferred specific examples of R 1 include a lauryl group, a tridecyl group, and an oleyl group.
• R 2 are a propylene group and a butylene group.
• p may be a number of 3 or more (for example, 5 to 200).
• q may be a number of 2 or more (for example, 5 to 200). That is, — (R 2 O) q — may form a polyoxyalkylene chain.
• the nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center.
• the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain. Among them, an oxypropylene chain is preferable.
• Preferred nonionic surfactants have the formula: R 1 O— (CH 2 CH 2 O) p —H Wherein R 1 and p are as defined above. ] Is a surfactant represented by
• nonionic surfactants include: C 10 H 21 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q —H C 12 H 25 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q —H C 16 H 31 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q —H C 16 H 33 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q —H C 18 H 35 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q —H C 18 H 37 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q —H C 12 H 25 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q— C 12 H 25 C 16 H 31 O— (CH 2 CH 2 O) p — (C 3 H 6 O) q— C 16 H 31 C 16 H 33 O— (CH 10 H
• nonionic surfactant examples include ethylene oxide and hexyl phenol, isooctyl phenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C 7 -C 19 ) or alkyl. Condensation products with (C 12 -C 18 ) amines and the like are included.
• the proportion of polyoxyethylene blocks can be from 5 to 80% by weight, for example from 30 to 75% by weight, in particular from 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).
• the average molecular weight of the nonionic surfactant is generally from 300 to 5,000, for example, from 500 to 3,000.
• One type of nonionic surfactant may be used alone, or two or more types may be used in combination.
• the nonionic surfactant is preferably a combination of two or more.
• the at least one nonionic surfactant is an R 1 O- (CH 2 CH) in which the R 1 group (and / or the R 3 group) is a branched alkyl group (eg, an isotridecyl group). 2 O) p- (R 2 O) q -R 3 [in particular, R 1 O- (CH 2 CH 2 O) p -H].
• the amount of the nonionic surfactant in which R 1 is a branched alkyl group is from 5 to 100 parts by weight, for example, from 8 to 50 parts by weight, especially from 10 to 100 parts by weight of the total of the nonionic surfactant (B2). It may be up to 40 parts by weight.
• the remaining nonionic surfactants are those in which R 1 (and / or R 3 ) is a linear (saturated and / or unsaturated) linear alkyl group (eg, a lauryl group (n- A compound represented by R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3 [particularly, R 1 O— (CH 2 CH 2 O) p —H] which is a lauryl group)) It may be.
• R 1 (and / or R 3 ) is a linear (saturated and / or unsaturated) linear alkyl group (eg, a lauryl group (n- A compound represented by R 1 O— (CH 2 CH 2 O) p — (R 2 O) q —R 3 [particularly, R 1 O— (CH 2 CH 2 O) p —H] which is a lauryl group)) It may be.
• nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, acetylene glycol oxyethylene adduct, Examples include polyethylene glycol polypropylene glycol block copolymer.
• the nonionic surfactant may be acetylene alcohol (particularly, acetylene glycol) or acetylene alcohol (particularly, acetylene alcohol). Oxyethylene adduct of (glycol) is preferred.
• a preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as "acetylene alcohol compounds").
• a particularly preferred nonionic surfactant is an alkylene oxide adduct of a monol or polyol having an unsaturated triple bond.
• An acetylene alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups.
• the acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include polyoxyethylene, polyoxypropylene, a random addition structure between polyoxyethylene and polyoxypropylene, and a block addition structure between polyoxyethylene and polyoxypropylene.
• the acetylene alcohol compound has the formula: HO-CR 11 R 12 -C ⁇ C-CR 13 R 14 -OH or HO-CR 15 R 16 -C ⁇ CH
• each of R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 is independently the same or different and is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.
• the acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by this chemical formula.
• the alkyl group is preferably a straight-chain or branched alkyl group having 1 to 12 carbon atoms, particularly preferably a straight-chain or branched alkyl group having 6 to 12 carbon atoms.
• a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group and the like can be mentioned.
• the alkylene oxide is preferably an alkylene oxide having 1 to 20 (particularly 2 to 5) carbon atoms such as ethylene oxide and propylene oxide, and the number of addition of the alkylene oxide is preferably 1 to 50.
• acetylenic alcohol compound examples include acetylenic diol, propargyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 2,4. , 7,9-Tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1- Pentyn-3-ol, 3-hexyne-2,5-diol, 2-butyn-1,4-diol and the like.
