WO2021020575A1 - Tire, surface modifier therefor, and surface modification method - Google Patents

Tire, surface modifier therefor, and surface modification method Download PDF

Info

Publication number
WO2021020575A1
WO2021020575A1 PCT/JP2020/029517 JP2020029517W WO2021020575A1 WO 2021020575 A1 WO2021020575 A1 WO 2021020575A1 JP 2020029517 W JP2020029517 W JP 2020029517W WO 2021020575 A1 WO2021020575 A1 WO 2021020575A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
independently
integer
composition
compound
Prior art date
Application number
PCT/JP2020/029517
Other languages
French (fr)
Japanese (ja)
Inventor
佳菜子 稲生
晋吾 奥野
哲郎 堀
Original Assignee
ダイキン工業株式会社
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 ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Priority to JP2021535468A priority Critical patent/JPWO2021020575A1/ja
Publication of WO2021020575A1 publication Critical patent/WO2021020575A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts

Definitions

  • This disclosure relates to a tire, its surface modifier and a surface modification method.
  • Patent Document 1 describes a protective polish for tires, which comprises an oil-in-water emulsified composition containing an acrylic fluororesin and an organopolysiloxane.
  • Patent Documents 2 and 3 describe a tire in which the entire surface of a groove or a recess for partitioning a tread land portion of the tire, and at least the entire surface of the shoulder region, are coated with a water-repellent polymer using a fluororesin. Has been described.
  • Japanese Unexamined Patent Publication No. 5-98213 Japanese Unexamined Patent Publication No. 5-208454 Japanese Unexamined Patent Publication No. 10-903
  • a tire surface modifier comprising any of the following compositions (1) to (5): (1) A composition containing a perfluoropolyether group-containing silane compound; (2) A composition containing a carbon-carbon double bond-containing perfluoropolyether compound; (3) A composition comprising a composite polymer particle composed of a fluoropolymer and an acrylic polymer and one or both of the fluoropolymer and the acrylic polymer having a hydroxyl group and a hydrolyzable silyl group, a polyisocyanate compound, and water.
  • a composition containing fluororesin particles, a curable silicone resin, and water is composed of a polymerization unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride monomer, an amino group-containing monomer, and a silicone-based vinyl monomer.
  • the perfluoropolyether group-containing silane compound has the following formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- (During the ceremony, a and b are independently integers from 0 to 30 and c and d are independently integers from 1 to 200, respectively. The sum of a, b, c, and d is an integer of 3 or more. The c / d ratio is in the range of 0.2 or more and less than 0.9. The order of existence of each repeating unit in parentheses with the subscripts a, b, c, or d is arbitrary in the equation.
  • the perfluoropolyether group-containing silane compound has the following formulas (1-1) to (1-6): [During the ceremony: PFPE independently represents-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- in each appearance, where a and b are. Each independently is an integer of 0 to 30, c and d are independently integers of 1 to 200, and the sum of a, b, c, and d is an integer of 3 or more.
  • each repeating unit in which the c / d ratio is in the range of 0.2 or more and less than 0.9 and is enclosed in parentheses with the subscripts a, b, c, or d is arbitrary in the formula.
  • Rf represents a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms at each appearance
  • R 1 independently represents a hydrogen atom or a C 1-22 alkyl group at each appearance
  • R 2 represents a hydroxyl group or a hydrolyzable group independently at each appearance
  • R 11 independently represents a hydrogen atom or a halogen atom at each appearance
  • R 12 independently represents a hydrogen atom or a lower alkyl group at each appearance
  • n is, (- SiR 1 n R 2 3-n) independently for each unit, an integer from 0 to 3; However, in equations (1-1), (1-2), (1-3), and (1-4), at least one R 2 is present
  • X 1 independently represents a single bond or a 2- to 10-valent organic group
  • X 2 independently represents a single bond or divalent organic group at each appearance
  • t is an integer from 1 to 10 independently for each occurrence
  • ⁇ is an integer from 1 to 9 independently of each other
  • Item 2 The surface modifier according to Item 2, which is a compound represented by any of the above.
  • the perfluoropolyether group-containing silane compound is represented by any of the formulas (1-1), (1-2), (1-3), (1-5), and (1-6), and is ⁇ , ⁇ .
  • Item 3 The surface modifier according to Item 3, wherein ′, ⁇ , ⁇ ′, ⁇ , and ⁇ ′ are 1, and n of the formula (1-3) is 0. Item 5.
  • composition (2) The carbon-carbon double bond-containing perfluoropolyether compound (2A) To the isocyanate group of polyisocyanate, which is a trimer of diisocyanate, (2B) A compound in which a group in which active hydrogen is eliminated from a compound having active hydrogen is bonded.
  • Component (2B) has (2B-1) perfluoropolyether having active hydrogen, (2B-2) silane compound having active hydrogen, and (2B-3) active hydrogen and carbon-carbon double bond. Is a compound The number of moles of isocyanate groups in component (2A) is equal to the total number of moles of component (2B).
  • the number of moles of the component (2B-1) is in the range of 0.1 to 2 moles
  • a compound in which the number of moles of the component (2B-2) is in the range of 0.05 to 2 mol and the number of moles of the component (2B-3) is in the range of 5 to 8.85 mol.
  • the component (2B-2) has the following formulas (2B-2-i) to (2B-2-iii): [During the ceremony, R 211 , R 212 , R 213 , R 214 , and R 215 are independently alkyl or aryl groups; R216 is a divalent organic group; l2 and n2 are independently 0 or 1; m2 is an integer from 1 to 500; o2 is an integer from 1 to 20; p2 is 0 or 1. ] Item 5.
  • Consists of composition (3) The composite polymer particles contain a fluoropolymer and an acrylic polymer in the same particles.
  • Item 2. The surface modifier according to Item 1, wherein the fluoropolymer contains 70 mol% or more of vinylidene fluoride units based on the total polymer constituting the fluoropolymer.
  • Item 8. Consists of composition (4) The average particle size of the fluororesin particles is in the range of 0.2 to 200 nm. The content of the curable silicone resin is in the range of 0.1 to 250% by mass with respect to the fluororesin particles.
  • the surface modifier according to Item 1. Item 9.
  • the composition (4) further contains 3 to 150% by mass of a surfactant with respect to the fluororesin particles.
  • the fluororesin particles consist of at least one selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers and tetrafluoroethylene / hexafluoropropylene copolymers.
  • the curable silicone resin is derived from an organopolysiloxane having at least two curable reactive groups bonded to silicon atoms in one molecule and having a viscosity at 23 ° C. in the range of 20 to 1,000,000 mPa ⁇ s. Become, Item 8.
  • Consists of composition (5) The fluoropolymer contains a polymerization unit based on tetrafluoroethylene and a polymerization unit based on a hydroxyl group-containing monomer.
  • Item 2. The surface modifier according to Item 1.
  • Item 11. A tire whose surface has been modified with the surface modifier according to any one of Items 1 to 10.
  • Item 12. A method for modifying the surface of a tire, which comprises a step of applying the surface modifier according to any one of Items 1 to 10 to the surface of the tire.
  • Item 13 Use of the composition according to any one of Items 1 to 10 or a surface modifier for modifying the surface of a tire.
  • a tire surface modifier and a surface modification method capable of achieving both water repellency and ozone resistance are provided. Further, according to the present disclosure, a tire having both water repellency and ozone resistance is provided.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the "organic group” means a group (monovalent organic group) formed by removing one hydrogen atom from an organic compound.
  • Examples of the “organic group” include Hydrocarbon groups, which may have one or more substituents, Non-aromatic heterocyclic group which may have one or more substituents Heteroaryl group which may have one or more substituents, Cyanide group, Aldehyde group, RO-, RS-, RCO-, RSO 2- , ROCO- and ROSO 2- (In these equations, R is independent Hydrocarbon groups, which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents). Can be mentioned.
  • substituted examples include a halogen atom, a cyano group, an amino group, an alkoxy group, and an alkylthio group.
  • the two or more substituents may be the same or different from each other.
  • hydrocarbon group in the present specification includes, for example, an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkazienyl group.
  • Aromatic hydrocarbon groups such as aryl group and aralkyl group can be mentioned.
  • alkyl group in the present specification includes, for example, methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), and the like. Examples thereof include linear or branched C 1-30 alkyl groups such as pentyl and hexyl.
  • alkoxy group in the present specification includes, for example, methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy). , Pentyloxy, and hexyloxy, which are linear or branched chain C 1-20 alkoxy groups.
  • alkylthio group in the present specification includes, for example, methylthio, ethylthio, propylthio (n-propylthio, isopropylthio), butylthio (n-butylthio, isobutylthio, sec-butylthio, tert-butylthio). ), Pentilthio, and hexylthio, which are linear or branched C 1-20 alkylthio groups.
  • aryloxy group in the present specification include C 6-18 aryloxy groups such as phenyloxy and naphthyloxy.
  • alkenyl groups in the present specification include, for example, vinyl, 1-propene-1-yl, 2-propen-1-yl, isopropenyl, 2-butene-1-yl, 4 Examples thereof include linear or branched C 2-20 alkenyl groups such as -pentene-1-yl and 5-hexene-1-yl.
  • alkynyl group in the present specification includes, for example, ethynyl, 1-propyne-1-yl, 2-propin-1-yl, 4-pentyne-1-yl, and 5-hexyne. Examples thereof include linear or branched C 2-20 alkynyl groups such as -1-yl.
  • cycloalkyl group examples include C 3-10 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • examples of the "cycloalkenyl group" in the present specification include C 3-10 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.
  • cyclo-alkazienyl group includes, for example, cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononazi. Examples thereof include C 4-10 cycloalkadienyl groups such as enyl and cyclodecadienyl.
  • the "aryl group” can be monocyclic, bicyclic, tricyclic, or tetracyclic. In the present specification, the “aryl group” can be a C 6-18 aryl group unless otherwise specified. Unless otherwise specified in the present specification, examples of the “aryl group” include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthrill.
  • the "aralkyl group" in the present specification includes, for example, benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4 Included are -phenylbutyl, 5-phenylpentyl, 2-biphenylmethyl, 3-biphenylmethyl, and 4-biphenylmethyl.
  • the "perfluoropolyether group” is a group in which two or more perfluoroalkylene oxide units are repeatedly bonded.
  • the perfluoroalkylene oxide unit include perfluoro C 1- such as-(OCF 2 )-,-(OC 2 F 4 )-,-(OC 3 F 6 )-,-(OC 4 F 8 )-. 6 alkylene oxide units can be mentioned. These units may be used alone or in combination of two or more.
  • -(OC 4 F 8 )- is-(OCF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 )-,-( OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 ) -,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-,-(OCF 2 CF (C 2 F 5 ))- It may be, but it is preferably ⁇ (OCF 2 CF 2 CF 2 CF 2 ) ⁇ .
  • -(OC 3 F 6 )- is either-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-,-(OCF 2 CF (CF 3 ))- It may be, but preferably ⁇ (OCF 2 CF 2 CF 2 ) ⁇ .
  • -(OC 2 F 4 )- may be any of-(OCF 2 CF 2 )-and-(OCF (CF 3 ))-, but preferably-(OCF 2 CF 2 )-. is there.
  • the "non-aromatic heterocyclic group” means a group formed by removing one hydrogen atom from the non-aromatic heterocycle.
  • the “non-aromatic heterocyclic group” can be monocyclic, bicyclic, tricyclic, or tetracyclic. Unless otherwise specified in the present specification, the “non-aromatic heterocyclic group” may be saturated or unsaturated. Unless otherwise specified in the present specification, the “non-aromatic heterocyclic group” can be, for example, a 5- to 18-membered non-aromatic heterocyclic group.
  • the "non-aromatic heterocyclic group” is, for example, 1 to 4 atoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to a carbon atom as ring-constituting atoms. It can be a non-aromatic heterocyclic group containing a hetero atom.
  • the "non-aromatic heterocyclic group” in the present specification includes, for example, tetrahydrofuryl, oxazolidinyl, imidazolinyl (eg, 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (eg, eg).
  • pyrrolidinyl eg 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl
  • piperidinyl eg 1-piperidinyl, 2-piperidinyl, 3-piperidinyl
  • azepanyl eg 1-azepanyl
  • 2-azepanyl eg 1-azepanyl
  • 4-azepanyl eg 1-azepanyl
  • azocanyl eg 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl
  • piperazinyl eg 1,4-piperazin-1-yl, 1) , 4-Piperazine-2-yl
  • diazepinyl eg 1,4-diazepine-1-yl, 1,4-diazepine-2-yl, 1,4-diazepine-5-yl, 1,4-diazepine- 6-yl
  • the "heteroaryl group” can be monocyclic, bicyclic, tricyclic, or tetracyclic. Unless otherwise specified in the present specification, the “heteroaryl group” can be, for example, a 5- to 18-membered heteroaryl group. Unless otherwise specified, in the present specification, the “heteroaryl group” includes, for example, 1 to 4 heteroatoms selected from oxygen atom, sulfur atom, and nitrogen atom in addition to carbon atom as a ring-constituting atom. It can be a heteroaryl group contained.
  • heteroaryl group includes a “monocyclic heteroaryl group” and an "aromatic condensed heterocyclic group”.
  • the "monocyclic heteroaryl group” in the present specification includes, for example, pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolill, 3-pyrrolill), frill (eg, 2-furyl, 3).
  • thienyl eg 2-thienyl, 3-thienyl
  • pyrazolyl eg 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl
  • imidazolyl eg 1-imidazolyl, 2-imidazolyl, 4-imidazolyl
  • Isooxazolyl eg 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl
  • oxazolyl eg 2-oxazolyl, 4-oxazolyl, 5-oxazolyl
  • isothiazolyl eg 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl
  • Thiazolyl eg 2-thiazolyl, 4-thiazolyl, 5-thiazolyl
  • triazolyl eg 1,2,3-triazole-3-yl, 1,2,4-triazole-4-yl
  • oxadiazolyl eg, 1,2,4
  • the "aromatically fused heterocyclic group" in the present specification includes, for example, isoindolyl (eg, 1-isoindrill, 2-isoindrill, 3-isoindrill, 4-isoindrill, 5-isoindol, 6- Isoindrill, 7-isoindrill), indrill (eg 1-indrill, 2-indrill, 3-indrill, 4-indrill, 5-indrill, 6-indrill, 7-indrill), benzo [b] flanil (eg 2-indrill) Benzo [b] flanyl, 3-benzo [b] flanil, 4-benzo [b] flanyl, 5-benzo [b] flanyl, 6-benzo [b] flanil, 7-benzo [b] flanyl), benzo [c] ] Furanyl (eg 1-benzo [c] flanyl, 4-benzo
  • N-valent (N is an integer of 2 or more) organic group is formed by further removing N-1 hydrogen atoms from the organic group (monovalent organic group). Means the group to be.
  • hydrolyzable group means a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction.
  • the tire surface modifier is described in (1) to (5): (1) A composition containing a perfluoropolyether group-containing silane compound; (2) A composition containing a carbon-carbon double bond-containing perfluoropolyether compound; (3) A composition comprising a composite polymer particle composed of a fluoropolymer and an acrylic polymer and one or both of the fluoropolymer and the acrylic polymer having a hydroxyl group and a hydrolyzable silyl group, a polyisocyanate compound, and water.
  • composition containing fluororesin particles, a curable silicone resin, and water comprising: (5) Consists of a polymerization unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. It comprises any composition of a composition containing a fluoropolymer containing a polymerization unit based on at least one curable functional group-containing monomer selected from the group.
  • the composition (1) is a composition containing a perfluoropolyether group-containing silane compound.
  • the perfluoropolyether group-containing silane compound is not particularly limited as long as it contains a perfluoropolyether group and a silicon atom, and preferably the following formula (1A): -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- (1A)
  • a and b are independently integers from 0 to 30 and c and d are independently integers from 1 to 200, respectively.
  • the sum of a, b, c, and d is an integer of 3 or more.
  • the c / d ratio is in the range of 0.2 or more and less than 0.9.
  • the order of existence of each repeating unit in parentheses with the subscripts a, b, c, or d is arbitrary in the equation.
  • It is a silane compound containing a perfluoropolyether group represented by.
  • the perfluoropolyether group-containing silane compound is more preferably represented by the following formulas (1-1) to (1-6): [During the ceremony: PFPE independently represents-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- in each appearance, a, b, c.
  • Rf represents a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms at each appearance
  • R 1 independently represents a hydrogen atom or a C 1-22 alkyl group at each appearance
  • R 2 represents a hydroxyl group or a hydrolyzable group independently at each appearance
  • R 11 independently represents a hydrogen atom or a halogen atom at each appearance
  • R 12 independently represents a hydrogen atom or a lower alkyl group at each appearance
  • n is, (- SiR 1 n R 2 3-n) independently for each unit, an integer from 0 to 3;
  • X 1 independently represents a single bond or a 2- to 10-valent organic group
  • X 2 independently represents a single bond or divalent organic group at each appearance
  • t is an integer from 1 to 10 independently for each occurrence
  • ⁇ is an integer from 1 to 9 independently of each other; ⁇ 'is
  • the PFPEs of formulas (1A) and (1-1) to (1-6) are ⁇ (OCF 2 CF 2 CF 2 CF 2 ) a ⁇ (OCF 2 CF 2 CF 2 ) b ⁇ (OCF 2 ).
  • CF 2 ) c ⁇ (OCF 2 ) d ⁇ in the equation, a, b, c, and d have the same meaning as above), for example, ⁇ (OCF 2 CF 2 ) c ⁇ (OCF 2 ). It may be d ⁇ (in the formula, c and d have the same meaning as described above).
  • a and b are each independently, preferably an integer of 1 to 30, more preferably an integer of 0 to 10; c and d are independently, preferably an integer of 10 to 100, more preferably an integer of 20 to 100; The sum of a, b, c, and d is preferably 10 or more, more preferably 20 or more, preferably 200 or less, and more preferably 100 or less.
  • the c / d ratio is preferably in the range of 0.2 or more and 0.85 or less, more preferably in the range of 0.2 or more and 0.75 or less, and further preferably 0.2 or more and 0.70 or less. It is within the range of, and even more preferably within the range of 0.3 or more and 0.6 or less.
  • C 1-16 alkyl group in the "C 1-16 alkyl group which may be substituted with one or more fluorine atoms" represented by PFPE is a straight chain or a branched chain. It may be a straight chain or branched C 1-6 alkyl group, more preferably a C 1-3 alkyl group, and even more preferably a straight chain C 1-3 alkyl group.
  • Rf is preferably a one or more C 1-16 alkyl group substituted by fluorine atoms, more preferably CF 2 H-C 1-15 fluoroalkylene group, more preferably C 1 It is a -16 perfluoroalkyl group.
  • the C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, more preferably C 1-. It is a 3 perfluoroalkyl group, more preferably a linear C 1-3 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 .
  • R 1 is preferably a C 1-4 alkyl group.
  • R' include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be generated by hydrolyzing a hydrolyzable group.
  • the halogen atom represented by R 11 is preferably an iodine atom, a chlorine atom, or a fluorine atom, and more preferably a fluorine atom.
  • the lower alkyl group represented by R 12 is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • n it is, (- SiR 1 n R 2 3-n) independently for each unit is preferably an integer of 0 to 2, more preferably 0. In the formula, not all n's become 3 at the same time. In other words, at least one R 2 is present in the equation.
  • X 1 is a perfluoropolyether portion (that is, an Rf-PFPE portion or a -PFPE- portion) that mainly provides water repellency and the like. , Can be interpreted as a linker that links a silane moiety (ie, a group enclosed in parentheses with ⁇ ) that provides binding ability to the tire. Therefore, X 1 may be any organic group as long as the compounds represented by the formulas (1-1) and (1-2) can be stably present.
  • ⁇ and ⁇ 'can vary depending on the valence of X 1 .
  • equation (1-1) the sum of ⁇ and ⁇ 'is the same as the valence of X 1 .
  • X 1 is a 10-valent organic group
  • the sum of ⁇ and ⁇ 'is 10 for example, ⁇ is 9 and ⁇ 'is 1, ⁇ is 5 and ⁇ 'is 5, or ⁇ is 1 and ⁇ .
  • ⁇ is the valence of X 1 minus one.
  • X 1 is preferably a divalent to 7 valent, more preferably a 2 to 4 valent, and even more preferably a divalent organic group.
  • X 1 is a 2- to tetravalent organic group, ⁇ is 1-3 and ⁇ 'is 1. In another embodiment, X 1 is a divalent organic group, ⁇ is 1, and ⁇ 'is 1.
  • the formulas (1-1) and (1-2) are represented by the following formulas (1-1-A) and (1-2-A).
  • X 1 is not particularly limited, but for example, the following equation: -(R 31 ) p' -(X a ) q'- [During the ceremony: R 31 represents a single bond, - (CH 2) s '-, or o-, represents m- or p- phenylene group, preferably - (CH 2) s' - a and, s'is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • X a represents-(X b ) l'- and represents X b is an independent -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R 33 ) 2 -,-( Si (R 33) 2 O) m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 -, and - (CH 2)
  • R 34 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group) at each appearance.
  • m' is an integer of 1 to 100, preferably an integer of 1 to 20, independently of each occurrence.
  • n' is an integer of 1 to 20, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3, independently of each occurrence.
  • l' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3.
  • R 31 and X a are substituted with one or more selected from fluorine atoms, C 1-3 alkyl groups, and C 1-3 fluoroalkyl groups. It may be substituted by a group.
  • X 1 is-(R 31 ) p' -(Xa) q'- R 32- .
  • R 32 represents a single bond, - (CH 2) t '-, or o-, represents m- or p- phenylene group, preferably - (CH 2) t' - a. t'is, for example, an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.
  • R 32 (typically the hydrogen atom of R 32 ) is substituted with one or more substituents selected from fluorine atoms, C 1-3 alkyl groups, and C 1-3 fluoroalkyl groups. May be good.
  • X 1 is C 1-20 alkylene group, -R 31 -X c -R 32- or-X d -R 32- [In the formula, R 31 and R 32 have the same meaning as above. ] Can be. More preferably, X 1 is C 1-20 alkylene group, - (CH 2) s' -X c -, - (CH 2) s '-X c - (CH 2) t' -, -X d- or -X d- (CH 2 ) t' [In the formula, s'and t'have the same meaning as above. ] Can be.
  • X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , - (Si (R 33) 2 O) m '-Si (R 33) 2 -, -O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -O- (CH 2) u '-Si (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -, -O- (CH 2) u '-Si (OCH 3) 2 OSi (OCH 3) 2 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, - CONR 34
  • X d is -S-, -C (O) O-, -CONR 34 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, - CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 - [In the formula, each symbol has the same meaning as above. ] Represents.
  • X 1 is C 1-20 alkylene group, - (CH 2) s '-X c - (CH 2) t' -, or -X d - (CH 2) t'- [In the formula, each symbol has the same meaning as above.
  • X 1 is C 1-20 alkylene group, -(CH 2 ) s'- O- (CH 2 ) t'- , - (CH 2) s '- (Si (R 33) 2 O) m' -Si (R 33) 2 - (CH 2) t '-, - (CH 2) s' -O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 - (CH 2) t '-, or - (CH 2) s' -O- (CH 2) t' -Si (R 33) 2 - (CH 2) u '-Si (R 33) 2 - (C v H 2v) - [In the formula, R 33 , m', s', t'and u'have the same meaning as above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably 2 to 3. It is
  • - (C v H 2v) - it may be a be branched straight-chain, for example, -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) - , -CH (CH 3 ) CH 2- .
  • X 1 is substituted with one or more substituents selected from the fluorine atom, C 1-3 alkyl group, and C 1-3 fluoroalkyl group (preferably C 1-3 perfluoroalkyl group). May be.
  • X 1 includes, for example, the following groups: [During the ceremony, R 41 is a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group; D is -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (In the formula, Ph means phenyl), and (In the formula, R 42 represents a hydrogen atom or a C 1-6 alkyl group, preferably a methyl group.) Is the group selected from E is ⁇ (CH 2 ) n ⁇ (n is an integer of 2 to 6
  • X 1 examples include: -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSI (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSI (CH 3 ) 2 OSI (CH 3 ) 2 OSI (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (
  • R 41 is a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group;
  • R 41 is a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group;
  • R 42 represents a hydrogen atom, a C 1-6 alkyl group (preferably a methyl group), or a methoxy group.
  • Ts are-(CH 2 ) n " -(n" is an integer of 2-6) that binds to the radical opposite the PFPE of the molecular main chain, and the rest, if present.
  • Ts are each independently a methyl group, a phenyl group, a C 1-6 alkoxy group, or a radical trapping group or an ultraviolet absorbing group.
  • the radical trapping group is not particularly limited as long as it can trap radicals generated by light irradiation, but for example, benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylate, crotonic acids, malonic acid esters, organoacrylates, etc. , Hindered amines, hindered phenols, or triazine residues.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays, and for example, benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, etc. Included are residues of oxanilides, benzoxadinones and benzoxazoles.
  • the preferred radical scavenging group or UV absorbing group is Can be mentioned.
  • X 1 is a group represented by the formula: ⁇ (R 16 ) x ⁇ (CFR 17 ) y ⁇ (CH 2 ) z ⁇ .
  • x, y, and z are independently integers from 0 to 10, the sum of x, y, and z is 1 or more, and the existence order of each repeating unit enclosed in parentheses is.
  • R 16 is independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 26 - (. Wherein, R 26 is, represents a hydrogen atom or an organic group), or a divalent organic group. Preferably, R 16 is an oxygen atom or a divalent organic group (preferably a polar group).
  • the lower alkyl group is, for example, a C 1-6 alkyl group, such as methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.
  • R 17 is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group at each appearance, preferably a fluorine atom.
  • the "lower fluoroalkyl group” is, for example, a C 1-6 fluoroalkyl group, preferably a C 1-3 fluoroalkyl group, more preferably a C 1-3 perfluoroalkyl group, still more preferably a trifluoromethyl group, or a penta. It is a fluoroethyl group, more preferably a trifluoromethyl group.
  • X 1 preferably has the same meaning as described above in the formula: ⁇ (O) x ⁇ (CF 2 ) y ⁇ (CH 2 ) z ⁇ (in the formula, x, y, and z have the same meanings as above.
  • the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.).
  • X 1 is, -O-CFR 13 - (CF 2) e - a.
  • R 13 independently represents a fluorine atom or a lower fluoroalkyl group.
  • the lower fluoroalkyl group is, for example, a C 1-3 fluoroalkyl group, preferably a C 1-3 perfluoroalkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • e is 0 or 1 independently of each other.
  • R 13 is a fluorine atom and e is 1.
  • t is an integer of 1-6. In another preferred embodiment, t is an integer of 2-10, preferably an integer of 2-6.
  • X 2 is preferably a C 1-20 alkylene group, more preferably ⁇ (CH 2 ) u ⁇ (where u is an integer of 0 to 2 in the formula).
  • PFPE, Rf, R 1 , R 2 , R 11 and R 12 have the same meaning as above; n is an integer from 0 to 2, preferably 0; X 1 is, -O-CFR 13 - (CF 2) e - a is; R 13 is a fluorine atom or lower fluoroalkyl group; e is 0 or 1; X 2 is-(CH 2 ) u- ; u is an integer from 0 to 2, Compounds are preferred.
  • Rf, PFPE, R 1 , R 2 , and n have the same meaning as the descriptions relating to formulas (1-1) and (1-2).
  • X 5 is a compound represented by the formulas (1-3) and (1-4), which mainly provides a perfluoropolyether portion (Rf-PFPE portion or -PFPE- portion) that provides water repellency and the like, and a tire. and of (specifically, -SiR 1 n R 2 3- n) silane portion to provide a binding ability it can be interpreted as a linker connecting the. Therefore, X 5 may be any organic group as long as the compounds represented by the formulas (1-3) and (1-4) can be stably present.
  • ⁇ is an integer of 1 to 9, and ⁇ 'is an integer of 1 to 9.
  • ⁇ and ⁇ 'are determined according to the valence of X 3 , and in formula (1-3), the sum of ⁇ and ⁇ 'is the same as the valence of X 5 .
  • X 5 is a 10-valent organic group
  • the sum of ⁇ and ⁇ 'is 10 for example ⁇ is 9 and ⁇ 'is 1, ⁇ is 5 and ⁇ 'is 5, or ⁇ is 1 and ⁇ .
  • ⁇ can be 9.
  • ⁇ is the value obtained by subtracting 1 from the value of the valence of X 5 .
  • X 5 is preferably a divalent to 7 valent, more preferably a 2 to 4 valent, even more preferably a divalent organic group.
  • X 5 is a 2- to tetravalent organic group
  • ⁇ is 1-3
  • ⁇ ' is 1.
  • X 5 is a divalent organic group
  • ⁇ is 1, and ⁇ 'is 1.
  • the formulas (1-3) and (1-4) are represented by the following formulas (1-3-A) and (1-4-A).
  • Examples of X 5 include, but are not limited to, the same as those described for X 1 .
  • PFPE, Rf, R 1 and R 2 have the same meaning as above; n is an integer of 0 to 2, preferably 0; X 5 is, -CH 2 O (CH 2) 2 -, - CH 2 O (CH 2) 3 -, or -CH 2 O (CH 2) 6 - , compound are preferred.
  • Rf and PFPE have the same meaning as the descriptions related to the above formulas (1-1) and (1-2).
  • X 7 is a perfluoropolyether portion (Rf-PFPE portion or -PFPE- portion) that mainly provides water repellency and the like, and a tire.
  • Rf-PFPE portion or -PFPE- portion perfluoropolyether portion
  • X 7 may be any organic group as long as the compounds represented by the formulas (1-5) and (1-6) can be stably present.
  • ⁇ and ⁇ 'are determined according to the valence of X 7 , and in equation (1-5), the sum of ⁇ and ⁇ 'is the same as the valence of X 7 .
  • X 7 is a 10-valent organic group
  • the sum of ⁇ and ⁇ 'is 10 for example, ⁇ is 9 and ⁇ 'is 1, ⁇ is 5 and ⁇ 'is 5, or ⁇ is 1 and ⁇ . 'Can be 9.
  • ⁇ and ⁇ 'are 1.
  • ⁇ is the value obtained by subtracting 1 from the value of the valence of X 7 .
  • X 7 is preferably a 2- to 7-valent, more preferably 2- to 4-valent, even more preferably divalent organic group.
  • X 7 is a 2- to tetravalent organic group
  • ⁇ is 1-3
  • ⁇ ' is 1.
  • X 7 is a divalent organic group
  • ⁇ is 1, and ⁇ 'is 1.
  • equations (1-5) and (1-6) are represented by the following equations (1-5-A) and (1-6-A).
  • Examples of X 7 include, but are not limited to, the same as those described for X 1 .
  • Z is preferably a divalent organic group, and is a siloxane bond with a Si atom (Si atom to which Ra is bonded) at the end of the molecular main chain in the formula (1-5) or the formula (1-6). Does not include those that form.
  • Z is preferably a C 1-6 alkylene group,-(CH 2 ) g- O- (CH 2 ) h- (in the formula, g is an integer of 1 to 6 and h is an integer of 1 to 6. It is an integer) or -phenylene- (CH 2 ) i- (in the formula, i is an integer of 0 to 6), more preferably a C 1-3 alkylene group.
  • substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. ..
  • Si is connected to the linear through the Z group is a five at the maximum. That is, in Ra , when at least one R 71 is present, two or more Si atoms linearly linked via the Z group are present in Ra , but the straight chain is present through the Z group.
  • the maximum number of Si atoms linked in a shape is five.
  • the "number of Si atoms linearly linked via a Z group in R a" is equal to -Z-Si- repeating number of which is connected to a linear during R a.
  • Si atoms are linked via a Z group in Ra is shown below.
  • * means a site that binds to Si in the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In the case, it means the end point of the repetition of ZSi.
  • the number on the right shoulder of Si means the number of occurrences of Si linearly connected via the Z group counted from *. That is, the chain in which the ZSi repetition is completed in Si 2 has "the number of Si atoms linearly connected via the Z group in Ra", and similarly, Si 3 , Si 4 and Si.
  • the chains in which the ZSi repetition is completed in Si 5 have "the number of Si atoms linearly linked via the Z group in Ra " of 3, 4, and 5, respectively.
  • the "number of Si atoms linearly linked via the Z group in Ra " is 1 (left) or 2 (right) in all chains. Equation).
  • the number of Si atoms linearly linked via the Z group in Ra is one or two, preferably one.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be generated by hydrolyzing a hydrolyzable group.
  • R 72 is -OR'(in the formula, R'represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
  • the lower alkyl group represented by R 73 is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • '(if R a' is absent, R a) R a terminal in R a in, q is preferably 2 or more, for example 2 or 3, more preferably 3.
  • At least one of the distal portion of the R a is, -Si (-Z-SiR 72 q R 73 r) 2 or -Si (-Z-SiR 72 q R 73 r) 3, preferably -Si ( -Z-SiR 72 q R 73 r ) 3 can be.
  • (- Z-SiR 72 q R 73 r) units is preferably (-Z-SiR 72 3).
  • the distal end of the R a, all -Si (-Z-SiR 72 q R 73 r) 3, may be preferably -Si (-ZSiR 72 3) 3.
  • R' includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be generated by hydrolyzing a hydrolyzable group. More preferably, R b is -OR'(in the formula, R'represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
  • Lower alkyl group represented by R c is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, more preferably a methyl group.
  • the composition (1) can further contain a solvent.
  • the solvent is not particularly limited, but is, for example, perfluorohexane, CF 3 CF 2 CHCl 2 , CF 3 CH 2 CF 2 CH 3 , CF 3 CHFCHFC 2 F 5 , 1, 1, 1, 2 , 2.
  • n 1 or more.
  • solvents selected from the group consisting of propene, 1,1,1,4,4,4-hexafluoro-2-butene. These solvents can be used alone or as a mixture of two or more.
  • the composition (1) can further contain other components. It may contain other components.
  • the other components are not particularly limited, but for example, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro (poly) ether compound (hereinafter, “fluorine-containing”).
  • fluorine-containing a perfluoro (poly) ether compound
  • examples include (referred to as "oil”), (non-reactive) silicone compounds (hereinafter referred to as "silicone oil”) that can be understood as silicone oil, and catalysts.
  • the fluorine-containing oil is not particularly limited, and examples thereof include a compound represented by the following formula (1B) (perfluoro (poly) ether compound).
  • Rf 1 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted with one or more fluorine atoms
  • Rf 2 is one.
  • C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group), a fluorine atom, or a hydrogen atom which may be substituted with an or more fluorine atom.
  • an alkyl group optionally substituted by one or more fluorine atoms above fluoroalkyl group terminal carbon atom is CF 2 H- all other carbon atoms are all substituted by fluorine ,
  • a perfluoroalkyl group more preferably a perfluoroalkyl group.
  • Rf 1 and Rf 2 are independently C 1-3 perfluoroalkyl groups.
  • a', b', c'and d' represent the number of four types of repeating units of the perfluoropolyether constituting the main skeleton of the polymer, and are independent integers of 0 to 300 (preferably 0 to 200). (For example, an integer of 1 to 200), and the sum of a', b', c'and d'is at least 1 (preferably 1 to 300, more preferably 20 to 300).
  • the order of existence of each repeating unit in parentheses with the subscripts a', b', c'or d' is arbitrary in the equation.
  • the c ′′ / d ′′ ratio is represented by the formula (1B-3) in the range of 0.2 or more and less than 0.9.
  • the fluorine-containing oil can have an average molecular weight of 1,000 to 30,000.
  • the compounds represented by the formulas (1B-1) to (1B-3) preferably have a number average molecular weight of 1,500 or more.
  • the fluorine-containing oil is, for example, 0 to 100 parts by mass of a total of 100 parts by mass of the perfluoropolyether group-containing silane compound (in the case of two or more kinds, the total of these, the same applies hereinafter). It may be contained in the range of 500 parts by mass, preferably 0 to 400 parts by mass, and more preferably 5 to 300 parts by mass.
  • the compound represented by the formula (1B-1) and the compound represented by the formula (1B-3) may be used alone or in combination. It is preferable to use the compound represented by the formula (1B-3) rather than the compound represented by the formula (1B-1).
  • the mass ratio of the compound represented by the formula (1B-1) to the compound represented by the formula (1B-3) is preferably in the range of 1: 1 to 1:30. The range of 1: 1 to 1:10 is more preferable.
  • the fluorine-containing oil contains one or more compounds represented by the formula (1B-3).
  • the mass ratio of the total of the perfluoropolyether group-containing silane compounds in the composition (1) to the compound represented by the formula (1B-3) is in the range of 4: 1 to 1: 4. Is preferable.
  • the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the perfluoropolyether group-containing silane compound.
  • the fluorine-containing oil may be a compound represented by the general formula Rf 3- F (in the formula, Rf 3 is a C 5-16 perfluoroalkyl group). Further, it may be a chlorotrifluoroethylene oligomer.
  • the compound represented by Rf 3- F and the chlorotrifluoroethylene oligomer are a compound represented by a fluorine-containing compound having a carbon-carbon unsaturated bond at the molecular end having a C 1-16 perfluoroalkyl group at the end. It is preferable in that a high affinity can be obtained.
  • the silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used.
  • the linear silicone oil may be either a so-called straight silicone oil or a modified silicone oil.
  • the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.
  • the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
  • the silicone oil is, for example, 0 to 300 parts by mass with respect to a total of 100 parts by mass of the perfluoropolyether group-containing silane compound (in the case of two or more kinds, the total of these, the same applies hereinafter). It may be contained in the range of 0 to 200 parts by mass.
  • the catalyst examples include acids (for example, acetic acid, trifluoroacetic acid, etc.), bases (for example, ammonia, triethylamine, diethylamine, etc.), transition metals (for example, Ti, Ni, Sn, etc.) and the like.
  • acids for example, acetic acid, trifluoroacetic acid, etc.
  • bases for example, ammonia, triethylamine, diethylamine, etc.
  • transition metals for example, Ti, Ni, Sn, etc.
  • the catalyst can promote the hydrolysis and dehydration condensation of the perfluoropolyether group-containing silane compound, and can promote the formation of the surface treatment layer.
  • the composition (1) can be made into pellets by impregnating a porous substance such as a porous ceramic material or a metal fiber, for example, steel wool into a cotton-like material.
  • the pellet can be used, for example, for vacuum deposition.
  • composition (1) can be, for example, the surface treatment agent described in US Patent Application Publication No. 2017/342210 or Japanese Patent No. 6332358.
  • composition (2) is a composition containing a carbon-carbon double bond-containing perfluoropolyether compound.
  • the carbon-carbon double bond-containing perfluoropolyether compound is not particularly limited as long as it contains a carbon-carbon double bond and a perfluoropolyether group.
  • Examples of the perfluoropolyether group include the same groups as those described in the composition (1).
  • the carbon-carbon double bond containing perfluoropolyether compound is (2A) To the isocyanate group of polyisocyanate, which is a trimer of diisocyanate, (2B) A compound in which a group in which active hydrogen is eliminated from a compound having active hydrogen is bonded.
  • Component (2B) has (2B-1) perfluoropolyether having active hydrogen, (2B-2) silane compound having active hydrogen, and (2B-3) active hydrogen and carbon-carbon double bond. It is a compound.
  • the component (2A) may exist as a polymer obtained by polymerizing polyisocyanate, which is a trimer of diisocyanate.
  • the component (2A) can be an isocyanurate-type polyisocyanate.
  • the isocyanurate-type polyisocyanate may exist as a polymer obtained by itself. That is, the isocyanurate-type polyisocyanate may be a monocyclic compound having only one isocyanurate ring, or a polycyclic compound obtained by polymerizing the monocyclic compound, or a mixture thereof. May be.
  • the isocyanurate-type polyisocyanate is commercially available, for example, as Sumijour (registered trademark) N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd.).
  • the diisocyanate used to obtain the component (2A) is not particularly limited, but is a diisocyanate in which an isocyanate group is bonded to an aliphatic group, for example, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl.
  • Methylene diisocyanate diisocyanates in which an isocyanate group is bonded to an aromatic group, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, trizine diisocyanate, naphthalene diisocyanate can be mentioned.
  • the specific component (2A) is not particularly limited, and examples thereof include a compound having the following structure.
  • polyisocyanates may exist as polymers.
  • an isocyanurate type polyisocyanate of hexamethylene diisocyanate the following structure: It may exist as a polymer having.
  • n is an integer of 1 or more.
  • the component (2B-1) has one active hydrogen-containing group (for example, a hydroxyl group) at one molecular end, or one active hydrogen-containing group at each of the two ends. It is a compound having (for example, a hydroxyl group).
  • the perfluoropolyether having the active hydrogen of the component (2B-1) is not particularly limited, but is, for example, 500 to 12,000, preferably 1,000 to 10,000, and more preferably 1,500 to 8,000. It has a number average molecular weight.
  • the component (2B-1) is one of the following formulas (2B-1-i) and (2B-1-ii): Rf 21- PFPE-R 21- CH 2 OH (2B-1-i) HO 2 HC-R 21- PFPE-R 21- CH 2 OH (2B-1-ii) It can be at least one compound represented by.
  • Rf 21 is a linear or branched C 1-16 alkyl group that may be substituted with one or more fluorine atoms. It is preferably a linear or branched C1-3 alkyl group which may be substituted with one or more fluorine atoms. Preferably, Rf 21 is linear. Further, preferably, the alkyl group which may be substituted with one or more fluorine atoms is fluoro, in which the terminal carbon atom is CF 2 H- and all other carbon atoms are totally substituted with fluorine. It can be an alkyl group or a perfluoroalkyl group, more preferably a perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 .
  • PFPE is the following formula: -(OC 4 F 8 ) a2- (OC 3 F 6 ) b2- (OC 2 F 4 ) c2- (OCF 2 ) d2- .
  • a2, b2, c2, and d2 represent four kinds of repeating units of perfluoropolyether, respectively, and are independently integers of 0 to 200, for example, integers of 1 to 200, and a2,
  • the sum of b2, c2, and d2 is in the range of at least 1, preferably 5 to 300, more preferably 10 to 200, and even more preferably 10 to 100.
  • each repeating unit in parentheses with the subscripts a2, b2, c2, or d2 is arbitrary in the equation.
  • a compound having such a perfluoropolyether group can exhibit excellent water repellency, oil repellency, and antifouling property.
  • the PFPE is one of the following formulas (2C-1) to (2C-3): -(OCF 2 CF 2 CF 2 ) b2- (2C-1) [In the formula, b2 is an integer from 1 to 200. ] -(OCF (CF 3 ) CF 2 ) b2- (2C-2) [In the formula, b2 is an integer from 1 to 200.
  • R 21 independently has the following formulas: -(Y) f2- (CF 2 ) g2- (CH 2 ) h2- It is a group represented by.
  • Y is a divalent polar group.
  • the divalent polar group are not particularly limited, but -COO-, -OCO-, -CONH-, -OCH 2 CH (OH) CH 2- , -CH 2 CH (OH) CH 2 O-, -COS-, -SCO-, -O- and the like can be mentioned, preferably -COO-, -CONH-, -CH 2 CH (OH) CH 2 O-, -O-.
  • the component (2B-1) is a compound represented by the formula (2B-1-i).
  • the component (2B-2) is a silane compound having one active hydrogen-containing group (for example, a hydroxyl group) at one molecular end or one active hydrogen-containing group (for example, a hydroxyl group) at each of the two ends. ..
  • the component (2B-2) is not particularly limited, but has, for example, a number average molecular weight of 100 to 20,000, preferably 500 to 15,000, and more preferably 800 to 12,000.
  • the component (2B-2) is composed of the following formulas (2B-2-i) and (2B-2-ii): It can be at least one compound represented by.
  • R 211 , R 212 , R 213 , R 214 , and R 215 are independently alkyl or aryl groups, respectively.
  • the alkyl group and aryl group may contain a hetero atom, for example, a nitrogen atom, an oxygen atom, or a sulfur atom in the molecular chain or ring.
  • alkyl group and aryl group may be optionally substituted with halogen; one or more halogens, C 1-6 alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group. , C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl group, C 6-10 aryl group, 5-10 member hetero It may be substituted with one or more substituents selected from the aryl groups.
  • R 216 represents a divalent organic group.
  • R 216 is, - (CH 2) r21 - ( wherein, r21 is an integer of 1 to 20, preferably an integer of 1 to 10) is.
  • l2 and n2 are independently 0 or 1, respectively;
  • m2 is an integer from 1 to 500, preferably from 1 to 200. It is preferably an integer of 5 to 150;
  • o2 is an integer of 0 to 20, for example an integer of 1 to 20, and
  • p2 is 0 or 1.
  • the component (2B-2) may be a silane compound having an amino group as an active hydrogen-containing group.
  • Examples of such compounds include, but are not limited to, the following.
  • the ratio of the number average molecular weight of the component (2B-1) to the component (2B-2) is not particularly limited, but is, for example, 1: 5 to 5: 1, preferably 1: 3 to 3: 1, and more preferably 1: 1. It is in the range of 3 to 3: 2.
  • the component (2B-3) is preferably an active hydrogen-containing group, particularly a (meth) acrylic acid ester having a hydroxyl group and a vinyl monomer.
  • R 22 may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine C.
  • R 22 may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine C.
  • R 22 is a C 1-10 alkyl group which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine).
  • poly (ethylene glycol) acrylate (2B-3-9) H (OCH (CH 3 ) CH 2 ) n OCO (R 22 ) C CH 2 (in the formula, n is an integer of 1 to 30, R 22 is C 1-10 alkyl group optionally substituted with hydrogen atom, chlorine atom, fluorine atom, or fluorine)
  • the total number of moles of the component (2B) [component (2B-1), (2B-2), and (2B-3)] to react with the component (2A) is the number of moles of the isocyanate group in the component (2A). Is preferably equal to. Furthermore, for 9 mol of isocyanate groups in component (2A), The number of moles of the component (2B-1) is in the range of 0.1 to 2 moles, It is preferable that the number of moles of the component (2B-2) is in the range of 0.05 to 2 mol and the number of moles of the component (2B-3) is in the range of 5 to 8.85 mol.
  • the number of moles of component (2B-1) is preferably in the range of 0.1-1.5 mol, more preferably 0.1-1 mol;
  • the number of moles of the component (2B-2) can be preferably in the range of 0.05 to 1.5 mol, more preferably 0.05 to 1 mol.
  • the number of moles of the component (2B-1) is in the range of 0.1 to 1 mole
  • the number of moles of the component (2B-2) can be in the range of 0.05 to 1 mol
  • the number of moles of the component (2B-3) can be in the range of 7 to 8.85 moles.
  • the composition (2) can further contain a fluorine-containing oil.
  • a fluorine-containing oil the same oil as that exemplified in the composition (1) can be used.
  • the fluorine-containing oil may be contained in the range of, for example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass with respect to 100 parts by mass of the carbon-carbon double bond-containing perfluoropolyether compound.
  • the composition (2) can further contain silicone oil.
  • silicone oil the same silicone oil as that exemplified in the composition (1) can be used.
  • the silicone oil may be contained, for example, in the range of 0 to 50 parts by mass, preferably 0 to 10 parts by mass with respect to 100 parts by mass of the carbon-carbon double bond-containing perfluoropolyether compound.
  • the composition (2) can further contain an active energy ray curing initiator.
  • an active energy ray curing initiator for example, radicals or cations are generated for the first time when irradiated with an electromagnetic wave in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, ⁇ -rays, etc. 2) It acts as a catalyst for initiating the curing (that is, cross-linking reaction) of the curable site (for example, carbon-carbon double bond) of the compound in, and usually generates radicals and cations with ultraviolet light. In particular, use one that generates radicals.
  • the active energy ray curing initiator in the composition (2) is appropriately selected depending on the type of the component (2B-3) having a carbon-carbon double bond, the type of active energy ray used (wavelength range, etc.), the irradiation intensity, and the like.
  • the initiator when an active energy ray in a general ultraviolet region is used, the following can be exemplified as the initiator. ⁇ Acetophenone-based acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, ⁇ -aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc.
  • Benzophenone benzoin benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.
  • -Benzophenone benzophenone benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propyl benzophenone , Acrylicized benzophenone, Michler's ketone, etc. ⁇ Thioxansons Thioxansone, Chlorothioxanthone, Methylthioxanthone, Diethylthioxanthone, Dimethylthioxanthone, etc. -Ketokumarin, 2-ethylanthraquinone, benzophenone, anthraquinone, etc.
  • one type may be used alone, or two or more types may be used in combination.
  • the active energy ray curing initiator is not particularly limited, but if a carbon-carbon double bond-containing perfluoropolyether compound or a fluorine-containing oil is present, the carbon-carbon double bond-containing perfluoropolyether compound and the fluorine-containing It may be contained in the range of 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total with the oil.
  • the composition (2) can further contain a solvent. Since the composition (2) exhibits high solubility not only in a fluorine-containing organic solvent but also in a fluorine-free machine solvent which is a general-purpose solvent, a fluorine-containing organic solvent and a fluorine-free machine solvent are used as the solvent. Can be used.
  • fluorine-containing organic solvent examples include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamine (florinate (trade name), etc.).
  • Perfluoroalkyl ether perfluorobutyl tetrahydrofuran, polyfluoroaliphatic hydrocarbon (Asahiclin AC6000 (trade name), etc.), Hydrochlorofluorocarbon (Asahiclin AK-225 (trade name), etc.), Hydrofluoroether (Novec) (Product name), HFE-7100 (trade name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name), etc.)), Fluorohydrate-containing alcohol (perfluoro) Alkyl bromide, perfluoroalkyl iodide, perfluoropolyether (Crytox (trade name), Demnum (trade name), Fombulin (trade name), etc.), 1,3-bistrifluoromethylbenzene, 2-(2) methacrylate Examples thereof include perfluoroalkyl) ethyl, 2- (perfluoroalkyl) ethyl
  • fluorine-free machine solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene.
  • Glycolmonobutyl ether acetate dipropylene glycol dimethyl etherpentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglime, triglime, acetate Included are ethyl, butyl acetate, dimethylformamide, dimethylsulfoxide, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.
  • one type may be used alone, or two or more types may be used in combination.
  • the solvent can be a fluorine-free machine solvent, preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate or the like, and more preferably acetone, methyl ethyl ketone, methyl isobutyl ketone or the like.
  • the solvent can be a mixed solvent of a fluorine-containing organic solvent and a fluorine-free machine solvent.
  • the solvent is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, or diacetone alcohol.
  • the carbon-carbon double bond-containing perfluoropolyether compound is obtained by the reaction of the component (2A) and the component (2B-1) with the compound obtained by the reaction of the component (2A) and the component (2B-2).
  • a mixed solvent of a fluorine-containing organic solvent and a fluorine-free machine solvent for example, hydrochlorofluorocarbon (Asahiclean AK-225 (trade name), etc.) and 1 , 1, 2, 2, 3, 3,4-Heptafluorocyclopentane, one or more solvents, methyl isobutyl ketone, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate , And a mixed solvent with one or more solvents selected from diacetone alcohol, preferably a mixture of 1,1,2,2,3,3,4-heptafluorocyclopentane, propylene glycol monomethyl ether and methyl ethyl ketone. Solvents are more preferred.
  • the solvent is not particularly limited, but if a carbon-carbon double bond-containing perfluoropolyether compound or a fluorine-containing oil is present, a total of 100 of the carbon-carbon double bond-containing perfluoropolyether compound and the fluorine-containing oil. It may be contained in the range of 5 to 10,000 parts by mass, preferably 5 to 5,000 parts by mass with respect to parts by mass.
  • the composition (2) can be added to the composition forming the matrix to form a curable composition.
  • the composition forming the matrix is a compound having at least one carbon-carbon double bond, for example, but not particularly limited, monofunctional and / or polyfunctional (meth) acrylate, monofunctional and / or. It means a composition containing a compound which is a polyfunctional urethane (meth) acrylate, a monofunctional and / or a polyfunctional epoxy (meth) acrylate.
  • the composition forming the matrix is not particularly limited, but is a composition generally regarded as a hard coating agent, and examples thereof include a hard coating agent containing a polyfunctional (meth) acrylate.
  • curable composition examples include, for example, beam sets 502H, 504H, 505A-6, 550B, 575CB, 575, 1402 (trade name) from Arakawa Chemical Industry Co., Ltd., and EBECRYL40 (trade name) from Daikin Corporation. , HR300 series (trade name) is commercially available from Yokohama Rubber Co., Ltd., and Optool AR-110 (trade name) is commercially available from Daikin Industries, Ltd.
  • the composition (2) is, for example, 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the total of the composition forming the matrix and the composition (2). More preferably, it is contained in the range of 0.1 to 10% by mass.
  • the curable composition may contain a solvent.
  • the solvent the fluorine-containing organic solvent and the fluorine-free machine solvent described in the composition (2) can be used.
  • the solvent one type may be used alone, or two or more types may be used in combination.
  • the solvent can be a fluorine-free machine solvent.
  • the solvent can be a mixed solvent of a fluorine-containing organic solvent and a fluorine-free machine solvent.
  • the solvent is not particularly limited, but is 0 to 19,900 mass with respect to a total of 100 parts by mass of the carbon-carbon double bond-containing perfluoropolyether compound, the fluorine-containing oil if present, and the composition forming the matrix. Parts, preferably in the range of 0 to 10,000 parts by mass.
  • the curable composition may contain other components such as silicone oil and an active energy ray curing initiator.
  • silicone oil and the active energy ray curing initiator the silicone oil and the active energy ray curing initiator described in the composition (2) can be used.
  • composition (2) and the curable composition further include an antioxidant, a thickener, a leveling agent, an antifoaming agent, an antioxidant, an antifogging agent, an ultraviolet absorber, a pigment, a dye, silica, hollow silica and the like. It may contain a filler such as inorganic fine particles, aluminum paste, talc, glass frit, metal powder, and a polymerization inhibitor such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).
  • BHT butylated hydroxytoluene
  • PTZ phenothiazine
  • composition (2) can be, for example, the composition described in US Patent Application Publication No. 2016/237199 or Japanese Patent No. 6056935.
  • composition (3) comprises a composite polymer particle composed of a fluoropolymer and an acrylic polymer, and one or both of the fluoropolymer and the acrylic polymer having a hydroxyl group and a hydrolyzable silyl group, a polyisocyanate compound, and water. It is a composition to be contained.
  • the composition can be an aqueous dispersion.
  • the composite polymer particles preferably contain a fluoropolymer and an acrylic polymer in the same particles.
  • the fluoropolymer and the acrylic polymer may or may not be chemically bonded.
  • the hydroxyl group and the hydrolyzable silyl group may contain either a fluoropolymer or an acrylic polymer, one polymer containing a hydroxyl group and the other polymer containing a hydrolyzable silyl group. You may. It is preferable that the acrylic polymer contains a hydroxyl group and a hydrolyzable silyl group because it is easy to produce.
  • the above-mentioned hydroxyl group is a group represented by -OH, but does not contain a hydroxyl group constituting a part of a carboxy group (-COOH).
  • the hydrolyzable silyl group is of the formula: -SiX 31 n X 32 3-n (X 31 represents a C 1-10 alkoxy group, X 32 represents an H or C 1-10 alkyl group, and n represents an integer of 1 to 3.) It is preferably a group represented by.
  • the hydrolyzable silyl group is more preferably -Si (OCH 3 ) n X 32 3-n or -Si (OC 2 H 5 ) n X 32 3-n , and -Si (OCH 3 ) 3 or-. It is more preferably Si (OC 2 H 5 ) 3 .
  • the mass ratio of the fluoropolymer to the acrylic polymer is preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, 70. It is more preferably 30/30 or less, further preferably 30/70 or more, and particularly preferably 50/50 or more.
  • the fluoropolymer preferably contains fluoroolefin units.
  • fluoroolefins include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE), and the like.
  • Perfluoroolefins such as: chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene, trifluoropropylene, hexafluoroisobutene, 2,3,3,3-tetrafluoro Examples thereof include non-perfluoroolefins such as propene, 1,3,3,3-tetrafluoropropene and 1,1,3,3,3-pentafluoropropene.
  • Examples of PAVE include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), and perfluoro (propyl vinyl ether) (PPVE).
  • a functional group-containing fluoroolefin can also be used.
  • Rf 31 is a divalent fluorine-containing alkylene group or a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, or a divalent fluorine-containing alkylene group or a fluorine-containing oxyalkylene group containing an ether bond having 2 to 40 carbon atoms.
  • m3 is 0 or 1.
  • Examples thereof include the compounds indicated by.
  • functional group-containing fluoroolefin examples include, for example, And so on.
  • fluoroolefin examples include iodine-containing monomers, for example, perfluoro (6,6-dihydro-6-iodo-3-oxa-1) described in JP-A-5-63482 or JP-A-62-12734. Iodinated products of perfluorovinyl ethers such as -hexene) and perfluoro (5-iodo-3-oxa-1-pentene) can also be used.
  • the fluoroolefin is preferably at least one selected from the group consisting of VF, VdF, TFE, HFP, and CTFE. Further, the fluoroolefin is more preferably a combination of VdF and at least one selected from the group consisting of TFE, HFP, and CTFE.
  • the fluoropolymer may contain a non-fluorine-based monomer unit copolymerizable with the fluoroolefin in addition to the fluoroolefin unit.
  • the non-fluorine-based monomer copolymerizable with the fluoroolefin include olefins such as ethylene, propylene, and isobutylene, vinyl ether-based monomer, allyl ether-based monomer, vinyl ester-based monomer, and acrylic-based monomer. Examples include monomers and methacrylic monomers.
  • One type of non-fluorine-based monomer may be used alone, or two or more types may be used in combination.
  • the fluoropolymer preferably contains a vinylidene fluoride unit as a fluoroolefin unit.
  • the vinylidene fluoride unit of the fluoropolymer is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total polymerization units constituting the fluoropolymer. It is preferably 95 mol% or less.
  • the fluoropolymer includes a group consisting of VdF / TFE / CTFE copolymers, VdF / TFE copolymers, VdF / TFE / HFP copolymers, VdF / CTFE copolymers, VdF / HFP copolymers, and PVdF.
  • the acrylic polymer preferably contains at least an acrylic monomer unit.
  • the acrylic monomer is preferably a (meth) acrylic acid ester.
  • the acrylic polymer preferably contains an acrylic acid ester unit or a methacrylic acid ester unit, and more preferably contains an acrylic acid ester unit and a methacrylic acid ester unit.
  • composition (3) when simply described as "(meth) acrylic acid ester”, “acrylic acid ester”, and “methacrylic acid ester", the acrylic monomer having a hydroxyl group or a hydrolyzable silyl group is not included.
  • the total amount of the (meth) acrylic acid ester unit is preferably in the range of 64 to 99.8% by mass, preferably 74 to 95.5% by mass, based on all the monomer units constituting the acrylic polymer. It is more preferable that it is within the range.
  • an acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms or a methacrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms is preferable.
  • Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, and 2 Examples thereof include (meth) acrylic acid alkyl esters such as ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate.
  • the (meth) acrylic acid ester at least one selected from the group consisting of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate is preferable.
  • the acrylic polymer preferably contains a hydroxyl group-containing monomer unit, and may contain at least one hydroxyl group-containing monomer unit selected from the group consisting of a hydroxyl group-containing (meth) acrylic acid ester and a hydroxyl group-containing alkyl vinyl ether. More preferably, it contains a hydroxyl group-containing (meth) acrylic acid ester unit.
  • the hydroxyl group-containing monomer unit is preferably in the range of 0.1 to 40% by mass, preferably in the range of 0.8 to 31% by mass, based on all the monomer units constituting the acrylic polymer. It is more preferably in the range of 4 to 23% by mass, and particularly preferably in the range of 4 to 18% by mass.
  • hydroxyl group-containing alkyl vinyl ether examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 4-hydroxy-2-methylbutyl vinyl ether. , 5-Hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether and the like. At least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is preferable because of its excellent polymerization reactivity.
  • hydroxyl group-containing (meth) acrylic acid ester examples include 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 2-hydroxy.
  • HEMA 2-hydroxyethyl methacrylate
  • HAA 2-hydroxyethyl acrylate
  • 3-hydroxypropyl methacrylate 3-hydroxypropyl acrylate
  • 2-hydroxypropyl methacrylate 2-hydroxypropyl methacrylate
  • 2-hydroxypropyl methacrylate 2-hydroxypropyl methacrylate
  • 2-hydroxypropyl methacrylate 2-hydroxypropyl methacrylate
  • 2-hydroxypropyl methacrylate 2-hydroxypropyl methacrylate
  • 2-hydroxypropyl methacrylate 2-hydroxypropyl methacrylate
  • 2-hydroxypropyl methacrylate 2-hydroxypropyl methacrylate
  • 2-hydroxypropyl methacrylate 2-
  • the hydroxyl group-containing (meth) acrylic acid ester unit is preferably in the range of 0.1 to 40% by mass, and preferably in the range of 0.8 to 31% by mass, based on all the monomer units constituting the acrylic polymer. It is more preferably within the range of 4 to 23% by mass, and particularly preferably within the range of 4 to 18% by mass.
  • the acrylic polymer preferably contains a hydrolyzable silyl group-containing unsaturated monomer unit.
  • CH 2 CHCOO (CH 2 ) 3 Si (OCH 3 ) 3
  • CH 2 CHCOO (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2
  • CH 2 CHCOO (CH 2 ) 3 Si (OC 2 H 5 ) 3
  • CH 2 CHCOO (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2
  • CH 2 CHCOO (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2
  • CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3
  • CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2
  • CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OC 2 H 5 ) 3
  • CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OC 2 H 5 ) 3
  • CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OC 2
  • the hydrolyzable silyl group-containing unsaturated monomer unit is preferably in the range of 0.1 to 5% by mass, and 0.5 to 3% by mass, based on all the monomer units constituting the acrylic polymer. More preferably, it is in the range of%.
  • the acrylic polymer preferably contains unsaturated carboxylic acid units.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, itaconic acid, and itaconic acid mono.
  • acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, maleic acid monoester because of its low homopolymerizability and difficulty in forming homopolymers and easy control of the introduction of carboxyl groups.
  • At least one selected from the group consisting of fumaric acid, fumaric acid monoester, 3-allyloxypropionic acid, and undecyleneic acid is preferable.
  • the unsaturated carboxylic acid unit is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 1 to 5% by mass, based on all the monomer units constituting the acrylic polymer. preferable.
  • the acrylic polymer contains a hydroxyl group-containing (meth) acrylic acid ester unit and a hydrolyzable silyl group-containing unsaturated monomer unit.
  • the acrylic polymer more preferably contains an acrylic acid ester unit, a methacrylic acid ester unit, an unsaturated carboxylic acid unit, a hydroxyl group-containing (meth) acrylic acid ester unit, and a hydrolyzable silyl group-containing unsaturated monomer unit.
  • the ratio (mass%) of the acrylic acid ester unit, the methacrylic acid ester unit, the unsaturated carboxylic acid unit, the hydroxyl group-containing (meth) acrylic acid ester unit, and the hydrolyzable silyl group-containing unsaturated monomer unit is 0 to 40. It is preferably in the range of / 42 to 90/1 to 5/1 to 31 / 0.5 to 3.
  • the acid value of the composite polymer particles is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and even more preferably 7 or more.
  • the hydroxyl value of the composite polymer particles is preferably in the range of 1 to 40, and more preferably in the range of 5 to 30.
  • the hydroxyl value and acid value can be calculated from the amount of each monomer used to synthesize the composite polymer particles.
  • the composite polymer particles preferably have a glass transition temperature (Tg) in the range of 0 to 70 ° C., more preferably in the range of 10 to 60 ° C., and in the range of 20 to 50 ° C. Is even more preferable.
  • Tg glass transition temperature
  • the composite polymer particles preferably have a particle size (or average particle size) in the range of 50 to 300 nm, and more preferably in the range of 50 to 250 nm.
  • the composite polymer particles are a step of aqueous dispersion polymerization of fluoroolefin to obtain an aqueous dispersion containing fluoropolymer particles.
  • aqueous dispersion containing the fluoropolymer particles at least an acrylic monomer is seed-polymerized into the fluoropolymer particles. It is preferable that the product is obtained by a production method including a step of
  • hexamethylene diisocyanate hexamethylene diisocyanate derived from at least one isocyanate selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI).
  • XDI xylylene diisocyanate
  • H6XDI bis (isocyanate methyl) cyclohexane
  • At least selected from the group consisting of blocked isocyanate compounds based on HDI polyisocyanate compounds derived from hexamethylene diisocyanate (HDI), polyisocyanate compounds derived from isophorone diisocyanate (IPDI), and water-dispersible polyisocyanate compounds.
  • One type of compound is preferred.
  • the polyisocyanate compound is also preferably a water-dispersible polyisocyanate compound.
  • the polyisocyanate compound is also referred to as at least one isocyanate (hereinafter, also referred to as isocyanate (3-i)) selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI). ) Derived from the polyisocyanate compound (hereinafter, also referred to as polyisocyanate compound (3-I)) is preferable.
  • isocyanate (hereinafter, also referred to as isocyanate (3-i)) selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI). ) Derived from the polyisocyanate compound (hereinafter, also referred to as polyisocyanate compound (3-I)) is preferable.
  • polyisocyanate compound (3-I) examples include adduct (3-I-1) and isocyanate (3-I-1) obtained by addition polymerization of isocyanate (3-i) and a trihydric or higher aliphatic polyhydric alcohol.
  • examples thereof include an isocyanurate structure (nulate structure) (3-I-2) composed of i) and a biuret (3-I-3) composed of isocyanate (3-i).
  • R 311 represents a C 3-20 aliphatic hydrocarbon group
  • R 312 represents a phenylene group or a cyclohexylene group
  • k31 is an integer of 3 to 20.
  • R 311 is a hydrocarbon group based on a trihydric or higher aliphatic polyhydric alcohol, with a C 3-10 aliphatic hydrocarbon group being more preferred and a C 3-6 aliphatic hydrocarbon group being even more preferred.
  • R 312 is a phenylene group
  • R 312 is a cyclohexylene group, it may be any of a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group.
  • a 1,3-cyclohexylene group is preferable.
  • all R 312s in the formula (3A) may have the same cyclohexylene group, or two or more kinds may be mixed.
  • k31 is a number corresponding to the valence of the trihydric or higher aliphatic polyhydric alcohol. k31 is more preferably an integer of 3 to 10, and even more preferably an integer of 3 to 6.
  • the isocyanurate structure (3-I-2) is contained in the molecule according to the following formula (3B): It has one or two or more isocyanurate rings represented by.
  • Examples of the isocyanurate structure (3-I-2) include a trimer obtained by a trimerization reaction of isocyanate, a pentamer obtained by a pentamerization reaction, and a heptamer obtained by a heptamerization reaction. it can.
  • the trimer represented by is preferable. That is, the isocyanurate structure is preferably a trimer of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane.
  • Biuret (3-I-3) has the following formula (3D): (In the equation, R 312 is the same as R 312 in equation (3A).) It is a compound having a structure represented by, and can be obtained by quantifying isocyanate under conditions different from those for obtaining an isocyanurate structure (3-I-2).
  • polyisocyanate compound (3-I) that is, at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane, and trivalent or higher valent isocyanates.
  • xylylene diisocyanate and bis (isocyanate methyl) cyclohexane
  • trivalent or higher valent isocyanates Those obtained by addition polymerization with an aliphatic polyhydric alcohol are preferable.
  • polyisocyanate compound (3-I) is an adduct of isocyanate (3-i) and a trihydric or higher aliphatic polyhydric alcohol
  • the trihydric or higher aliphatic polyhydric alcohol may be used.
  • TMP Trimethylol Propane
  • 1,2,6-Hexanetriol Trimethylol Ethan
  • 2,4-Dihydroxy-3-hydroxymethylpentane 1,1,1-Tris (bishydroxymethyl) Propane
  • 2, , 3-hydric alcohols such as 2-bis (hydroxymethyl) butanol-3
  • tetrahydric alcohols such as pentaerythritol and diglycerol
  • pentahydric alcohols such as arabite, ribitol and xylitol (pentit)
  • sorbit mannit, galactitol
  • Examples thereof include hexahydric alcohols (hexits) such as Arosulcit.
  • trimethylolpropane and pentaerythritol are particularly preferable.
  • the xylylene diisocyanate (XDI) used as a component of adduct (3-I-1) includes 1,3-xylylene diisocyanate (m-xylylene diisocyanate) and 1,2-xylylene diisocyanate (o-xylylene diisocyanate). Isocyanate), 1,4-xylylene diisocyanate (p-xylylene diisocyanate), and among them, 1,3-xylylene diisocyanate (m-xylylene diisocyanate) is preferable.
  • 1,3-bis (isocyanate methyl) cyclohexane and 1,2-bis (isocyanate methyl) examples thereof include cyclohexane and 1,4-bis (isocyanatemethyl) cyclohexane, and among them, 1,3-bis (isocyanatemethyl) cyclohexane is preferable.
  • R 313 represents a phenylene group or a cyclohexylene group.
  • TMP trimethylolpropane
  • the phenylene group or cyclohexylene group represented by R 313 is the same as that of R 312 in the formula (3A).
  • polyisocyanate compound (3-I) is an isocyanurate structure (3-I-2)
  • D121N manufactured by Mitsui Chemicals, Inc., H6XDI nurate, NCO content 14.0%
  • D127N manufactured by Mitsui Chemicals, Inc., H6XDI nurate, trimer of H6XDI, NCO content 13.5%
  • polyisocyanate compound it is also preferable to use a blocked isocyanate based on hexamethylene diisocyanate (HDI) (hereinafter, also simply referred to as a blocked isocyanate).
  • a blocked isocyanate those obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate (hereinafter, also referred to as polyisocyanate compound (3-II)) with a blocking agent are preferable.
  • polyisocyanate compound (3-II) examples include isocyanurate composed of adduct (3-II-1) and hexamethylene diisocyanate obtained by addition polymerization of hexamethylene diisocyanate and a trihydric or higher aliphatic polyhydric alcohol.
  • examples thereof include a structure (nurate structure) (3-II-2) and a biuret (3-II-3) composed of hexamethylene diisocyanate.
  • R 314 represents a C 3-20 aliphatic hydrocarbon group.
  • K32 is an integer of 3 to 20.
  • R314 is a hydrocarbon group based on the above trihydric or higher aliphatic polyhydric alcohol, a C 3-10 aliphatic hydrocarbon group is more preferable, and a C 3-6 aliphatic hydrocarbon group is further preferable.
  • k32 is a number corresponding to the valence of the trihydric or higher aliphatic polyhydric alcohol. k32 is more preferably an integer of 3 to 10, and even more preferably an integer of 3 to 6.
  • the isocyanurate structure (3-II-2) has one or more isocyanurate rings represented by the formula (3B) in the molecule.
  • Examples of the isocyanurate structure (3-II-2) include a trimer obtained by a trimerization reaction of isocyanate, a pentamer obtained by a pentamerization reaction, and a heptamer obtained by a heptamerization reaction. it can. Above all, the following formula (3G): The trimer represented by is preferable.
  • Biuret (3-II-3) has the following formula (3H): It is a compound having a structure represented by, and can be obtained by quantifying hexamethylene diisocyanate under conditions different from those for obtaining an isocyanurate structure (3-II-2).
  • blocked isocyanate products include Duranate K6000 (manufactured by Asahi Kasei Chemicals Co., Ltd., HDI active methylene compound blocked isocyanate), Duranate TPA-B80E (manufactured by Asahi Kasei Chemicals Co., Ltd.), Duranate MF-B60X (manufactured by Asahi Kasei Chemicals Co., Ltd.), Duranate 17B-60PX (Asahi Kasei Chemicals Co., Ltd.), Coronate 2507 (Nippon Polyurethane Industry Co., Ltd.), Coronate 2513 (Nippon Polyurethane Industry Co., Ltd.), Coronate 2515 (Nippon Polyurethane Industry Co., Ltd.), Sumijour BL-3175 (Manufactured by Sumika Bayer Urethane Co., Ltd.), LuxateHC1170 (manufactured by Olin Chemicals), LuxateHC2170 (manufactured by
  • polyisocyanate compound a polyisocyanate compound derived from hexamethylene diisocyanate (HDI) (hereinafter, also referred to as a polyisocyanate compound (3-III)) can be used.
  • a polyisocyanate compound (3-III) examples include those described above as the polyisocyanate compound (3-II).
  • polyisocyanate compound (3-III) examples include Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%), Sumijour N3300 (Sumika Bayer Urethane).
  • polyisocyanate compound (3-IV) a polyisocyanate compound derived from isophorone diisocyanate (IPDI) (hereinafter, polyisocyanate compound (3-IV)) is also preferable.
  • polyisocyanate compound (3-IV) examples include an isocyanurate structure composed of adduct (3-IV-1) obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, and isophorone diisocyanate. (Nurate structure) (3-IV-2) and biuret (3-IV-3) composed of isophorone diisocyanate can be mentioned.
  • R 315 represents a C 3-20 aliphatic hydrocarbon group.
  • R 316 is expressed by the following equation (3J): It is a group represented by k34 is an integer of 3 to 20.
  • k34 is a number corresponding to the valence of the trihydric or higher aliphatic polyhydric alcohol. k34 is more preferably an integer of 3 to 10, and even more preferably an integer of 3 to 6.
  • the isocyanurate structure (3-IV-2) has one or more isocyanurate rings represented by the formula (3B) in the molecule.
  • Examples of the isocyanurate structure (3-IV-2) include a trimer obtained by a trimerization reaction of isocyanate, a pentamer obtained by a pentamerization reaction, and a heptamer obtained by a heptamerization reaction. it can. Above all, the following formula (3K): (Wherein, R 316 is the same as R 316 in formula (3I).)
  • the trimer represented by is preferable. That is, the isocyanurate structure (3-IV-2) is preferably a trimer of isophorone diisocyanate.
  • R 317 is a group represented by the formula (3J).
  • TMP trimethylolpropane
  • TMP adduct of isophorone diisocyanate examples include Takenate D140N (manufactured by Mitsui Chemicals, Inc., NCO content 11%).
  • Examples of commercially available isocyanurate structures made of isophorone diisocyanate include Death Module Z4470 (manufactured by Sumika Bayer Urethane Co., Ltd., NCO content 11%).
  • a water-dispersible polyisocyanate compound can also be used.
  • the water-dispersible polyisocyanate compound refers to a polyisocyanate compound capable of forming an aqueous dispersion when added to an aqueous medium and stirred.
  • Examples of such an water-dispersible polyisocyanate compound include (3-1) a mixture of a hydrophobic polyisocyanate and a polyisocyanate having a hydrophilic group, and (3-2) a hydrophobic polyisocyanate and an isocyanate group. Examples thereof include a mixture with a dispersant having a hydrophilic group, and (3-3) only a polyisocyanate having a hydrophilic group.
  • the hydrophilic group means an anionic group, a cationic group, or a nonionic group.
  • the water-dispersible polyisocyanate compound is particularly preferably a polyisocyanate having a hydrophilic group.
  • the hydrophobic polyisocyanate does not have a hydrophilic group, and is, for example, 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, 1,6-hexamethylene diisocyanate, 1, Aliphatic diisocyanates such as 12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4- Isocyanate Methyloctane, 2-isocyanate ethyl (2,6-diisocyanate) hexanoate and other aliphatic triisocyanates; 1,3-bis (isocyanate methylcyclohexane), 1,4-bis (isocyanatomethylcyclohexane) , 1,3-Diisocyanate cyclohexane, 1,4-
  • polyisocyanate having a hydrophilic group examples include polyethers having a hydrophilic group and an isocyanate group, polyester, polyurethane, vinyl polymer, alkyd resin, fluororesin, silicon resin and the like.
  • a polyether having a hydrophilic group and an isocyanate group or a vinyl polymer is preferable, and a polyether having a hydrophilic group and an isocyanate group is more preferable, because the water dispersibility is good.
  • the polyisocyanates having these hydrophilic groups can be used alone or in combination of two or more.
  • Examples of commercially available products of polyisocyanates having a hydrophilic group include Bayer Jules XP 2700 (manufactured by Sumika Bayer Urethane Co., Ltd.).
  • the content of the polyisocyanate compound is such that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the polyisocyanate compound and the hydroxyl group (OH) contained in the composite polymer particles is in the range of 0.1 to 5. Is more preferable, it is more preferably in the range of 0.5 to 5, further preferably in the range of 0.5 to 3, and particularly preferably in the range of 1 to 2.
  • the blending amount is the equivalent ratio (NCO) of the isocyanate group (NCO) in the water-dispersible polyisocyanate compound and the hydroxyl group (OH) contained in the composite polymer particles.
  • NCO equivalent ratio
  • / OH is preferably in the range of 0.1 to 5, more preferably in the range of 0.3 to 3, further preferably in the range of 0.3 to 2, and in the range of 0.5 to 1.5. Is particularly preferable.
  • composition (3) may contain an organic solvent such as alcohol, glycol ether, or ester in addition to water.
  • composition (3) can contain, for example, 10 to 60% by mass of composite polymer particles.
  • the composition (3) preferably further contains a film-forming auxiliary.
  • the film-forming auxiliary include dipropylene glycol dimethyl ether (DPGDME), diethyl diglycol (DEDG), diethyl adipate (ADE) and other film-forming aids that do not have active hydrogen.
  • Active hydrogen is a hydrogen atom contained in a hydroxyl group or an amino group.
  • the composition (3) may contain pigments, antifreezes, fillers, defoamers, leveling agents, rheology regulators, pH regulators, preservatives, UV absorbers, antioxidants, matting agents, as required. , Lubricants and the like may be added.
  • composition (3) can be, for example, the aqueous dispersion described in US Patent Application Publication No. 2018/118969 or Patent No. 6103107.
  • composition (4) is a composition containing fluororesin particles, a curable silicone resin, and water.
  • the fluororesin constituting the fluororesin particles at least one selected from the group consisting of polytetrafluoroethylene [PTFE] and melt-processable fluororesin (excluding polytetrafluoroethylene) is preferable, and PTFE, TFE / PAVE copolymer [PFA], TFE / HFP copolymer [FEP], ethylene [Et] / TFE copolymer [ETFE], Et / TFE / HFP copolymer, polychlorotrifluoroethylene [PCTFE] , CTFE / TFE copolymer, Et / CTFE copolymer, and at least one selected from the group consisting of polyvinyl fluoride [PVF], more preferably, from the highly versatile and easily available PTFE, PFA, and FEP. At least one selected from the above group is more preferable, and PTFE is particularly preferable from the viewpoint of economy.
  • the fluororesin particles preferably contain fluororesin particles having an average particle diameter of 0.2 to 200 nm. Usually, the fluororesin primary particles easily aggregate to form secondary particles with a larger particle size.
  • the fluororesin may be present in the composition (4) as secondary particles, but is preferably present in the composition (4) as primary particles.
  • the average particle size (primary average particle size) of the fluororesin particles is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, still more preferably 10 nm or less. It is preferable, and less than 5 nm is particularly preferable.
  • the average particle size of the fluororesin particles is the volume average particle size, which is measured by a transmission electron microscope (TEM) when it is 10 nm or more, and by a dynamic light scattering method (DLS) when it is less than 10 nm. Be measured.
  • TEM transmission electron microscope
  • DLS dynamic light scattering method
  • the obtained fluororesin aqueous dispersion is diluted with deionized water so that the fluororesin solid content concentration is 100 ppm with respect to water, and the diluted fluororesin aqueous dispersion is made of Cu for observation.
  • a sample-attached mesh is prepared by adhering to the mesh and drying. Using TEM, the particle size of the fluororesin particles in the sample attachment mesh is observed, and the average particle size is obtained by taking an electron micrograph.
  • the refractive index of the solvent (water) is 1.3328
  • the viscosity of the solvent (water) is 0.8878 mPa ⁇ s.
  • the average particle size can be the average particle size in a state of being dispersed in the primary particles.
  • the fluororesin preferably has an MFR in the range of 0.1 to 500 g / 10 minutes, more preferably in the range of 1 g / 10 minutes or more, and 300 g / 10 minutes or less. Is more preferable.
  • the MFR uses a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) in accordance with ASTM D1238, and the measurement temperature determined by the type of fluororesin (for example, 372 ° C for PFA or FEP, 297 for ETFE).
  • Mass of polymer (g / 10) flowing out from a nozzle with an inner diameter of 2 mm and a length of 8 mm under a load for example, 5 kg for PFA, FEP, ETFE, and PTFE) at ° C. and 380 ° C. for PTFE). It is a value obtained as minutes).
  • the fluororesin preferably has a melting point in the range of 150 ° C. or higher and lower than 324 ° C.
  • the melting point is the temperature corresponding to the maximum value in the heat of fusion curve when 3 mg of a sample having no history of heating to 300 ° C. or higher is heated at a rate of 10 ° C./min using a differential scanning calorimeter [DSC]. ..
  • the PFA is not particularly limited, but a copolymer in which the molar ratio of the TFE unit to the PAVE unit (TFE unit / PAVE unit) is in the range of 70/30 or more and less than 99/1 is preferable. A more preferred molar ratio is in the range of 70/30 to 98.9 / 1.1, and a more preferred molar ratio is in the range of 80/20 to 98.9 / 1.1.
  • the monomer unit derived from the monomer copolymerizable with TFE and PAVE is in the range of 0.1 to 10 mol%, and the total amount of TFE unit and PAVE unit is 90 to 99.9 mol%. It is also preferable that the copolymer is within the range of.
  • Z 44 represents a hydrogen atom, a fluorine atom, or a chlorine atom
  • n4 represents an integer of 2 to 10
  • CF 2 CF-.
  • Examples thereof include an alkyl perfluorovinyl ether derivative represented by OCH 2- Rf 42 (in the formula, Rf 42 represents a C 1-5 perfluoroalkyl group).
  • the melting point of PFA is lower than the melting point of PTFE, preferably in the range of 180 to less than 324 ° C, more preferably in the range of 230 to 320 ° C, and in the range of 280 to 320 ° C. Is even more preferable.
  • melt flow rate is preferably in the range of 1 to 500 g / 10 minutes.
  • the FEP is not particularly limited, but a copolymer in which the molar ratio of TFE units to HFP units (TFE units / HFP units) is in the range of 70/30 or more and less than 99/1 is preferable. A more preferred molar ratio is in the range of 70/30 to 98.9 / 1.1, and a more preferred molar ratio is in the range of 80/20 to 98.9 / 1.1.
  • the monomer unit derived from the monomer copolymerizable with TFE and HFP is in the range of 0.1 to 10 mol%, and the total amount of TFE unit and HFP unit is 90 to 99.9 mol%. It is also preferable that the copolymer is within the range of. Examples of the monomer copolymerizable with TFE and HFP include PAVE and an alkyl perfluorovinyl ether derivative.
  • the melting point of FEP is lower than the melting point of PTFE, preferably in the range of 150 to less than 324 ° C, more preferably in the range of 200 to 320 ° C, and in the range of 240 to 320 ° C. Is even more preferable.
  • the FEP preferably has an MFR in the range of 1 to 500 g / 10 minutes.
  • the PTFE may be homo-PTFE or denatured PTFE.
  • the modified PTFE contains a TFE unit and a modified monomer unit based on a modified monomer copolymerizable with TFE.
  • the above-mentioned PTFE may be a high molecular weight PTFE having non-melt processability and fibrillation property, or a low molecular weight PTFE having melt processability and not having fibrillation property.
  • the non-melt processability means a property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.
  • the modified monomer is not particularly limited as long as it can be copolymerized with TFE, and is, for example, a perfluoroolefin such as HFP; a chlorofluoroolefin such as CTFE; a hydrogen-containing fluoroolefin such as trifluoroethylene or VdF; Perfluorovinyl ether; perfluoroalkylethylene; ethylene; fluorine-containing vinyl ether having a nitrile group and the like can be mentioned. Further, the modified monomer used may be one kind or a plurality of kinds.
  • the above-mentioned "perfluoroorganic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms.
  • the perfluoroorganic group may have ether oxygen.
  • perfluorovinyl ether examples include PAVE in which Rf 43 represents a C 1-10 perfluoroalkyl group (preferably a C 1-5 perfluoroalkyl group) in the above formula.
  • Examples of the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group and the like.
  • Purple olomethyl vinyl ether [PMVE] in which the perfluoroalkyl group is a perfluoromethyl group and purple olopropyl vinyl ether [PPVE] in which the perfluoroalkyl group is a perfluoropropyl group are preferable.
  • Rf 43 is a C 4-9 perfluoro (alkoxyalkyl) group, and Rf 43 is the following formula: (In the formula, m4 represents 0 or an integer of 1 to 4). Rf 43 , which is a group represented by, is expressed by the following formula: (In the formula, n41 represents an integer of 1 to 4.) Examples include those that are the basis represented by.
  • the perfluoroalkylethylene is not particularly limited, and examples thereof include perfluorobutylethylene (PFBE), perfluorohexylethylene (PFHE), and perfluorooctylethylene (PFOE).
  • the fluorine-containing vinyl ether to be used is more preferable.
  • examples of the fluorine-containing vinyl ether having a nitrile group include perfluoro [3- (1-methyl-2-vinyloxy-ethoxy) propionitrile] (CNVE).
  • the modified monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PMVE, PPVE, PFBE, PFHE, CNVE, and ethylene. More preferably, it is at least one monomer selected from the group consisting of PMVE, PPVE, PFHE, CNVE, HFP, and CTFE.
  • the modified PTFE has a modified monomer unit in the range of 0.001 to 2 mol%, more preferably in the range of 0.001 to 1 mol%, and 0.001 to 0.5 mol%. It is more preferably in the range of 0.001 to 0.03 mol%, and particularly preferably in the range of 0.001 to 0.03 mol%.
  • each monomer constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.
  • melt flow rate is preferably in the range of 0 to 500 g / 10 minutes.
  • the MFR of PTFE is more preferably less than 400 g / 10 minutes, and even more preferably 300 g / 10 minutes or less.
  • the melting point of PTFE is preferably in the range of 324 to 360 ° C.
  • the melting point is preferably 350 ° C. or lower, and more preferably 348 ° C. or lower.
  • the curable silicone resin is a silicone resin that is crosslinked at room temperature (for example, within the range of 10 to 30 ° C.) or in the presence or absence of a cross-linking agent by heating.
  • the curable silicone resin consists only of the main agent (base polymer) described later, and in the case of a silicone resin that cross-links in the presence of a cross-linking agent, the curable silicone resin is It consists of a combination of a main agent (base polymer) and a cross-linking agent.
  • a room temperature curable silicone resin consists of a combination of an organopolysiloxane having a room temperature curable reactive group and a cross-linking agent that crosslinks the organopolysiloxane.
  • the main agent (base polymer) of the curable silicone resin is an organopolysiloxane having at least two curable reactive groups bonded to silicon atoms in one molecule.
  • the curing reactive group when this organopolysiloxane is room temperature curable include a hydroxyl group and a hydrolyzable group.
  • the hydrolyzable group include C 1-8 alkoxy groups such as methoxy group, ethoxy group and propoxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group and methoxypropoxy group; acetoxy group and octanoyloxy group.
  • Asyloxy group such as benzoyloxy group
  • Alkoxyoxy group such as vinyloxy group, isopropenyloxy group, 1-ethyl-2-methylvinyloxy group
  • Ketooxime group such as dimethylketooxime group, methylethylketooxime group, diethylketooxime group
  • Amino groups such as dimethylamino group, diethylamino group, butylamino group, cyclohexylamino group; aminoxi group such as dimethylaminoxy group and diethylaminoxi group
  • N-methylacetamide group, N-ethylacetamide group, N-methylbenzamide group Such as an amide group and the like, and an alkoxy group is preferable.
  • Groups other than the curing reactive group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and octadecyl group; cyclopentyl group, Cycloalkyl group such as cyclohexyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aryl group such as phenyl group, tolyl group, xsilyl group, ⁇ -, ⁇ -naphthyl group; benzyl group , 2-Phenylethyl group, 3-phenylpropyl group and other aralkyl groups; and some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl and Br and cyan
  • a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group and the like can be exemplified.
  • a methyl group, an ethyl group, a vinyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
  • the organopolysiloxane is polymerized so that the viscosity at 23 ° C. is in the range of 20 to 1,000,000 mPa ⁇ s, preferably 100 to 500,000 mPa ⁇ s, and more preferably 1,000 to 50,000 mPa ⁇ s. It is preferable to use a degree of polymerization.
  • the viscosity is 20 mPa ⁇ s (23 ° C.) or more, a coating film having excellent physical and mechanical strength can be obtained, and when the viscosity is 1,000,000 mPa ⁇ s (23 ° C.) or less, it is used. Excellent workability at times.
  • the viscosity can be measured with a rotational viscometer.
  • organopolysiloxane such as dimethylpolysiloxane having a silanol group or a silyl group having a hydrolyzable group at both ends as shown in the following formula is preferable.
  • R 411 and R 413 are independently exemplified as groups other than the curing reactive group.
  • R412 is an alkyl group such as a methyl group, an ethyl group, and a propyl group.
  • n42 and m42 are numbers having a viscosity of 20 to 1,000,000 mPa ⁇ s (23 ° C.). a4 is 0 or 1.
  • a silane having a hydrolyzable group and / or a partially hydrolyzed condensate thereof should be used as a cross-linking agent.
  • the silane and / or its partially hydrolyzable condensate has at least two hydrolyzable groups in its molecule, preferably has three or more hydrolyzable groups, and silicon.
  • a group other than a hydrolyzable group may be bonded to the atom, and the molecular structure thereof may be either a silane or a siloxane structure. In particular, in the case of a siloxane structure, it may be linear, branched or cyclic.
  • hydrolyzable group examples include those exemplified as the above-mentioned hydrolyzable group, and an alkoxy group, a ketoxim group, and an isopropenoxy group are particularly preferable.
  • an unsubstituted or substituted monovalent hydrocarbon group for example, a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • a methyl group, an ethyl group, or a propyl group for example, a methyl group, an ethyl group, or a propyl group.
  • cross-linking agent examples include, for example, ethyl silicate, propyl silicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltris (methoxyethoxy) silane, vinyltris (methoxyethoxy) silane, and the like.
  • the blending amount of the cross-linking agent is preferably in the range of 0.5 to 20 parts by mass, and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the organopolysiloxane.
  • the blending amount is 0.5 parts by mass or more, sufficient cross-linking can be obtained, and when it is 20 parts by mass or less, a cured product having appropriate hardness can be obtained, which is economically advantageous.
  • a catalyst for further promoting curing may be added.
  • various catalysts used in the condensation curing type room temperature curable composition can be used, and specific examples thereof include lead-2-ethyloctate, dibutyltin dioctate, and dibutyl.
  • the amount used is not particularly limited and may be an effective amount as a catalyst, but it is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of organopolysiloxane. It is preferably in the range of 0.1 to 10 parts by mass.
  • increasing the content of the catalyst gives sufficient curability of the obtained composition regardless of the type of cross-linking agent, while decreasing the content of the catalyst provides stable storage of the obtained composition. Improves sex.
  • curable silicone resin examples include Polon MF-56, Polon MF-40, Polon MF-23, Polon MF-20, Polon MF-206, Polon MWS, and KM-2002L- manufactured by Shin-Etsu Chemical Co., Ltd. 1, KM-2002T, X-51-1318, X-52-1631, KM-9794, etc., and IE7170, etc. manufactured by Toray Dow Corning Co., Ltd., but are not limited thereto. ..
  • the curable silicone resin may be only one type or a combination of two or more types.
  • the blending amount (active component amount) of the curable silicone resin is 0.1 to 250% by mass, preferably 1% by mass or more, more preferably 10% by mass or more, and 150% by mass or less with respect to the fluororesin particles. Is preferable, and 100% by mass or less is more preferable.
  • the composition (4) may further contain silicone oil.
  • Silicone oil is a chain of siloxane bonds.
  • the curable silicone resin can form a three-dimensional crosslinked structure composed of siloxane bonds by a crosslinking reaction (curing reaction), whereas the silicone oil cannot form the above crosslinked structure. It is preferable to have.
  • Silicone oil has the following formula: R 421 R 422 R 423 SiO- [R 424 R 425 SiO] p4 [R 426 R 427 SiO] q4-SiR 428 R 429 R 430 (In the formula, R 421 to R 430 independently represent an alkyl group, an aryl group, or another organic group. P4 and q4 represent integers whose viscosities are within the range described below.) Examples thereof include a compound having a linear siloxane structure represented by (1), a compound in which substituents R 421 to R 430 in the compound having a linear siloxane structure are substituted with another substituent, and the like.
  • the alkyl group in the substituents R 421 to R 430 is usually a C 1-12 alkyl group, and more specific examples thereof include a methyl group and an ethyl group.
  • Examples of the aryl group include a phenyl group and the like.
  • silicone oil examples include dimethyl silicone oil, phenylmethyl silicone oil, alkyl-aralkyl-modified silicone oil, fluorosilicone oil, polyether-modified silicone oil, fatty acid ester-modified silicone oil, methyl hydrogen silicone oil, and silanol group-containing silicone oil.
  • the viscosity of the silicone oil is usually in the range of 1 to 200,000 mPa ⁇ s at 25 ° C.
  • silicone oils those that have been given water dispersibility by denaturation can be used as they are, but when using ordinary silicone oil, it is desirable to use one that has been emulsified with an emulsifier or the like.
  • silicone oil emulsion examples include Polon MF-14, Polon MF-14E, Polon MF-18T, Polon MF-51, Polon MF-52, Polon MF-140, and X-51 manufactured by Shin-Etsu Chemical Co., Ltd. -1178, X-51-1264, etc., and FZ-4658, FZ-4634EX, SM8709SR, SM8716SR, FZ-4602, BY22-818EX, etc. manufactured by Toray Dow Corning Co., Ltd. are mentioned, but are limited thereto. It is not something that is done.
  • the content of the silicone oil is preferably in the range of 0.1 to 100% by mass, more preferably in the range of 1 to 50% by mass with respect to the curable silicone resin.
  • the fluororesin By containing water in the composition (4), the fluororesin can be present as primary particles in the composition (4), and the coating of the composition (4) can be facilitated.
  • the composition (4) preferably contains fluororesin particles in the range of 0.1 to 50% by mass, more preferably 0.5% by mass or more, and 1% by mass with respect to the composition (4). More preferably, it contains more than 20% by mass, more preferably 10% by mass or less.
  • the concentration of the fluororesin particles is such that 1 g of the composition (4) is dried in a blower dryer at 300 ° C. for 60 minutes, and the ratio of the mass of the heat residue to the mass (1 g) of the composition (4). Is expressed as a percentage (solid content concentration).
  • the composition (4) preferably further contains a surfactant.
  • a surfactant By containing the surfactant, it is possible to prevent the fluororesin particles from aggregating or settling during storage of the composition (4).
  • a nonionic surfactant is preferable, and a non-fluorinated nonionic surfactant is more preferable.
  • nonionic surfactant examples include ether-type nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene alkylene alkyl ether; and polyoxy such as ethylene oxide / propylene oxide block copolymer. Ethylene derivatives; ester-type nonionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester; polyoxyethylene alkylamine, alkylalkanolamide, etc. Amine-based nonionic surfactant; and the like. All of these are non-fluorinated nonionic surfactants.
  • ether-type nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene alkylene alkyl ether
  • polyoxy
  • polyoxyethylene alkyl ether is preferable as the nonionic surfactant.
  • the composition (4) may contain a surfactant in the range of 3 to 150% by mass with respect to the fluororesin particles.
  • the content of the surfactant is more preferably 10% by mass or more, further preferably 30% by mass or more, particularly preferably 50% by mass or more, more preferably 100% by mass or less, and 80% by mass or less with respect to the fluororesin particles. Is more preferable, and 70% by mass or less is particularly preferable.
  • the composition (4) may contain alcohols represented by the structural formula: R 431- OH (in the formula, R 431 is a hydrocarbon group of C3 to C20) in order to improve the wettability at the time of application. Good.
  • the alcohols may be secondary or tertiary alcohols.
  • the amount of alcohols is in the range of, for example, 0.1 to 30% by mass, preferably 0.1 to 20% by mass, and more preferably 0.2 to 15% by mass with respect to 100% by mass of the composition (4). Is.
  • the composition (4) contains, if necessary, a film-forming auxiliary, an antifreeze agent, a pigment, a filler, a pigment dispersant, an antifoaming agent, a leveling agent, a rheology regulator, a preservative, an ultraviolet absorber, and an antioxidant.
  • a film-forming auxiliary an antifreeze agent
  • a pigment e.g., a pigment that is a pigment that isolymer of a pigment
  • a filler e.g., a pigment dispersant, an antifoaming agent, a leveling agent, a rheology regulator, a preservative, an ultraviolet absorber, and an antioxidant.
  • a preservative e.g., an ultraviolet absorber, and an antioxidant.
  • Agents, matting agents, lubricants, sulphurizers, thickeners, pH regulators, antistatic agents, antibacterial agents, flame retardants and the like can also be added.
  • the required additives may be added
  • composition (4) may not contain any polymer other than the fluororesin and the curable silicone resin.
  • composition (4) can be, for example, the paint described in US Patent Application Publication No. 2018/223116 or Patent No. 6098751.
  • composition (5) contains a polymerization unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride monomer, an amino group-containing monomer, and a silicone-based vinyl simple substance. It is a composition containing a fluoropolymer containing a polymerization unit based on at least one curable functional group-containing monomer selected from the group consisting of quants.
  • Fluorine-containing monomers that is, monomers for forming a fluorine-containing polymer into which a curable functional group is introduced, include, for example, TFE, CTFE, VdF, VF, HFP, and fluorovinyl ether (eg, PAVE). These can be mentioned, and one or more of these can be used. Among them, at least one selected from the group consisting of TFE, CTFE, and VdF is preferable, and TFE is more preferable.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 4-hydroxy-2-methyl.
  • Hydroxyl-containing vinyl ethers such as butyl vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether can be mentioned. ..
  • hydroxyl group-containing vinyl ethers particularly 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether, are preferable because they are excellent in polymerization reactivity and curability of functional groups.
  • examples of other hydroxyl group-containing monomers include hydroxyalkyl esters of (meth) acrylic acids such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
  • the carboxyl group-containing monomer described later is not included in the hydroxyl group-containing monomer.
  • Examples of the carboxyl group-containing monomer include the formula (5A) :.
  • R 51 , R 52 , and R 53 are the same or different, and they are all hydrogen atoms, alkyl groups, aryl groups, carboxyl groups, or alkoxycarbonyl groups; n51 is 0 or 1.
  • R 54 and R 55 are the same or different and are both saturated or unsaturated linear or cyclic alkyl groups; n52 is 0 or 1; m52 is 0 or 1.) Examples thereof include a carboxyl group-containing vinyl ether monomer represented by.
  • unsaturated carboxylic acids represented by the formula (5A) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, and maleic acid monoester.
  • examples thereof include fumaric acid and fumaric acid monoester.
  • crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, and fumaric acid monoester are preferable because they have low homopolymerizability and it is difficult to form a homopolymer.
  • carboxyl group-containing vinyl ether monomer represented by the formula (5B) include 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, and 3- (2-allyloxybutoxy).
  • Examples thereof include one or more types such as carbonyl) propionic acid, 3- (2-vinyloxyethoxycarbonyl) propionic acid, and 3- (2-vinyloxybutoxycarbonyl) propionic acid.
  • 3- (2-allyloxyethoxycarbonyl) propionic acid is preferable because it is advantageous in terms of monomer stability and polymerization reactivity.
  • an alkenyl ester of a polybasic carboxylic acid such as vinyl phthalate or vinyl pyromellitic acid may be used. Can be done.
  • Examples of the acid anhydride monomer include unsaturated dicarboxylic acid anhydrides such as maleic anhydride.
  • a perfluoroolefin-based polymer mainly composed of a perfluoroolefin unit is preferable, and specific examples thereof include a homopolymer of TFE, TFE and HFP, PAVE and the like. Examples thereof include copolymers of the above, and copolymers with other monomers copolymerizable with these.
  • copolymerizable monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl laurate, vinyl stearate, cyclohexylcarboxylic acid.
  • Carboxylic acid vinyl esters such as vinyl, vinyl benzoate, parat-butyl vinyl benzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; ethylene, propylene, n-butene, isobutene, etc.
  • Non-fluoroolefins examples include, but are not limited to, fluoromonomers such as VdF, CTFE, VF, and fluorovinyl ether. Of these, TFE-based polymers mainly composed of TFE are preferable.
  • Specific curable functional group-containing perfluoroolefin-based polymers include, for example, TFE / isobutylene / hydroxybutyl vinyl ether / copolymer of other monomers, TFE / vinyl versatic acid / hydroxyethyl allyl ether / other single amount. Examples thereof include polymer of the body, polymer of TFE / vinyl versatic acid / hydroxybutyl vinyl ether / other monomer, and polymer of TFE / VdF / hydroxybutyl vinyl ether / other monomer.
  • the content of the curable functional group-containing fluoropolymer in the composition (5) is preferably in the range of 20 to 90% by mass with respect to 100% by mass of the total amount of non-volatile components in the composition (5). ..
  • Examples of the organic solvent in the composition (5) include esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate and propylene glycol methyl ether acetate; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
  • esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate and propylene glycol methyl ether acetate
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
  • Glycol ethers such as; diethylene glycol esters such as carbitol acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, mineral spirit, etc.
  • the composition (5) preferably contains a curing agent.
  • a curing agent By including a curing agent, a cured coating film can be formed using the composition (5).
  • the curing agent is selected according to the functional group of the curable polymer.
  • an isocyanate-based curing agent, a melamine resin, a silicate compound, an isocyanate group-containing silane compound and the like can be preferably exemplified. ..
  • amino-based curing agents and epoxy-based curing agents are used for carboxyl group-containing fluoropolymers
  • carbonyl group-containing curing agents, epoxy-based curing agents, and acid anhydride-based curing agents are used for amino group-containing fluoropolymers. Is usually adopted.
  • curing agent examples include the polyisocyanate compound described in the composition (3).
  • the content of the curing agent in the composition (5) is preferably in the range of 0.1 to 5 equivalents with respect to 1 equivalent of the curable functional group in the fluoropolymer containing a curable functional group, and is preferably 0.5. More preferably, it is in the range of ⁇ 1.5 equivalents.
  • the composition (5) may contain an inorganic pigment.
  • the inorganic pigment is not particularly limited as long as it is a generally known inorganic pigment, and for example, titanium oxide, zinc oxide, aluminum oxide, iron oxide, silicon oxide, barium sulfate, calcium carbonate, carbon black, titanium yellow, chrome green, etc. Examples include ultramarine, aluminum powder, mica, barium carbonate, and talc. Of these, titanium oxide and carbon black are preferable because they have good dispersibility in paint and good shielding property against ultraviolet rays.
  • the content of the inorganic pigment is preferably in the range of 10 to 150 parts by mass with respect to 100 parts by mass of the fluoropolymer in the composition (5). When the content of the inorganic pigment is within the above range, it can be well dispersed in the composition (5).
  • the content of the inorganic pigment is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, more preferably 130 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the curable functional group-containing fluoropolymer. More preferred.
  • the composition (5) may further contain other components if necessary.
  • other components include other resins and additives.
  • the additives include a dispersant for improving the dispersibility of an inorganic pigment, a precipitation stabilizer for preventing the precipitation of an inorganic pigment, and a curing accelerator. Examples thereof include defoaming agents, leveling agents, ultraviolet absorbers, light stabilizers, thickeners, adhesion improvers, matting agents, and hydrophilic agents.
  • composition (5) examples include the Zeffle GK series (GK-500, GK-510, GK-550, GK-570, GK-580, etc.) manufactured by Daikin Industries, Ltd.
  • composition (5) examples include the Zeffle SE series (SE-300A, SE-310, SE-405, SE-600, SE-700, SE-3183D, etc.) manufactured by Daikin Industries, Ltd. ..
  • the composition (5) can be, for example, the coating composition described in Japanese Patent No. 5708740.
  • the surface modifier can be applied to all or part of the tire (eg, grooves, treads, carcass, sidewalls, beads, two or more of these parts).
  • Conventionally known methods and conditions can be adopted as a method for applying (or painting) the surface modifier to the tire.
  • a method of forming a coating film on a tire (or a rubber composition for a tire) by a coating method such as dip coating, spin coating, spray coating, roll coating, flow coating, roller, brush, gravure screen printing, and then drying.
  • a coating method such as dip coating, spin coating, spray coating, roll coating, flow coating, roller, brush, gravure screen printing, and then drying.
  • a method of depositing a surface modifier on a tire (or a rubber composition for a tire) by vapor deposition (eg, vacuum vapor deposition), sputtering, CVD (eg, plasma CVD, optical CVD, thermal CVD) or the like can be mentioned.
  • CVD eg, plasma CVD, optical CVD, thermal CVD
  • a method may be used in which the tire rubber composition is released from the mold release surface containing the surface modifier and the surface modifier is transferred to the tire rubber composition.
  • Tire A tire is a tire whose surface has been modified with the surface modifier.
  • the portion modified by the surface modifier may be the entire tire surface, or a part of the tire surface (for example, a groove, a tread, a carcass, a sidewall, a bead, or two or more of these portions). There may be.
  • the rubber composition (rubber composition for tires) that forms a tire usually contains a diene-based rubber.
  • the diene rubber is not particularly limited, and for example, natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), isoprene rubber (IR), styrene isoprene rubber (SIR), and isoprene butadiene rubber (IBR). ), Chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR).
  • NR, SBR, BR, and IR are preferable. Further, two or more kinds of rubber may be mixed and used.
  • the amount of styrene bond is not particularly limited, but can be in the range of, for example, 5 to 60% by mass, preferably 5 to 40% by mass, and the amount of vinyl bond is, for example, 20 to 80% by mass, preferably 20 to 80% by mass. It can be in the range of 30 to 70% by mass.
  • the amount of styrene bond can be measured by 1H-NMR.
  • the vinyl bond amount is not particularly limited, but can be, for example, in the range of 1 to 95% by mass, preferably 5 to 50% by mass.
  • the amount of vinyl bond can be measured by 1H-NMR.
  • the end of the diene rubber may be modified with a denaturing agent.
  • the denaturant include the formula: (In the formula, R 61 to R 68 are C 1-6 alkyl groups or C 6-12 aryl groups, which may be the same or different from each other.
  • X 61 and X 64 are dienes. system rubber active terminal functional group reactive with the, C 1-6 alkyl group, or a C 6-12 aryl group, X 61 and X 64 .X good be different be the same as each other 62 Is a functional group capable of reacting with the active terminal of the diene rubber.
  • X 63 is a group containing a repeating unit of 2 to 20 alkylene glycols.
  • M6 is an integer of 3 to 200, and n6 is 0 to 200.
  • K6 is an integer from 0 to 200.
  • Compound represented by, formula: (In the formula, R 69 to R 76 are C 1-6 alkyl groups or C 6-12 aryl groups, which may be the same or different from each other.
  • X 65 to X 68 are dienes. It is a functional group that can react with the active terminal of the rubber system.)
  • X 69 to X 71 are dienes. It is a functional group that can react with the active terminal of the rubber system.
  • S6 is an integer of 1 to 18.) Examples thereof include compounds represented by.
  • Examples of the C 1-6 alkyl group constituting R 61 to R 68 , X 61 , and X 64 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl. Group etc. can be mentioned.
  • Examples of the C 6-12 aryl group include a phenyl group and a methylphenyl group. Of these alkyl and aryl groups, a methyl group is particularly preferred.
  • the functional group capable of reacting with the active terminal of the diene-based rubber constituting X 61 , X 62 , and X 64 is not particularly limited, but is a hydrocarbon group containing a C 1-5 alkoxy group and a 2-pyrrolidnyl group. And a group having 4 to 12 carbon atoms containing an epoxy group is preferable.
  • Examples of the C 1-5 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Of these, a methoxy group is preferable.
  • hydrocarbon group containing a 2-pyrrolidnyl group a group represented by the following formula is preferably mentioned.
  • j6 is an integer of 2 to 10. In particular, j6 is preferably 2.
  • Examples of the group having an epoxy group having 4 to 12 carbon atoms include a group represented by the following formula. -Z 61- Z 62- E
  • Z 61 is a C 1-10 alkylene group or an alkylarylene group
  • Z 62 is a methylene group, a sulfur atom or an oxygen atom
  • E is a substituted hydrocarbon having an epoxy group and having 2 to 10 carbon atoms. It is a group.
  • those in which Z 62 is an oxygen atom are preferable, those in which Z 62 is an oxygen atom and E is a glycidyl group are more preferable
  • Z 61 is a C 3 alkylene group
  • Z 62 is an oxygen. It is particularly preferable that the atom is an atom and E is a glycidyl group.
  • X 61 and X 64 are preferably an epoxy group-containing group having 4 to 12 carbon atoms or a C 1-6 alkyl group, and X 62 is preferably an epoxy group containing an epoxy group. A group having 4 to 12 carbon atoms is preferable.
  • t6 is an integer of 2 to 20
  • P 6 is a C 2-10 alkylene group or an alkyl arylene group
  • R 80 is a hydrogen atom or a methyl group
  • Q 6 is a C 1-10 alkoxy group or. It is an aryloxy group.
  • an integer t6, 2 ⁇ 8 P 6 is a C 3 alkylene group
  • an R 80 is a hydrogen atom
  • Q 6 are those preferably a methoxy group.
  • M6 is an integer of 3 to 200, preferably 20 to 150, and more preferably 30 to 120.
  • n6 is an integer of 0 to 200, preferably 0 to 150, and more preferably 0 to 120.
  • k is an integer of 0 to 200, preferably 0 to 150, and more preferably 0 to 120.
  • the total number of m6, n6, and k6 is preferably 400 or less, more preferably 300 or less, and particularly preferably 250 or less.
  • R 69 to R 79 and X 65 to X 71 can be the same as R 61 to R 68 and X 61 to X 64 .
  • the Mooney viscosity (ML 1 + 4 ) of the diene rubber is not particularly limited, but can be, for example, in the range of 10 to 150, preferably 20 to 120. Mooney viscosity is measured at 100 ° C. according to JIS K6300 (1994).
  • fillers eg silica, carbon black, talc, clay, calcium carbonate
  • cross-linking agents eg sulfur, sulfur halides, organic peroxides
  • Kinondioximes organic polyvalent amine compounds, alkylphenol resins having methylol groups
  • cross-linking accelerators eg, sulfenamide-based cross-linking promoters, guanidine-based cross-linking promoters, thiourea-based cross-linking promoters, thiazole-based cross-linking promoters
  • Agents thiuram-based cross-linking accelerators, dithiocarbamic acid-based cross-linking accelerators, xanthogenic acid-based cross-linking accelerators
  • cross-linking activators eg, higher fatty acids such as stearic acid, zinc oxide
  • antiaging agents activators, process oils
  • process oils Example: Paraffin-based, aromatic, naphthen-
  • each component may be kneaded according to a conventional method.
  • a compounding agent excluding a cross-linking agent and a cross-linking accelerator and a rubber component the kneaded product is mixed with a cross-linking agent and a cross-linking agent.
  • the desired composition can be obtained by mixing the cross-linking accelerator.
  • the kneading temperature of the compounding agent excluding the cross-linking agent and the cross-linking accelerator and the rubber component is preferably in the range of 80 to 200 ° C., more preferably 120 to 180 ° C.
  • the kneading time is preferably in the range of 30 seconds to 30 minutes.
  • Mixing of the kneaded product with the cross-linking agent and the cross-linking accelerator is usually carried out after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.
  • a method of adding a compounding agent to solid rubber and kneading it dry kneading method
  • a method of adding a compounding agent to a rubber solution and coagulating and drying it a method of coagulating and drying. Any of the wet kneading method) may be used.
  • the rubber crosslinked product of the present invention can be obtained by cross-linking the above-mentioned polymer composition.
  • the cross-linking method is not particularly limited and may be selected according to the shape, size and the like of the rubber cross-linked product.
  • the polymer composition may be filled in a mold and crosslinked at the same time as molding by heating, or the polymer composition previously molded may be heated and crosslinked.
  • the crosslinking temperature is preferably in the range of 120 to 200 ° C., more preferably 140 to 180 ° C., and the crosslinking time is usually in the range of 1 to 120 minutes.
  • the rubber crosslinked product even if the surface is crosslinked, it may not be sufficiently crosslinked to the inside, so further heating may be performed for secondary crosslinking.
  • a general method used for rubber cross-linking such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
  • the method of modifying the surface of a tire includes a step of applying (or painting) the surface modifier to the surface of the tire.
  • the application method the application method described in the above-mentioned "surface modifier" can be adopted.
  • compositions (1)-(5) for modifying the surface of a tire
  • surface modifier for modifying the surface of a tire
  • the following formula: 0.024 mmol of the polyorganosiloxane represented by (1) was added in the form of a 40 mass% xylene solution, and the reaction was carried out at 65 ° C. for 20 minutes. Then, as a polymerization inhibitor, methanol in an amount corresponding to twice the mole of n-butyllithium used in the polymerization reaction was added to obtain a solution containing a hydroxyl group-modified styrene-butadiene rubber.
  • the obtained hydroxyl group-modified solution-polymerized styrene-butadiene rubber has a bonded styrene content of 21% by mass, a vinyl bond content of the butadiene unit portion of 63% by mass, a Mooney viscosity (ML1 + 4,100 ° C.) 62, and a glass transition temperature (Tg). ) -25 ° C., and a hydroxyl group was introduced as a functional group.
  • the terminal-modified butadiene rubber was obtained by vacuum drying for 24 hours.
  • the kneaded product was cooled to room temperature and then kneaded again in a lavender type mixer for 3 minutes with 110 ° C. as the starting temperature, and then the kneaded product was discharged from the mixer.
  • a cross-linking accelerator cyclohexyl-2-benzothiazolyl sulphenamide (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) -G ”
  • 2 parts and 4 parts of diphenylguanidine mixture of 2 parts of diphenylguanidine (trade name" Noxeller D ") manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
  • a sheet-shaped rubber composition is obtained and used as a sample.
  • the rubber composition was press-crosslinked at 160 ° C. for 20 minutes to prepare a crosslinked test piece.
  • process oil (trade name "Aromax T-DAE”, manufactured by JX Nikko Nisseki Energy Co., Ltd.), and silane coupling agent: 3-octanoylthio-1-propyltriethoxysilane (trade name "NXTsilane”, Add 6.4 parts of Momentive Performance Materials (manufactured by Solvay) and knead for 1.5 minutes with 110 ° C as the starting temperature, then 20 parts of silica (trade name "Zeosil1165MP", manufactured by Solvay), carbon black (trade name "" Seest 3 ”, manufactured by Tokai Carbon Co., Ltd.) 10 parts, zinc oxide 3 parts, stearic acid 2 parts, and anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (trade name) Two parts of "Nocrack 6C” (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
  • the temperature of the kneaded product at the end of kneading was 150 ° C.
  • the kneaded product was cooled to room temperature and then kneaded again in a lavender type mixer for 3 minutes with 110 ° C. as the starting temperature, and then the kneaded product was discharged from the mixer.
  • the ozone resistance (the size of cracks in the test piece) was evaluated according to the following criteria. 1. 1. The cracks cannot be seen with the naked eye, but the cracks can be seen with a 10x magnifying glass. 2. 2. The cracks can be seen with the naked eye. 3. 3. Those with deep cracks and relatively large cracks (less than 1 mm). 4. Those with deep and large cracks (1 mm or more and less than 3 mm). Those with cracks of 5.3 mm or more or those that are likely to cause cutting.
  • Example 1 The following perfluoropolyether group-containing trimethoxysilane compound: by the same method as in Synthesis Example 13 of Japanese Patent No. 6332358: CF 3 O (CF 2 CF 2 O) 22 (CF 2 O) 26 CF 2 CH 2 OCH 2 CH 2 CH 2 Si (CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ) 3 Got A surface treatment agent prepared by dissolving the obtained compound in hydrofluoroether (Novec HFE7200, manufactured by 3M Ltd.) so as to have a concentration of 20 wt%. The surface treatment agent prepared above was vacuum-deposited on the SBR sheet and the BR sheet.
  • the treatment conditions for vacuum vapor deposition were a pressure of 3.0 ⁇ 10 -3 Pa, and 2 mg of a surface treatment agent was deposited per SBR sheet and one BR sheet (55 mm ⁇ 100 mm) as a guide. Then, the SBR sheet with a thin-film deposition film and the BR sheet were heated to form a surface treatment layer.
  • the obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 124 and an ozone resistance of 2.
  • Example 2 By the same method as in Example 1 of Japanese Patent No. 6056935, a perfluoropolyether-containing alcohol represented by an average composition: CF 3 CF 2 CFO (CF 2 CF 2 CF 2 O) 14 CF 2 CF 2 CH 2 OH was prepared. The composition to be contained was obtained. This composition was added to ethyl acetate so that the solid content concentration became 20% by mass, and the mixture was dissolved by stirring at 25 ° C. for 60 minutes. The SBR sheet or BR sheet was immersed in this solution and dried at 70 ° C. for 5 minutes. Then, it was irradiated with ultraviolet rays of 500 mJ / cm 2 . The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 120 and an ozone resistance of 2.
  • Example 3 Containing perfluoropolyether represented by average composition: CF 3 O (CF 2 CF 2 O) 15 (CF 2 O) 15 CF 2 CF 2 CH 2 OH by the same method as in Example 1 of Japanese Patent No. 6056935.
  • a composition containing an alcohol was obtained. This composition was added to ethyl acetate so that the solid content concentration became 20% by mass, and the mixture was dissolved by stirring at 25 ° C. for 60 minutes.
  • the SBR sheet or BR sheet was immersed in this solution and dried at 70 ° C. for 5 minutes. Then, it was irradiated with ultraviolet rays of 500 mJ / cm 2 .
  • the obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 119 and an ozone resistance of 2.
  • Example 4 A composition containing a perfluoropolyether-containing alcohol represented by an average composition of F (CFCF 3 CF 2 O) 14 CF 2 CF 2 CH 2 OH is obtained by the same method as in Example 1 of Japanese Patent No. 6056935. It was. This composition was added to ethyl acetate so that the solid content concentration became 20% by mass, and the mixture was dissolved by stirring at 25 ° C. for 60 minutes. The SBR sheet or BR sheet was immersed in this solution and dried at 70 ° C. for 5 minutes. Then, it was irradiated with ultraviolet rays of 500 mJ / cm 2 . The water repellency of the obtained SBR and the crosslinked rubber test piece of BR was 118, and the ozone resistance was 2.
  • a clear coating material containing a hydrophilic group-containing polyisocyanate (Baihijour XP 2700 (manufactured by Sumika Bayer Urethane Co., Ltd.)) and water was obtained.
  • This clear paint was applied to an SBR sheet or BR sheet with a bar coater (No. 24) in the same manner as in paragraph 0905 of the same patent, and dried at 20 ° C. for 7 days.
  • the obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 109 and an ozone resistance of 1.
  • Example 6 The SBR sheet or BR sheet was dipped and coated on the paint P1 shown in Table 1 of Japanese Patent No. 6098751, and after being withdrawn, dried at 110 ° C. for 3 minutes.
  • the obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 111 and an ozone resistance of 1.
  • Example 7 The SBR sheet or BR sheet was dipped and coated on Zeffle SE-700 manufactured by Daikin Industries, Ltd., and dried at 20 ° C. for 7 days after being withdrawn.
  • the obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 109 and an ozone resistance of 1.
  • Example 8 Duranate TPA-100 manufactured by Asahi Kasei Chemicals Co., Ltd. is mixed with Zeffle GK-570 manufactured by Daikin Industries, Ltd. at a ratio of 100: 13.6 (mass ratio), and the SBR sheet or BR sheet is dipped and coated. It was dried for 3 minutes. The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 111 and an ozone resistance of 1.
  • the BR sheet had a water repellency of 104 and an ozone resistance of 5.
  • the surface-coated SBR and BR crosslinked rubber test pieces are superior in water repellency and ozone resistance, and have water repellency and ozone resistance as compared with the untreated Comparative Examples 1 and 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The problem of the present invention is to provide a tire surface modifier and a surface modification method with which both water repellent properties and ozone resistant properties can be achieved. The aforementioned problem can be solved by a tire surface modifier comprising any of the following compositions (1)-(5): (1) a composition containing a perfluoropolyether group-containing silane compound; (2) a composition containing a carbon-carbon double bond-containing perfluoropolyether compound; (3) a composition containing water, a polyisocyanate compound, and composite polymer particles which comprise a fluoropolymer and an acrylic polymer and in which either one or both of the fluoropolymer and the acrylic polymer have a hydroxyl group and a hydrolyzable silyl group; (4) a composition containing fluororesin particles, a curable silicone resin, and water; and (5) a composition containing a fluoropolymer which includes a polymerization unit based on a fluorine-containing monomer and further includes a polymerization unit based on at least one curable functional group-containing monomer selected from the group consisting of hydroxyl group-containing monomers, carboxyl group-containing monomers, acid anhydride monomers, amino group-containing monomers, and silicone-based vinyl monomers.

