Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • 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

Definitions

• the present disclosure relates to compounds, compositions, surface treatment agents, methods of manufacturing articles, and articles.
• Patent Document 1 describes a surface treatment agent containing a perfluoro(poly)ether group-containing silane compound and a perfluoro(poly)ether group-containing amidosilane compound.
• Patent Document 2 describes a composition containing an organosilicon compound having at least one trialkylsilyl group and two or more hydrolyzable silicon groups, and a metal compound having at least one hydrolyzable group bonded to a metal atom. things are listed.
• Patent Document 3 describes a method for producing an organic thin film using an organic solvent solution containing a metal surfactant having at least one hydrolyzable group or hydroxyl group.
• compositions used as surface treatment agents and the like are required to be further improved in terms of water repellency and abrasion resistance.
• the present disclosure has been made in view of the above circumstances, and the problem to be solved by an embodiment of the present invention is to form a surface treatment layer with excellent water repellency and abrasion resistance on a base material.
• An object of the present invention is to provide novel compounds and compositions useful as surface treatment agents.
• the problem to be solved by an embodiment of the present invention is to provide a surface treatment agent that can form a surface treatment layer with excellent water repellency and abrasion resistance on a base material.
• the problem to be solved by an embodiment of the present invention is to provide an article having a surface treatment layer with excellent water repellency and abrasion resistance, and a method for manufacturing the same.
• the present disclosure includes the following aspects.
• ⁇ 1> A compound containing a triptycene skeleton, a reactive silyl group, and a hydrophobic partial structure.
• the reactive silyl group is bonded to either the 9-position or the 10-position of the triptycene skeleton directly or via a linking group
• the hydrophobic partial structure is bonded to the other of the 9-position and 10-position of the triptycene skeleton directly or via a linking group, The compound described in ⁇ 1>.
• the hydrophobic partial structure includes at least one selected from the group consisting of a polyoxyfluoroalkylene chain, a polydialkylsiloxane residue, a polyoxyalkylene chain, and an alkylene chain having 10 or more carbon atoms, ⁇ 1> Compounds described in. ⁇ 4>
• the hydrophobic partial structure includes at least one selected from the group consisting of a polyoxyfluoroalkylene chain, a polydialkylsiloxane residue, a polyoxyalkylene chain, and an alkylene chain having 10 or more carbon atoms, ⁇ 2> Compounds described in. ⁇ 5> A compound represented by the following formula (1).
• T is each independently a hydrogen atom or a monovalent organic group
• Z is each independently a polyoxyfluoroalkylene chain, a polydialkylsiloxane residue, a polyoxyalkylene chain, or an alkylene chain having 10 or more carbon atoms
• L 1 is a single bond or a (m+1)-valent linking group, which is bonded to the 9-position of the linking group represented by Tr
• Tr is a linking group obtained by removing the hydrogen atom at the 9-position and the hydrogen atom at the 10-position from triptycene
• Y 1 is a single bond or a (g+1)-valent linking group, which is bonded to the 10th position of the linking group represented by Tr
• R 1 is each independently a monovalent hydrocarbon group
• L 2 is each independently a hydrolyzable group or a hydroxyl group
• ⁇ 6> The compound according to ⁇ 5>, wherein m in the formula (1) is 1.
• ⁇ 7> A composition comprising the compound according to any one of ⁇ 1> to ⁇ 6> and a liquid medium.
• ⁇ 8> A surface treatment agent containing the compound according to any one of ⁇ 1> to ⁇ 6>.
• the surface treatment agent according to ⁇ 8> further comprising a liquid medium.
• a method for manufacturing an article comprising performing a surface treatment on a base material using the surface treatment agent according to ⁇ 8> to manufacture an article having a surface treatment layer formed on the base material.
• a method for manufacturing an article comprising performing a surface treatment on a base material using the surface treatment agent according to ⁇ 9> to manufacture an article having a surface treatment layer formed on the base material.
• An article comprising a base material and a surface treatment layer disposed on the base material and surface treated with the surface treatment agent according to ⁇ 8>.
• novel compounds and compositions useful as a surface treatment agent capable of forming a surface treatment layer with excellent water repellency and abrasion resistance on a substrate are provided.
• a surface treatment agent capable of forming a surface treatment layer with excellent water repellency and abrasion resistance on a base material is provided.
• an article having a surface treatment layer with excellent water repellency and abrasion resistance, and a method for manufacturing the article are provided.
• numerical ranges indicated using “ ⁇ ” include the numerical values written before and after " ⁇ " as minimum and maximum values, respectively.
• each component may contain multiple types of corresponding substances. If there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition, unless otherwise specified. means quantity.
• the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
• the term “layer” or “film” refers to the case where the layer or film is formed only in a part of the region, in addition to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present. This also includes cases where it is formed.
• the term “surface treated layer” refers to a layer formed on the surface of a base material by surface treatment.
• a compound or group is represented by a specific formula (X)
• the compound or group represented by the formula (X) may be referred to as a compound (X) and a group (X), respectively.
• a (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
• the compounds of the present disclosure include a triptycene skeleton, a reactive silyl group, and a hydrophobic moiety.
• a surface treated layer with excellent water repellency and abrasion resistance can be formed.
• the reason for this is not certain, it is assumed as follows. Since the compound of the present disclosure contains a triptycene skeleton, it is easily oriented on the surface of a substrate. Therefore, in the compound of the present disclosure, the reactive silyl group is in close contact with the base material in an oriented state due to the action of the triptycene skeleton, and the hydrophobic partial structures are arranged on the surface. Therefore, it is considered that by using a composition containing the compound of the present disclosure, a surface treatment layer having excellent both water repellency and abrasion resistance can be formed on a substrate.
• triptycene skeleton Compounds of the present disclosure include a triptycene skeleton.
• the triptycene skeleton refers to a partial structure obtained by removing one or more hydrogen atoms from triptycene.
• the chemical structure and position numbers of triptycene are shown below.
• a reactive silyl group and a hydrophobic partial structure are bonded directly or via a linking group to the triptycene skeleton contained in the compound of the present disclosure.
• the bonding positions of the reactive silyl group and the hydrophobic partial structure in the triptycene skeleton are not particularly limited. That is, the reactive silyl group and the hydrophobic partial structure may each be bonded to any of the 1st to 16th positions in the triptycene skeleton.
• the reactive silyl group and the hydrophobic partial structure may be bonded to different positions in the triptycene skeleton, respectively, or may be bonded to one position of the triptycene skeleton via a trivalent or higher valent linking group.
• the reactive silyl group and the hydrophobic partial structure are preferably bonded to different positions in the triptycene skeleton, and are bonded to opposite sides of the plane of symmetry of the triptycene skeleton. More preferably, they are combined.
• the two or more reactive silyl groups may be bonded to different positions on the triptycene skeleton, and one of the reactive silyl groups may be bonded to one of the triptycene skeletons via a trivalent or higher valent linking group. May be combined in one position. From the viewpoint of obtaining a surface treatment layer with excellent water repellency and abrasion resistance, it is preferable that all two or more reactive silyl groups are bonded to one side of the plane of symmetry of the triptycene skeleton, and bonded to one position of the triptycene skeleton. It is more preferable to do so.
• the two or more hydrophobic partial structures may be bonded to different positions in the triptycene skeleton, and one of the hydrophobic partial structures may be bonded to one of the triptycene skeletons via a trivalent or higher valent linking group. May be combined in one position. From the viewpoint of obtaining a surface treatment layer with excellent water repellency and abrasion resistance, it is preferable that all two or more hydrophobic partial structures are bonded to one side of the plane of symmetry of the triptycene skeleton, and bonded to one position of the triptycene skeleton. It is more preferable to do so.
• the compound of the present disclosure has a reactive silyl group bonded to either the 9-position or the 10-position of the triptycene skeleton, and a hydrophobic partial structure. It is preferable that it be bonded to the other of the 9th and 10th positions of the triptycene skeleton.
• the compound of the present disclosure has a reactive silyl group bonded to the 9-position of the triptycene skeleton and a hydrophobic partial structure bonded to the 10-position of the triptycene skeleton, or has a reactive silyl group bonded to the 10-position of the triptycene skeleton. It is preferable that a hydrophobic silyl group is bonded thereto, and a hydrophobic partial structure is bonded to the 9-position of the triptycene skeleton.
• the compound of the present disclosure contains two or more reactive silyl groups
• at least one reactive silyl group among the two or more reactive silyl groups is bonded to one of the 9-position and 10-position of the triptycene skeleton.
• At least one hydrophobic partial structure among the two or more hydrophobic partial structures may be bonded to one of the 9-position and 10-position of the triptycene skeleton.
• the compound of the present disclosure includes two or more reactive silyl groups and two or more hydrophobic moieties
• at least one reactive silyl group is bonded to one of the 9- and 10-positions of the triptycene skeleton
• at least one hydrophobic moieties are bonded to the other of the 9- and 10-positions of the triptycene skeleton.
• all two or more reactive silyl groups are bonded to one side of the plane of symmetry of the triptycene skeleton, and all two or more hydrophobic substructures are bonded to the other side of the plane of symmetry of the triptycene skeleton. It is more preferable.
• all two or more reactive silyl groups are bonded to either the 9th and 10th positions of the triptycene skeleton, and all of the two or more hydrophobic partial structures are bonded to the other of the 9th and 10th positions of the triptycene skeleton. More preferably, it is bonded to.
• the triptycene skeleton may have substituents other than the reactive silyl group and the hydrophobic partial structure.
• substituents include an alkyl group having 9 or less carbon atoms, a halogen atom (specifically, fluorine, chlorine, bromine, and iodine), a hydroxy group, an amino group, and a carbonyl group.
• the number of carbon atoms in the alkyl group as another substituent is preferably 5 or less, and may be 3 or less, for example.
• the bonding positions of the other substituents on the triptycene skeleton are not particularly limited.
• the positions where neither the reactive silyl group nor the hydrophobic partial structure are bonded are Can be mentioned.
• the triptycene skeleton has no other substituents.
• the compound of the present disclosure only needs to have one or more triptycene skeletons in one molecule, and may have two or more triptycene skeletons. From the viewpoint of obtaining a surface-treated layer with excellent water repellency and abrasion resistance, it is preferable that one triptycene skeleton is contained in one molecule of the compound of the present disclosure.
• Reactive silyl group Compounds of the present disclosure contain reactive silyl groups.
• the reactive silyl group is located at the end of the compound.
• a reactive silyl group means a group in which a reactive group is bonded to a Si atom.
• the reactive group is preferably a hydrolyzable group or a hydroxyl group.
• a hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH through a hydrolysis reaction.
• the silanol groups further react among themselves to form Si--O--Si bonds. Further, the silanol group can undergo a dehydration condensation reaction with a silanol group derived from an oxide present on the surface of the base material to form a Si--O--Si bond.
• the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanato group (-NCO).
• the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
• the aryl group of the aryloxy group includes a heteroaryl group.
• the halogen atom is preferably a chlorine atom.
• the acyl group is preferably an acyl group having 1 to 6 carbon atoms.
• the acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
• the reactive silyl group is preferably an alkoxysilyl group or a trichlorosilyl group. From the viewpoint of ease of handling by-products generated in the reaction with the base material, the reactive silyl group is more preferably an alkoxysilyl group.
• the alkoxysilyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group, and more preferably a trialkoxysilyl group.
• the number of reactive silyl groups possessed by the compound of the present disclosure is 1 or more, and from the viewpoint of further improving the wear resistance of the surface treatment layer, the number is preferably 1 to 18, more preferably 2 to 12, and 2 to 8. More preferred.
• the number of reactive silyl groups that the compound of the present disclosure has may be one.
• R 1 is each independently a monovalent hydrocarbon group
• L 2 is each independently a hydrolyzable group or a hydroxyl group
• n is an integer from 0 to 2.
• the multiple groups (2) may be the same or different. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that the plurality of groups (2) are the same.
• Each R 1 is independently a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferable.
• the number of carbon atoms in R 1 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.
• the hydrolyzable group is preferably the one described above.
• L 2 is preferably an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms) or a halogen atom from the viewpoint of excellent ease of manufacturing the compound.
• L 2 is preferably an alkoxy group having 1 to 4 carbon atoms, from the viewpoint of less outgassing during coating and better storage stability of the compound.
• L 2 is more preferably an ethoxy group.
• L 2 is more preferably a methoxy group.
• at least one of L 2 is preferably the above group, and more preferably all of L 2 are the above groups.
