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  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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  • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
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  • 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
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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Definitions

• the present invention relates to a hydrocarbon end group-containing compound, and more specifically to a hydrocarbon end group-containing compound, particularly an alkyl end group-containing compound, which forms a coating that is excellent in water repellency, abrasion resistance, low visibility of fingerprints, and chemical resistance, a surface treatment agent containing said compound, and an article that has been surface-treated with said surface treatment agent.
• touch panels for displays, such as smartphones and in-vehicle displays
• touch panels have exposed screens and are often in direct contact with fingers or cheeks, which makes them susceptible to dirt such as sebum.
• fingerprints are easily stained on the surface of touch panel displays, it is desirable to provide a water- and oil-repellent layer.
• conventional water- and oil-repellent layers are highly water- and oil-repellent and easy to wipe off, they have problems with insufficient abrasion resistance and fingerprints are noticeable when they appear on the surface.
• fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, and stain resistance. Taking advantage of these properties, they are widely used industrially as water and oil repellent and stain resistant agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, and more. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and although they can be applied to the surface of a substrate, it has been difficult to make the coating adhere to it.
• Silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates.
• Silane coupling agents have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule.
• the hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating.
• the coating becomes a strong and durable coating as the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.
• compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, and that can form coatings on the substrate surface that are easily adhered to the substrate surface and have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, and JP-A-2015-199906).
• Patent Document 7 the compound disclosed in International Publication No. 2017/212850 (Patent Document 7) is said to have particularly excellent abrasion resistance, but it has been pointed out that it has a drawback in that fingerprints become noticeable when they are left on it due to its high water and oil repellency.
• Patent Document 8 proposes a surface treatment agent that does not use fluorine groups and suppresses fingerprint repelling.
• the abrasion resistance of the agent was not sufficient to withstand harsh usage environments.
• fluorine-based compounds are difficult to decompose in nature and tend to accumulate in the natural environment, there is a growing demand for the development of surface protection agents for non-fluorine-based materials.
• the present invention has been made in consideration of the above circumstances, and aims to provide a non-fluorine-based (i.e., having no fluorine atoms in the molecule) hydrocarbon end group-containing compound capable of forming a cured coating that is excellent in water repellency, slipperiness, dirt wipeability, abrasion resistance, and chemical resistance, a substantially non-fluorine-based surface treatment agent that contains the compound, and an article that has been surface-treated with the surface treatment agent.
• a non-fluorine-based hydrocarbon end group-containing compound capable of forming a cured coating that is excellent in water repellency, slipperiness, dirt wipeability, abrasion resistance, and chemical resistance
• a substantially non-fluorine-based surface treatment agent that contains the compound
• an article that has been surface-treated with the surface treatment agent i.e., having no fluorine atoms in the molecule
• a surface treatment agent containing said compound can form a hardened coating that is excellent in water repellency, slipperiness, dirt wiping ability, abrasion resistance, particularly steel wool abrasion resistance, and chemical resistance, and thus completed the present invention.
• R 1 is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may contain at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, and may be linear, branched, or cyclic, or a combination thereof;
• R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms;
• R 1 or -Y-A U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group,
• V is a single bond or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom
• Z is
• the hydrocarbon terminal group-containing compound represented by the formula: [2] A in the formula (1) is represented by the following general formula (2): (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) Or the following general formula (3) (In the formula, n′′ is a number from 0 to 3, and n′ is (3 ⁇ n′′)/2.) The hydrocarbon terminal group-containing compound according to [1], wherein the hydrocarbon terminal group is a group represented by the formula: [3]
• R 1 is represented by the following formula: (In the formula, R A is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms which may be linear, branched, or cyclic, or a combination thereof; Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganos
• U is a trivalent or tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic ring-containing group.
• the hydrocarbon end group-containing compound of the present invention has two or more hydrocarbon chains with a specified number of carbon atoms at the molecular chain end, which improves the mobility of the molecular chain, and as a result, an article surface-treated with a surface treatment agent containing the compound has excellent water repellency, slipperiness, dirt wipeability, and abrasion resistance. It also has excellent chemical resistance.
• R 1 is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may contain at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, and may be linear, branched, or cyclic, or a combination thereof;
• R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms;
• R 1 or -Y-A U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group,
• V is a single bond or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom
• Z is a single bond, a carbon atom,
• the hydrocarbon end group-containing compound of the present invention has at least two hydrocarbon chain end groups with a predetermined carbon number, particularly at least two groups selected from an alkyl group with 3 to 32 carbon atoms, preferably at 6 to 28 carbon atoms, and an aryl group with 6 to 32 carbon atoms, at the end, and has a reactive group that exhibits adhesion to a substrate at the other end, and these are bonded via a linking group.