Description

タイヤ、その表面改質剤及び表面改質方法Tires, their surface modifiers and surface modifiers
　本開示は、タイヤ、その表面改質剤及び表面改質方法に関する。 This disclosure relates to a tire, its surface modifier and a surface modification method.
　タイヤの意匠性又は撥水性を向上するため、タイヤの表面を改質することが知られている。例えば、特許文献１には、アクリルフッ素樹脂及びオルガノポリシロキサンを含有する水中油滴型乳化組成物からなるタイヤ用保護艶出し剤が記載されている。また、特許文献２及び３には、タイヤのトレッド陸部を区画する溝又は窪みの全表面、及びこれらに少なくともショルダ域の全表面が、フッ素樹脂を用いた撥水性ポリマーのコーティングからなるタイヤが記載されている。 It is known to modify the surface of a tire in order to improve the design or water repellency of the tire. For example, Patent Document 1 describes a protective polish for tires, which comprises an oil-in-water emulsified composition containing an acrylic fluororesin and an organopolysiloxane. Further, Patent Documents 2 and 3 describe a tire in which the entire surface of a groove or a recess for partitioning a tread land portion of the tire, and at least the entire surface of the shoulder region, are coated with a water-repellent polymer using a fluororesin. Has been described.
特開平５－９８２１３号公報Japanese Unexamined Patent Publication No. 5-98213 特開平５－２０８４５４号公報Japanese Unexamined Patent Publication No. 5-208454 特開平１０－９０３号公報Japanese Unexamined Patent Publication No. 10-903
　本開示は、撥水性及び耐オゾン性を両立させることができる、タイヤの表面改質剤及び表面改質方法を提供することを目的とする。
　また、本開示は、撥水性及び耐オゾン性を両立したタイヤを提供することを目的とする。 An object of the present disclosure is to provide a tire surface modifier and a surface modification method capable of achieving both water repellency and ozone resistance.
Another object of the present disclosure is to provide a tire having both water repellency and ozone resistance.
　本開示は、次の態様を包含する。
項１．
　下記（１）～（５）のいずれかの組成物からなる、タイヤの表面改質剤：
（１）パーフルオロポリエーテル基含有シラン化合物を含有する組成物；
（２）炭素－炭素二重結合含有パーフルオロポリエーテル化合物を含有する組成物；
（３）フルオロポリマー及びアクリルポリマーからなり、フルオロポリマー及びアクリルポリマーのいずれか一方又は両方が水酸基及び加水分解性シリル基を有する複合重合体粒子と、ポリイソシアネート化合物と、水とを含有する組成物；
（４）フッ素樹脂粒子と、硬化性シリコーン樹脂と、水とを含有する組成物；
（５）含フッ素単量体に基づく重合単位と、水酸基含有単量体、カルボキシル基含有単量体、酸無水物単量体、アミノ基含有単量体、及びシリコーン系ビニル単量体からなる群より選択される少なくとも一種の硬化性官能基含有単量体に基づく重合単位とを含むフッ素ポリマーを含有する組成物。
項２．
　組成物（１）からなり、
　パーフルオロポリエーテル基含有シラン化合物が、下記式：
－(ＯＣ４Ｆ８)ａ－(ＯＣ３Ｆ６)ｂ－(ＯＣ２Ｆ４)ｃ－(ＯＣＦ２)ｄ－
（式中、
　ａ及びｂは、それぞれ独立して、０～３０の整数であり、
　ｃ及びｄは、それぞれ独立して、１～２００の整数であり、
　ａ、ｂ、ｃ、及びｄの和は、３以上の整数であり、
　ｃ／ｄ比が、０．２以上０．９未満の範囲内であり、
　添字ａ、ｂ、ｃ、又はｄを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。）
で表されるパーフルオロポリエーテル基を含有するシラン化合物である、
項１に記載の表面改質剤。
項３．
　パーフルオロポリエーテル基含有シラン化合物が、下記式（1-1）～（1-6）：
Figure JPOXMLDOC01-appb-C000003
 ［式中：
　ＰＦＰＥは、各出現においてそれぞれ独立して、－(ＯＣ４Ｆ８)ａ－(ＯＣ３Ｆ６)ｂ－(ＯＣ２Ｆ４)ｃ－(ＯＣＦ２)ｄ－を表し、ａ及びｂは、それぞれ独立して、０～３０の整数であり、ｃ及びｄは、それぞれ独立して、１～２００の整数であり、ａ、ｂ、ｃ、及びｄの和は、３以上の整数であり、ｃ／ｄ比が、０．２以上０．９未満の範囲内であり、添字ａ、ｂ、ｃ、又はｄを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個又はそれ以上のフッ素原子により置換されていてもよいＣ１－１６アルキル基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、水素原子又はＣ１－２２アルキル基を表し；
　Ｒ２は、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
　Ｒ１１は、各出現においてそれぞれ独立して、水素原子又はハロゲン原子を表し；
　Ｒ１２は、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；
　ｎは、(－ＳｉＲ１ ｎＲ２ ３－ｎ)単位毎に独立して、０～３の整数であり；
　ただし、式（1-1）、（1-2）、（1-3）、及び（1-4）において、少なくとも１つのＲ２が存在し；
　Ｘ１は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
　Ｘ２は、各出現においてそれぞれ独立して、単結合又は２価の有機基を表し；
　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
　αは、それぞれ独立して、１～９の整数であり；
　α’は、それぞれ独立して、１～９の整数であり；
　Ｘ５は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
　βは、それぞれ独立して、１～９の整数であり；
　β’は、それぞれ独立して、１～９の整数であり；
　Ｘ７は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
　γは、それぞれ独立して、１～９の整数であり；
　γ’は、それぞれ独立して、１～９の整数であり；
　Ｒａは、各出現においてそれぞれ独立して、－Ｚ－ＳｉＲ７１ ｐＲ７２ ｑＲ７３ ｒを表し；
　Ｚは、各出現においてそれぞれ独立して、酸素原子又は２価の有機基を表し；
　Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
　Ｒａ’は、Ｒａと同意義であり；
　Ｒａ中、Ｚ基を介して直鎖状に連結されるＳｉは最大で５個であり；
　Ｒ７２は、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
　Ｒ７３は、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；
　ｐは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒは、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、一のＲａにおいて、ｐ、ｑ、及びｒの和は３であり、式（1-5）及び（1-6）において、少なくとも１つのＲ７２が存在し；
　Ｒｂは、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
　Ｒｃは、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；
　ｋは、各出現においてそれぞれ独立して、１～３の整数であり；
　ｌは、各出現においてそれぞれ独立して、０～２の整数であり；
　ｍは、各出現においてそれぞれ独立して、０～２の整数であり；
　ただし、γを付して括弧でくくられた単位において、ｋ、ｌ、及びｍの和は３である。］
のいずれかで表される化合物である、項２に記載の表面改質剤。
項４．
　パーフルオロポリエーテル基含有シラン化合物が式（1-1）、（1-2）、（1-3）、（1-5）、及び（1-6）のいずれかで表され、α、α’、β、β’、γ、及びγ’が１であり、式（1-3）のｎが０である、項３に記載の表面改質剤。
項５．
　組成物（２）からなり、
　炭素－炭素二重結合含有パーフルオロポリエーテル化合物が、
　（2A）ジイソシアネートの三量体であるポリイソシアネート
のイソシアネート基に、
　（2B）活性水素を有する化合物
から活性水素が脱離した基が結合した化合物であり、
　成分（2B）が、（2B-1）活性水素を有するパーフルオロポリエーテル、（2B-2）活性水素を有するシラン化合物、及び（2B-3）活性水素と炭素－炭素二重結合とを有する化合物であり、
　成分（2A）中のイソシアネート基のモル数と、成分（2B）の合計のモル数が等しく、
　成分（2A）中のイソシアネート基９モルに対して、
　成分（2B-1）のモル数が、０．１～２モルの範囲内、
　成分（2B-2）のモル数が、０．０５～２モルの範囲内、及び
　成分（2B-3）のモル数が、５～８．８５モルの範囲内
にある化合物である、
請求項１に記載の表面改質剤。
項６．
　成分（2B-2）が、下記式（2B-2-i）～（2B-2-iii）：
Figure JPOXMLDOC01-appb-C000004
 ［式中、
　Ｒ２１１、Ｒ２１２、Ｒ２１３、Ｒ２１４、及びＲ２１５は、それぞれ独立して、アルキル基又はアリール基であり；
　Ｒ２１６は、２価の有機基であり；
　ｌ２及びｎ２は、それぞれ独立して、０又は１であり；
　ｍ２は、１～５００の整数であり；
　ｏ２は、１～２０の整数であり；
　ｐ２は、０又は１である。］
から選択される少なくとも一種であり、及び
　成分（2B-1）と成分（2B-2）の数平均分子量の比が１：３～３：１である、項５に記載の表面改質剤。
項７．
　組成物（３）からなり、
　複合重合体粒子が、フルオロポリマー及びアクリルポリマーを同一粒子内に含有しており、
　フルオロポリマーが、フルオロポリマーを構成する全重合体に対して７０モル％以上のビニリデンフルオライド単位を含む、項１に記載の表面改質剤。
項８．
　組成物（４）からなり、
　フッ素樹脂粒子の平均粒子径が、０．２～２００ｎｍの範囲内であり、
　硬化性シリコーン樹脂の含有量が、フッ素樹脂粒子に対して０．１～２５０質量％の範囲内である、
項１に記載の表面改質剤。
項９．
　組成物（４）が、フッ素樹脂粒子に対して３～１５０質量％の界面活性剤をさらに含有し、
　フッ素樹脂粒子は、ポリテトラフルオロエチレン、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体及びテトラフルオロエチレン／ヘキサフルオロプロピレン共重合体からなる群より選択される少なくとも一種からなり、
　硬化性シリコーン樹脂は、１分子中に少なくとも２個の、ケイ素原子に結合した硬化反応性基を有する、２３℃における粘度が２０～１，０００，０００ｍＰａ・ｓの範囲内であるオルガノポリシロキサンからなる、
項８に記載の表面改質剤。
項１０．
　組成物（５）からなり、
　フッ素ポリマーが、テトラフルオロエチレンに基づく重合単位と、水酸基含有単量体に基づく重合単位とを含む、
項１に記載の表面改質剤。
項１１．
　項１～１０のいずれか一項に記載の表面改質剤で表面が改質された、タイヤ。
項１２．
　項１～１０のいずれか一項に記載の表面改質剤をタイヤの表面に適用する工程を含む、タイヤの表面を改質する方法。
項１３．
　タイヤの表面を改質するための、項１～１０のいずれか一項に記載の組成物、又は表面改質剤の使用。 The present disclosure includes the following aspects.
Item 1.
A tire surface modifier comprising any of the following compositions (1) to (5):
(1) A composition containing a perfluoropolyether group-containing silane compound;
(2) A composition containing a carbon-carbon double bond-containing perfluoropolyether compound;
(3) A composition comprising a composite polymer particle composed of a fluoropolymer and an acrylic polymer and one or both of the fluoropolymer and the acrylic polymer having a hydroxyl group and a hydrolyzable silyl group, a polyisocyanate compound, and water. ;
(4) A composition containing fluororesin particles, a curable silicone resin, and water;
(5) It is composed of a polymerization unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. A composition containing a fluoropolymer containing a polymerization unit based on at least one curable functional group-containing monomer selected from the group.
Item 2.
Consists of composition (1)
The perfluoropolyether group-containing silane compound has the following formula:
-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
(During the ceremony,
a and b are independently integers from 0 to 30 and
c and d are independently integers from 1 to 200, respectively.
The sum of a, b, c, and d is an integer of 3 or more.
The c / d ratio is in the range of 0.2 or more and less than 0.9.
The order of existence of each repeating unit in parentheses with the subscripts a, b, c, or d is arbitrary in the equation. )
A silane compound containing a perfluoropolyether group represented by.
Item 2. The surface modifier according to Item 1.
Item 3.
The perfluoropolyether group-containing silane compound has the following formulas (1-1) to (1-6):
Figure JPOXMLDOC01-appb-C000003
 [During the ceremony:
PFPE independently represents-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- in each appearance, where a and b are. Each independently is an integer of 0 to 30, c and d are independently integers of 1 to 200, and the sum of a, b, c, and d is an integer of 3 or more. The order of existence of each repeating unit in which the c / d ratio is in the range of 0.2 or more and less than 0.9 and is enclosed in parentheses with the subscripts a, b, c, or d is arbitrary in the formula. Is;
Rf represents a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms at each appearance;
R 1 independently represents a hydrogen atom or a C 1-22 alkyl group at each appearance;
R 2 represents a hydroxyl group or a hydrolyzable group independently at each appearance;
R 11 independently represents a hydrogen atom or a halogen atom at each appearance;
R 12 independently represents a hydrogen atom or a lower alkyl group at each appearance;
n is, (- SiR 1 n R 2 3-n) independently for each unit, an integer from 0 to 3;
However, in equations (1-1), (1-2), (1-3), and (1-4), at least one R 2 is present;
X 1 independently represents a single bond or a 2- to 10-valent organic group;
X 2 independently represents a single bond or divalent organic group at each appearance;
t is an integer from 1 to 10 independently for each occurrence;
α is an integer from 1 to 9 independently of each other;
α'is an integer from 1 to 9 independently of each other;
X 5 each independently represents a single bond or a 2-10 valent organic group;
β is an integer from 1 to 9 independently of each other;
β'is an integer from 1 to 9 independently of each other;
X 7 each independently represents a single bond or a 2-10 valent organic group;
γ is an integer from 1 to 9 independently of each other;
γ'is an integer from 1 to 9 independently of each other;
R a independently represents −Z—SiR 71 p R 72 q R 73 r ;
Z independently represents an oxygen atom or a divalent organic group at each appearance;
R 71 is independently at each occurrence, represents a R a ';
R a 'is located in the same meaning as R a;
In Ra, a maximum of 5 Sis are linearly linked via a Z group;
R 72 independently represents a hydroxyl group or a hydrolyzable group at each appearance;
R 73 independently represents a hydrogen atom or lower alkyl group at each appearance;
p is an integer from 0 to 3 independently for each occurrence;
q is an integer from 0 to 3 independently for each occurrence;
r is an integer from 0 to 3 independently for each occurrence;
However, in one Ra, the sum of p, q, and r is 3, and in equations (1-5) and (1-6), there is at least one R 72 ;
R b represents a hydroxyl group or a hydrolyzable group independently at each appearance;
R c independently represents a hydrogen atom or a lower alkyl group at each appearance;
k is an integer of 1 to 3 independently for each occurrence;
l is an integer from 0 to 2 independently for each occurrence;
m is an integer from 0 to 2 independently for each occurrence;
However, the sum of k, l, and m is 3 in the unit with γ and enclosed in parentheses. ]
Item 2. The surface modifier according to Item 2, which is a compound represented by any of the above.
Item 4.
The perfluoropolyether group-containing silane compound is represented by any of the formulas (1-1), (1-2), (1-3), (1-5), and (1-6), and is α, α. Item 3. The surface modifier according to Item 3, wherein ′, β, β ′, γ, and γ ′ are 1, and n of the formula (1-3) is 0.
Item 5.
Consists of composition (2)
The carbon-carbon double bond-containing perfluoropolyether compound
(2A) To the isocyanate group of polyisocyanate, which is a trimer of diisocyanate,
(2B) A compound in which a group in which active hydrogen is eliminated from a compound having active hydrogen is bonded.
Component (2B) has (2B-1) perfluoropolyether having active hydrogen, (2B-2) silane compound having active hydrogen, and (2B-3) active hydrogen and carbon-carbon double bond. Is a compound
The number of moles of isocyanate groups in component (2A) is equal to the total number of moles of component (2B).
For 9 mol of isocyanate groups in component (2A)
The number of moles of the component (2B-1) is in the range of 0.1 to 2 moles,
A compound in which the number of moles of the component (2B-2) is in the range of 0.05 to 2 mol and the number of moles of the component (2B-3) is in the range of 5 to 8.85 mol.
The surface modifier according to claim 1.
Item 6.
The component (2B-2) has the following formulas (2B-2-i) to (2B-2-iii):
Figure JPOXMLDOC01-appb-C000004
 [During the ceremony,
R 211 , R 212 , R 213 , R 214 , and R 215 are independently alkyl or aryl groups;
R216 is a divalent organic group;
l2 and n2 are independently 0 or 1;
m2 is an integer from 1 to 500;
o2 is an integer from 1 to 20;
p2 is 0 or 1. ]
Item 5. The surface modifier according to Item 5, wherein the surface modifier is at least one selected from the above, and the ratio of the number average molecular weight of the component (2B-1) to the component (2B-2) is 1: 3 to 3: 1.
Item 7.
Consists of composition (3)
The composite polymer particles contain a fluoropolymer and an acrylic polymer in the same particles.
Item 2. The surface modifier according to Item 1, wherein the fluoropolymer contains 70 mol% or more of vinylidene fluoride units based on the total polymer constituting the fluoropolymer.
Item 8.
Consists of composition (4)
The average particle size of the fluororesin particles is in the range of 0.2 to 200 nm.
The content of the curable silicone resin is in the range of 0.1 to 250% by mass with respect to the fluororesin particles.
Item 2. The surface modifier according to Item 1.
Item 9.
The composition (4) further contains 3 to 150% by mass of a surfactant with respect to the fluororesin particles.
The fluororesin particles consist of at least one selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers and tetrafluoroethylene / hexafluoropropylene copolymers.
The curable silicone resin is derived from an organopolysiloxane having at least two curable reactive groups bonded to silicon atoms in one molecule and having a viscosity at 23 ° C. in the range of 20 to 1,000,000 mPa · s. Become,
Item 8. The surface modifier according to Item 8.
Item 10.
Consists of composition (5)
The fluoropolymer contains a polymerization unit based on tetrafluoroethylene and a polymerization unit based on a hydroxyl group-containing monomer.
Item 2. The surface modifier according to Item 1.
Item 11.
A tire whose surface has been modified with the surface modifier according to any one of Items 1 to 10.
Item 12.
A method for modifying the surface of a tire, which comprises a step of applying the surface modifier according to any one of Items 1 to 10 to the surface of the tire.
Item 13.
Use of the composition according to any one of Items 1 to 10 or a surface modifier for modifying the surface of a tire.
　本開示によれば、撥水性及び耐オゾン性を両立させることができる、タイヤの表面改質剤及び表面改質方法が提供される。また、本開示によれば、撥水性及び耐オゾン性を両立したタイヤが提供される。 According to the present disclosure, a tire surface modifier and a surface modification method capable of achieving both water repellency and ozone resistance are provided. Further, according to the present disclosure, a tire having both water repellency and ozone resistance is provided.
　本開示の前記概要は、本開示の各々の開示された実施形態又は全ての実装を記述することを意図するものではない。
　本開示の後記説明は、実例の実施形態をより具体的に例示する。
　本開示のいくつかの箇所では、例示を通してガイダンスが提供され、及びこの例示は、様々な組み合わせにおいて使用できる。
　それぞれの場合において、例示の群は、非排他的な、及び代表的な群として機能できる。
　本明細書で引用した全ての刊行物、特許及び特許出願はそのまま引用により本明細書に組み入れられる。 The above overview of the present disclosure is not intended to describe each disclosed embodiment or all implementations of the present disclosure.
The subsequent description of the present disclosure will more specifically exemplify an embodiment of an example.
Guidance is provided through illustrations in some parts of the disclosure, and the examples can be used in various combinations.
In each case, the illustrated group can function as a non-exclusive and representative group.
All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety.
用語
　本明細書中の記号及び略号は、特に限定のない限り、本明細書の文脈に沿い、本開示が属する技術分野において通常用いられる意味に理解できる。
　本明細書中、語句「含有する」は、語句「から本質的になる」、及び語句「からなる」を包含することを意図して用いられる。
　特に限定されない限り、本明細書中に記載されている工程、処理、又は操作は、室温で実施され得る。
　本明細書中、室温は、１０～４０℃の範囲内の温度を意味することができる。
　本明細書中、表記「Ｃｎ－ｍ」（ここで、ｎ、及びｍは、それぞれ、数である。）は、当業者が通常理解する通り、炭素数がｎ以上、且つｍ以下であることを表す。 Terms The symbols and abbreviations herein are in the context of this specification and can be understood as commonly used in the art to which this disclosure belongs, unless otherwise specified.
In the present specification, the phrase "contains" is used with the intention of including the phrase "consisting of" and the phrase "consisting of".
Unless otherwise specified, the steps, treatments, or operations described herein can be performed at room temperature.
In the present specification, room temperature can mean a temperature in the range of 10 to 40 ° C.
In the present specification, the notation "C nm " (where n and m are numbers, respectively) has a carbon number of n or more and m or less, as is usually understood by those skilled in the art. Represents that.
　本明細書中、特に断りのない限り、「ハロゲン原子」としては、例えば、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。 Unless otherwise specified in the present specification, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　本明細書中、「有機基」とは、有機化合物から１個の水素原子を除去して形成される基（１価の有機基）を意味する。
　当該「有機基」としては、例えば、
１個以上の置換基を有していてもよい炭化水素基、
１個以上の置換基を有していてもよい非芳香族複素環基
１個以上の置換基を有していてもよいヘテロアリール基、
シアノ基、
アルデヒド基、
ＲＯ－、
ＲＳ－、
ＲＣＯ－、
ＲＳＯ２－、
ＲＯＣＯ－、及び
ＲＯＳＯ２－
（これらの式中、Ｒは、独立して、
１個以上の置換基を有していてもよい炭化水素基、
１個以上の置換基を有していてもよい非芳香族複素環基、又は
１個以上の置換基を有していてもよいヘテロアリール基である）
が挙げられる。 In the present specification, the "organic group" means a group (monovalent organic group) formed by removing one hydrogen atom from an organic compound.
Examples of the "organic group" include
Hydrocarbon groups, which may have one or more substituents,
Non-aromatic heterocyclic group which may have one or more substituents Heteroaryl group which may have one or more substituents,
Cyanide group,
Aldehyde group,
RO-,
RS-,
RCO-,
RSO 2- ,
ROCO- and ROSO 2-
(In these equations, R is independent
Hydrocarbon groups, which may have one or more substituents,
A non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents).
Can be mentioned.
　「置換基」としては、例えば、ハロゲン原子、シアノ基、アミノ基、アルコキシ基、及びアルキルチオ基が挙げられる。なお、２個以上の置換基は、互いに同一であってもよく、異なっていてもよい。 Examples of the "substituent" include a halogen atom, a cyano group, an amino group, an alkoxy group, and an alkylthio group. The two or more substituents may be the same or different from each other.
　本明細書中、特に断りのない限り、「炭化水素基」としては、例えば、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、シクロアルカジエニル基などの脂肪族炭化水素基；アリール基、アラルキル基などの芳香族炭化水素基が挙げられる。 Unless otherwise specified, the "hydrocarbon group" in the present specification includes, for example, an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkazienyl group. Aromatic hydrocarbon groups such as aryl group and aralkyl group can be mentioned.
　本明細書中、特に断りのない限り、「アルキル基」としては、例えば、メチル、エチル、プロピル（ｎ－プロピル、イソプロピル）、ブチル（ｎ－ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル）、ペンチル、及びヘキシル等の、直鎖又は分岐鎖状のＣ１－３０アルキル基が挙げられる。 Unless otherwise specified, the "alkyl group" in the present specification includes, for example, methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), and the like. Examples thereof include linear or branched C 1-30 alkyl groups such as pentyl and hexyl.
　本明細書中、特に断りのない限り、「アルコキシ基」としては、例えば、メトキシ、エトキシ、プロポキシ（ｎ－プロポキシ、イソプロポキシ）、ブトキシ（ｎ－ブトキシ、イソブトキシ、ｓｅｃ－ブトキシ、ｔｅｒｔ－ブトキシ）、ペンチルオキシ、及びヘキシルオキシ等の、直鎖状又は分岐鎖状のＣ１－２０アルコキシ基が挙げられる。 Unless otherwise specified, the "alkoxy group" in the present specification includes, for example, methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy). , Pentyloxy, and hexyloxy, which are linear or branched chain C 1-20 alkoxy groups.
　本明細書中、特に断りのない限り、「アルキルチオ基」としては、例えば、メチルチオ、エチルチオ、プロピルチオ（ｎ－プロピルチオ、イソプロピルチオ）、ブチルチオ（ｎ－ブチルチオ、イソブチルチオ、ｓｅｃ－ブチルチオ、ｔｅｒｔ－ブチルチオ）、ペンチルチオ、及びヘキシルチオ等の、直鎖状又は分岐鎖状のＣ１－２０アルキルチオ基が挙げられる。 Unless otherwise specified, the "alkylthio group" in the present specification includes, for example, methylthio, ethylthio, propylthio (n-propylthio, isopropylthio), butylthio (n-butylthio, isobutylthio, sec-butylthio, tert-butylthio). ), Pentilthio, and hexylthio, which are linear or branched C 1-20 alkylthio groups.
　本明細書中、特に断りのない限り、「アリールオキシ基」としては、例えば、フェニルオキシ、及びナフチルオキシ等の、Ｃ６－１８アリールオキシ基が挙げられる。 Unless otherwise specified, examples of the "aryloxy group" in the present specification include C 6-18 aryloxy groups such as phenyloxy and naphthyloxy.
　本明細書中、特に断りのない限り、「アルケニル基」としては、例えば、ビニル、１－プロペン－１－イル、２－プロペン－１－イル、イソプロペニル、２－ブテン－１－イル、４－ペンテン－１－イル、及び５－ヘキセン－１－イル等の、直鎖状又は分岐鎖状のＣ２－２０アルケニル基が挙げられる。 Unless otherwise specified, the "alkenyl groups" in the present specification include, for example, vinyl, 1-propene-1-yl, 2-propen-1-yl, isopropenyl, 2-butene-1-yl, 4 Examples thereof include linear or branched C 2-20 alkenyl groups such as -pentene-1-yl and 5-hexene-1-yl.
　本明細書中、特に断りのない限り、「アルキニル基」としては、例えば、エチニル、１－プロピン－１－イル、２－プロピン－１－イル、４－ペンチン－１－イル、及び５－ヘキシン－１－イル等の、直鎖状又は分岐鎖状のＣ２－２０アルキニル基が挙げられる。 Unless otherwise specified, the "alkynyl group" in the present specification includes, for example, ethynyl, 1-propyne-1-yl, 2-propin-1-yl, 4-pentyne-1-yl, and 5-hexyne. Examples thereof include linear or branched C 2-20 alkynyl groups such as -1-yl.
　本明細書中、特に断りのない限り、「シクロアルキル基」としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、及びシクロヘプチル等の、Ｃ３－１０シクロアルキル基が挙げられる。 Unless otherwise specified in the present specification, examples of the "cycloalkyl group" include C 3-10 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
　本明細書中、特に断りのない限り、「シクロアルケニル基」としては、例えば、シクロプロペニル、シクロブテニル、シクロペンテニル、シクロヘキセニル、及びシクロヘプテニル等の、Ｃ３－１０シクロアルケニル基が挙げられる。 Unless otherwise specified, examples of the "cycloalkenyl group" in the present specification include C 3-10 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.
　本明細書中、特に断りのない限り、「シクロアルカジエニル基」としては、例えば、シクロブタジエニル、シクロペンタジエニル、シクロヘキサジエニル、シクロヘプタジエニル、シクロオクタジエニル、シクロノナジエニル、及びシクロデカジエニル等の、Ｃ４－１０シクロアルカジエニル基が挙げられる。 Unless otherwise specified in the present specification, the "cyclo-alkazienyl group" includes, for example, cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononazi. Examples thereof include C 4-10 cycloalkadienyl groups such as enyl and cyclodecadienyl.
　本明細書中、特に断りのない限り、「アリール基」は、単環性、２環性、３環性、又は４環性であることができる。
　本明細書中、特に断りのない限り、「アリール基」は、Ｃ６－１８アリール基であることができる。
　本明細書中、特に断りのない限り、「アリール基」としては、例えば、フェニル、１－ナフチル、２－ナフチル、２－ビフェニル、３－ビフェニル、４－ビフェニル、及び２－アンスリルが挙げられる。 In the present specification, unless otherwise specified, the "aryl group" can be monocyclic, bicyclic, tricyclic, or tetracyclic.
In the present specification, the "aryl group" can be a C 6-18 aryl group unless otherwise specified.
Unless otherwise specified in the present specification, examples of the "aryl group" include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthrill.
　本明細書中、特に断りのない限り、「アラルキル基」としては、例えば、ベンジル、フェネチル、ジフェニルメチル、１－ナフチルメチル、２－ナフチルメチル、２，２－ジフェニルエチル、３－フェニルプロピル、４－フェニルブチル、５－フェニルペンチル、２－ビフェニルメチル、３－ビフェニルメチル、及び４－ビフェニルメチルが挙げられる。 Unless otherwise specified, the "aralkyl group" in the present specification includes, for example, benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4 Included are -phenylbutyl, 5-phenylpentyl, 2-biphenylmethyl, 3-biphenylmethyl, and 4-biphenylmethyl.
　本明細書中、特に断りのない限り、「パーフルオロポリエーテル基」とは、２以上のパーフルオロアルキレンオキシド単位が繰り返し結合した基である。パーフルオロアルキレンオキシド単位としては、例えば、－(ＯＣＦ２)－、－(ＯＣ２Ｆ４)－、－(ＯＣ３Ｆ６)－、－(ＯＣ４Ｆ８)－等のパーフルオロＣ１－６アルキレンオキシド単位が挙げられる。これらの単位は、１種単独でもよく、２種以上を組み合わせてもよい。 Unless otherwise specified in the present specification, the "perfluoropolyether group" is a group in which two or more perfluoroalkylene oxide units are repeatedly bonded. Examples of the perfluoroalkylene oxide unit include perfluoro C 1- such as-(OCF 2 )-,-(OC 2 F 4 )-,-(OC 3 F 6 )-,-(OC 4 F 8 )-. 6 alkylene oxide units can be mentioned. These units may be used alone or in combination of two or more.
　本明細書中、特に断りのない限り、－(ＯＣ４Ｆ８)－は、－(ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２)－、－(ＯＣＦ(ＣＦ３)ＣＦ２ＣＦ２)－、－(ＯＣＦ２ＣＦ(ＣＦ３)ＣＦ２)－、－(ＯＣＦ２ＣＦ２ＣＦ(ＣＦ３))－、－(ＯＣ(ＣＦ３)２ＣＦ２)－、－(ＯＣＦ２Ｃ(ＣＦ３)２)－、－(ＯＣＦ(ＣＦ３)ＣＦ(ＣＦ３))－、－(ＯＣＦ(Ｃ２Ｆ５)ＣＦ２)－、及び－(ＯＣＦ２ＣＦ(Ｃ２Ｆ５))－のいずれであってもよいが、好ましくは－(ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２)－である。－(ＯＣ３Ｆ６)－は、－(ＯＣＦ２ＣＦ２ＣＦ２)－、－(ＯＣＦ(ＣＦ３)ＣＦ２)－、及び－(ＯＣＦ２ＣＦ(ＣＦ３))－のいずれであってもよいが、好ましくは－(ＯＣＦ２ＣＦ２ＣＦ２)－である。また、－(ＯＣ２Ｆ４)－は、－(ＯＣＦ２ＣＦ２)－及び－(ＯＣＦ(ＣＦ３))－のいずれであってもよいが、好ましくは－(ＯＣＦ２ＣＦ２)－である。 In the present specification, unless otherwise specified,-(OC 4 F 8 )-is-(OCF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 )-,-( OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 ) -,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-,-(OCF 2 CF (C 2 F 5 ))- It may be, but it is preferably − (OCF 2 CF 2 CF 2 CF 2 ) −. -(OC 3 F 6 )-is either-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-,-(OCF 2 CF (CF 3 ))- It may be, but preferably − (OCF 2 CF 2 CF 2 ) −. Further,-(OC 2 F 4 )-may be any of-(OCF 2 CF 2 )-and-(OCF (CF 3 ))-, but preferably-(OCF 2 CF 2 )-. is there.
　本明細書中、「非芳香族複素環基」とは、非芳香族複素環から１個の水素原子を除去して形成される基を意味する。
　本明細書中、特に断りのない限り、「非芳香族複素環基」は、単環性、２環性、３環性、又は４環性であることができる。
　本明細書中、特に断りのない限り、「非芳香族複素環基」は、飽和、又は不飽和であることができる。
　本明細書中、特に断りのない限り、「非芳香族複素環基」は、例えば、５～１８員の非芳香族複素環基であることができる。
　本明細書中、特に断りのない限り、「非芳香族複素環基」は、例えば、環構成原子として、炭素原子に加えて酸素原子、硫黄原子、及び窒素原子から選ばれる１～４個のヘテロ原子を含有する非芳香族複素環基であることができる。
　本明細書中、特に断りのない限り、「非芳香族複素環基」としては、例えば、テトラヒドロフリル、オキサゾリジニル、イミダゾリニル（例：１－イミダゾリニル、２－イミダゾリニル、４－イミダゾリニル）、アジリジニル（例：１－アジリジニル、２－アジリジニル）、ピロリジニル（例：１－ピロリジニル、２－ピロリジニル、３－ピロリジニル）、ピペリジニル（例：１－ピペリジニル、２－ピペリジニル、３－ピペリジニル）、アゼパニル（例：１－アゼパニル、２－アゼパニル、３－アゼパニル、４－アゼパニル）、アゾカニル（例：１－アゾカニル、２－アゾカニル、３－アゾカニル、４－アゾカニル）、ピペラジニル（例：１，４－ピペラジン－１－イル、１，４－ピペラジン－２－イル）、ジアゼピニル（例：１，４－ジアゼピン－１－イル、１，４－ジアゼピン－２－イル、１，４－ジアゼピン－５－イル、１，４－ジアゼピン－６－イル）、ジアゾカニル（例：１，４－ジアゾカン－１－イル、１，４－ジアゾカン－２－イル、１，４－ジアゾカン－５－イル、１，４－ジアゾカン－６－イル、１，５－ジアゾカン－１－イル、１，５－ジアゾカン－２－イル、１，５－ジアゾカン－３－イル）、テトラヒドロピラニル（例：テトラヒドロフラン－４－イル）、モルホリニル（例：４－モルホリニル）、チオモルホリニル（例：４－チオモルホリニル）、２－オキサゾリジニル、ジヒドロフリル、ジヒドロピラニル、及びジヒドロキノリル等が挙げられる。 In the present specification, the "non-aromatic heterocyclic group" means a group formed by removing one hydrogen atom from the non-aromatic heterocycle.
In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" can be monocyclic, bicyclic, tricyclic, or tetracyclic.
Unless otherwise specified in the present specification, the "non-aromatic heterocyclic group" may be saturated or unsaturated.
Unless otherwise specified in the present specification, the "non-aromatic heterocyclic group" can be, for example, a 5- to 18-membered non-aromatic heterocyclic group.
In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" is, for example, 1 to 4 atoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to a carbon atom as ring-constituting atoms. It can be a non-aromatic heterocyclic group containing a hetero atom.
Unless otherwise specified, the "non-aromatic heterocyclic group" in the present specification includes, for example, tetrahydrofuryl, oxazolidinyl, imidazolinyl (eg, 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (eg, eg). 1-aziridinyl, 2-aziridinyl), pyrrolidinyl (eg 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl), piperidinyl (eg 1-piperidinyl, 2-piperidinyl, 3-piperidinyl), azepanyl (eg 1-azepanyl) , 2-azepanyl, 3-azepanyl, 4-azepanyl), azocanyl (eg 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl), piperazinyl (eg 1,4-piperazin-1-yl, 1) , 4-Piperazine-2-yl), diazepinyl (eg 1,4-diazepine-1-yl, 1,4-diazepine-2-yl, 1,4-diazepine-5-yl, 1,4-diazepine- 6-yl), diazocanyl (eg 1,4-diazocan-1-yl, 1,4-diazocan-2-yl, 1,4-diazocan-5-yl, 1,4-diazocan-6-yl, 1 , 5-Diazocan-1-yl, 1,5-diazocan-2-yl, 1,5-diazocan-3-yl), tetrahydropyranyl (eg tetrahydrofuran-4-yl), morpholinyl (eg 4-morpholinyl) ), Thiomorpholinyl (eg 4-thiomorpholinyl), 2-oxazolidinyl, dihydrofuryl, dihydropyranyl, dihydroquinolyl and the like.
　本明細書中、特に断りのない限り、「ヘテロアリール基」は、単環性、２環性、３環性、又は４環性であることができる。
　本明細書中、特に断りのない限り、「ヘテロアリール基」は、例えば、５～１８員のヘテロアリール基であることができる。
　本明細書中、特に断りのない限り、「ヘテロアリール基」は、例えば、環構成原子として、炭素原子に加えて酸素原子、硫黄原子、及び窒素原子から選ばれる１～４個のヘテロ原子を含有するヘテロアリール基であることができる。
　本明細書中、特に断りのない限り、「ヘテロアリール基」は、「単環性ヘテロアリール基」、及び「芳香族縮合複素環基」を包含する。
　本明細書中、特に断りのない限り、「単環性へテロアリール基」としては、例えば、ピロリル（例：１－ピロリル、２－ピロリル、３－ピロリル）、フリル（例：２－フリル、３－フリル）、チエニル（例：２－チエニル、３－チエニル）、ピラゾリル（例：１－ピラゾリル、３－ピラゾリル、４－ピラゾリル）、イミダゾリル（例：１－イミダゾリル、２－イミダゾリル、４－イミダゾリル）、イソオキサゾリル（例：３－イソオキサゾリル、４－イソオキサゾリル、５－イソオキサゾリル）、オキサゾリル（例：２－オキサゾリル、４－オキサゾリル、５－オキサゾリル）、イソチアゾリル（例：３－イソチアゾリル、４－イソチアゾリル、５－イソチアゾリル）、チアゾリル（例：２－チアゾリル、４－チアゾリル、５－チアゾリル）、トリアゾリル（例：１，２，３－トリアゾール－３－イル、１，２，４－トリアゾール－４－イル）、オキサジアゾリル（例：１，２，４－オキサジアゾール－３－イル、１，２，４－オキサジアゾール－５－イル）、チアジアゾリル（例：１，２，４－チアジアゾール－３－イル、１，２，４－５－イル）、テトラゾリル、ピリジル（例：２－ピリジル、３－ピリジル、４－ピリジル）、ピリダジニル（例：３－ピリダジニル、４－ピリダジニル）、ピリミジニル（例：２－ピリミジニル、４－ピリミジニル、５－ピリミジニル）、及びピラジニル等が挙げられる。
　本明細書中、特に断りのない限り、「芳香族縮合複素環基」としては、例えば、イソインドリル（例：１－イソインドリル、２－イソインドリル、３－イソインドリル、４－イソインドリル、５－イソインドリル、６－イソインドリル、７－イソインドリル）、インドリル（例：１－インドリル、２－インドリル、３－インドリル、４－インドリル、５－インドリル、６－インドリル、７－インドリル）、ベンゾ［ｂ］フラニル（例：２－ベンゾ［ｂ］フラニル、３－ベンゾ［ｂ］フラニル、４－ベンゾ［ｂ］フラニル、５－ベンゾ［ｂ］フラニル、６－ベンゾ［ｂ］フラニル、７－ベンゾ［ｂ］フラニル）、ベンゾ［ｃ］フラニル（例：１－ベンゾ［ｃ］フラニル、４－ベンゾ［ｃ］フラニル、５－ベンゾ［ｃ］フラニル）、ベンゾ［ｂ］チエニル、（例：２－ベンゾ［ｂ］チエニル、３－ベンゾ［ｂ］チエニル、４－ベンゾ［ｂ］チエニル、５－ベンゾ［ｂ］チエニル、６－ベンゾ［ｂ］チエニル、７－ベンゾ［ｂ］チエニル）、ベンゾ［ｃ］チエニル（例：１－ベンゾ［ｃ］チエニル、４－ベンゾ［ｃ］チエニル、５－ベンゾ［ｃ］チエニル）、インダゾリル（例：１－インダゾリル、２－インダゾリル、３－インダゾリル、４－インダゾリル、５－インダゾリル、６－インダゾリル、７－インダゾリル）、ベンゾイミダゾリル（例：１－ベンゾイミダゾリル、２－ベンゾイミダゾリル、４－ベンゾイミダゾリル、５－ベンゾイミダゾリル）、１，２－ベンゾイソオキサゾリル（例：１，２－ベンゾイソオキサゾール－３－イル、１，２－ベンゾイソオキサゾール－４－イル、１，２－ベンゾイソオキサゾール－５－イル、１，２－ベンゾイソオキサゾール－６－イル、１，２－ベンゾイソオキサゾール－７－イル）、ベンゾオキサゾリル（例：２－ベンゾオキサゾリル、４－ベンゾオキサゾリル、５－ベンゾオキサゾリル、６－ベンゾオキサゾリル、７－ベンゾオキサゾリル）、１，２－ベンゾイソチアゾリル（例：１，２－ベンゾイソチアゾール－３－イル、１，２－ベンゾイソチアゾール－４－イル、１，２－ベンゾイソチアゾール－５－イル、１，２－ベンゾイソチアゾール－６－イル、１，２－ベンゾイソチアゾール－７－イル）、ベンゾチアゾリル（例：２－ベンゾチアゾリル、４－ベンゾチアゾリル、５－ベンゾチアゾリル、６－ベンゾチアゾリル、７－ベンゾチアゾリル）、イソキノリル（例：１－イソキノリル、３－イソキノリル、４－イソキノリル、５－イソキノリル）、キノリル（例：２－キノリル、３－キノリル、４－キノリル、５－キノリル、８－キノリル）、シンノリニル（例：３－シンノリニル、４－シンノリニル、５－シンノリニル、６－シンノリニル、７－シンノリニル、８－シンノリニル）、フタラジニル（例：１－フタラジニル、４－フタラジニル、５－フタラジニル、６－フタラジニル、７－フタラジニル、８－フタラジニル）、キナゾリニル（例：２－キナゾリニル、４－キナゾリニル、５－キナゾリニル、６－キナゾリニル、７－キナゾリニル、８－キナゾリニル）、キノキサリニル（例：２－キノキサリニル、３－キノキサリニル、５－キノキサリニル、６－キノキサリニル、７－キノキサリニル、８－キノキサリニル）、ピラゾロ［１，５－ａ］ピリジル（例：ピラゾロ［１，５－ａ］ピリジン－２－イル、ピラゾロ［１，５－ａ］ピリジン－３－イル、ピラゾロ［１，５－ａ］ピリジン－４－イル、ピラゾロ［１，５－ａ］ピリジン－５－イル、ピラゾロ［１，５－ａ］ピリジン－６－イル、ピラゾロ［１，５－ａ］ピリジン－７－イル）、イミダゾ［１，２－ａ］ピリジル（例：イミダゾ［１，２－ａ］ピリジン－２－イル、イミダゾ［１，２－ａ］ピリジン－３－イル、イミダゾ［１，２－ａ］ピリジン－５－イル、イミダゾ［１，２－ａ］ピリジン－６－イル、イミダゾ［１，２－ａ］ピリジン－７－イル、及びイミダゾ［１，２－ａ］ピリジン－８－イル）等が挙げられる。 Unless otherwise specified in the present specification, the "heteroaryl group" can be monocyclic, bicyclic, tricyclic, or tetracyclic.
Unless otherwise specified in the present specification, the "heteroaryl group" can be, for example, a 5- to 18-membered heteroaryl group.
Unless otherwise specified, in the present specification, the "heteroaryl group" includes, for example, 1 to 4 heteroatoms selected from oxygen atom, sulfur atom, and nitrogen atom in addition to carbon atom as a ring-constituting atom. It can be a heteroaryl group contained.
In the present specification, unless otherwise specified, the "heteroaryl group" includes a "monocyclic heteroaryl group" and an "aromatic condensed heterocyclic group".
Unless otherwise specified, the "monocyclic heteroaryl group" in the present specification includes, for example, pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolill, 3-pyrrolill), frill (eg, 2-furyl, 3). -Frill), thienyl (eg 2-thienyl, 3-thienyl), pyrazolyl (eg 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (eg 1-imidazolyl, 2-imidazolyl, 4-imidazolyl) , Isooxazolyl (eg 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl), oxazolyl (eg 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (eg 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl ), Thiazolyl (eg 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (eg 1,2,3-triazole-3-yl, 1,2,4-triazole-4-yl), oxadiazolyl (eg, 1,2,4-triazole-4-yl) Example: 1,2,4-oxadiazole-3-yl, 1,2,4-oxadiazole-5-yl), thiadiazolyl (example: 1,2,4-thiazazole-3-yl, 1,2) , 4-5-yl), tetrazolyl, pyridyl (eg 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridadinyl (eg 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (eg 2-pyrimidinyl, 4-pyridinyl) Pyrimidinyl, 5-pyrimidinyl), pyrazinyl and the like.
Unless otherwise specified, the "aromatically fused heterocyclic group" in the present specification includes, for example, isoindolyl (eg, 1-isoindrill, 2-isoindrill, 3-isoindrill, 4-isoindrill, 5-isoindol, 6- Isoindrill, 7-isoindrill), indrill (eg 1-indrill, 2-indrill, 3-indrill, 4-indrill, 5-indrill, 6-indrill, 7-indrill), benzo [b] flanil (eg 2-indrill) Benzo [b] flanyl, 3-benzo [b] flanil, 4-benzo [b] flanyl, 5-benzo [b] flanyl, 6-benzo [b] flanil, 7-benzo [b] flanyl), benzo [c] ] Furanyl (eg 1-benzo [c] flanyl, 4-benzo [c] flanyl, 5-benzo [c] flanyl), benzo [b] thienyl, (eg 2-benzo [b] thienyl, 3-benzo) [B] thienyl, 4-benzo [b] thienyl, 5-benzo [b] thienyl, 6-benzo [b] thienyl, 7-benzo [b] thienyl), benzo [c] thienyl (eg 1-benzo [eg] c] Thienyl, 4-benzo [c] thienyl, 5-benzo [c] thienyl), indazolyl (eg 1-indazolyl, 2-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7 -Indazolyl), benzoimidazolyl (eg 1-benzoimidazolyl, 2-benzoimidazolyl, 4-benzoimidazolyl, 5-benzoimidazolyl), 1,2-benzoisoxazole (eg 1,2-benzoisoxazole-3-yl, 1) , 2-benzoisoxazole-4-yl, 1,2-benzoisoxazole-5-yl, 1,2-benzoisoxazole-6-yl, 1,2-benzoisoxazole-7-yl), benzoxazole Zoryl (eg 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzothiazolyl (eg) Examples: 1,2-benzoisothiazole-3-yl, 1,2-benzoisothiazole-4-yl, 1,2-benzoisothiazole-5-yl, 1,2-benzoisothiazole-6-yl, 1,2-benzoisothiazole-7-yl), benzothiazolyl (eg 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), isoquinolyl (eg 1-) Isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl), quinolyl (eg 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), cinnolinyl (eg 3-cinnolinyl, 4- Synnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (eg 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (eg Examples: 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (eg 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl) , 8-Kinoxalinyl), pyrazolo [1,5-a] pyridyl (eg, pyrazolo [1,5-a] pyridin-2-yl, pyrazolo [1,5-a] pyridin-3-yl, pyrazolo [1,5-a] 5-a] Pyridine-4-yl, Pyrazoro [1,5-a] Pyridine-5-yl, Pyrazoro [1,5-a] Pyridine-6-yl, Pyrazoro [1,5-a] Pyridine-7- Il), imidazo [1,2-a] pyridyl (eg, imidazo [1,2-a] pyridin-2-yl, imidazo [1,2-a] pyridin-3-yl, imidazo [1,2-a] ] Pyridine-5-yl, imidazo [1,2-a] pyridin-6-yl, imidazo [1,2-a] pyridin-7-yl, and imidazo [1,2-a] pyridin-8-yl) And so on.
　本明細書中、「Ｎ価（Ｎは２以上の整数である。）の有機基」とは、前記有機基（１価の有機基）からＮ－１個の水素原子をさらに除去して形成される基を意味する。 In the present specification, the "N-valent (N is an integer of 2 or more) organic group" is formed by further removing N-1 hydrogen atoms from the organic group (monovalent organic group). Means the group to be.
　本明細書中、「加水分解可能な基」とは、加水分解反応により、化合物の主骨格から脱離し得る基を意味する。 In the present specification, the "hydrolyzable group" means a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction.
タイヤの表面改質剤
　本開示の一態様において、タイヤの表面改質剤は、下記（１）～（５）：
（１）パーフルオロポリエーテル基含有シラン化合物を含有する組成物；
（２）炭素－炭素二重結合含有パーフルオロポリエーテル化合物を含有する組成物；
（３）フルオロポリマー及びアクリルポリマーからなり、フルオロポリマー及びアクリルポリマーのいずれか一方又は両方が水酸基及び加水分解性シリル基を有する複合重合体粒子と、ポリイソシアネート化合物と、水とを含有する組成物；
（４）フッ素樹脂粒子と、硬化性シリコーン樹脂と、水とを含有する組成物；
（５）含フッ素単量体に基づく重合単位と、水酸基含有単量体、カルボキシル基含有単量体、酸無水物単量体、アミノ基含有単量体、及びシリコーン系ビニル単量体からなる群より選択される少なくとも一種の硬化性官能基含有単量体に基づく重合単位とを含むフッ素ポリマーを含有する組成物
のいずれかの組成物からなる。 Tire surface modifier In one aspect of the present disclosure, the tire surface modifier is described in (1) to (5):
(1) A composition containing a perfluoropolyether group-containing silane compound;
(2) A composition containing a carbon-carbon double bond-containing perfluoropolyether compound;
(3) A composition comprising a composite polymer particle composed of a fluoropolymer and an acrylic polymer and one or both of the fluoropolymer and the acrylic polymer having a hydroxyl group and a hydrolyzable silyl group, a polyisocyanate compound, and water. ;
(4) A composition containing fluororesin particles, a curable silicone resin, and water;
(5) Consists of a polymerization unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. It comprises any composition of a composition containing a fluoropolymer containing a polymerization unit based on at least one curable functional group-containing monomer selected from the group.
組成物（１）
　組成物（１）は、パーフルオロポリエーテル基含有シラン化合物を含有する組成物である。パーフルオロポリエーテル基含有シラン化合物は、パーフルオロポリエーテル基及びケイ素原子を含有する限り、特に制限されず、好ましくは、下記式（1A）：
－(ＯＣ４Ｆ８)ａ－(ＯＣ３Ｆ６)ｂ－(ＯＣ２Ｆ４)ｃ－(ＯＣＦ２)ｄ－　（1A）
（式中、
　ａ及びｂは、それぞれ独立して、０～３０の整数であり、
　ｃ及びｄは、それぞれ独立して、１～２００の整数であり、
　ａ、ｂ、ｃ、及びｄの和は、３以上の整数であり、
　ｃ／ｄ比が、０．２以上０．９未満の範囲内であり、
　添字ａ、ｂ、ｃ、又はｄを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。）
で表されるパーフルオロポリエーテル基を含有するシラン化合物である。 Composition (1)
The composition (1) is a composition containing a perfluoropolyether group-containing silane compound. The perfluoropolyether group-containing silane compound is not particularly limited as long as it contains a perfluoropolyether group and a silicon atom, and preferably the following formula (1A):
-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- (1A)
(During the ceremony,
a and b are independently integers from 0 to 30 and
c and d are independently integers from 1 to 200, respectively.
The sum of a, b, c, and d is an integer of 3 or more.
The c / d ratio is in the range of 0.2 or more and less than 0.9.
The order of existence of each repeating unit in parentheses with the subscripts a, b, c, or d is arbitrary in the equation. )
It is a silane compound containing a perfluoropolyether group represented by.
　パーフルオロポリエーテル基含有シラン化合物は、より好ましくは、下記式（1-1）～（1-6）：
Figure JPOXMLDOC01-appb-C000005
 ［式中：
　ＰＦＰＥは、各出現においてそれぞれ独立して、－(ＯＣ４Ｆ８)ａ－(ＯＣ３Ｆ６)ｂ－(ＯＣ２Ｆ４)ｃ－(ＯＣＦ２)ｄ－を表し、ａ、ｂ、ｃ、及びｄは前記と同意義であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個又はそれ以上のフッ素原子により置換されていてもよいＣ１－１６アルキル基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、水素原子又はＣ１－２２アルキル基を表し；
　Ｒ２は、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
　Ｒ１１は、各出現においてそれぞれ独立して、水素原子又はハロゲン原子を表し；
　Ｒ１２は、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；
　ｎは、(－ＳｉＲ１ ｎＲ２ ３－ｎ)単位毎に独立して、０～３の整数であり；
　ただし、式（1-1）、（1-2）、（1-3）、及び（1-4）において、少なくとも１つのＲ２が存在し；
　Ｘ１は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
　Ｘ２は、各出現においてそれぞれ独立して、単結合又は２価の有機基を表し；
　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
　αは、それぞれ独立して、１～９の整数であり；
　α’は、それぞれ独立して、１～９の整数であり；
　Ｘ５は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
　βは、それぞれ独立して、１～９の整数であり；
　β’は、それぞれ独立して、１～９の整数であり；
　Ｘ７は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
　γは、それぞれ独立して、１～９の整数であり；
　γ’は、それぞれ独立して、１～９の整数であり；
　Ｒａは、各出現においてそれぞれ独立して、－Ｚ－ＳｉＲ７１ ｐＲ７２ ｑＲ７３ ｒを表し；
　Ｚは、各出現においてそれぞれ独立して、酸素原子又は２価の有機基を表し；
　Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
　Ｒａ’は、Ｒａと同意義であり；
　Ｒａ中、Ｚ基を介して直鎖状に連結されるＳｉは最大で５個であり；
　Ｒ７２は、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
　Ｒ７３は、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；
　ｐは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒは、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、一のＲａにおいて、ｐ、ｑ、及びｒの和は３であり、式（1-5）及び（1-6）において、少なくとも１つのＲ７２が存在し；
　Ｒｂは、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
　Ｒｃは、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；
　ｋは、各出現においてそれぞれ独立して、１～３の整数であり；
　ｌは、各出現においてそれぞれ独立して、０～２の整数であり；
　ｍは、各出現においてそれぞれ独立して、０～２の整数であり；
　ただし、γを付して括弧でくくられた単位において、ｋ、ｌ、及びｍの和は３である。］
のいずれかで表される化合物である。 The perfluoropolyether group-containing silane compound is more preferably represented by the following formulas (1-1) to (1-6):
Figure JPOXMLDOC01-appb-C000005
 [During the ceremony:
PFPE independently represents-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- in each appearance, a, b, c. , And D have the same meaning as above;
Rf represents a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms at each appearance;
R 1 independently represents a hydrogen atom or a C 1-22 alkyl group at each appearance;
R 2 represents a hydroxyl group or a hydrolyzable group independently at each appearance;
R 11 independently represents a hydrogen atom or a halogen atom at each appearance;
R 12 independently represents a hydrogen atom or a lower alkyl group at each appearance;
n is, (- SiR 1 n R 2 3-n) independently for each unit, an integer from 0 to 3;
However, in equations (1-1), (1-2), (1-3), and (1-4), at least one R 2 is present;
X 1 independently represents a single bond or a 2- to 10-valent organic group;
X 2 independently represents a single bond or divalent organic group at each appearance;
t is an integer from 1 to 10 independently for each occurrence;
α is an integer from 1 to 9 independently of each other;
α'is an integer from 1 to 9 independently of each other;
X 5 each independently represents a single bond or a 2-10 valent organic group;
β is an integer from 1 to 9 independently of each other;
β'is an integer from 1 to 9 independently of each other;
X 7 each independently represents a single bond or a 2-10 valent organic group;
γ is an integer from 1 to 9 independently of each other;
γ'is an integer from 1 to 9 independently of each other;
R a independently represents −Z—SiR 71 p R 72 q R 73 r ;
Z independently represents an oxygen atom or a divalent organic group at each appearance;
R 71 is independently at each occurrence, represents a R a ';
R a 'is located in the same meaning as R a;
In Ra, a maximum of 5 Sis are linearly linked via a Z group;
R 72 independently represents a hydroxyl group or a hydrolyzable group at each appearance;
R 73 independently represents a hydrogen atom or lower alkyl group at each appearance;
p is an integer from 0 to 3 independently for each occurrence;
q is an integer from 0 to 3 independently for each occurrence;
r is an integer from 0 to 3 independently for each occurrence;
However, in one Ra, the sum of p, q, and r is 3, and in equations (1-5) and (1-6), there is at least one R 72 ;
R b represents a hydroxyl group or a hydrolyzable group independently at each appearance;
R c independently represents a hydrogen atom or a lower alkyl group at each appearance;
k is an integer of 1 to 3 independently for each occurrence;
l is an integer from 0 to 2 independently for each occurrence;
m is an integer from 0 to 2 independently for each occurrence;
However, the sum of k, l, and m is 3 in the unit with γ and enclosed in parentheses. ]
It is a compound represented by any of.
　好ましい態様において、式（1A）及び（1-1）～（1-6）のＰＦＰＥは、－(ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２)ａ－(ＯＣＦ２ＣＦ２ＣＦ２)ｂ－(ＯＣＦ２ＣＦ２)ｃ－(ＯＣＦ２)ｄ－（式中、ａ、ｂ、ｃ、及びｄは上記と同意義である。）であり、例えば、－(ＯＣＦ２ＣＦ２)ｃ－(ＯＣＦ２)ｄ－（式中、ｃ及びｄは上記と同意義である。）であってもよい。 In a preferred embodiment, the PFPEs of formulas (1A) and (1-1) to (1-6) are − (OCF 2 CF 2 CF 2 CF 2 ) a − (OCF 2 CF 2 CF 2 ) b − (OCF 2 ). CF 2 ) c − (OCF 2 ) d − (in the equation, a, b, c, and d have the same meaning as above), for example, − (OCF 2 CF 2 ) c − (OCF 2 ). It may be d − (in the formula, c and d have the same meaning as described above).
　前記式（1A）及び（1-1）～（1-6）のＰＦＰＥにおいて、
　ａ及びｂは、それぞれ独立して、好ましくは１～３０の整数、より好ましくは０～１０の整数であり；
　ｃ及びｄは、それぞれ独立して、好ましくは１０～１００の整数、より好ましくは２０～１００の整数であり；
　ａ、ｂ、ｃ、及びｄの和は、好ましくは１０以上、より好ましくは２０以上であり、好ましくは２００以下、より好ましくは１００以下である。 In the PFPEs of the formulas (1A) and (1-1) to (1-6),
a and b are each independently, preferably an integer of 1 to 30, more preferably an integer of 0 to 10;
c and d are independently, preferably an integer of 10 to 100, more preferably an integer of 20 to 100;
The sum of a, b, c, and d is preferably 10 or more, more preferably 20 or more, preferably 200 or less, and more preferably 100 or less.
　ｃ／ｄ比は、好ましくは０．２以上０．８５以下の範囲内であり、より好ましくは０．２以上０．７５以下の範囲内であり、さらに好ましくは０．２以上０．７０以下の範囲内であり、さらにより好ましくは０．３以上０．６以下の範囲内である。 The c / d ratio is preferably in the range of 0.2 or more and 0.85 or less, more preferably in the range of 0.2 or more and 0.75 or less, and further preferably 0.2 or more and 0.70 or less. It is within the range of, and even more preferably within the range of 0.3 or more and 0.6 or less.
　ＰＦＰＥで表される「１個又はそれ以上のフッ素原子により置換されていてもよいＣ１－１６アルキル基」における「Ｃ１－１６アルキル基」は、直鎖であっても分枝鎖であってもよく、好ましくは直鎖又は分枝鎖のＣ１－６アルキル基、より好ましくはＣ１－３アルキル基であり、さらに好ましくは直鎖のＣ１－３アルキル基である。 The "C 1-16 alkyl group" in the "C 1-16 alkyl group which may be substituted with one or more fluorine atoms" represented by PFPE is a straight chain or a branched chain. It may be a straight chain or branched C 1-6 alkyl group, more preferably a C 1-3 alkyl group, and even more preferably a straight chain C 1-3 alkyl group.
　Ｒｆは、好ましくは、１個又はそれ以上のフッ素原子により置換されているＣ１－１６アルキル基であり、より好ましくはＣＦ２Ｈ－Ｃ１－１５フルオロアルキレン基であり、さらに好ましくはＣ１－１６パーフルオロアルキル基である。該Ｃ１－１６パーフルオロアルキル基は、直鎖であっても分枝鎖であってもよく、好ましくは直鎖又は分枝鎖のＣ１－６パーフルオロアルキル基、より好ましくはＣ１－３パーフルオロアルキル基であり、さらに好ましくは直鎖のＣ１－３パーフルオロアルキル基、具体的には－ＣＦ３、－ＣＦ２ＣＦ３、又は－ＣＦ２ＣＦ２ＣＦ３である。 Rf is preferably a one or more C 1-16 alkyl group substituted by fluorine atoms, more preferably CF 2 H-C 1-15 fluoroalkylene group, more preferably C 1 It is a -16 perfluoroalkyl group. The C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, more preferably C 1-. It is a 3 perfluoroalkyl group, more preferably a linear C 1-3 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 .
　Ｒ１は、好ましくはＣ１－４アルキル基である。 R 1 is preferably a C 1-4 alkyl group.
　Ｒ２で表される加水分解可能な基の例としては、－ＯＲ’、－ＯＣＯＲ’、－Ｏ－Ｎ＝Ｃ(Ｒ’)２、－Ｎ(Ｒ’)２、－ＮＨＲ’、ハロゲン（これら式中、Ｒ’は、置換又は非置換のＣ１－４アルキル基を示す。）などが挙げられ、好ましくは－ＯＲ’（即ち、アルコキシ基）である。Ｒ’の例には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基又はエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってもよい。 Examples of hydrolyzable groups represented by R 2 are -OR', -OCOR', -ON = C (R') 2 , -N (R') 2 , -NHR', halogen ( In these formulas, R'shows a substituted or unsubstituted C 1-4 alkyl group) and the like, and is preferably −OR'(that is, an alkoxy group). Examples of R'include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be generated by hydrolyzing a hydrolyzable group.
　Ｒ１１で表されるハロゲン原子は、好ましくはヨウ素原子、塩素原子、フッ素原子であり、より好ましくはフッ素原子である。 The halogen atom represented by R 11 is preferably an iodine atom, a chlorine atom, or a fluorine atom, and more preferably a fluorine atom.
　Ｒ１２で表される低級アルキル基は、好ましくはＣ１－２０アルキル基であり、より好ましくはＣ１－６アルキル基であり、例えばメチル基、エチル基、プロピル基等が挙げられる。 The lower alkyl group represented by R 12 is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and examples thereof include a methyl group, an ethyl group, and a propyl group.
　ｎは、(－ＳｉＲ１ ｎＲ２ ３－ｎ)単位毎に独立して、好ましくは０～２の整数であり、より好ましくは０である。なお、式中、すべてのｎが同時に３になることはない。換言すれば、式中、少なくとも１つはＲ２が存在する。 n it is, (- SiR 1 n R 2 3-n) independently for each unit is preferably an integer of 0 to 2, more preferably 0. In the formula, not all n's become 3 at the same time. In other words, at least one R 2 is present in the equation.
　Ｘ１は、式（1-1）及び（1-2）で表される化合物において、主に撥水性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部又は－ＰＦＰＥ－部）と、タイヤとの結合能を提供するシラン部（即ち、αを付して括弧でくくられた基）とを連結するリンカーと解することができる。従って、Ｘ１は、式（1-1）及び（1-2）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the compounds represented by the formulas (1-1) and (1-2), X 1 is a perfluoropolyether portion (that is, an Rf-PFPE portion or a -PFPE- portion) that mainly provides water repellency and the like. , Can be interpreted as a linker that links a silane moiety (ie, a group enclosed in parentheses with α) that provides binding ability to the tire. Therefore, X 1 may be any organic group as long as the compounds represented by the formulas (1-1) and (1-2) can be stably present.
　α及びα’は、Ｘ１の価数に応じて変化し得る。式（1-1）では、α及びα’の和は、Ｘ１の価数と同じである。例えば、Ｘ１が１０価の有機基である場合、α及びα’の和は１０であり、例えばαが９かつα’が１、αが５かつα’が５、又はαが１かつα’が９となり得る。また、Ｘ１が２価の有機基である場合、α及びα’は１である。式（1-2）では、αはＸ１の価数から１を引いた値である。 α and α'can vary depending on the valence of X 1 . In equation (1-1), the sum of α and α'is the same as the valence of X 1 . For example, when X 1 is a 10-valent organic group, the sum of α and α'is 10, for example, α is 9 and α'is 1, α is 5 and α'is 5, or α is 1 and α. 'Can be 9. Further, when X 1 is a divalent organic group, α and α'are 1. In equation (1-2), α is the valence of X 1 minus one.
　Ｘ１は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 X 1 is preferably a divalent to 7 valent, more preferably a 2 to 4 valent, and even more preferably a divalent organic group.
　一の態様において、Ｘ１は２～４価の有機基であり、αは１～３であり、α’は１である。別の態様において、Ｘ１は２価の有機基であり、αは１であり、α’は１である。この場合、式（1-1）及び（1-2）は、下記式（1-1-A）及び（1-2-A）で表される。
Figure JPOXMLDOC01-appb-C000006
 In one embodiment, X 1 is a 2- to tetravalent organic group, α is 1-3 and α'is 1. In another embodiment, X 1 is a divalent organic group, α is 1, and α'is 1. In this case, the formulas (1-1) and (1-2) are represented by the following formulas (1-1-A) and (1-2-A).
Figure JPOXMLDOC01-appb-C000006
　Ｘ１の例としては、特に限定するものではないが、例えば、下記式：
　－(Ｒ３１)ｐ’－(Ｘａ)ｑ’－
［式中：
　Ｒ３１は、単結合、－(ＣＨ２)ｓ’－、又はｏ－、ｍ－若しくはｐ－フェニレン基を表し、好ましくは－(ＣＨ２)ｓ’－であり、
　ｓ’は、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数、さらに好ましくは１又は２であり、
　Ｘａは、－(Ｘｂ)ｌ’－を表し、
　Ｘｂは、各出現においてそれぞれ独立して、－Ｏ－、－Ｓ－、ｏ－、ｍ－若しくはｐ－フェニレン基、－Ｃ(Ｏ)Ｏ－、－Ｓｉ(Ｒ３３)２－、－(Ｓｉ(Ｒ３３)２Ｏ)ｍ’－Ｓｉ(Ｒ３３)２－、－ＣＯＮＲ３４－、－Ｏ－ＣＯＮＲ３４－、－ＮＲ３４－、及び－(ＣＨ２)ｎ’－からなる群から選択される基を表し、
　Ｒ３３は、各出現においてそれぞれ独立して、フェニル基、Ｃ１－６アルキル基、又はＣ１－６アルコキシ基を表し、好ましくはフェニル基又はＣ１－６アルキル基であり、より好ましくはメチル基であり、
　Ｒ３４は、各出現においてそれぞれ独立して、水素原子、フェニル基、又はＣ１－６アルキル基（好ましくはメチル基）を表し、
　ｍ’は、各出現において、それぞれ独立して、１～１００の整数、好ましくは１～２０の整数であり、
　ｎ’は、各出現において、それぞれ独立して、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数であり、
　ｌ’は、１～１０の整数、好ましくは１～５の整数、より好ましくは１～３の整数であり、
　ｐ’は、０又は１であり、
　ｑ’は、０又は１であり、
　ｐ’及びｑ’を付して括弧でくくられた各繰り返し単位の存在順序は任意である。］で表される２価の有機基が挙げられる。Ｒ３１及びＸａ（典型的にはＲ３１及びＸａの水素原子）は、フッ素原子、Ｃ１－３アルキル基、及びＣ１－３フルオロアルキル基から選択される１個又はそれ以上の置換基により置換されていてもよい。 The example of X 1 is not particularly limited, but for example, the following equation:
-(R 31 ) p' -(X a ) q'-
[During the ceremony:
R 31 represents a single bond, - (CH 2) s '-, or o-, represents m- or p- phenylene group, preferably - (CH 2) s' - a and,
s'is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
X a represents-(X b ) l'- and represents
X b is an independent -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R 33 ) 2 -,-( Si (R 33) 2 O) m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 -, and - (CH 2) n' - selected from the group consisting of Represents the group to be
R 33 independently represents a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group at each appearance, preferably a phenyl group or a C 1-6 alkyl group, more preferably methyl. Is the basis
R 34 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group) at each appearance.
m'is an integer of 1 to 100, preferably an integer of 1 to 20, independently of each occurrence.
n'is an integer of 1 to 20, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3, independently of each occurrence.
l'is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3.
p'is 0 or 1 and
q'is 0 or 1 and
The order of existence of each repeating unit enclosed in parentheses with p'and q'is arbitrary. ], A divalent organic group represented by] can be mentioned. R 31 and X a (typically hydrogen atoms of R 31 and X a ) are substituted with one or more selected from fluorine atoms, C 1-3 alkyl groups, and C 1-3 fluoroalkyl groups. It may be substituted by a group.
　好ましくは、Ｘ１は、－(Ｒ３１)ｐ’－(Ｘａ)ｑ’－Ｒ３２－である。
　Ｒ３２は、単結合、－(ＣＨ２)ｔ’－、又はｏ－、ｍ－若しくはｐ－フェニレン基を表し、好ましくは－(ＣＨ２)ｔ’－である。ｔ’は、例えば１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。Ｒ３２（典型的にはＲ３２の水素原子）は、フッ素原子、Ｃ１－３アルキル基、及びＣ１－３フルオロアルキル基から選択される１個又はそれ以上の置換基により置換されていてもよい。
　より好ましくは、Ｘ１は、
Ｃ１－２０アルキレン基、
－Ｒ３１－Ｘｃ－Ｒ３２－、又は
－Ｘｄ－Ｒ３２－
［式中、Ｒ３１及びＲ３２は、上記と同意義である。］
であることができる。
　さらに好ましくは、Ｘ１は、
Ｃ１－２０アルキレン基、
－(ＣＨ２)ｓ’－Ｘｃ－、
－(ＣＨ２)ｓ’－Ｘｃ－(ＣＨ２)ｔ’－、
－Ｘｄ－、又は
－Ｘｄ－(ＣＨ２)ｔ’
［式中、ｓ’及びｔ’は、上記と同意義である。］
であることができる。 Preferably, X 1 is-(R 31 ) p' -(Xa) q'- R 32- .
R 32 represents a single bond, - (CH 2) t '-, or o-, represents m- or p- phenylene group, preferably - (CH 2) t' - a. t'is, for example, an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. R 32 (typically the hydrogen atom of R 32 ) is substituted with one or more substituents selected from fluorine atoms, C 1-3 alkyl groups, and C 1-3 fluoroalkyl groups. May be good.
More preferably, X 1 is
C 1-20 alkylene group,
-R 31 -X c -R 32- or-X d -R 32-
[In the formula, R 31 and R 32 have the same meaning as above. ]
Can be.
More preferably, X 1 is
C 1-20 alkylene group,
- (CH 2) s' -X c -,
- (CH 2) s '-X c - (CH 2) t' -,
-X d- or -X d- (CH 2 ) t'
[In the formula, s'and t'have the same meaning as above. ]
Can be.
　Ｘｃは、
－Ｏ－、
－Ｓ－、
－Ｃ(Ｏ)Ｏ－、
－ＣＯＮＲ３４－、
－Ｏ－ＣＯＮＲ３４－、
－Ｓｉ(Ｒ３３)２－、
－(Ｓｉ(Ｒ３３)２Ｏ)ｍ’－Ｓｉ(Ｒ３３)２－、
－Ｏ－(ＣＨ２)u’－(Ｓｉ(Ｒ３３)２Ｏ)ｍ’－Ｓｉ(Ｒ３３)２－、
－Ｏ－(ＣＨ２)u’－Ｓｉ(Ｒ３３)２－Ｏ－Ｓｉ(Ｒ３３)２－ＣＨ２ＣＨ２－Ｓｉ(Ｒ３３)２－Ｏ－Ｓｉ(Ｒ３３)２－、
－Ｏ－(ＣＨ２)u’－Ｓｉ(ＯＣＨ３)２ＯＳｉ(ＯＣＨ３)２－、
－ＣＯＮＲ３４－(ＣＨ２)u’－(Ｓｉ(Ｒ３３)２Ｏ)ｍ’－Ｓｉ(Ｒ３３)２－、－ＣＯＮＲ３４－(ＣＨ２)u’－Ｎ(Ｒ３４)－、又は
－ＣＯＮＲ３４－(ｏ－、ｍ－又はｐ－フェニレン)－Ｓｉ(Ｒ３３)２－
［式中、Ｒ３３、Ｒ３４及びｍ’は、上記と同意義であり、ｕ’は１～２０の整数、好ましくは２～６の整数、より好ましくは２又は３である。］
を表す。Ｘｃは、好ましくは－Ｏ－である。 X c is
-O-,
-S-,
-C (O) O-,
-CONR 34 -,
-O-CONR 34 -,
-Si (R 33 ) 2- ,
- (Si (R 33) 2 O) m '-Si (R 33) 2 -,
-O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -,