• n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
• the presence of a plurality of L 2 makes the adhesion of the surface treatment layer to the base material stronger.
• n is 1 or less, the plurality of L2s present in one molecule may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that the plurality of L 2 's are the same.
• n is 2
• multiple R 1s present in one molecule may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that a plurality of R 1 's are the same.
• the reactive silyl group is bonded to the triptycene skeleton directly or via a linking group.
• the linking group existing between the reactive silyl group and the triptycene skeleton may be any group that does not impair the purpose of the present disclosure, and is described below.
• a polyvalent linking group illustrated as Y 1 in formula (1) can be mentioned.
• hydrophobic partial structure means a partial structure that has a low affinity for water.
• examples of the hydrophobic partial structure include partial structures that do not have a group that can be ionized in an aqueous solution or a group that can form a hydrogen bond.
• examples of the group that can be ionized in an aqueous solution include an amino group and a carboxy group.
• groups capable of hydrogen bonding include hydroxy groups and the like.
• the hydrophobic partial structure is preferably a chain partial structure.
• a chain partial structure refers to a chain partial structure that does not include a cyclic structure.
• the number of atoms constituting the main chain in the hydrophobic partial structure is 3 or more, preferably 10 or more, more preferably 15 or more from the viewpoint of obtaining a surface treated layer with excellent water repellency. Further, from the viewpoint of wear resistance, the number of constituent atoms of the main chain in the hydrophobic partial structure is preferably 500 or less, more preferably 250 or less, and even more preferably 150 or less.
• the number of constituent atoms of the main chain in the hydrophobic partial structure is preferably 3 to 500, more preferably 10 to 250, even more preferably 15 to 150.
• the "number of atoms constituting the main chain” refers to the number of atoms constituting the longest linear chain in the hydrophobic partial structure.
• the hydrophobic partial structure is a polyoxyfluoroalkylene chain or a polyoxyalkylene chain
• the total number of carbon atoms and oxygen atoms constituting the main chain is defined as the number of atoms constituting the main chain.
• the hydrophobic partial structure is a polydialkylsiloxane residue
• the total number of silicon atoms and oxygen atoms that constitute the main chain and are alternately bonded is defined as the number of atoms constituting the main chain.
• the hydrophobic partial structure is an alkylene chain
• the total number of carbon atoms constituting the main chain is defined as the number of atoms constituting the main chain.
• the compound of the present disclosure is composed of a polyoxyfluoroalkylene chain, a polydialkylsiloxane residue, a polyoxyalkylene chain, and an alkylene chain having 10 or more carbon atoms as a hydrophobic partial structure. It is preferable to include at least one selected from the group consisting of:
• the number of hydrophobic partial structures possessed by the compound of the present disclosure is 1 or more, and from the viewpoint of further improving the abrasion resistance of the surface treatment layer, the number is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. .
• the compound of the present disclosure includes two or more hydrophobic partial structures
• the two or more hydrophobic partial structures may be different types of partial structures or may be the same type of partial structures.
• the two or more hydrophobic partial structures are preferably of the same type from the viewpoint of ease of manufacturing the compound.
• hydrophobic partial structures are the same type of partial structure, for example, when two or more hydrophobic partial structures are both polyoxyfluoroalkylene chains, two or more hydrophobic partial structures are both polyoxyfluoroalkylene chains.
• examples include dialkylsiloxane residues, cases where two or more hydrophobic partial structures are all polyoxyalkylene chains, cases where two or more hydrophobic partial structures are all alkylene chains, etc.
• two or more hydrophobic partial structures are of the same type, it is sufficient that they are the same type, and they may be different in carbon number, chain length, etc.
• the polyoxyfluoroalkylene chain is represented by the following formula (C). (OX f ) k ...(C)
• X f is each independently a fluoroalkylene group
• k is an integer of 2 or more.
• the number of carbon atoms in the fluoroalkylene group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4 from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer.
• the fluoroalkylene group may be linear, branched, or cyclic, and from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer, linear or branched is preferred. Preferably, linear is more preferable.
• the fluoroalkylene group may be any alkylene group in which one or more fluorine atoms are bonded to each of the carbon atoms at both ends, and from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer, it should be a perfluoroalkylene group. is preferred.
• the fluoroalkylene group may have both a fluorine atom and a hydrogen atom.
• the bonding position and number of hydrogen atoms in the fluoroalkylene group containing hydrogen atoms are not particularly limited.
• X f examples include -CHF-, -CF 2 -, -C 2 F 4 -, -CF 2 CHF-, -C 3 F 6 -, -C 2 F 4 CHF-, -CF 2 CHFCF 2 -, -CF 2 CH 2 CF 2 -, -CF(CF 3 )CF 2 -, -C 4 F 8 -, -CHFC 3 F 6 -, -CF 2 CH 2 C 2 F 4 -, -CF(CF 3 ) C 2 F 4 -, -C 5 F 10 -, -CHFC 4 F 8 -, -C 2 F 4 CH 2 C 2 F 4 -, -C 6 F 12 -, -C 5 F 10 CHF-, -cycloC 4 F 6 -, -cycloC 5 F 8 -, and -cycloC 6 F 10 -.
• -cycloC 4 F 6 - means a perfluorocyclobutanediyl group.
• the perfluorocyclobutanediyl group include a perfluorocyclobutane-1,2-diyl group and a perfluorocyclobutane-1,3-diyl group.
• -cycloC 5 F 8 - means a perfluorocyclopentanediyl group.
• Examples of the perfluorocyclopentanediyl group include a perfluorocyclopentane-1,2-diyl group and a perfluorocyclopentane-1,3-diyl group.
• -cycloC 6 F 10 - means a perfluorocyclohexanediyl group.
• the perfluorocyclohexanediyl group include perfluorocyclohexane-1,2-diyl group, perfluorocyclohexane-1,3-diyl group, and perfluorocyclohexane-1,4-diyl group.
• the repetition number k of (OX f ) is an integer of 2 or more, more preferably an integer of 2 to 200, even more preferably an integer of 5 to 150, particularly preferably an integer of 5 to 100, and an integer of 10 to 50. Most preferred.
• the k X fs included in formula (C) may be the same or different. That is, (OX f ) k may include two or more types of (OX f ).
• the order in which two or more types of (OX f ) are combined is not limited, and may be arranged randomly, alternately, or in blocks. Containing two or more types of (OX f ) means that two or more types of (OX f ) with different numbers of carbon atoms exist in the compound, or two or more types with the same number of carbon atoms but different numbers of fluorine atoms.
• (OX f ) exists, and even if the number of carbon atoms and the number of fluorine atoms are the same, the presence or absence of a side chain and the type of side chain (for example, the number of side chains, the number of carbon atoms in the side chain, etc.) are different2 This means that there are more than one species (OX f ).
• the structure represented by ⁇ (OCF 2 ) k21 (OC 2 F 4 ) k22 ⁇ has k21 (OCF 2 ) and k22 (OC 2 F 4 ) are randomly arranged.
• the structure represented by (OC 2 F 4 -OC 3 F 6 ) k25 means that k25 (OC 2 F 4 ) and k25 (OC 3 F 6 ) are arranged alternately. represent.
• (OX f ) k is [(OCF 2 ) k1 (OC 2 F 4 ) k2 (OC 3 F 6 ) k3 (OC 4 F 8 ) k4 (OC 5 F 10 ) k5 (OC 6 F 12 ) k6 (O-cycloC 4 F 6 ) k7 (O-cycloC 5 F 8 ) k8 (O-cycloC 6 F 10 ) k9 ].
• k1, k2, k3, k4, k5, k6, k7, k8, and k9 are each independently an integer greater than or equal to 0, and preferably less than or equal to 100.
• k1 + k2 + k3 + k4 + k5 + k6 + k7 + k8 + k9 is an integer of 2 or more, more preferably an integer of 2 to 200, more preferably an integer of 5 to 150, even more preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.
• C 3 F 6 , C 4 F 8 , C 5 F 10 , and C 6 F 12 may be linear or branched, but the wear resistance of the surface treatment layer From the viewpoint of improving the properties, a straight chain is preferable. Note that the above formula represents the type and number of units, but does not represent the arrangement of the units.
• k1 to k9 represent the number of units; for example, (OCF 2 ) k1 does not represent a block in which k1 (OCF 2 ) units are consecutive.
• the order in which (OCF 2 ) to (O-cycloC 6 F 10 ) are written does not indicate that they are arranged in the order in which they are written.
• the arrangement of different units can be random arrangement, alternating arrangement, block It may be either an arrangement or a combination of these arrangements.
• (OX f ) k preferably includes a structure in which consecutive (OX f )s are represented by -(OX f1 -OX f2 ) k10 -.
• X f1 is a fluoroalkylene group
• X f2 is a fluoroalkylene group different from X f1
• k10 is an integer of 1 or more
• 2 ⁇ (2 ⁇ k10) ⁇ k Specific examples of the fluoroalkylene group represented by X f1 and the fluoroalkylene group represented by X f2 are the same as those of the fluoroalkylene group represented by X f .
• (OX f ) k preferably has at least one of the following structures as a part thereof. ⁇ (OCF 2 ) k11 (OCF 2 CF 2 ) k12 ⁇ , (OCF 2 CF 2 ) k13 , (OCF 2 CF 2 CF 2 ) k14 , (OCF 2 CF 2 -OCF 2 CF 2 CF 2 ) k15 , (OCF 2 CF 2 CF 2 ) k16 (OCF 2 CF 2 ) k17 , (OCF 2 CF 2 CF 2 CF 2 ) k16 (OCF 2 ) k17 , (OCF 2 CF 2 CF 2 CF 2 ) k16 (OCF 2 ) k17 , (OCF 2 CF 2 CF 2 CF 2 ) k16 (OCF 2 CF 2 ) k17 , (OCF 2 CF 2 CF 2 CF 2 CF 2 ) k16 (OCF 2 CF 2
• k11, k12, k13, k14, k15, k16, k17, k18, k19, k20, k21, and k22 are integers greater than or equal to 1, and the upper limit is the upper limit of the number of repetitions k of (OX f ).
• k12/k11 is preferably from 0.1 to 10, and from 0.2 to 10, from the viewpoint of better abrasion resistance and water repellency of the surface treatment layer. 5.0 is more preferred, 0.2 to 2.0 is even more preferred, 0.2 to 1.5 is particularly preferred, and 0.2 to 0.85 is most preferred.
• the fluorination rate expressed by the following formula in (OX f ) k is preferably 60% or more, more preferably 80% or more, from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer. More preferably, it is 100% perfluoropolyether.
• Fluorination rate (%) (number of fluorine atoms) / ⁇ (number of fluorine atoms) + (number of hydrogen atoms) ⁇ x 100
• the polydialkylsiloxane residue is a divalent chain organopolysiloxane residue.
• a partial structure represented by the following formula (B1) is preferable.
• R 3 is each independently an alkyl group, and X 2 is an integer of 1 or more.
• the alkyl group represented by R 3 may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and among these, a linear alkyl group or a cyclic alkyl group is preferable, and a linear alkyl group or a cyclic alkyl group is preferable. More preferred are alkyl groups.
• the number of carbon atoms in the alkyl group represented by R 3 is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• the alkyl group represented by R 3 is more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and even more preferably a methyl group.
• the (2 ⁇ X2+2) R 3 's included in formula (B1) may be the same or different.
• X2 is an integer of 1 or more, and from the viewpoint of obtaining a surface treated layer with excellent water repellency, it is preferably 5 to 200, more preferably 10 to 100, and even more preferably 20 to 80. From the viewpoint of obtaining a surface treated layer with excellent wear resistance, X2 is preferably from 9 to 50, more preferably from 11 to 30, particularly preferably from 11 to 25.
• the polyoxyalkylene chain is represented by the following formula (A). ( OXh ) X3 ...(A)
• X h is each independently an alkylene group, and X3 is an integer of 2 or more.
• the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 8, even more preferably 3 to 8, particularly preferably 3 to 6, 4 to 6 are highly preferred.
• the number of carbon atoms in the alkylene group is preferably 3 or more, especially from the viewpoint of improving the water repellency of the surface treatment layer.
• the alkylene group may be linear, branched, or cyclic, and from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer, the alkylene group is preferably linear or branched. , linear is more preferable.
• (OX h ) include -OCH 2 -, -OC 2 H 4 -, -OC 3 H 6 -, -OC 4 H 8 -, -OC 5 H 10 -, -OC 6 H 12 -, -OCH(CH 3 )CH 2 -, -OCH(CH 3 )CH 2 CH 2 -, -O-cycloC 4 H 6 -, -O-cycloC 5 H 8 -, and -O-cycloC 6 H 10 - Can be mentioned.