• the cured coating of the surface treatment agent containing the compound is characterized by excellent water repellency, slipperiness, dirt wipeability, abrasion resistance, and chemical resistance.
• R 1 independently represents a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, and more preferably 8 to 28 carbon atoms, which may contain at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and which may be linear, branched, or cyclic, or a combination thereof.
• the group contained is an ether group, a carbonyl (ketone) group, an ester group, a carbonate group, a thioether group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, an oxazole group, an imidazole group, a triazole group, a cyanurate group, an isocyanurate group, a diorganosilylene group, an organopolysiloxane residue, a silalkylene group, a silarylene group, or the like.
• R 1 is preferably a group represented by the following formula: (In the formula, R A is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms which may be linear, branched, or cyclic, or a combination thereof; Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a silalkylene structure or a silarylene structure, a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group,
• R A is independently a monovalent hydrocarbon group which may be linear, branched, or cyclic, or a combination thereof, having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, and more preferably 8 to 28 carbon atoms.
• R A include the following. (In the formula, x is an integer of 2 to 31, preferably 5 to 27, and more preferably 7 to 27, and y and y' are each an integer of 1 or more such that the total number of carbon atoms in each structure is 32 or less.)
• Q is independently a divalent group selected from the group consisting of oxygen atoms, sulfur atoms, divalent cyclic hydrocarbon groups having 6 to 8 carbon atoms, diorganosilylene groups, silalkylene structures or silarylene structures, linear divalent organopolysiloxane residues having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or branched or cyclic divalent organopolysiloxane residues having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, carbonyl (ketone) groups, ester groups, carbonate groups, sulfinyl groups, sulfonyl groups, thioester groups, thiocarbonate groups, thiocarbamate groups, amino groups, amide groups, carbamate groups, urea groups, and divalent nitrogen-containing heterocyclic groups (divalent oxazole groups, divalent imidazole groups, divalent triazole groups, etc.).
• the groups bonded to silicon atoms in the diorganosilylene group, silalkylene structure, silarylene structure, and organopolysiloxane residue are preferably alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl, or phenyl groups.
• the alkylene groups in the silalkylene structure are preferably ethylene groups having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), and the like.
• the organopolysiloxane residue may contain a silalkylene structure in which two silicon atoms are bonded by an alkylene group such as an ethylene group or a propylene group.
• Q examples include the following: In the following structure, the left bond is bonded to R A or R B , and the right bond is bonded to R B. (In the formula, f is an integer from 2 to 4, and e is an integer from 1 to 9.)
• Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group).
• a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent organo
• the organopolysiloxane residue preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group.
• the organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded with an alkylene group, such as an ethylene group or a propylene group.
• Q' examples include those shown below.
• the left bond is bonded to R A or R B
• the right bond is bonded to R B
• the other bond is bonded to R C.
• f is an integer from 2 to 4.
• Q'' is independently a tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.
• the organopolysiloxane residue preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group.
• the organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded with an alkylene group, such as an ethylene group or a propylene group.
• Examples of such Q" include those shown below.
• the left bond is bonded to R A or R B
• the right bond is bonded to R B
• the other bond is bonded to R C.
• R B is independently a single bond or a divalent hydrocarbon group having 1 to 32 carbon atoms which may be linear, branched or cyclic, and examples thereof include the following: (In the formula, z is an integer from 1 to 10.)
• R C is independently R A or a hydrogen atom.
• R C is R A , it may be the same as or different from R A.
• p is an integer of 0 to 10, and is preferably 0, 1 or 2. However, the total number of carbon atoms in each structure of R 1 is 32 or less.
• R 1 the following are preferably used. (In the formula, x, y, and z are the same as above, except that the total number of carbon atoms in each structure is 3 to 32.)
• R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms (methyl group, ethyl group), R 1 , or -YA.
• R 2 is preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group, an ethyl group, or R 1 -YA.
• U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group
• the trivalent or tetravalent organic group is preferably a trivalent or tetravalent group selected from a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic ring-containing group (such as a trivalent cyanurate group, a trivalent isocyanurate group, and a trivalent triazine ring-containing group).
• the organopolysiloxane residue preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group.