• examples thereof include polyethoxylates and ethylene oxide adducts of these specific compounds.
• the nonionic surfactant may have no triple bond or may have a triple bond.
• the nonionic surfactant may be only one of a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, but a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond It may be a combination of activators.
• a nonionic surfactant having no triple bond for example, a nonionic surfactant having an oxyalkylene group
• the weight ratio of nonionic surfactant may be from 10:90 to 90:10, for example, from 20:80 to 80:20.
• the cationic surfactant is preferably a compound having no amide group.
• cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts.
• the cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt.
• cationic surfactant examples include, but are not particularly limited to, an alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative, an amine salt type surfactant such as imidazoline, an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, Examples include quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.
• cationic surfactants are R 21 -N + (-R 22) (- R 23) (- R 24) X -
• each of R 21 , R 22 , R 23 and R 24 is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms
• X is an anionic group.
• Is a compound of The hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene such as a polyoxyalkylene group (the alkylene has 2 to 5 carbon atoms, for example).
• R 21 , R 22 , R 23 and R 24 are preferably a hydrocarbon group having 1 to 30 carbon atoms (eg, aliphatic hydrocarbon, aromatic hydrocarbon or araliphatic hydrocarbon).
• R 21 , R 22 , R 23 and R 24 include an alkyl group (eg, methyl group, butyl group, stearyl group, palmityl group), an aryl group (eg, phenyl group), an aralkyl group (eg, benzyl group) (Phenylmethyl group) and phenethyl group (phenylethyl group).
• X include halogens (eg, chlorine) and acids (eg, inorganic acids such as hydrochloric acid, and organic acids (particularly, fatty acids) such as acetic acid). It is particularly preferred that the cationic surfactant is a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).
• the cationic surfactant is preferably an ammonium salt, particularly a quaternary ammonium salt.
• the cationic surfactant has the formula: R 31 p -N + R 32 q X - Wherein each of R 31 is independently the same or different and is a C12 or more (eg, C 12 -C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) group.
• Each of R 32 is independently the same or different and is an H or C 1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups such as 1 (particularly 2, particularly 3) to 50) (CH 3 and C 2 H 5 are particularly preferred),
• May be the ammonium salt represented by R 31 may have from 12 to 50 carbon atoms, for example from 12 to 30 carbon atoms.
• cationic surfactant examples include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride and benzyldodecyldi (hydropolyoxyethylene) ammonium chloride are included.
• amphoteric surfactant examples include alanines, imidazolinium betaines, amido betaines, betaine acetate and the like.
• alanines imidazolinium betaines
• amido betaines betaine acetate and the like.
• lauryl betaine stearyl betaine
• lauryl carboxymethyl hydroxyethyl imidazolinium betaine lauryl dimethyl Betaine aminoacetate
• the surfactant may be an amidoamine surfactant which is a compound having an amide group and an amino group.
• R 12 , R 13 and R 14 are preferably a hydrogen atom or an alkyl group.
• the carbon number of R 12 , R 13 and R 14 is preferably 1 to 6, particularly preferably 1 to 4.
• n is 0-10, for example 1-10, especially 2-5.
• amidoamine surfactant examples include diethylaminoethylamide isostearate, dimethylaminoethylamide oleate, dimethylaminopropylamide oleate, diethylaminoethylamide oleate, diethylaminopropylamide oleate, diethylaminoethylamide stearate, and stearic acid.
• the amidoamine surfactant may be non-ionic or ionic (cationic), but is preferably non-ionic. In the case of non-ionic, it is preferable to add an
• Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more kinds.
• the amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.
• the surface treatment agent may contain an additive as another component.
• additives include silicon-containing compounds, waxes, acrylic emulsions, and the like.
• Other examples of additives include fluoropolymers, drying rate regulators, crosslinkers, coalescents, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, defoamers, hand adjusters, slip adjusters, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants and the like.
• the amount of the other components may be from 0.1 to 70% by weight, for example from 0.5 to 50% by weight, based on the surface treatment agent.
• the block copolymer is preferably produced by using a living polymerization method, for example, a living radical polymerization method, a living anion polymerization method, or a living cationic polymerization method. Living radical polymerization is particularly preferred.
• the living radical polymerization method is based on establishing a quick equilibrium between a small amount of growing radicals (free radicals) and a large amount of dormant species in a growth reaction by applying heat, light, a metal catalyst, or the like.
• Various forms of living radical polymerization have been proposed with dormant chains.