• -cycloC 4 H 6 - means a cyclobutanediyl group.
• Examples of the cyclobutanediyl group include a cyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group.
• -cycloC 5 H 8 - means a cyclopentanediyl group.
• Examples of the cyclopentanediyl group include a cyclopentane-1,2-diyl group and a cyclopentane-1,3-diyl group.
• -cycloC 6 H 10 - means a cyclohexanediyl group.
• Examples of the cyclohexanediyl group include a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and a cyclohexane-1,4-diyl group.
• the repetition number X3 of (OX h ) is an integer of 2 or more, preferably an integer of 3 or more, more preferably an integer of 3 to 200, even more preferably an integer of 5 to 150, an integer of 5 to 100. is particularly preferred, and an integer of 10 to 50 is most preferred.
• the X3 X hs included in formula (A) may be the same or different. That is, (OX h ) X3 may contain two or more types of (OX h ). The order in which two or more types of (OX h ) are combined is not limited, and may be arranged randomly, alternately, or in blocks.
• Containing two or more types of (OX h ) means that there are two or more types of (OX h ) with different numbers of carbon atoms in the compound, and even if the number of carbon atoms is the same, the presence or absence of side chains and the side This means that there are two or more types of (OX h ) having different chain types (for example, number of side chains, number of carbon atoms in side chains, etc.).
• the arrangement of two or more types of (OX h ) for example, the structure represented by ⁇ (OCH 2 ) m21 (OC 2 H 4 ) m22 ⁇ has m21 (OCH 2 )s and m22 (OC 2 H 4 ) H 4 ) are randomly arranged.
• the structure represented by (OC 2 H 4 -OC 3 H 6 ) m25 means that m25 (OC 2 H 4 ) and m25 (OC 3 H 6 ) are arranged alternately. represent.
• m11, m12, m13, m14, m15, m16, m17, m18, and m19 are each independently an integer of 0 or more, and preferably 100 or less.
• m11 + m12 + m13 + m14 + m15 + m16 + m17 + m18 + m19 is an integer of 2 or more, more preferably an integer of 2 to 200, more preferably an integer of 5 to 150, even more preferably an integer of 5 to 100, particularly preferably an integer of 10 to 50.
• m13+m14+m15+m16+m17+m18+m19 is preferably an integer of 2 or more, and more preferably 2 to 200. Furthermore, among these, m13 is preferably an integer of 2 or more, and more preferably 2 to 200.
• C 3 H 6 , C 4 H 8 , C 5 H 10 , and C 6 H 12 may be linear or branched, but the wear resistance of the surface treatment layer From the viewpoint of improving the properties, a straight chain is preferable.
• the above formula represents the type and number of units, but does not represent the arrangement of the units. That is, m11 to m19 represent the number of units; for example, (OCH 2 ) m11 does not represent a block containing m11 consecutive (OCH 2 ) units. Similarly, the order in which (OCH 2 ) to (O-cycloC 6 H 10 ) are written does not indicate that they are arranged in the order in which they are written. In the above formula, when 2 or more of m11 to m19 are not 0 (that is, when ( OX h ) or a combination of these sequences.
• (OX h ) X3 preferably has the following structure. (OC 2 H 4 ) m21 , (OC 3 H 6 ) m22 , (OC 2 H 4 ) m23 (OC 3 H 6 ) m24 , (OC 2 H 4 -OC 3 H 6 ) m25 , (OC 4 H 8 ) m26 , (OC 3 H 6 ) m27 (OC 4 H 8 ) m28 , (OC 3 H 6 -OC 4 H 8 ) m29 .
• m21 is an integer of 2 or more
• m22 is an integer of 2 or more
• m23 and m24 are each independently an integer of 1 or more
• m25 is an integer of 1 or more
• m26 is an integer of 1 or more
• m27 and m28 are each independently an integer of 1 or more
• m29 is an integer of 1 or more.
• the number of carbon atoms in the alkylene chain is 10 or more, preferably 12 or more, more preferably 14 or more, and even more preferably 16 or more from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer.
• the number of carbon atoms in the alkylene chain may be 21 or more. From the viewpoint of wear resistance, the number of carbon atoms in the alkylene chain is preferably 100 or less, more preferably 60 or less, and even more preferably 40 or less.
• the alkylene chain preferably has 12 to 100 carbon atoms, more preferably 14 to 60 carbon atoms, and still more preferably 16 to 40 carbon atoms.
• the alkylene chain may be linear, branched, or cyclic. From the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer, the alkylene chain is preferably linear or branched. The shape is more preferable.
• the hydrophobic partial structure is bonded to the triptycene skeleton directly or via a linking group.
• the connecting group existing between the hydrophobic partial structure and the triptycene skeleton may be any group that does not impair the purpose of the present disclosure, and is described below.
• the polyvalent linking group illustrated as L 1 in formula (1) can be mentioned.
• the hydrophobic partial structure is a polyoxyfluoroalkylene chain
• the terminal of the polyvalent linking group bonded to the polyoxyfluoroalkylene chain has a structure other than -CF 2 - or -CFH-.
• the hydrophobic partial structure is an alkylene chain
• the terminal of the polyvalent linking group that is bonded to the alkylene chain has a structure other than -CH 2 -.
• the hydrophobic partial structure may have a substituent.
• the substituent that the hydrophobic partial structure has may be any group that does not impair the purpose of the present disclosure, and includes groups other than the above-mentioned reactive silyl group, specifically described as T in formula (1) below. Examples include monovalent organic groups.
• the above-mentioned substituent is bonded, for example, to the end of the hydrophobic partial structure opposite to the end bonded to the triptycene skeleton directly or via a linking group.
• the hydrophobic partial structure is a polyoxyfluoroalkylene chain or a polyoxyalkylene chain
• the terminal bonded to the hydrophobic partial structure in the above substituent has a structure other than -O-.
• the hydrophobic partial structure is an alkylene chain having 10 or more carbon atoms
• the terminal of the substituent that is bonded to the hydrophobic partial structure has a structure other than -CH 2 -.
• the compound of the present disclosure is preferably a compound represented by the following formula (1) from the viewpoint of excellent water repellency and abrasion resistance.
• T is each independently a hydrogen atom or a monovalent organic group
• Z is each independently a polyoxyfluoroalkylene chain, a polydialkylsiloxane residue, a polyoxyalkylene chain, or an alkylene chain having 10 or more carbon atoms
• L 1 is a single bond or a (m+1)-valent linking group, which is bonded to the 9-position of the linking group represented by Tr
• Tr is a linking group obtained by removing the hydrogen atom at the 9-position and the hydrogen atom at the 10-position from triptycene
• Y 1 is a single bond or a (g+1)-valent linking group, which is bonded to the 10th position of the linking group represented by Tr
• R 1 is each independently a monovalent hydrocarbon group
• L 2 is each independently a hydrolyzable group or a hydroxyl group
• m is an integer from 1 to 3
• n is an integer from 0 to 2
• g is an integer of 1 or more.
• Z in formula (1) is the same as the above-mentioned polyoxyfluoroalkylene chain, polydialkylsiloxane residue, polyoxyalkylene chain, or alkylene chain having 10 or more carbon atoms as a hydrophobic partial structure, so the explanation will be omitted.
• Tr in formula (1) has a hydrophobic partial structure bonded to the 9th position of the triptycene skeleton directly or via a linking group, and a reactive silyl group bonded to the 10th position directly or via a linking group. Since this is the same as the one to be combined, the explanation will be omitted.
• R 1 , L 2 , and n in formula (1) are the same as R 1 , L, and n in formula (2) described above as the reactive silyl group.
• T in formula (1) is each independently a hydrogen atom or a monovalent organic group.
• m is 2 or more, two or more T's contained in the compound represented by formula (1) may be the same or different from each other.
• the monovalent organic group represented by T includes substituents such as an alkyl group, a fluoroalkyl group, a pentafluorosulfanyl group, a group -MR 2 3 , an aryl group, a fluoroaryl group, and a monovalent polysiloxane residue; Examples include groups that combine these substituents and linking groups.
• M is Si, Sn, or Ge, and Si is preferable. That is, the group -MR 2 3 is preferably -SiR 2 3 .
• Each R 2 is independently a hydrocarbon group or a trialkylsilyloxy group.
• Linking groups to be combined with the above substituents include alkylene groups, arylene groups, carbonyl groups, ether bonds, thioether bonds, sulfonyl groups, -NR 4 -, -SiR 4 2 -, and the like.
• R 4 is a hydrogen atom or a hydrocarbon group.
• Two or more of these linking groups may be used in combination, or two or more types of these linking groups may be used in combination.
• Examples of the linking group in which two or more of the above linking groups are combined include an ester bond, a thioester bond, an amide bond, a sulfonamide bond, a combination of an arylene group and an ether bond, and the like.
• Combinations of the above-mentioned substituents and linking groups include the combination of the group -SiR 2 3 and an alkylene group, the combination of the group -SiR 2 3 and an ether bond, the combination of an aryl group and an ether bond, and the combination of a fluoroalkyl group and an arylene group.
• Examples include a combination of a group and an ether bond, a combination of a pentafluorosulfanyl group, an arylene group, and an ether bond, a combination of a fluoroaryl group and an ether bond, and the like.
• the alkyl group that can be included in the monovalent organic group represented by T may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and among them, a linear alkyl group or Cyclic alkyl groups are preferred, and linear alkyl groups are more preferred.
• the number of carbon atoms in the alkyl group is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• the alkyl group is more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and even more preferably a methyl group.
• the fluoroalkyl group that may be included in the monovalent organic group represented by T may be linear, branched, or cyclic, and among these, a linear fluoroalkyl group is preferable, and a linear fluoroalkyl group is preferable. A perfluoroalkyl group is more preferred.
• the number of carbon atoms in the fluoroalkyl group is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• the fluoroalkyl group is more preferably a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, or an n-nonafluorobutyl group, and even more preferably a trifluoromethyl group.
• Examples of the hydrocarbon group represented by R 2 of the group -SiR 2 3 that can be included in the monovalent organic group represented by T include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.
• the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable, and a methyl group, an ethyl group, an n-propyl group, or an n-propyl group is preferable.
• -butyl group is more preferred, and methyl group is even more preferred.
• the alkyl group contained in the trialkylsilyloxy group represented by R 2 may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable. , methyl group, ethyl group, n-propyl group, or n-butyl group, and even more preferably methyl group.
• R 2 is a trialkylsilyloxy group
• the three alkylsilyloxy groups may be the same or different from each other, but from the viewpoint of ease of production, they are preferably the same.
• the trialkylsilyloxy group represented by R 2 is preferably a trimethylsilyloxy group, a triethylsilyloxy group, a tri-n-propylsilyloxy group, or a tri-n-butylsilyloxy group, and a trimethylsilyloxy group or a triethylsilyloxy group is preferable. groups are more preferred.
• Examples of the group -SiR 2 3 include methyldiethylsilyl group, methylethylpropylsilyl group, methylethylbutylsilyl group, methyldipropylsilyl group, methylpropylbutylsilyl group, methyldibutylsilyl group, dimethylethylsilyl group, dimethyl
• Examples include propylsilyl group, dimethylbutylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-isopropylsilyl group, and trialkylsilyloxysilyl group having these groups.
• the group -SiR 2 3 is preferably a trialkylsilyloxysilyl group, more preferably a trimethylsilyloxysilyl group or a triethylsilyloxysilyl group.
• the aryl group that can be included in the monovalent organic group represented by T is a group obtained by removing one hydrogen from an aromatic ring.
• the aromatic ring may be monocyclic or polycyclic, and is preferably monocyclic from the viewpoint of excellent liquid repellency.
• Examples of the aromatic ring include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a furan ring, a thiophene ring, and a pyridine ring.
• Examples of the fluoroaryl group that can be included in the monovalent organic group represented by T include a group in which the hydrogen atom of the above aryl group is replaced with a fluorine atom.
• the number of fluorine atoms that the fluoroaryl group has is not particularly limited.
• the fluoroaryl group is preferably a perfluoroaryl group, and more preferably a pentafluorophenyl group.
• Examples of the monovalent polysiloxane residue that can be included in the monovalent organic group represented by T include monovalent cyclic polysiloxane residues.
• Examples of the monovalent cyclic polysiloxane residue include a group represented by the following formula (T1).