-O- (CH 2) u '-Si (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -,
-O- (CH 2) u '-Si (OCH 3) 2 OSi (OCH 3) 2 -,
-CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, - CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 -
[In the formula, R 33 , R 34 and m'have the same meaning as above, and u'is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably 2 or 3. ]
Represents. Xc is preferably —O—.
　Ｘｄは、
－Ｓ－、
－Ｃ(Ｏ)Ｏ－、
－ＣＯＮＲ３４－、
－ＣＯＮＲ３４－(ＣＨ２)u’－(Ｓｉ(Ｒ３３)２Ｏ)ｍ’－Ｓｉ(Ｒ３３)２－、－ＣＯＮＲ３４－(ＣＨ２)u’－Ｎ(Ｒ３４)－、又は
－ＣＯＮＲ３４－(ｏ－、ｍ－又はｐ－フェニレン)－Ｓｉ(Ｒ３３)２－
［式中、各記号は、上記と同意義である。］
を表す。 X d is
-S-,
-C (O) O-,
-CONR 34 -,
-CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, - CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 -
[In the formula, each symbol has the same meaning as above. ]
Represents.
　より好ましくは、Ｘ１は、
Ｃ１－２０アルキレン基、
－(ＣＨ２)ｓ’－Ｘｃ－(ＣＨ２)ｔ’－、又は
－Ｘｄ－(ＣＨ２)ｔ’－
［式中、各記号は、上記と同意義である。］
であり、
　さらにより好ましくは、Ｘ１は、
Ｃ１－２０アルキレン基、
－(ＣＨ２)ｓ’－Ｏ－(ＣＨ２)ｔ’－、
－(ＣＨ２)ｓ’－(Ｓｉ(Ｒ３３)２Ｏ)ｍ’－Ｓｉ(Ｒ３３)２－(ＣＨ２)ｔ’－、－(ＣＨ２)ｓ’－Ｏ－(ＣＨ２)u’－(Ｓｉ(Ｒ３３)２Ｏ)ｍ’－Ｓｉ(Ｒ３３)２－(ＣＨ２)ｔ’－、又は
－(ＣＨ２)ｓ’－Ｏ－(ＣＨ２)ｔ’－Ｓｉ(Ｒ３３)２－(ＣＨ２)u’－Ｓｉ(Ｒ３３)２－(ＣvＨ２v)－
［式中、Ｒ３３、ｍ’、ｓ’、ｔ’及びｕ’は、上記と同意義であり、ｖは１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］
である。 More preferably, X 1 is
C 1-20 alkylene group,
- (CH 2) s '-X c - (CH 2) t' -, or -X d - (CH 2) t'-
[In the formula, each symbol has the same meaning as above. ]
And
Even more preferably, X 1 is
C 1-20 alkylene group,
-(CH 2 ) s'- O- (CH 2 ) t'- ,
- (CH 2) s '- (Si (R 33) 2 O) m' -Si (R 33) 2 - (CH 2) t '-, - (CH 2) s' -O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 - (CH 2) t '-, or - (CH 2) s' -O- (CH 2) t' -Si (R 33) 2 - (CH 2) u '-Si (R 33) 2 - (C v H 2v) -
[In the formula, R 33 , m', s', t'and u'have the same meaning as above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably 2 to 3. It is an integer. ]
Is.
　－(ＣvＨ２v)－は、直鎖であっても分枝鎖であってもよく、例えば、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ(ＣＨ３)－、－ＣＨ(ＣＨ３)ＣＨ２－であり得る。 - (C v H 2v) - it may be a be branched straight-chain, for example, -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) - , -CH (CH 3 ) CH 2- .
　Ｘ１は、フッ素原子、Ｃ１－３アルキル基、及びＣ１－３フルオロアルキル基（好ましくは、Ｃ１－３パーフルオロアルキル基）から選択される１個又はそれ以上の置換基により置換されていてもよい。 X 1 is substituted with one or more substituents selected from the fluorine atom, C 1-3 alkyl group, and C 1-3 fluoroalkyl group (preferably C 1-3 perfluoroalkyl group). May be.
　別の態様において、Ｘ１としては、例えば、下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000007
 ［式中、
　Ｒ４１は、水素原子、フェニル基、Ｃ１－６アルキル基、又はＣ１－６アルコキシ基、好ましくはメチル基であり；
　Ｄは、
－ＣＨ２Ｏ(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３－、
－ＣＦ２Ｏ(ＣＨ２)３－、
－(ＣＨ２)２－、
－(ＣＨ２)３－、
－(ＣＨ２)４－、
－ＣＯＮＨ－(ＣＨ２)３－、
－ＣＯＮ(ＣＨ３)－(ＣＨ２)３－、
－ＣＯＮ(Ｐｈ)－(ＣＨ２)３－（式中、Ｐｈはフェニルを意味する）、及び
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ４２は水素原子又はＣ１－６アルキル基、好ましくはメチル基を表す。）
から選択される基であり、
　Ｅは、－(ＣＨ２)ｎ－（ｎは２～６の整数）であり、
　Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, X 1 includes, for example, the following groups:
Figure JPOXMLDOC01-appb-C000007
 [During the ceremony,
R 41 is a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group;
D is
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CF 2 O (CH 2 ) 3- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (In the formula, Ph means phenyl), and
Figure JPOXMLDOC01-appb-C000008
 (In the formula, R 42 represents a hydrogen atom or a C 1-6 alkyl group, preferably a methyl group.)
Is the group selected from
E is − (CH 2 ) n − (n is an integer of 2 to 6).
D binds to the PFPE of the molecular backbone and E binds to the opposite group to the PFPE. ]
　Ｘ１の具体的な例としては、例えば：
－ＣＨ２Ｏ(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３－、
－ＣＨ２Ｏ(ＣＨ２)６－、
－ＣＨ２Ｏ(ＣＨ２)３Ｓｉ(ＣＨ３)２ＯＳｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３Ｓｉ(ＣＨ３)２ＯＳｉ(ＣＨ３)２ＯＳｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)２Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)３Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)１０Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)２０Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ(ＣＦ３)ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ(ＣＦ３)ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ(ＣＦ３)ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ(ＣＦ３)ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ(ＣＦ３)ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ(ＣＦ３)ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２(ＣＨ２)７ＣＨ２Ｓｉ(ＯＣＨ３)２ＯＳｉ(ＯＣＨ３)２(ＣＨ２)２Ｓｉ(ＯＣＨ３)２ＯＳｉ(ＯＣＨ３)２(ＣＨ２)２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＣＨ３)２ＯＳｉ(ＯＣＨ３)２(ＣＨ２)３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＣＨ２ＣＨ３)２ＯＳｉ(ＯＣＨ２ＣＨ３)２(ＣＨ２)３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＣＨ３)２ＯＳｉ(ＯＣＨ３)２(ＣＨ２)２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＣＨ２ＣＨ３)２ＯＳｉ(ＯＣＨ２ＣＨ３)２(ＣＨ２)２－、
－(ＣＨ２)２－、
－(ＣＨ２)３－、
－(ＣＨ２)４－、
－(ＣＨ２)６－、
－(ＣＨ２)２－Ｓｉ(ＣＨ３)２－(ＣＨ２)２－
－ＣＯＮＨ－(ＣＨ２)３－、
－ＣＯＮ(ＣＨ３)－(ＣＨ２)３－、
－ＣＯＮ(Ｐｈ)－(ＣＨ２)３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－(ＣＨ２)６－、
－ＣＯＮ(ＣＨ３)－(ＣＨ２)６－、
－ＣＯＮ(Ｐｈ)－(ＣＨ２)６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－(ＣＨ２)２ＮＨ(ＣＨ２)３－、
－ＣＯＮＨ－(ＣＨ２)６ＮＨ(ＣＨ２)３－、
－ＣＨ２Ｏ－ＣＯＮＨ－(ＣＨ２)３－、
－ＣＨ２Ｏ－ＣＯＮＨ－(ＣＨ２)６－、
－Ｓ－(ＣＨ２)３－、
－(ＣＨ２)２Ｓ(ＣＨ２)３－、
－ＣＯＮＨ－(ＣＨ２)３Ｓｉ(ＣＨ３)２ＯＳｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＯＮＨ－(ＣＨ２)３Ｓｉ(ＣＨ３)２ＯＳｉ(ＣＨ３)２ＯＳｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＯＮＨ－(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)２Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＯＮＨ－(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)３Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＯＮＨ－(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)１０Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－ＣＯＮＨ－(ＣＨ２)３Ｓｉ(ＣＨ３)２Ｏ(Ｓｉ(ＣＨ３)２Ｏ)２０Ｓｉ(ＣＨ３)２(ＣＨ２)２－、
－Ｃ(Ｏ)Ｏ－(ＣＨ２)３－、
－Ｃ(Ｏ)Ｏ－(ＣＨ２)６－、
－ＣＨ２－Ｏ－(ＣＨ２)３－Ｓｉ(ＣＨ３)２－(ＣＨ２)２－Ｓｉ(ＣＨ３)２－(ＣＨ２)２－、
－ＣＨ２－Ｏ－(ＣＨ２)３－Ｓｉ(ＣＨ３)２－(ＣＨ２)２－Ｓｉ(ＣＨ３)２－ＣＨ(ＣＨ３)－、
－ＣＨ２－Ｏ－(ＣＨ２)３－Ｓｉ(ＣＨ３)２－(ＣＨ２)２－Ｓｉ(ＣＨ３)２－(ＣＨ２)３－、
－ＣＨ２－Ｏ－(ＣＨ２)３－Ｓｉ(ＣＨ３)２－(ＣＨ２)２－Ｓｉ(ＣＨ３)２－ＣＨ(ＣＨ３)－ＣＨ２－、
Figure JPOXMLDOC01-appb-C000009
 などが挙げられる。 Specific examples of X 1 include:
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSI (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSI (CH 3 ) 2 OSI (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSI (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSI (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSI (OCH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSI (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSI (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSI (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 6- ,
-(CH 2 ) 2- Si (CH 3 ) 2- (CH 2 ) 2-
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (In the formula, Ph means phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (In the formula, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSI (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSI (CH 3 ) 2 OSI (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
-CH 2- O- (CH 2 ) 3- Si (CH 3 ) 2- (CH 2 ) 2- Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2- O- (CH 2 ) 3- Si (CH 3 ) 2- (CH 2 ) 2- Si (CH 3 ) 2- CH (CH 3 )-,
-CH 2- O- (CH 2 ) 3- Si (CH 3 ) 2- (CH 2 ) 2- Si (CH 3 ) 2- (CH 2 ) 3- ,
-CH 2- O- (CH 2 ) 3- Si (CH 3 ) 2- (CH 2 ) 2- Si (CH 3 ) 2- CH (CH 3 ) -CH 2- ,
Figure JPOXMLDOC01-appb-C000009
 And so on.
　さらに別のＸ１の例として、下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000010
 ［式中、
　Ｒ４１は、水素原子、フェニル基、Ｃ１－６アルキル基、又はＣ１－６アルコキシ基、好ましくはメチル基であり；
　各Ｘ１において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
－ＣＨ２Ｏ(ＣＨ２)２－、
－ＣＨ２Ｏ(ＣＨ２)３－、
－ＣＦ２Ｏ(ＣＨ２)３－、
－(ＣＨ２)２－、
－(ＣＨ２)３－、
－(ＣＨ２)４－、
－ＣＯＮＨ－(ＣＨ２)３－、
－ＣＯＮ(ＣＨ３)－(ＣＨ２)３－、
－ＣＯＮ(Ｐｈ)－(ＣＨ２)３－（式中、Ｐｈはフェニルを意味する）、又は
Figure JPOXMLDOC01-appb-C000011
 ［式中、Ｒ４２は水素原子、Ｃ１－６アルキル基（好ましくはメチル基）、又はメトキシ基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対側の基に結合する－(ＣＨ２)ｎ”－（ｎ”は２～６の整数）であり、存在する場合、残りは、それぞれ独立して、メチル基、フェニル基、Ｃ１－６アルコキシ基、又はラジカル捕捉基若しくは紫外線吸収基である。 Yet another example of X 1 is the following group:
Figure JPOXMLDOC01-appb-C000010
 [During the ceremony,
R 41 is a hydrogen atom, a phenyl group, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group;
In each X 1, some of any of T, then the following groups bonded to the PFPE molecule backbone:
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CF 2 O (CH 2 ) 3- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (In the formula, Ph means phenyl), or
Figure JPOXMLDOC01-appb-C000011
 [In the formula, R 42 represents a hydrogen atom, a C 1-6 alkyl group (preferably a methyl group), or a methoxy group. ]
And some of the other Ts are-(CH 2 ) n " -(n" is an integer of 2-6) that binds to the radical opposite the PFPE of the molecular main chain, and the rest, if present. Are each independently a methyl group, a phenyl group, a C 1-6 alkoxy group, or a radical trapping group or an ultraviolet absorbing group.
　ラジカル捕捉基は、光照射で生じるラジカルを捕捉できるものであれば特に限定されないが、例えばベンゾフェノン類、ベンゾトリアゾール類、安息香酸エステル類、サリチル酸フェニル類、クロトン酸類、マロン酸エステル類、オルガノアクリレート類、ヒンダードアミン類、ヒンダードフェノール類、又はトリアジン類の残基が挙げられる。 The radical trapping group is not particularly limited as long as it can trap radicals generated by light irradiation, but for example, benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylate, crotonic acids, malonic acid esters, organoacrylates, etc. , Hindered amines, hindered phenols, or triazine residues.
　紫外線吸収基は、紫外線を吸収できるものであれば特に限定されないが、例えばベンゾトリアゾール類、ヒドロキシベンゾフェノン類、置換及び未置換安息香酸若しくはサリチル酸化合物のエステル類、アクリレート又はアルコキシシンナメート類、オキサミド類、オキサニリド類、ベンゾキサジノン類、ベンゾキサゾール類の残基が挙げられる。 The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays, and for example, benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, etc. Included are residues of oxanilides, benzoxadinones and benzoxazoles.
　好ましい態様において、好ましいラジカル捕捉基又は紫外線吸収基としては、
Figure JPOXMLDOC01-appb-C000012
 が挙げられる。 In a preferred embodiment, the preferred radical scavenging group or UV absorbing group is
Figure JPOXMLDOC01-appb-C000012
 Can be mentioned.
　別の好ましい態様において、Ｘ１は、式：－(Ｒ１６)ｘ－(ＣＦＲ１７)ｙ－(ＣＨ２)ｚ－で表される基である。式中、ｘ、ｙ、及びｚは、それぞれ独立して、０～１０の整数であり、ｘ、ｙ、及びｚの和は１以上であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In another preferred embodiment, X 1 is a group represented by the formula: − (R 16 ) x − (CFR 17 ) y − (CH 2 ) z −. In the formula, x, y, and z are independently integers from 0 to 10, the sum of x, y, and z is 1 or more, and the existence order of each repeating unit enclosed in parentheses is. Optional in the formula.
　Ｒ１６は、各出現においてそれぞれ独立して、酸素原子、フェニレン、カルバゾリレン、－ＮＲ２６－（式中、Ｒ２６は、水素原子又は有機基を表す。）、又は２価の有機基である。好ましくは、Ｒ１６は、酸素原子又は２価の有機基（好ましくは極性基）である。 R 16 is independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 26 - (. Wherein, R 26 is, represents a hydrogen atom or an organic group), or a divalent organic group. Preferably, R 16 is an oxygen atom or a divalent organic group (preferably a polar group).
　Ｒ１６で表される２価の極性基としては、特に限定されないが、－Ｃ(Ｏ)－、－Ｃ(＝ＮＲ２７)－、及び－Ｃ(Ｏ)ＮＲ２７－（これらの式中、Ｒ２７は、水素原子又は低級アルキル基を表す。）が挙げられる。当該低級アルキル基は、例えば、Ｃ１－６アルキル基、例えばメチル、エチル、ｎ－プロピルであり、これらは、１個又はそれ以上のフッ素原子により置換されていてもよい。 The divalent polar group represented by R 16, but are not limited to, -C (O) -, - C (= NR 27) -, and -C (O) NR 27 - (in these formulas, R 27 represents a hydrogen atom or a lower alkyl group). The lower alkyl group is, for example, a C 1-6 alkyl group, such as methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.
　Ｒ１７は、各出現においてそれぞれ独立して、水素原子、フッ素原子、又は低級フルオロアルキル基であり、好ましくはフッ素原子である。当該「低級フルオロアルキル基」は、例えば、Ｃ１－６フルオロアルキル基、好ましくはＣ１－３フルオロアルキル基、より好ましくはＣ１－３パーフルオロアルキル基、さらに好ましくはトリフルオロメチル基、ペンタフルオロエチル基、よりさらに好ましくはトリフルオロメチル基である。 R 17 is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group at each appearance, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a C 1-6 fluoroalkyl group, preferably a C 1-3 fluoroalkyl group, more preferably a C 1-3 perfluoroalkyl group, still more preferably a trifluoromethyl group, or a penta. It is a fluoroethyl group, more preferably a trifluoromethyl group.
　この態様において、Ｘ１は、好ましくは、式：－(Ｏ)ｘ－(ＣＦ２)ｙ－(ＣＨ２)ｚ－（式中、ｘ、ｙ、及びｚは、上記と同意義であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）で表される基である。 In this embodiment, X 1 preferably has the same meaning as described above in the formula: − (O) x − (CF 2 ) y − (CH 2 ) z − (in the formula, x, y, and z have the same meanings as above. The order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.).
　式：－(Ｏ)ｘ－(ＣＦ２)ｙ－(ＣＨ２)ｚ－で表される基としては、例えば、
－(Ｏ)ｘ’－(ＣＨ２)ｚ”－Ｏ－[(ＣＨ２)ｚ’’’－Ｏ－]ｚ””、及び
－(Ｏ)ｘ’－(ＣＦ２)ｙ”－(ＣＨ２)ｚ”－Ｏ－[(ＣＨ２)ｚ’’’－Ｏ－]ｚ””
（式中、ｘ’は０又は１であり、ｙ”、ｚ”、及びｚ’’’は、それぞれ独立して、１～１０の整数であり、ｚ””は０又は１である。）
で表される基が挙げられる。なお、これらの基は左端がＰＦＰＥ側に結合する。 Formula: As a group represented by − (O) x − (CF 2 ) y − (CH 2 ) z −, for example,
-(O) x' -(CH 2 ) z " -O-[(CH 2 ) z'''- O-] z"" , and-(O) x' -(CF 2 ) y" -(CH 2 ) z " -O- [(CH 2 ) z'''- O-] z"""
(In the formula, x'is 0 or 1, y ", z", and z "" are independently integers from 1 to 10, and z "" is 0 or 1.)
The groups represented by are mentioned. The left end of these groups is bonded to the PFPE side.
　別の好ましい態様において、Ｘ１は、－Ｏ－ＣＦＲ１３－(ＣＦ２)ｅ－である。
　Ｒ１３は、それぞれ独立して、フッ素原子又は低級フルオロアルキル基を表す。低級フルオロアルキル基は、例えばＣ１－３フルオロアルキル基、好ましくはＣ１－３パーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、さらに好ましくはトリフルオロメチル基である。
　ｅは、それぞれ独立して、０又は１である。
　一の具体例において、Ｒ１３はフッ素原子であり、ｅは１である。 In another preferred embodiment, X 1 is, -O-CFR 13 - (CF 2) e - a.
R 13 independently represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a C 1-3 fluoroalkyl group, preferably a C 1-3 perfluoroalkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
e is 0 or 1 independently of each other.
In one specific example, R 13 is a fluorine atom and e is 1.
　好ましい態様において、ｔは１～６の整数である。別の好ましい態様において、ｔは２～１０の整数であり、好ましくは２～６の整数である。 In a preferred embodiment, t is an integer of 1-6. In another preferred embodiment, t is an integer of 2-10, preferably an integer of 2-6.
　Ｘ２は、好ましくは、Ｃ１－２０アルキレン基であり、より好ましくは、－(ＣＨ２)ｕ－（式中、ｕは、０～２の整数である）である。 X 2 is preferably a C 1-20 alkylene group, more preferably − (CH 2 ) u − (where u is an integer of 0 to 2 in the formula).
　式（1-1-A）及び（1-2-A）において、
　ＰＦＰＥ、Ｒｆ、Ｒ１、Ｒ２、Ｒ１１、及びＲ１２は、前記と同意義であり；
　ｎは、０～２の整数、好ましくは０であり；
　Ｘ１は、－Ｏ－ＣＦＲ１３－(ＣＦ２)ｅ－であり；
　Ｒ１３は、フッ素原子又は低級フルオロアルキル基であり；
　ｅは、０又は１であり；
　Ｘ２は、－(ＣＨ２)ｕ－であり；
　ｕは、０～２の整数である、
化合物が好ましい。 In equations (1-1-A) and (1-2-A),
PFPE, Rf, R 1 , R 2 , R 11 and R 12 have the same meaning as above;
n is an integer from 0 to 2, preferably 0;
X 1 is, -O-CFR 13 - (CF 2) e - a is;
R 13 is a fluorine atom or lower fluoroalkyl group;
e is 0 or 1;
X 2 is-(CH 2 ) u- ;
u is an integer from 0 to 2,
Compounds are preferred.
　式（1-3）及び（1-4）中、Ｒｆ、ＰＦＰＥ、Ｒ１、Ｒ２、及びｎは、式（1-1）及び（1-2）に関する記載と同意義である。 In formulas (1-3) and (1-4), Rf, PFPE, R 1 , R 2 , and n have the same meaning as the descriptions relating to formulas (1-1) and (1-2).
　Ｘ５は、式（1-3）及び（1-4）で表される化合物において、主に撥水性等を提供するパーフルオロポリエーテル部（Ｒｆ－ＰＦＰＥ部又は－ＰＦＰＥ－部）と、タイヤとの結合能を提供するシラン部（具体的には、－ＳｉＲ１ ｎＲ２ ３－ｎ）とを連結するリンカーと解することができる。従って、Ｘ５は、式（1-3）及び（1-4）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 X 5 is a compound represented by the formulas (1-3) and (1-4), which mainly provides a perfluoropolyether portion (Rf-PFPE portion or -PFPE- portion) that provides water repellency and the like, and a tire. and of (specifically, -SiR 1 n R 2 3- n) silane portion to provide a binding ability it can be interpreted as a linker connecting the. Therefore, X 5 may be any organic group as long as the compounds represented by the formulas (1-3) and (1-4) can be stably present.
　βは、１～９の整数であり、β’は、１～９の整数である。β及びβ’は、Ｘ３の価数に応じて決定され、式（1-3）において、β及びβ’の和は、Ｘ５の価数と同じである。例えば、Ｘ５が１０価の有機基である場合、β及びβ’の和は１０であり、例えばβが９かつβ’が１、βが５かつβ’が５、又はβが１かつβ’が９となり得る。また、Ｘ５が２価の有機基である場合、β及びβ’は１である。式（1-4）において、βはＸ５の価数の値から１を引いた値である。 β is an integer of 1 to 9, and β'is an integer of 1 to 9. β and β'are determined according to the valence of X 3 , and in formula (1-3), the sum of β and β'is the same as the valence of X 5 . For example, when X 5 is a 10-valent organic group, the sum of β and β'is 10, for example β is 9 and β'is 1, β is 5 and β'is 5, or β is 1 and β. 'Can be 9. Further, when X 5 is a divalent organic group, β and β'are 1. In equation (1-4), β is the value obtained by subtracting 1 from the value of the valence of X 5 .
　Ｘ５は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 X 5 is preferably a divalent to 7 valent, more preferably a 2 to 4 valent, even more preferably a divalent organic group.
　一の態様において、Ｘ５は２～４価の有機基であり、βは１～３であり、β’は１である。 In one embodiment, X 5 is a 2- to tetravalent organic group, β is 1-3, and β'is 1.
　別の態様において、Ｘ５は２価の有機基であり、βは１であり、β’は１である。この場合、式（1-3）及び（1-4）は、下記式（1-3-A）及び（1-4-A）で表される。
Figure JPOXMLDOC01-appb-C000013
 In another embodiment, X 5 is a divalent organic group, β is 1, and β'is 1. In this case, the formulas (1-3) and (1-4) are represented by the following formulas (1-3-A) and (1-4-A).
Figure JPOXMLDOC01-appb-C000013
　Ｘ５の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 5 include, but are not limited to, the same as those described for X 1 .
　式（1-3-A）及び（1-4-A）において、
　ＰＦＰＥ、Ｒｆ、Ｒ１、及びＲ２は、前記と同意義であり；
　ｎは、０～２の整数であり、好ましくは０であり；
　Ｘ５は、－ＣＨ２Ｏ(ＣＨ２)２－、－ＣＨ２Ｏ(ＣＨ２)３－、又は－ＣＨ２Ｏ(ＣＨ２)６－である
化合物が好ましい。 In equations (1-3-A) and (1-4-A),
PFPE, Rf, R 1 and R 2 have the same meaning as above;
n is an integer of 0 to 2, preferably 0;
X 5 is, -CH 2 O (CH 2) 2 -, - CH 2 O (CH 2) 3 -, or -CH 2 O (CH 2) 6 - , compound are preferred.
　式（1-5）及び（1-6）中、Ｒｆ及びＰＦＰＥは、上記式（1-1）及び（1-2）に関する記載と同意義である。 In formulas (1-5) and (1-6), Rf and PFPE have the same meaning as the descriptions related to the above formulas (1-1) and (1-2).
　Ｘ７は、式（1-5）及び（1-6）で表される化合物において、主に撥水性等を提供するパーフルオロポリエーテル部（Ｒｆ－ＰＦＰＥ部又は－ＰＦＰＥ－部）と、タイヤとの結合能を提供するシラン部（具体的には、－ＳｉＲａ ｋＲｂ ｌＲｃ ｍ基）とを連結するリンカーと解することができる。従って、Ｘ７は、式（1-5）及び（1-6）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the compounds represented by the formulas (1-5) and (1-6), X 7 is a perfluoropolyether portion (Rf-PFPE portion or -PFPE- portion) that mainly provides water repellency and the like, and a tire. the ability to bind (specifically, -SiR a k R b l R c m group) silane unit to provide a can be interpreted as linker connecting. Therefore, X 7 may be any organic group as long as the compounds represented by the formulas (1-5) and (1-6) can be stably present.
　γ及びγ’は、Ｘ７の価数に応じて決定され、式（1-5）において、γ及びγ’の和は、Ｘ７の価数と同じである。例えば、Ｘ７が１０価の有機基である場合、γ及びγ’の和は１０であり、例えばγが９かつγ’が１、γが５かつγ’が５、又はγが１かつγ’が９となり得る。また、Ｘ７が２価の有機基である場合、γ及びγ’は１である。式（1-5）において、γはＸ７の価数の値から１を引いた値である。 γ and γ'are determined according to the valence of X 7 , and in equation (1-5), the sum of γ and γ'is the same as the valence of X 7 . For example, when X 7 is a 10-valent organic group, the sum of γ and γ'is 10, for example, γ is 9 and γ'is 1, γ is 5 and γ'is 5, or γ is 1 and γ. 'Can be 9. Further, when X 7 is a divalent organic group, γ and γ'are 1. In equation (1-5), γ is the value obtained by subtracting 1 from the value of the valence of X 7 .
　Ｘ７は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 X 7 is preferably a 2- to 7-valent, more preferably 2- to 4-valent, even more preferably divalent organic group.
　一の態様において、Ｘ７は２～４価の有機基であり、γは１～３であり、γ’は１である。 In one embodiment, X 7 is a 2- to tetravalent organic group, γ is 1-3, and γ'is 1.
　別の態様において、Ｘ７は２価の有機基であり、γは１であり、γ’は１である。この場合、式（1-5）及び（1-6）は、下記式（1-5-A）及び（1-6-A）で表される。
Figure JPOXMLDOC01-appb-C000014
 In another embodiment, X 7 is a divalent organic group, γ is 1, and γ'is 1. In this case, equations (1-5) and (1-6) are represented by the following equations (1-5-A) and (1-6-A).
Figure JPOXMLDOC01-appb-C000014
　Ｘ７の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 7 include, but are not limited to, the same as those described for X 1 .
　Ｚは、好ましくは、２価の有機基であり、式（1-5）又は式（1-6）における分子主鎖の末端のＳｉ原子（Ｒａが結合しているＳｉ原子）とシロキサン結合を形成するものを含まない。 Z is preferably a divalent organic group, and is a siloxane bond with a Si atom (Si atom to which Ra is bonded) at the end of the molecular main chain in the formula (1-5) or the formula (1-6). Does not include those that form.
　Ｚは、好ましくは、Ｃ１－６アルキレン基、－(ＣＨ２)ｇ－Ｏ－(ＣＨ２)ｈ－（式中、ｇは、１～６の整数であり、ｈは、１～６の整数である）、又は－フェニレン－(ＣＨ２)ｉ－（式中、ｉは、０～６の整数である）であり、より好ましくはＣ１－３アルキレン基である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、及びＣ２－６アルキニル基から選択される１個又はそれ以上の置換基により置換されていてもよい。 Z is preferably a C 1-6 alkylene group,-(CH 2 ) g- O- (CH 2 ) h- (in the formula, g is an integer of 1 to 6 and h is an integer of 1 to 6. It is an integer) or -phenylene- (CH 2 ) i- (in the formula, i is an integer of 0 to 6), more preferably a C 1-3 alkylene group. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. ..
　Ｒａ中、Ｚ基を介して直鎖状に連結されるＳｉは最大で５個である。即ち、Ｒａにおいて、Ｒ７１が少なくとも１つ存在する場合、Ｒａ中にＺ基を介して直鎖状に連結されるＳｉ原子が２個以上存在するが、かかるＺ基を介して直鎖状に連結されるＳｉ原子の数は最大で５個である。なお、「Ｒａ中のＺ基を介して直鎖状に連結されるＳｉ原子の数」とは、Ｒａ中において直鎖状に連結される－Ｚ－Ｓｉ－の繰り返し数と等しくなる。 During R a, Si is connected to the linear through the Z group is a five at the maximum. That is, in Ra , when at least one R 71 is present, two or more Si atoms linearly linked via the Z group are present in Ra , but the straight chain is present through the Z group. The maximum number of Si atoms linked in a shape is five. The "number of Si atoms linearly linked via a Z group in R a" is equal to -Z-Si- repeating number of which is connected to a linear during R a.
　例えば、下記にＲａ中においてＺ基を介してＳｉ原子が連結された一例を示す。
Figure JPOXMLDOC01-appb-C000015
 For example, an example in which Si atoms are linked via a Z group in Ra is shown below.
Figure JPOXMLDOC01-appb-C000015
　上記式において、＊は、主鎖のＳｉに結合する部位を意味し、…は、ＺＳｉ以外の所定の基が結合していること、即ち、Ｓｉ原子の３本の結合手がすべて…である場合、ＺＳｉの繰り返しの終了箇所を意味する。また、Ｓｉの右肩の数字は、＊から数えたＺ基を介して直鎖状に連結されたＳｉの出現数を意味する。即ち、Ｓｉ２でＺＳｉ繰り返しが終了している鎖は「Ｒａ中のＺ基を介して直鎖状に連結されるＳｉ原子の数」が２個であり、同様に、Ｓｉ３、Ｓｉ４及びＳｉ５でＺＳｉ繰り返しが終了している鎖は、それぞれ、「Ｒａ中のＺ基を介して直鎖状に連結されるＳｉ原子の数」が３、４、及び５個である。なお、上記の式から明らかなように、Ｒａ中には、ＺＳｉ鎖が複数存在するが、これらはすべて同じ長さである必要はなく、それぞれ任意の長さであってもよい。 In the above formula, * means a site that binds to Si in the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In the case, it means the end point of the repetition of ZSi. The number on the right shoulder of Si means the number of occurrences of Si linearly connected via the Z group counted from *. That is, the chain in which the ZSi repetition is completed in Si 2 has "the number of Si atoms linearly connected via the Z group in Ra", and similarly, Si 3 , Si 4 and Si. The chains in which the ZSi repetition is completed in Si 5 have "the number of Si atoms linearly linked via the Z group in Ra " of 3, 4, and 5, respectively. As is apparent from the above equation, is in the R a, but ZSi chain there are multiple, they need not be all the same length, each may be of any length.
　好ましい態様において、下記に示すように、「Ｒａ中のＺ基を介して直鎖状に連結されるＳｉ原子の数」は、すべての鎖において、１個（左式）又は２個（右式）である。
Figure JPOXMLDOC01-appb-C000016
 In a preferred embodiment, as shown below, the "number of Si atoms linearly linked via the Z group in Ra " is 1 (left) or 2 (right) in all chains. Equation).
Figure JPOXMLDOC01-appb-C000016
　一の態様において、Ｒａ中のＺ基を介して直鎖状に連結されるＳｉ原子の数は１個又は２個、好ましくは１個である。 In one embodiment, the number of Si atoms linearly linked via the Z group in Ra is one or two, preferably one.
　Ｒ７２で表される加水分解可能な基の例としては、－ＯＲ’、－ＯＣＯＲ’、－Ｏ－Ｎ＝Ｃ(Ｒ’)２、－Ｎ(Ｒ’)２、－ＮＨＲ’、ハロゲン（これら式中、Ｒ’は、置換又は非置換のＣ１－４アルキル基を示す）などが挙げられ、好ましくは－ＯＲ’（アルコキシ基）である。Ｒ’の例には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基又はエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。 Examples of hydrolyzable groups represented by R 72 are -OR', -OCOR', -ON = C (R') 2 , -N (R') 2 , -NHR', halogen ( In these formulas, R'indicates a substituted or unsubstituted C 1-4 alkyl group) and the like, and is preferably −OR'(alkoxy group). Examples of R'include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be generated by hydrolyzing a hydrolyzable group.
　好ましくは、Ｒ７２は、－ＯＲ’（式中、Ｒ’は、置換又は非置換のＣ１－３アルキル基、より好ましくはメチル基を表す。）である。 Preferably, R 72 is -OR'(in the formula, R'represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
　Ｒ７３で表される低級アルキル基は、好ましくはＣ１－２０アルキル基、より好ましくはＣ１－６アルキル基、さらに好ましくはメチル基である。 The lower alkyl group represented by R 73 is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
　好ましい態様において、Ｒａ中の末端のＲａ’（Ｒａ’が存在しない場合、Ｒａ）において、ｑは、好ましくは２以上、例えば２又は３であり、より好ましくは３である。 In a preferred embodiment, '(if R a' is absent, R a) R a terminal in R a in, q is preferably 2 or more, for example 2 or 3, more preferably 3.
　好ましい態様において、Ｒａの末端部の少なくとも１つは、－Ｓｉ(－Ｚ－ＳｉＲ７２ ｑＲ７３ ｒ)２又は－Ｓｉ(－Ｚ－ＳｉＲ７２ ｑＲ７３ ｒ)３、好ましくは－Ｓｉ(－Ｚ－ＳｉＲ７２ ｑＲ７３ ｒ)３であり得る。式中、(－Ｚ－ＳｉＲ７２ ｑＲ７３ ｒ)の単位は、好ましくは(－Ｚ－ＳｉＲ７２ ３）である。さらに好ましい態様において、Ｒａの末端部は、すべて－Ｓｉ(－Ｚ－ＳｉＲ７２ ｑＲ７３ ｒ)３、好ましくは－Ｓｉ(－ＺＳｉＲ７２ ３)３であり得る。 In a preferred embodiment, at least one of the distal portion of the R a is, -Si (-Z-SiR 72 q R 73 r) 2 or -Si (-Z-SiR 72 q R 73 r) 3, preferably -Si ( -Z-SiR 72 q R 73 r ) 3 can be. Wherein, (- Z-SiR 72 q R 73 r) units is preferably (-Z-SiR 72 3). In a further preferred embodiment, the distal end of the R a, all -Si (-Z-SiR 72 q R 73 r) 3, may be preferably -Si (-ZSiR 72 3) 3.
　Ｒｂは、好ましくは、水酸基、－ＯＲ’、－ＯＣＯＲ’、－Ｏ－Ｎ＝Ｃ(Ｒ’)２、－Ｎ(Ｒ’)２、－ＮＨＲ’、ハロゲン（これら式中、Ｒ’は、置換又は非置換のＣ１－４アルキル基を示す。）であり、好ましくは－ＯＲ’である。Ｒ’は、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基又はエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。より好ましくは、Ｒｂは、－ＯＲ’（式中、Ｒ’は、置換又は非置換のＣ１－３アルキル基、より好ましくはメチル基を表す）である。 Rb is preferably hydroxyl group, -OR', -OCOR', -ON = C (R') 2 , -N (R') 2 , -NHR', halogen (in these formulas, R'is , Substituent or unsubstituted C 1-4 alkyl group), preferably −OR ′. R'includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be generated by hydrolyzing a hydrolyzable group. More preferably, R b is -OR'(in the formula, R'represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
　Ｒｃで表される低級アルキル基は、好ましくはＣ１－２０アルキル基、より好ましくはＣ１－６アルキル基、さらに好ましくはメチル基である。 Lower alkyl group represented by R c is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, more preferably a methyl group.
　組成物（１）は、さらに溶媒を含有することができる。溶媒としては、特に限定するものではないが、例えば、パーフルオロヘキサン、ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＦ３ＣＨ２ＣＦ２ＣＨ３、ＣＦ３ＣＨＦＣＨＦＣ２Ｆ５、１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタン、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（ゼオローラＨ（商品名）等）、Ｃ４Ｆ９ＯＣＨ３、Ｃ４Ｆ９ＯＣ２Ｈ５、ＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２、Ｃ６Ｆ１３ＣＨ＝ＣＨ２、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、ＨＣＦ２ＣＦ２ＣＨ２ＯＨ、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸及びＣＦ３Ｏ(ＣＦ２ＣＦ２Ｏ)ｍ(ＣＦ２Ｏ)ｎＣＦ２ＣＦ３［式中、ｍ及びｎは、それぞれ独立して０以上１０００以下の整数であり、ｍ又はｎを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、但しｍ及びｎの和は１以上である。］、１，１－ジクロロ－２，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－１，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１，２－トリクロロ―３，３，３－トリフルオロ－１－プロペン、１，１，１，４，４，４－ヘキサフルオロ－２－ブテンからなる群から選択される溶媒が挙げられる。これらの溶媒は、単独で又は２種以上の混合物として用いることができる。 The composition (1) can further contain a solvent. The solvent is not particularly limited, but is, for example, perfluorohexane, CF 3 CF 2 CHCl 2 , CF 3 CH 2 CF 2 CH 3 , CF 3 CHFCHFC 2 F 5 , 1, 1, 1, 2 , 2. , 3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane (Zeorolla H (trade name), etc.), C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , CF 3 CH 2 OCF 2 CHF 2 , C 6 F 13 CH = CH 2 , xylene hexafluoride, perfluorobenzene, methylpentadecafluoroheptyl ketone, Trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH, methyltrifluoromethanesulfonate, trifluoroacetic acid and CF 3 O (CF 2 CF 2 O) m (CF 2 O) n CF 2 CF 3 [In the formula, m and n are independently integers of 0 or more and 1000 or less, and the order of existence of each repeating unit enclosed in parentheses with m or n is arbitrary in the formula, except that m. And the sum of n is 1 or more. ], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro- 3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1 Examples thereof include solvents selected from the group consisting of propene, 1,1,1,4,4,4-hexafluoro-2-butene. These solvents can be used alone or as a mixture of two or more.
　組成物（１）は、さらに他の成分を含有することができる。他の成分を含んでいてもよい。他の成分としては、特に限定されるものではないが、例えば、含フッ素オイルとして理解され得る（非反応性の）フルオロポリエーテル化合物、好ましくはパーフルオロ（ポリ）エーテル化合物（以下、「含フッ素オイル」と言う）、シリコーンオイルとして理解され得る（非反応性の）シリコーン化合物（以下、「シリコーンオイル」と言う）、触媒などが挙げられる。 The composition (1) can further contain other components. It may contain other components. The other components are not particularly limited, but for example, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro (poly) ether compound (hereinafter, “fluorine-containing”). Examples include (referred to as "oil"), (non-reactive) silicone compounds (hereinafter referred to as "silicone oil") that can be understood as silicone oil, and catalysts.
　含フッ素オイルとしては、特に限定されるものではないが、例えば、以下の式（1B）で表される化合物（パーフルオロ（ポリ）エーテル化合物）が挙げられる。
　Ｒｆ１－(ＯＣ４Ｆ８)ａ’－(ＯＣ３Ｆ６)ｂ’－(ＯＣ２Ｆ４)ｃ’－(ＯＣＦ２)ｄ’－Ｒｆ２（1B）
　式中、Ｒｆ１は、１個又はそれ以上のフッ素原子により置換されていてもよいＣ１－１６アルキル基（好ましくは、Ｃ１―１６パーフルオロアルキル基）を表し、Ｒｆ２は、１個又はそれ以上のフッ素原子により置換されていてもよいＣ１－１６アルキル基（好ましくは、Ｃ１－１６パーフルオロアルキル基）、フッ素原子、又は水素原子を表す。
　好ましくは、上記１個又はそれ以上のフッ素原子により置換されていてもよいアルキル基は、末端炭素原子がＣＦ２Ｈ－であり他のすべての炭素原子がフッ素により全置換されているフルオロアルキル基、又はパーフルオロアルキル基であり、より好ましくはパーフルオロアルキル基である。より好ましくは、Ｒｆ１及びＲｆ２は、それぞれ独立して、Ｃ１－３パーフルオロアルキル基である。
　ａ’、ｂ’、ｃ’及びｄ’は、ポリマーの主骨格を構成するパーフルオロポリエーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０～３００の整数（好ましくは０～２００の整数、例えば１～２００の整数）であって、ａ’、ｂ’、ｃ’及びｄ’の和は少なくとも１（好ましくは１～３００、より好ましくは２０～３００）である。添字ａ’、ｂ’、ｃ’又はｄ’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 The fluorine-containing oil is not particularly limited, and examples thereof include a compound represented by the following formula (1B) (perfluoro (poly) ether compound).
Rf 1- (OC 4 F 8 ) a' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c' -(OCF 2 ) d'- Rf 2 (1B)
In the formula, Rf 1 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted with one or more fluorine atoms, and Rf 2 is one. It represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group), a fluorine atom, or a hydrogen atom which may be substituted with an or more fluorine atom.
Preferably, an alkyl group optionally substituted by one or more fluorine atoms above fluoroalkyl group terminal carbon atom is CF 2 H- all other carbon atoms are all substituted by fluorine , Or a perfluoroalkyl group, more preferably a perfluoroalkyl group. More preferably, Rf 1 and Rf 2 are independently C 1-3 perfluoroalkyl groups.
a', b', c'and d'represent the number of four types of repeating units of the perfluoropolyether constituting the main skeleton of the polymer, and are independent integers of 0 to 300 (preferably 0 to 200). (For example, an integer of 1 to 200), and the sum of a', b', c'and d'is at least 1 (preferably 1 to 300, more preferably 20 to 300). The order of existence of each repeating unit in parentheses with the subscripts a', b', c'or d'is arbitrary in the equation.
　式（1B）で表されるパーフルオロポリエーテル化合物の例として、以下の式（1B-1）及び（1B-2）のいずれかで示される化合物（１種又は２種以上の混合物であってもよい）が挙げられる。
　Ｒｆ１－(ＯＣＦ２ＣＦ２ＣＦ２)ｂ’’－Ｒｆ２　（1B-1）
　Ｒｆ１－(ＯＣＦ(ＣＦ３)ＣＦ２)ｂ’’－Ｒｆ２　（1B-2）
　Ｒｆ１－(ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２)ａ’’－(ＯＣＦ２ＣＦ２ＣＦ２)ｂ’’－(ＯＣＦ２ＣＦ２)ｃ’’－(ＯＣＦ２)ｄ’’－Ｒｆ２　（1B-3）
　これら式中、Ｒｆ１及びＲｆ２は上記の通りであり；
式（1B-1）において、ｂ’’は１～３００の整数（好ましくは１～１００の整数）であり；
式（1B-2）において、ｂ’’は１～３００の整数であり；
式（1B-3）において、ａ’’及びｂ’’は、それぞれ独立して０～３０の整数（例えば１～３０の整数）であり、ｃ’’及びｄ’’はそれぞれ独立して１～３００の整数である。添字ａ’’、ｂ’’、ｃ’’、ｄ’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 As an example of the perfluoropolyether compound represented by the formula (1B), a compound (one or a mixture of two or more) represented by any of the following formulas (1B-1) and (1B-2). May be good).
Rf 1- (OCF 2 CF 2 CF 2 ) b'' -Rf 2 (1B-1)
Rf 1- (OCF (CF 3 ) CF 2 ) b'' -Rf 2 (1B-2)
Rf 1- (OCF 2 CF 2 CF 2 CF 2 ) a'' -(OCF 2 CF 2 CF 2 ) b'' -(OCF 2 CF 2 ) c'' -(OCF 2 ) d''- Rf 2 ( 1B-3)
In these equations, Rf 1 and Rf 2 are as described above;
In equation (1B-1), b'' is an integer from 1 to 300 (preferably an integer from 1 to 100);
In equation (1B-2), b'' is an integer from 1 to 300;
In the formula (1B-3), a'' and b'' are independently integers of 0 to 30 (for example, integers of 1 to 30), and c'' and d'' are independently 1 respectively. It is an integer of ~ 300. The order of existence of each repeating unit in parentheses with the subscripts a'', b'', c'', and d'' is arbitrary in the equation.
　一の態様において、式（1B-3）で表される化合物において、ｃ’’／ｄ’’比は、０．２以上０．９未満の範囲内である式（1B-3）で表される１種又はそれ以上の化合物である。 In one embodiment, in the compound represented by the formula (1B-3), the c ″ / d ″ ratio is represented by the formula (1B-3) in the range of 0.2 or more and less than 0.9. One or more compounds.
　含フッ素オイルは、１，０００～３０，０００の平均分子量を有することができる。代表的には、式（1B-1）～（1B-3）で表される化合物は、１，５００以上の数平均分子量を有することが好ましい。 The fluorine-containing oil can have an average molecular weight of 1,000 to 30,000. Typically, the compounds represented by the formulas (1B-1) to (1B-3) preferably have a number average molecular weight of 1,500 or more.
　組成物（１）中、含フッ素オイルは、パーフルオロポリエーテル基含有シラン化合物の合計１００質量部（それぞれ、２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～５００質量部、好ましくは０～４００質量部、より好ましくは５～３００質量部の範囲内で含まれ得る。 In the composition (1), the fluorine-containing oil is, for example, 0 to 100 parts by mass of a total of 100 parts by mass of the perfluoropolyether group-containing silane compound (in the case of two or more kinds, the total of these, the same applies hereinafter). It may be contained in the range of 500 parts by mass, preferably 0 to 400 parts by mass, and more preferably 5 to 300 parts by mass.
　式（1B-1）で示される化合物及び式（1B-3）で示される化合物は、それぞれ単独で用いても、組み合わせて用いてもよい。式（1B-1）で示される化合物よりも、式（1B-3）で示される化合物を用いるほうが好ましい。これらを組み合わせて用いる場合、式（1B-1）で表される化合物と、式（1B-3）で表される化合物との質量比は、１：１～１：３０の範囲内が好ましく、１：１～１：１０の範囲内がより好ましい。 The compound represented by the formula (1B-1) and the compound represented by the formula (1B-3) may be used alone or in combination. It is preferable to use the compound represented by the formula (1B-3) rather than the compound represented by the formula (1B-1). When these are used in combination, the mass ratio of the compound represented by the formula (1B-1) to the compound represented by the formula (1B-3) is preferably in the range of 1: 1 to 1:30. The range of 1: 1 to 1:10 is more preferable.
　一の態様において、含フッ素オイルは、式（1B-3）で表される１種又はそれ以上の化合物を含む。かかる態様において、組成物（１）中のパーフルオロポリエーテル基含有シラン化合物の合計と、式（1B-3）で表される化合物との質量比は、４：１～１：４の範囲内であることが好ましい。 In one embodiment, the fluorine-containing oil contains one or more compounds represented by the formula (1B-3). In such an embodiment, the mass ratio of the total of the perfluoropolyether group-containing silane compounds in the composition (1) to the compound represented by the formula (1B-3) is in the range of 4: 1 to 1: 4. Is preferable.
　好ましい態様において、真空蒸着法により表面処理層を形成する場合には、パーフルオロポリエーテル基含有シラン化合物の平均分子量よりも、含フッ素オイルの平均分子量を大きくしてもよい。 In a preferred embodiment, when the surface treatment layer is formed by the vacuum vapor deposition method, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the perfluoropolyether group-containing silane compound.
　また、別の観点から、含フッ素オイルは、一般式Ｒｆ３－Ｆ（式中、Ｒｆ３はＣ５－１６パーフルオロアルキル基である。）で表される化合物であってよい。また、クロロトリフルオロエチレンオリゴマーであってもよい。Ｒｆ３－Ｆで表される化合物及びクロロトリフルオロエチレンオリゴマーは、末端がＣ１－１６パーフルオロアルキル基である上記分子末端に炭素－炭素不飽和結合を有する含フッ素化合物で表される化合物と高い親和性が得られる点で好ましい。 From another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf 3- F (in the formula, Rf 3 is a C 5-16 perfluoroalkyl group). Further, it may be a chlorotrifluoroethylene oligomer. The compound represented by Rf 3- F and the chlorotrifluoroethylene oligomer are a compound represented by a fluorine-containing compound having a carbon-carbon unsaturated bond at the molecular end having a C 1-16 perfluoroalkyl group at the end. It is preferable in that a high affinity can be obtained.
　シリコーンオイルとしては、例えばシロキサン結合が２，０００以下の直鎖状又は環状のシリコーンオイルを用い得る。直鎖状のシリコーンオイルは、いわゆるストレートシリコーンオイル及び変性シリコーンオイルのいずれであってもよい。ストレートシリコーンオイルとしては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイルが挙げられる。変性シリコーンオイルとしては、ストレートシリコーンオイルを、アルキル、アラルキル、ポリエーテル、高級脂肪酸エステル、フルオロアルキル、アミノ、エポキシ、カルボキシル、アルコールなどにより変性したものが挙げられる。環状のシリコーンオイルは、例えば環状ジメチルシロキサンオイルなどが挙げられる。 As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be either a so-called straight silicone oil or a modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
　組成物（１）中、かかるシリコーンオイルは、パーフルオロポリエーテル基含有シラン化合物の合計１００質量部（２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～３００質量部、好ましくは０～２００質量部の範囲内で含まれ得る。 In the composition (1), the silicone oil is, for example, 0 to 300 parts by mass with respect to a total of 100 parts by mass of the perfluoropolyether group-containing silane compound (in the case of two or more kinds, the total of these, the same applies hereinafter). It may be contained in the range of 0 to 200 parts by mass.
　触媒としては、酸（例えば酢酸、トリフルオロ酢酸等）、塩基（例えばアンモニア、トリエチルアミン、ジエチルアミン等）、遷移金属（例えばＴｉ、Ｎｉ、Ｓｎ等）等が挙げられる。 Examples of the catalyst include acids (for example, acetic acid, trifluoroacetic acid, etc.), bases (for example, ammonia, triethylamine, diethylamine, etc.), transition metals (for example, Ti, Ni, Sn, etc.) and the like.
　触媒は、パーフルオロポリエーテル基含有シラン化合物の加水分解及び脱水縮合を促進し、表面処理層の形成を促進することができる。 The catalyst can promote the hydrolysis and dehydration condensation of the perfluoropolyether group-containing silane compound, and can promote the formation of the surface treatment layer.
　組成物（１）は、多孔質物質、例えば多孔質のセラミック材料、金属繊維、例えばスチールウールを綿状に固めたものに含浸させて、ペレットとすることができる。当該ペレットは、例えば、真空蒸着に用いることができる。 The composition (1) can be made into pellets by impregnating a porous substance such as a porous ceramic material or a metal fiber, for example, steel wool into a cotton-like material. The pellet can be used, for example, for vacuum deposition.
　組成物（１）は、例えば、米国特許出願公開第２０１７／３４２２１０号、又は特許第６３３２３５８号に記載の表面処理剤であることができる。 The composition (1) can be, for example, the surface treatment agent described in US Patent Application Publication No. 2017/342210 or Japanese Patent No. 6332358.
組成物（２）
　組成物（２）は、炭素－炭素二重結合含有パーフルオロポリエーテル化合物を含有する組成物である。炭素－炭素二重結合含有パーフルオロポリエーテル化合物は、炭素－炭素二重結合及びパーフルオロポリエーテル基を含有する限り、特に制限されない。パーフルオロポリエーテル基としては、組成物（１）に記載したものと同様のものが挙げられる。 Composition (2)
The composition (2) is a composition containing a carbon-carbon double bond-containing perfluoropolyether compound. The carbon-carbon double bond-containing perfluoropolyether compound is not particularly limited as long as it contains a carbon-carbon double bond and a perfluoropolyether group. Examples of the perfluoropolyether group include the same groups as those described in the composition (1).
　好ましくは、炭素－炭素二重結合含有パーフルオロポリエーテル化合物は、
　（2A）ジイソシアネートの三量体であるポリイソシアネート
のイソシアネート基に、
　（2B）活性水素を有する化合物
から活性水素が脱離した基が結合した化合物であり、
　成分（2B）が、（2B-1）活性水素を有するパーフルオロポリエーテル、（2B-2）活性水素を有するシラン化合物、及び（2B-3）活性水素と炭素－炭素二重結合とを有する化合物である。 Preferably, the carbon-carbon double bond containing perfluoropolyether compound is
(2A) To the isocyanate group of polyisocyanate, which is a trimer of diisocyanate,
(2B) A compound in which a group in which active hydrogen is eliminated from a compound having active hydrogen is bonded.
Component (2B) has (2B-1) perfluoropolyether having active hydrogen, (2B-2) silane compound having active hydrogen, and (2B-3) active hydrogen and carbon-carbon double bond. It is a compound.
　成分（2A）は、ジイソシアネートの三量体であるポリイソシアネートが重合した重合体として存在してもよい。 The component (2A) may exist as a polymer obtained by polymerizing polyisocyanate, which is a trimer of diisocyanate.
　好ましい態様において、成分（2A）は、イソシアヌレート型ポリイソシアネートであることができる。イソシアヌレート型ポリイソシアネートは、それ自体が重合した重合体として存在してもよい。即ち、イソシアヌレート型ポリイソシアネートは、イソシアヌレート環を１つのみ有する単環式化合物であってもよく、又はこの単環式化合物が重合して得られる多環式化合物、或いはこれらの混合物であってもよい。イソシアヌレート型ポリイソシアネートは、例えば、スミジュール（登録商標）Ｎ３３００（住友バイエルウレタン株式会社製）として市販されている。 In a preferred embodiment, the component (2A) can be an isocyanurate-type polyisocyanate. The isocyanurate-type polyisocyanate may exist as a polymer obtained by itself. That is, the isocyanurate-type polyisocyanate may be a monocyclic compound having only one isocyanurate ring, or a polycyclic compound obtained by polymerizing the monocyclic compound, or a mixture thereof. May be. The isocyanurate-type polyisocyanate is commercially available, for example, as Sumijour (registered trademark) N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd.).
　成分（2A）を得るために用いられるジイソシアネートとしては、特に限定されないが、イソシアネート基が脂肪族基に結合したジイソシアネート、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート；イソシアネート基が芳香族基に結合したジイソシアネート、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、トリジンジイソシアネート、ナフタレンジイソシアネートが挙げられる。 The diisocyanate used to obtain the component (2A) is not particularly limited, but is a diisocyanate in which an isocyanate group is bonded to an aliphatic group, for example, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl. Methylene diisocyanate; diisocyanates in which an isocyanate group is bonded to an aromatic group, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, trizine diisocyanate, naphthalene diisocyanate can be mentioned.
　具体的な成分（2A）としては、特に限定するものではないが、下記の構造を有する化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000017
 The specific component (2A) is not particularly limited, and examples thereof include a compound having the following structure.
Figure JPOXMLDOC01-appb-C000017
　これらのポリイソシアネートは重合体として存在してもよく、例えば、ヘキサメチレンジイソシアネートのイソシアヌレート型ポリイソシアネートである場合、下記構造：
Figure JPOXMLDOC01-appb-C000018
 を有する重合体として存在してもよい。ｎは１以上の整数である。 These polyisocyanates may exist as polymers. For example, in the case of an isocyanurate type polyisocyanate of hexamethylene diisocyanate, the following structure:
Figure JPOXMLDOC01-appb-C000018
 It may exist as a polymer having. n is an integer of 1 or more.
　成分（2B-1）は、パーフルオロポリエーテル基に加えて、１つの分子末端に１つの活性水素含有基（例えば水酸基）を有するか、或いは、２つの末端のそれぞれに１つの活性水素含有基（例えば水酸基）を有する化合物である。 In addition to the perfluoropolyether group, the component (2B-1) has one active hydrogen-containing group (for example, a hydroxyl group) at one molecular end, or one active hydrogen-containing group at each of the two ends. It is a compound having (for example, a hydroxyl group).
　成分（2B-1）の活性水素を有するパーフルオロポリエーテルは、特に限定されないが、例えば５００～１２，０００、好ましくは１，０００～１０，０００、より好ましくは１，５００～８，０００の数平均分子量を有する。 The perfluoropolyether having the active hydrogen of the component (2B-1) is not particularly limited, but is, for example, 500 to 12,000, preferably 1,000 to 10,000, and more preferably 1,500 to 8,000. It has a number average molecular weight.
　好ましくは、成分（2B-1）は、以下の式（2B-1-i）及び（2B-1-ii）のいずれか：
　Ｒｆ２１－ＰＦＰＥ－Ｒ２１－ＣＨ２ＯＨ　　　　　　　　　（2B-1-i）
　ＨＯ２ＨＣ－Ｒ２１－ＰＦＰＥ－Ｒ２１－ＣＨ２ＯＨ　　　　（2B-1-ii）
で表される少なくとも１種の化合物であることができる。 Preferably, the component (2B-1) is one of the following formulas (2B-1-i) and (2B-1-ii):
Rf 21- PFPE-R 21- CH 2 OH (2B-1-i)
HO 2 HC-R 21- PFPE-R 21- CH 2 OH (2B-1-ii)
It can be at least one compound represented by.
　式（2B-1-i）及び（2B-1-ii）中、Ｒｆ２１は、１個又はそれ以上のフッ素原子により置換されていてもよい直鎖又は分枝鎖のＣ１－１６アルキル基を表し、好ましくは、１個又はそれ以上のフッ素原子により置換されていてもよい直鎖又は分枝鎖のＣ１－３アルキル基である。好ましくは、Ｒｆ２１は直鎖である。また、好ましくは、上記１個又はそれ以上のフッ素原子により置換されていてもよいアルキル基は、末端炭素原子がＣＦ２Ｈ－であり他のすべての炭素原子がフッ素により全置換されているフルオロアルキル基又はパーフルオロアルキル基であり、より好ましくはパーフルオロアルキル基であり、具体的には－ＣＦ３、－ＣＦ２ＣＦ３、又は－ＣＦ２ＣＦ２ＣＦ３であることができる。 In formulas (2B-1-i) and (2B-1-ii), Rf 21 is a linear or branched C 1-16 alkyl group that may be substituted with one or more fluorine atoms. It is preferably a linear or branched C1-3 alkyl group which may be substituted with one or more fluorine atoms. Preferably, Rf 21 is linear. Further, preferably, the alkyl group which may be substituted with one or more fluorine atoms is fluoro, in which the terminal carbon atom is CF 2 H- and all other carbon atoms are totally substituted with fluorine. It can be an alkyl group or a perfluoroalkyl group, more preferably a perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 .
　式（2B-1-i）及び（2B-1-ii）中、ＰＦＰＥは、以下の式：
　－(ＯＣ４Ｆ８)ａ２－(ＯＣ３Ｆ６)ｂ２－(ＯＣ２Ｆ４)ｃ２－(ＯＣＦ２)ｄ２－で表される基である。式中、ａ２、ｂ２、ｃ２、及びｄ２は、パーフルオロポリエーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０～２００の整数、例えば１～２００の整数であって、ａ２、ｂ２、ｃ２、及びｄ２の和は少なくとも１、好ましくは５～３００、より好ましくは１０～２００、さらに好ましくは１０～１００の範囲内である。添字ａ２、ｂ２、ｃ２、又はｄ２を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。かかるパーフルオロポリエーテル基を有する化合物は、優れた撥水性、撥油性、及び防汚性を発現し得る。 In formulas (2B-1-i) and (2B-1-ii), PFPE is the following formula:
-(OC 4 F 8 ) a2- (OC 3 F 6 ) b2- (OC 2 F 4 ) c2- (OCF 2 ) d2- . In the formula, a2, b2, c2, and d2 represent four kinds of repeating units of perfluoropolyether, respectively, and are independently integers of 0 to 200, for example, integers of 1 to 200, and a2, The sum of b2, c2, and d2 is in the range of at least 1, preferably 5 to 300, more preferably 10 to 200, and even more preferably 10 to 100. The order of existence of each repeating unit in parentheses with the subscripts a2, b2, c2, or d2 is arbitrary in the equation. A compound having such a perfluoropolyether group can exhibit excellent water repellency, oil repellency, and antifouling property.
　好ましい態様において、ＰＦＰＥは、以下の式（2C-1）～（2C-3）のいずれか：
　－(ＯＣＦ２ＣＦ２ＣＦ２)ｂ２－　　　　　　　　　（2C-1）
［式中、ｂ２は１～２００の整数である。］
　－(ＯＣＦ(ＣＦ３)ＣＦ２)ｂ２－　　　　　　　　 （2C-2）
［式中、ｂ２は１～２００の整数である。］又は
　－(ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２)ａ２－(ＯＣＦ２ＣＦ２ＣＦ２)ｂ２－(ＯＣＦ２ＣＦ２)ｃ２－(ＯＣＦ２)ｄ２－　　　　　　　　　　　　　　　　　 （2C-3）
［式中、ａ２及びｂ２は、それぞれ独立して、０又は１～３０の整数であり、ｃ２及びｄ２は、それぞれ独立して、１～２００の整数であり、添字ａ２、ｂ２、ｃ２、又はｄ２を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。］
で表される基である。 In a preferred embodiment, the PFPE is one of the following formulas (2C-1) to (2C-3):
-(OCF 2 CF 2 CF 2 ) b2- (2C-1)
[In the formula, b2 is an integer from 1 to 200. ]
-(OCF (CF 3 ) CF 2 ) b2- (2C-2)
[In the formula, b2 is an integer from 1 to 200. ] Or-(OCF 2 CF 2 CF 2 CF 2 ) a2- (OCF 2 CF 2 CF 2 ) b2- (OCF 2 CF 2 ) c2- (OCF 2 ) d2- (2C-3)
[In the equation, a2 and b2 are independently integers of 0 or 1 to 30, c2 and d2 are independently integers of 1 to 200, and the subscripts a2, b2, c2, or The order of existence of each repeating unit in parentheses with d2 is arbitrary in the equation. ]
It is a group represented by.
　式（2B-1-i）及び（2B-1-ii）中、Ｒ２１は、それぞれ独立して、以下の式：
　－(Ｙ)ｆ２－(ＣＦ２)ｇ２－(ＣＨ２)ｈ２－
で表される基である。この式中、Ｙは二価の極性基である。二価の極性基の例としては、特に限定されないが、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＯＣＨ２ＣＨ(ＯＨ)ＣＨ２－、－ＣＨ２ＣＨ(ＯＨ)ＣＨ２Ｏ－、－ＣＯＳ－、－ＳＣＯ－、－Ｏ－などが挙げられ、好ましくは－ＣＯＯ－、－ＣＯＮＨ－、－ＣＨ２ＣＨ(ＯＨ)ＣＨ２Ｏ－、－Ｏ－である。また、この式中、ｆ２、ｇ２、及びｈ２は、それぞれ独立して、０～５０、好ましくは０～２０、例えば１～２０の整数であって、ｆ２、ｇ２、及びｈ２の和は少なくとも１、好ましくは１～１０の整数である。ｆ２、ｇ２、及びｈ２は０～２の整数であることがより好ましく、ｆ２＝０又は１、ｇ２＝２、ｈ２＝０又は１であることがさらに好ましい。また、添字ｆ２、ｇ２、及びｈ２を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 In the formulas (2B-1-i) and (2B-1-ii), R 21 independently has the following formulas:
-(Y) f2- (CF 2 ) g2- (CH 2 ) h2-
It is a group represented by. In this formula, Y is a divalent polar group. Examples of the divalent polar group are not particularly limited, but -COO-, -OCO-, -CONH-, -OCH 2 CH (OH) CH 2- , -CH 2 CH (OH) CH 2 O-, -COS-, -SCO-, -O- and the like can be mentioned, preferably -COO-, -CONH-, -CH 2 CH (OH) CH 2 O-, -O-. Further, in this formula, f2, g2, and h2 are independently integers of 0 to 50, preferably 0 to 20, for example, 1 to 20, and the sum of f2, g2, and h2 is at least 1. , Preferably an integer of 1-10. It is more preferable that f2, g2, and h2 are integers of 0 to 2, and it is further preferable that f2 = 0 or 1, g2 = 2, h2 = 0 or 1. Further, the order of existence of each repeating unit enclosed in parentheses with the subscripts f2, g2, and h2 is arbitrary in the equation.
　好ましい態様において、成分（2B-1）は、式（2B-1-i）で表される化合物である。 In a preferred embodiment, the component (2B-1) is a compound represented by the formula (2B-1-i).
　成分（2B-2）は、１つの分子末端に１つの活性水素含有基（例えば水酸基）を有するか、或いは２つの末端のそれぞれに１つの活性水素含有基（例えば水酸基）を有するシラン化合物である。 The component (2B-2) is a silane compound having one active hydrogen-containing group (for example, a hydroxyl group) at one molecular end or one active hydrogen-containing group (for example, a hydroxyl group) at each of the two ends. ..
　成分（2B-2）は、特に限定されないが、例えば１００～２０，０００、好ましくは５００～１５，０００、より好ましくは８００～１２，０００の数平均分子量を有する。 The component (2B-2) is not particularly limited, but has, for example, a number average molecular weight of 100 to 20,000, preferably 500 to 15,000, and more preferably 800 to 12,000.
　好ましくは、成分（2B-2）は、以下の式（2B-2-i）及び（2B-2-ii）：
Figure JPOXMLDOC01-appb-C000019
 で表される少なくとも１種の化合物であり得る。 Preferably, the component (2B-2) is composed of the following formulas (2B-2-i) and (2B-2-ii):
Figure JPOXMLDOC01-appb-C000019
 It can be at least one compound represented by.
　式（2B-2-i）及び（2B-2-ii）中、Ｒ２１１、Ｒ２１２、Ｒ２１３、Ｒ２１４、及びＲ２１５は、それぞれ独立して、アルキル基又はアリール基である。 In formulas (2B-2-i) and (2B-2-ii), R 211 , R 212 , R 213 , R 214 , and R 215 are independently alkyl or aryl groups, respectively.
　上記アルキル基及びアリール基は、所望により、その分子鎖又は環中に、ヘテロ原子、例えば窒素原子、酸素原子、硫黄原子を含有していてもよい。 If desired, the alkyl group and aryl group may contain a hetero atom, for example, a nitrogen atom, an oxygen atom, or a sulfur atom in the molecular chain or ring.
　さらに、上記アルキル基及びアリール基は、所望により、ハロゲン；１個又はそれ以上のハロゲンにより置換されていてもよい、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、Ｃ２－６アルキニル基、Ｃ３－１０シクロアルキル基、Ｃ３－１０不飽和シクロアルキル基、５～１０員のヘテロシクリル基、５～１０員の不飽和ヘテロシクリル基、Ｃ６－１０アリール基、５～１０員のヘテロアリール基から選択される、１個又はそれ以上の置換基により置換されていてもよい。 Further, the alkyl group and aryl group may be optionally substituted with halogen; one or more halogens, C 1-6 alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group. , C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl group, C 6-10 aryl group, 5-10 member hetero It may be substituted with one or more substituents selected from the aryl groups.
　式（2B-2-i）及び（2B-2-ii）中、Ｒ２１６は、２価の有機基を表す。好ましくは、Ｒ２１６は、－(ＣＨ２)ｒ２１－（式中、ｒ２１は１～２０の整数、好ましくは１～１０の整数である）である。 In formulas (2B-2-i) and (2B-2-ii), R 216 represents a divalent organic group. Preferably, R 216 is, - (CH 2) r21 - ( wherein, r21 is an integer of 1 to 20, preferably an integer of 1 to 10) is.
　式（2B-2-i）及び（2B-2-ii）中、ｌ２及びｎ２は、それぞれ独立して、０又は１であり；ｍ２は、１～５００の整数、好ましくは１～２００、より好ましくは５～１５０の整数であり；ｏ２は、０～２０の整数、例えば１～２０の整数であり、ｐ２は０又は１である。 In formulas (2B-2-i) and (2B-2-ii), l2 and n2 are independently 0 or 1, respectively; m2 is an integer from 1 to 500, preferably from 1 to 200. It is preferably an integer of 5 to 150; o2 is an integer of 0 to 20, for example an integer of 1 to 20, and p2 is 0 or 1.
　式（2B-2-i）で示される具体的な化合物としては、例えば、下記の化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000020
 Specific examples of the compound represented by the formula (2B-2-i) include the following compounds.
Figure JPOXMLDOC01-appb-C000020
　成分（2B-2）は、活性水素含有基としてアミノ基を有するシラン化合物であってもよい。かかる化合物としては、限定するものではないが、例えば、以下のものが挙げられる。
Figure JPOXMLDOC01-appb-C000021
 The component (2B-2) may be a silane compound having an amino group as an active hydrogen-containing group. Examples of such compounds include, but are not limited to, the following.
Figure JPOXMLDOC01-appb-C000021
　成分（2B-1）と成分（2B-2）の数平均分子量の比は、特に限定されないが、例えば１：５～５：１、好ましくは１：３～３：１、より好ましくは１：３～３：２の範囲内である。成分（2B-1）と成分（2B-2）の数平均分子量の比を上記の範囲とすることにより、よりフッ素不含溶媒への溶解性が向上する。 The ratio of the number average molecular weight of the component (2B-1) to the component (2B-2) is not particularly limited, but is, for example, 1: 5 to 5: 1, preferably 1: 3 to 3: 1, and more preferably 1: 1. It is in the range of 3 to 3: 2. By setting the ratio of the number average molecular weights of the component (2B-1) and the component (2B-2) to the above range, the solubility in a fluorine-free solvent is further improved.
　成分（2B-3）は、活性水素含有基、特に水酸基を有する（メタ）アクリル酸エステル及びビニルモノマーであることが好ましい。成分（2B-3）としては、限定するものではないが、例えば、以下の化合物：
（2B-3-1）ＨＯ(ＣＨ２ＣＨ２)ｉＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２（式中、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基、ｉ＝２～１０）
例えば、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート；
（2B-3-2）ＣＨ３ＣＨ(ＯＨ)ＣＨ２ＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２（式中、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えば、２－ヒドロキシプロピル（メタ）アクリレート；
（2B-3-3）ＣＨ３ＣＨ２ＣＨ(ＯＨ)ＣＨ２ＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２（式中、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えば、２－ヒドロキシブチル（メタ）アクリレート；
（2B-3-4）Ｃ６Ｈ５ＯＣＨ２ＣＨ(ＯＨ)ＣＨ２ＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２（式中、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えば、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート；
（2B-3-5）ＨＯＣＨ２Ｃ(ＣＨ２ＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２)３（式中、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えば、ペンタエリスリトールトリアクリレート；
（2B-3-6）Ｃ(ＣＨ２ＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２)３ＣＨ２ＯＣＨ２Ｃ(ＣＨ２ＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２)２ＣＨ２ＯＨ（式中、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えば、ジペンタエリスリトールポリアクリレート；
（2B-3-7）ＨＯＣＨ２ＣＨ２ＯＣＯＣ６Ｈ５ＯＣＯＣＨ２ＣＨ２ＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２（式中、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えば、２－アクリロイロキシエチル－２－ヒドロキシエチルフタル酸
（2B-3-8）Ｈ(ＯＣＨ２ＣＨ２)ｎＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２（式中、ｎは１～３０の整数、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えば、ポリ（エチレングリコール）アクリレート
（2B-3-9）Ｈ(ＯＣＨ(ＣＨ３)ＣＨ２)ｎＯＣＯ(Ｒ２２)Ｃ＝ＣＨ２（式中、ｎは１～３０の整数、Ｒ２２は水素原子、塩素原子、フッ素原子、又はフッ素により置換されていてもよいＣ１－１０アルキル基）
例えばポリ（プロピレングリコール）アクリレート
（2B-3-10）アリルアルコール；
（2B-3-11）ＨＯ(ＣＨ２)ｋ２ＣＨ＝ＣＨ２（ｋ２＝２～２０）；
（2B-3-12）(ＣＨ３)３ＳｉＣＨ(ＯＨ)ＣＨ＝ＣＨ２；及び
（2B-3-13）スチリルフェノール
が挙げられる。 The component (2B-3) is preferably an active hydrogen-containing group, particularly a (meth) acrylic acid ester having a hydroxyl group and a vinyl monomer. The component (2B-3) is not limited, but for example, the following compounds:
(2B-3-1) HO (CH 2 CH 2 ) i OCO (R 22 ) C = CH 2 (In the formula, R 22 may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine C. 1-10 alkyl group, i = 2-10 )
For example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
(2B-3-2) CH 3 CH (OH) CH 2 OCO (R 22 ) C = CH 2 (In the formula, R 22 may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine C. 1-10 alkyl group)
For example, 2-hydroxypropyl (meth) acrylate;
(2B-3-3) CH 3 CH 2 CH (OH) CH 2 OCO (R 22 ) C = CH 2 (In the formula, R 22 may be replaced by a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine. Good C 1-10 alkyl group)
For example, 2-hydroxybutyl (meth) acrylate;
(2B-3-4) C 6 H 5 OCH 2 CH (OH) CH 2 OCO (R 22 ) C = CH 2 (In the formula, R 22 is replaced by a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine. May be C 1-10 alkyl group)
For example, 2-hydroxy-3-phenoxypropyl (meth) acrylate;
(2B-3-5) HOCH 2 C (CH 2 OCO (R 22 ) C = CH 2 ) 3 (In the formula, R 22 may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine C. 1-10 alkyl group)
For example, pentaerythritol triacrylate;
(2B-3-6) C (CH 2 OCO (R 22 ) C = CH 2 ) 3 CH 2 OCH 2 C (CH 2 OCO (R 22 ) C = CH 2 ) 2 CH 2 OH (in the formula, R 22) Is a C 1-10 alkyl group optionally substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine)
For example, dipentaerythritol polyacrylate;
(2B-3-7) HOCH 2 CH 2 OCOC 6 H 5 OCOCCH 2 CH 2 OCO (R 22 ) C = CH 2 (In the formula, R 22 is replaced by hydrogen atom, chlorine atom, fluorine atom, or fluorine. May be C 1-10 alkyl group)
For example, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid (2B-3-8) H (OCH 2 CH 2 ) n OCO (R 22 ) C = CH 2 (in the formula, n is an integer of 1 to 30). , R 22 is a C 1-10 alkyl group which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine).
For example, poly (ethylene glycol) acrylate (2B-3-9) H (OCH (CH 3 ) CH 2 ) n OCO (R 22 ) C = CH 2 (in the formula, n is an integer of 1 to 30, R 22 is C 1-10 alkyl group optionally substituted with hydrogen atom, chlorine atom, fluorine atom, or fluorine)
For example, poly (propylene glycol) acrylate (2B-3-10) allyl alcohol;
(2B-3-11) HO (CH 2 ) k2 CH = CH 2 (k2 = 2 to 20);
(2B-3-12) (CH 3 ) 3 SiCH (OH) CH = CH 2 ; and (2B-3-13) styrylphenol.
　成分（2A）と反応させる成分（2B）［成分（2B-1）、（2B-2）、及び（2B-3）］の合計のモル数は、成分（2A）中のイソシアネート基のモル数と等しいことが好ましい。さらに、成分（2A）中のイソシアネート基９モルに対し、
成分（2B-1）のモル数が、０．１～２モルの範囲内、
成分（2B-2）のモル数が、０．０５～２モルの範囲内、及び
成分（2B-3）のモル数が、５～８．８５モルの範囲内
であることが好ましい。 The total number of moles of the component (2B) [component (2B-1), (2B-2), and (2B-3)] to react with the component (2A) is the number of moles of the isocyanate group in the component (2A). Is preferably equal to. Furthermore, for 9 mol of isocyanate groups in component (2A),
The number of moles of the component (2B-1) is in the range of 0.1 to 2 moles,
It is preferable that the number of moles of the component (2B-2) is in the range of 0.05 to 2 mol and the number of moles of the component (2B-3) is in the range of 5 to 8.85 mol.
　成分（2A）中のイソシアネート基９モルに対し、
成分（2B-1）のモル数が、好ましくは０．１～１．５モル、より好ましくは０．１～１モルの範囲内であり；
成分（2B-2）のモル数が、好ましくは０．０５～１．５モル、より好ましくは０．０５～１モルの範囲内であることができる。 For 9 mol of isocyanate groups in component (2A)
The number of moles of component (2B-1) is preferably in the range of 0.1-1.5 mol, more preferably 0.1-1 mol;
The number of moles of the component (2B-2) can be preferably in the range of 0.05 to 1.5 mol, more preferably 0.05 to 1 mol.
　より好ましくは、成分（2A）中のイソシアネート基９モルに対し、
成分（2B-1）のモル数が、０．１～１モルの範囲内、
成分（2B-2）のモル数が、０．０５～１モルの範囲内、及び
成分（2B-3）のモル数が、７～８．８５モルの範囲内であることができる。 More preferably, with respect to 9 mol of isocyanate groups in component (2A)
The number of moles of the component (2B-1) is in the range of 0.1 to 1 mole,
The number of moles of the component (2B-2) can be in the range of 0.05 to 1 mol, and the number of moles of the component (2B-3) can be in the range of 7 to 8.85 moles.
　組成物（２）は、さらに、含フッ素オイルを含有することができる。含フッ素オイルは、組成物（１）で例示したものと同様のものが使用できる。含フッ素オイルは、炭素－炭素二重結合含有パーフルオロポリエーテル化合物１００質量部に対して、例えば０～８０質量部、好ましくは０～４０質量部の範囲内で含まれ得る。 The composition (2) can further contain a fluorine-containing oil. As the fluorine-containing oil, the same oil as that exemplified in the composition (1) can be used. The fluorine-containing oil may be contained in the range of, for example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass with respect to 100 parts by mass of the carbon-carbon double bond-containing perfluoropolyether compound.
　組成物（２）は、さらに、シリコーンオイルを含有することができる。シリコーンオイルは、組成物（１）で例示したものと同様のものが使用できる。シリコーンオイルは、炭素－炭素二重結合含有パーフルオロポリエーテル化合物１００質量部に対して、例えば０～５０質量部、好ましくは０～１０質量部の範囲内で含まれ得る。 The composition (2) can further contain silicone oil. As the silicone oil, the same silicone oil as that exemplified in the composition (1) can be used. The silicone oil may be contained, for example, in the range of 0 to 50 parts by mass, preferably 0 to 10 parts by mass with respect to 100 parts by mass of the carbon-carbon double bond-containing perfluoropolyether compound.
　組成物（２）は、さらに、活性エネルギー線硬化開始剤を含有することができる。活性エネルギー線硬化開始剤としては、例えば、３５０ｎｍ以下の波長領域の電磁波、つまり紫外光線、電子線、Ｘ線、γ線などが照射されることによって初めてラジカル又はカチオンなどを発生し、組成物（２）中の化合物の硬化性部位（例えば、炭素－炭素二重結合）の硬化（即ち、架橋反応）を開始させる触媒として働くものであり、通常、紫外光線でラジカルやカチオンを発生させるもの、特にラジカルを発生するものを使用する。 The composition (2) can further contain an active energy ray curing initiator. As the active energy ray curing initiator, for example, radicals or cations are generated for the first time when irradiated with an electromagnetic wave in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, γ-rays, etc. 2) It acts as a catalyst for initiating the curing (that is, cross-linking reaction) of the curable site (for example, carbon-carbon double bond) of the compound in, and usually generates radicals and cations with ultraviolet light. In particular, use one that generates radicals.
　組成物（２）における活性エネルギー線硬化開始剤は、炭素－炭素二重結合を有する成分（2B-3）の種類、使用する活性エネルギー線の種類（波長域など）と照射強度などによって適宜選択されるが、一般的な紫外線領域の活性エネルギー線を用いる場合、開始剤としては、例えば、以下のものが例示できる。
・アセトフェノン系
　アセトフェノン、クロロアセトフェノン、ジエトキシアセトフェノン、ヒドロキシアセトフェノン、α－アミノアセトフェノン、ヒドロキシプロピオフェノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパンー１－オンなど
・ベンゾイン系
　ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタールなど
・ベンゾフェノン系
　ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、ヒドロキシ－プロピルベンゾフェノン、アクリル化ベンゾフェノン、ミヒラーズケトンなど
・チオキサンソン類
　チオキサンソン、クロロチオキサンソン、メチルチオキサンソン、ジエチルチオキサンソン、ジメチルチオキサンソンなど
・その他
　ベンジル、α－アシルオキシムエステル、アシルホスフィンオキサイド、グリオキシエステル、３－ケトクマリン、２－エチルアンスラキノン、カンファーキノン、アンスラキノンなど The active energy ray curing initiator in the composition (2) is appropriately selected depending on the type of the component (2B-3) having a carbon-carbon double bond, the type of active energy ray used (wavelength range, etc.), the irradiation intensity, and the like. However, when an active energy ray in a general ultraviolet region is used, the following can be exemplified as the initiator.
・ Acetophenone-based acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Benzophenone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.-Benzophenone benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propyl benzophenone , Acrylicized benzophenone, Michler's ketone, etc. ・ Thioxansons Thioxansone, Chlorothioxanthone, Methylthioxanthone, Diethylthioxanthone, Dimethylthioxanthone, etc. -Ketokumarin, 2-ethylanthraquinone, benzophenone, anthraquinone, etc.
　活性エネルギー線硬化開始剤は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 As the active energy ray curing initiator, one type may be used alone, or two or more types may be used in combination.
　活性エネルギー線硬化開始剤は、特に限定されないが、炭素－炭素二重結合含有パーフルオロポリエーテル化合物、又は含フッ素オイルが存在する場合、炭素－炭素二重結合含有パーフルオロポリエーテル化合物と含フッ素オイルとの合計１００質量部に対して、０．０１～３０質量部、好ましくは０．１～２０質量部の範囲内で含まれ得る。 The active energy ray curing initiator is not particularly limited, but if a carbon-carbon double bond-containing perfluoropolyether compound or a fluorine-containing oil is present, the carbon-carbon double bond-containing perfluoropolyether compound and the fluorine-containing It may be contained in the range of 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total with the oil.
　組成物（２）は、さらに、溶媒を含有することができる。組成物（２）は、フッ素含有有機溶媒のみならず、汎用溶剤であるフッ素不含有機溶媒に対しても高い溶解性を示すため、溶媒としては、フッ素含有有機溶媒及びフッ素不含有機溶媒を用いることができる。 The composition (2) can further contain a solvent. Since the composition (2) exhibits high solubility not only in a fluorine-containing organic solvent but also in a fluorine-free machine solvent which is a general-purpose solvent, a fluorine-containing organic solvent and a fluorine-free machine solvent are used as the solvent. Can be used.
　フッ素含有有機溶媒としては、例えば、パーフルオロヘキサン、パーフルオロオクタン、パーフルオロジメチルシクロヘキサン、パーフルオロデカリン、パーフルオロアルキルエタノール、パーフルオロベンゼン、パーフルオロトルエン、パーフルオロアルキルアミン（フロリナート（商品名）等）、パーフルオロアルキルエーテル、パーフルオロブチルテトラヒドロフラン、ポリフルオロ脂肪族炭化水素（アサヒクリンＡＣ６０００（商品名）等）、ハイドロクロロフルオロカーボン（アサヒクリンＡＫ－２２５（商品名）等）、ハイドロフルオロエーテル（ノベック（商品名）、ＨＦＥ－７１００（商品名）等）、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（（ゼオローラＨ（商品名）等）、含フッ素アルコール（パーフルオロアルキルブロミド、パーフルオロアルキルヨージド、パーフルオロポリエーテル（クライトックス（商品名）、デムナム（商品名）、フォンブリン（商品名）等）、１，３－ビストリフルオロメチルベンゼン、メタクリル酸２－（パーフルオロアルキル）エチル、アクリル酸２－（パーフルオロアルキル）エチル、パーフルオロアルキルエチレン、フロン１３４ａ、及びヘキサフルオロプロペンオリゴマーが挙げられる。 Examples of the fluorine-containing organic solvent include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamine (florinate (trade name), etc.). ), Perfluoroalkyl ether, perfluorobutyl tetrahydrofuran, polyfluoroaliphatic hydrocarbon (Asahiclin AC6000 (trade name), etc.), Hydrochlorofluorocarbon (Asahiclin AK-225 (trade name), etc.), Hydrofluoroether (Novec) (Product name), HFE-7100 (trade name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name), etc.)), Fluorohydrate-containing alcohol (perfluoro) Alkyl bromide, perfluoroalkyl iodide, perfluoropolyether (Crytox (trade name), Demnum (trade name), Fombulin (trade name), etc.), 1,3-bistrifluoromethylbenzene, 2-(2) methacrylate Examples thereof include perfluoroalkyl) ethyl, 2- (perfluoroalkyl) ethyl acrylate, perfluoroalkylethylene, benzene 134a, and hexafluoropropene oligomers.
　フッ素不含有機溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールジメチルエーテルペンタン、ヘキサン、ヘプタン、オクタン、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、二硫化炭素、ベンゼン、トルエン、キシレン、ニトロベンゼン、ジエチルエーテル、ジメトキシエタン、ダイグライム、トリグライム、酢酸エチル、酢酸ブチル、ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリル、ベンゾニトリル、ブタノール、１－プロパノール、２－プロパノール、エタノール、メタノール、及びジアセトンアルコールが挙げられる。 Examples of the fluorine-free machine solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene. Glycolmonobutyl ether acetate, dipropylene glycol dimethyl etherpentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglime, triglime, acetate Included are ethyl, butyl acetate, dimethylformamide, dimethylsulfoxide, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.
　溶媒は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 As the solvent, one type may be used alone, or two or more types may be used in combination.
　好ましい態様において、溶媒はフッ素不含有機溶媒であることができ、好ましくはアセトン、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル等であり、より好ましくはアセトン、メチルエチルケトン、メチルイソブチルケトン等である。 In a preferred embodiment, the solvent can be a fluorine-free machine solvent, preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate or the like, and more preferably acetone, methyl ethyl ketone, methyl isobutyl ketone or the like.
　別の好ましい態様において、溶媒はフッ素含有有機溶媒とフッ素不含有機溶媒の混合溶媒であることができる。 In another preferred embodiment, the solvent can be a mixed solvent of a fluorine-containing organic solvent and a fluorine-free machine solvent.
　溶媒は、好ましくはメチルイソブチルケトン、プロピレングリコールモノメチルエーテル、アセトン、メチルエチルケトン、シクロヘキサノン、酢酸エチル、酢酸ブチル、又はジアセトンアルコールである。また、炭素－炭素二重結合含有パーフルオロポリエーテル化合物が、成分（2A）と成分（2B-1）の反応により得られた化合物と、成分（2A）と成分（2B-2）の反応により得られた化合物との混合物である場合、用いられる溶媒としては、フッ素含有有機溶媒及びフッ素不含有機溶媒の混合溶媒、例えば、ハイドロクロロフルオロカーボン（アサヒクリンＡＫ－２２５（商品名）等）及び１，１，２，２，３，３，４－ヘプタフルオロシクロペンタンから選択される１種又はそれ以上の溶媒と、メチルイソブチルケトン、プロピレングリコールモノメチルエーテル、アセトン、メチルエチルケトン、シクロヘキサノン、酢酸エチル、酢酸ブチル、及びジアセトンアルコールから選択される１種又はそれ以上の溶媒との混合溶媒が好ましく、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン、プロピレングリコールモノメチルエーテル及びメチルエチルケトンの混合溶媒がより好ましい。 The solvent is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, or diacetone alcohol. Further, the carbon-carbon double bond-containing perfluoropolyether compound is obtained by the reaction of the component (2A) and the component (2B-1) with the compound obtained by the reaction of the component (2A) and the component (2B-2). In the case of a mixture with the obtained compound, as the solvent used, a mixed solvent of a fluorine-containing organic solvent and a fluorine-free machine solvent, for example, hydrochlorofluorocarbon (Asahiclean AK-225 (trade name), etc.) and 1 , 1, 2, 2, 3, 3,4-Heptafluorocyclopentane, one or more solvents, methyl isobutyl ketone, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate , And a mixed solvent with one or more solvents selected from diacetone alcohol, preferably a mixture of 1,1,2,2,3,3,4-heptafluorocyclopentane, propylene glycol monomethyl ether and methyl ethyl ketone. Solvents are more preferred.
　溶媒は、特に限定されないが、炭素－炭素二重結合含有パーフルオロポリエーテル化合物、又は含フッ素オイルが存在する場合、炭素－炭素二重結合含有パーフルオロポリエーテル化合物と含フッ素オイルとの合計１００質量部に対して、５～１０，０００質量部、好ましくは５～５，０００質量部の範囲内で含まれ得る。 The solvent is not particularly limited, but if a carbon-carbon double bond-containing perfluoropolyether compound or a fluorine-containing oil is present, a total of 100 of the carbon-carbon double bond-containing perfluoropolyether compound and the fluorine-containing oil. It may be contained in the range of 5 to 10,000 parts by mass, preferably 5 to 5,000 parts by mass with respect to parts by mass.
　一の態様において、組成物（２）は、マトリックスを形成する組成物に加えることにより、硬化性組成物とすることができる。マトリックスを形成する組成物とは、少なくとも１つの炭素－炭素二重結合を有する化合物、例えば、特に限定されるものではないが、単官能及び／又は多官能（メタ）アクリレート、単官能及び／又は多官能ウレタン（メタ）アクリレート、単官能及び／又は多官能エポキシ（メタ）アクリレートである化合物を含有する組成物を意味する。当該マトリックスを形成する組成物としては、特に限定されるものではないが、一般的にハードコーティング剤とされる組成物であり、例えば多官能性（メタ）アクリレートを含むハードコーティング剤が挙げられる。硬化性組成物の例としては、例えば、ビームセット５０２Ｈ、５０４Ｈ、５０５Ａ－６、５５０Ｂ、５７５ＣＢ、５７７、１４０２（商品名）として荒川化学工業株式会社から、ＥＢＥＣＲＹＬ４０（商品名）としてダイセルサイテック社から、ＨＲ３００系（商品名）として横浜ゴム社から、オプツールＡＲ－１１０（商品名）としてダイキン工業株式会社から市販されている。 In one embodiment, the composition (2) can be added to the composition forming the matrix to form a curable composition. The composition forming the matrix is a compound having at least one carbon-carbon double bond, for example, but not particularly limited, monofunctional and / or polyfunctional (meth) acrylate, monofunctional and / or. It means a composition containing a compound which is a polyfunctional urethane (meth) acrylate, a monofunctional and / or a polyfunctional epoxy (meth) acrylate. The composition forming the matrix is not particularly limited, but is a composition generally regarded as a hard coating agent, and examples thereof include a hard coating agent containing a polyfunctional (meth) acrylate. Examples of the curable composition include, for example, beam sets 502H, 504H, 505A-6, 550B, 575CB, 575, 1402 (trade name) from Arakawa Chemical Industry Co., Ltd., and EBECRYL40 (trade name) from Daikin Corporation. , HR300 series (trade name) is commercially available from Yokohama Rubber Co., Ltd., and Optool AR-110 (trade name) is commercially available from Daikin Industries, Ltd.
　硬化性組成物は、組成物（２）を、マトリックスを形成する組成物と組成物（２）の合計に対して、例えば０．０１～２０質量％、好ましくは０．０１～１０質量％、より好ましくは０．１～１０質量％の範囲内で含有する。 In the curable composition, the composition (2) is, for example, 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the total of the composition forming the matrix and the composition (2). More preferably, it is contained in the range of 0.1 to 10% by mass.
　硬化性組成物は、溶媒を含んでいてもよい。溶媒としては、組成物（２）について記載したフッ素含有有機溶媒及びフッ素不含有機溶媒を用いることができる。溶媒は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。好ましい態様において、溶媒はフッ素不含有機溶媒であることができる。別の好ましい態様において、溶媒はフッ素含有有機溶媒とフッ素不含有機溶媒の混合溶媒であることができる。溶媒は、特に限定されないが、炭素－炭素二重結合含有パーフルオロポリエーテル化合物、存在する場合含フッ素オイル、及びマトリックスを形成する組成物の合計１００質量部に対して、０～１９，９００質量部、好ましくは０～１０，０００質量部の範囲内で含まれ得る。 The curable composition may contain a solvent. As the solvent, the fluorine-containing organic solvent and the fluorine-free machine solvent described in the composition (2) can be used. As the solvent, one type may be used alone, or two or more types may be used in combination. In a preferred embodiment, the solvent can be a fluorine-free machine solvent. In another preferred embodiment, the solvent can be a mixed solvent of a fluorine-containing organic solvent and a fluorine-free machine solvent. The solvent is not particularly limited, but is 0 to 19,900 mass with respect to a total of 100 parts by mass of the carbon-carbon double bond-containing perfluoropolyether compound, the fluorine-containing oil if present, and the composition forming the matrix. Parts, preferably in the range of 0 to 10,000 parts by mass.
　硬化性組成物は、上記以外に、他の成分、例えばシリコーンオイル、活性エネルギー線硬化開始剤などを含んでいてもよい。シリコーンオイル及び活性エネルギー線硬化開始剤としては、組成物（２）について記載したシリコーンオイル及び活性エネルギー線硬化開始剤を用いることができる。 In addition to the above, the curable composition may contain other components such as silicone oil and an active energy ray curing initiator. As the silicone oil and the active energy ray curing initiator, the silicone oil and the active energy ray curing initiator described in the composition (2) can be used.
　組成物（２）及び硬化性組成物は、さらに、酸化防止剤、増粘剤、レベリング剤、消泡剤、帯電防止剤、防曇剤、紫外線吸収剤、顔料、染料、シリカ、中空シリカなどの無機微粒子、アルミニウムペースト、タルク、ガラスフリット、金属粉などの充填剤、ブチル化ヒドロキシトルエン（ＢＨＴ）、フェノチアジン（ＰＴＺ）などの重合禁止剤などを含んでいてもよい。 The composition (2) and the curable composition further include an antioxidant, a thickener, a leveling agent, an antifoaming agent, an antioxidant, an antifogging agent, an ultraviolet absorber, a pigment, a dye, silica, hollow silica and the like. It may contain a filler such as inorganic fine particles, aluminum paste, talc, glass frit, metal powder, and a polymerization inhibitor such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).
　組成物（２）は、例えば、米国特許出願公開第２０１６／２３７１９９号明細書、又は特許第６０５６９３５号に記載の組成物であることができる。 The composition (2) can be, for example, the composition described in US Patent Application Publication No. 2016/237199 or Japanese Patent No. 6056935.
組成物（３）
　組成物（３）は、フルオロポリマー及びアクリルポリマーからなり、フルオロポリマー及びアクリルポリマーのいずれか一方又は両方が水酸基及び加水分解性シリル基を有する複合重合体粒子と、ポリイソシアネート化合物と、水とを含有する組成物である。当該組成物は、水性分散体であることができる。 Composition (3)
The composition (3) comprises a composite polymer particle composed of a fluoropolymer and an acrylic polymer, and one or both of the fluoropolymer and the acrylic polymer having a hydroxyl group and a hydrolyzable silyl group, a polyisocyanate compound, and water. It is a composition to be contained. The composition can be an aqueous dispersion.
　複合重合体粒子は、フルオロポリマーとアクリルポリマーとを同一粒子内に含有していることが好ましい。フルオロポリマーとアクリルポリマーとが同一粒子内に存在している場合、両者は化学的に結合していてもよく、結合していなくてもよい。 The composite polymer particles preferably contain a fluoropolymer and an acrylic polymer in the same particles. When the fluoropolymer and the acrylic polymer are present in the same particle, they may or may not be chemically bonded.
　水酸基及び加水分解性シリル基は、フルオロポリマー又はアクリルポリマーのいずれかが含有していればよく、一方のポリマーが水酸基を含有しており、もう一方のポリマーが加水分解性シリル基を含有していてもよい。製造が容易である点で、アクリルポリマーが水酸基及び加水分解性シリル基を含有していることが好ましい。 The hydroxyl group and the hydrolyzable silyl group may contain either a fluoropolymer or an acrylic polymer, one polymer containing a hydroxyl group and the other polymer containing a hydrolyzable silyl group. You may. It is preferable that the acrylic polymer contains a hydroxyl group and a hydrolyzable silyl group because it is easy to produce.
　上記水酸基は、－ＯＨで示される基であるが、カルボキシ基（－ＣＯＯＨ）の一部を構成する水酸基を含まない。 The above-mentioned hydroxyl group is a group represented by -OH, but does not contain a hydroxyl group constituting a part of a carboxy group (-COOH).
　加水分解性シリル基は、式：
－ＳｉＸ３１ ｎＸ３２ ３－ｎ
（Ｘ３１はＣ１－１０アルコキシ基、Ｘ３２はＨ又はＣ１－１０アルキル基、ｎは１～３の整数を表す。）
で示される基であることが好ましい。加水分解性シリル基は、－Ｓｉ(ＯＣＨ３)ｎＸ３２ ３－ｎ又は－Ｓｉ(ＯＣ２Ｈ５)ｎＸ３２ ３－ｎであることがより好ましく、－Ｓｉ(ＯＣＨ３)３又は－Ｓｉ(ＯＣ２Ｈ５)３であることがさらに好ましい。 The hydrolyzable silyl group is of the formula:
-SiX 31 n X 32 3-n
(X 31 represents a C 1-10 alkoxy group, X 32 represents an H or C 1-10 alkyl group, and n represents an integer of 1 to 3.)
It is preferably a group represented by. The hydrolyzable silyl group is more preferably -Si (OCH 3 ) n X 32 3-n or -Si (OC 2 H 5 ) n X 32 3-n , and -Si (OCH 3 ) 3 or-. It is more preferably Si (OC 2 H 5 ) 3 .
　複合重合体粒子において、フルオロポリマーとアクリルポリマーとの質量比は９０／１０～１０／９０の範囲内であることが好ましく、８０／２０～２０／８０の範囲内であることがより好ましく、７０／３０以下であることがさらに好ましく、３０／７０以上であることがさらに好ましく、５０／５０以上が特に好ましい。 In the composite polymer particles, the mass ratio of the fluoropolymer to the acrylic polymer is preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, 70. It is more preferably 30/30 or less, further preferably 30/70 or more, and particularly preferably 50/50 or more.
　フルオロポリマーは、フルオロオレフィン単位を含むことが好ましい。フルオロオレフィンとしては、例えば、テトラフルオロエチレン（ＴＦＥ）、ヘキサフルオロプロピレン（ＨＦＰ）、パーフルオロ(アルキルビニルエーテル)（ＰＡＶＥ）、
Figure JPOXMLDOC01-appb-C000022
 などのパーフルオロオレフィン；クロロトリフルオロエチレン（ＣＴＦＥ）、フッ化ビニル（ＶＦ）、ビニリデンフルオライド（ＶｄＦ）、トリフルオロエチレン、トリフルオロプロピレン、ヘキサフルオロイソブテン、２，３，３，３－テトラフルオロプロペン、１，３，３，３－テトラフルオロプロペン、１，１，３，３，３－ペンタフルオロプロペンなどの非パーフルオロオレフィンが挙げられる。
　なお、ＰＡＶＥとしては、パーフルオロ(メチルビニルエーテル)（ＰＭＶＥ）、パーフルオロ(エチルビニルエーテル)（ＰＥＶＥ）、パーフルオロ(プロピルビニルエーテル)（ＰＰＶＥ）などが挙げられる。 The fluoropolymer preferably contains fluoroolefin units. Examples of fluoroolefins include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE), and the like.
Figure JPOXMLDOC01-appb-C000022
 Perfluoroolefins such as: chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene, trifluoropropylene, hexafluoroisobutene, 2,3,3,3-tetrafluoro Examples thereof include non-perfluoroolefins such as propene, 1,3,3,3-tetrafluoropropene and 1,1,3,3,3-pentafluoropropene.
Examples of PAVE include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), and perfluoro (propyl vinyl ether) (PPVE).
　フルオロオレフィンとして、官能基含有フルオロオレフィンも使用できる。上記官能基含有フルオロオレフィンとしては、例えば、式：
ＣＸ３３ ２＝ＣＸ３４－(Ｒｆ３１)ｍ３－Ｙ３１
［式中、
　Ｙ３１は－ＯＨ、－ＣＯＯＭ３２、－ＳＯ２Ｆ、－ＳＯ３Ｍ３２（Ｍ３２は水素原子、ＮＨ４、又はアルカリ金属）、カルボン酸塩、カルボキシエステル基、エポキシ基又はシアノ基であり；
　Ｘ３３及びＸ３４は同じか又は異なりいずれも水素原子又はフッ素原子であり；
　Ｒｆ３１は炭素数１～４０の２価の含フッ素アルキレン基若しくは含フッ素オキシアルキレン基、又は炭素数２～４０のエーテル結合を含有する２価の含フッ素アルキレン基若しくは含フッ素オキシアルキレン基であり；
　ｍ３は０又は１である。］
で示される化合物が挙げられる。 As the fluoroolefin, a functional group-containing fluoroolefin can also be used. Examples of the functional group-containing fluoroolefin include the formula:
CX 33 2 = CX 34 - ( Rf 31) m3 -Y 31
[During the ceremony,
Y 31 is -OH, -COM 32 , -SO 2 F, -SO 3 M 32 (M 32 is a hydrogen atom, NH 4 , or alkali metal), carboxylate, carboxyester group, epoxy group or cyano group. ;
X 33 and X 34 are the same or different, both hydrogen or fluorine atoms;
Rf 31 is a divalent fluorine-containing alkylene group or a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, or a divalent fluorine-containing alkylene group or a fluorine-containing oxyalkylene group containing an ether bond having 2 to 40 carbon atoms. ;
m3 is 0 or 1. ]
Examples thereof include the compounds indicated by.
　官能基含有フルオロオレフィンの具体例としては、例えば、
Figure JPOXMLDOC01-appb-C000023
 等が挙げられる。 Specific examples of the functional group-containing fluoroolefin include, for example,
Figure JPOXMLDOC01-appb-C000023
 And so on.
　フルオロオレフィンとしては、ヨウ素含有モノマー、例えば、特公平５－６３４８２号公報又は特開昭６２－１２７３４号公報に記載されているパーフルオロ（６，６－ジヒドロ－６－ヨード－３－オキサ－１－ヘキセン）、パーフルオロ（５－ヨード－３－オキサ－１－ペンテン）などのパーフルオロビニルエーテルのヨウ素化物も使用できる。 Examples of the fluoroolefin include iodine-containing monomers, for example, perfluoro (6,6-dihydro-6-iodo-3-oxa-1) described in JP-A-5-63482 or JP-A-62-12734. Iodinated products of perfluorovinyl ethers such as -hexene) and perfluoro (5-iodo-3-oxa-1-pentene) can also be used.
　フルオロオレフィンとしては、ＶＦ、ＶｄＦ、ＴＦＥ、ＨＦＰ、及びＣＴＦＥからなる群より選択される少なくとも１種であることが好ましい。また、フルオロオレフィンとしては、ＶｄＦと、ＴＦＥ、ＨＦＰ、及びＣＴＦＥからなる群より選択される少なくとも１種との組合せであることがより好ましい。 The fluoroolefin is preferably at least one selected from the group consisting of VF, VdF, TFE, HFP, and CTFE. Further, the fluoroolefin is more preferably a combination of VdF and at least one selected from the group consisting of TFE, HFP, and CTFE.
　フルオロポリマーは、フルオロオレフィン単位の他に、フルオロオレフィンと共重合可能な非フッ素系単量体単位を含んでいてもよい。フルオロオレフィンと共重合可能な非フッ素系単量体としては、例えば、エチレン、プロピレン、イソブチレンなどのオレフィン類、ビニルエーテル系単量体、アリルエーテル系単量体、ビニルエステル系単量体、アクリル系単量体、メタクリル系単量体などが挙げられる。非フッ素系単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。 The fluoropolymer may contain a non-fluorine-based monomer unit copolymerizable with the fluoroolefin in addition to the fluoroolefin unit. Examples of the non-fluorine-based monomer copolymerizable with the fluoroolefin include olefins such as ethylene, propylene, and isobutylene, vinyl ether-based monomer, allyl ether-based monomer, vinyl ester-based monomer, and acrylic-based monomer. Examples include monomers and methacrylic monomers. One type of non-fluorine-based monomer may be used alone, or two or more types may be used in combination.
　フルオロポリマーは、フルオロオレフィン単位として、ビニリデンフルオライド単位を含むことが好ましい。アクリルポリマーとの相溶性の観点から、フルオロポリマーは、ビニリデンフルオライド単位が、フルオロポリマーを構成する全重合単位に対して５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、９５モル％以下であることが好ましい。 The fluoropolymer preferably contains a vinylidene fluoride unit as a fluoroolefin unit. From the viewpoint of compatibility with the acrylic polymer, the vinylidene fluoride unit of the fluoropolymer is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total polymerization units constituting the fluoropolymer. It is preferably 95 mol% or less.
　フルオロポリマーとしては、ＶｄＦ／ＴＦＥ／ＣＴＦＥ共重合体、ＶｄＦ／ＴＦＥ共重合体、ＶｄＦ／ＴＦＥ／ＨＦＰ共重合体、ＶｄＦ／ＣＴＦＥ共重合体、ＶｄＦ／ＨＦＰ共重合体、及びＰＶｄＦからなる群より選択される少なくとも１種であることが好ましく、ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝４０～９９／１～５０／０～３０（モル％）、ＶｄＦ／ＴＦＥ＝５０～９９／１～５０（モル％）、ＶｄＦ／ＴＦＥ／ＨＦＰ＝４５～９９／０～３５／５～５０（モル％）、ＶｄＦ／ＣＴＦＥ＝４０～９９／１～６０（モル％）、及びＶｄＦ／ＨＦＰ＝５０～９９／１～５０（モル％）からなる群より選択される少なくとも１種であることがより好ましい。 The fluoropolymer includes a group consisting of VdF / TFE / CTFE copolymers, VdF / TFE copolymers, VdF / TFE / HFP copolymers, VdF / CTFE copolymers, VdF / HFP copolymers, and PVdF. It is preferably at least one selected, VdF / TFE / CTFE = 40 to 99/1 to 50/0 to 30 (mol%), VdF / TFE = 50 to 99/1 to 50 (mol%), VdF / TFE / HFP = 45-99 / 0-35 / 5-50 (mol%), VdF / CTFE = 40-99 / 1-60 (mol%), and VdF / HFP = 50-99 / 1-50 More preferably, it is at least one selected from the group consisting of (mol%).
　アクリルポリマーは、少なくともアクリルモノマー単位を含むことが好ましい。アクリルモノマーとしては、（メタ）アクリル酸エステルであることが好ましい。 The acrylic polymer preferably contains at least an acrylic monomer unit. The acrylic monomer is preferably a (meth) acrylic acid ester.
　アクリルポリマーは、アクリル酸エステル単位又はメタクリル酸エステル単位を含むことが好ましく、アクリル酸エステル単位及びメタクリル酸エステル単位を含むことがより好ましい。 The acrylic polymer preferably contains an acrylic acid ester unit or a methacrylic acid ester unit, and more preferably contains an acrylic acid ester unit and a methacrylic acid ester unit.
　組成物（３）の記載において、単に「（メタ）アクリル酸エステル」「アクリル酸エステル」「メタクリル酸エステル」と記載した場合には、水酸基又は加水分解性シリル基を有するアクリルモノマーを含まない。 In the description of the composition (3), when simply described as "(meth) acrylic acid ester", "acrylic acid ester", and "methacrylic acid ester", the acrylic monomer having a hydroxyl group or a hydrolyzable silyl group is not included.
　（メタ）アクリル酸エステル単位は、アクリルポリマーを構成する全単量体単位に対して、合計で、６４～９９．８質量％の範囲内であることが好ましく、７４～９５．５質量％の範囲内であることがより好ましい。 The total amount of the (meth) acrylic acid ester unit is preferably in the range of 64 to 99.8% by mass, preferably 74 to 95.5% by mass, based on all the monomer units constituting the acrylic polymer. It is more preferable that it is within the range.
　（メタ）アクリル酸エステルとしては、アルキル基の炭素数が１～１０のアクリル酸アルキルエステル、又はアルキル基の炭素数が１～１０のメタクリル酸アルキルエステルが好ましい。（メタ）アクリル酸エステルとしては、例えば、メチルアクリレート、エチルアクリレート、ｎ－プロピルアクリレート、イソプロピルアクリレート、ｎ－ブチルアクリレート、メチルメタクリレート、ｎ－プロピルメタクリレート、エチルメタクリレート、ｎ－ブチルメタクリレート、イソプロピルメタクリレート、２－エチルへキシルアクリレート、２－エチルヘキシルメタクリレート、シクロヘキシルアクリレート、シクロヘキシルメタクリレートなどの（メタ）アクリル酸アルキルエステルが挙げられる。 As the (meth) acrylic acid ester, an acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms or a methacrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms is preferable. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, and 2 Examples thereof include (meth) acrylic acid alkyl esters such as ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate.
　（メタ）アクリル酸エステルとしては、メチルメタクリレート、ｎ－ブチルアクリレート、２－エチルへキシルメタクリレート、及びシクロヘキシルメタクリレートからなる群より選択される少なくとも１種が好ましい。 As the (meth) acrylic acid ester, at least one selected from the group consisting of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate is preferable.
　アクリルポリマーは、水酸基含有単量体単位を含むことが好ましく、水酸基含有（メタ）アクリル酸エステル及び水酸基含有アルキルビニルエーテルからなる群より選択される少なくとも１種の水酸基含有単量体単位を含むことがより好ましく、水酸基含有（メタ）アクリル酸エステル単位を含むことがさらに好ましい。 The acrylic polymer preferably contains a hydroxyl group-containing monomer unit, and may contain at least one hydroxyl group-containing monomer unit selected from the group consisting of a hydroxyl group-containing (meth) acrylic acid ester and a hydroxyl group-containing alkyl vinyl ether. More preferably, it contains a hydroxyl group-containing (meth) acrylic acid ester unit.
　水酸基含有単量体単位は、アクリルポリマーを構成する全単量体単位に対して、０．１～４０質量％の範囲内であることが好ましく、０．８～３１質量％の範囲内であることがより好ましく、４～２３質量％の範囲内であることがさらに好ましく、４～１８質量％の範囲内であることが特に好ましい。 The hydroxyl group-containing monomer unit is preferably in the range of 0.1 to 40% by mass, preferably in the range of 0.8 to 31% by mass, based on all the monomer units constituting the acrylic polymer. It is more preferably in the range of 4 to 23% by mass, and particularly preferably in the range of 4 to 18% by mass.
　水酸基含有アルキルビニルエーテルとしては、２－ヒドロキシエチルビニルエーテル、３－ヒドロキシプロピルビニルエーテル、２－ヒドロキシプロピルビニルエーテル、２－ヒドロキシ－２－メチルプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、４－ヒドロキシ－２－メチルブチルビニルエーテル、５－ヒドロキシペンチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル、２－ヒドロキシエチルアリルエーテル、４－ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等が挙げられる。重合反応性が優れる点で、４－ヒドロキシブチルビニルエーテル、及び２－ヒドロキシエチルビニルエーテルからなる群より選択される少なくとも１種が好ましい。 Examples of the hydroxyl group-containing alkyl vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 4-hydroxy-2-methylbutyl vinyl ether. , 5-Hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether and the like. At least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is preferable because of its excellent polymerization reactivity.
　水酸基含有（メタ）アクリル酸エステルとしては、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）、２－ヒドロキシエチルアクリレート（ＨＥＡ）、３－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、４－ヒドロキシブチルメタクリレート、２－ヒドロキシブチルアクリレート、２－ヒドロキシブチルメタクリレート、６－ヒドロキシヘキシルアクリレート、６－ヒドロキシヘキシルメタクリレート等が挙げられ、なかでも、ＨＥＭＡ及びＨＥＡからなる群より選択される少なくとも１種が好ましい。 Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 2-hydroxy. Propyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate and the like can be mentioned, and among them, from HEMA and HEA. At least one selected from the group is preferred.
　水酸基含有（メタ）アクリル酸エステル単位は、アクリルポリマーを構成する全単量体単位に対して、０．１～４０質量％の範囲内であることが好ましく、０．８～３１質量％の範囲内であることがより好ましく、４～２３質量％の範囲内であることがさらに好ましく、４～１８質量％の範囲内であることが特に好ましい。 The hydroxyl group-containing (meth) acrylic acid ester unit is preferably in the range of 0.1 to 40% by mass, and preferably in the range of 0.8 to 31% by mass, based on all the monomer units constituting the acrylic polymer. It is more preferably within the range of 4 to 23% by mass, and particularly preferably within the range of 4 to 18% by mass.
　アクリルポリマーは、加水分解性シリル基含有不飽和単量体単位を含むことが好ましい。 The acrylic polymer preferably contains a hydrolyzable silyl group-containing unsaturated monomer unit.
　加水分解性シリル基含有不飽和単量体としては、
ＣＨ２＝ＣＨＣＯＯ(ＣＨ２)３Ｓｉ(ＯＣＨ３)３、
ＣＨ２＝ＣＨＣＯＯ(ＣＨ２)３Ｓｉ(ＣＨ３)(ＯＣＨ３)２、
ＣＨ２＝ＣＨＣＯＯ(ＣＨ２)３Ｓｉ(ＯＣ２Ｈ５)３、
ＣＨ２＝ＣＨＣＯＯ(ＣＨ２)３Ｓｉ(ＣＨ３)(ＯＣ２Ｈ５)２、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)３Ｓｉ(ＯＣＨ３)３、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)３Ｓｉ(ＣＨ３)(ＯＣＨ３)２、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)３Ｓｉ(ＯＣ２Ｈ５)３、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)３Ｓｉ(ＣＨ３)(ＯＣ２Ｈ５)２、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)２Ｏ(ＣＨ２)３Ｓｉ(ＯＣＨ３)３、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)２(ＣＨ２)３Ｓｉ(ＣＨ３)(ＯＣＨ３)２、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)１１Ｓｉ(ＯＣＨ３)３、
ＣＨ２＝Ｃ(ＣＨ３)ＣＯＯ(ＣＨ２)１１Ｓｉ(ＣＨ３)(ＯＣＨ３)２
等が挙げられる。 As a hydrolyzable silyl group-containing unsaturated monomer,
CH 2 = CHCOO (CH 2 ) 3 Si (OCH 3 ) 3 ,
CH 2 = CHCOO (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2 ,
CH 2 = CHCOO (CH 2 ) 3 Si (OC 2 H 5 ) 3 ,
CH 2 = CHCOO (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 3 Si (OC 2 H 5 ) 3 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 2 O (CH 2 ) 3 Si (OCH 3 ) 3 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 2 (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 11 Si (OCH 3 ) 3 ,
CH 2 = C (CH 3 ) COO (CH 2 ) 11 Si (CH 3 ) (OCH 3 ) 2
And so on.
　加水分解性シリル基含有不飽和単量体単位は、アクリルポリマーを構成する全単量体単位に対して、０．１～５質量％の範囲内であることが好ましく、０．５～３質量％の範囲内であることがより好ましい。 The hydrolyzable silyl group-containing unsaturated monomer unit is preferably in the range of 0.1 to 5% by mass, and 0.5 to 3% by mass, based on all the monomer units constituting the acrylic polymer. More preferably, it is in the range of%.
　アクリルポリマーは、不飽和カルボン酸単位を含むことが好ましい。 The acrylic polymer preferably contains unsaturated carboxylic acid units.
　不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸、３－アリルオキシプロピオン酸、３－（２－アリロキシエトキシカルボニル）プロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニル、ウンデシレン酸などが挙げられる。なかでも、単独重合性が低く単独重合体ができにくい点、カルボキシル基の導入を制御しやすい点から、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、イタコン酸、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステル、３－アリルオキシプロピオン酸、及び、ウンデシレン酸からなる群より選択される少なくとも１種が好ましい。 Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, itaconic acid, and itaconic acid mono. Examples thereof include esters, maleic acid, maleic acid monoesters, maleic acid anhydrides, fumaric acid, fumaric acid monoesters, vinyl phthalates, vinyl pyromellitic acid, and undecylene acid. Among them, acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, because of its low homopolymerizability and difficulty in forming homopolymers and easy control of the introduction of carboxyl groups. At least one selected from the group consisting of fumaric acid, fumaric acid monoester, 3-allyloxypropionic acid, and undecyleneic acid is preferable.
　不飽和カルボン酸単位は、アクリルポリマーを構成する全単量体単位に対して、０．１～１０質量％の範囲内であることが好ましく、１～５質量％の範囲内であることがより好ましい。 The unsaturated carboxylic acid unit is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 1 to 5% by mass, based on all the monomer units constituting the acrylic polymer. preferable.
　アクリルポリマーは、水酸基含有（メタ）アクリル酸エステル単位及び加水分解性シリル基含有不飽和単量体単位を含むことがより好ましい。アクリルポリマーは、アクリル酸エステル単位、メタクリル酸エステル単位、不飽和カルボン酸単位、水酸基含有（メタ）アクリル酸エステル単位、及び加水分解性シリル基含有不飽和単量体単位を含むことがさらに好ましい。 It is more preferable that the acrylic polymer contains a hydroxyl group-containing (meth) acrylic acid ester unit and a hydrolyzable silyl group-containing unsaturated monomer unit. The acrylic polymer more preferably contains an acrylic acid ester unit, a methacrylic acid ester unit, an unsaturated carboxylic acid unit, a hydroxyl group-containing (meth) acrylic acid ester unit, and a hydrolyzable silyl group-containing unsaturated monomer unit.
　アクリル酸エステル単位、メタクリル酸エステル単位、不飽和カルボン酸単位、水酸基含有（メタ）アクリル酸エステル単位、及び加水分解性シリル基含有不飽和単量体単位の比（質量％）は、０～４０／４２～９０／１～５／１～３１／０．５～３の範囲内であることが好ましい。 The ratio (mass%) of the acrylic acid ester unit, the methacrylic acid ester unit, the unsaturated carboxylic acid unit, the hydroxyl group-containing (meth) acrylic acid ester unit, and the hydrolyzable silyl group-containing unsaturated monomer unit is 0 to 40. It is preferably in the range of / 42 to 90/1 to 5/1 to 31 / 0.5 to 3.
　複合重合体粒子は、酸価が１～２０の範囲内であることが好ましく、１～１０の範囲内であることがより好ましく、７以上であることがさらに好ましい。複合重合体粒子は、水酸基価が１～４０の範囲内であることが好ましく、５～３０の範囲内であることがさらに好ましい。水酸基価及び酸価は、複合重合体粒子を合成するために使用した各モノマーの量から計算することができる。 The acid value of the composite polymer particles is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and even more preferably 7 or more. The hydroxyl value of the composite polymer particles is preferably in the range of 1 to 40, and more preferably in the range of 5 to 30. The hydroxyl value and acid value can be calculated from the amount of each monomer used to synthesize the composite polymer particles.
　複合重合体粒子は、ガラス転移温度（Ｔｇ）が０～７０℃の範囲内であることが好ましく、１０～６０℃の範囲内であることがより好ましく、２０～５０℃の範囲内であることがさらに好ましい。 The composite polymer particles preferably have a glass transition temperature (Tg) in the range of 0 to 70 ° C., more preferably in the range of 10 to 60 ° C., and in the range of 20 to 50 ° C. Is even more preferable.
　複合重合体粒子は、粒子径（又は平均粒子径）が５０～３００ｎｍの範囲内であることが好ましく、５０～２５０ｎｍの範囲内であることがより好ましい。 The composite polymer particles preferably have a particle size (or average particle size) in the range of 50 to 300 nm, and more preferably in the range of 50 to 250 nm.
　複合重合体粒子は、フルオロオレフィンを水性分散重合して、フルオロポリマー粒子を含む水性分散体を得る工程、前記フルオロポリマー粒子を含む水性分散体中で、少なくともアクリルモノマーを、フルオロポリマー粒子にシード重合する工程を含む製造方法により得られたものであることが好ましい。 The composite polymer particles are a step of aqueous dispersion polymerization of fluoroolefin to obtain an aqueous dispersion containing fluoropolymer particles. In the aqueous dispersion containing the fluoropolymer particles, at least an acrylic monomer is seed-polymerized into the fluoropolymer particles. It is preferable that the product is obtained by a production method including a step of
　ポリイソシアネート化合物としては、キシリレンジイソシアネート（ＸＤＩ）及びビス（イソシアネートメチル）シクロヘキサン（水素化ＸＤＩ、Ｈ６ＸＤＩ）からなる群より選択される少なくとも１種のイソシアネートから誘導されるポリイソシアネート化合物、ヘキサメチレンジイソシアネート（ＨＤＩ）に基づくブロックイソシアネート化合物、ヘキサメチレンジイソシアネート（ＨＤＩ）から誘導されるポリイソシアネート化合物、イソホロンジイソシアネート（ＩＰＤＩ）から誘導されるポリイソシアネート化合物、及び水分散性ポリイソシアネート化合物からなる群より選択される少なくとも１種の化合物が好ましい。ポリイソシアネート化合物としては、水分散性ポリイソシアネート化合物であることも好ましい。 As the polyisocyanate compound, hexamethylene diisocyanate (hexamethylene diisocyanate) derived from at least one isocyanate selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI). At least selected from the group consisting of blocked isocyanate compounds based on HDI), polyisocyanate compounds derived from hexamethylene diisocyanate (HDI), polyisocyanate compounds derived from isophorone diisocyanate (IPDI), and water-dispersible polyisocyanate compounds. One type of compound is preferred. The polyisocyanate compound is also preferably a water-dispersible polyisocyanate compound.
　ポリイソシアネート化合物としては、キシリレンジイソシアネート（ＸＤＩ）及びビス（イソシアネートメチル）シクロヘキサン（水素化ＸＤＩ、Ｈ６ＸＤＩ）からなる群より選択される少なくとも１種のイソシアネート（以下、イソシアネート（3-i）ともいう。）から誘導されるポリイソシアネート化合物（以下、ポリイソシアネート化合物（3-I）ともいう。）が好ましい。ポリイソシアネート化合物（3-I）としては、例えば、イソシアネート（3-i）と３価以上の脂肪族多価アルコールとを付加重合して得られるアダクト（3-I-1）、イソシアネート（3-i）からなるイソシアヌレート構造体（ヌレート構造体）（3-I-2）、及びイソシアネート（3-i）からなるビウレット（3-I-3）を挙げることができる。 The polyisocyanate compound is also referred to as at least one isocyanate (hereinafter, also referred to as isocyanate (3-i)) selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI). ) Derived from the polyisocyanate compound (hereinafter, also referred to as polyisocyanate compound (3-I)) is preferable. Examples of the polyisocyanate compound (3-I) include adduct (3-I-1) and isocyanate (3-I-1) obtained by addition polymerization of isocyanate (3-i) and a trihydric or higher aliphatic polyhydric alcohol. Examples thereof include an isocyanurate structure (nulate structure) (3-I-2) composed of i) and a biuret (3-I-3) composed of isocyanate (3-i).
　アダクト（3-I-1）としては、例えば、下記式（3A）：
Figure JPOXMLDOC01-appb-C000024
 （式中、Ｒ３１１は、Ｃ３－２０脂肪族炭化水素基を表し、Ｒ３１２は、フェニレン基又はシクロヘキシレン基を表し、ｋ３１は、３～２０の整数である。）
で表される構造を有するものが好ましい。
　Ｒ３１１は、３価以上の脂肪族多価アルコールに基づく炭化水素基であり、Ｃ３－１０脂肪族炭化水素基がより好ましく、Ｃ３－６脂肪族炭化水素基がさらに好ましい。
　Ｒ３１２がフェニレン基である場合、１，２－フェニレン基（ｏ－フェニレン基）、１，３－フェニレン基（ｍ－フェニレン基）、及び１，４－フェニレン基（ｐ－フェニレン基）のいずれであってもよい。中でも、１，３－フェニレン基（ｍ－フェニレン基）が好ましい。また、式（3A）中の全てのＲ３１２が同じフェニレン基であってもよく、２種以上が混在していてもよい。
　Ｒ３１２がシクロヘキシレン基である場合、１，２－シクロヘキシレン基、１，３－シクロヘキシレン基、及び１，４－シクロヘキシレン基のいずれであってもよい。中でも、１，３－シクロヘキシレン基が好ましい。また、式（3A）中の全てのＲ３１２が同じシクロヘキシレン基であってもよく、２種以上が混在していてもよい。
　ｋ３１は、３価以上の脂肪族多価アルコールの価数に対応する数である。ｋ３１は、より好ましくは３～１０の整数であり、さらに好ましくは３～６の整数である。 As the adduct (3-I-1), for example, the following formula (3A):
Figure JPOXMLDOC01-appb-C000024
 (In the formula, R 311 represents a C 3-20 aliphatic hydrocarbon group, R 312 represents a phenylene group or a cyclohexylene group, and k31 is an integer of 3 to 20.)
Those having a structure represented by are preferable.
R 311 is a hydrocarbon group based on a trihydric or higher aliphatic polyhydric alcohol, with a C 3-10 aliphatic hydrocarbon group being more preferred and a C 3-6 aliphatic hydrocarbon group being even more preferred.
When R 312 is a phenylene group, any of 1,2-phenylene group (o-phenylene group), 1,3-phenylene group (m-phenylene group), and 1,4-phenylene group (p-phenylene group) It may be. Of these, a 1,3-phenylene group (m-phenylene group) is preferable. Further, all R 312s in the formula (3A) may have the same phenylene group, or two or more kinds may be mixed.
When R 312 is a cyclohexylene group, it may be any of a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group. Of these, a 1,3-cyclohexylene group is preferable. Further, all R 312s in the formula (3A) may have the same cyclohexylene group, or two or more kinds may be mixed.
k31 is a number corresponding to the valence of the trihydric or higher aliphatic polyhydric alcohol. k31 is more preferably an integer of 3 to 10, and even more preferably an integer of 3 to 6.
　イソシアヌレート構造体（3-I-2）は、分子中に、下記式（3B）：
Figure JPOXMLDOC01-appb-C000025
 で表されるイソシアヌレート環を１個又は２個以上有するものである。
　イソシアヌレート構造体（3-I-2）としては、イソシアネートの三量化反応により得られる三量体、五量化反応により得られる五量体、七量化反応により得られる七量体等を挙げることができる。中でも、下記式（3C）：
Figure JPOXMLDOC01-appb-C000026
 （式中、Ｒ３１２は、式（3A）中のＲ３１２と同じである。）
で表される三量体が好ましい。すなわち、イソシアヌレート構造体は、キシリレンジイソシアネート及びビス（イソシアネートメチル）シクロヘキサンからなる群より選択される少なくとも１種のイソシアネートの三量体であることが好ましい。 The isocyanurate structure (3-I-2) is contained in the molecule according to the following formula (3B):
Figure JPOXMLDOC01-appb-C000025
 It has one or two or more isocyanurate rings represented by.
Examples of the isocyanurate structure (3-I-2) include a trimer obtained by a trimerization reaction of isocyanate, a pentamer obtained by a pentamerization reaction, and a heptamer obtained by a heptamerization reaction. it can. Above all, the following formula (3C):
Figure JPOXMLDOC01-appb-C000026
 (In the equation, R 312 is the same as R 312 in equation (3A).)
The trimer represented by is preferable. That is, the isocyanurate structure is preferably a trimer of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane.
　ビウレット（3-I-3）は、下記式（3D）：
Figure JPOXMLDOC01-appb-C000027
 （式中、Ｒ３１２は、式（3A）中のＲ３１２と同じである。）
で表される構造を有する化合物であり、イソシアヌレート構造体（3-I-2）を得る場合とは異なる条件下で、イソシアネートを三量化することにより、得ることができる。 Biuret (3-I-3) has the following formula (3D):
Figure JPOXMLDOC01-appb-C000027
 (In the equation, R 312 is the same as R 312 in equation (3A).)
It is a compound having a structure represented by, and can be obtained by quantifying isocyanate under conditions different from those for obtaining an isocyanurate structure (3-I-2).
　ポリイソシアネート化合物（3-I）としては、アダクト（3-I-1）、すなわち、キシリレンジイソシアネート及びビス（イソシアネートメチル）シクロヘキサンからなる群より選択される少なくとも１種のイソシアネートと、３価以上の脂肪族多価アルコールとを付加重合して得られるものが好ましい。 As the polyisocyanate compound (3-I), adduct (3-I-1), that is, at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane, and trivalent or higher valent isocyanates. Those obtained by addition polymerization with an aliphatic polyhydric alcohol are preferable.
　ポリイソシアネート化合物（3-I）が、イソシアネート（3-i）と３価以上の脂肪族多価アルコールとのアダクトである場合、該３価以上の脂肪族多価アルコールとしては、具体的には、グリセロール、トリメチロールプロパン（ＴＭＰ）、１，２，６－ヘキサントリオール、トリメチロールエタン、２，４－ジヒドロキシ－３－ヒドロキシメチルペンタン、１，１，１－トリス（ビスヒドロキシメチル）プロパン、２，２－ビス（ヒドロキシメチル）ブタノール－３等の３価アルコール；ペンタエリスリトール、ジグリセロール等の４価アルコール；アラビット、リビトール、キシリトール等の５価アルコール（ペンチット）；ソルビット、マンニット、ガラクチトール、アロズルシット等の６価アルコール（ヘキシット）等が挙げられる。中でも、トリメチロールプロパン、ペンタエリスリトールが特に好ましい。 When the polyisocyanate compound (3-I) is an adduct of isocyanate (3-i) and a trihydric or higher aliphatic polyhydric alcohol, specifically, the trihydric or higher aliphatic polyhydric alcohol may be used. , Glycohol, Trimethylol Propane (TMP), 1,2,6-Hexanetriol, Trimethylol Ethan, 2,4-Dihydroxy-3-hydroxymethylpentane, 1,1,1-Tris (bishydroxymethyl) Propane, 2, , 3-hydric alcohols such as 2-bis (hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabite, ribitol and xylitol (pentit); sorbit, mannit, galactitol, Examples thereof include hexahydric alcohols (hexits) such as Arosulcit. Of these, trimethylolpropane and pentaerythritol are particularly preferable.
　アダクト（3-I-1）の構成成分として用いられるキシリレンジイソシアネート（ＸＤＩ）としては、１，３－キシリレンジイソシアネート（ｍ－キシリレンジイソシアネート）、１，２－キシリレンジイソシアネート（ｏ－キシリレンジイソシアネート）、１，４－キシリレンジイソシアネート（ｐ－キシリレンジイソシアネート）が挙げられるが、中でも、１，３－キシリレンジイソシアネート（ｍ－キシリレンジイソシアネート）が好ましい。 The xylylene diisocyanate (XDI) used as a component of adduct (3-I-1) includes 1,3-xylylene diisocyanate (m-xylylene diisocyanate) and 1,2-xylylene diisocyanate (o-xylylene diisocyanate). Isocyanate), 1,4-xylylene diisocyanate (p-xylylene diisocyanate), and among them, 1,3-xylylene diisocyanate (m-xylylene diisocyanate) is preferable.
　アダクト（3-I-1）の構成成分として用いられるビス（イソシアネートメチル）シクロヘキサン（水素化ＸＤＩ、Ｈ６ＸＤＩ）としては、１，３－ビス（イソシアネートメチル）シクロヘキサン、１，２－ビス（イソシアネートメチル）シクロヘキサン、１，４－ビス（イソシアネートメチル）シクロヘキサンが挙げられるが、中でも、１，３－ビス（イソシアネートメチル）シクロヘキサンが好ましい。 As the bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI) used as a component of adduct (3-I-1), 1,3-bis (isocyanate methyl) cyclohexane and 1,2-bis (isocyanate methyl) Examples thereof include cyclohexane and 1,4-bis (isocyanatemethyl) cyclohexane, and among them, 1,3-bis (isocyanatemethyl) cyclohexane is preferable.
　アダクト（3-I-1）として、具体的には、下記式（3E）：
Figure JPOXMLDOC01-appb-C000028
 （式中、Ｒ３１３は、フェニレン基又はシクロヘキシレン基を表す。）
で表される化合物、すなわち、キシリレンジイソシアネート及びビス（イソシアネートメチル）シクロヘキサンからなる群より選択される少なくとも１種のイソシアネートと、トリメチロールプロパン（ＴＭＰ）とを付加重合することにより得られるポリイソシアネート化合物を挙げることができる。
　Ｒ３１３で表されるフェニレン基又はシクロヘキシレン基は、式（3A）におけるＲ３１２と同様である。 As the adduct (3-I-1), specifically, the following formula (3E):
Figure JPOXMLDOC01-appb-C000028
 (In the formula, R 313 represents a phenylene group or a cyclohexylene group.)
A polyisocyanate compound obtained by addition polymerization of trimethylolpropane (TMP) with at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanatemethyl) cyclohexane. Can be mentioned.
The phenylene group or cyclohexylene group represented by R 313 is the same as that of R 312 in the formula (3A).
　式（3E）で表されるポリイソシアネート化合物の市販品としては、タケネートＤ１１０Ｎ（三井化学株式会社製、ＸＤＩとＴＭＰとのアダクト、ＮＣＯ含有量１１．８％）、タケネートＤ１２０Ｎ（三井化学株式会社製、Ｈ６ＸＤＩとＴＭＰとのアダクト、ＮＣＯ含有量１１．０％）等が挙げられる。 Commercially available products of the polyisocyanate compound represented by the formula (3E) include Takenate D110N (manufactured by Mitsui Chemicals, Inc., Adduct of XDI and TMP, NCO content 11.8%), Takenate D120N (manufactured by Mitsui Chemicals, Inc.). , Adduct of H6XDI and TMP, NCO content 11.0%) and the like.
　ポリイソシアネート化合物（3-I）が、イソシアヌレート構造体（3-I-2）である場合の具体例としては、タケネートＤ１２１Ｎ（三井化学株式会社製、Ｈ６ＸＤＩヌレート、ＮＣＯ含有量１４．０％）、タケネートＤ１２７Ｎ（三井化学株式会社製、Ｈ６ＸＤＩヌレート、Ｈ６ＸＤＩの３量体、ＮＣＯ含有量１３．５％）等が挙げられる。 A specific example of the case where the polyisocyanate compound (3-I) is an isocyanurate structure (3-I-2) is Takenate D121N (manufactured by Mitsui Chemicals, Inc., H6XDI nurate, NCO content 14.0%). , Takenate D127N (manufactured by Mitsui Chemicals, Inc., H6XDI nurate, trimer of H6XDI, NCO content 13.5%) and the like.
　ポリイソシアネート化合物として、ヘキサメチレンジイソシアネート（ＨＤＩ）に基づくブロックイソシアネート（以下、単にブロックイソシアネートともいう。）を用いることも好ましい。ブロックイソシアネートとしては、ヘキサメチレンジイソシアネートから誘導されるポリイソシアネート化合物（以下、ポリイソシアネート化合物（3-II）ともいう。）をブロック化剤で反応させて得られるものが好ましい。
　ポリイソシアネート化合物（3-II）としては、例えば、ヘキサメチレンジイソシアネートと３価以上の脂肪族多価アルコールとを付加重合して得られるアダクト（3-II-1）、ヘキサメチレンジイソシアネートからなるイソシアヌレート構造体（ヌレート構造体）（3-II-2）、及びヘキサメチレンジイソシアネートからなるビウレット（3-II-3）を挙げることができる。 As the polyisocyanate compound, it is also preferable to use a blocked isocyanate based on hexamethylene diisocyanate (HDI) (hereinafter, also simply referred to as a blocked isocyanate). As the blocked isocyanate, those obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate (hereinafter, also referred to as polyisocyanate compound (3-II)) with a blocking agent are preferable.
Examples of the polyisocyanate compound (3-II) include isocyanurate composed of adduct (3-II-1) and hexamethylene diisocyanate obtained by addition polymerization of hexamethylene diisocyanate and a trihydric or higher aliphatic polyhydric alcohol. Examples thereof include a structure (nurate structure) (3-II-2) and a biuret (3-II-3) composed of hexamethylene diisocyanate.
　アダクト（3-II-1）としては、例えば、下記式（3F）：
Figure JPOXMLDOC01-appb-C000029
 （式中、Ｒ３１４は、Ｃ３－２０脂肪族炭化水素基を表す。ｋ３２は、３～２０の整数である。）で表される構造を有するものが好ましい。
　Ｒ３１４は、上記３価以上の脂肪族多価アルコールに基づく炭化水素基であり、Ｃ３－１０脂肪族炭化水素基がより好ましく、Ｃ３－６脂肪族炭化水素基がさらに好ましい。　ｋ３２は、３価以上の脂肪族多価アルコールの価数に対応する数である。ｋ３２は、より好ましくは３～１０の整数であり、さらに好ましくは３～６の整数である。 As an adduct (3-II-1), for example, the following formula (3F):
Figure JPOXMLDOC01-appb-C000029
 (In the formula, R 314 represents a C 3-20 aliphatic hydrocarbon group. K32 is an integer of 3 to 20.) It is preferable that the structure is represented by.
R314 is a hydrocarbon group based on the above trihydric or higher aliphatic polyhydric alcohol, a C 3-10 aliphatic hydrocarbon group is more preferable, and a C 3-6 aliphatic hydrocarbon group is further preferable. k32 is a number corresponding to the valence of the trihydric or higher aliphatic polyhydric alcohol. k32 is more preferably an integer of 3 to 10, and even more preferably an integer of 3 to 6.
　イソシアヌレート構造体（3-II-2）は、分子中に、式（3B）で表されるイソシアヌレート環を１個又は２個以上有するものである。
　イソシアヌレート構造体（3-II-2）としては、イソシアネートの三量化反応により得られる三量体、五量化反応により得られる五量体、七量化反応により得られる七量体等を挙げることができる。中でも、下記式（3G）：
Figure JPOXMLDOC01-appb-C000030
 で表される三量体が好ましい。 The isocyanurate structure (3-II-2) has one or more isocyanurate rings represented by the formula (3B) in the molecule.
Examples of the isocyanurate structure (3-II-2) include a trimer obtained by a trimerization reaction of isocyanate, a pentamer obtained by a pentamerization reaction, and a heptamer obtained by a heptamerization reaction. it can. Above all, the following formula (3G):
Figure JPOXMLDOC01-appb-C000030
 The trimer represented by is preferable.
　ビウレット（3-II-3）は、下記式（3H）：
Figure JPOXMLDOC01-appb-C000031
 で表される構造を有する化合物であり、イソシアヌレート構造体（3-II-2）を得る場合とは異なる条件下で、ヘキサメチレンジイソシアネートを三量化することにより、得ることができる。 Biuret (3-II-3) has the following formula (3H):
Figure JPOXMLDOC01-appb-C000031
 It is a compound having a structure represented by, and can be obtained by quantifying hexamethylene diisocyanate under conditions different from those for obtaining an isocyanurate structure (3-II-2).
　ブロックイソシアネートの市販品としては、デュラネートＫ６０００（旭化成ケミカルズ株式会社製、ＨＤＩの活性メチレン化合物ブロックイソシアネート）、デュラネートＴＰＡ－Ｂ８０Ｅ（旭化成ケミカルズ株式会社製）、デュラネートＭＦ－Ｂ６０Ｘ（旭化成ケミカルズ株式会社製）、デュラネート１７Ｂ－６０ＰＸ（旭化成ケミカルズ株式会社製）、コロネート２５０７（日本ポリウレタン工業株式会社製）、コロネート２５１３（日本ポリウレタン工業株式会社製）、コロネート２５１５（日本ポリウレタン工業株式会社製）、スミジュールＢＬ－３１７５（住化バイエルウレタン株式会社製）、ＬｕｘａｔｅＨＣ１１７０（オリン・ケミカルズ社製）、ＬｕｘａｔｅＨＣ２１７０（オリン・ケミカルズ社製）等が挙げられる。 Commercially available blocked isocyanate products include Duranate K6000 (manufactured by Asahi Kasei Chemicals Co., Ltd., HDI active methylene compound blocked isocyanate), Duranate TPA-B80E (manufactured by Asahi Kasei Chemicals Co., Ltd.), Duranate MF-B60X (manufactured by Asahi Kasei Chemicals Co., Ltd.), Duranate 17B-60PX (Asahi Kasei Chemicals Co., Ltd.), Coronate 2507 (Nippon Polyurethane Industry Co., Ltd.), Coronate 2513 (Nippon Polyurethane Industry Co., Ltd.), Coronate 2515 (Nippon Polyurethane Industry Co., Ltd.), Sumijour BL-3175 (Manufactured by Sumika Bayer Urethane Co., Ltd.), LuxateHC1170 (manufactured by Olin Chemicals), LuxateHC2170 (manufactured by Olin Chemicals) and the like can be mentioned.
　ポリイソシアネート化合物として、ヘキサメチレンジイソシアネート（ＨＤＩ）から誘導されるポリイソシアネート化合物（以下、ポリイソシアネート化合物（3-III）ともいう。）を用いることもできる。ポリイソシアネート化合物（3-III）としては、ポリイソシアネート化合物（3-II）として上述したものが挙げられる。 As the polyisocyanate compound, a polyisocyanate compound derived from hexamethylene diisocyanate (HDI) (hereinafter, also referred to as a polyisocyanate compound (3-III)) can be used. Examples of the polyisocyanate compound (3-III) include those described above as the polyisocyanate compound (3-II).
　ポリイソシアネート化合物（3-III）の具体例としては、コロネートＨＸ（日本ポリウレタン工業株式会社製、ヘキサメチレンジイソシアネートのイソシアヌレート構造体、ＮＣＯ含有量２１．１％）、スミジュールＮ３３００（住化バイエルウレタン株式会社製、ヘキサメチレンジイソシアネートのイソシアヌレート構造体）、タケネートＤ１７０Ｎ（三井化学社製、ヘキサメチレンジイソシアネートのイソシアヌレート構造体）、スミジュールＮ３８００（住化バイエルウレタン株式会社製、ヘキサメチレンジイソシアネートのイソシアヌレート構造体プレポリマータタイプ）等が挙げられる。 Specific examples of the polyisocyanate compound (3-III) include Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%), Sumijour N3300 (Sumika Bayer Urethane). Hexamethylene diisocyanate isocyanurate structure manufactured by Sumika Bayer Urethane Co., Ltd.), Takenate D170N (Mitsui Chemicals Co., Ltd., hexamethylene diisocyanate isocyanurate structure), Sumijuru N3800 (Isocyanurate structure of hexamethylene diisocyanate manufactured by Sumika Bayer Urethane Co., Ltd.) Structure prepolymer type) and the like.
　ポリイソシアネート化合物として、イソホロンジイソシアネート（ＩＰＤＩ）から誘導されるポリイソシアネート化合物（以下、ポリイソシアネート化合物（3-IV））も好ましい。 As the polyisocyanate compound, a polyisocyanate compound derived from isophorone diisocyanate (IPDI) (hereinafter, polyisocyanate compound (3-IV)) is also preferable.