• the organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded with an alkylene group, such as an ethylene group or a propylene group.
• Examples of such U include the following: In the following structure, it is preferable that the bond on the right side is bonded to V.
• V is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and is a linking group connecting the U group and the Z group.
• Z is a single bond
• V is preferably a single bond.
• the divalent hydrocarbon group include an alkylene group having 1 to 10 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms).
• V include the following, in addition to a single bond:
• the left bond is bonded to U, and the right bond is bonded to Z.
• q is an integer from 1 to 10
• r, s, and t are each an integer from 1 to 8
• the sum of r and s is an integer from 2 to 10
• the sum of r, s, and t is an integer from 3 to 10.
• Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group.
• the organopolysiloxane residue preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group.
• the organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded with an alkylene group, such as an ethylene group or a propylene group.
• Z examples include, in addition to a single bond, the following: In the following structure, the bond on the left side is bonded to V, and the other bond is bonded to Y. (In the formula, f is an integer from 2 to 4.)
• Y may independently contain at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the Z group and the A group.
• the divalent hydrocarbon group examples include an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and sulfur atoms; an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms); a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, a silarylene structure, or a nitrogen-containing heterocyclic group; and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to
• the groups bonded to silicon atoms in the diorganosilylene group, silalkylene structure, silarylene structure, and organopolysiloxane residue are preferably alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl, or phenyl groups.
• the alkylene groups in the silalkylene structure are preferably ethylene groups having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), and the like.
• the organopolysiloxane residue may contain a silalkylene structure in which two silicon atoms are bonded by an alkylene group such as an ethylene group or a propylene group.
• Examples of such Y include the following groups: In the following structure, the left bond is bonded to Z, and the right bond is bonded to A. (In the formula, a is independently an integer of 1 to 10, b, c, and d are each an integer of 1 to 8, the sum of b and c is an integer of 2 to 10, and the sum of b, c, and d is an integer of 3 to 10. e is an integer of 1 to 9, and f is an integer of 2 to 4.)
• A is independently a monovalent reactive group, and is preferably a functional group that has adhesion (adhesion) reactivity to the surface of the substrate, which is made of various materials such as paper, cloth, metal and its oxide, glass, plastic (resin), ceramic, and quartz, which is the target of the surface treatment.
• monovalent reactive groups include monovalent groups selected from carbon-carbon double bond-containing groups (limited to groups involved in ionic addition polymerization or curing reactions due to active energy rays (light), excluding alkenyl groups (groups that undergo hydrosilylation addition polymerization)), carbon-carbon triple bond-containing groups, cyclic ether groups, hydroxyl group-containing groups (excluding those consisting only of hydroxyl groups), thiol groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, phosphate-containing groups, hydroxyl group-containing silyl groups (silanol groups), and hydrolyzable silyl groups.
• A may, for example, be a carbon-carbon double bond-containing group such as a cinnamic acid group, a sorbic acid group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamide group, a methacrylamide group, or a vinyl ether group; a carbon-carbon triple bond-containing group such as an alkynyl group having 2 to 20 carbon atoms, such as an ethynyl group, a propargyl group, a 2-methyl-2-propynyl group, a 3-butynyl group, a 4-pentynyl group, or a 5-hexynyl group, and a propargyloxy group, a 2-methyl-2-propynyloxy group, a 3-butynyloxy group, a 4-pentynyloxy group, or a Examples of the alkynyloxy group include al
• the hydroxyl group-containing silyl group and the hydrolyzable silyl group are represented by the following general formula (2): (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) Or the following general formula (3) (In the formula, n′′ is a number from 0 to 3, and n′ is (3 ⁇ n′′)/2.) A group represented by the following formula is preferred.
• R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, with a methyl group being preferred.
• X is independently a hydroxyl group or a hydrolyzable group, and examples of X include a hydroxyl group; an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group; an alkoxyalkoxy group having 2 to 10 carbon atoms, such as a methoxymethoxy group or a methoxyethoxy group; an acyloxy group having 1 to 10 carbon atoms, such as an acetoxy group; an alkenyloxy group having 2 to 10 carbon atoms, such as an isopropenoxy group or a cyclopentenyloxy group; a halogen group, such as a chlorine group, a bromo group, or an iodo group; and a dialkylamino group having 2 to 10 carbon atoms, such as a dimethylamino group or a diethylamino
• the above general formula (1) represents the molecular formula (structural formula) of a hydrocarbon terminal group-containing compound (monomer)
• the above general formula (1) represents the composition formula of a polymer of a hydrocarbon terminal group-containing compound (polysilazane compound).