• R 5 is each independently an alkyl group or an alkyl group having a substituent, and s is an integer of 1 to 4. * is the bond to Z in formula (1).
• the alkyl group represented by R 5 may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms.
• the alkyl group represented by R 5 is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and more preferably a methyl group.
• the alkyl group contained in the substituted alkyl group represented by R 5 may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable.
• the number of carbon atoms in the alkyl group contained in the substituted alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 4.
• Examples of the substituent in the substituted alkyl group represented by R 5 include a halogen atom, a hydroxyl group, an alkoxy group, a trialkylsilyl ether group, a trialkylsilyl group, an amino group, a nitro group, a cyano group, a sulfonyl group, and a trimethylsilyl group. Examples include fluoromethyl group.
• a plurality of R 5 's may be the same or different from each other, but from the viewpoint of ease of manufacture, it is preferable that they are the same.
• Examples of monovalent cyclic polysiloxane residues include the following groups.
• the alkylene group that can be included in the monovalent organic group represented by T may be linear, branched, or cyclic, and among these, linear or branched is preferable; A chain shape is more preferable.
• the number of carbon atoms in the alkylene group is, for example, 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
• the arylene group that can be included in the monovalent organic group represented by T is a group obtained by removing two hydrogen atoms from an aromatic ring, and the aromatic ring is as described above.
• Hydrocarbon groups represented by R 4 of -NR 4 - and -SiR 4 2 - that may be included in the monovalent organic group represented by T include, for example, aliphatic hydrocarbon groups and aromatic hydrocarbon groups. can be mentioned.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.
• the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable, and a methyl group, an ethyl group, an n-propyl group, or an n-propyl group is preferable.
• -butyl group is more preferred, and methyl group is even more preferred.
• T in formula (1) is a hydrogen atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, from the viewpoint of ease of manufacturing the compound. is preferred, an alkyl group or a fluoroalkyl group is more preferred, a perfluoroalkyl group is even more preferred, and a trifluoromethyl group is particularly preferred.
• T in formula (1) is an alkyl group, a trialkylsilyloxy group, a trialkylsilyloxysilyloxy group, A trialkylsilyloxysilylalkylene group, a group combining a group represented by formula (T1) and an ether bond, or a group combining a group represented by formula (T1) and an alkylene group are preferred, and trimethylsilyloxysilyl An oxy group, a trimethylsilyloxysilylethylene group, a group represented by formula (T1) in which s is 2 and R 5 is a methyl group, and an ether bond; or a group represented by formula (T1) in which s is a methyl group; A combination of a group in which R 5 is 2 and R 5 is a methyl group, and an ethylene group is more preferable.
• T in formula (1) is a hydrogen atom, an alkyl group, a pentafluorosulfanyl group, a group -SiR 2 3 ,
• a trialkylsilylalkylene group, an aryl group, a fluoroaryl group, an alkylaryl group, a fluoroalkylaryl group, or a pentafluorosulfanylaryl group are preferred, and an alkyl group, a trimethylsilylalkylene group, a triethylsilylalkylene group, a phenyl group, and a pentafluorophenyl group. , trifluoromethylphenyl group, or pentafluorosulfanylphenyl group are more preferred.
• T in formula (1) is a hydrogen atom, a pentafluorosulfanyl group, a group -SiR 2 3 , an aryl group, a fluoroaryl group, from the viewpoint of ease of manufacturing the compound.
• aryloxy group, fluoroaryloxy group, alkylaryl group, alkylaryloxy group, fluoroalkylaryloxy group, or pentafluorosulfanylaryloxy group are preferred, and hydrogen atom, trimethylsilyl group, triethylsilyl group, phenyloxy group, pentafluorosulfanylaryloxy group are preferable.
• a fluorophenyloxy group, a trifluoromethylphenyloxy group, or a pentafluorosulfanylphenyloxy group is more preferred.
• the monovalent organic group represented by T include organic groups having the following structure.
• the organic group represented by T is not limited to the specific examples below.
• a and b are each independently an integer of 1 to 6, preferably an integer of 1 to 3. Note that a and b may be the same or different.
• Ph is a benzene ring; when Ph is monovalent, it is a phenyl group; when Ph is divalent, it is a phenylene group; and F 5 Ph is a pentafluorophenyl group.
• * is the bond to Z in formula (1).
• Me is a methyl group and Et is an ethyl group.
• m in formula (1) is an integer of 1 to 3, preferably an integer of 1 to 2, and more preferably 1, from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer.
• L 1 in formula (1) is a single bond or a (m+1)-valent linking group, and is bonded to the 9-position of the linking group represented by Tr. That is, L 1 is a single bond or a divalent to tetravalent linking group, and is bonded to the 9-position of the triptycene skeleton. Note that when L 1 is a single bond, m is 1.
• the linking group represented by L 1 includes an alkylene group, a carbonyl group, an ether bond, a thioether bond, a sulfonyl group, -NR 4 -, -N ⁇ , -SiR 4 2 -, >SiR 4 -, >Si ⁇ , etc. can be mentioned.
• R 4 is a hydrogen atom or a hydrocarbon group. Two or more of these linking groups may be used in combination, or two or more types of these linking groups may be used in combination.
• Linking groups that combine two or more of the above linking groups include ester bonds, thioester bonds, amide bonds, sulfonamide bonds, combinations of alkylene groups and arylene groups, combinations of alkylene groups and carbonyl groups, and combinations of alkylene groups and ether bonds.
• the alkylene group that can be included in the linking group represented by L 1 may be linear, branched, or cyclic, and among these, linear or branched is preferable, and linear is preferable. More preferred.
• the number of carbon atoms in the alkylene group is, for example, 1 to 10, preferably 1 to 5, and more preferably 1 to 3.
• the alkylene group may have 1 to 30 carbon atoms, 4 to 20 carbon atoms, or 5 to 15 carbon atoms.
• the linking group represented by L 1 may contain two or more alkylene groups.
• Hydrocarbon groups represented by R 4 of -NR 4 -, -SiR 4 2 -, and >SiR 4 - that can be included in the linking group represented by L 1 include, for example, aliphatic hydrocarbon groups and aromatic group hydrocarbon groups.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.
• the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable, and a methyl group, an ethyl group, an n-propyl group, or an n-propyl group is preferable.
• -butyl group is more preferred, and methyl group is even more preferred.
• the Tr-side terminal of the linking group represented by L 1 is preferably a carbon atom or an oxygen atom, more preferably a carbon atom, and even more preferably an alkylene group or a carbonyl group.
• the Tr-side terminal of the linking group represented by L 1 is -S-CH 2 -* Tr , -O-CH 2 -* Tr , -NH-CH 2 -* Tr , -CH 2 -CH 2 -* Preferred examples include Tr , -S-CO-* Tr , -O-CO-* Tr , -NH-CO-* Tr , and -O-* Tr .
• Tr means a bond to Tr, and the same applies hereinafter.
• Z in formula (1) is a polyoxyfluoroalkylene chain
• the Z-side terminal of the linking group represented by L1 is a group other than a fluoroalkylene group, such as an alkylene group, a carbonyl group, an ether bond, or a thioether A bond is preferred.
• the Z-side terminal of the linking group represented by L 1 is * Z -CH 2 -CH 2 -, * Z -CH 2 -O-, * Z -CH 2 -S-, * Z -O-CH 2 -, * Z -CO-NH-CH 2 -, * Z -CO-O-CH 2 -, * Z -S-CH 2 -, etc.
• * Z means a bond to Z, and the same applies hereinafter.
• the Z-side terminal of the linking group represented by L 1 is preferably an alkylene group.
• the Z-side terminal of the linking group represented by L 1 is * Z -(CH 2 ) a -O-CH 2 -, * Z -( CH 2 ) a -O-(CH 2 ) b -O-CH 2 -, * Z -(CH 2 ) a -O-CO-, * Z -(CH 2 ) a -O-(CH 2 ) b -
• Preferable examples include O--CO- and the like.
• a and b are each independently an integer of 1 to 6, preferably an integer of 1 to 3. Note that a and b may be the same or different.
• the Z-side terminal of the linking group represented by L 1 is a group other than an alkylene group, and is preferably an ether bond.
• preferred examples of the Z-side terminal of the linking group represented by L 1 include * Z -O-CO- and the like.
• the Z-side terminal of the linking group represented by L 1 is a group other than an alkylene group, and is preferably an ether bond.
• preferred examples of the Z-side terminal of the linking group represented by L 1 include * Z -O-CO- and the like.
• linking group represented by L 1 include linking groups having the following structure.
• the linking group represented by L 1 is not limited to the specific examples below.
• a, b, and c are each independently an integer of 1 to 6, preferably an integer of 1 to 3. Note that a, b, and c may be the same or different.
• * Z is the bond to Z and * Tr is the bond to Tr.
• Y 1 is, for example, a group containing an etheric oxygen atom or an alkylene group which may have a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organopolysiloxane.
• g is an integer of 1 or more. In one embodiment, g is preferably from 1 to 15, more preferably from 1 to 6, from the viewpoint of the abrasion resistance and fingerprint removability of the surface treatment layer. In one embodiment, g is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 or 3 from the viewpoint of excellent wear resistance of the surface treatment layer. In one embodiment, g is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1 from the viewpoint of excellent fingerprint removability of the surface treatment layer.
• two or more (-Si(R 1 ) n L 2 3-n ) contained in the compound represented by formula (1) may be the same or different from each other. Good too.
• the Tr-side terminal of the connecting group represented by Y 1 is preferably a carbon atom or an oxygen atom, more preferably a carbon atom, and more preferably an alkylene group or a carbonyl group.
• the Tr side terminal of the linking group represented by Y 1 is * Tr -CH 2 -O-, * Tr -CH 2 -S-, * Tr -CH 2 -CH 2 -, * Tr -CH 2 -NH -, * Tr -CO-S-, * Tr -CO-O-, * Tr -CO-NH-, * Tr -O-, * Tr -O-CO-, etc. are preferably mentioned.
• a combination of the Tr-side end of the linking group represented by L 1 and the Tr-side end of the linking group represented by Y 1 is a combination of -S-CH 2 -* Tr and * Tr -CH 2 -O-. combination, -O-CH 2 -* Tr and * Tr -CH 2 -O-, -NH-CH 2 -* Tr and * Tr -CH 2 -S-, -CH 2 -CH 2 Combination of -* Tr and * Tr -CH 2 -CH 2 -, -S-CO-* Combination of Tr and * Tr -CO-O-, -O-CO-* Tr and * Tr -CO-O combination with -, combination with -NH-CO-* Tr and * Tr -CO-S-, combination with -O-* Tr and * Tr -O-, -CO-O-* Tr and * Tr - Examples include combinations with O--CO-.
• the group represented by -Y 1 (-Si(R 1 ) n L 2 3-n ) g in formula (1) is preferably the group (3-1A) or the group (3-1B), and the group (3- 1A) is more preferred.
• Q a is a single bond or a divalent linking group
• X 31 is a group having a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a 2- to 8-valent organopolysiloxane residue, or a (h+i+1)-valent ring
• Q b is a single bond or a divalent linking group
• R 31 is a hydrogen atom, a hydroxyl group or an alkyl group
• h is an integer of 1 or more
• i is an integer of 0 or more
• the definitions and specific examples of R 1 , L 2 , and n are the same as the definitions and specific examples of each symbol in the reactive silyl group.
• Q c is a single bond or a divalent linking group
• R 32 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• Q d is a single bond or an alkylene group
• R 33 is a hydrogen atom or a halogen atom
• y is an integer from 1 to 10
• the definitions and specific examples of R 1 , L 2 , and n are the same as the definitions and specific examples of each symbol in the reactive silyl group.
• Q a is a single bond or a divalent linking group.
• divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO 2 -, -N(R d )-, -C(O) -, -Si(R a ) 2 -, and a combination of two or more thereof.
• the divalent hydrocarbon group may be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group.
• the divalent saturated hydrocarbon group may be linear, branched, or cyclic, and includes, for example, an alkylene group.
• the divalent saturated hydrocarbon group preferably has 1 to 20 carbon atoms.
• the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, such as a phenylene group.
• the divalent hydrocarbon group may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms.
• the above R a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.