• the ATRP method atom transfer radical polymerization method using an alkyl halide as a dormant
• the RAFT method reversible addition fragmentation chain transfer
• the NMP method nitroxide mediated polymerization
• the ATRP method (atom transfer radical polymerization method) is a method of polymerizing a vinyl monomer using a polymerization initiator having a highly reactive carbon-halogen bond and a transition metal complex serving as a polymerization catalyst (Table 2000-). 514479, Mitsuo Sawamoto et al., Macromolecules $ 1995, $ 28, $ 1721).
• the RAFT method is a method in which a vinyl-based monomer is polymerized by adding a chain transfer agent having a high chain transfer constant called a RAFT agent to an ordinary radical polymerization system (M. G. G. Mod et al., Macromolecules 1998, 31. 5559).
• a RAFT agent a thioester can be used.
• the NMP method is a method in which a stable nitroxide and a polymer radical are generated by thermally cleaving an alkoxyamine, and a vinyl monomer is polymerized on the polymer radical (M. K. Georges et al., Macromolecules 1993, 26, 2987).
• the nitroxide under cleavage reacts only with carbon-centered free radicals without initiating polymerization.
• the nitroxide and the polymer radical that has reacted with the monomer are recombined and can stably exist as a dormant. Living radical polymerization proceeds in the above process.
• the ATRP method (atom transfer radical polymerization method) will be described in detail below.
• a vinyl monomer is polymerized using a polymerization initiator having a highly reactive carbon-halogen bond and a transition metal complex serving as a polymerization catalyst.
• Examples of polymerization initiators are benzyl halide, alkane halide, haloester, haloketone, halonitrile and sulfonyl halide.
• examples of benzyl halide include 1-phenylethyl chloride and 1-bromoethylbenzene.
• Examples of the halogenated alkane include chloroform and carbon tetrachloride.
• Examples of haloesters include ethyl 2-bromoisobutyrate or ethyl 2-bromopropionate.
• Examples of the haloketone include bromoacetone and bromoacetophenone.
• Halonitrile includes 2-bromopropionitrile.
• Examples of the sulfonyl halide include p-toluenesulfonyl chloride.
• the amount of the polymerization initiator used is not particularly limited, but is generally 0.001 to 10 mol / L, preferably 0.010 to 5 mol / L, as the concentration in the reaction system.
• the transition metal complex is not particularly limited, but is a metal complex having a transition metal (M) selected from Groups 7 to 11 of the periodic table as a central metal.
• transition metal for example, Cu0, Cu +, Ni0, Ni +, Ni 2+, Pd 0, Pd +, Pt 0, Pt +, Pt 2+, Rh +, Rh 2+, Rh 3+, Co +, Co 2+, Ir 0 , Ir +, Ir 2+, Ir 3+, Fe 2+, Ru 2+, Ru 3+, Ru 4+, Ru 5+, Os 2+, Os 3+, Re 2+, Re 3+, Re 4+, Re 6+ , Mn 2+ and Mn 3+ .
• Cu + , Ni 2 + , Fe 2+ , and Ru 2+ are preferable from the viewpoint of catalyst activity.
• Examples of metal compounds used for transition metal complexes examples include cuprous chloride, cuprous bromide, cuprous iodide, and cuprous cyanide.
• Nickel compounds having divalent nickel include nickel dichloride. Iron compounds having divalent iron, such as nickel dibromide and nickel diiodide; ruthenium compounds having divalent ruthenium, such as iron dichloride, iron dibromide, and iron diiodide; Ruthenium chloride, ruthenium dibromide, ruthenium diiodide and the like can be mentioned.
• an organic ligand to the transition metal (M) from the viewpoint of enabling solubilization in a polymerization solvent and reversible change of a redox conjugate complex to enhance catalytic activity.
• the coordination atom to the metal include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom, and a nitrogen atom or a phosphorus atom is preferable.
• organic ligand examples include 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, triphenylphosphine, Tributylphosphine and the like.
• the amount of the organic ligand to be used is not particularly limited, but is usually 0.1 to 100 times, preferably 1 to 10 times the amount of the transition metal (M).
• the amount of the transition metal (M) to be used is not particularly limited, but is usually from 0.01 to 100 mol, preferably from 0.1 to 50 mol, more preferably from 0.1 to 50 mol, per mol of the polymerization initiation terminal of the polymerization initiator. 1010 mol.
• a reducing agent for a transition metal may be allowed to coexist.