　ポリイソシアネート化合物（3-IV）としては、例えば、イソホロンジイソシアネートと３価以上の脂肪族多価アルコールとを付加重合して得られるアダクト（3-IV-1）、イソホロンジイソシアネートからなるイソシアヌレート構造体（ヌレート構造体）（3-IV-2）、及びイソホロンジイソシアネートからなるビウレット（3-IV-3）を挙げることができる。 Examples of the polyisocyanate compound (3-IV) include an isocyanurate structure composed of adduct (3-IV-1) obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, and isophorone diisocyanate. (Nurate structure) (3-IV-2) and biuret (3-IV-3) composed of isophorone diisocyanate can be mentioned.
　アダクト（3-IV-1）としては、例えば、下記式（3I）：
Figure JPOXMLDOC01-appb-C000032
 （式中、
Ｒ３１５は、Ｃ３－２０脂肪族炭化水素基を表し、
Ｒ３１６は、下記式（3J）：
Figure JPOXMLDOC01-appb-C000033
 で表される基であり、
ｋ３４は、３～２０の整数である。）
で表される構造を有するものが好ましい。
　Ｒ３１５は、上記３価以上の脂肪族多価アルコールに基づく炭化水素基であり、Ｃ３－１０脂肪族炭化水素基がより好ましく、Ｃ３－６脂肪族炭化水素基がさらに好ましい。
　ｋ３４は、３価以上の脂肪族多価アルコールの価数に対応する数である。ｋ３４は、より好ましくは３～１０の整数であり、さらに好ましくは３～６の整数である。 As an adduct (3-IV-1), for example, the following equation (3I):
Figure JPOXMLDOC01-appb-C000032
 (During the ceremony,
R 315 represents a C 3-20 aliphatic hydrocarbon group.
R 316 is expressed by the following equation (3J):
Figure JPOXMLDOC01-appb-C000033
 It is a group represented by
k34 is an integer of 3 to 20. )
Those having a structure represented by are preferable.
R 315 is a hydrocarbon group based on the above-mentioned trihydric or higher aliphatic polyhydric alcohol, a C 3-10 aliphatic hydrocarbon group is more preferable, and a C 3-6 aliphatic hydrocarbon group is further preferable.
k34 is a number corresponding to the valence of the trihydric or higher aliphatic polyhydric alcohol. k34 is more preferably an integer of 3 to 10, and even more preferably an integer of 3 to 6.
　イソシアヌレート構造体（3-IV-2）は、分子中に、式（3B）で表されるイソシアヌレート環を１個又は２個以上有するものである。イソシアヌレート構造体（3-IV-2）としては、イソシアネートの三量化反応により得られる三量体、五量化反応により得られる五量体、七量化反応により得られる七量体等を挙げることができる。中でも、下記式（3K）：
Figure JPOXMLDOC01-appb-C000034
 （式中、Ｒ３１６は、式（3I）中のＲ３１６と同じである。）
で表される三量体が好ましい。すなわち、イソシアヌレート構造体（3-IV-2）は、イソホロンジイソシアネートの三量体であることが好ましい。 The isocyanurate structure (3-IV-2) has one or more isocyanurate rings represented by the formula (3B) in the molecule. Examples of the isocyanurate structure (3-IV-2) include a trimer obtained by a trimerization reaction of isocyanate, a pentamer obtained by a pentamerization reaction, and a heptamer obtained by a heptamerization reaction. it can. Above all, the following formula (3K):
Figure JPOXMLDOC01-appb-C000034
 (Wherein, R 316 is the same as R 316 in formula (3I).)
The trimer represented by is preferable. That is, the isocyanurate structure (3-IV-2) is preferably a trimer of isophorone diisocyanate.
　好ましく用いられるアダクトとして、具体的には、下記式（3L）：
Figure JPOXMLDOC01-appb-C000035
 （式中、Ｒ３１７は、式（3J）で表される基である。）
で表される化合物、すなわち、イソホロンジイソシアネートとトリメチロールプロパン（ＴＭＰ）とを付加重合することにより得られるポリイソシアネート化合物を挙げることができる。 Specifically, the following formula (3L):
Figure JPOXMLDOC01-appb-C000035
 (In the formula, R 317 is a group represented by the formula (3J).)
Examples of the compound represented by, that is, a polyisocyanate compound obtained by addition polymerization of isophorone diisocyanate and trimethylolpropane (TMP).
　式（3J）で表されるポリイソシアネート化合物（イソホロンジイソシアネートのＴＭＰアダクト体）の市販品としては、タケネートＤ１４０Ｎ（三井化学株式会社製、ＮＣＯ含有量１１％）等が挙げられる。 Examples of commercially available products of the polyisocyanate compound represented by the formula (3J) (TMP adduct of isophorone diisocyanate) include Takenate D140N (manufactured by Mitsui Chemicals, Inc., NCO content 11%).
　イソホロンジイソシアネートからなるイソシアヌレート構造体の市販品としては、デスモジュールＺ４４７０（住化バイエルウレタン株式会社製、ＮＣＯ含有量１１％）等が挙げられる。 Examples of commercially available isocyanurate structures made of isophorone diisocyanate include Death Module Z4470 (manufactured by Sumika Bayer Urethane Co., Ltd., NCO content 11%).
　ポリイソシアネート化合物として、水分散性ポリイソシアネート化合物を用いることもできる。水分散性ポリイソシアネート化合物とは、水性媒体中に加えて攪拌したときに水分散体を形成しうるポリイソシアネート化合物をいう。このような水分散性ポリイソシアネート化合物としては、例えば、（3-1）疎水性ポリイソシアネートと親水性基を有するポリイソシアネートとの混合物、（3-2）疎水性ポリイソシアネートとイソシアネート基を有さず親水性基を有する分散剤との混合物、（3-3）親水性基を有するポリイソシアネートのみ等が挙げられる。なお、親水性基とは、アニオン性基、カチオン性基、又はノニオン性基をいう。水分散性ポリイソシアネート化合物としては、親水性基を有するポリイソシアネートであることが特に好ましい。 As the polyisocyanate compound, a water-dispersible polyisocyanate compound can also be used. The water-dispersible polyisocyanate compound refers to a polyisocyanate compound capable of forming an aqueous dispersion when added to an aqueous medium and stirred. Examples of such an water-dispersible polyisocyanate compound include (3-1) a mixture of a hydrophobic polyisocyanate and a polyisocyanate having a hydrophilic group, and (3-2) a hydrophobic polyisocyanate and an isocyanate group. Examples thereof include a mixture with a dispersant having a hydrophilic group, and (3-3) only a polyisocyanate having a hydrophilic group. The hydrophilic group means an anionic group, a cationic group, or a nonionic group. The water-dispersible polyisocyanate compound is particularly preferably a polyisocyanate having a hydrophilic group.
　疎水性ポリイソシアネートとは、親水性基を有さないものであり、例えば、１，４－テトラメチレンジイソシアネート、エチル（２，６－ジイソシアナート）ヘキサノエート、１，６－ヘキサメチレンジイソシアネート、１，１２－ドデカメチレンジイソシアネート、２，２，４－又は２，４，４－トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート；１，３，６－ヘキサメチレントリイソシアネート、１，８－ジイソシアナート－４－イソシアナートメチルオクタン、２－イソシアナートエチル（２，６－ジイソシアナート）ヘキサノエート等の脂肪族トリイソシアネート；１，３－ビス（イソシアナートメチルシクロヘキサン）、１，４－ビス（イソシアナートメチルシクロヘキサン）、１，３－ジイソシアナートシクロヘキサン、１，４－ジイソシアナートシクロヘキサン、３，５，５－トリメチル（３－イソシアナートメチル）シクロヘキシルイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、２，５－ジイソシアナートメチルノルボルナン、２，６－ジイソシアナートメチルノルボルナン等の脂環族ジイソシアネート；２，５－ジイソシアナートメチル－２－イソシネートプロピルノルボルナン、２，６－ジイソシアナートメチル－２－イソシネートプロピルノルボルナン等の脂環族トリイソシアネート；ｍ－キシリレンジイソシアネート、α，α，α’α’－テトラメチル－ｍ－キシリレンジイソシアネート等のアラルキレンジイソシアネート；ｍ－又はｐ－フェニレンジイソシアネート、トリレン－２，４－ジイソシアネート、トリレン－２，６－ジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ナフタレン－１，５－ジイソシアネート、ジフェニル－４，４’－ジイソシアネート、４，４’－ジイソシアナート－３，３’－ジメチルジフェニル、３－メチル－ジフェニルメタン－４，４’－ジイソシアネート、ジフェニルエーテル－４，４’－ジイソシアネート等の芳香族ジイソシアネート；トリフェニルメタントリイソシアネート、トリス（イソシアナートフェニル）チオホスフェート等の芳香族トリイソシアネート；前記のジイソシアネート又はトリイソシアネートのイソシアネート基同士を環化二量化して得られるウレトジオン構造を有するポリイソシアネート；前記のジイソシアネート又はトリイソシアネートのイソシアネート基同士を環化三量化して得られるイソシアヌレート構造を有するポリイソシアネート；前記のジイソシアネート又はトリイソシアネートを水と反応させることにより得られるビュレット構造を有するポリイソシアネート；前記のジイソシアネート又はトリイソシアネートを二酸化炭素と反応させて得られるオキサダイアジントリオン構造を有するポリイソシアネート；アロファネート構造を有するポリイソシアネートなどが挙げられる。これらの中でも、イソシアヌレート構造を有するポリイソシアネートが好ましい。 The hydrophobic polyisocyanate does not have a hydrophilic group, and is, for example, 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, 1,6-hexamethylene diisocyanate, 1, Aliphatic diisocyanates such as 12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4- Isocyanate Methyloctane, 2-isocyanate ethyl (2,6-diisocyanate) hexanoate and other aliphatic triisocyanates; 1,3-bis (isocyanate methylcyclohexane), 1,4-bis (isocyanatomethylcyclohexane) , 1,3-Diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, 3,5,5-trimethyl (3-isocyanatomethyl) cyclohexylisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,5- Alicyclic diisocyanates such as diisocyanatomethylnorbornan and 2,6-diisocyanatomethylnorbornan; 2,5-diisocyanatemethyl-2-isocinatepropylnorbornan, 2,6-diisocyanatomethyl-2- Alicyclic triisocyanates such as isocyanate propyl norbornan; aralkylenedisocyanates such as m-xylylene diisocyanate, α, α, α'α'-tetramethyl-m-xylylene diisocyanate; m- or p-phenylenediocyanates, Trilen-2,4-diisocyanate, trilen-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanate Aromatic diisocyanates such as -3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate; triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate Aromatic triisocyanates such as; polyisocyanates having a uretdione structure obtained by cyclizing and dimerizing the isocyanate groups of the diisocyanates or triisocyanates; isocyanates of the diisocyanates or triisocyanates. Polyisocyanate having an isocyanurate structure obtained by cyclizing triisocyanates of groups; polyisocyanate having a burette structure obtained by reacting the diisocyanate or triisocyanate with water; Polyisocyanates having an oxadiazine trione structure obtained by reacting with carbon; polyisocyanates having an allophanate structure and the like can be mentioned. Among these, a polyisocyanate having an isocyanurate structure is preferable.
　親水性基を有するポリイソシアネートとしては、例えば、親水性基及びイソシアネート基を有するポリエーテル、ポリエステル、ポリウレタン、ビニル重合体、アルキド樹脂、フッ素樹脂、シリコン樹脂等が挙げられる。これらの中でも、水分散性が良好であることから、親水性基とイソシアネート基とを有するポリエーテル又はビニル重合体が好ましく、親水性基とイソシアネート基を有するポリエーテルがより好ましい。これらの親水性基を有するポリイソシアネートは、単独で用いることも２種以上併用することもできる。 Examples of the polyisocyanate having a hydrophilic group include polyethers having a hydrophilic group and an isocyanate group, polyester, polyurethane, vinyl polymer, alkyd resin, fluororesin, silicon resin and the like. Among these, a polyether having a hydrophilic group and an isocyanate group or a vinyl polymer is preferable, and a polyether having a hydrophilic group and an isocyanate group is more preferable, because the water dispersibility is good. The polyisocyanates having these hydrophilic groups can be used alone or in combination of two or more.
　親水性基を有するポリイソシアネートの市販品としては、バイヒジュール　ＸＰ　２７００（住化バイエルウレタン株式会社製）等が挙げられる。 Examples of commercially available products of polyisocyanates having a hydrophilic group include Bayer Jules XP 2700 (manufactured by Sumika Bayer Urethane Co., Ltd.).
　ポリイソシアネート化合物の含有量は、ポリイソシアネート化合物中のイソシアネート基（ＮＣＯ）と複合重合体粒子が含有する水酸基（ＯＨ）の当量比（ＮＣＯ／ＯＨ）が０．１～５の範囲内であることが好ましく、０．５～５の範囲内であることがより好ましく、０．５～３の範囲内であることがさらに好ましく、１～２の範囲内であることが特に好ましい。 The content of the polyisocyanate compound is such that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the polyisocyanate compound and the hydroxyl group (OH) contained in the composite polymer particles is in the range of 0.1 to 5. Is more preferable, it is more preferably in the range of 0.5 to 5, further preferably in the range of 0.5 to 3, and particularly preferably in the range of 1 to 2.
　ポリイソシアネート化合物が水分散性ポリイソシアネート化合物の場合の配合量としては、水分散性ポリイソシアネート化合物中のイソシアネート基（ＮＣＯ）と、複合重合体粒子が含有する水酸基（ＯＨ）との当量比（ＮＣＯ／ＯＨ）が、０．１～５の範囲内が好ましく、０．３～３の範囲内がより好ましく、０．３～２の範囲内がさらに好ましく、０．５～１．５の範囲内が特に好ましい。 When the polyisocyanate compound is a water-dispersible polyisocyanate compound, the blending amount is the equivalent ratio (NCO) of the isocyanate group (NCO) in the water-dispersible polyisocyanate compound and the hydroxyl group (OH) contained in the composite polymer particles. / OH) is preferably in the range of 0.1 to 5, more preferably in the range of 0.3 to 3, further preferably in the range of 0.3 to 2, and in the range of 0.5 to 1.5. Is particularly preferable.
　組成物（３）は、水に加えて、アルコール、グリコールエーテル、エステル等の有機溶媒を含有してもよい。 The composition (3) may contain an organic solvent such as alcohol, glycol ether, or ester in addition to water.
　組成物（３）は、例えば１０～６０質量％の複合重合体粒子を含むことができる。 The composition (3) can contain, for example, 10 to 60% by mass of composite polymer particles.
　組成物（３）は、さらに造膜助剤を含有することが好ましい。造膜助剤としては、ジプロピレングリコールジメチルエーテル（ＤＰＧＤＭＥ）、ジエチルジグリコール（ＤＥＤＧ）、アジピン酸ジエチル（ＡＤＥ）等の活性水素を持たない造膜助剤が挙げられる。活性水素とは、水酸基やアミノ基などに含まれる水素原子のことである。 The composition (3) preferably further contains a film-forming auxiliary. Examples of the film-forming auxiliary include dipropylene glycol dimethyl ether (DPGDME), diethyl diglycol (DEDG), diethyl adipate (ADE) and other film-forming aids that do not have active hydrogen. Active hydrogen is a hydrogen atom contained in a hydroxyl group or an amino group.
　組成物（３）には、必要に応じて、顔料、凍結防止剤、充填剤、消泡剤、レベリング剤、レオロジー調整剤、ｐＨ調整剤、防腐剤、紫外線吸収剤、酸化防止剤、つや消し剤、潤滑剤等を添加してもよい。 The composition (3) may contain pigments, antifreezes, fillers, defoamers, leveling agents, rheology regulators, pH regulators, preservatives, UV absorbers, antioxidants, matting agents, as required. , Lubricants and the like may be added.
　組成物（３）は、例えば、米国特許出願公開第２０１８／１１８９６９号明細書、又は特許第６１０３１０７号に記載の水性分散体であることができる。 The composition (3) can be, for example, the aqueous dispersion described in US Patent Application Publication No. 2018/118969 or Patent No. 6103107.
組成物（４）
　組成物（４）は、フッ素樹脂粒子と、硬化性シリコーン樹脂と、水とを含有する組成物である。 Composition (4)
The composition (4) is a composition containing fluororesin particles, a curable silicone resin, and water.
　フッ素樹脂粒子を構成するフッ素樹脂としては、ポリテトラフルオロエチレン〔ＰＴＦＥ〕及び溶融加工性のフッ素樹脂（但し、ポリテトラフルオロエチレンを除く）からなる群より選択される少なくとも１種が好ましく、ＰＴＦＥ、ＴＦＥ／ＰＡＶＥ共重合体〔ＰＦＡ〕、ＴＦＥ／ＨＦＰ共重合体〔ＦＥＰ〕、エチレン〔Ｅｔ〕／ＴＦＥ共重合体〔ＥＴＦＥ〕、Ｅｔ／ＴＦＥ／ＨＦＰ共重合体、ポリクロロトリフルオロエチレン〔ＰＣＴＦＥ〕、ＣＴＦＥ／ＴＦＥ共重合体、Ｅｔ／ＣＴＦＥ共重合体、及びポリビニルフルオライド〔ＰＶＦ〕からなる群より選択される少なくとも１種がより好ましく、汎用性が高く入手容易なＰＴＦＥ、ＰＦＡ、及びＦＥＰからなる群より選択される少なくとも１種がさらに好ましく、経済性からＰＴＦＥが特に好ましい。 As the fluororesin constituting the fluororesin particles, at least one selected from the group consisting of polytetrafluoroethylene [PTFE] and melt-processable fluororesin (excluding polytetrafluoroethylene) is preferable, and PTFE, TFE / PAVE copolymer [PFA], TFE / HFP copolymer [FEP], ethylene [Et] / TFE copolymer [ETFE], Et / TFE / HFP copolymer, polychlorotrifluoroethylene [PCTFE] , CTFE / TFE copolymer, Et / CTFE copolymer, and at least one selected from the group consisting of polyvinyl fluoride [PVF], more preferably, from the highly versatile and easily available PTFE, PFA, and FEP. At least one selected from the above group is more preferable, and PTFE is particularly preferable from the viewpoint of economy.
　ＰＡＶＥは、ＣＦ２＝ＣＦ－ＯＲｆ４１（式中、Ｒｆ４１は、Ｃ１－８パーフルオロアルキル基を表す。）で表されるＰＡＶＥであってよく、ＣＦ２＝ＣＦ－ＯＣＦ３、ＣＦ２＝ＣＦ－ＯＣＦ２ＣＦ３、及びＣＦ２＝ＣＦ－ＯＣＦ２ＣＦ２ＣＦ３からなる群より選択される少なくとも１種であることが好ましい。 The PAVE may be a PAVE represented by CF 2 = CF-ORf 41 (in the formula, Rf 41 represents a C 1-8 perfluoroalkyl group), and CF 2 = CF-OCF 3 , CF 2. It is preferably at least one selected from the group consisting of = CF-OCF 2 CF 3 and CF 2 = CF-OCF 2 CF 2 CF 3 .
　フッ素樹脂粒子は、平均粒子径が０．２～２００ｎｍであるフッ素樹脂粒子を含むことが好ましい。通常、フッ素樹脂の一次粒子は、容易に凝集して、より大きな粒子径を有する二次粒子を形成する。フッ素樹脂は、二次粒子として組成物（４）中に存在してもよいが、一次粒子として組成物（４）中に存在することが好ましい。 The fluororesin particles preferably contain fluororesin particles having an average particle diameter of 0.2 to 200 nm. Usually, the fluororesin primary particles easily aggregate to form secondary particles with a larger particle size. The fluororesin may be present in the composition (4) as secondary particles, but is preferably present in the composition (4) as primary particles.
　フッ素樹脂粒子の平均粒子径（一次平均粒子径）は、０．５ｎｍ以上が好ましく、１ｎｍ以上がより好ましく、１００ｎｍ以下が好ましく、５０ｎｍ以下がより好ましく、２０ｎｍ以下がさらに好ましく、１０ｎｍ以下がさらにより好ましく、５ｎｍ未満が特に好ましい。 The average particle size (primary average particle size) of the fluororesin particles is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, still more preferably 10 nm or less. It is preferable, and less than 5 nm is particularly preferable.
　フッ素樹脂粒子の平均粒子径は、体積平均粒子径であり、１０ｎｍ以上である場合には透過型電子顕微鏡（ＴＥＭ）により測定され、１０ｎｍ未満である場合には動的光散乱法（ＤＬＳ）により測定される。ＴＥＭにより測定する場合は、得られたフッ素樹脂水性分散液をフッ素樹脂固形分濃度が水に対して１００ｐｐｍとなるように脱イオン水で希釈し、希釈したフッ素樹脂水性分散液を観察用Ｃｕ製メッシュに付着させ、乾燥させることにより試料付着メッシュを作製する。ＴＥＭを用いて、上記試料付着メッシュにおけるフッ素樹脂粒子の粒子径を観察し、電子顕微鏡写真を撮影することにより平均粒子径を求める。ＤＬＳにより測定する場合は、上記フッ素樹脂の固形分濃度が１．０質量％になるように調整した後、ＥＬＳＺ－１０００Ｓ（大塚電子株式会社製）を使用して２５℃、積算７０回にて測定する値である。溶媒（水）の屈折率は１．３３２８、溶媒（水）の粘度は０．８８７８ｍＰａ・ｓとする。上記平均粒子径は一次粒子に分散した状態の平均粒子径であることができる。 The average particle size of the fluororesin particles is the volume average particle size, which is measured by a transmission electron microscope (TEM) when it is 10 nm or more, and by a dynamic light scattering method (DLS) when it is less than 10 nm. Be measured. When measuring by TEM, the obtained fluororesin aqueous dispersion is diluted with deionized water so that the fluororesin solid content concentration is 100 ppm with respect to water, and the diluted fluororesin aqueous dispersion is made of Cu for observation. A sample-attached mesh is prepared by adhering to the mesh and drying. Using TEM, the particle size of the fluororesin particles in the sample attachment mesh is observed, and the average particle size is obtained by taking an electron micrograph. When measuring by DLS, after adjusting the solid content concentration of the fluororesin to 1.0% by mass, use ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) at 25 ° C., and perform a total of 70 times. It is a value to be measured. The refractive index of the solvent (water) is 1.3328, and the viscosity of the solvent (water) is 0.8878 mPa · s. The average particle size can be the average particle size in a state of being dispersed in the primary particles.
　一の態様において、フッ素樹脂は、ＭＦＲが０．１～５００ｇ／１０分の範囲内であることが好ましく、１ｇ／１０分以上の範囲内であることがより好ましく、３００ｇ／１０分以下であることがより好ましい。 In one embodiment, the fluororesin preferably has an MFR in the range of 0.1 to 500 g / 10 minutes, more preferably in the range of 1 g / 10 minutes or more, and 300 g / 10 minutes or less. Is more preferable.
　ＭＦＲは、ＡＳＴＭ　Ｄ１２３８に従って、メルトインデクサー（（株）安田精機製作所製）を用いて、フッ素樹脂の種類によって定められた測定温度（例えば、ＰＦＡ又はＦＥＰの場合は３７２℃、ＥＴＦＥの場合は２９７℃、ＰＴＦＥの場合は３８０℃）、荷重（例えば、ＰＦＡ、ＦＥＰ、ＥＴＦＥ、及びＰＴＦＥの場合は５ｋｇ）において内径２ｍｍ、長さ８ｍｍのノズルから１０分間あたりに流出するポリマーの質量（ｇ／１０分）として得られる値である。 The MFR uses a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) in accordance with ASTM D1238, and the measurement temperature determined by the type of fluororesin (for example, 372 ° C for PFA or FEP, 297 for ETFE). Mass of polymer (g / 10) flowing out from a nozzle with an inner diameter of 2 mm and a length of 8 mm under a load (for example, 5 kg for PFA, FEP, ETFE, and PTFE) at ° C. and 380 ° C. for PTFE). It is a value obtained as minutes).
　一の態様において、フッ素樹脂は、融点が１５０℃以上３２４℃未満の範囲内であることが好ましい。 In one embodiment, the fluororesin preferably has a melting point in the range of 150 ° C. or higher and lower than 324 ° C.
　融点は、示差走査熱量計〔ＤＳＣ〕を用いて、３００℃以上に加熱した履歴の無い試料３ｍｇを１０℃／分の速度で昇温したときの融解熱曲線における極大値に対応する温度である。 The melting point is the temperature corresponding to the maximum value in the heat of fusion curve when 3 mg of a sample having no history of heating to 300 ° C. or higher is heated at a rate of 10 ° C./min using a differential scanning calorimeter [DSC]. ..
　ＰＦＡとしては、特に限定されないが、ＴＦＥ単位とＰＡＶＥ単位とのモル比（ＴＦＥ単位／ＰＡＶＥ単位）が７０／３０以上９９／１未満の範囲内である共重合体が好ましい。より好ましいモル比は、７０／３０～９８．９／１．１の範囲内であり、さらに好ましいモル比は、８０／２０～９８．９／１．１の範囲内である。ＰＦＡは、ＴＦＥ及びＰＡＶＥと共重合可能な単量体に由来する単量体単位が０．１～１０モル％の範囲内であり、ＴＦＥ単位及びＰＡＶＥ単位が合計で９０～９９．９モル％の範囲内である共重合体であることも好ましい。ＴＦＥ及びＰＡＶＥと共重合可能な単量体としては、ＨＦＰ、ＣＺ４１Ｚ４２＝ＣＺ４３(ＣＦ２)ｎ４Ｚ４４（式中、Ｚ４１、Ｚ４２、及びＺ４３は、同一若しくは異なって、水素原子又はフッ素原子を表し、Ｚ４４は、水素原子、フッ素原子、又は塩素原子を表し、ｎ４は２～１０の整数を表す。）で表されるビニル単量体、及びＣＦ２＝ＣＦ－ＯＣＨ２－Ｒｆ４２（式中、Ｒｆ４２はＣ１－５パーフルオロアルキル基を表す。）で表されるアルキルパーフルオロビニルエーテル誘導体等が挙げられる。 The PFA is not particularly limited, but a copolymer in which the molar ratio of the TFE unit to the PAVE unit (TFE unit / PAVE unit) is in the range of 70/30 or more and less than 99/1 is preferable. A more preferred molar ratio is in the range of 70/30 to 98.9 / 1.1, and a more preferred molar ratio is in the range of 80/20 to 98.9 / 1.1. In PFA, the monomer unit derived from the monomer copolymerizable with TFE and PAVE is in the range of 0.1 to 10 mol%, and the total amount of TFE unit and PAVE unit is 90 to 99.9 mol%. It is also preferable that the copolymer is within the range of. Examples of the monomer copolymerizable with TFE and PAVE include HFP, CZ 41 Z 42 = CZ 43 (CF 2 ) n4 Z 44 (in the formula, Z 41 , Z 42 , and Z 43 are the same or different. Represents a hydrogen atom or a fluorine atom, Z 44 represents a hydrogen atom, a fluorine atom, or a chlorine atom, n4 represents an integer of 2 to 10), and CF 2 = CF-. Examples thereof include an alkyl perfluorovinyl ether derivative represented by OCH 2- Rf 42 (in the formula, Rf 42 represents a C 1-5 perfluoroalkyl group).
　ＰＦＡは、融点がＰＴＦＥの融点よりも低く、１８０～３２４℃未満の範囲内であることが好ましく、２３０～３２０℃の範囲内であることがより好ましく、２８０～３２０℃の範囲内であることがさらに好ましい。 The melting point of PFA is lower than the melting point of PTFE, preferably in the range of 180 to less than 324 ° C, more preferably in the range of 230 to 320 ° C, and in the range of 280 to 320 ° C. Is even more preferable.
　ＰＦＡは、メルトフローレート（ＭＦＲ）が１～５００ｇ／１０分の範囲内であることが好ましい。 For PFA, the melt flow rate (MFR) is preferably in the range of 1 to 500 g / 10 minutes.
　ＦＥＰとしては、特に限定されないが、ＴＦＥ単位とＨＦＰ単位とのモル比（ＴＦＥ単位／ＨＦＰ単位）が７０／３０以上９９／１未満の範囲内である共重合体が好ましい。より好ましいモル比は、７０／３０～９８．９／１．１の範囲内であり、さらに好ましいモル比は、８０／２０～９８．９／１．１の範囲内である。ＦＥＰは、ＴＦＥ及びＨＦＰと共重合可能な単量体に由来する単量体単位が０．１～１０モル％の範囲内であり、ＴＦＥ単位及びＨＦＰ単位が合計で９０～９９．９モル％の範囲内である共重合体であることも好ましい。ＴＦＥ及びＨＦＰと共重合可能な単量体としては、ＰＡＶＥ、アルキルパーフルオロビニルエーテル誘導体等が挙げられる。 The FEP is not particularly limited, but a copolymer in which the molar ratio of TFE units to HFP units (TFE units / HFP units) is in the range of 70/30 or more and less than 99/1 is preferable. A more preferred molar ratio is in the range of 70/30 to 98.9 / 1.1, and a more preferred molar ratio is in the range of 80/20 to 98.9 / 1.1. In FEP, the monomer unit derived from the monomer copolymerizable with TFE and HFP is in the range of 0.1 to 10 mol%, and the total amount of TFE unit and HFP unit is 90 to 99.9 mol%. It is also preferable that the copolymer is within the range of. Examples of the monomer copolymerizable with TFE and HFP include PAVE and an alkyl perfluorovinyl ether derivative.
　ＦＥＰは、融点がＰＴＦＥの融点よりも低く、１５０～３２４℃未満の範囲内であることが好ましく、２００～３２０℃の範囲内であることがより好ましく、２４０～３２０℃の範囲内であることがさらに好ましい。 The melting point of FEP is lower than the melting point of PTFE, preferably in the range of 150 to less than 324 ° C, more preferably in the range of 200 to 320 ° C, and in the range of 240 to 320 ° C. Is even more preferable.
　ＦＥＰは、ＭＦＲが１～５００ｇ／１０分の範囲内であることが好ましい。 The FEP preferably has an MFR in the range of 1 to 500 g / 10 minutes.
　ＰＴＦＥとしては、ホモＰＴＦＥであっても、変性ＰＴＦＥであってもよい。変性ＰＴＦＥは、ＴＦＥ単位とＴＦＥと共重合可能な変性モノマーに基づく変性モノマー単位とを含む。また、上記ＰＴＦＥは、非溶融加工性及びフィブリル化性を有する高分子量ＰＴＦＥであってもよいし、溶融加工性を有し、フィブリル化性を有しない低分子量ＰＴＦＥであってもよい。上記非溶融加工性とは、ＡＳＴＭ　Ｄ－１２３８及びＤ－２１１６に準拠して、結晶化融点より高い温度でメルトフローレートを測定できない性質を意味する。 The PTFE may be homo-PTFE or denatured PTFE. The modified PTFE contains a TFE unit and a modified monomer unit based on a modified monomer copolymerizable with TFE. Further, the above-mentioned PTFE may be a high molecular weight PTFE having non-melt processability and fibrillation property, or a low molecular weight PTFE having melt processability and not having fibrillation property. The non-melt processability means a property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.
　変性モノマーとしては、ＴＦＥとの共重合が可能なものであれば特に限定されず、例えば、ＨＦＰ等のパーフルオロオレフィン；ＣＴＦＥ等のクロロフルオロオレフィン；トリフルオロエチレン、ＶｄＦ等の水素含有フルオロオレフィン；パーフルオロビニルエーテル；パーフルオロアルキルエチレン；エチレン；ニトリル基を有するフッ素含有ビニルエーテル等が挙げられる。また、用いる変性モノマーは１種であってもよいし、複数種であってもよい。 The modified monomer is not particularly limited as long as it can be copolymerized with TFE, and is, for example, a perfluoroolefin such as HFP; a chlorofluoroolefin such as CTFE; a hydrogen-containing fluoroolefin such as trifluoroethylene or VdF; Perfluorovinyl ether; perfluoroalkylethylene; ethylene; fluorine-containing vinyl ether having a nitrile group and the like can be mentioned. Further, the modified monomer used may be one kind or a plurality of kinds.
　パーフルオロビニルエーテルとしては特に限定されず、例えば、ＣＦ２＝ＣＦ－ＯＲｆ４３（式中、Ｒｆ４３は、パーフルオロ有機基を表す。）で表されるパーフルオロ不飽和化合物等が挙げられる。上記「パーフルオロ有機基」とは、炭素原子に結合する水素原子が全てフッ素原子に置換されてなる有機基を意味する。上記パーフルオロ有機基は、エーテル酸素を有していてもよい。 The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorounsaturated compounds represented by CF 2 = CF-ORf 43 (in the formula, Rf 43 represents a perfluoroorganic group). The above-mentioned "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoroorganic group may have ether oxygen.
　パーフルオロビニルエーテルとしては、例えば、上記式において、Ｒｆ４３がＣ１－１０パーフルオロアルキル基（好ましくはＣ１－５パーフルオロアルキル基）を表すものであるＰＡＶＥが挙げられる。 Examples of the perfluorovinyl ether include PAVE in which Rf 43 represents a C 1-10 perfluoroalkyl group (preferably a C 1-5 perfluoroalkyl group) in the above formula.
　ＰＡＶＥにおけるパーフルオロアルキル基としては、例えば、パーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロペンチル基、パーフルオロヘキシル基等が挙げられる。パーフルオロアルキル基がパーフルオロメチル基であるパープルオロメチルビニルエーテル〔ＰＭＶＥ〕、パーフルオロアルキル基がパーフルオロプロピル基であるパープルオロプロピルビニルエーテル〔ＰＰＶＥ〕が好ましい。
　パーフルオロビニルエーテルとしては、さらに、上記式において、Ｒｆ４３がＣ４－９パーフルオロ（アルコキシアルキル）基であるもの、Ｒｆ４３が下記式：
Figure JPOXMLDOC01-appb-C000036
 （式中、ｍ４は、０又は１～４の整数を表す。）
で表される基であるもの、Ｒｆ４３が下記式：
Figure JPOXMLDOC01-appb-C000037
 （式中、ｎ４１は、１～４の整数を表す。）
で表される基であるもの等が挙げられる。
　パーフルオロアルキルエチレンとしては特に限定されず、例えば、パーフルオロブチルエチレン（ＰＦＢＥ）、パーフルオロヘキシルエチレン（ＰＦＨＥ）、パーフルオロオクチルエチレン（ＰＦＯＥ）等が挙げられる。 Examples of the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group and the like. Purple olomethyl vinyl ether [PMVE] in which the perfluoroalkyl group is a perfluoromethyl group and purple olopropyl vinyl ether [PPVE] in which the perfluoroalkyl group is a perfluoropropyl group are preferable.
Further, as the perfluorovinyl ether, in the above formula, Rf 43 is a C 4-9 perfluoro (alkoxyalkyl) group, and Rf 43 is the following formula:
Figure JPOXMLDOC01-appb-C000036
 (In the formula, m4 represents 0 or an integer of 1 to 4).
Rf 43 , which is a group represented by, is expressed by the following formula:
Figure JPOXMLDOC01-appb-C000037
 (In the formula, n41 represents an integer of 1 to 4.)
Examples include those that are the basis represented by.
The perfluoroalkylethylene is not particularly limited, and examples thereof include perfluorobutylethylene (PFBE), perfluorohexylethylene (PFHE), and perfluorooctylethylene (PFOE).
　ニトリル基を有するフッ素含有ビニルエーテルとしては、ＣＦ２＝ＣＦＯＲｆ４４ＣＮ（式中、Ｒｆ４４は２つの炭素原子間に酸素原子が挿入されていてもよいＣ２－７アルキレン基を表す。）で表されるフッ素含有ビニルエーテルがより好ましい。ニトリル基を有するフッ素含有ビニルエーテルとしては、例えば、パーフルオロ［３－（１－メチル－２－ビニルオキシ－エトキシ）プロピオニトリル］（ＣＮＶＥ）等が挙げられる。 As the fluorine-containing vinyl ether having a nitrile group, CF 2 = CFORf 44 CN (in the formula, Rf 44 represents a C 2-7 alkylene group in which an oxygen atom may be inserted between two carbon atoms). The fluorine-containing vinyl ether to be used is more preferable. Examples of the fluorine-containing vinyl ether having a nitrile group include perfluoro [3- (1-methyl-2-vinyloxy-ethoxy) propionitrile] (CNVE).
　変性ＰＴＦＥにおける変性モノマーとしては、ＨＦＰ、ＣＴＦＥ、ＶＤＦ、ＰＭＶＥ、ＰＰＶＥ、ＰＦＢＥ、ＰＦＨＥ、ＣＮＶＥ、及びエチレンからなる群より選択される少なくとも１種であることが好ましい。より好ましくは、ＰＭＶＥ、ＰＰＶＥ、ＰＦＨＥ、ＣＮＶＥ、ＨＦＰ、及びＣＴＦＥからなる群より選択される少なくとも１種の単量体である。 The modified monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PMVE, PPVE, PFBE, PFHE, CNVE, and ethylene. More preferably, it is at least one monomer selected from the group consisting of PMVE, PPVE, PFHE, CNVE, HFP, and CTFE.
　変性ＰＴＦＥは、変性モノマー単位が０．００１～２モル％の範囲内であることが好ましく、０．００１～１モル％の範囲内であることがより好ましく、０．００１～０．５モル％の範囲内であることがさらに好ましく、０．００１～０．０３モル％の範囲内であることが特に好ましい。 The modified PTFE has a modified monomer unit in the range of 0.001 to 2 mol%, more preferably in the range of 0.001 to 1 mol%, and 0.001 to 0.5 mol%. It is more preferably in the range of 0.001 to 0.03 mol%, and particularly preferably in the range of 0.001 to 0.03 mol%.
　ＰＴＦＥを構成する各単量体の含有量は、ＮＭＲ、ＦＴ－ＩＲ、元素分析、蛍光Ｘ線分析を単量体の種類によって適宜組み合わせることで算出できる。 The content of each monomer constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.
　ＰＴＦＥは、メルトフローレート（ＭＦＲ）が０～５００ｇ／１０分の範囲内であることが好ましい。ＰＴＦＥのＭＦＲは、４００ｇ／１０分未満であることがより好ましく、３００ｇ／１０分以下であることがさらに好ましい。 For PTFE, the melt flow rate (MFR) is preferably in the range of 0 to 500 g / 10 minutes. The MFR of PTFE is more preferably less than 400 g / 10 minutes, and even more preferably 300 g / 10 minutes or less.
　ＰＴＦＥは、融点が３２４～３６０℃の範囲内であることが好ましい。上記融点は、３５０℃以下であることが好ましく、３４８℃以下であることがより好ましい。 The melting point of PTFE is preferably in the range of 324 to 360 ° C. The melting point is preferably 350 ° C. or lower, and more preferably 348 ° C. or lower.
　硬化性シリコーン樹脂は、室温下（例えば、１０～３０℃の範囲内）又は加熱により架橋剤の存在下又は不在下に架橋するシリコーン樹脂である。架橋剤の不在下で架橋するシリコーン樹脂である場合、硬化性シリコーン樹脂は後述する主剤（ベースポリマー）のみからなり、架橋剤の存在下で架橋するシリコーン樹脂である場合は、硬化性シリコーン樹脂は主剤（ベースポリマー）と架橋剤との組み合わせからなる。例えば、室温硬化性シリコーン樹脂は、室温硬化反応性基を有するオルガノポリシロキサンとこのオルガノポリシロキサンを架橋する架橋剤との組み合わせからなる。 The curable silicone resin is a silicone resin that is crosslinked at room temperature (for example, within the range of 10 to 30 ° C.) or in the presence or absence of a cross-linking agent by heating. In the case of a silicone resin that crosslinks in the absence of a cross-linking agent, the curable silicone resin consists only of the main agent (base polymer) described later, and in the case of a silicone resin that cross-links in the presence of a cross-linking agent, the curable silicone resin is It consists of a combination of a main agent (base polymer) and a cross-linking agent. For example, a room temperature curable silicone resin consists of a combination of an organopolysiloxane having a room temperature curable reactive group and a cross-linking agent that crosslinks the organopolysiloxane.
　硬化性シリコーン樹脂の主剤（ベースポリマー）は、１分子中に少なくとも２個の、ケイ素原子に結合した硬化反応性基を有するオルガノポリシロキサンである。このオルガノポリシロキサンが室温硬化性である場合の硬化反応性基としては、水酸基、加水分解性基が挙げられる。加水分解性基としては、例えば、メトキシ基、エトキシ基、プロポキシ基等のＣ１－８アルコキシ基；メトキシエトキシ基、エトキシエトキシ基、メトキシプロポキシ基等のアルコキシアルコキシ基；アセトキシ基、オクタノイルオキシ基、ベンゾイルオキシ基等のアシロキシ基；ビニロキシ基、イソプロペニルオキシ基、１－エチル－２－メチルビニルオキシ基等のアルケニルオキシ基；ジメチルケトオキシム基、メチルエチルケトオキシム基、ジエチルケトオキシム基等のケトオキシム基；ジメチルアミノ基、ジエチルアミノ基、ブチルアミノ基、シクロヘキシルアミノ基等のアミノ基；ジメチルアミノキシ基、ジエチルアミノキシ基等のアミノキシ基；Ｎ－メチルアセトアミド基、Ｎ－エチルアセトアミド基、Ｎ－メチルベンズアミド基等のアミド基等が挙げられ、アルコキシ基が好ましい。 The main agent (base polymer) of the curable silicone resin is an organopolysiloxane having at least two curable reactive groups bonded to silicon atoms in one molecule. Examples of the curing reactive group when this organopolysiloxane is room temperature curable include a hydroxyl group and a hydrolyzable group. Examples of the hydrolyzable group include C 1-8 alkoxy groups such as methoxy group, ethoxy group and propoxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group and methoxypropoxy group; acetoxy group and octanoyloxy group. , Asyloxy group such as benzoyloxy group; Alkoxyoxy group such as vinyloxy group, isopropenyloxy group, 1-ethyl-2-methylvinyloxy group; Ketooxime group such as dimethylketooxime group, methylethylketooxime group, diethylketooxime group Amino groups such as dimethylamino group, diethylamino group, butylamino group, cyclohexylamino group; aminoxi group such as dimethylaminoxy group and diethylaminoxi group; N-methylacetamide group, N-ethylacetamide group, N-methylbenzamide group Such as an amide group and the like, and an alkoxy group is preferable.
　硬化反応性基以外の基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、オクタデシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基；フェニル基、トリル基、キシリル基、α－，β－ナフチル基等のアリール基；ベンジル基、２－フェニルエチル基、３－フェニルプロピル基等のアラルキル基；また、これらの基の水素原子の一部又は全部が、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子やシアノ基等で置換された基、例えば、３－クロロプロピル基、３，３，３－トリフルオロプロピル基、２－シアノエチル基等を例示することができる。これらの中で、メチル基、エチル基、ビニル基、フェニル基が好ましく、メチル基が特に好ましい。 Groups other than the curing reactive group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and octadecyl group; cyclopentyl group, Cycloalkyl group such as cyclohexyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aryl group such as phenyl group, tolyl group, xsilyl group, α-, β-naphthyl group; benzyl group , 2-Phenylethyl group, 3-phenylpropyl group and other aralkyl groups; and some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl and Br and cyano groups. For example, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group and the like can be exemplified. Among these, a methyl group, an ethyl group, a vinyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
　オルガノポリシロキサンは、２３℃における粘度が２０～１，０００，０００ｍＰａ・ｓ、好ましくは１００～５００，０００ｍＰａ・ｓ、より好ましくは１，０００～５０，０００ｍＰａ・ｓの範囲内であるような重合度のものを用いることが好ましい。上記粘度が２０ｍＰａ・ｓ（２３℃）以上であると、物理的・機械的強度に優れたコーティング塗膜を得ることができ、１，０００，０００ｍＰａ・ｓ（２３℃）以下であると、使用時における作業性が優れる。なお、粘度は回転粘度計により測定できる。 The organopolysiloxane is polymerized so that the viscosity at 23 ° C. is in the range of 20 to 1,000,000 mPa · s, preferably 100 to 500,000 mPa · s, and more preferably 1,000 to 50,000 mPa · s. It is preferable to use a degree of polymerization. When the viscosity is 20 mPa · s (23 ° C.) or more, a coating film having excellent physical and mechanical strength can be obtained, and when the viscosity is 1,000,000 mPa · s (23 ° C.) or less, it is used. Excellent workability at times. The viscosity can be measured with a rotational viscometer.
　オルガノポリシロキサンとしては、下記式のような両末端にシラノール基、又は加水分解性基を有するシリル基を有するジメチルポリシロキサン等のジオルガノポリシロキサンが好ましい。
Figure JPOXMLDOC01-appb-C000038
 ［式中、
　Ｒ４１１及びＲ４１３は、それぞれ独立して、硬化反応性基以外の基として例示したものが挙げられ、
　Ｒ４１２はメチル基、エチル基、プロピル基等のアルキル基であり、
　ｎ４２及びｍ４２は粘度が２０～１，０００，０００ｍＰａ・ｓ（２３℃）となる数であり、
　ａ４は０又は１である。］ As the organopolysiloxane, diorganopolysiloxane such as dimethylpolysiloxane having a silanol group or a silyl group having a hydrolyzable group at both ends as shown in the following formula is preferable.
Figure JPOXMLDOC01-appb-C000038
 [During the ceremony,
Examples of R 411 and R 413 are independently exemplified as groups other than the curing reactive group.
R412 is an alkyl group such as a methyl group, an ethyl group, and a propyl group.
n42 and m42 are numbers having a viscosity of 20 to 1,000,000 mPa · s (23 ° C.).
a4 is 0 or 1. ]
　両末端にシラノール基又は加水分解性基を有するシリル基を有する室温硬化性のオルガノポリシロキサンを用いる場合、架橋剤として、加水分解性基を有するシラン及び／又はその部分加水分解縮合物を用いることが好ましい。シラン及び／又はその部分加水分解縮合物は、その分子中に加水分解可能な基を少なくとも２個有するものであり、好適には加水分解可能な基を３個以上有することが好ましく、また、ケイ素原子には加水分解可能な基以外の基が結合していてもよく、さらに、その分子構造はシラン又はシロキサン構造のいずれであってもよい。特に、シロキサン構造のものにあっては直鎖状、分岐鎖状、又は環状のいずれであってもよい。 When a room temperature curable organopolysiloxane having a silanol group or a silyl group having a hydrolyzable group at both ends is used, a silane having a hydrolyzable group and / or a partially hydrolyzed condensate thereof should be used as a cross-linking agent. Is preferable. The silane and / or its partially hydrolyzable condensate has at least two hydrolyzable groups in its molecule, preferably has three or more hydrolyzable groups, and silicon. A group other than a hydrolyzable group may be bonded to the atom, and the molecular structure thereof may be either a silane or a siloxane structure. In particular, in the case of a siloxane structure, it may be linear, branched or cyclic.
　加水分解可能な基としては、上記加水分解性基として例示したものが挙げられ、特にアルコキシ基、ケトキシム基、イソプロペノキシ基が好ましい。 Examples of the hydrolyzable group include those exemplified as the above-mentioned hydrolyzable group, and an alkoxy group, a ketoxim group, and an isopropenoxy group are particularly preferable.
　加水分解可能な基以外の基は、非置換又は置換の１価炭化水素基（例えば、炭素原子数１～６の１価炭化水素基）が用いられ、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基等のアリール基；ベンジル基、２－フェニルエチル基等のアラルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基；３，３，３－トリフルオロプロピル基、３－クロロプロピル基等のハロゲン化アルキル基等が挙げられる。これらの中でも、メチル基、エチル基、フェニル基、ビニル基が好ましい。 As the group other than the hydrolyzable group, an unsubstituted or substituted monovalent hydrocarbon group (for example, a monovalent hydrocarbon group having 1 to 6 carbon atoms) is used, and for example, a methyl group, an ethyl group, or a propyl group. , Butyl group, pentyl group, hexyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group, tolyl group and other aryl groups; benzyl group, 2-phenylethyl group and other aralkyl groups; vinyl group , Alkenyl groups such as allyl group, butenyl group, pentenyl group and hexenyl group; alkyl halide groups such as 3,3,3-trifluoropropyl group and 3-chloropropyl group can be mentioned. Among these, a methyl group, an ethyl group, a phenyl group and a vinyl group are preferable.
　架橋剤の具体例としては、例えば、エチルシリケート、プロピルシリケート、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メチルトリス（メトキシエトキシ）シラン、ビニルトリス（メトキシエトキシ）シラン、メチルトリプロペノキシシラン、メチルトリアセトキシシラン、ビニルトリアセトキシシラン、メチルトリ（メチルエチルケトキシム）シラン、ビニルトリ（メチルエチルケトキシム）シラン、フェニルトリ（メチルエチルケトキシム）シラン、プロピルトリ（メチルエチルケトキシム）シラン、テトラ（メチルエチルケトキシム）シラン、３，３，３－トリフルオロプロピルトリ（メチルエチルケトキシム）シラン、３－クロロプロピルトリ（メチルエチルケトキシム）シラン、メチルトリ（ジメチルケトキシム）シラン、メチルトリ（ジエチルケトキシム）シラン、メチルトリ（メチルイソプロピルケトキシム）シラン、トリ（シクロへキサノキシム）シラン等及びこれらの部分加水分解縮合物が挙げられる。これらは１種単独でも２種以上を組み合わせても使用することができる。 Specific examples of the cross-linking agent include, for example, ethyl silicate, propyl silicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltris (methoxyethoxy) silane, vinyltris (methoxyethoxy) silane, and the like. Methyltripropenoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, methyltri (methylethylketoxim) silane, vinyltri (methylethylketoxim) silane, phenyltri (methylethylketoxim) silane, propyltri (methylethylketoxim) silane, tetra (methylethylketoxim) ) Silane, 3,3,3-trifluoropropyltri (methylethylketoxim) silane, 3-chloropropyltri (methylethylketoxim) silane, methyltri (dimethylketoxim) silane, methyltri (diethylketoxim) silane, methyltri (methylisopropyl) Examples thereof include ketoxim) silane, tri (cyclohexanoxime) silane, and partial hydrolysis condensates thereof. These can be used alone or in combination of two or more.
　架橋剤の配合量は、オルガノポリシロキサン１００質量部に対して０．５～２０質量部の範囲内であることが好ましく、より好ましくは１～１０質量部の範囲内である。上記配合量が０．５質量部以上であると十分な架橋が得られ、また、２０質量部以下であると適切な硬度の硬化物が得られ、経済的にも有利である。 The blending amount of the cross-linking agent is preferably in the range of 0.5 to 20 parts by mass, and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the organopolysiloxane. When the blending amount is 0.5 parts by mass or more, sufficient cross-linking can be obtained, and when it is 20 parts by mass or less, a cured product having appropriate hardness can be obtained, which is economically advantageous.
　主剤が室温硬化性オルガノポリシロキサンである場合、硬化をより促進させるための触媒を配合してもよい。このような硬化用触媒としては、縮合硬化型の室温硬化性組成物に使用されている種々のものを使用することができ、具体例として、鉛－２－エチルオクトエート、ジブチルすずジオクトエート、ジブチルすずアセテート、ジブチルすずジラウレート、ブチルすず－２－エチルヘキソエート、鉄－２－エチルヘキソエート、コバルト－２－エチルヘキソエート、マンガン－２－エチルヘキソエート、亜鉛－２－エチルヘキソエート、カプリル酸第１すず、ナフテン酸すず、オレイン酸すず、ブタン酸すず、ナフテン酸チタン、ナフテン酸亜鉛、ナフテン酸コバルト、ステアリン酸亜鉛等の有機カルボン酸の金属塩；テトラブチルチタネート、テトラ－２－エチルヘキシルチタネート、トリエタノールアミンチタネート、テトラ（イソプロペニルオキシ）チタネート等の有機チタン酸エステル；オルガノシロキシチタン、β－カルボニルチタン、ジイソプロポキシチタンビス（エチルアセトアセテート）、チタンテトラ（アセチルアセトナート）等の有機チタン化合物、有機チタンキレート；アルコキシアルミニウム化合物、３－アミノプロピルトリエトキシシラン、Ｎ－（トリメトキシシリルプロピル）エチレンジアミン等のアミノアルキル基置換アルコキシシラン；ヘキシルアミン、リン酸ドデシルアミン等のアミン化合物及びその塩；酢酸カリウム、酢酸ナトリウム、臭酸リチウム等のアルカリ金属の低級脂肪酸塩；ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のジアルキルヒドロキシルアミン；下記式：
Figure JPOXMLDOC01-appb-C000039
 で表されるグアニジル基含有シラン及びシロキサン等を挙げることができる。これらは単独でも２種以上を組み合わせても使用することができる。 When the main agent is a room temperature curable organopolysiloxane, a catalyst for further promoting curing may be added. As such a curing catalyst, various catalysts used in the condensation curing type room temperature curable composition can be used, and specific examples thereof include lead-2-ethyloctate, dibutyltin dioctate, and dibutyl. Tin acetate, dibutyl tin dilaurate, butyl tin-2-ethylhexoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhe Metal salts of organic carboxylic acids such as xoate, primary tin caprylate, tin naphthenate, tin oleate, tin butanoate, titanium naphthenate, zinc naphthenate, cobalt naphthenate, zinc stearate; tetrabutyl titanate, tetra Organic titanates such as -2-ethylhexyl titanate, triethanolamine titanate, tetra (isopropenyloxy) titanate; organosiloxytitanium, β-carbonyl titanium, diisopropoxytitanium bis (ethylacetoacetate), titanium tetra (acetylacetonate) ) Etc., organic titanium chelate; alkoxyaluminum compound, 3-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine and other aminoalkyl group-substituted alkoxysilanes; hexylamine, dodecylamine phosphate and the like. Amine compounds and salts thereof; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate and lithium bromide; dialkyl hydroxylamines such as dimethyl hydroxylamine and diethyl hydroxylamine;
Figure JPOXMLDOC01-appb-C000039
 Examples thereof include guanidine group-containing silane and siloxane represented by. These can be used alone or in combination of two or more.
　硬化用触媒を用いる場合、その使用量は特に制限されず、触媒としての有効量であってもよいが、通常、オルガノポリシロキサン１００質量部に対して０．０１～２０質量部の範囲内であることが好ましく、特に０．１～１０質量部の範囲内であることが好ましい。触媒を用いる場合、触媒の含有量を増大すると、架橋剤の種類によらず得られる組成物の十分な硬化性が得られ、一方、触媒の含有量を低減すると、得られる組成物の貯蔵安定性が向上する。 When a curing catalyst is used, the amount used is not particularly limited and may be an effective amount as a catalyst, but it is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of organopolysiloxane. It is preferably in the range of 0.1 to 10 parts by mass. When a catalyst is used, increasing the content of the catalyst gives sufficient curability of the obtained composition regardless of the type of cross-linking agent, while decreasing the content of the catalyst provides stable storage of the obtained composition. Improves sex.
　硬化性シリコーン樹脂の具体例としては、信越化学工業株式会社製の、Ｐｏｌｏｎ　ＭＦ－５６、Ｐｏｌｏｎ　ＭＦ－４０、Ｐｏｌｏｎ　ＭＦ－２３、Ｐｏｌｏｎ　ＭＦ－２０、Ｐｏｌｏｎ　ＭＦ－２０６、Ｐｏｌｏｎ　ＭＷＳ、ＫＭ－２００２Ｌ－１、ＫＭ－２００２Ｔ、Ｘ－５１－１３１８、Ｘ－５２－１６３１、ＫＭ－９７４９等が挙げられ、東レ・ダウコーニング株式会社製の、ＩＥ７１７０等が挙げられるが、これらに限定されるものではない。 Specific examples of the curable silicone resin include Polon MF-56, Polon MF-40, Polon MF-23, Polon MF-20, Polon MF-206, Polon MWS, and KM-2002L- manufactured by Shin-Etsu Chemical Co., Ltd. 1, KM-2002T, X-51-1318, X-52-1631, KM-9794, etc., and IE7170, etc. manufactured by Toray Dow Corning Co., Ltd., but are not limited thereto. ..
　硬化性シリコーン樹脂は、１種のみであってもよいし、２種以上の組合せであってもよい。 The curable silicone resin may be only one type or a combination of two or more types.
　硬化性シリコーン樹脂の配合量（有効成分量）は、フッ素樹脂粒子に対し０．１～２５０質量％であり、１質量％以上が好ましく、１０質量％以上がより好ましく、また、１５０質量％以下が好ましく、１００質量％以下がより好ましい。 The blending amount (active component amount) of the curable silicone resin is 0.1 to 250% by mass, preferably 1% by mass or more, more preferably 10% by mass or more, and 150% by mass or less with respect to the fluororesin particles. Is preferable, and 100% by mass or less is more preferable.
　組成物（４）は、さらにシリコーンオイルを含んでもよい。シリコーンオイルは、シロキサン結合が鎖状に延びたものである。硬化性シリコーン樹脂は、架橋反応（硬化反応）によりシロキサン結合からなる３次元的な架橋構造を形成することが可能であるのに対し、シリコーンオイルは、上記架橋構造を形成することができないものであることが好ましい。 The composition (4) may further contain silicone oil. Silicone oil is a chain of siloxane bonds. The curable silicone resin can form a three-dimensional crosslinked structure composed of siloxane bonds by a crosslinking reaction (curing reaction), whereas the silicone oil cannot form the above crosslinked structure. It is preferable to have.
　シリコーンオイルは、以下の式：
Ｒ４２１Ｒ４２２Ｒ４２３ＳｉＯ－[Ｒ４２４Ｒ４２５ＳｉＯ]ｐ４[Ｒ４２６Ｒ４２７ＳｉＯ]ｑ４－ＳｉＲ４２８Ｒ４２９Ｒ４３０
（式中、Ｒ４２１～Ｒ４３０はそれぞれ独立にアルキル基、アリール基、又はその他の有機基を示す。ｐ４及びｑ４は粘度が後述の範囲内となる整数を示す。）
で示される直鎖シロキサン構造を有する化合物、上記直鎖シロキサン構造を有する化合物における置換基Ｒ４２１～Ｒ４３０が他の置換基で置換された化合物等が挙げられる。置換基Ｒ４２１～Ｒ４３０におけるアルキル基としては通常、Ｃ１－１２アルキル基であり、より具体的にはメチル基、エチル基等が挙げられる。アリール基としてはフェニル基等が挙げられる。 Silicone oil has the following formula:
R 421 R 422 R 423 SiO- [R 424 R 425 SiO] p4 [R 426 R 427 SiO] q4-SiR 428 R 429 R 430
(In the formula, R 421 to R 430 independently represent an alkyl group, an aryl group, or another organic group. P4 and q4 represent integers whose viscosities are within the range described below.)
Examples thereof include a compound having a linear siloxane structure represented by (1), a compound in which substituents R 421 to R 430 in the compound having a linear siloxane structure are substituted with another substituent, and the like. The alkyl group in the substituents R 421 to R 430 is usually a C 1-12 alkyl group, and more specific examples thereof include a methyl group and an ethyl group. Examples of the aryl group include a phenyl group and the like.
　シリコーンオイルの具体例としては、ジメチルシリコーンオイル、フェニルメチルシリコーンオイル、アルキル・アラルキル変性シリコーンオイル、フルオロシリコーンオイル、ポリエーテル変性シリコーンオイル、脂肪酸エステル変性シリコーンオイル、メチル水素シリコーンオイル、シラノール基含有シリコーンオイル、アルコキシ基含有シリコーンオイル、フェノール基含有シリコーンオイル、メタクリル変性シリコーンオイル、アミノ変性シリコーンオイル、カルボキシ変性シリコーンオイル、カルビノール変性シリコーンオイル、エポキシ変性シリコーンオイル、メルカプト変性シリコーンオイル、フッ素変性シリコーンオイル、ポリエーテル変性シリコーンオイル等が挙げられる。これらシリコーンオイルは１種のみを用いてもよいし、また２種以上を併用して用いてもよい。シリコーンオイルの粘度は、通常２５℃で１～２００，０００ｍＰａ・ｓの範囲内である。 Specific examples of silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, alkyl-aralkyl-modified silicone oil, fluorosilicone oil, polyether-modified silicone oil, fatty acid ester-modified silicone oil, methyl hydrogen silicone oil, and silanol group-containing silicone oil. , Alkoxy group-containing silicone oil, phenol group-containing silicone oil, methacryl-modified silicone oil, amino-modified silicone oil, carboxy-modified silicone oil, carbinol-modified silicone oil, epoxy-modified silicone oil, mercapto-modified silicone oil, fluorine-modified silicone oil, poly Examples include ether-modified silicone oil. Only one kind of these silicone oils may be used, or two or more kinds may be used in combination. The viscosity of the silicone oil is usually in the range of 1 to 200,000 mPa · s at 25 ° C.
　シリコーンオイルの中で、変性により水分散性を付与されたものは、そのまま使用できるが、通常のシリコーンオイルを使用するときには乳化剤等によりエマルション化したものを使用するのが望ましい。 Among silicone oils, those that have been given water dispersibility by denaturation can be used as they are, but when using ordinary silicone oil, it is desirable to use one that has been emulsified with an emulsifier or the like.
　シリコーンオイルエマルションの具体例としては、信越化学工業株式会社製の、Ｐｏｌｏｎ　ＭＦ－１４、Ｐｏｌｏｎ　ＭＦ－１４Ｅ、Ｐｏｌｏｎ　ＭＦ－１８Ｔ、Ｐｏｌｏｎ　ＭＦ－５１、Ｐｏｌｏｎ　ＭＦ－５２、Ｐｏｌｏｎ　ＭＦ－１４０、Ｘ－５１－１１７８、Ｘ－５１－１２６４等が挙げられ、東レ・ダウコーニング株式会社製の、ＦＺ－４６５８、ＦＺ－４６３４ＥＸ、ＳＭ８７０９ＳＲ、ＳＭ８７１６ＳＲ、ＦＺ－４６０２、ＢＹ２２－８１８ＥＸ等が挙げられるが、これらに限定されるものではない。 Specific examples of the silicone oil emulsion include Polon MF-14, Polon MF-14E, Polon MF-18T, Polon MF-51, Polon MF-52, Polon MF-140, and X-51 manufactured by Shin-Etsu Chemical Co., Ltd. -1178, X-51-1264, etc., and FZ-4658, FZ-4634EX, SM8709SR, SM8716SR, FZ-4602, BY22-818EX, etc. manufactured by Toray Dow Corning Co., Ltd. are mentioned, but are limited thereto. It is not something that is done.
　シリコーンオイルの含有量は、硬化性シリコーン樹脂に対し０．１～１００質量％の範囲内であることが好ましく、１～５０質量％の範囲内であることがより好ましい。 The content of the silicone oil is preferably in the range of 0.1 to 100% by mass, more preferably in the range of 1 to 50% by mass with respect to the curable silicone resin.
　組成物（４）は、水を含むことにより、組成物（４）中にフッ素樹脂が一次粒子として存在でき、また組成物（４）の塗布を容易にすることができる。 By containing water in the composition (4), the fluororesin can be present as primary particles in the composition (4), and the coating of the composition (4) can be facilitated.
　組成物（４）は、フッ素樹脂粒子を組成物（４）に対して０．１～５０質量％の範囲内で含むことが好ましく、０．５質量％以上含むことがより好ましく、１質量％以上含むことがさらに好ましく、２０質量％以下含むことがより好ましく、１０質量％以下含むことがさらに好ましい。 The composition (4) preferably contains fluororesin particles in the range of 0.1 to 50% by mass, more preferably 0.5% by mass or more, and 1% by mass with respect to the composition (4). More preferably, it contains more than 20% by mass, more preferably 10% by mass or less.
　フッ素樹脂粒子の濃度は、組成物（４）１ｇを、送風乾燥機中で３００℃、６０分の条件で乾燥し、組成物（４）の質量（１ｇ）に対する、加熱残分の質量の割合を百分率で表したもの（固形分濃度）である。 The concentration of the fluororesin particles is such that 1 g of the composition (4) is dried in a blower dryer at 300 ° C. for 60 minutes, and the ratio of the mass of the heat residue to the mass (1 g) of the composition (4). Is expressed as a percentage (solid content concentration).
　組成物（４）は、さらに界面活性剤を含むことが好ましい。界面活性剤を含むことにより、組成物（４）の保管中にフッ素樹脂粒子が凝集したり、沈降したりすることを防げる。 The composition (4) preferably further contains a surfactant. By containing the surfactant, it is possible to prevent the fluororesin particles from aggregating or settling during storage of the composition (4).
　界面活性剤としては、ノニオン界面活性剤が好ましく、非フッ素化ノニオン界面活性剤がより好ましい。 As the surfactant, a nonionic surfactant is preferable, and a non-fluorinated nonionic surfactant is more preferable.
　ノニオン界面活性剤としては、例えば、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキレンアルキルエーテル等のエーテル型ノニオン界面活性剤；エチレンオキサイド／プロピレンオキサイドブロック共重合体等のポリオキシエチレン誘導体；ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル等のエステル型ノニオン界面活性剤；ポリオキシエチレンアルキルアミン、アルキルアルカノールアミド等のアミン系ノニオン界面活性剤；等が挙げられる。これらはいずれも非フッ素化ノニオン界面活性剤である。 Examples of the nonionic surfactant include ether-type nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene alkylene alkyl ether; and polyoxy such as ethylene oxide / propylene oxide block copolymer. Ethylene derivatives; ester-type nonionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester; polyoxyethylene alkylamine, alkylalkanolamide, etc. Amine-based nonionic surfactant; and the like. All of these are non-fluorinated nonionic surfactants.
　ノニオン界面活性剤としては、なかでも、ポリオキシエチレンアルキルエーテルが好ましい。 Among them, polyoxyethylene alkyl ether is preferable as the nonionic surfactant.
　組成物（４）は、フッ素樹脂粒子に対して３～１５０質量％の範囲内の界面活性剤を含むものであってもよい。界面活性剤の含有量は、フッ素樹脂粒子に対して１０質量％以上がより好ましく、３０質量％以上がさらに好ましく、５０質量％以上が特に好ましく、１００質量％以下がより好ましく、８０質量％以下がさらに好ましく、７０質量％以下が特に好ましい。 The composition (4) may contain a surfactant in the range of 3 to 150% by mass with respect to the fluororesin particles. The content of the surfactant is more preferably 10% by mass or more, further preferably 30% by mass or more, particularly preferably 50% by mass or more, more preferably 100% by mass or less, and 80% by mass or less with respect to the fluororesin particles. Is more preferable, and 70% by mass or less is particularly preferable.
　組成物（４）は、塗布する際の濡れ性を向上させるために構造式：Ｒ４３１－ＯＨ（式中、Ｒ４３１はＣ３～Ｃ２０の炭化水素基である）で示されるアルコール類を含んでもよい。アルコール類は、２級又は３級のアルコールであってもよい。アルコール類の量は、組成物（４）１００質量％に対して、例えば０．１～３０質量％、好ましくは０．１～２０質量％、より好ましくは０．２～１５質量％の範囲内である。 The composition (4) may contain alcohols represented by the structural formula: R 431- OH (in the formula, R 431 is a hydrocarbon group of C3 to C20) in order to improve the wettability at the time of application. Good. The alcohols may be secondary or tertiary alcohols. The amount of alcohols is in the range of, for example, 0.1 to 30% by mass, preferably 0.1 to 20% by mass, and more preferably 0.2 to 15% by mass with respect to 100% by mass of the composition (4). Is.
　組成物（４）には、必要に応じ、造膜補助剤、凍結防止剤、顔料、充填剤、顔料分散剤、消泡剤、レベリング剤、レオロジー調整剤、防腐剤、紫外線吸収剤、酸化防止剤、つや消し剤、潤滑剤、加硫剤、増粘剤、ｐＨ調整剤、帯電防止剤、抗菌剤、難燃剤等を添加することもできる。所要の添加剤を加えて公知の方法で撹拌混合すればよい。 The composition (4) contains, if necessary, a film-forming auxiliary, an antifreeze agent, a pigment, a filler, a pigment dispersant, an antifoaming agent, a leveling agent, a rheology regulator, a preservative, an ultraviolet absorber, and an antioxidant. Agents, matting agents, lubricants, sulphurizers, thickeners, pH regulators, antistatic agents, antibacterial agents, flame retardants and the like can also be added. The required additives may be added and the mixture may be stirred and mixed by a known method.
　組成物（４）は、フッ素樹脂及び硬化性シリコーン樹脂以外の他のポリマーを含まないものであってもよい。 The composition (4) may not contain any polymer other than the fluororesin and the curable silicone resin.
　組成物（４）は、例えば、米国特許出願公開第２０１８／２２３１１６号明細書、又は特許第６０９８７５１号に記載の塗料であることができる。 The composition (4) can be, for example, the paint described in US Patent Application Publication No. 2018/223116 or Patent No. 6098751.
組成物（５）
　組成物（５）は、含フッ素単量体に基づく重合単位と、水酸基含有単量体、カルボキシル基含有単量体、酸無水物単量体、アミノ基含有単量体、及びシリコーン系ビニル単量体からなる群より選択される少なくとも一種の硬化性官能基含有単量体に基づく重合単位とを含むフッ素ポリマーを含有する組成物である。 Composition (5)
The composition (5) contains a polymerization unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride monomer, an amino group-containing monomer, and a silicone-based vinyl simple substance. It is a composition containing a fluoropolymer containing a polymerization unit based on at least one curable functional group-containing monomer selected from the group consisting of quants.
　含フッ素単量体、すなわち、硬化性官能基が導入される含フッ素ポリマーを形成するための単量体としては、例えば、ＴＦＥ、ＣＴＦＥ、ＶｄＦ、ＶＦ、ＨＦＰ、及びフルオロビニルエーテル（例：ＰＡＶＥ）を挙げることができ、これらの１種又は２種以上を用いることができる。中でも、ＴＦＥ、ＣＴＦＥ、及びＶｄＦからなる群より選択される少なくとも１種であることが好ましく、ＴＦＥであることがより好ましい。 Fluorine-containing monomers, that is, monomers for forming a fluorine-containing polymer into which a curable functional group is introduced, include, for example, TFE, CTFE, VdF, VF, HFP, and fluorovinyl ether (eg, PAVE). These can be mentioned, and one or more of these can be used. Among them, at least one selected from the group consisting of TFE, CTFE, and VdF is preferable, and TFE is more preferable.
　水酸基含有単量体としては、例えば２－ヒドロキシエチルビニルエーテル、３－ヒドロキシプロピルビニルエーテル、２－ヒドロキシプロピルビニルエーテル、２－ヒドロキシ－２－メチルプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、４－ヒドロキシ－２－メチルブチルビニルエーテル、５－ヒドロキシペンチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル等の水酸基含有ビニルエーテル類；２－ヒドロキシエチルアリルエーテル、４－ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等の水酸基含有アリルエーテル類等が挙げられる。これらのなかでも水酸基含有ビニルエーテル類、特に４－ヒドロキシブチルビニルエーテル、２－ヒドロキシエチルビニルエーテルが重合反応性、官能基の硬化性が優れる点で好ましい。他の水酸基含有単量体としては、例えばアクリル酸２－ヒドロキシエチル、メタクリル酸２－ヒドロキシエチル等の（メタ）アクリル酸のヒドロキシアルキルエステル等が例示できる。なお、後述するカルボキシル基含有単量体は、上記水酸基含有単量体には含まれないものとする。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 4-hydroxy-2-methyl. Hydroxyl-containing vinyl ethers such as butyl vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether can be mentioned. .. Among these, hydroxyl group-containing vinyl ethers, particularly 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether, are preferable because they are excellent in polymerization reactivity and curability of functional groups. Examples of other hydroxyl group-containing monomers include hydroxyalkyl esters of (meth) acrylic acids such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. The carboxyl group-containing monomer described later is not included in the hydroxyl group-containing monomer.
　カルボキシル基含有単量体としては、例えば式（5A）：
Figure JPOXMLDOC01-appb-C000040
 （式中、Ｒ５１、Ｒ５２、及びＲ５３は同じか又は異なり、いずれも水素原子、アルキル基、アリール基、カルボキシル基、又はアルコキシカルボニル基であり；ｎ５１は０又は１である。）
で表される不飽和モノカルボン酸、不飽和ジカルボン酸、そのモノエステル等の不飽和カルボン酸類；又は式（5B）：
Figure JPOXMLDOC01-appb-C000041
 （式中、Ｒ５４及びＲ５５は同じか又は異なり、いずれも飽和又は不飽和の直鎖又は環状アルキル基であり；ｎ５２は０又は１；ｍ５２は０又は１である。）
で表されるカルボキシル基含有ビニルエーテル単量体等が挙げられる。 Examples of the carboxyl group-containing monomer include the formula (5A) :.