• the above R d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
• Examples of groups combining two or more of the above-mentioned types include -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d )-, - N(R d )C(O)-, -N(R d )C(O)N(R d )-, -N(R d )C(O)O-, -OC(O)N(R d )-, -SO 2 N(R d )-, -N(R d )SO 2 -, -C(O)N(R d )-, an alkylene group having -N(R d )C(O)- an alkylene group having an etheric oxygen atom, an alkylene group having -OC(O)-, an alkylene group having -C(O)O-, an alkylene group having -C(O)S-, - Examples include an alky
• Q a is a single bond, -O-, -S-, -N(R d )-, -C(O)N(R d )-, -OC(O)N(R d ) -, -C(O)O-, -OC(O)-, and -C(O)S-, an alkylene group having an etheric oxygen atom, an alkylene group having a thioether bond, and an alkylene group are preferred, and single bonds, -O-, -C(O)O-, -C(O)S-, alkylene group -O-, alkylene group -S-, alkylene group, and -OC(O)- are more preferred.
• X 31 is a group having a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a 2- to 8-valent organopolysiloxane residue, or a (h+i+1)-valent ring.
• the alkylene group may have -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group.
• the alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
• the alkylene group represented by X 31 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
• Examples of the divalent to octavalent organopolysiloxane residues include divalent organopolysiloxane residues and (w2+1)-valent organopolysiloxane residues described below.
• the ring is a ring other than an organopolysiloxane ring.
• the ring in X 31 means a ring other than an organopolysiloxane ring.
• the ring in X 31 may be a monocyclic ring, a fused polycyclic ring, a bridged ring, a spiro ring, or an assembled polycyclic ring, and the atoms constituting the ring may be a carbocyclic ring consisting only of carbon atoms, or a divalent ring.
• a heterocycle consisting of a heteroatom having the above valence and a carbon atom may also be used.
• the bond between atoms constituting the ring may be a single bond or a multiple bond.
• the ring may be an aromatic ring or a non-aromatic ring.
• the monocyclic ring is preferably a 4- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring.
• the fused polycyclic ring is preferably a fused polycyclic ring in which two or more 4- to 8-membered rings are fused together, and fused polycyclic rings in which 2 or 3 rings selected from 5-membered rings and 6-membered rings are bonded together; A fused polycyclic ring in which one or two rings selected from membered rings and six-membered rings and one four-membered ring are bonded is more preferred.
• the bridged ring is preferably a bridged ring whose largest ring is a 5- or 6-membered ring
• the spiro ring is preferably a spiro ring consisting of two 4- to 6-membered rings.
• a collective polycyclic ring two or three rings selected from 5-membered rings and 6-membered rings are bonded via a single bond, 1 to 3 carbon atoms, or 1 heteroatom with a valence of 2 or 3.
• a set of polycyclic rings is preferred.
• the hetero atoms constituting the ring are preferably nitrogen atoms, oxygen atoms, and sulfur atoms, and more preferably nitrogen atoms and oxygen atoms.
• the number of heteroatoms constituting the ring is preferably 3 or less. Furthermore, when the number of heteroatoms constituting the ring is two or more, these heteroatoms may be the same or different.
• a heterocycle of a membered ring a condensed ring in which two or three of these rings are fused together, a bridged ring in which the largest ring is a 5- or 6-membered ring, and two or more of these rings
• One type selected from the group consisting of a single bond, an alkylene group having 3 or less carbon atoms, an oxygen atom, or a sulfur atom as a linking group is preferable.
• Preferred rings include a benzene ring, a 5- or 6-membered aliphatic ring, a 5- or 6-membered heterocycle having a nitrogen atom or an oxygen atom, and a 5- or 6-membered carbon ring and a 4- to 6-membered heterocycle.
• rings include the rings shown below, 1,3-cyclohexadiene ring, 1,4-cyclohexadiene ring, anthracene ring, cyclopropane ring, decahydronaphthalene ring, norbornene ring, norbornadiene ring, furan ring, Examples include a pyrrole ring, a thiophene ring, a pyrazine ring, a morpholine ring, an aziridine ring, an isoquinoline ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, a pyran ring, a pyridazine ring, a pyrimidine ring, and an indene ring.
• Q a and Q b are bonded to different ring constituent atoms.
• Each of the i R 31s may be bonded to a separate ring atom, or two of the i R 31s may be bonded to one ring carbon atom. There may be two or more ring-constituting carbon atoms to which two R 31s are bonded.
• X 31 is a group having a carbon atom, a nitrogen atom, a silicon atom, a 4- to 8-valent organopolysiloxane residue, or a (h+i+1)-valent ring, from the viewpoint of improving the abrasion resistance of the surface treatment layer. is preferable, and carbon atom is more preferable.
• Q b is a single bond or a divalent linking group.
• divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO 2 -, -N(R d )-, -C(O) -, -Si(R a ) 2 -, and a combination of two or more thereof.
• the divalent hydrocarbon group may be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group.
• the divalent saturated hydrocarbon group may be linear, branched, or cyclic, and includes, for example, an alkylene group.
• the number of carbon atoms in the divalent saturated hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and examples thereof include 2, 3, 8, 9, and 11.
• the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, such as a phenylene group.
• the divalent hydrocarbon group may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms.
• the above R a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.
• the above R d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
• Examples of groups combining two or more of the above include -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d )- , -N(R d )C(O)-, -N(R d )C(O)N(R d )-, -N(R d )C(O)O-, -OC(O)N( R d )-, -SO 2 N(R d )-, -N(R d )SO 2 -, -C(O)N(R d )-, -N(R d )C(O )-, an alkylene group having an etheric oxygen atom, an alkylene group having -OC(O)-, an alkylene group having -C(O)O-, a -C(O)S-alkylene group, - Examples include an alkylene group having SO 2 N(R
• Q c is a single bond, -O-, -S-, -N(R d )-, -C(O)N(R d )-, -OC(O)N(R d ) -, -C(O)O-, -OC(O)-, and -C(O)S- are preferred, and single bonds, -OC(O)N(R d )-, and -OC(O)- is more preferable.
• R 31 is a hydrogen atom, a hydroxyl group or an alkyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
• h is an integer greater than or equal to 1
• i is an integer greater than or equal to 0.
• X 31 is a single bond or an alkylene group
• h is 1 and i is 0.
• X 31 is a nitrogen atom
• h is an integer of 1 to 2
• i is an integer of 0 to 1
• X 31 is a carbon atom or a silicon atom
• h is an integer of 1 to 3
• i is an integer of 0 to 2
• X 31 is a divalent to octavalent organopolysiloxane residue
• h is an integer of 1 to 7
• i is an integer of 0 to 6
• X 31 is a group having a (h+i+1)-valent ring
• h is an integer of 1 to 7
• i is an integer of 0 to 6
• two or more (-Q b -Si(R 1 ) n L 2 3-n ) are the same. It may be different or different.
• two or more (-R 31 )s may be the same or different.
• i is preferably 0 from the viewpoint of improving the wear resistance of the surface treatment layer.
• Q c is a single bond or a divalent linking group.
• the definition and details of the divalent linking group are the same as those explained in Q a above.
• R 32 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.
• the alkyl group a methyl group is preferred.
• Q d is a single bond or an alkylene group.
• the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. From the viewpoint of easy production of the compound, Q d is preferably a single bond or -CH 2 -.
• R 33 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.
• y is an integer from 1 to 10, preferably from 1 to 6.
• Two or more [CH 2 C(R 32 )(-Q d -Si(R) n L 3-n )] may be the same or different.
• groups (3-1A-1) to (3-1A-7) are preferable.
• X 32 is -O-, -C(O)O-, -SO 2 N(R d )-, -N(R d )SO 2 -, -N(R d ) C(O)-, -C(O)N(R d )-, -OC(O)-, -OC(O)N(R d )-, -S-, -C(O)S- , or -N(R d )- (wherein N in the formula is bonded to Q b1 ).
• the definition of R d is as described above. s1 is 0 or 1.
• Q b1 is an alkylene group.
• the alkylene group may have -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group.
• the alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
• alkylene group has -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group
• Q b1 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms.
• (X 32 ) s1 is -C(O)N(R d )-, it is preferably an alkylene group having 2 to 6 carbon atoms (however, N in the formula is bonded to Q b1 ).
• Q b1 is one of these groups, the compound can be easily produced.
• group (3-1A-1) include the following groups.
• * represents the bonding position with the triptycene skeleton.
• X 33 is -O-, -NH-, -C(O)O-, -SO 2 N(R d )-, -N(R d )SO 2 -, -N(R d )C(O)- or -C(O)N(R d )-.
• R d is as described above.
• Q a2 is a single bond, an alkylene group, -C(O)-, or an etheric oxygen atom, -C(O)-, -C(O) between carbon atoms of an alkylene group having 2 or more carbon atoms.
• the alkylene group represented by Q a2 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• Ether oxygen atom -C(O)-, -C(O)O-, -OC(O)-, -C between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q a2 (O)N(R d )-, -N(R d )C(O)-, -N(R d )C(O)N(R d )-, -N(R d )C(O)O -, -OC(O)N(R d )-, -SO 2 N(R d )-, -N(R d )SO 2 -, -C(O)N(R d )-, or -NH-
• the number of carbon atoms in the group having is preferably 2 to 10, more preferably 2 to 6.
• Q a2 is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 - , -CH 2 NHCH 2 CH 2 - from the viewpoint of easy production of the compound.
• -CH 2 OC(O)CH 2 CH 2 -, or -C(O)- are preferred.
• s2 is 0 or 1. From the viewpoint of easy production of the compound, 0 is preferable.
• Q b2 is an alkylene group or a group having a divalent organopolysiloxane residue, an ether oxygen atom, or -NH- between carbon atoms of an alkylene group having 2 or more carbon atoms.
• the number of carbon atoms in the alkylene group represented by Q b2 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
• the number of carbon atoms in the group having a divalent organopolysiloxane residue, ether oxygen atom or -NH- between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q b2 is 2 to 10. is preferable, and 2 to 6 are more preferable.
• the two [-Q b2 -Si(R 1 ) n L 2 3-n ] may be the same or different.
• group (3-1A-2) include the following groups.
• * represents the bonding position with the triptycene skeleton.
• ⁇ in (CH 2 ) ⁇ bonded to the reactive silyl group is an integer representing the number of methylene groups, preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, It may be from 2 to 10, or from 2 to 6. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
• a plurality of ⁇ 's contained in the same compound may be the same or different, but are preferably the same. For example, all of the plurality of ⁇ s contained in the same compound are 2, 3, 8, 9, and 11. The same applies below.
• Q a3 is a single bond or an alkylene group which may have an etheric oxygen atom, and a single bond is preferred from the viewpoint of ease of manufacturing the compound.
• the alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.
• R g is a hydrogen atom, a hydroxyl group, or an alkyl group. From the viewpoint of easy production of the compound, R g is preferably a hydrogen atom or an alkyl group.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably a methyl group.
• Q b3 is an alkylene group or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
• the number of carbon atoms in the alkylene group represented by Q b3 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
• the carbon number of the group having an ether oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms, represented by Q b3 is preferably 2 to 20, and 2 to 20. 10 is more preferable, and 2 to 6 is even more preferable.
• Q b3 is preferably -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, or -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 - from the viewpoint of easy production of the compound.
• the two [-Q b3 -Si(R 1 ) n L 2 3-n ] may be the same or different.
• group (3-1A-3) include the following groups.
• * represents the bonding position with the triptycene skeleton.
• Q e is -C(O)O-, -SO 2 N(R d )-, -N(R d )SO 2 -, -N(R d )C( O)- or -C(O)N(R d )-.
• R 31 is as described above.
• s4 is 0 or 1.
• Q a4 is a single bond or an alkylene group which may have an ether oxygen atom.
• the alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• t4 is 0 or 1 (however, when Q a4 is a single bond, it is 0).
• -Q a4 -(O) t4 - is a single bond, -CH 2 O-, -CH 2 OCH 2 -, -CH 2 OCH 2 CH 2 when s4 is 0, from the viewpoint of easy production of the compound.
• O-, -CH 2 OCH 2 CH 2 OCH 2 -, -CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 - are preferred (however, the left side is bonded to the triptycene skeleton), and when s4 is 1, A single bond, -CH 2 -, and -CH 2 CH 2 - are preferred.
• Q b4 is an alkylene group, and the alkylene group is -O-, -C(O)N(R d )- (the definition of R d is as described above), a silphenylene skeleton group, a divalent It may or may not have an organopolysiloxane residue or a dialkylsilylene group.
• the alkylene group has -O- or a silphenylene skeleton group, it is preferable to have -O- or a silphenylene skeleton group between carbon atoms.
• the terminal between carbon atoms or the side bonded to (O) u4 preferably has these groups.