• the coexistence of a reducing agent can reduce the deactivation of the catalyst and allow the polymerization to proceed without strictly controlling deoxygenation.
• the amount of transition metal used can be reduced, the transition metal can be easily removed from the product, and the cost is superior.
• the reducing agent include zero-valent copper, ascorbic acid, sodium ascorbate, divalent tin, and sugar.
• the amount of the reducing agent is generally about 10 molar equivalents relative to the transition metal catalyst.
• a radical polymerization initiator such as an azo compound may be added as a reducing agent.
• Atom transfer radical polymerization can be carried out in the absence of a solvent, but can also be carried out in the presence of a solvent.
• the solvent used as needed include water; ethers such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; acetonitrile; Nitriles such as propionitrile and benzonitrile; ester compounds or carbonate compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene carbonate and propylene carbonate; methanol, ethanol, propanol, isopropanol and n-butyl alcohol , Alcohols such as t-butyl alcohol and isoamyl alcohol; aromatic hydrocarbons such as benzene and tolu
• the amount of the solvent used is not particularly limited, but is usually 30 to 5,000 parts by weight, preferably 50 to 2,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the charged monomer.
• Atom transfer radical polymerization is usually carried out at a temperature of -50 to 200 ° C, preferably 0 to 150 ° C, more preferably 20 to 130 ° C.
• a substance other than the polymerization initiator is dissolved first to prepare a uniform solution, and the initiator is prepared immediately before the temperature is raised to the polymerization temperature. It is preferable to add and polymerize.
• the first block chain may be separated from the polymerization reaction solution.
• the remaining monomer and the solvent can be distilled off, reprecipitation in an appropriate solvent, filtration or centrifugation of the precipitated polymer, washing and drying of the polymer can be performed.
• the transition metal complex and the organic ligand used as a catalyst are diluted by diluting the polymerization solution with a good solvent for the produced polymer, for example, tetrahydrofuran (THF), toluene or the like, and passing the solution through an alumina, silica or clay column or pad. Can be removed from the reaction solution.
• a good solvent for the produced polymer for example, tetrahydrofuran (THF), toluene or the like
• THF tetrahydrofuran
• alumina, silica or clay column or pad can be removed from the reaction solution.
• a method of treating the transition metal and the organic ligand contained in the reaction solution by an extraction operation such as liquid separation, or a method of treating the reaction solution by dispersing a metal adsorbent in the reaction solution can also be adopted.
• RAFT irreversible addition-fragmentation chain transfer polymerization
• polymerization proceeds by allowing a dithiocarbamate derivative (RAFT agent), a vinyl monomer and a radical polymerization initiator to coexist.
• polymerization proceeds through exchange chain transfer in which radical addition and cleavage to the thioester are reversibly repeated.
• RAFT agent any type known to those skilled in the art can be used.
• Formula A shows the structure of a typical RAFT agent.
• the optimal functional groups Z and R are determined by the type of the monomer to be polymerized.
• R is -CH 2 R 1, 'is selected from 1, R 1, R' -CHR 1 R '1 and -CR 1 R' 1 R '1 and R' '1 is be independently substituted one another Good alkyl, saturated or unsaturated or aromatic carbocyclic or heterocyclic ring, optionally substituted alkylthio, optionally substituted alkoxy group, optionally substituted dialkylamino, organometallic group , Acyl, acyloxy, carboxy (and its esters and / or salts), sulfonates (and its salts and / or sulfonates), alkoxy or aryloxycarbonyl, polymer chains made by any polymerization mechanism, May be the same or different, Z is hydrogen, halogen (chlorine, bromine, iodine), optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocycle, —SR 2 , optionally substituted alkoxycarbonyl , Optionally substituted ary
• the amount of RAFT agent is determined by the molecular weight of the desired polymer. Since the RAFT agent binds to the terminal of each monomer, when a 100-mer polymer is used as the target substance, it is used in an amount of about 1 mol% (0.5 to 3 mol%) based on 100 mol% of the monomers.
• the trithiocarbonate-type RAFT agent having a symmetrical structural formula an ABA-type triblock is formed, and the trithiocarbonate group derived from the RAFT agent is located not at the terminal but at the center. The amount of the triblock-type RAFT agent is determined in the same manner as the above-mentioned RAFT agent.
• Radical polymerization initiators are known to those skilled in the art, and can be any type of radical polymerization initiator selected from among azo compounds, peroxides, or redox type initiators. Conventional chemical species capable of producing free radicals are called radical polymerization initiators.