Figure JPOXMLDOC01-appb-C000040
 (In the formula, R 51 , R 52 , and R 53 are the same or different, and they are all hydrogen atoms, alkyl groups, aryl groups, carboxyl groups, or alkoxycarbonyl groups; n51 is 0 or 1.)
Unsaturated monocarboxylic acid represented by, unsaturated dicarboxylic acid, unsaturated carboxylic acid such as monoester thereof; or formula (5B) :.
Figure JPOXMLDOC01-appb-C000041
 (In the formula, R 54 and R 55 are the same or different and are both saturated or unsaturated linear or cyclic alkyl groups; n52 is 0 or 1; m52 is 0 or 1.)
Examples thereof include a carboxyl group-containing vinyl ether monomer represented by.
　式（5A）で表される不飽和カルボン酸類の具体例としては、例えばアクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステル等が挙げられる。それらのなかでもクロトン酸、イタコン酸、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステルが、単独重合性が低く単独重合体ができにくいことから好ましい。 Specific examples of unsaturated carboxylic acids represented by the formula (5A) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, and maleic acid monoester. Examples thereof include fumaric acid and fumaric acid monoester. Among them, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, and fumaric acid monoester are preferable because they have low homopolymerizability and it is difficult to form a homopolymer.
　式（5B）で表されるカルボキシル基含有ビニルエーテル単量体の具体例としては、例えば３－アリルオキシプロピオン酸、３－（２－アリロキシエトキシカルボニル）プロピオン酸、３－（２－アリロキシブトキシカルボニル）プロピオン酸、３－（２－ビニロキシエトキシカルボニル）プロピオン酸、３－（２－ビニロキシブトキシカルボニル）プロピオン酸等の１種又は２種以上が挙げられる。これらの中でも３－（２－アリロキシエトキシカルボニル） プロピオン酸が、単量体の安定性や重合反応性がよい点で有利であり、好ましい。 Specific examples of the carboxyl group-containing vinyl ether monomer represented by the formula (5B) include 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, and 3- (2-allyloxybutoxy). Examples thereof include one or more types such as carbonyl) propionic acid, 3- (2-vinyloxyethoxycarbonyl) propionic acid, and 3- (2-vinyloxybutoxycarbonyl) propionic acid. Among these, 3- (2-allyloxyethoxycarbonyl) propionic acid is preferable because it is advantageous in terms of monomer stability and polymerization reactivity.
　カルボキシル基含有単量体としては、式（5A）又は（5B）で表されるもの以外にも、例えば、フタル酸ビニル、ピロメリット酸ビニル等の、多塩基カルボン酸のアルケニルエステル等を用いることができる。 As the carboxyl group-containing monomer, in addition to those represented by the formula (5A) or (5B), for example, an alkenyl ester of a polybasic carboxylic acid such as vinyl phthalate or vinyl pyromellitic acid may be used. Can be done.
　酸無水物単量体としては、例えば、マレイン酸無水物等の、不飽和ジカルボン酸の無水物が挙げられる。 Examples of the acid anhydride monomer include unsaturated dicarboxylic acid anhydrides such as maleic anhydride.
　アミノ基含有単量体としては、例えばＣＨ２＝ＣＨ－Ｏ－(ＣＨ２)ｘ５１－ＮＨ２（ｘ５１＝０～１０の整数）で示されるアミノビニルエーテル類；ＣＨ２＝ＣＨ－Ｏ－ＣＯ(ＣＨ２)ｘ５２－ＮＨ２（ｘ５２＝１～１０の整数）で示されるアミン類；そのほかアミノメチルスチレン、ビニルアミン、アクリルアミド、ビニルアセトアミド、ビニルホルムアミド等が挙げられる。 Examples of the amino group-containing monomer include amino vinyl ethers represented by CH 2 = CH-O- (CH 2 ) x51- NH 2 (x51 = an integer of 0 to 10); CH 2 = CH-O-CO ( amines represented by CH 2) x52 integer -NH 2 (x52 = 1 ~ 10 ); other aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide or the like.
　シリコーン系ビニル単量体としては、例えばＣＨ２＝ＣＨＣＯ２(ＣＨ２)３Ｓｉ(ＯＣＨ３)３、ＣＨ２＝ＣＨＣＯ２(ＣＨ２)３Ｓｉ(ＯＣ２Ｈ５)３、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３Ｓｉ(ＯＣＨ３)３、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３Ｓｉ(ＯＣ２Ｈ５)３、ＣＨ２＝ＣＨＣＯ２(ＣＨ２)３ＳｉＣＨ３(ＯＣ２Ｈ５)２、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３ＳｉＣ２Ｈ５(ＯＣＨ３)２、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３Ｓｉ(ＣＨ３)２(ＯＣ２Ｈ５)、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３Ｓｉ(ＣＨ３)２ＯＨ、ＣＨ２＝ＣＨ(ＣＨ２)３Ｓｉ(ＯＣＯＣＨ３)３、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３ＳｉＣ２Ｈ５(ＯＣＯＣＨ３)２、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３ＳｉＣＨ３(Ｎ(ＣＨ３)ＣＯＣＨ３)２、ＣＨ２＝ＣＨＣＯ２(ＣＨ２)３ＳｉＣＨ３[ＯＮ(ＣＨ３)Ｃ２Ｈ５]２、ＣＨ２＝Ｃ(ＣＨ３)ＣＯ２(ＣＨ２)３ＳｉＣ６Ｈ５[ＯＮ(ＣＨ３)Ｃ２Ｈ５]２等の（メタ）アクリル酸エステル類；ＣＨ２＝ＣＨＳｉ[ＯＮ＝Ｃ(ＣＨ３)(Ｃ２Ｈ５)]３、ＣＨ２＝ＣＨＳｉ(ＯＣＨ３)３、ＣＨ２＝ＣＨＳｉ(ＯＣ２Ｈ５)３、ＣＨ２＝ＣＨＳｉＣＨ３(ＯＣＨ３)２、ＣＨ２＝ＣＨＳｉ(ＯＣＯＣＨ３)３、ＣＨ２＝ＣＨＳｉ(ＣＨ３)２(ＯＣ２Ｈ５)、ＣＨ２＝ＣＨＳｉ(ＣＨ３)２ＳｉＣＨ３(ＯＣＨ３)２、ＣＨ２＝ＣＨＳｉＣ２Ｈ５(ＯＣＯＣＨ３)２、ＣＨ２＝ＣＨＳｉＣＨ３[ＯＮ(ＣＨ３)Ｃ２Ｈ５]２、ビニルトリクロロシラン又はこれらの部分加水分解物等のビニルシラン類；トリメトキシシリルエチルビニルエーテル、トリエトキシシリルエチルビニルエーテル、トリメトキシシリルブチルビニルエーテル、メチルジメトキシシリルエチルビニルエーテル、トリメトキシシリルプロピルビニルエーテル、トリエトキシシリルプロピルビニルエーテル等のビニルエーテル類等が例示される。 Examples of the silicone-based vinyl monomer include CH 2 = CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = CHCO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 , CH 2 = C. (CH 3 ) CO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 , CH 2 = CHCO 2 (CH 2) ) 3 SOC 3 (OC 2 H 5 ) 2 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 SiC 2 H 5 (OCH 3 ) 2 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) ) 3 Si (CH 3 ) 2 (OC 2 H 5 ), CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (CH 3 ) 2 OH, CH 2 = CH (CH 2 ) 3 Si (OCOCCH) 3 ) 3 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 SiC 2 H 5 (OCOCH 3 ) 2 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 SiCH 3 (N (CH 2 ) 3 ) COCH 3 ) 2 , CH 2 = CHCO 2 (CH 2 ) 3 SiCH 3 [ON (CH 3 ) C 2 H 5 ] 2 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 SiC 6 H 5 [ON (CH 3 ) C 2 H 5 ] 2 etc. (meth) acrylic acid esters; CH 2 = CHSi [ON = C (CH 3 ) (C 2 H 5 )] 3 , CH 2 = CHSi (OCH) 3 ) 3 , CH 2 = CHSi (OC 2 H 5 ) 3 , CH 2 = CHSiCH 3 (OCH 3 ) 2 , CH 2 = CHSi (OCOCH 3 ) 3 , CH 2 = CHSi (CH 3 ) 2 (OC 2 H) 5 ), CH 2 = CHSi (CH 3 ) 2 SiCH 3 (OCH 3 ) 2 , CH 2 = CHSiC 2 H 5 (OCOCH 3 ) 2 , CH 2 = CHSiCH 3 [ON (CH 3 ) C 2 H 5 ] 2 , Vinyl trichlorosilanes or vinyl silanes such as partial hydrolyzates thereof; trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinylae Examples thereof include vinyl ethers such as ter, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, and triethoxysilylpropyl vinyl ether.
　硬化性官能基が導入される含フッ素ポリマーとしては、パーフルオロオレフィン単位を主体とするパーフルオロオレフィン系ポリマーが好ましく、その具体例としては、ＴＦＥの単独重合体、又はＴＦＥとＨＦＰ、ＰＡＶＥ等との共重合体、さらにはこれらと共重合可能な他の単量体との共重合体等が挙げられる。 As the fluorine-containing polymer into which the curable functional group is introduced, a perfluoroolefin-based polymer mainly composed of a perfluoroolefin unit is preferable, and specific examples thereof include a homopolymer of TFE, TFE and HFP, PAVE and the like. Examples thereof include copolymers of the above, and copolymers with other monomers copolymerizable with these.
　共重合可能な他の単量体としては、例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニル、安息香酸ビニル、パラ－ｔ－ブチル安息香酸ビニル等のカルボン酸ビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテル等のアルキルビニルエーテル類；エチレン、プロピレン、ｎ－ブテン、イソブテン等の非フッ素系オレフィン類；ＶｄＦ、ＣＴＦＥ、ＶＦ、フルオロビニルエーテル等のフッ素系単量体等が挙げられるが、これらのみに限定されるものではない。これらのうち、ＴＦＥを主体とするＴＦＥ系ポリマーが好ましい。 Other copolymerizable monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl laurate, vinyl stearate, cyclohexylcarboxylic acid. Carboxylic acid vinyl esters such as vinyl, vinyl benzoate, parat-butyl vinyl benzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; ethylene, propylene, n-butene, isobutene, etc. Non-fluoroolefins; examples include, but are not limited to, fluoromonomers such as VdF, CTFE, VF, and fluorovinyl ether. Of these, TFE-based polymers mainly composed of TFE are preferable.
　具体的な硬化性官能基含有パーフルオロオレフィン系ポリマーとしては、例えばＴＦＥ／イソブチレン／ヒドロキシブチルビニルエーテル／他の単量体の共重合体、ＴＦＥ／バーサチック酸ビニル／ヒドロキシエチルアリルエーテル／他の単量体の共重合体、ＴＦＥ／バーサチック酸ビニル／ヒドロキシブチルビニルエーテル／他の単量体の共重合体、ＴＦＥ／ＶｄＦ／ヒドロキシブチルビニルエーテル／他の単量体の共重合体等が挙げられる。 Specific curable functional group-containing perfluoroolefin-based polymers include, for example, TFE / isobutylene / hydroxybutyl vinyl ether / copolymer of other monomers, TFE / vinyl versatic acid / hydroxyethyl allyl ether / other single amount. Examples thereof include polymer of the body, polymer of TFE / vinyl versatic acid / hydroxybutyl vinyl ether / other monomer, and polymer of TFE / VdF / hydroxybutyl vinyl ether / other monomer.
　組成物（５）中の硬化性官能基含有含フッ素ポリマーの含有量は、組成物（５）中の不揮発分の総量１００質量％に対し、２０～９０質量％の範囲内であることが好ましい。 The content of the curable functional group-containing fluoropolymer in the composition (5) is preferably in the range of 20 to 90% by mass with respect to 100% by mass of the total amount of non-volatile components in the composition (5). ..
　組成物（５）における有機溶媒としては、例えば、酢酸エチル、酢酸ブチル、酢酸イソプロピル、酢酸イソブチル、酢酸セロソルブ、プロピレングリコールメチルエーテルアセテート等のエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；テトラヒドロフラン、ジオキサン等の環状エーテル類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド類；キシレン、トルエン、ソルベントナフサ等の芳香族炭化水素類；プロピレングリコールメチルエーテル、エチルセロソルブ等のグリコールエーテル類；カルビトールアセテート等のジエチレングリコールエステル類；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン、ｎ－ノナン、ｎ－デカン、ｎ－ウンデカン、ｎ－ドデカン、ミネラルスピリット等の脂肪族炭化水素類；これらの混合等が挙げられる。これらは、単独で又は２種以上を併用してもよい。なかでも、エステル類が好ましく、酢酸ブチルが特に好ましい。 Examples of the organic solvent in the composition (5) include esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate and propylene glycol methyl ether acetate; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Classes; cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as xylene, toluene and solvent naphtha; propylene glycol methyl ether and ethyl cellosolve. Glycol ethers such as; diethylene glycol esters such as carbitol acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, mineral spirit, etc. Ester aliphatic hydrocarbons; examples thereof include a mixture thereof. These may be used alone or in combination of two or more. Of these, esters are preferable, and butyl acetate is particularly preferable.
　組成物（５）は、硬化剤を含むことが好ましい。硬化剤を含むことにより、組成物（５）を用いて硬化塗膜を形成することができる。上記硬化剤は、硬化性ポリマーの官能基に応じて選択され、例えば、水酸基含有含フッ素ポリマーに対しては、イソシアネート系硬化剤、メラミン樹脂、シリケート化合物、イソシアネート基含有シラン化合物などが好ましく例示できる。また、カルボキシル基含有含フッ素ポリマーに対してはアミノ系硬化剤やエポキシ系硬化剤が、アミノ基含有含フッ素ポリマーに対してはカルボニル基含有硬化剤やエポキシ系硬化剤、酸無水物系硬化剤が通常採用される。 The composition (5) preferably contains a curing agent. By including a curing agent, a cured coating film can be formed using the composition (5). The curing agent is selected according to the functional group of the curable polymer. For example, for the hydroxyl group-containing fluoropolymer, an isocyanate-based curing agent, a melamine resin, a silicate compound, an isocyanate group-containing silane compound and the like can be preferably exemplified. .. In addition, amino-based curing agents and epoxy-based curing agents are used for carboxyl group-containing fluoropolymers, and carbonyl group-containing curing agents, epoxy-based curing agents, and acid anhydride-based curing agents are used for amino group-containing fluoropolymers. Is usually adopted.
　硬化剤としては、組成物（３）に記載のポリイソシアネート化合物が挙げられる。 Examples of the curing agent include the polyisocyanate compound described in the composition (3).
　組成物（５）における硬化剤の含有量は、硬化性官能基含有含フッ素ポリマー中の硬化性官能基１当量に対して０．１～５当量の範囲内であることが好ましく、０．５～１．５当量の範囲内であることがより好ましい。 The content of the curing agent in the composition (5) is preferably in the range of 0.1 to 5 equivalents with respect to 1 equivalent of the curable functional group in the fluoropolymer containing a curable functional group, and is preferably 0.5. More preferably, it is in the range of ~ 1.5 equivalents.
　組成物（５）は、無機顔料を含有していてもよい。無機顔料としては、一般に公知の無機顔料であれば特に限定されず、例えば、酸化チタン、酸化亜鉛、酸化アルミニウム、酸化鉄、酸化ケイ素、硫酸バリウム、炭酸カルシウム、カーボンブラック、チタンイエロー、クロムグリーン、群青、アルミニウム粉、雲母、炭酸バリウム、タルク等が挙げられる。なかでも、塗料への分散性及び紫外線の遮蔽性が良好である点で、酸化チタン、カーボンブラックが好ましい。 The composition (5) may contain an inorganic pigment. The inorganic pigment is not particularly limited as long as it is a generally known inorganic pigment, and for example, titanium oxide, zinc oxide, aluminum oxide, iron oxide, silicon oxide, barium sulfate, calcium carbonate, carbon black, titanium yellow, chrome green, etc. Examples include ultramarine, aluminum powder, mica, barium carbonate, and talc. Of these, titanium oxide and carbon black are preferable because they have good dispersibility in paint and good shielding property against ultraviolet rays.
　無機顔料の含有量は、組成物（５）中のフッ素ポリマー１００質量部に対して１０～１５０質量部の範囲内であることが好ましい。無機顔料の含有量が上述の範囲内であると、組成物（５）中によく分散できる。無機顔料の含有量は、硬化性官能基含有含フッ素ポリマー１００質量部に対して３０質量部以上がより好ましく、５０質量部以上がさらに好ましく、１３０質量部以下がより好ましく、１００質量部以下がさらに好ましい。 The content of the inorganic pigment is preferably in the range of 10 to 150 parts by mass with respect to 100 parts by mass of the fluoropolymer in the composition (5). When the content of the inorganic pigment is within the above range, it can be well dispersed in the composition (5). The content of the inorganic pigment is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, more preferably 130 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the curable functional group-containing fluoropolymer. More preferred.
　組成物（５）は、さらに必要に応じて他の成分を含んでいてもよい。他の成分としては、他の樹脂や添加剤が挙げられ、上記添加剤としては、例えば、無機顔料の分散性を改善する分散剤、無機顔料の沈降を防止する沈降安定剤、硬化促進剤、消泡剤、レベリング剤、紫外線吸収剤、光安定剤、増粘剤、密着改良剤、つや消し剤、親水化剤等を挙げることができる。 The composition (5) may further contain other components if necessary. Examples of other components include other resins and additives. Examples of the additives include a dispersant for improving the dispersibility of an inorganic pigment, a precipitation stabilizer for preventing the precipitation of an inorganic pigment, and a curing accelerator. Examples thereof include defoaming agents, leveling agents, ultraviolet absorbers, light stabilizers, thickeners, adhesion improvers, matting agents, and hydrophilic agents.
　組成物（５）としては、例えば、ダイキン工業（株）製のゼッフルＧＫシリーズ（ＧＫ－５００、ＧＫ－５１０、ＧＫ－５５０、ＧＫ－５７０、ＧＫ－５８０等）等が例示できる。
　組成物（５）としては、例えば、ダイキン工業（株）製のゼッフルＳＥシリーズ（ＳＥ－３００Ａ、ＳＥ－３１０、ＳＥ－４０５、ＳＥ－６００、ＳＥ－７００、ＳＥ－３１８３Ｄ等）等が例示できる。 Examples of the composition (5) include the Zeffle GK series (GK-500, GK-510, GK-550, GK-570, GK-580, etc.) manufactured by Daikin Industries, Ltd.
Examples of the composition (5) include the Zeffle SE series (SE-300A, SE-310, SE-405, SE-600, SE-700, SE-3183D, etc.) manufactured by Daikin Industries, Ltd. ..
　組成物（５）は、例えば、特許第５７０８７４０号に記載の塗料組成物であることができる。 The composition (5) can be, for example, the coating composition described in Japanese Patent No. 5708740.
　表面改質剤は、タイヤの全体又は一部（例えば、溝、トレッド、カーカス、サイドウォール、ビード、これら２つ以上の部位）に適用することができる。表面改質剤をタイヤに適用（又は塗装）する方法としては従来公知の方法と条件が採用できる。例えば、浸漬コーティング、スピンコーティング、スプレーコーティング、ロールコーティング、フローコーティング、ローラー、刷毛、グラビア・スクリーン印刷などの塗装方法によりタイヤ（又はタイヤ用ゴム組成物）に塗膜を形成した後、乾燥する方法が挙げられる。また、蒸着（例：真空蒸着）、スパッタリング、ＣＶＤ（例：プラズマＣＶＤ、光学ＣＶＤ、熱ＣＶＤ）などにより、タイヤ（又はタイヤ用ゴム組成物）に表面改質剤を堆積させる方法が挙げられる。さらに、表面改質剤を含有する離型面からタイヤ用ゴム組成物を離型し、タイヤ用ゴム組成物に表面改質剤を転写する方法であってもよい。このように表面改質剤をタイヤの表面に適用することによって、表面の撥水性及び耐オゾン性を向上させることができる。 The surface modifier can be applied to all or part of the tire (eg, grooves, treads, carcass, sidewalls, beads, two or more of these parts). Conventionally known methods and conditions can be adopted as a method for applying (or painting) the surface modifier to the tire. For example, a method of forming a coating film on a tire (or a rubber composition for a tire) by a coating method such as dip coating, spin coating, spray coating, roll coating, flow coating, roller, brush, gravure screen printing, and then drying. Can be mentioned. Further, a method of depositing a surface modifier on a tire (or a rubber composition for a tire) by vapor deposition (eg, vacuum vapor deposition), sputtering, CVD (eg, plasma CVD, optical CVD, thermal CVD) or the like can be mentioned. Further, a method may be used in which the tire rubber composition is released from the mold release surface containing the surface modifier and the surface modifier is transferred to the tire rubber composition. By applying the surface modifier to the surface of the tire in this way, the water repellency and ozone resistance of the surface can be improved.
タイヤ
　タイヤは、前記表面改質剤で表面が改質されたタイヤである。前記表面改質剤で改質される部位は、タイヤ表面の全体であってもよく、タイヤ表面の一部（例えば、溝、トレッド、カーカス、サイドウォール、ビード、これら２つ以上の部位）であってもよい。 Tire A tire is a tire whose surface has been modified with the surface modifier. The portion modified by the surface modifier may be the entire tire surface, or a part of the tire surface (for example, a groove, a tread, a carcass, a sidewall, a bead, or two or more of these portions). There may be.
　タイヤを形成するゴム組成物（タイヤ用ゴム組成物）は、通常、ジエン系ゴムを含有する。ジエン系ゴムとしては、特に制限されず、例えば、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、イソプレンゴム（ＩＲ）、スチレンイソプレンゴム（ＳＩＲ）、イソプレンブタジエンゴム（ＩＢＲ）、クロロプレンゴム（ＣＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）が挙げられる。これらのうち、ＮＲ、ＳＢＲ、ＢＲ、ＩＲが好ましい。また２種類以上のゴムを混ぜて使用しても構わない。 The rubber composition (rubber composition for tires) that forms a tire usually contains a diene-based rubber. The diene rubber is not particularly limited, and for example, natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), isoprene rubber (IR), styrene isoprene rubber (SIR), and isoprene butadiene rubber (IBR). ), Chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR). Of these, NR, SBR, BR, and IR are preferable. Further, two or more kinds of rubber may be mixed and used.
　ＳＢＲにおいて、スチレン結合量は、特に限定されないが、例えば５～６０質量％、好ましくは５～４０質量％の範囲内であることができ、ビニル結合量は、例えば２０～８０質量％、好ましくは３０～７０質量％の範囲内であることができる。スチレン結合量は、１Ｈ－ＮＭＲにより測定できる。 In SBR, the amount of styrene bond is not particularly limited, but can be in the range of, for example, 5 to 60% by mass, preferably 5 to 40% by mass, and the amount of vinyl bond is, for example, 20 to 80% by mass, preferably 20 to 80% by mass. It can be in the range of 30 to 70% by mass. The amount of styrene bond can be measured by 1H-NMR.
　ＢＲにおいて、ビニル結合量は、特に限定されないが、例えば１～９５質量％、好ましくは５～５０質量％の範囲内であることができる。ビニル結合量は、１Ｈ－ＮＭＲにより測定できる。 In BR, the vinyl bond amount is not particularly limited, but can be, for example, in the range of 1 to 95% by mass, preferably 5 to 50% by mass. The amount of vinyl bond can be measured by 1H-NMR.
　ジエン系ゴムの末端は変性剤によって変性されていてもよい。変性剤としては、例えば、式：
Figure JPOXMLDOC01-appb-C000042
 （式中、Ｒ６１～Ｒ６８は、Ｃ１－６アルキル基又はＣ６－１２アリール基であり、これらは互いに同一であっても相違していてもよい。Ｘ６１及びＸ６４は、ジエン系ゴムの活性末端と反応可能な官能基、Ｃ１－６アルキル基、又はＣ６－１２アリール基であり、Ｘ６１及びＸ６４は互いに同一であっても相違していてもよい。Ｘ６２は、ジエン系ゴムの活性末端と反応可能な官能基である。Ｘ６３は、２～２０のアルキレングリコールの繰返し単位を含有する基である。ｍ６は３～２００の整数、ｎ６は０～２００の整数、ｋ６は０～２００の整数である。）
で表される化合物、式：
Figure JPOXMLDOC01-appb-C000043
 （式中、Ｒ６９～Ｒ７６は、Ｃ１－６アルキル基又はＣ６－１２アリール基であり、これらは互いに同一であっても相違していてもよい。Ｘ６５～Ｘ６８は、ジエン系ゴムの活性末端と反応可能な官能基である。）
で表される化合物、式：
Figure JPOXMLDOC01-appb-C000044
 （式中、Ｒ７７～Ｒ７９は、Ｃ１－６アルキル基又はＣ６－１２アリール基であり、これらは互いに同一であっても相違していてもよい。Ｘ６９～Ｘ７１は、ジエン系ゴムの活性末端と反応可能な官能基である。ｓ６は１～１８の整数である。）
で表される化合物などが挙げられる。 The end of the diene rubber may be modified with a denaturing agent. Examples of the denaturant include the formula:
Figure JPOXMLDOC01-appb-C000042
 (In the formula, R 61 to R 68 are C 1-6 alkyl groups or C 6-12 aryl groups, which may be the same or different from each other. X 61 and X 64 are dienes. system rubber active terminal functional group reactive with the, C 1-6 alkyl group, or a C 6-12 aryl group, X 61 and X 64 .X good be different be the same as each other 62 Is a functional group capable of reacting with the active terminal of the diene rubber. X 63 is a group containing a repeating unit of 2 to 20 alkylene glycols. M6 is an integer of 3 to 200, and n6 is 0 to 200. , K6 is an integer from 0 to 200.)
Compound represented by, formula:
Figure JPOXMLDOC01-appb-C000043
 (In the formula, R 69 to R 76 are C 1-6 alkyl groups or C 6-12 aryl groups, which may be the same or different from each other. X 65 to X 68 are dienes. It is a functional group that can react with the active terminal of the rubber system.)
Compound represented by, formula:
Figure JPOXMLDOC01-appb-C000044
 (In the formula, R 77 to R 79 are C 1-6 alkyl groups or C 6-12 aryl groups, which may be the same or different from each other. X 69 to X 71 are dienes. It is a functional group that can react with the active terminal of the rubber system. S6 is an integer of 1 to 18.)
Examples thereof include compounds represented by.
　Ｒ６１～Ｒ６８、Ｘ６１、及びＸ６４を構成するＣ１－６アルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基などが挙げられる。Ｃ６－１２アリール基としては、例えば、フェニル基、メチルフェニル基などが挙げられる。これらのアルキル基及びアリール基の中では、メチル基が特に好ましい。 Examples of the C 1-6 alkyl group constituting R 61 to R 68 , X 61 , and X 64 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl. Group etc. can be mentioned. Examples of the C 6-12 aryl group include a phenyl group and a methylphenyl group. Of these alkyl and aryl groups, a methyl group is particularly preferred.
　Ｘ６１、Ｘ６２、及びＸ６４を構成するジエン系ゴムの活性末端と反応可能な官能基としては、特に限定されないが、Ｃ１－５アルコキシ基、２－ピロリドニル基を含有する炭化水素基、及びエポキシ基を含有する炭素数４～１２の基が好ましい。 The functional group capable of reacting with the active terminal of the diene-based rubber constituting X 61 , X 62 , and X 64 is not particularly limited, but is a hydrocarbon group containing a C 1-5 alkoxy group and a 2-pyrrolidnyl group. And a group having 4 to 12 carbon atoms containing an epoxy group is preferable.
　Ｃ１－５アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などが挙げられる。なかでも、メトキシ基が好ましい。 Examples of the C 1-5 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Of these, a methoxy group is preferable.
　２－ピロリドニル基を含有する炭化水素基としては、下記式で表される基が好ましく挙げられる。
Figure JPOXMLDOC01-appb-C000045
 （式中、ｊ６は２～１０の整数である。特に、ｊ６は２であることが好ましい。） As the hydrocarbon group containing a 2-pyrrolidnyl group, a group represented by the following formula is preferably mentioned.
Figure JPOXMLDOC01-appb-C000045
 (In the formula, j6 is an integer of 2 to 10. In particular, j6 is preferably 2.)
　エポキシ基を有する炭素数４～１２の基は、下記式で表される基が挙げられる。
　－Ｚ６１－Ｚ６２－Ｅ
　式中、Ｚ６１は、Ｃ１－１０アルキレン基又はアルキルアリーレン基であり、Ｚ６２はメチレン基、硫黄原子、又は酸素原子であり、Ｅはエポキシ基を有する炭素数２～１０の置換炭化水素基である。これらの中でも、Ｚ６２が酸素原子であるものが好ましく、Ｚ６２が酸素原子であり、かつ、Ｅがグリシジル基であるものがより好ましく、Ｚ６１がＣ３アルキレン基であり、Ｚ６２が酸素原子であり、かつ、Ｅがグリシジル基であるものが特に好ましい。 Examples of the group having an epoxy group having 4 to 12 carbon atoms include a group represented by the following formula.
-Z 61- Z 62- E
In the formula, Z 61 is a C 1-10 alkylene group or an alkylarylene group, Z 62 is a methylene group, a sulfur atom or an oxygen atom, and E is a substituted hydrocarbon having an epoxy group and having 2 to 10 carbon atoms. It is a group. Among these, those in which Z 62 is an oxygen atom are preferable, those in which Z 62 is an oxygen atom and E is a glycidyl group are more preferable, Z 61 is a C 3 alkylene group, and Z 62 is an oxygen. It is particularly preferable that the atom is an atom and E is a glycidyl group.
　Ｘ６１及びＸ６４としては、上記の中でも、エポキシ基を含有する炭素数４～１２の基又はＣ１－６アルキル基が好ましく、また、Ｘ６２としては、上記の中でも、エポキシ基を含有する炭素数４～１２の基が好ましい。 Among the above, X 61 and X 64 are preferably an epoxy group-containing group having 4 to 12 carbon atoms or a C 1-6 alkyl group, and X 62 is preferably an epoxy group containing an epoxy group. A group having 4 to 12 carbon atoms is preferable.
　Ｘ６３、すなわち２～２０のアルキレングリコールの繰返し単位を含有する基としては、下記式で表される基が好ましい。
Figure JPOXMLDOC01-appb-C000046
 　式中、ｔ６は２～２０の整数であり、Ｐ６はＣ２－１０アルキレン基又はアルキルアリーレン基であり、Ｒ８０は水素原子又はメチル基であり、Ｑ６はＣ１－１０アルコキシ基又はアリールオキシ基である。これらの中でも、ｔ６が２～８の整数であり、Ｐ６がＣ３アルキレン基であり、Ｒ８０が水素原子であり、かつＱ６がメトキシ基であるものが好ましい。 As the group containing X 63 , that is, a repeating unit of 2 to 20 alkylene glycols, a group represented by the following formula is preferable.
Figure JPOXMLDOC01-appb-C000046
 In the formula, t6 is an integer of 2 to 20, P 6 is a C 2-10 alkylene group or an alkyl arylene group, R 80 is a hydrogen atom or a methyl group, and Q 6 is a C 1-10 alkoxy group or. It is an aryloxy group. Among these, an integer t6, 2 ~ 8, P 6 is a C 3 alkylene group, an R 80 is a hydrogen atom, and Q 6 are those preferably a methoxy group.
　ｍ６は３～２００、好ましくは２０～１５０、より好ましくは３０～１２０の整数である。また、ｎ６は０～２００、好ましくは０～１５０、より好ましくは０～１２０の整数である。ｋは０～２００、好ましくは０～１５０、より好ましくは０～１２０の整数である。さらに、ｍ６、ｎ６、及びｋ６の合計数は、４００以下であることが好ましく、３００以下であることがより好ましく、２５０以下であることが特に好ましい。 M6 is an integer of 3 to 200, preferably 20 to 150, and more preferably 30 to 120. Further, n6 is an integer of 0 to 200, preferably 0 to 150, and more preferably 0 to 120. k is an integer of 0 to 200, preferably 0 to 150, and more preferably 0 to 120. Further, the total number of m6, n6, and k6 is preferably 400 or less, more preferably 300 or less, and particularly preferably 250 or less.
　Ｒ６９～Ｒ７９及びＸ６５～Ｘ７１も、Ｒ６１～Ｒ６８及びＸ６１～Ｘ６４と同様とすることができる。 R 69 to R 79 and X 65 to X 71 can be the same as R 61 to R 68 and X 61 to X 64 .
　ジエン系ゴムのムーニー粘度（ＭＬ１＋４）は、特に限定されないが、例えば１０～１５０、好ましくは２０～１２０の範囲内であることができる。ムーニー粘度は、ＪＩＳ　Ｋ６３００（１９９４）に従って、１００℃にて測定される。 The Mooney viscosity (ML 1 + 4 ) of the diene rubber is not particularly limited, but can be, for example, in the range of 10 to 150, preferably 20 to 120. Mooney viscosity is measured at 100 ° C. according to JIS K6300 (1994).
　タイヤ用ゴム組成物には、常法に従って、充填剤（例：シリカ、カーボンブラック、タルク、クレー、炭酸カルシウム）、シランカップリング剤、架橋剤（例：硫黄、ハロゲン化硫黄、有機過酸化物、キノンジオキシム類、有機多価アミン化合物、メチロール基を有するアルキルフェノール樹脂）、架橋促進剤（例：スルフェンアミド系架橋促進剤、グアニジン系架橋促進剤、チオウレア系架橋促進剤、チアゾール系架橋促進剤、チウラム系架橋促進剤、ジチオカルバミン酸系架橋促進剤、キサントゲン酸系架橋促進剤）、架橋活性化剤（例：ステアリン酸などの高級脂肪酸、酸化亜鉛）、老化防止剤、活性剤、プロセス油（例：パラフィン系、芳香族系、ナフテン系の石油系軟化剤；植物系軟化剤；脂肪酸）、可塑剤、滑剤、粘着付与剤、水酸化アルミニウムなどの１種又は２種以上の配合剤をそれぞれ必要量配合できる。 For rubber compositions for tires, according to conventional methods, fillers (eg silica, carbon black, talc, clay, calcium carbonate), silane coupling agents, cross-linking agents (eg sulfur, sulfur halides, organic peroxides) , Kinondioximes, organic polyvalent amine compounds, alkylphenol resins having methylol groups), cross-linking accelerators (eg, sulfenamide-based cross-linking promoters, guanidine-based cross-linking promoters, thiourea-based cross-linking promoters, thiazole-based cross-linking promoters Agents, thiuram-based cross-linking accelerators, dithiocarbamic acid-based cross-linking accelerators, xanthogenic acid-based cross-linking accelerators), cross-linking activators (eg, higher fatty acids such as stearic acid, zinc oxide), antiaging agents, activators, process oils (Example: Paraffin-based, aromatic, naphthen-based petroleum-based softener; plant-based softener; fatty acid), plasticizer, lubricant, tackifier, aluminum hydroxide, etc. Each can be mixed in the required amount.
　タイヤ用ゴム組成物を得るためには、常法に従って各成分を混練すればよく、例えば、架橋剤及び架橋促進剤を除く配合剤と、ゴム成分とを混練後、その混練物に架橋剤及び架橋促進剤を混合して目的の組成物を得ることができる。架橋剤及び架橋促進剤を除く配合剤とゴム成分の混練温度は、好ましくは８０～２００℃、より好ましくは１２０～１８０℃の範囲内である。また、混練時間は、好ましくは３０秒～３０分の範囲内である。混練物と架橋剤及び架橋促進剤との混合は、通常１００℃以下、好ましくは８０℃以下まで冷却後に行われる。なお、タイヤ用ゴム組成物を得る際には、固形ゴムに配合剤を添加して混練する方法（乾式混練法）、或いは、ゴムの溶液に配合剤を添加して、凝固・乾燥させる方法（湿式混練法）のいずれでもよい。 In order to obtain a rubber composition for a tire, each component may be kneaded according to a conventional method. For example, after kneading a compounding agent excluding a cross-linking agent and a cross-linking accelerator and a rubber component, the kneaded product is mixed with a cross-linking agent and a cross-linking agent. The desired composition can be obtained by mixing the cross-linking accelerator. The kneading temperature of the compounding agent excluding the cross-linking agent and the cross-linking accelerator and the rubber component is preferably in the range of 80 to 200 ° C., more preferably 120 to 180 ° C. The kneading time is preferably in the range of 30 seconds to 30 minutes. Mixing of the kneaded product with the cross-linking agent and the cross-linking accelerator is usually carried out after cooling to 100 ° C. or lower, preferably 80 ° C. or lower. When obtaining a rubber composition for a tire, a method of adding a compounding agent to solid rubber and kneading it (dry kneading method), or a method of adding a compounding agent to a rubber solution and coagulating and drying it (a method of coagulating and drying). Any of the wet kneading method) may be used.
　本発明のゴム架橋物は、上述した重合体組成物を架橋することにより得ることができる。架橋方法は、特に限定されず、ゴム架橋物の形状、大きさなどに応じて選択すればよい。金型中に、重合体組成物を充填して加熱することにより成形と同時に架橋してもよく、予め成形しておいた重合体組成物を加熱して架橋してもよい。架橋温度は、好ましくは１２０～２００℃、より好ましくは１４０～１８０℃の範囲内であり、架橋時間は、通常、１～１２０分の範囲内である。 The rubber crosslinked product of the present invention can be obtained by cross-linking the above-mentioned polymer composition. The cross-linking method is not particularly limited and may be selected according to the shape, size and the like of the rubber cross-linked product. The polymer composition may be filled in a mold and crosslinked at the same time as molding by heating, or the polymer composition previously molded may be heated and crosslinked. The crosslinking temperature is preferably in the range of 120 to 200 ° C., more preferably 140 to 180 ° C., and the crosslinking time is usually in the range of 1 to 120 minutes.
　また、ゴム架橋物の形状、大きさなどによっては、表面が架橋していても内部まで十分に架橋していない場合があるので、さらに加熱して二次架橋を行ってもよい。 Further, depending on the shape and size of the rubber crosslinked product, even if the surface is crosslinked, it may not be sufficiently crosslinked to the inside, so further heating may be performed for secondary crosslinking.
　加熱方法としては、プレス加熱、スチーム加熱、オーブン加熱、熱風加熱などのゴムの架橋に用いられる一般的な方法を適宜選択すればよい。 As the heating method, a general method used for rubber cross-linking such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
タイヤの表面を改質する方法
　タイヤの表面を改質する方法は、前記表面改質剤をタイヤの表面に適用（又は塗装）する工程を含む。適用方法は、前記「表面改質剤」に記載の適用方法を採用することができる。 Method of Modifying the Surface of a Tire The method of modifying the surface of a tire includes a step of applying (or painting) the surface modifier to the surface of the tire. As the application method, the application method described in the above-mentioned "surface modifier" can be adopted.
タイヤの表面を改質するための、組成物、又は表面改質剤の使用
　本開示は、タイヤの表面を改質するための、前記組成物（１）～（５）のいずれかの使用、又は前記表面改質剤の使用を包含する。 Use of a composition or surface modifier for modifying the surface of a tire The present disclosure describes the use of any of the compositions (1)-(5) for modifying the surface of a tire. Alternatively, it includes the use of the surface modifier.
　以下、本開示を、さらに詳細な実施例に基づき説明するが、本開示は、これら実施例に限定されない。なお、以下において、「部」は、特に断りのない限り質量基準である。また、各種の試験及び評価は、下記の方法にしたがって行った。 Hereinafter, the present disclosure will be described based on more detailed examples, but the present disclosure is not limited to these examples. In the following, "part" is based on mass unless otherwise specified. In addition, various tests and evaluations were carried out according to the following methods.
［スチレンブタジエンゴムのスチレン単量体単位含有量、ビニル結合量とブタジエンゴムのビニル結合量］
　スチレン単量体単位含有量及びビニル結合量は、１Ｈ－ＮＭＲにより測定した。 [Styrene monomer unit content of styrene-butadiene rubber, vinyl bond amount and vinyl bond amount of butadiene rubber]
The styrene monomer unit content and the vinyl bond amount were measured by 1H-NMR.
［スチレンブタジエンゴム、ブタジエンゴムのガラス転移温度（Ｔｇ）］
　示差走査型熱量計（ＤＳＣ，パーキンエルマー社製）を用いて、２３℃から１２０℃まで昇温（加熱速度１００℃／分）、１２０℃を１０分間保持、－１２０℃まで降温（冷却速度１００℃／分）、－１２０℃を１０分間保持、２３℃まで昇温（加熱速度１０℃／分）の順で測定試料の温度を変化させ、オンセット値の２回平均値をガラス転移温度の測定値とした。 [Styrene-butadiene rubber, glass transition temperature (Tg) of butadiene rubber]
Using a differential scanning calorimeter (DSC, manufactured by PerkinElmer), raise the temperature from 23 ° C to 120 ° C (heating rate 100 ° C / min), hold 120 ° C for 10 minutes, and lower the temperature to -120 ° C (cooling rate 100). ℃ / min), hold −120 ℃ for 10 minutes, change the temperature of the measurement sample in the order of raising to 23 ℃ (heating rate 10 ℃ / min), and set the two-time average value of the onset value to the glass transition temperature. It was used as a measured value.
［スチレンブタジエンゴム、ブタジエンゴムのムーニー粘度］
　スチレンブタジエンゴムのムーニー粘度（ポリマームーニー）をＪＩＳ　Ｋ６３００に従って測定した（単位は（ＭＬ１＋４、１００℃））。 [Styrene-butadiene rubber, Mooney viscosity of butadiene rubber]
The Mooney viscosity (polymer Mooney) of styrene-butadiene rubber was measured according to JIS K6300 (unit: (ML1 + 4, 100 ° C.)).
［合成例１（ＳＢＲ）］
　攪拌機付きオートクレーブに、窒素雰囲気下、シクロヘキサン５６７０ｇ、スチレン１７０ｇ、１，３－ブタジエン４３０ｇ、及びテトラメチルエチレンジアミン１０．０ｍｍｏｌを仕込んだ後、ｎ－ブチルリチウムを、シクロヘキサン、スチレン、１，３－ブタジエンに含まれる重合を阻害する不純物の中和に必要な量を添加した。その後、ｎ－ブチルリチウムを重合反応に用いる分として５．６ｍｍｏｌを加え、４０℃で重合を開始した。　重合を開始してから１０分経過後、スチレン４０ｇ、１，３－ブタジエン３６０ｇを６０分間かけて連続的に添加した。重合反応中の最高温度は７０℃であった。連続添加終了後、さらに１０分間重合反応を継続し、重合転化率が９５％から１００％の範囲になったことを確認してから、カップリング剤として四塩化錫を０．２７８ｍｍｏｌを２０質量％シクロへキサン溶液の状態で加え、６５℃で１０分間反応させた。
　次に、変性剤として下記式：
Figure JPOXMLDOC01-appb-C000047
 で表されるポリオルガノシロキサン０．０２４ｍｍｏｌを４０質量％キシレン溶液の状態で添加し、６５℃で２０分間反応させた。
　その後、重合停止剤として、重合反応に使用したｎ－ブチルリチウムの２倍モルに相当する量のメタノールを添加して、水酸基変性スチレンブタジエンゴムを含有する溶液を得た。 
　この水酸基変性スチレンブタジエンゴムを含有する溶液のゴム成分１００部あたり、老化防止剤として、２，４－ビス（ｎ－オクチルチオメチル）－６－メチルフェノール０．２部を添加した。次に、スチームストリッピングにより溶媒を除去し、固形状ゴムの回収を行ない、ロールにかけて脱水し、さらに熱風乾燥機にて乾燥し、水酸基変性溶液重合スチレンブタジエンゴムを得た。 [Synthesis Example 1 (SBR)]
In an autoclave with a stirrer, 5670 g of cyclohexane, 170 g of styrene, 430 g of 1,3-butadiene, and 10.0 mmol of tetramethylethylenediamine were charged under a nitrogen atmosphere, and then n-butyllithium was added to cyclohexane, styrene, and 1,3-butadiene. The amount required to neutralize the contained impurities that inhibit polymerization was added. Then, 5.6 mmol was added as the amount of n-butyllithium used in the polymerization reaction, and the polymerization was started at 40 ° C. After 10 minutes from the start of the polymerization, 40 g of styrene and 360 g of 1,3-butadiene were continuously added over 60 minutes. The maximum temperature during the polymerization reaction was 70 ° C. After the completion of continuous addition, the polymerization reaction was continued for another 10 minutes, and after confirming that the polymerization conversion rate was in the range of 95% to 100%, 0.278 mmol of tin tetrachloride as a coupling agent was added to 20% by mass. It was added in the form of a cyclohexane solution and reacted at 65 ° C. for 10 minutes.
Next, as a denaturant, the following formula:
Figure JPOXMLDOC01-appb-C000047
 0.024 mmol of the polyorganosiloxane represented by (1) was added in the form of a 40 mass% xylene solution, and the reaction was carried out at 65 ° C. for 20 minutes.
Then, as a polymerization inhibitor, methanol in an amount corresponding to twice the mole of n-butyllithium used in the polymerization reaction was added to obtain a solution containing a hydroxyl group-modified styrene-butadiene rubber.
0.2 part of 2,4-bis (n-octylthiomethyl) -6-methylphenol was added as an antiaging agent per 100 parts of the rubber component of the solution containing the hydroxyl group-modified styrene-butadiene rubber. Next, the solvent was removed by steam stripping, the solid rubber was recovered, dehydrated by rolling, and further dried by a hot air dryer to obtain a hydroxyl group-modified solution-polymerized styrene-butadiene rubber.
　得られた水酸基変性溶液重合スチレンブタジエンゴムは、結合スチレン量が２１質量％であり、ブタジエン単位部分のビニル結合含有量が６３質量％、ムーニー粘度（ＭＬ１＋４，１００℃）６２、ガラス転移温度（Ｔｇ）－２５℃であり、官能基として水酸基が導入されたものであった。 The obtained hydroxyl group-modified solution-polymerized styrene-butadiene rubber has a bonded styrene content of 21% by mass, a vinyl bond content of the butadiene unit portion of 63% by mass, a Mooney viscosity (ML1 + 4,100 ° C.) 62, and a glass transition temperature (Tg). ) -25 ° C., and a hydroxyl group was introduced as a functional group.
［合成例２（ＢＲ）］
　攪拌機付きオートクレーブに、窒素雰囲気下、シクロヘキサン５６７０ｇ、及び１，３－ブタジエン７００ｇを仕込んだ後、ｎ－ブチルリチウムをシクロヘキサンと１，３－ブタジエンとに含まれる重合を阻害する不純物の中和に必要な量を添加し、さらに、ｎ－ブチルリチウムを重合反応に用いる分として８．３３ｍｍｏｌを加え、５０℃で重合を開始した。重合を開始してから２０分経過後、１，３－ブタジエン３００ｇを３０分間かけて連続的に添加した。重合反応中の最高温度は８０℃であった。連続添加終了後、さらに１５分間重合反応を継続し、重合転化率が９５％から１００％の範囲になったことを確認してから、重合溶液に、１，６－ビス（トリクロロシリル）ヘキサン０．３３３ｍｍｏｌ（重合に使用したｎ－ブチルリチウムの０．０４倍モルに相当）を４０質量％シクロヘキサン溶液の状態で添加し、３０分間反応させた。さらに、その後、下記式：
Figure JPOXMLDOC01-appb-C000048
 で表されるポリオルガノシロキサン２．９２ｍｍｏｌ（重合に使用したｎ－ブチルリチウムの０．３５倍モルに相当）を２０質量％キシレン溶液の状態で添加し、３０分間反応させ、次いでテトラメトキシシランを８．３３ｍｍｏｌ（重合に使用したｎ－ブチルリチウムの１倍モルに相当）を２５質量％シクロヘキサン溶液の状態で添加し、３０分間反応させた。その後、重合停止剤として、使用したｎ－ブチルリチウムの２倍モルに相当する量のメタノールを添加して、末端変性ポリブタジエンを含有する溶液を得た。そして、得られた溶液に、ゴム成分１００部あたり、老化防止剤としてイルガノックス１５２０Ｌ（チバスペシャリティーケミカルズ社製）を０．２部添加し、スチームストリッピングにより溶媒を除去した後、６０℃で２４時間真空乾燥することにより、末端変性ブタジエンゴムを得た。得られた末端変性ブタジエンゴムのムーニー粘度（ＭＬ１＋４，１００℃）５９、ガラス転移温度（Ｔｇ）－９０℃、ビニル／シス／トランス＝１０／４５／４５であった。 [Synthesis Example 2 (BR)]
After charging 5670 g of cyclohexane and 700 g of 1,3-butadiene in an autoclave with a stirrer under a nitrogen atmosphere, n-butyllithium is required to neutralize impurities contained in cyclohexane and 1,3-butadiene that inhibit polymerization. A large amount was added, and 8.33 mmol was added as the amount of n-butyllithium used in the polymerization reaction, and the polymerization was started at 50 ° C. After 20 minutes from the start of the polymerization, 300 g of 1,3-butadiene was continuously added over 30 minutes. The maximum temperature during the polymerization reaction was 80 ° C. After the completion of continuous addition, the polymerization reaction was continued for another 15 minutes, and after confirming that the polymerization conversion rate was in the range of 95% to 100%, 1,6-bis (trichlorosilyl) hexane 0 was added to the polymerization solution. .333 mmol (corresponding to 0.04 times the molar amount of n-butyllithium used for polymerization) was added in a 40 mass% cyclohexane solution and reacted for 30 minutes. After that, the following formula:
Figure JPOXMLDOC01-appb-C000048
 2.92 mmol of polyorganosiloxane represented by (corresponding to 0.35 times mol of n-butyllithium used for polymerization) was added in a 20 mass% xylene solution, reacted for 30 minutes, and then tetramethoxysilane was added. 8.33 mmol (corresponding to 1-fold molar amount of n-butyllithium used for polymerization) was added in the form of a 25 mass% cyclohexane solution and reacted for 30 minutes. Then, as a polymerization terminator, methanol corresponding to twice the molar amount of n-butyllithium used was added to obtain a solution containing terminal-modified polybutadiene. Then, 0.2 part of Irganox 1520L (manufactured by Ciba Speciality Chemicals) as an antiaging agent was added to the obtained solution per 100 parts of the rubber component, the solvent was removed by steam stripping, and then at 60 ° C. The terminal-modified butadiene rubber was obtained by vacuum drying for 24 hours. The obtained terminally modified butadiene rubber had a Mooney viscosity (ML1 + 4,100 ° C.) 59, a glass transition temperature (Tg) −90 ° C., and vinyl / cis / trans = 10/45/45.
［ＳＢＲゴムシートの作製］
　容量２５０ｍｌのブラベンダータイプミキサー中で、水酸基末端変性溶液重合スチレンブタジエンゴム１００部を３０秒素練りし、次いでシリカ（商品名「Ｚｅｏｓｉｌ１１６５ＭＰ」、ソルベイ社製、窒素吸着比表面積（ＢＥＴ法）：１６３ｍ２／ｇ）６０部、プロセスオイル（商品名「アロマックスＴ－ＤＡＥ」、ＪＸ日鉱日石エネルギー社製）２６部、及びシランカップリング剤：３－オクタノイルチオ－１－プロピルトリエトキシシラン（商品名「ＮＸＴシラン」、モメンティブパフォーマンスマテリアルズ社製）６．４部を添加して、１１０℃を開始温度として１．５分間混練後、シリカ（商品名「Ｚｅｏｓｉｌ１１６５ＭＰ」、ソルベイ社製）２０部、カーボンブラック（商品名「シースト３」、東海カーボン社製）１０部、酸化亜鉛３部、ステアリン酸２部、及び老化防止剤：Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン（商品名「ノクラック６Ｃ」、大内新興化学工業社製）２部を添加し、さらに２．５分間混練し、ミキサーから混練物を排出させた。混練終了時の混練物の温度は１５０℃であった。混練物を、室温まで冷却した後、再度ブラベンダータイプミキサー中で、１１０℃を開始温度として３分間混練した後、ミキサーから混練物を排出させた。次いで、５０℃のオープンロールで、得られた混練物と、硫黄１．５部及び架橋促進剤（シクロヘキシル－２－ベンゾチアゾリルスルフェンアミド（大内新興化学工業社製、商品名「ノクセラーＣＺ－Ｇ」）２部とジフェニルグアニジン（大内新興化学工業社製、商品名「ノクセラーＤ」）２部との混合物）４部を混練した後、シート状のゴム組成物を得、試料となるゴム組成物を、１６０℃で２０分間プレス架橋して架橋された試験片を作製した。 [Making SBR rubber sheet]
In a Brabender type mixer with a capacity of 250 ml, 100 parts of hydroxyl-terminated modified solution-polymerized styrene-butadiene rubber is kneaded for 30 seconds, and then silica (trade name "Zeosil1165MP", manufactured by Solvay, nitrogen adsorption specific surface area (BET method): 163 m). 2 / g) 60 parts, process oil (trade name "Aromax T-DAE", manufactured by JX Nikko Nisseki Energy Co., Ltd.), and silane coupling agent: 3-octanoylthio-1-propyltriethoxysilane (trade name) Add 6.4 parts of "NXT silane" (manufactured by Momentive Performance Materials) and knead for 1.5 minutes with 110 ° C as the starting temperature, then 20 parts of silica (trade name "Zeosil1165MP", manufactured by Solvay), carbon. Black (trade name "Seast 3", manufactured by Tokai Carbon Co., Ltd.) 10 parts, zinc oxide 3 parts, stearic acid 2 parts, and anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl) -p- Two parts of phenylenediamine (trade name "Nocrack 6C", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) were added and kneaded for another 2.5 minutes, and the kneaded product was discharged from the mixer. The temperature of the kneaded product at the end of kneading was 150 ° C. The kneaded product was cooled to room temperature and then kneaded again in a lavender type mixer for 3 minutes with 110 ° C. as the starting temperature, and then the kneaded product was discharged from the mixer. Next, on an open roll at 50 ° C., the obtained kneaded product, 1.5 parts of sulfur and a cross-linking accelerator (cyclohexyl-2-benzothiazolyl sulphenamide (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) -G ") 2 parts and 4 parts of diphenylguanidine (mixture of 2 parts of diphenylguanidine (trade name" Noxeller D ") manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) are kneaded, and then a sheet-shaped rubber composition is obtained and used as a sample. The rubber composition was press-crosslinked at 160 ° C. for 20 minutes to prepare a crosslinked test piece.
［ＢＲゴムシートの作製］
　容量２５０ｍｌのブラベンダータイプミキサー中で、末端変性ブタジエンゴム１００部を３０秒素練りし、次いでシリカ（商品名「Ｚｅｏｓｉｌ１１６５ＭＰ」、ソルベイ社製、窒素吸着比表面積（ＢＥＴ法）：１６３ｍ２／ｇ）６０部、プロセスオイル（商品名「アロマックスＴ－ＤＡＥ」、ＪＸ日鉱日石エネルギー社製）２６部、及びシランカップリング剤：３－オクタノイルチオ－１－プロピルトリエトキシシラン（商品名「ＮＸＴシラン」、モメンティブパフォーマンスマテリアルズ社製）６．４部を添加して、１１０℃を開始温度として１．５分間混練後、シリカ（商品名「Ｚｅｏｓｉｌ１１６５ＭＰ」、ソルベイ社製）２０部、カーボンブラック（商品名「シースト３」、東海カーボン社製）１０部、酸化亜鉛３部、ステアリン酸２部、及び老化防止剤：Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン（商品名「ノクラック６Ｃ」、大内新興化学工業社製）２部を添加し、さらに２．５分間混練し、ミキサーから混練物を排出させた。混練終了時の混練物の温度は１５０℃であった。混練物を、室温まで冷却した後、再度ブラベンダータイプミキサー中で、１１０℃を開始温度として３分間混練した後、ミキサーから混練物を排出させた。次いで、５０℃のオープンロールで、得られた混練物と、硫黄１．５部及び架橋促進剤（シクロヘキシル－２－ベンゾチアゾリルスルフェンアミド（大内新興化学工業社製、商品名「ノクセラーＣＺ－Ｇ」）２部とジフェニルグアニジン（大内新興化学工業社製、商品名「ノクセラーＤ」）２部との混合物）４部を混練した後、シート状のゴム組成物を得、試料となるゴム組成物を、１６０℃で２０分間プレス架橋して架橋された試験片を作製した。 [Making BR rubber sheet]
In a Brabender type mixer with a capacity of 250 ml, 100 parts of end-modified butadiene rubber is kneaded for 30 seconds, and then silica (trade name "Zeosil1165MP", manufactured by Solvay, nitrogen adsorption specific surface area (BET method): 163 m2 / g) 60. Part, process oil (trade name "Aromax T-DAE", manufactured by JX Nikko Nisseki Energy Co., Ltd.), and silane coupling agent: 3-octanoylthio-1-propyltriethoxysilane (trade name "NXTsilane", Add 6.4 parts of Momentive Performance Materials (manufactured by Solvay) and knead for 1.5 minutes with 110 ° C as the starting temperature, then 20 parts of silica (trade name "Zeosil1165MP", manufactured by Solvay), carbon black (trade name "" Seest 3 ”, manufactured by Tokai Carbon Co., Ltd.) 10 parts, zinc oxide 3 parts, stearic acid 2 parts, and anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (trade name) Two parts of "Nocrack 6C" (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) were added and kneaded for another 2.5 minutes, and the kneaded product was discharged from the mixer. The temperature of the kneaded product at the end of kneading was 150 ° C. The kneaded product was cooled to room temperature and then kneaded again in a lavender type mixer for 3 minutes with 110 ° C. as the starting temperature, and then the kneaded product was discharged from the mixer. Next, on an open roll at 50 ° C., the obtained kneaded product, 1.5 parts of sulfur and a cross-linking accelerator (cyclohexyl-2-benzothiazolyl sulphenamide (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) -G ") 2 parts and 4 parts of diphenylguanidine (mixture of 2 parts of diphenylguanidine (trade name" Noxeller D ") manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) are kneaded, and then a sheet-shaped rubber composition is obtained and used as a sample. The rubber composition was press-crosslinked at 160 ° C. for 20 minutes to prepare a crosslinked test piece.
［純水の接触角］
　協和界面科学社製、「ＤｒｏｐＭａｓｔｅｒ」を用いて、純水１μＬの液量で対水接触角を測定した。ＳＢＲシートの接触角を１００とする指数で撥水性を評価した。この指数が大きいものほど、タイヤの撥水性に優れるといえる。 [Contact angle of pure water]
Using "DropMaster" manufactured by Kyowa Interface Science Co., Ltd., the contact angle with water was measured with a liquid volume of 1 μL of pure water. The water repellency was evaluated by an index with the contact angle of the SBR sheet as 100. It can be said that the larger this index is, the better the water repellency of the tire is.
［静的オゾン劣化試験］
　架橋物シートを、列理方向に対して平行方向に、ダンベル状１号形に打ち抜くことで、ダンベル状試験片を得た。そして、ダンベル状１号形試験片について、試験機としてオゾン発生機（製品名「オゾンウェザーメータ　ＯＭＳ－ＨＮ」、スガ試験機社製）を使用し、ＪＩＳ　Ｋ６２５９：２００４に準拠して、４０℃、オゾン濃度５０ｐｐｈｍ、引張ひずみ２０％の環境下に、１４４時間保持することでオゾン処理を行い、き裂状態観察法により、試験片のき裂の大きさを観察した。なお、耐オゾン性（試験片のき裂の大きさ）については、以下の基準で評価した。
１．肉眼ではき裂が見えないが、１０倍の拡大鏡ではき裂が確認できるもの。
２．き裂が肉眼で確認できるもの。
３．き裂が深くて比較的大きいもの（１ｍｍ未満）。
４．き裂が深くて大きいもの（１ｍｍ以上３ｍｍ未満）。
５．３ｍｍ以上のき裂がある又は切断を起こしそうなもの。 [Static ozone deterioration test]
A dumbbell-shaped test piece was obtained by punching the crosslinked sheet into a dumbbell-shaped No. 1 shape in a direction parallel to the rowing direction. Then, for the dumbbell-shaped No. 1 test piece, an ozone generator (product name "Ozone Weather Meter OMS-HN", manufactured by Suga Test Instruments Co., Ltd.) was used as a testing machine, and the temperature was 40 ° C. in accordance with JIS K6259: 2004. , Ozone treatment was carried out by holding for 144 hours in an environment of ozone concentration of 50 pphm and tensile strain of 20%, and the size of cracks in the test piece was observed by the crack state observation method. The ozone resistance (the size of cracks in the test piece) was evaluated according to the following criteria.
1. 1. The cracks cannot be seen with the naked eye, but the cracks can be seen with a 10x magnifying glass.
2. 2. The cracks can be seen with the naked eye.
3. 3. Those with deep cracks and relatively large cracks (less than 1 mm).
4. Those with deep and large cracks (1 mm or more and less than 3 mm).
Those with cracks of 5.3 mm or more or those that are likely to cause cutting.
［実施例１］
　特許第６３３２３５８号の合成例１３と同様の方法により、下記のパーフルオロポリエーテル基含有トリメトキシシラン化合物：
　ＣＦ３Ｏ(ＣＦ２ＣＦ２Ｏ)２２(ＣＦ２Ｏ)２６ＣＦ２ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＣＨ２ＣＨ２ＣＨ２Ｓｉ(ＯＣＨ３)３)３
を得た。得られた化合物を、濃度２０ｗｔ％になるように、ハイドロフルオロエーテル（スリーエム社製、ノベックＨＦＥ７２００）に溶解した表面処理剤を調製した。上記で調製した表面処理剤をＳＢＲシート及びＢＲシート上に真空蒸着した。真空蒸着の処理条件は、圧力３．０×１０－３Ｐａとし、ＳＢＲシート及びＢＲシート１枚（５５ｍｍ×１００ｍｍ）あたり、表面処理剤２ｍｇを目安に蒸着させた。その後、蒸着膜付きＳＢＲシート及びＢＲシートを加熱し、表面処理層を形成した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１２４であり、耐オゾン性は２であった。 [Example 1]
The following perfluoropolyether group-containing trimethoxysilane compound: by the same method as in Synthesis Example 13 of Japanese Patent No. 6332358:
CF 3 O (CF 2 CF 2 O) 22 (CF 2 O) 26 CF 2 CH 2 OCH 2 CH 2 CH 2 Si (CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ) 3
Got A surface treatment agent prepared by dissolving the obtained compound in hydrofluoroether (Novec HFE7200, manufactured by 3M Ltd.) so as to have a concentration of 20 wt%. The surface treatment agent prepared above was vacuum-deposited on the SBR sheet and the BR sheet. The treatment conditions for vacuum vapor deposition were a pressure of 3.0 × 10 -3 Pa, and 2 mg of a surface treatment agent was deposited per SBR sheet and one BR sheet (55 mm × 100 mm) as a guide. Then, the SBR sheet with a thin-film deposition film and the BR sheet were heated to form a surface treatment layer.
The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 124 and an ozone resistance of 2.
［実施例２］
　特許第６０５６９３５号の実施例１と同様の方法により、平均組成：ＣＦ３ＣＦ２ＣＦＯ(ＣＦ２ＣＦ２ＣＦ２Ｏ)１４ＣＦ２ＣＦ２ＣＨ２ＯＨで表されるパーフルオロポリエーテル含有アルコールを含有する組成物を得た。この組成物を、固形分濃度が２０質量％になるように酢酸エチルに加え、２５℃で６０分撹拌して溶解した。この溶液にＳＢＲシート又はＢＲシートを浸漬し、７０℃で５分間乾燥した。次いで、５００ｍＪ／ｃｍ２の紫外線を照射した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１２０であり、耐オゾン性は２であった。 [Example 2]
By the same method as in Example 1 of Japanese Patent No. 6056935, a perfluoropolyether-containing alcohol represented by an average composition: CF 3 CF 2 CFO (CF 2 CF 2 CF 2 O) 14 CF 2 CF 2 CH 2 OH was prepared. The composition to be contained was obtained. This composition was added to ethyl acetate so that the solid content concentration became 20% by mass, and the mixture was dissolved by stirring at 25 ° C. for 60 minutes. The SBR sheet or BR sheet was immersed in this solution and dried at 70 ° C. for 5 minutes. Then, it was irradiated with ultraviolet rays of 500 mJ / cm 2 .
The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 120 and an ozone resistance of 2.
［実施例３］
　特許第６０５６９３５号の実施例１と同様の方法により、平均組成：ＣＦ３Ｏ(ＣＦ２ＣＦ２Ｏ)１５(ＣＦ２Ｏ)１５ＣＦ２ＣＦ２ＣＨ２ＯＨで表されるパーフルオロポリエーテル含有アルコールを含有する組成物を得た。この組成物を、固形分濃度が２０質量％になるように酢酸エチルに加え、２５℃で６０分撹拌して溶解した。この溶液にＳＢＲシート又はＢＲシートを浸漬し、７０℃で５分間乾燥した。次いで、５００ｍＪ／ｃｍ２の紫外線を照射した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１１９であり、耐オゾン性は２であった。 [Example 3]
Containing perfluoropolyether represented by average composition: CF 3 O (CF 2 CF 2 O) 15 (CF 2 O) 15 CF 2 CF 2 CH 2 OH by the same method as in Example 1 of Japanese Patent No. 6056935. A composition containing an alcohol was obtained. This composition was added to ethyl acetate so that the solid content concentration became 20% by mass, and the mixture was dissolved by stirring at 25 ° C. for 60 minutes. The SBR sheet or BR sheet was immersed in this solution and dried at 70 ° C. for 5 minutes. Then, it was irradiated with ultraviolet rays of 500 mJ / cm 2 .
The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 119 and an ozone resistance of 2.
［実施例４］
　特許第６０５６９３５号の実施例１と同様の方法により、平均組成：Ｆ(ＣＦＣＦ３ＣＦ２Ｏ)１４ＣＦ２ＣＦ２ＣＨ２ＯＨで表されるパーフルオロポリエーテル含有アルコールを含有する組成物を得た。この組成物を、固形分濃度が２０質量％になるように酢酸エチルに加え、２５℃で６０分撹拌して溶解した。この溶液にＳＢＲシート又はＢＲシートを浸漬し、７０℃で５分間乾燥した。次いで、５００ｍＪ／ｃｍ２の紫外線を照射した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１１８であり、耐オゾン２であった。 [Example 4]
A composition containing a perfluoropolyether-containing alcohol represented by an average composition of F (CFCF 3 CF 2 O) 14 CF 2 CF 2 CH 2 OH is obtained by the same method as in Example 1 of Japanese Patent No. 6056935. It was. This composition was added to ethyl acetate so that the solid content concentration became 20% by mass, and the mixture was dissolved by stirring at 25 ° C. for 60 minutes. The SBR sheet or BR sheet was immersed in this solution and dried at 70 ° C. for 5 minutes. Then, it was irradiated with ultraviolet rays of 500 mJ / cm 2 .
The water repellency of the obtained SBR and the crosslinked rubber test piece of BR was 118, and the ozone resistance was 2.
［実施例５］
　特許第６１０３１０７号の実施例１と同様の方法により、ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２．１／１４．９／１３．０（モル％）のフルオロポリマーとアクリルポリマーとからなる複合重合体粒子と、親水性基含有ポリイソシアネート（バイヒジュール　ＸＰ　２７００（住化バイエルウレタン株式会社製））と、水とを含有するクリア塗料を得た。このクリア塗料を、同特許の段落００９５に記載の方法と同様に、ＳＢＲシート又はＢＲシートにバーコーター（Ｎｏ．２４）で塗布し、２０℃で７日間乾燥した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１０９であり、耐オゾン性は１であった。 [Example 5]
By the same method as in Example 1 of Patent No. 6103107, composite polymer particles composed of VdF / TFE / CTFE = 72.1 / 14.9 / 13.0 (mol%) fluoropolymer and acrylic polymer, and composite polymer particles. A clear coating material containing a hydrophilic group-containing polyisocyanate (Baihijour XP 2700 (manufactured by Sumika Bayer Urethane Co., Ltd.)) and water was obtained. This clear paint was applied to an SBR sheet or BR sheet with a bar coater (No. 24) in the same manner as in paragraph 0905 of the same patent, and dried at 20 ° C. for 7 days.
The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 109 and an ozone resistance of 1.
［実施例６］
　特許第６０９８７５１号の表１に記載の塗料Ｐ１にＳＢＲシート又はＢＲシートを浸漬塗装し、引き揚げ後に１１０℃、３分間乾燥した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１１１であり、耐オゾン性は１であった。 [Example 6]
The SBR sheet or BR sheet was dipped and coated on the paint P1 shown in Table 1 of Japanese Patent No. 6098751, and after being withdrawn, dried at 110 ° C. for 3 minutes.
The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 111 and an ozone resistance of 1.
［実施例７］
　ダイキン工業(株)製ゼッフルＳＥ－７００にＳＢＲシート又はＢＲシートを浸漬塗装し、引き揚げ後２０℃、７日間乾燥した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１０９であり、耐オゾン性は１であった。 [Example 7]
The SBR sheet or BR sheet was dipped and coated on Zeffle SE-700 manufactured by Daikin Industries, Ltd., and dried at 20 ° C. for 7 days after being withdrawn.
The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 109 and an ozone resistance of 1.
［実施例８］
　ダイキン工業(株)製ゼッフルＧＫ－５７０に旭化成ケミカルズ(株)製デュラネートＴＰＡ－１００を、１００：１３．６（質量比）で混合し、ＳＢＲシート又はＢＲシートを浸漬塗装し、引き揚げ後に１１０℃、３分間乾燥した。
　得られたＳＢＲ及びＢＲの架橋ゴム試験片の撥水性は１１１であり、耐オゾン性は１であった。 [Example 8]
Duranate TPA-100 manufactured by Asahi Kasei Chemicals Co., Ltd. is mixed with Zeffle GK-570 manufactured by Daikin Industries, Ltd. at a ratio of 100: 13.6 (mass ratio), and the SBR sheet or BR sheet is dipped and coated. It was dried for 3 minutes.
The obtained SBR and the crosslinked rubber test piece of BR had a water repellency of 111 and an ozone resistance of 1.
［比較例１］
　ＳＢＲシートの撥水性は１００であり、耐オゾン性は４であった。 [Comparative Example 1]
The water repellency of the SBR sheet was 100, and the ozone resistance was 4.
［比較例２］
　ＢＲシートの撥水性は１０４であり、耐オゾン性は５であった。 [Comparative Example 2]
The BR sheet had a water repellency of 104 and an ozone resistance of 5.
　実施例１～８に示すように、表面コートしたＳＢＲ及びＢＲの架橋ゴム試験片は未処理の比較例１～２と比較し、撥水性と耐オゾン性に優れ、撥水性及び耐オゾン性を両立したタイヤを提供できる。 As shown in Examples 1 to 8, the surface-coated SBR and BR crosslinked rubber test pieces are superior in water repellency and ozone resistance, and have water repellency and ozone resistance as compared with the untreated Comparative Examples 1 and 2. We can provide compatible tires.