• the number of carbon atoms in the alkylene group represented by Q b4 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the range may be from 1 to 10.
• u4 is 0 or 1.
• -(O) u4 -Q b4 - includes -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 CH 2 -, -CH 2 from the viewpoint of easy production of the compound.
• OCH 2 CH 2 CH 2 CH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -, -OSi(CH 3 ) 2 OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -- and --CH 2 CH 2 CH 2 Si(CH 3 ) 2 PhSi(CH 3 ) 2 CH 2 CH 2 -- are preferred (however, the right side is bonded to Si).
• w1 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0. If there are two or more [-(O) u4 -Q b4 -Si(R 1 ) n L 2 3-n ], two or more [-(O) u4 -Q b4 -Si(R 1 ) n L 2 3-n ] may be the same or different. When there are two or more R 31 s, two or more (-R 31 )s may be the same or different.
• group (3-1A-4) include the following groups.
• * represents the bonding position with the triptycene skeleton.
• Q a5 is an alkylene group which may have an ether oxygen atom.
• the alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.
• Q a5 is -CH 2 OCH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, -CH 2 CH 2 - , -CH 2 CH 2 from the viewpoint of easy production of the compound. 2 CH 2 - is preferred (provided that the right side is bonded to Si).
• Q b5 is an alkylene group or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
• the number of carbon atoms in the alkylene group represented by Q b5 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
• the carbon number of the group having an ether oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q b5 is preferably 2 to 20, and 2 to 20. 10 is more preferable, and 2 to 6 is even more preferable.
• Q b5 is preferably -CH 2 CH 2 CH 2 - and -CH 2 CH 2 OCH 2 CH 2 CH 2 - (provided that the right side is Si(R 1 ) n L 2 3-n .).
• the three [-Q b5 -Si(R 1 ) n L 2 3-n ] may be the same or different.
• group (3-1A-5) include the following groups.
• * represents the bonding position with the triptycene skeleton.
• Q a6 is an alkylene group which may have an etheric oxygen atom.
• the alkylene group which may have an etheric oxygen atom preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms.
• Q a6 is -CH 2 OCH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, -CH 2 CH 2 - , -CH 2 CH 2 from the viewpoint of easy production of the compound. 2 CH 2 - is preferred (provided that the right side is bonded to Z a ).
• Z a is a (w2+1)-valent organopolysiloxane residue or a (w2+1)-valent group having an alkylene group between the organopolysiloxane residues.
• w2 is an integer from 2 to 7.
• Examples of (w2+1)-valent organopolysiloxane residues and (w2+1)-valent groups having an alkylene group between organopolysiloxane residues include the following groups: .
• R a in the following formula is as described above.
• Q b6 is an alkylene group or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
• the number of carbon atoms in the alkylene group represented by Q b6 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
• the carbon number of the group having an ether oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q b6 is preferably 2 to 20, and 2 to 20. 10 is more preferable, and 2 to 6 is even more preferable.
• Q b6 -CH 2 CH 2 - and -CH 2 CH 2 CH 2 - are preferable from the viewpoint of easy production of the compound.
• w2 [-Q b6 -Si(R 1 ) n3 L 2 3-n ] may be the same or different.
• group (3-1A-6) include the following groups.
• * represents the bonding position with the triptycene skeleton.
• Z c is a (w3+w4+1)-valent hydrocarbon group.
• w3 is an integer of 4 or more.
• w4 is an integer greater than or equal to 0.
• the definitions and preferred ranges of Q e , s4, Q a4 , t4, Q b4 , and u4 are the same as the definitions of each symbol in group (3-1A-4).
• Z c may consist of a hydrocarbon chain, may have an ether oxygen atom between carbon atoms of the hydrocarbon chain, and is preferably composed of a hydrocarbon chain.
• the valence of Z c is preferably 5 to 20, more preferably 5 to 10, even more preferably 5 to 8, particularly preferably penta or hexavalent.
• the number of carbon atoms in Z c is preferably 3 to 50, more preferably 4 to 40, even more preferably 5 to 30.
• w3 is preferably 4 to 20, more preferably 4 to 16, even more preferably 4 to 8, and particularly preferably 4 or 5.
• w4 is preferably 0 to 10, more preferably 0 to 8, even more preferably 0 to 6, particularly preferably 0 to 3, and most preferably 0 or 1.
• two or more [-(O-Q b4 ) u4 -Si(R 1 ) n L 2 3-n ] may be the same or different.
• group (3-1A-7) include the following groups.
• * represents the bonding position with the triptycene skeleton.
• the A 1 side is bonded to the triptycene skeleton, and the Q 22 , Q 23 , Q 24 , Q 25 or Q 26 side is (-Si(R 1 ) n L 2 3-n ).
• a 1 is a single bond, -C(O)NR 6 -, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -NHC( O)O-, -NHC(O)NR 6 -, -O- or SO 2 NR 6 -.
• Q 11 is a single bond, -O-, an alkylene group, or a bond between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR 6 -, -C(O)-, -NR 6 -, or It is a group having -O-.
• Q 12 is a single bond, an alkylene group, or a bond between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR 6 -, -C(O)-, -NR 6 -, -S-, Or a group having -O-.
• Q 13 is a single bond (A 1 is -C(O)-), an alkylene group, or -C(O)NR 6 -, - between carbon atoms of an alkylene group having 2 or more carbon atoms.
• Q 14 is Q 12 when the atom in Z 1 to which Q 14 is bonded is a carbon atom, and is Q 13 when the atom in Z 1 to which Q 14 is bonded is a nitrogen atom.
• Q 15 is an alkylene group, or -C(O)NR 6 -, -C(O)-, -NR 6 -, -S-, or -O between carbon atoms of an alkylene group having 2 or more carbon atoms. It is a group having -.
• Q 22 is an alkylene group, a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms, an alkylene group A group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- at the end not bonded to Si, or between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR 6 -, -C(O)-, -NR 6 - or O- and -C(O)NR 6 -, -C(O) at the end that does not bond to Si It is a group having -, -NR 6 - or O-, and when Y 1 has two or more Q 22s , two or more Q 22s may be the same or different.
• Q 23 is an alkylene group or a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms; , two Q23s may be the same or different.
• Q 24 is Q 22 when the atom in Z 1 to which Q 24 is bonded is a carbon atom, and Q 23 when the atom in Z 1 to which Q 24 is bonded is a nitrogen atom; When there are two or more, two or more Q24 may be the same or different.
• Q 25 is an alkylene group or a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms; , Y 1 has two or more Q 25s , the two or more Q 25s may be the same or different.
• Q 26 is a single bond, an alkylene group, or a bond between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR 6 -, -C(O)-, -NR 6 -, -S-, Or a group having -O-.
• Z 1 is a group having an h1+h2 valent ring structure in which Q 14 has a carbon atom or nitrogen atom to which Q 14 is directly bonded, and Q 24 has a carbon atom or nitrogen atom to which Q 24 is directly bonded.
• R e1 is a hydrogen atom or an alkyl group, and when Y 1 has two or more R e1s , the two or more R e1s may be the same or different.
• R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group.
• R e3 is an alkyl group.
• R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• d1 is an integer from 0 to 1.
• d2 is an integer from 0 to 3, preferably 1 or 2.
• d1+d2 is an integer from 1 to 3.
• d3 is an integer from 0 to 1.
• d4 is an integer from 0 to 3, preferably 2 or 3.
• d3+d4 is an integer from 1 to 3.
• d1+d3 is 1.
• d2+d4 is an integer from 1 to 5, preferably 4 or 5.
• e1+e2 is 3 or 4.
• e1 is 1.
• e2 is an integer from 1 to 3, preferably 2 or 3.
• h1 is 1.
• h2 is an integer of 1 or more, preferably 2 or 3.
• i1+i2 is 3 or 4.
• i1 is 1.
• i2 is an integer from 1 to 3, preferably 2 or 3. i3 is 2 or 3.
• the number of carbon atoms in the alkylene groups of Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 22 , Q 23 , Q 24 , Q 25 and Q 26 is determined from the viewpoint of ease of manufacturing the compound and the durability of the surface treatment layer. From the viewpoint of better abrasion resistance, the number is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10, 1 to 6, or 1 to 4. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
• Examples of the ring structure in Z 1 include the ring structures described above, and preferred forms are also the same.
• Q 14 and Q 24 are directly bonded to the ring structure in Z 1 , for example, an alkylene group is not connected to the ring structure and Q 14 or Q 24 is not connected to the alkylene group.
• the number of carbon atoms in the alkyl group of R e1 , R e2 or R e3 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the compound.
• the number of carbon atoms in the alkyl group portion of the acyloxy group of R e2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the compound.
• h2 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of ease of manufacturing the compound and superior wear resistance of the surface treatment layer.
• the A 1 side is bonded to the triptycene skeleton, and the G 1 side is bonded to (-Si(R 1 ) n L 2 3-n ).
• G 1 is a group (g3), and two or more G 1s in Y 1 may be the same or different.
• the symbols other than G 1 are the same as those in equations (g2-1) to (g2-7).
• R 8 is an alkyl group.
• Q 3 is an alkylene group, a group having -C(O)NR 6 -, -C(O)-, -NR 6 - or -O- between carbon atoms of an alkylene group having 2 or more carbon atoms, or (OSi(R 9 ) 2 ) p -O-, and two or more Q 3 may be the same or different.
• R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• R 9 is an alkyl group, a phenyl group, or an alkoxy group, and two R 9s may be the same or different.
• p is an integer from 0 to 5, and when p is 2 or more, two or more (OSi(R 9 ) 2 ) may be the same or different.
• the number of carbon atoms in the alkylene group of Q3 is preferably 1 to 30, more preferably 1 to 20, and still more preferably 2 to 20, from the viewpoint of easy production of the compound and superior wear resistance of the surface treatment layer. Preferably, it may be from 2 to 10, or from 2 to 6. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10, 1 to 6, or 1 to 4. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
• the number of carbon atoms in the alkyl group of R 8 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the compound.
• the number of carbon atoms in the alkyl group of R 9 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the compound.
• the number of carbon atoms in the alkoxy group of R 9 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of excellent storage stability of the compound.
• p is preferably 0 or 1.
• Examples of the compound (1) include compounds of the following formula.
• the compound of the following formula is preferred from the viewpoints of easy industrial production, ease of handling, and superior abrasion resistance of the surface treatment layer.
• R t in the compound of the following formula is the same as (TZ) m -L 1 -Tr- in the above-mentioned formula (1), and the preferred form is also the same.
• Examples of the compound (1) in which Y 1 is a group (g2-1) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-2) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-3) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-4) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-5) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-6) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-7) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-8) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-9) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-10) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-11) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-12) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-13) include compounds of the following formula.
• Examples of the compound (1) in which Y 1 is a group (g2-14) include compounds of the following formula.
• Examples of the compounds of the present disclosure include the following compounds.
• X1 is an integer of 2 to 30
• X2 is an integer of 2 to 100
• X3 is an integer of 2 to 100.
• all of the compounds shown below are compounds in which a reactive silyl group is bonded to one of the 9th and 10th positions of the triptycene skeleton, and a hydrophobic partial structure is bonded to the other.
• the number average molecular weight (Mn) of the compound of the present disclosure is preferably 400 to 20,000, more preferably 500 to 18,000, and even more preferably 600 to 15,000.
• Mn is 400 or more
• water repellency and abrasion resistance are excellent.
• Mn is 20,000 or less
• the viscosity can be easily controlled within an appropriate range, and solubility is improved, resulting in excellent handling properties during film formation.
• Method for producing compound The method for producing the compound of the present disclosure is not particularly limited. Examples of synthetic schemes for compounds of the present disclosure are shown below.
• compositions of the present disclosure only needs to contain the compound of the present disclosure, and components other than the compound of the present disclosure are not particularly limited.
• Compositions of the present disclosure preferably include a compound of the present disclosure and a liquid medium.
• the composition of the present disclosure may be in a liquid state, and may be a solution or a dispersion.
• the composition of the present disclosure only needs to contain the compound of the present disclosure, and may contain impurities such as by-products generated in the manufacturing process of the compound of the present disclosure.
• the composition of the present disclosure may contain one type of compound of the present disclosure, or may contain two or more types of compounds of the present disclosure.
• the content of the compound of the present disclosure is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and further preferably 0.1 to 10% by mass, based on the total amount of the composition of the present disclosure. preferable.