• n' is (3-n'')/2, and is preferably 1.5.
• k is 0 or 1, and is 0 when U is trivalent, and is 1 when U is tetravalent. Furthermore, m is an integer of 1 to 7, preferably an integer of 1 to 3.
• a hydrocarbon terminal group-containing compound represented by the following formula (Z) can form a cured coating film having particularly excellent chemical resistance.
• R 1 ' is independently a monovalent hydrocarbon group having 13 to 32 carbon atoms which may be linear, branched, or cyclic, or a combination thereof
• R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms, R 1 , or -Y-A
• U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group
• V is a single bond, or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom
• Z is a single bond, a carbon atom,
• R 1 ' is independently a hydrocarbon group having 13 to 32 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof, and is preferably a hydrocarbon group having 15 to 28 carbon atoms.
• R 1 ' has 13 or more carbon atoms, an effect of preventing penetration of chemicals into the substrate adhesive portion is exhibited, and chemical resistance is improved.
• R 2 , U, V and Z in the above formula (Z) are the same as in the above formula (1).
• Examples of the structure of the hydrocarbon end group-containing compound represented by the above formula (1) include the following structures: By changing the combination of R1 , R2 , U, V, Z, Y, A, k, and m in the above formula (1), several types of hydrocarbon end group-containing compounds can be obtained.
• the hydrocarbon terminal group-containing compound of the present invention represented by the general formula (1) can be prepared, for example, by the following method.
• Preparation method 1 A hydrocarbon terminal group-containing compound having an alkenyl group at the end and a compound having a SiH group and a hydrolyzable silyl group are mixed and subjected to a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst, thereby producing a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a hydrolyzable silyl group at the end).
• the compound When a compound having a SiH group and a hydrolyzable silyl group in which the hydrolyzable group is a halogen group is used, the compound can be produced by subsequently converting the substituent (halogen atom) on the silyl group to another hydrolyzable group.
• an example of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal is a compound represented by the following formula (1A).
• R 1 , R 2 , U, V, Z, k, and m are the same as above.
• Y 1 may independently contain at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms, and is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms.
• Y1 may independently contain at least one atom selected from oxygen, nitrogen, sulfur and silicon atoms, and is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, examples of which include those shown below.
• the bond on the left is bonded to Z, and the bond on the right is bonded to a carbon atom.
• a' is independently an integer of 0 to 8
• b and c are each an integer of 1 to 8
• c' and d' are each an integer of 0 to 6
• the sum of b and c' is an integer of 2 to 8
• the sum of b, c, and d' is an integer of 3 to 8.
• e is an integer of 1 to 9
• f is an integer of 2 to 4.
• Examples of the compound represented by formula (1A) include those shown below. (In the formula, x, y, z, q, a, a', b, c, and c' are each independently the same as above.)
• Examples of compounds having a SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, trichlorosilane, etc.
• the amount of the compound having a SiH group and a hydrolyzable silyl group used is preferably 1 to 6 moles, and more preferably 1.5 to 4 moles, per mole of alkenyl group in the hydrocarbon end group-containing compound having an alkenyl group at the end.
• examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium.
• platinum compounds such as vinylsiloxane coordination compounds. It is preferable to use the platinum compounds by dissolving them in a solvent such as toluene, lower alcohols, higher alcohols, or silicones.
• the amount of the hydrosilylation catalyst used is preferably 0.001 to 1,000 ppm, and more preferably 0.01 to 100 ppm, calculated as transition metal (by mass), based on the mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the end.
• a solvent can be used when carrying out the reaction in Preparation Method 1.
• the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having an alkenyl group at the terminal.
• the reaction conditions for the hydrocarbon end group-containing compound having an alkenyl group at the end and the compound having a SiH group and a hydrolyzable silyl group are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, particularly 1 to 36 hours.
• the substituent (halogen atom) on the silyl group is then converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.
• examples of compounds that can be used when converting the substituent (halogen atom) on the silyl group to another hydrolyzable group include methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, and trimethyl orthoformate.
• the amount of this compound used is preferably 3 to 9 moles, particularly 3 to 5 moles, per mole of halogen atoms in the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and the SiH group- and halogenated silyl group-containing compound.
• the reaction conditions for converting the substituent (halogen atom) on the silyl group to another hydrolyzable group are preferably a temperature of 0 to 80°C, particularly 20 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• hydrocarbon terminal group-containing compound of the present invention represented by general formula (1) include the following methods.