• azo compound examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis 2,4-dimethylvaleronitrile, and 2,2′-azobis (2-methylpropionamidine) dihydrochloride Salt, 4,4′-azobis (4-cyanovaleric acid).
• peroxide compounds include tert-butyl peroxyacetate, tert-butyl peroxybenzoate (TBPO), dicumyl peroxide or dibenzoyl peroxide.
• redox compounds include peroxosulfates, such as potassium persulfate, sodium persulfate, and ammonium persulfate, and can be used with metabisulfites, such as isomeric sodium bisulfite, if desired.
• the polymerization initiator is generally used in an amount of 1 to 50 mol%, preferably 2 to 35 mol%, based on the weight of the RAFT agent.
• the reaction of the RAFT method depends on the radical polymerization initiator used, but is generally performed at 40 ° C. to 150 ° C. Although many polymerizations are performed under atmospheric pressure, polymerization can be performed under pressure.
• the RAFT method can be performed in the absence of a solvent, but can also be performed in the presence of a solvent.
• the solvent used as necessary is the same as in the ATRP method described above.
• the reaction can be performed in water, and the reaction proceeds even in emulsion polymerization.
• a nonionic emulsifier, a cationic emulsifier, and an anionic emulsifier that can be used for general emulsion polymerization can be used.
• the physical properties such as the melting point and water repellency of the obtained block copolymer do not depend on the synthesis method.
• the terminal of the obtained copolymer has a structure derived from its synthesis method (for example, thioester group in the case of RAFT), but as long as it does not have a specific functional group (hydrophilic group), the obtained copolymer Have the same physical properties such as melting point and water repellency.
• the obtained block copolymer is diluted or dispersed in water or an organic solvent, if necessary, and then can be prepared in any form such as an emulsion, an organic solvent solution, or an aerosol.
• the surface treatment agent of the present disclosure may be in the form of a solution, an emulsion (particularly, an aqueous dispersion) or an aerosol.
• the surface treatment agent comprises a block copolymer (the active ingredient of the surface treatment agent) and a medium (particularly, a liquid medium such as an organic solvent and / or water).
• the amount of medium may be, for example, from 5 to 99.9% by weight, especially from 10 to 80% by weight, based on the surface treatment agent.
• the concentration of the copolymer may be 0.01 to 70% by weight, for example, 0.1 to 50% by weight.
• the surface treatment agent can be used as a water / oil repellent, an antifouling agent, a soil release agent, a release agent or a release agent.
• Surface treatment agents are particularly suitable as water repellents.
• the surface treatment agent can be applied to the object by a conventionally known method.
• the surface treating agent is dispersed in an organic solvent or water, diluted, adhered to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating and the like, and dried.
• the composition may be applied together with a suitable crosslinking agent (for example, a blocked isocyanate) and cured.
• a suitable crosslinking agent for example, a blocked isocyanate
• the concentration of the copolymer in the treatment liquid to be brought into contact with the substrate may be from 0.01 to 10% by weight (particularly in the case of dip coating), for example from 0.05 to 10% by weight.
• the objects to be treated with the surface treatment agent (for example, water and oil repellent) of the present disclosure include textiles, stone materials, filters (for example, electrostatic filters), dust masks, parts of fuel cells (for example, gas diffusion). Electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like.
• fiber products For example, animal and plant natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; glass fibers; and carbon fibers. And inorganic fibers such as asbestos fibers, or a mixed fiber thereof.
• the fiber product may be in any form of fiber, cloth, and the like.
• the water repellent composition of the present disclosure can also be used as an antifouling agent, a release agent, and a release agent (for example, an internal release agent or an external release agent).
• a release agent for example, an internal release agent or an external release agent.
• the surface of the substrate can be easily peeled off from another surface (another surface on the substrate or a surface on another substrate).
• the block copolymer can be applied to a fibrous substrate (eg, a textile) by any of the methods known for treating textiles with liquids.
• a fibrous substrate eg, a textile
• the textile is a cloth
• the cloth may be dipped in the solution, or the solution may be applied or sprayed on the cloth.
• the treated fiber product is dried and preferably heated, for example, at 80 ° C. to 200 ° C. in order to develop liquid repellency (water repellency and / or oil repellency).
• the block copolymer may be applied to the textile by a cleaning method, such as in a laundry application or dry cleaning method.
• the textile products to be treated are typically fabrics, including fabrics, knits and nonwovens, fabrics and carpets in the form of clothing, but with fibers or yarns or intermediate textiles (eg slivers or slivers). Roving, etc.).