• the content of the compound of the present disclosure may be 0.01 to 10% by mass, based on the total amount of the composition of the present disclosure, and 0. It may be 0.02 to 5% by weight, 0.03 to 3% by weight, or 0.05 to 2% by weight.
• the liquid medium is preferably an organic solvent.
• organic solvent examples include fluorine-based organic solvents and non-fluorine-based organic solvents. Fluorine-based organic solvents are preferably used when the compound of the present disclosure contains a polyoxyfluoroalkylene chain as a hydrophobic moiety. Specific examples of fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
• the fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, such as C 6 F 13 H (AC-2000: product name, manufactured by AGC Corporation), C 6 F 13 C 2 H 5 (AC-6000: product name) , manufactured by AGC), and C 2 F 5 CHFCHFCF 3 (Battrell: product name, manufactured by DuPont).
• fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene.
• the fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, such as CF 3 CH 2 OCF 2 CF 2 H (AE-3000: product name, manufactured by AGC), C 4 F 9 OCH 3 (Novec-7100: Product name, manufactured by 3M Company), C 4 F 9 OC 2 H 5 (Novec-7200: Product name, manufactured by 3M Company), C 2 F 5 CF (OCH 3 ) C 3 F 7 (Novec-7300: Product name, (manufactured by 3M).
• Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
• fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
• non-fluorine-based organic solvents include compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms, and specifically, hydrocarbon-based organic solvents, ketone-based organic solvents, etc.
• examples include solvents, ether organic solvents, ester organic solvents, glycol organic solvents, and alcohol organic solvents.
• hydrocarbon organic solvents include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, bicyclohexyl, benzene, toluene, ethylbenzene, o-xylene, m-xylene, Examples include p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.
• ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and 3,5,5-trimethyl-2-cyclohexen-1-one. Examples include 3,5-trimethylcyclohexanone and isophorone.
• ether organic solvents include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.
• ester organic solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl ethylene glycol lactate.
• glycol-based organic solvents include ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, and ethylene glycol mono-2.
• alcoholic organic solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3 -Butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4 -Methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol , 3-methoxybutanol, cyclo
• non-fluorine organic solvents include halogen organic solvents having halogen atoms other than fluorine, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds.
• halogen-based organic solvents having halogen atoms other than fluorine include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, 1 , 2,3-trichloropropane.
• nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
• sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.
• siloxane compound include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.
• the content of the liquid medium is preferably 60 to 99.999% by mass, more preferably 80 to 99.99% by mass, and even more preferably 90 to 99.9% by mass, based on the total amount of the composition of the present disclosure.
• the content of the liquid medium may be 90-99.99% by weight, 95-99% by weight, based on the total amount of the composition of the present disclosure. It may be .98% by mass, 97 to 99.97% by mass, or 98 to 99.95% by mass.
• the composition of the present disclosure may contain only one type of liquid medium, or may contain two or more types.
• composition of the present disclosure may contain other components in addition to the compound of the present disclosure and the liquid medium, as long as the effects of the present disclosure are not impaired.
• other components include known additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reactions of reactive silyl groups.
• a metal compound having a hydrolyzable group is also referred to as a "specific metal compound”
• Specific metal compounds include the following formulas (M1) to (M3).
• M represents a trivalent or tetravalent metal atom.
• Each of X b1 independently represents a hydrolyzable group.
• Each of X b2 independently represents a siloxane skeleton-containing group.
• Each of X b3 independently represents a hydrocarbon chain-containing group.
• m1 is an integer from 2 to 4
• m2 and m3 are each independently an integer of 0 to 2
• When M is a trivalent metal atom, m1+m2+m3 is 3, and when M is a tetravalent metal atom, m1+m2+m3 is 4.
• X b4 represents a hydrolyzable silane oligomer residue.
• Each of X b5 independently represents a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms.
• X b6 and X b7 each independently represent a hydrolyzable group or a hydroxyl group.
• Y b1 represents a divalent organic group.
• the metal represented by M also includes semimetals such as Si and Ge.
• M is preferably a trivalent metal or a tetravalent metal, more preferably Al, Fe, In, Hf, Si, Ti, Sn, and Zr, even more preferably Al, Si, Ti, and Zr, and particularly preferably Si. .
• the hydrolyzable group represented by X b1 is the hydrolyzable group represented by L 2 in (-Si(R 1 ) n L 2 3-n ) in the above reactive silyl group. The same can be mentioned.
• the siloxane skeleton-containing group represented by X b2 has a siloxane unit (-Si-O-) and may be linear or branched.
• the siloxane unit is preferably a dialkylsilyloxy group, such as a dimethylsilyloxy group or a diethylsilyloxy group.
• the number of repeating siloxane units in the siloxane skeleton-containing group is 1 or more, preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.
• the siloxane skeleton-containing group may include a divalent hydrocarbon group in a part of the siloxane skeleton.
• some oxygen atoms in the siloxane skeleton may be replaced with divalent hydrocarbon groups.
• the divalent hydrocarbon group include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group.
• a hydrolyzable group, a hydrocarbon group (preferably an alkyl group), etc. may be bonded to the terminal silicon atom of the siloxane skeleton-containing group.
• the number of elements in the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. The number of elements is preferably 10 or more.
• the siloxane skeleton-containing group is preferably a group represented by * -(O-Si(CH 3 ) 2 ) n CH 3 , where n is an integer from 1 to 5, and * represents a bond with an adjacent atom. Represents a part.
• the hydrocarbon chain-containing group represented by X b3 may be a group consisting only of a hydrocarbon chain, or may be a group having an etheric oxygen atom between carbon atoms of the hydrocarbon chain.
• the hydrocarbon chain may be straight or branched, preferably straight.
• the hydrocarbon chain may be a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, with a saturated hydrocarbon chain being preferred.
• the number of carbon atoms in the hydrocarbon chain-containing group is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• the hydrocarbon chain-containing group is preferably an alkyl group, more preferably a methyl group, an ethyl group, or a propyl group.
• m1 is 3 or 4.
• compound represented by formula (M1) compounds represented by the following formulas (M1-1) to (M1-5) where M is Si are preferable, and the compound represented by formula (M1-1) is More preferred.
• compound represented by formula (M1-1) tetraethoxysilane, tetramethoxysilane, and triethoxymethylsilane are preferred.
• the number of silicon atoms contained in the hydrolyzable silane oligomer residue represented by X b4 is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more.
• the number of silicon atoms is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.
• the hydrolyzable silane oligomer residue may have an alkoxy group bonded to a silicon atom. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and methoxy group and ethoxy group are preferred.
• the hydrolyzable silane oligomer residue may have one or more types of these alkoxy groups, and preferably has one type. Examples of the hydrolyzable silane oligomer residue include (C 2 H 5 O) 3 Si-(OSi(OC 2 H 5 ) 2 ) 4 O- * and the like.
• * represents a bonding site with an adjacent atom.
• the hydrolyzable group represented by X b5 is the hydrolyzable group represented by L 2 in (-Si(R 1 ) n L 2 3-n ) in the above reactive silyl group.
• Examples include those similar to , a cyano group, a hydrogen atom, and an allyl group, with an alkoxy group or an isocyanato group being preferred.
• the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
• X b5 a hydrolyzable group is preferable.
• Examples of the compound represented by formula (M2) include (H 5 C 2 O) 3 -Si-(OSi(OC 2 H 5 ) 2 ) 4 OC 2 H 5 and the like.
• the compound represented by formula (M3) is a compound having a reactive silyl group at both ends of a divalent organic group, that is, bissilane.
• the hydrolyzable groups represented by X b6 and X b7 include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanato group, and a halogen atom.
• an alkoxy group and an isocyanato group are preferred.
• the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group.
• X b6 and X b7 may be the same group or different groups. From the viewpoint of availability, it is preferable that X b6 and X b7 are the same group.
• Y b1 is a divalent organic group that connects the reactive silyl groups at both ends.
• the number of carbon atoms in Y b1 of the divalent organic group is preferably 1 to 8, more preferably 1 to 3.
• Examples of Y b1 include an alkylene group, a phenylene group, and an alkylene group having an etheric oxygen atom between carbon atoms.
• Examples of the compound represented by formula (M3) include (CH 3 O) 3 Si(CH 2 ) 2 Si(OCH 3 ) 3 , (C 2 H 5 O) 3 Si(CH 2 ) 2 Si(OC 2 H 5 ) 3 , (OCN) 3Si ( CH2 ) 2Si ( NCO ) 3 , Cl3Si( CH2 ) 2SiCl3 , ( CH3O ) 3Si ( CH2 ) 6Si ( OCH3 ) 3 , ( C2H5O ) 3Si ( CH2 ) 6Si ( OC2H5 ) 3 is mentioned.
• the content of other components that may be included in the composition of the present disclosure is preferably 10% by mass or less, more preferably 1% by mass or less, based on the total amount of the composition of the present disclosure.
• the content of the specific metal compound is preferably 0.01 to 30% by mass, more preferably 0.01 to 10% by mass based on the total amount of the composition of the present disclosure. , more preferably 0.05 to 5% by mass.
• the total content of the compound of the present disclosure and other components is preferably 0.001 to 40% by mass, and 0.01% by mass, based on the total amount of the composition of the present disclosure. ⁇ 20% by mass is more preferred, and 0.1 ⁇ 10% by mass is even more preferred.
• the solid content concentration of the composition of the present disclosure is a value calculated from the mass of the composition before heating and the mass after heating in a convection dryer at 120° C. for 4 hours.
• composition of the present disclosure contains a liquid medium, it is useful for coating purposes and can be used as a coating liquid.
• the surface treatment agent of the present disclosure comprises a compound of the present disclosure.
• the surface treatment agent of the present disclosure may include the compound of the present disclosure and a liquid medium.
• the surface treating agent of the present disclosure may be a composition of the present disclosure. Preferred embodiments of the liquid medium contained in the surface treatment agent are the same as those of the liquid medium contained in the composition of the present disclosure.
• a surface treatment layer with excellent water repellency and abrasion resistance can be formed by using a surface treatment agent containing the compound of the present disclosure.
• the article of the present disclosure includes a base material and a surface treatment layer surface treated with the surface treatment agent.
• the surface treatment layer may be formed on a part of the surface of the base material, or may be formed on the entire surface of the base material.
• the surface treatment layer may be spread over the surface of the base material in the form of a film, or may be scattered in the form of dots.
• the compound of the present disclosure is contained in a state in which hydrolysis of some or all of the reactive silyl groups has proceeded, and a dehydration condensation reaction of the silanol groups has proceeded.
• the thickness of the surface treatment layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the thickness of the surface treatment layer is 1 nm or more, the effect of the surface treatment is likely to be sufficiently obtained. If the thickness of the surface treatment layer is 100 nm or less, the utilization efficiency is high.
• the thickness of the surface treatment layer is determined by using an X-ray diffractometer for thin film analysis (product name "ATX-G", manufactured by RIGAKU) to obtain an interference pattern of reflected X-rays by the X-ray reflectance method. It can be calculated from the vibration period of
• the type of base material is not particularly limited, and includes, for example, base materials that are required to have water repellency.
• a base material for example, a base material that may be used in contact with another article (e.g., a stylus) or a person's fingers; a base material that may be held by a person's fingers during operation; , a mounting table).
• the base material include metal, resin, glass, sapphire, ceramic, stone, fiber, nonwoven fabric, paper, wood, natural leather, artificial leather, and composite materials thereof.
• the glass may be chemically strengthened.
• Base materials include building materials, decorative building materials, interior goods, transportation equipment (e.g. cars), signboards, bulletin boards, drinking vessels and tableware, aquariums, ornamental equipment (e.g. frames, boxes), laboratory equipment, furniture, and textile products.
• Packaging containers Glass or resin used for art, sports, games, etc.; Used for the exterior parts (excluding display parts) of devices such as mobile phones (e.g. smartphones), personal digital assistants, game consoles, remote controls, etc. Examples include glass or resin.
• the shape of the base material may be plate-like or film-like.
• touch panel base materials As the base material, touch panel base materials, display base materials, and eyeglass lenses are suitable, and touch panel base materials are particularly suitable.
• touch panel base materials As the material for the touch panel base material, glass or transparent resin is preferable.
• the base material may be a base material that has been subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc. on one surface or both surfaces.
• a surface-treated base material has better adhesion with the surface-treated layer, and the abrasion resistance of the surface-treated layer is further improved. Therefore, it is preferable to perform surface treatment on the surface of the base material that is in contact with the surface treatment layer.