• Preparation method 2 A hydrocarbon terminal group-containing compound having a SiH group at the terminal and a compound having a reactive group such as an alkenyl group and a hydrolyzable silyl group are mixed and subjected to a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst, thereby producing a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a hydrolyzable silyl group at the terminal).
• Examples of the hydrocarbon terminal group-containing compound having a SiH group at the end include compounds represented by the following formula (1B) or (1C).
• R 1 , R 2 , U, V, Z, k, and m are the same as above.
• Z 1 is a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms and having a valence of 3 to 8
• Y 2 is independently a monovalent hydrocarbon group having a silicon atom or a siloxane bond and a terminal SiH group.
• Z1 is a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, with a valence of 3 to 8, examples of which are shown below.
• the bond on the left is bonded to V, and the other bonds are bonded to H.
• f is an integer from 2 to 4.
• Examples of the compound represented by formula (1B) include the following. (In the formula, x, q, r, and s are each independently the same as above.)
• Y 2 independently represents a monovalent hydrocarbon group having a silicon atom or a siloxane bond and a SiH group at the terminal, and examples thereof include those shown below.
• a is an integer from 1 to 10
• b is an integer from 1 to 8
• e is an integer from 1 to 9
• f is an integer from 2 to 4.
• Examples of the compound represented by formula (1C) include the following. (In the formula, x and b are each independently the same as above.)
• examples of the compound having a reactive group such as an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane. Further, examples of compounds having a reactive group other than an alkenyl group and a hydrolyzable silyl group include allyl glycidyl ether.
• the amount of the compound having a reactive group such as an alkenyl group or a hydrolyzable silyl group used is preferably 1 to 5 moles, and more preferably 1 to 3 moles, per mole of SiH group in the hydrocarbon end group-containing compound having a SiH group at the end.
• examples of the hydrosilylation catalyst include the same as those in Preparation Method 1.
• Preferred are platinum compounds such as vinylsiloxane coordination compounds.
• the platinum compounds are preferably used by dissolving them in a solvent such as toluene, lower alcohols, higher alcohols, or silicones.
• the amount of the hydrosilylation catalyst used is preferably 0.001 to 1,000 ppm, and more preferably 0.01 to 100 ppm, calculated as transition metal (by mass), based on the mass of the compound containing a hydrocarbon terminal group having a SiH group at the terminal.
• a solvent may be used when carrying out the reaction.
• the solvent include the same solvents as those in Preparation Method 1.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a SiH group at the end.
• the reaction conditions are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• hydrocarbon terminal group-containing compound of the present invention represented by general formula (1) include the following methods.
• Preparation method 3 A hydrocarbon terminal group-containing compound having an alkenyl group at the terminal is mixed with trichlorosilane, reacted in the presence of a hydrosilylation reaction catalyst, and then the resulting compound is reacted with ammonia gas, thereby producing a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having an amino group-containing silyl group at the terminal and/or a polysilazane compound which is a polymer thereof).
• reaction product of the hydrocarbon end group-containing compound having an alkenyl group at the end and trichlorosilane can be prepared in the same manner as in Preparation Method 1.
• the amount of ammonia gas used is preferably 1 to 300 cc/min, and more preferably 30 to 200 cc/min.
• reaction conditions for the reaction of the hydrocarbon end group-containing compound having an alkenyl group at the end and trichlorosilane reactant with ammonia gas are preferably room temperature (23 ⁇ 15°C, same below), particularly 20 to 30°C, for 2 to 36 hours, particularly 4 to 12 hours.
• a hydrocarbon terminal group-containing compound having a hydroxyl group at the end is mixed with a compound having an isocyanate group and a reactive group (e.g., a hydrolyzable silyl group, a (meth)acryloyloxy group, etc.) and reacted in the presence of a catalyst to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a hydrolyzable silyl group or a (meth)acryloyloxy group at the end via a urethane bond).
• the (meth)acryloyloxy group refers to an acryloyloxy group or a methacryloyloxy group.
• Examples of the hydrocarbon terminal group-containing compound having a hydroxyl group at the end include compounds represented by the following formula (1D) or (1E). (In the formula, R 1 , R 2 , U, V, Z, k, m, and b are the same as above. V 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms.)
• Examples of the compound represented by formula (1D) include those shown below. (In the formula, x, z, and b are each independently the same as above.)