• the textile material can be natural fibers (such as cotton or wool), synthetic fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or , A mixture of fibers (eg, a mixture of natural and synthetic fibers, etc.).
• the methods of the present disclosure generally render textiles hydrophobic and water repellent.
• the fibrous substrate may be leather.
• the aqueous solution or aqueous emulsification of the produced polymer at various stages of the leather processing, for example during wet processing of the leather or during finishing of the leather, to make the leather hydrophobic and oleophobic It can be applied from object to leather.
• the fibrous substrate may be paper.
• the production polymer may be applied to preformed paper or may be applied at various stages of the papermaking, for example, during the drying of the paper.
• Treatment means that the surface treatment agent is applied to the object by dipping, spraying, coating, or the like.
• the copolymer which is an active ingredient of the surface treatment agent, penetrates into the inside of the object to be treated and / or adheres to the surface of the object to be treated.
• test procedure is as follows.
• Mn Number average molecular weight
• Mw weight average molecular weight
• Mw / Mn The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). GPC was carried out using tetrahydrofuran as a developing solution, and using KF-606M, KF-601, and KF-800D manufactured by Shodex as columns, and calculating the molecular weight and the like in terms of polystyrene.
• the melting point of the copolymer was calculated by differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• the temperature was raised to 170 ° C. at 10 ° C./min, then cooled again to ⁇ 30 ° C., and then observed at a temperature of 170 ° C. at 10 ° C./min.
• the melting point was determined.
• the peak having the largest heat of fusion derived from the melting of the long-chain alkyl was defined as the melting point.
• the dynamic contact angle is the drop angle at which 20 ⁇ L of water or 5 ⁇ L of n-hexadecane is dropped on a coating film, and the substrate is inclined at a rate of 2 ° per second to start dropping.
• “> 85” indicates that the droplet does not fall even when the substrate is tilted by 85 °.
• the annealing temperature of "none" in Table 1 indicates that the measurement value is a measurement value of a sample that is air-dried only.
• Example 1 Synthesis by ATRP method StA / HEA
• a reaction vessel purged with nitrogen
• 179 mg of 2,2′-bipyridyl 4.3 g
• stearyl acrylate (StA) as the first monomer
• ethyl 2-bromoisobutyrate 28 ⁇ l was added, and the mixture was heated and stirred at 110 ° C. to perform a reaction.
• hydroxyethyl acrylate (HEA) was added as the second monomer.
• Example 2 StA / HEA With respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 1 mol equivalent of Cu (0), 2 mol equivalent of CuBr (I), 6 mol equivalent of 2,2′-bipyridyl, 50 mol equivalent of StA as a first monomer, and 50 mol equivalent of HEA as a second monomer. The reaction was carried out in the same manner as in Example 1 except that the copolymer was used, and a block copolymer (2) was obtained.
• Example 3 StA / AA
• the reaction was carried out in the same manner as in Example 2 except that 50 mol equivalents of StA was used as the first monomer and 50 mol equivalents of t-butyl acrylate (tBuA) was used as the second monomer with respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator.
• tBuA t-butyl acrylate
• a block copolymer (3 ′) was obtained.
• the tBuA1 unit was reacted with 5 equivalents of trifluoroacetic acid to perform a deprotection reaction, and reprecipitated in acetone to obtain a block copolymer (3).
• Example 4 StA / DMS For 1 mol equivalent of ethyl 2-bromoisobutyrate of the initiator, 50 mol equivalent of StA as the first monomer and CH 2 CC (CH 3 ) CO 2 (CH 2 ) 3 Si (CH 3 ) 2 [OSi (CH 3 ) 2 ] n OSi (CH 3 ) 2 C 4 H 9 (DMS) The reaction was carried out in the same manner as in Example 2 except that 4 mol equivalent of DMS was used to obtain a block copolymer (4).
• Example 5 StA / HEMA The reaction was carried out in the same manner as in Example 2 except that 50 mol equivalents of StA was used as the first monomer and 50 mol equivalents of hydroxyl methacrylate (HEMA) was used as the second monomer with respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator. Thus, a block copolymer (5) was obtained.
• HEMA hydroxyl methacrylate
• the reaction was carried out in the same manner as in Example 2 except that 50 mol equivalent of HEA was used as a dimonomer to obtain a block copolymer (6).
• the reaction was carried out in the same manner as in Example 2 except that 50 mol equivalent of HEA was used as a dimonomer to obtain a block copolymer (7).