Claims (13)

  1. 　下記（１）～（５）のいずれかの組成物からなる、タイヤの表面改質剤：
    （１）パーフルオロポリエーテル基含有シラン化合物を含有する組成物；
    （２）炭素－炭素二重結合含有パーフルオロポリエーテル化合物を含有する組成物；
    （３）フルオロポリマー及びアクリルポリマーからなり、フルオロポリマー及びアクリルポリマーのいずれか一方又は両方が水酸基及び加水分解性シリル基を有する複合重合体粒子と、ポリイソシアネート化合物と、水とを含有する組成物；
    （４）フッ素樹脂粒子と、硬化性シリコーン樹脂と、水とを含有する組成物；
    （５）含フッ素単量体に基づく重合単位と、水酸基含有単量体、カルボキシル基含有単量体、酸無水物単量体、アミノ基含有単量体、及びシリコーン系ビニル単量体からなる群より選択される少なくとも一種の硬化性官能基含有単量体に基づく重合単位とを含むフッ素ポリマーを含有する組成物。     A tire surface modifier comprising any of the following compositions (1) to (5):
    (1) A composition containing a perfluoropolyether group-containing silane compound;
    (2) A composition containing a carbon-carbon double bond-containing perfluoropolyether compound;
    (3) A composition comprising a composite polymer particle composed of a fluoropolymer and an acrylic polymer and one or both of the fluoropolymer and the acrylic polymer having a hydroxyl group and a hydrolyzable silyl group, a polyisocyanate compound, and water. ;
    (4) A composition containing fluororesin particles, a curable silicone resin, and water;
    (5) It is composed of a polymerization unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. A composition containing a fluoropolymer containing a polymerization unit based on at least one curable functional group-containing monomer selected from the group.
  2. 　組成物（１）からなり、
    　パーフルオロポリエーテル基含有シラン化合物が、下記式：
    －(ＯＣ４Ｆ８)ａ－(ＯＣ３Ｆ６)ｂ－(ＯＣ２Ｆ４)ｃ－(ＯＣＦ２)ｄ－
    （式中、
    　ａ及びｂは、それぞれ独立して、０～３０の整数であり、
    　ｃ及びｄは、それぞれ独立して、１～２００の整数であり、
    　ａ、ｂ、ｃ、及びｄの和は、３以上の整数であり、
    　ｃ／ｄ比が、０．２以上０．９未満の範囲内であり、
    　添字ａ、ｂ、ｃ、又はｄを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。）
    で表されるパーフルオロポリエーテル基を含有するシラン化合物である、
    請求項１に記載の表面改質剤。     Consists of composition (1)
    The perfluoropolyether group-containing silane compound has the following formula:
    -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
    (During the ceremony,
    a and b are independently integers from 0 to 30 and
    c and d are independently integers from 1 to 200, respectively.
    The sum of a, b, c, and d is an integer of 3 or more.
    The c / d ratio is in the range of 0.2 or more and less than 0.9.
    The order of existence of each repeating unit in parentheses with the subscripts a, b, c, or d is arbitrary in the equation. )
    A silane compound containing a perfluoropolyether group represented by.
    The surface modifier according to claim 1.
  3. 　パーフルオロポリエーテル基含有シラン化合物が、下記式（1-1）～（1-6）：
    Figure JPOXMLDOC01-appb-C000001
     ［式中：
    　ＰＦＰＥは、各出現においてそれぞれ独立して、－(ＯＣ４Ｆ８)ａ－(ＯＣ３Ｆ６)ｂ－(ＯＣ２Ｆ４)ｃ－(ＯＣＦ２)ｄ－を表し、ａ及びｂは、それぞれ独立して、０～３０の整数であり、ｃ及びｄは、それぞれ独立して、１～２００の整数であり、ａ、ｂ、ｃ、及びｄの和は、３以上の整数であり、ｃ／ｄ比が、０．２以上０．９未満の範囲内であり、添字ａ、ｂ、ｃ、又はｄを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意であり；
    　Ｒｆは、各出現においてそれぞれ独立して、１個又はそれ以上のフッ素原子により置換されていてもよいＣ１－１６アルキル基を表し；
    　Ｒ１は、各出現においてそれぞれ独立して、水素原子又はＣ１－２２アルキル基を表し；
    　Ｒ２は、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
    　Ｒ１１は、各出現においてそれぞれ独立して、水素原子又はハロゲン原子を表し；
    　Ｒ１２は、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；　ｎは、(－ＳｉＲ１ ｎＲ２ ３－ｎ)単位毎に独立して、０～３の整数であり；
    　ただし、式（1-1）、（1-2）、（1-3）、及び（1-4）において、少なくとも１つのＲ２が存在し；
    　Ｘ１は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
    　Ｘ２は、各出現においてそれぞれ独立して、単結合又は２価の有機基を表し；
    　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
    　αは、それぞれ独立して、１～９の整数であり；
    　α’は、それぞれ独立して、１～９の整数であり；
    　Ｘ５は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
    　βは、それぞれ独立して、１～９の整数であり；
    　β’は、それぞれ独立して、１～９の整数であり；
    　Ｘ７は、それぞれ独立して、単結合又は２～１０価の有機基を表し；
    　γは、それぞれ独立して、１～９の整数であり；
    　γ’は、それぞれ独立して、１～９の整数であり；
    　Ｒａは、各出現においてそれぞれ独立して、－Ｚ－ＳｉＲ７１ ｐＲ７２ ｑＲ７３ ｒを表し；
    　Ｚは、各出現においてそれぞれ独立して、酸素原子又は２価の有機基を表し；
    　Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
    　Ｒａ’は、Ｒａと同意義であり；
    　Ｒａ中、Ｚ基を介して直鎖状に連結されるＳｉは最大で５個であり；
    　Ｒ７２は、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；　Ｒ７３は、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；　ｐは、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｑは、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｒは、各出現においてそれぞれ独立して、０～３の整数であり；
    　ただし、一のＲａにおいて、ｐ、ｑ、及びｒの和は３であり、式（1-5）及び（1-6）において、少なくとも１つのＲ７２が存在し；
    　Ｒｂは、各出現においてそれぞれ独立して、水酸基又は加水分解可能な基を表し；
    　Ｒｃは、各出現においてそれぞれ独立して、水素原子又は低級アルキル基を表し；
    　ｋは、各出現においてそれぞれ独立して、１～３の整数であり；
    　ｌは、各出現においてそれぞれ独立して、０～２の整数であり；
    　ｍは、各出現においてそれぞれ独立して、０～２の整数であり；
    　ただし、γを付して括弧でくくられた単位において、ｋ、ｌ、及びｍの和は３である。］
    のいずれかで表される化合物である、請求項２に記載の表面改質剤。     The perfluoropolyether group-containing silane compound has the following formulas (1-1) to (1-6):
    Figure JPOXMLDOC01-appb-C000001
     [During the ceremony:
    PFPE independently represents-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- in each appearance, where a and b are. Each independently is an integer of 0 to 30, c and d are independently integers of 1 to 200, and the sum of a, b, c, and d is an integer of 3 or more. The order of existence of each repeating unit in which the c / d ratio is in the range of 0.2 or more and less than 0.9 and is enclosed in parentheses with the subscripts a, b, c, or d is arbitrary in the formula. Is;
    Rf represents a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms at each appearance;
    R 1 independently represents a hydrogen atom or a C 1-22 alkyl group at each appearance;
    R 2 represents a hydroxyl group or a hydrolyzable group independently at each appearance;
    R 11 independently represents a hydrogen atom or a halogen atom at each appearance;
    R 12 is independently at each occurrence, a represents a hydrogen atom or a lower alkyl group; n is, (- SiR 1 n R 2 3-n) independently for each unit, an integer from 0 to 3;
    However, in equations (1-1), (1-2), (1-3), and (1-4), at least one R 2 is present;
    X 1 independently represents a single bond or a 2- to 10-valent organic group;
    X 2 independently represents a single bond or divalent organic group at each appearance;
    t is an integer from 1 to 10 independently for each occurrence;
    α is an integer from 1 to 9 independently of each other;
    α'is an integer from 1 to 9 independently of each other;
    X 5 each independently represents a single bond or a 2-10 valent organic group;
    β is an integer from 1 to 9 independently of each other;
    β'is an integer from 1 to 9 independently of each other;
    X 7 each independently represents a single bond or a 2-10 valent organic group;
    γ is an integer from 1 to 9 independently of each other;
    γ'is an integer from 1 to 9 independently of each other;
    R a independently represents −Z—SiR 71 p R 72 q R 73 r ;
    Z independently represents an oxygen atom or a divalent organic group at each appearance;
    R 71 is independently at each occurrence, represents a R a ';
    R a 'is located in the same meaning as R a;
    In Ra, a maximum of 5 Sis are linearly linked via a Z group;
    R 72 represents a hydroxyl group or a hydrolyzable group independently at each appearance; R 73 independently represents a hydrogen atom or a lower alkyl group at each appearance; p represents a hydrogen atom or a lower alkyl group at each appearance. Independently, it is an integer from 0 to 3;
    q is an integer from 0 to 3 independently for each occurrence;
    r is an integer from 0 to 3 independently for each occurrence;
    However, in one Ra, the sum of p, q, and r is 3, and in equations (1-5) and (1-6), there is at least one R 72 ;
    R b represents a hydroxyl group or a hydrolyzable group independently at each appearance;
    R c independently represents a hydrogen atom or a lower alkyl group at each appearance;
    k is an integer of 1 to 3 independently for each occurrence;
    l is an integer from 0 to 2 independently for each occurrence;
    m is an integer from 0 to 2 independently for each occurrence;
    However, the sum of k, l, and m is 3 in the unit with γ and enclosed in parentheses. ]
    The surface modifier according to claim 2, which is a compound represented by any of the above.
  4. 　パーフルオロポリエーテル基含有シラン化合物が式（1-1）、（1-2）、（1-3）、（1-5）、及び（1-6）のいずれかで表され、α、α’、β、β’、γ、及びγ’が１であり、式（1-3）のｎが０である、請求項３に記載の表面改質剤。 The perfluoropolyether group-containing silane compound is represented by any of the formulas (1-1), (1-2), (1-3), (1-5), and (1-6), and is α, α. The surface modifier according to claim 3, wherein ′, β, β ′, γ, and γ ′ are 1, and n of the formula (1-3) is 0.
  5. 　組成物（２）からなり、
    　炭素－炭素二重結合含有パーフルオロポリエーテル化合物が、
    　（2A）ジイソシアネートの三量体であるポリイソシアネート
    のイソシアネート基に、
    　（2B）活性水素を有する化合物
    から活性水素が脱離した基が結合した化合物であり、
    　成分（2B）が、（2B-1）活性水素を有するパーフルオロポリエーテル、（2B-2）活性水素を有するシラン化合物、及び（2B-3）活性水素と炭素－炭素二重結合とを有する化合物であり、
    　成分（2A）中のイソシアネート基のモル数と、成分（2B）の合計のモル数が等しく、　成分（2A）中のイソシアネート基９モルに対して、
    　成分（2B-1）のモル数が、０．１～２モルの範囲内、
    　成分（2B-2）のモル数が、０．０５～２モルの範囲内、及び
    　成分（2B-3）のモル数が、５～８．８５モルの範囲内
    にある化合物である、
    請求項１に記載の表面改質剤。     Consists of composition (2)
    The carbon-carbon double bond-containing perfluoropolyether compound
    (2A) To the isocyanate group of polyisocyanate, which is a trimer of diisocyanate,
    (2B) A compound in which a group in which active hydrogen is eliminated from a compound having active hydrogen is bonded.
    Component (2B) has (2B-1) perfluoropolyether having active hydrogen, (2B-2) silane compound having active hydrogen, and (2B-3) active hydrogen and carbon-carbon double bond. Is a compound
    The number of moles of isocyanate groups in component (2A) is equal to the total number of moles of component (2B), with respect to 9 moles of isocyanate groups in component (2A).
    The number of moles of the component (2B-1) is in the range of 0.1 to 2 moles,
    A compound in which the number of moles of the component (2B-2) is in the range of 0.05 to 2 mol and the number of moles of the component (2B-3) is in the range of 5 to 8.85 mol.
    The surface modifier according to claim 1.
  6. 　成分（2B-2）が、下記式（2B-2-i）～（2B-2-iii）：
    Figure JPOXMLDOC01-appb-C000002
     ［式中、
    　Ｒ２１１、Ｒ２１２、Ｒ２１３、Ｒ２１４、及びＲ２１５は、それぞれ独立して、アルキル基又はアリール基であり；
    　Ｒ２１６は、２価の有機基であり；
    　ｌ２及びｎ２は、それぞれ独立して、０又は１であり；
    　ｍ２は、１～５００の整数であり；
    　ｏ２は、１～２０の整数であり；
    　ｐ２は、０又は１である。］
    から選択される少なくとも一種であり、及び
    　成分（2B-1）と成分（2B-2）の数平均分子量の比が１：３～３：１である、請求項５に記載の表面改質剤。     The component (2B-2) has the following formulas (2B-2-i) to (2B-2-iii):
    Figure JPOXMLDOC01-appb-C000002
     [During the ceremony,
    R 211 , R 212 , R 213 , R 214 , and R 215 are independently alkyl or aryl groups;
    R216 is a divalent organic group;
    l2 and n2 are independently 0 or 1;
    m2 is an integer from 1 to 500;
    o2 is an integer from 1 to 20;
    p2 is 0 or 1. ]
    The surface modifier according to claim 5, which is at least one selected from the above, and has a ratio of the number average molecular weight of the component (2B-1) to the component (2B-2) of 1: 3 to 3: 1. ..
  7. 　組成物（３）からなり、
    　複合重合体粒子が、フルオロポリマー及びアクリルポリマーを同一粒子内に含有しており、
    　フルオロポリマーが、フルオロポリマーを構成する全重合体に対して７０モル％以上のビニリデンフルオライド単位を含む、請求項１に記載の表面改質剤。     Consists of composition (3)
    The composite polymer particles contain a fluoropolymer and an acrylic polymer in the same particles.
    The surface modifier according to claim 1, wherein the fluoropolymer contains 70 mol% or more of vinylidene fluoride units based on the total polymer constituting the fluoropolymer.
  8. 　組成物（４）からなり、
    　フッ素樹脂粒子の平均粒子径が、０．２～２００ｎｍの範囲内であり、
    　硬化性シリコーン樹脂の含有量が、フッ素樹脂粒子に対して０．１～２５０質量％の範囲内である、
    請求項１に記載の表面改質剤。     Consists of composition (4)
    The average particle size of the fluororesin particles is in the range of 0.2 to 200 nm.
    The content of the curable silicone resin is in the range of 0.1 to 250% by mass with respect to the fluororesin particles.
    The surface modifier according to claim 1.
  9. 　組成物（４）が、フッ素樹脂粒子に対して３～１５０質量％の界面活性剤をさらに含有し、
    　フッ素樹脂粒子は、ポリテトラフルオロエチレン、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体及びテトラフルオロエチレン／ヘキサフルオロプロピレン共重合体からなる群より選択される少なくとも一種からなり、
    　硬化性シリコーン樹脂は、１分子中に少なくとも２個の、ケイ素原子に結合した硬化反応性基を有する、２３℃における粘度が２０～１，０００，０００ｍＰａ・ｓの範囲内であるオルガノポリシロキサンからなる、
    請求項８に記載の表面改質剤。     The composition (4) further contains 3 to 150% by mass of a surfactant with respect to the fluororesin particles.
    The fluororesin particles consist of at least one selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers and tetrafluoroethylene / hexafluoropropylene copolymers.
    The curable silicone resin is derived from an organopolysiloxane having at least two curable reactive groups bonded to silicon atoms in one molecule and having a viscosity at 23 ° C. in the range of 20 to 1,000,000 mPa · s. Become,
    The surface modifier according to claim 8.
  10. 　組成物（５）からなり、
    　フッ素ポリマーが、テトラフルオロエチレンに基づく重合単位と、水酸基含有単量体に基づく重合単位とを含む、
    請求項１に記載の表面改質剤。     Consists of composition (5)
    The fluoropolymer contains a polymerization unit based on tetrafluoroethylene and a polymerization unit based on a hydroxyl group-containing monomer.
    The surface modifier according to claim 1.
  11. 　請求項１～１０のいずれか一項に記載の表面改質剤で表面が改質された、タイヤ。 A tire whose surface has been modified with the surface modifier according to any one of claims 1 to 10.
  12. 　請求項１～１０のいずれか一項に記載の表面改質剤をタイヤの表面に適用する工程を含む、タイヤの表面を改質する方法。 A method for modifying the surface of a tire, which comprises a step of applying the surface modifier according to any one of claims 1 to 10 to the surface of the tire.
  13. 　タイヤの表面を改質するための、請求項１～１０のいずれか一項に記載の組成物、又は表面改質剤の使用。 Use of the composition according to any one of claims 1 to 10 or a surface modifier for modifying the surface of a tire.
PCT/JP2020/029517 2019-07-31 2020-07-31 Tire, surface modifier therefor, and surface modification method WO2021020575A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021535468A JPWO2021020575A1 (en) 2019-07-31 2020-07-31