• V 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkylene group, and examples thereof include those shown below. (In the formula, q is the same as above.)
• Examples of the compound represented by formula (1E) include those shown below. (In the formula, x, z, and q are each independently the same as above.)
• Examples of compounds having an isocyanate group and a reactive group include (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)triethoxysilane, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.
• the amount of the compound having an isocyanate group and a reactive group used is preferably 1 to 3 moles, and more preferably 1 to 1.5 moles, per mole of hydroxyl group in the hydrocarbon end group-containing compound having a hydroxyl group at the end.
• examples of the catalyst include titanium compounds such as titanium tetra-2-ethylhexoxide, tetra n-butyl titanate, and tetra n-propyl titanate; zirconium compounds such as tetra n-butyl zirconate and tetra n-propyl zirconate; tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate; bismuth compounds such as bismuth tris(2-ethylhexanoate); and amine catalysts such as diazabicycloundecene.
• the amount of the catalyst used is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a hydroxyl group at the end.
• a solvent may be used when carrying out the reaction.
• the solvent include the same solvents as those in Preparation Method 1.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a hydroxyl group at the end.
• the reaction conditions are preferably a temperature of 20 to 100°C, particularly 30 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• hydrocarbon terminal group-containing compound of the present invention represented by general formula (1) include the following methods.
• Preparation method 5 A hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal is mixed with phosphorus oxychloride to cause a reaction, and then water is added and the reaction is continued, whereby a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a phosphoric acid group at the terminal) can be produced.
• examples of the hydrocarbon end group-containing compound having a hydroxyl group at the end include the compound represented by formula (1D) in Preparation Method 4 above.
• the amount of phosphorus oxychloride used is preferably 1 to 4 moles, and more preferably 1 to 2 moles, per mole of hydroxyl group in the hydrocarbon end group-containing compound having a terminal hydroxyl group.
• a solvent can be used when reacting the hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal with phosphorus oxychloride.
• the solvent include the same solvents as those in the preparation method 1.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a hydroxyl group at the end.
• the reaction conditions for the hydrocarbon end group-containing compound having a hydroxyl group at the end and phosphorus oxychloride are preferably a temperature of 0 to 80°C, particularly 15 to 50°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• the amount of water used is 50 to 1,000 parts by mass, preferably 100 to 500 parts by mass, per 100 parts by mass of the hydrocarbon end group-containing compound having a hydroxyl group at the end.
• the reaction conditions for the reaction between the reaction product of the hydrocarbon end group-containing compound having a hydroxyl group at the end and phosphorus oxychloride and water are preferably a temperature of 0 to 80°C, particularly 15 to 50°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• a hydrocarbon end group-containing compound having a leaving group at the end can be mixed and reacted with a trialkyl phosphite to produce a hydrocarbon end group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a phosphate ester group at the end).
• hydrocarbon end group-containing compounds having a leaving group at the end include compounds similar to those represented by (1G) and (1H) in Preparation Method 8 described below.
• examples of trialkyl phosphite include trimethyl phosphite and triethyl phosphite.
• the amount of trialkyl phosphite used is preferably 1 to 8 moles, particularly 1 to 4 moles, per mole of leaving group in the hydrocarbon end group-containing compound having a leaving group at the end.
• a solvent can be used when reacting the hydrocarbon terminal group-containing compound having a leaving group at the terminal with the trialkyl phosphite.
• the solvent include the same solvents as those in the preparation method 1.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 0 to 200 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a leaving group at the end.
• reaction conditions for the hydrocarbon end group-containing compound having a leaving group at the end and the trialkyl phosphite are preferably a temperature of 25 to 160°C, particularly 80 to 140°C, for 0.5 to 72 hours, particularly 1 to 36 hours.
• hydrocarbon terminal group-containing compound of the present invention represented by general formula (1) includes the following methods.
• Preparation Method 6 A hydrocarbon terminal group-containing compound having an NH group at the terminal and a compound having an isocyanate group and a reactive group (e.g., a hydrolyzable silyl group, a (meth)acryloyloxy group, etc.) are mixed and reacted to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a hydrolyzable silyl group or a (meth)acryloyloxy group at the terminal via a urea bond).
• a reactive group e.g., a hydrolyzable silyl group, a (meth)acryloyloxy group, etc.
• an example of the hydrocarbon terminal group-containing compound having an NH group at the terminal is a compound represented by the following formula (1F). (In the formula, R1 is the same as above.)
• Examples of the compound represented by formula (1F) include those shown below. (In the formula, x is independently the same as above.)