• Example 8 C18URA / tBuA The reaction was carried out in the same manner as in Example 2 except that 50 mol equivalents of C18URA and 50 mol equivalents of tBuA were used as the first monomer and the second monomer, respectively, relative to 1 mol equivalent of ethyl 2-bromoisobutyrate of the initiator. 8) was obtained.
• Example 11 Synthesis by RAFT method C18URA / StA 35 mg of RAFT initiator cyanomethyldodecyltrithiocarbonate, 2,2′-azobisisobutyronitrile (AIBN) and C18URA as the first monomer were added to the RAFT initiator in a nitrogen-replaced reaction vessel, respectively. 1 mol equivalent, 65 mol equivalent, and 3.0 ml of toluene were added, and the mixture was heated and stirred at 70 ° C. to perform a reaction. After confirming the consumption of the first monomer by 1 H NMR measurement, 35 mol equivalent of StA (based on the RAFT initiator) was added as the second monomer. After confirming that the unreacted monomer was consumed by 1 H NMR measurement, the block copolymer (11) was obtained by reprecipitation in acetone. The reaction proceeded quantitatively.
• AIBN 2,2′-azobisisobutyronitrile
• Example 12 C18URA / StA The reaction was carried out in the same manner as in Example 11, except that 50 mol equivalent of C18URA was used as the first monomer and 50 mol equivalent of StA was used as the second monomer with respect to 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. (12) was obtained.
• Example 13 C18URA / HEA / StA RAFT initiator cyanomethyldodecyltrithiocarbonate (35 mg), 2,2′-azobisisobutyronitrile (AIBN) and C18URA as the first monomer were added to the RAFT initiator in a nitrogen-substituted reaction vessel in an amount of 35 mg. 1 mol equivalent, 30 mol equivalent, and 3.0 ml of toluene were added, and the mixture was heated and stirred at 70 ° C. to perform a reaction. After confirming the consumption of the first monomer by 1 H NMR measurement, 40 mol equivalents of HEA (relative to the RAFT initiator) was added as the second monomer.
• AIBN 2,2′-azobisisobutyronitrile
• Example 11 was the same as Example 11 except that 100 mol equivalents of StA was used as the first monomer and 1 mol equivalent of 1,6-bisacryloylhexane (diA) was used as the second monomer with respect to 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was carried out in the same manner to obtain a block copolymer (14).
• Example 11 was the same as Example 11 except that 100 mol equivalents of C18URA was used as the first monomer and 1 mol equivalent of 1,6-bisacryloylhexane (diA) was used as the second monomer with respect to 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was carried out in the same manner to obtain a block copolymer (15).
• Example 17 Emulsion polymerization StA / HEA
• the reaction was performed in the same manner as in Example 16 except that 50 mol equivalent of StA was used as the first monomer and 5 mol equivalent of HEA was used as the second monomer with respect to 1 mol equivalent of RAFT initiator 2-[(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid.
• the weight average molecular weight (Mw) of the block copolymer (17) was 14,800, and the molecular weight distribution (Mw / Mn) was 1.17.
• Example 18 StA / HEA The reaction was carried out in the same manner as in Example 11, except that 80 mol equivalents of StA was used as the first monomer and 20 mol equivalents of HEA was used as the second monomer with respect to 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. (18) was obtained.
• Example 19 StA / (HBA / HBAGE) Two kinds of monomers, 80 mol equivalents of StA as a first monomer, 10 mol equivalents of hydroxybutyl acrylate (HBA) and 10 mol equivalents of hydroxybutyl acrylate glycidyl ether (HBAGE) as a second monomer, based on 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate The reaction was carried out in the same manner as in Example 11 except that was added at the same time, to obtain a block copolymer (19). In the water repellency test of the block copolymer (19), 95 points (PET) and 95-point (Ny) were obtained even after washing the cloth 20 times after application, and the water repellency was maintained even after the washing. .
• HBA hydroxybutyl acrylate
• HBAGE hydroxybutyl acrylate glycidyl ether
• Example 21 C18AmEA / HEA
• the reaction was carried out in the same manner as in Example 11, except that 50 mol equivalents of C18AmEA and 50 mol equivalents of HEA were used as the first monomer and 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate, respectively. (21) was obtained.
• Example 22 C18AmEA / HEA
• the reaction was carried out in the same manner as in Example 11, except that 100 mol equivalents of C18AmEA and 100 mol equivalents of HEA were used as the first monomer and 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate, respectively. (22) was obtained.