• the surface-treated base material is provided with a base layer, which will be described later, the adhesion with the base layer is better, and the wear resistance of the surface-treated layer is further improved. Therefore, when a base layer is provided, it is preferable to perform a surface treatment on the surface of the base material that is in contact with the base layer.
• the surface treatment layer may be provided directly on the surface of the base material, or a base layer may be provided between the base material and the surface treatment layer.
• the article of the present disclosure includes a base material, a base layer disposed on the base material, and a surface treatment of the present disclosure disposed on the base layer. It is preferable to include a surface treatment layer whose surface is treated with an agent.
• the base layer includes silicon and at least one selected from the group consisting of a group 1 element, a group 2 element, a group 4 element, a group 5 element, a group 13 element, and a group 15 element of the periodic table.
• a layer containing an oxide containing a specific element is preferable.
• Group 1 elements of the periodic table mean lithium, sodium, potassium, rubidium, and cesium.
• Group 1 elements lithium, sodium, and potassium are used because they enable the surface treatment layer to be formed more uniformly on the underlayer without defects, and from the viewpoint of suppressing variations in the composition of the underlayer between samples.
• the underlayer may contain two or more types of Group 1 elements.
• Group 2 elements of the periodic table mean beryllium, magnesium, calcium, strontium, and barium.
• Group 2 elements magnesium, calcium, and barium are used because they enable the surface treatment layer to be formed more uniformly on the underlayer without defects, and from the viewpoint of suppressing variations in the composition of the underlayer between samples.
• magnesium and calcium are more preferable.
• the underlayer may contain two or more types of Group 2 elements.
• Group 4 elements of the periodic table mean titanium, zirconium, and hafnium.
• Group 4 element titanium and zirconium are preferable from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects or from the viewpoint of suppressing variations in the composition of the underlayer between samples. Titanium is more preferred.
• the base layer may contain two or more types of Group 4 elements.
• Group 5 elements of the periodic table mean vanadium, niobium, and tantalum.
• Group 5 element vanadium is particularly preferable from the viewpoint of providing better wear resistance of the surface treatment layer.
• the underlayer may contain two or more types of Group 5 elements.
• Group 13 elements of the periodic table mean boron, aluminum, gallium, and indium.
• Group 13 elements boron, aluminum, and gallium are selected from the viewpoint of forming a surface treatment layer on the underlayer more uniformly without defects, or from the viewpoint of suppressing variations in the composition of the underlayer between samples.
• boron and aluminum are more preferable.
• the base layer may contain two or more types of Group 13 elements.
• Group 15 elements of the periodic table mean nitrogen, phosphorus, arsenic, antimony, and bismuth.
• Group 15 elements, phosphorus, antimony, and bismuth are used from the viewpoint of forming a surface treatment layer on the underlayer more uniformly without defects or from the viewpoint of suppressing variations in the composition of the underlayer between samples.
• phosphorus and bismuth are more preferable.
• the base layer may contain two or more types of Group 15 elements.
• Group 1 elements, Group 2 elements, and Group 13 elements are preferable because the wear resistance of the surface treatment layer is better, and Group 1 elements and Group 2 elements are more preferable. , Group 1 elements are more preferred. As the specific element, only one type of element may be included, or two or more types of elements may be included.
• the oxide contained in the base layer may be a mixture of oxides of the above elements (silicon and specific elements) alone (for example, a mixture of silicon oxide and an oxide of a specific element), or a mixture of the above elements (silicon and specific elements). It may be a composite oxide containing two or more types, or a mixture of an oxide of the above element alone and a composite oxide.
• the ratio of the total molar concentration of the specific element in the underlayer to the molar concentration of silicon in the underlayer (specific element/silicon) is 0.02 to 2.90 from the viewpoint of better wear resistance of the surface treatment layer. It is preferably 0.10 to 2.00, even more preferably 0.20 to 1.80.
• the molar concentration (mol %) of each element in the underlayer can be measured, for example, by depth direction analysis using X-ray photoelectron spectroscopy (XPS) using ion sputtering.
• the base layer may be a single layer or a multilayer.
• the base layer may have an uneven surface.
• the thickness of the underlayer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 2 to 20 nm. If the thickness of the base layer is equal to or greater than the above lower limit, the adhesion of the surface treatment layer to the base layer will be further improved, and the wear resistance of the surface treatment layer will be more excellent. If the thickness of the base layer is below the above upper limit, the base layer itself will have excellent wear resistance.
• the thickness of the base layer is measured by observing a cross section of the base layer using a transmission electron microscope (TEM).
• TEM transmission electron microscope
• the base layer can be formed, for example, by a vapor deposition method using a vapor deposition material or a wet coating method.
• the vapor deposition material used in the vapor deposition method preferably contains an oxide containing silicon and a specific element.
• Specific examples of the form of the vapor deposition material include powder, molten body, sintered body, granulated body, and crushed body, and from the viewpoint of ease of handling, molten body, sintered body, and granulated body are preferable.
• the melt means a solid obtained by melting the powder of the vapor deposition material at a high temperature and then cooling and solidifying the powder.
• a sintered body means a solid obtained by firing a powder of a vapor deposition material, and if necessary, a molded body obtained by press-molding the powder may be used instead of a powder of a vapor deposition material.
• the granule refers to a solid material obtained by kneading a powder of a vapor deposition material and a liquid medium (for example, water, an organic solvent) to obtain particles, and then drying the particles.
• the vapor deposition material can be manufactured, for example, by the following method.
• ⁇ Powders containing silicon e.g. powder of silicon oxide, silica sand, silica gel
• powders containing specific elements e.g.
• ⁇ Powders containing silicon e.g. powder of silicon oxide, silica sand, silica gel
• powders containing specific elements e.g. powder of oxides of specific elements, carbonates, sulfates, nitrates, oxalic acid
• a specific example of a vapor deposition method using a vapor deposition material includes a vacuum vapor deposition method.
• the vacuum deposition method is a method in which a deposition material is evaporated in a vacuum chamber and adhered to the surface of a base material.
• the temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100 to 3,000°C, more preferably 500 to 3,000°C.
• the pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, more preferably 0.1 Pa or less.
• one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.
• evaporation methods include resistance heating, in which the evaporation material is melted and evaporated on a resistance heating boat made of high-melting-point metal, and irradiation of an electron beam onto the evaporation material to directly heat the evaporation material on the surface.
• An example is the electron gun method, which melts and evaporates.
• the method of evaporating the deposition material is that it can evaporate high-melting point substances because it can be heated locally, and that there is no risk of reaction with the container or contamination with impurities because the area that is not hit by the electron beam is at a low temperature. Gun law is preferred.
• a plurality of boats may be used, or all the evaporation materials may be placed in a single boat.
• the vapor deposition method may be codeposition, alternate vapor deposition, or the like. Specifically, examples include mixing silica and a specific element source in the same boat, co-evaporating silica and a specific element source in separate boats, and alternately depositing silica and a specific element source in separate boats. can be mentioned.
• the conditions, order, etc. of vapor deposition are appropriately selected depending on the structure of the underlying layer.
• the base layer on the base material by a wet coating method using a coating liquid containing a compound containing silicon, a compound containing a specific element, and a liquid medium.
• silicon compounds include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partially hydrolyzed condensates of alkoxysilanes.
• Specific examples of compounds containing specific elements include oxides of specific elements, alkoxides of specific elements, carbonates of specific elements, sulfates of specific elements, nitrates of specific elements, oxalates of specific elements, and water of specific elements. Examples include oxides.
• liquid medium examples include those similar to the liquid medium contained in the composition of the present disclosure described above.
• the content of the liquid medium is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the coating liquid used to form the base layer.
• wet coating methods for forming the base layer include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, Examples include the cast method, Langmuir-Blodgett method, and gravure coating method.
• the drying temperature of the coating film is preferably 20 to 200°C, more preferably 80 to 160°C.
• the article of the present disclosure is preferably an optical member.
• optical components include medical devices such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras.
• medical devices such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras.
• Examples include personal appliances, copying machines, PCs, displays (eg, liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and antireflection films.
• the article is preferably a display or a touch panel.
• a method for producing an article of the present disclosure is, for example, a method of surface-treating a base material using the surface treatment agent of the present disclosure to produce an article in which a surface-treated layer is formed on the base material.
• Surface treatments include dry coating methods and wet coating methods.
• dry coating methods include vacuum deposition, CVD, and sputtering.
• a vacuum evaporation method is preferable from the viewpoint of suppressing decomposition of the compound and the simplicity of the apparatus.
• a pellet-like substance obtained by impregnating a porous metal body such as iron or steel with the compound of the present disclosure may be used.
• a pellet-like material impregnated with the compound of the present disclosure may be used by impregnating a porous metal body such as iron or steel with a composition containing the compound of the present disclosure and a liquid medium, and drying the liquid medium.
• wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, and Langmuir-Blodgett methods. , gravure coating method.
• an operation may be performed to accelerate the reaction between the compound of the present disclosure and the base material, if necessary.
• Such operations include heating, humidification, light irradiation, and the like.
• a hydrolysis reaction of hydrolyzable groups, a reaction between hydroxyl groups, etc. on the surface of the base material and silanol groups, and a condensation reaction of silanol groups. can promote reactions such as the formation of siloxane bonds.
• compounds in the surface treatment layer that are not chemically bonded to other compounds or the base material may be removed as necessary. Examples of the removal method include a method of pouring a solvent onto the surface treatment layer, a method of wiping with a cloth impregnated with a solvent, and the like.
• the base material was surface-treated using each compound obtained in Synthesis Examples 6, 12, 15, 17, 23, 18, and 19, and octadecyltrimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd., product code: O0256), and each Articles of Examples 1-8 were obtained.
• a surface treatment method the following dry coating method was used for each example. Chemically strengthened glass was used as the base material.
• the obtained article was evaluated by the following method. The results are shown in Table 1.
• the dry coating was performed using a vacuum evaporation device (VTR350M, manufactured by ULVAC) (vacuum evaporation method).
• VTR350M vacuum evaporation device
• 0.5 g of a 20% by mass ethyl acetate solution of each compound was filled into a molybdenum boat in a vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 1 ⁇ 10 ⁇ 3 Pa or less.
• the boat containing the compound solution is heated at a temperature increase rate of 10°C/min or less, and when the deposition rate exceeds 1 nm/sec using a crystal oscillation type film thickness meter, the shutter is opened to deposit the compound solution onto the surface of the substrate.
• the membrane was started.
• the shutter was closed to complete the film formation on the surface of the substrate.
• the substrate on which the compound was deposited was heat-treated at 150° C. for 30 minutes to obtain an article having a surface layer on the surface of the substrate.
• Examples 1 to 5 are examples, and Examples 6 to 8 are comparative examples. As shown in Table 1, Examples 1 to 5 have good evaluations of both water repellency and abrasion resistance, but Examples 6 to 8 cannot achieve both excellent water repellency and abrasion resistance. Comparing Examples 3 and 5, Example 5 in which X2 in formula (B1) was 21 was superior in wear resistance.
• the compounds of the present disclosure are useful as surface treatment agents.
• the surface treatment agent can be used, for example, for substrates in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like.
• the surface treatment agent can be used for bodies, window glasses (windshields, side glasses, rear glasses), mirrors, bumpers, etc. of transportation equipment such as trains, automobiles, ships, and airplanes.
• the surface treatment agent can be used for outdoor articles such as building exterior walls, tents, solar power generation modules, sound insulation boards, and concrete; fishing nets, insect nets, and aquariums.
• the surface treatment agent can be used for various indoor equipment such as kitchens, bathrooms, washstands, mirrors, toilet peripheral parts; ceramics such as chandeliers and tiles; artificial marble, and air conditioners.
• the surface treatment agent can be used as an antifouling treatment for jigs, inner walls, piping, etc. in a factory.
• the surface treatment agent can be used for goggles, glasses, helmets, pachinko machines, textiles, umbrellas, play equipment, and soccer balls.
• the surface treatment agent can also be used as an adhesion prevention agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.
• surface treatment agents are used for medical applications such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras. It can be used for optical members such as appliances, copying machines, PCs, displays (for example, liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and antireflection films.
• medical applications such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras.
• optical members such as appliances, copying machines, PCs, displays (for example, liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and antireflection films.

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• 2023
  • 2023-04-12 JP JP2024517982A patent/JPWO2023210378A1/ja active Pending
  • 2023-04-12 WO PCT/JP2023/014916 patent/WO2023210378A1/ja not_active Ceased

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