• Examples of compounds having an isocyanate group and a reactive group include (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)triethoxysilane, and 2-isocyanatoethyl methacrylate.
• the amount of the compound having an isocyanate group and a reactive group used is preferably 1 to 3 moles, and more preferably 1 to 1.5 moles, per mole of the hydrocarbon end group-containing compound having an NH group at the end.
• a solvent may be used when carrying out the reaction.
• the solvent include the same solvents as those in Preparation Method 1.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having an NH group at the end.
• the reaction conditions are preferably a temperature of 0 to 100°C, particularly 20 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• the hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a thiol group (mercapto group) at its terminal) can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal with thioacetic acid and reacting them in the presence of a polymerization initiator, and then mixing the resulting compound having a thioester group with a hydrosilane compound and reacting them in the presence of a Pd/C catalyst.
• examples of the hydrocarbon end group-containing compound having an alkenyl group at the end include the compound represented by formula (1A) in Preparation Method 1 above.
• the amount of thioacetic acid used is preferably 1 to 5 moles, and more preferably 1 to 3 moles, per mole of alkenyl group in the hydrocarbon end group-containing compound having an alkenyl group at the end.
• examples of the polymerization initiator include peroxide compounds such as azo compounds such as 2,2'-azobisisobutyronitrile, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide, peroxycarbonates such as diisopropyl peroxydicarbonate and bis(4-tert-butylcyclohexyl)peroxydicarbonate, and alkyl peresters such as t-butyl peroxyoctoate and tert-butyl peroxybenzoate.
• the amount of the polymerization initiator used is preferably 0.01 to 3 moles, particularly preferably 0.1 to 1.5 moles, per mole of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.
• reaction conditions for the hydrocarbon end group-containing compound having an alkenyl group at the end and thioacetic acid are preferably a temperature of 20 to 100°C, particularly 40 to 80°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• examples of the hydrosilane compound include trialkoxysilanes such as triethylsilane.
• the amount of the hydrosilane compound used is preferably 1 to 6 moles, and particularly 1.5 to 4 moles, per mole of thioester group in the reaction product of the above-mentioned hydrocarbon terminal group-containing compound having an alkenyl group at the terminal with thioacetic acid (compound having a thioester group).
• the amount of Pd/C catalyst used is preferably such that 0.001 to 1 mole, and particularly 0.01 to 0.5 moles of Pd atoms are used per mole of thioester group in the reaction product (compound having a thioester group) of the hydrocarbon end group-containing compound having an alkenyl group at the end and thioacetic acid.
• the reaction conditions for the reaction of the hydrosilane compound with the reaction product of the hydrocarbon end group-containing compound having an alkenyl group at the end and thioacetic acid are preferably a temperature of 20 to 100°C, particularly 40 to 80°C, for 0.5 to 72 hours, particularly 1 to 36 hours.
• a solvent can be used when carrying out the reaction.
• the solvent include the same solvents as those in the preparation method 1.
• the amount of the solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at its terminal, or the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at its terminal and thioacetic acid (a compound having a thioester group).
• a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having an amino group at its terminal) can be produced by reacting a hydrocarbon terminal group-containing compound having a leaving group at its terminal (e.g., a halogen atom or a sulfonyl ester group) with an amination reagent.
• a hydrocarbon terminal group-containing compound having a leaving group at its terminal e.g., a halogen atom or a sulfonyl ester group
• Examples of the compound represented by formula (1H) include those shown below. (In the formula, x, z, and q are each independently the same as above.)
• Examples of amination reagents include phthalimide, potassium phthalimide, and sodium phthalimide.
• the reaction conditions for the hydrocarbon end group-containing compound having a leaving group at the end and the amination reagent are preferably a temperature of 40 to 150°C, particularly 60 to 120°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.
• the reaction conditions for deprotection are preferably a temperature of 0 to 90°C, particularly 20 to 70°C, for 0.5 to 72 hours, particularly 1 to 36 hours.
• the surface treatment agent may contain a hydrolysis condensation catalyst, for example, an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, tetra n-propyl titanate, etc.), an organic zirconium compound (tetra n-butyl zirconate, tetra n-propyl zirconate, etc.), an organic acid (acetic acid, methanesulfonic acid, carboxylic acid, etc.), an inorganic acid (hydrochloric acid, sulfuric acid, etc.), an organic base (amine, trialkylamine, nitrogen-containing cyclic compound, etc.).