• Example 23 C18AmEA / HEA
• the reaction was carried out in the same manner as in Example 2, except that 69 mol equivalents of C18AmEA and 31 mol equivalents of HEA were used as the first monomer and 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator, respectively. 23) was obtained.
• Example 11 was the same as Example 11 except that two kinds of monomers, C18AmEA 30 mol equivalent as the first monomer and 40 mol equivalent of StA and 30 mol equivalent of HEA, were simultaneously added as the first monomer to 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was carried out in the same manner to obtain a block copolymer (24).
• Example 11 was the same as Example 11 except that two kinds of monomers, 70 mol equivalents of C18AmEA as the first monomer and 6 mol equivalents of GMA and 24 mol equivalents of HEA as the second monomer were simultaneously added to 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was carried out in the same manner to obtain a block copolymer (25).
• Example 26 C18AmEA / tBuA The reaction was carried out in the same manner as in Example 2, except that 60 mol equivalents of C18AmEA and 40 mol equivalents of tBuA were used as the first monomer and 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator, respectively. 26) was obtained.
• Example 27 C18AmEA / tBuA The reaction was carried out in the same manner as in Example 2, except that 47 mol equivalents of C18AmEA and 53 mol equivalents of tBuA were used as the first monomer and 1 mol equivalent of ethyl 2-bromoisobutyrate of the initiator, respectively. 27) was obtained.
• Example 28 C18AmEA / AA
• the tBuA1 unit of the block copolymer (26) was reacted with 5 equivalents of trifluoroacetic acid to perform a deprotection reaction, and reprecipitated in acetone to obtain a block copolymer (28).
• Example 29 C18AmEA / StA
• the reaction was carried out in the same manner as in Example 11 except that 30 mol equivalents of C18AmEA and 70 mol equivalents of StA were used as the first monomer and 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate, respectively. A coalescence (29) was obtained.
• Example 30 C18AmEA / StA
• the reaction was carried out in the same manner as in Example 11 except that 50 mol equivalents of C18AmEA and 50 mol equivalents of StA were used as the first monomer and 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate, respectively. A coalescence (30) was obtained.
• Example 32 C18AmEA / tBuA / diA Using 1 mol equivalent of C18AmEA as the first monomer, 1 mol equivalent of tBuA as the second monomer, and 1 mol equivalent of diA as the third monomer with respect to 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was carried out in the same manner as in Example 11 except that the monomer was added, to obtain a block copolymer (32).
• Example 33 C18AmEA / AA / diA
• the tBuA1 unit of the block copolymer (32) was deprotected by reacting it with 5 equivalents of trifluoroacetic acid, and reprecipitated in acetone to obtain a block copolymer (33).
• Example 34 C18AmEA / HEA / diA Using 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 38 mol equivalent of C18AmEA as the first monomer, 51 mol equivalent of HEA as the second monomer, and 11 mol equivalent of StA as the third monomer, and after confirming the consumption of the second monomer, the third monomer was used. The reaction was carried out in the same manner as in Example 11 except that the monomer was added, to obtain a block copolymer (34).
• Example 35 C18AmEA / diA
• the reaction was carried out in the same manner as in Example 11, except that 100 mol equivalent of C18AmEA and 1 mol equivalent of diA were used as the first monomer and 1 mol equivalent of the first monomer, respectively, based on 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate. A combination (35) was obtained.
• Example 36 C18AmEA / HEA As in Example 16, except that 50 mol equivalents of C18AmEA as the first monomer and 5 mol equivalents of HEA as the second monomer were used per 1 mol equivalent of the RAFT initiator 2-[(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid. The reaction was performed to obtain a block copolymer (36).
• Example 37 (C18AmEA / StA) / HEA
• a reaction was carried out in the same manner as in Example 11, except that 40 mol equivalents of C18AmEA and 4040 mol equivalents of StA as the first monomer and 20 mol equivalents of HEA as the second monomer were used for 1 mol equivalent of the RAFT initiator cyanomethyldodecyltrithiocarbonate.
• a block copolymer (37) was obtained.
• 95 points (PET) and 95+ points (Ny) were obtained on the cloth after washing 20 times after application, and the water repellency was maintained even after washing.
• the surface treatment agent of the present disclosure can be used as a water / oil repellent or an antifouling agent.
• the surface treatment agent can be suitably used for substrates such as textiles and masonry, and imparts excellent water and oil repellency to the substrate.

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