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019140539 2019-07-31
JP2019-140539 2019-07-31

Publications (1)

Publication Number Publication Date
WO2021020575A1 true WO2021020575A1 (en) 2021-02-04

Family

ID=74228937

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/029517 WO2021020575A1 (en) 2019-07-31 2020-07-31 Tire, surface modifier therefor, and surface modification method

Country Status (2)

Country Link
JP (1) JPWO2021020575A1 (en)
WO (1) WO2021020575A1 (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62187739A (en) * 1985-10-18 1987-08-17 Mitsui Petrochem Ind Ltd Molding having coating layer of fluorocarbon polymer
JPH0598213A (en) * 1991-10-02 1993-04-20 Nikka Chem Co Ltd Protective lustering agent for tire
JPH05208454A (en) * 1991-09-20 1993-08-20 Bridgestone Corp Vehicular tire
JPH06238771A (en) * 1993-02-19 1994-08-30 Bridgestone Corp Manufacture of mud-adherence preventive tire
JP2014083832A (en) * 2012-10-26 2014-05-12 Bridgestone Corp Laminate and tire
JP2015081263A (en) * 2013-10-21 2015-04-27 住友ゴム工業株式会社 Method of producing rubber composition, and rubber composition
JP2015232064A (en) * 2014-06-09 2015-12-24 旭硝子株式会社 Fluorine-containing coating composition and article

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62187739A (en) * 1985-10-18 1987-08-17 Mitsui Petrochem Ind Ltd Molding having coating layer of fluorocarbon polymer
JPH05208454A (en) * 1991-09-20 1993-08-20 Bridgestone Corp Vehicular tire
JPH0598213A (en) * 1991-10-02 1993-04-20 Nikka Chem Co Ltd Protective lustering agent for tire
JPH06238771A (en) * 1993-02-19 1994-08-30 Bridgestone Corp Manufacture of mud-adherence preventive tire
JP2014083832A (en) * 2012-10-26 2014-05-12 Bridgestone Corp Laminate and tire
JP2015081263A (en) * 2013-10-21 2015-04-27 住友ゴム工業株式会社 Method of producing rubber composition, and rubber composition
JP2015232064A (en) * 2014-06-09 2015-12-24 旭硝子株式会社 Fluorine-containing coating composition and article

Also Published As

Publication number Publication date
JPWO2021020575A1 (en) 2021-02-04

Similar Documents

Publication Publication Date Title
JP5270359B2 (en) Perfluoroelastomer composition for low temperature applications
KR101530105B1 (en) Ultra low viscosity iodine containing amorphous fluoropolymers
JP6635025B2 (en) Compositions and articles for fluorine-containing coatings
JP5209167B2 (en) Novel fluoropolymers with improved properties
JP5952383B2 (en) Fluoropolyether elastomer composition having low glass transition temperature
KR101703372B1 (en) Low temperature curable amorphous fluoropolymers
JP2007517964A (en) Fluoroelastomer having improved low temperature characteristics and method for producing the same
JP4824311B2 (en) Fluoroelastomer with low temperature properties and solvent resistance
TW200535189A (en) Perfluoroelastomer composition for use in vulcanization and method for making a molded perfluoroelastomer product
WO2019073934A1 (en) Fluorine-containing elastic copolymer composition, paint, and painted article
WO2019126016A1 (en) Fluorinated elastomers cured by actinic radiation and methods thereof
EP3670132B1 (en) Tire production method
WO2021020575A1 (en) Tire, surface modifier therefor, and surface modification method
JP6777179B2 (en) Coating film and painted articles
JP2008280530A (en) Fluorine-containing copolymer solution and method for producing the same
JP2012168330A (en) Manufacturing method of antireflection film
JPH0366714A (en) Fluorine-containing elastic copolymer
JPWO2018163746A1 (en) Curable composition, paint, electric wire and resin article
EP3807355B1 (en) Curable fluoroelastomer composition
JP2021075716A (en) Film and composition for film formation
JPH09137113A (en) Composition for fluororesin paint
US20230139485A1 (en) A Method of Deriviatizing a Highly Fluorinated Polymer with a Nonfluorinated Carbon-Carbon Double Bond, a Polymer Therefrom, and Curable Compositions Comprising the Polymer
KR100695508B1 (en) Water dispersed polyurethane
JP2015067783A (en) Method for producing fluorine-containing polymer solution and method for producing fluorine-containing coating material composition
CN111511777A (en) Peroxide-cured halogenated elastomers with silicon-containing surface layers

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20846749

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021535468

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20846749

Country of ref document: EP

Kind code of ref document: A1