• a hydrolysis condensation catalyst for example, an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate,
• the amount of the hydrolysis and condensation catalyst added is a catalytic amount, which is usually 0.001 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound (and/or its partial (hydrolysis) condensate).
• toluene, hexane, heptane, isooctane, isononane, cyclopentanone, dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate are preferred in terms of solubility, wettability, etc.
• the above solvents may be used in combination of two or more kinds, and it is preferable to dissolve the hydrocarbon end group-containing compound (and its partial (hydrolyzed) condensate) uniformly.
• the optimal concentration of the hydrocarbon end group-containing compound (and its partial (hydrolyzed) condensate) to be dissolved in the solvent varies depending on the processing method, and may be any amount that is easy to weigh.
• the amount of 100 parts by mass refers to coating without using a solvent.
• the surface treatment agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition.
• the heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited.
• the curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferably at 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, particularly 1 to 24 hours, and in the case of application by vapor deposition, it is preferably at a temperature in the range of 20 to 200°C for 1 to 24 hours. Curing may also be performed under humid conditions.
• a compound containing a hydrocarbon terminal group having a hydrolyzable silyl group for example, in spray coating, if the compound is diluted in an organic solvent to which moisture has been added in advance and then hydrolyzed, that is, after generating Si-OH, the compound is spray coated, whereby curing after coating is rapid.
• the thickness of the cured coating is selected appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, and particularly 1 to 20 nm.
• the thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.
• the substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc.
• the surface treatment agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO2- treated glass or film.
• the surface treatment agent of the present invention can form a hardened coating that has high levels of water repellency, slipperiness, dirt wipeability, abrasion resistance, and chemical resistance.
• the surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins, an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., headlamp covers, etc., a water-repellent coating for exterior building materials, a stain-preventing coating for kitchen building materials, an anti-fouling coating and anti-posting/anti-graffiti coating for telephone booths, a coating to prevent the adhesion of stains to artworks, etc., a stain-preventing coating for compact discs, DVDs, etc., a release agent or paint additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, and a lubricity improver for tapes, films, etc.
• the present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.
• the molar amount of a compound is a value calculated by dividing the measured mass of the target compound by the molecular weight of the polymer identified by 1 H-NMR analysis.
• the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer.
• the room temperature is 23°C.
• the resulting compound was confirmed to have a structure represented by the following formula (AH) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (AJ) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (AL) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (AP) by 1 H-NMR.
• the obtained product was mixed with 1.00g of toluene and 0.151g (1.99 ⁇ 10 ⁇ 3 mol) of ethylene glycol monomethyl ether and aged at 50° C. for 8 hours. Subsequently, 1.27 ⁇ 10 ⁇ 2 g (3.99 ⁇ 10 ⁇ 4 mol) of methanol and 0.633g (5.97 ⁇ 10 ⁇ 3 mol) of trimethyl orthoformate were mixed and aged at room temperature for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.20 g of a product.
• the resulting compound was confirmed to have a structure represented by the following formula (AT) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (AV) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (AZ) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BB) by 1 H-NMR.
• the obtained product was mixed with 3.00g of toluene, and aged for 6 hours at room temperature while bubbling ammonia gas (ammonia gas used at 40cc/min). Thereafter, the mixture was filtered, and the solvent and unreacted matter were distilled off under reduced pressure to obtain 1.01g of product.
• the resulting compound was confirmed to have a structure represented by the following formula (BD) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BF) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BH) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BL) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BN) by 1 H-NMR.
• the obtained compound was mixed with 1.00g of toluene, 0.826g (7.10 ⁇ 10 -3 mol) of triethylsilane, and 1.26 ⁇ 10 -2 g of Pd/C (containing 1.18 ⁇ 10 -4 mol as Pd alone), and aged at 50°C for 6 hours.
• 2.00 g of 2M hydrochloric acid was added, and the mixture was aged for 24 hours at 80° C.
• the aqueous layer was removed by a separation operation, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 0.976 g of a product.
• the resulting compound was confirmed to have a structure represented by the following formula (BP) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BR) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BT) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (BV) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (CD) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (CF) by 1 H-NMR.
• the resulting compound was confirmed to have a structure represented by the following formula (CH) by 1 H-NMR.
• Example 2 The compound obtained in Synthesis Example 2 was dissolved in isooctane to a concentration of 20% by mass to prepare a surface treatment agent.
• Example 3 The compound obtained in Synthesis Example 3 was dissolved in dibutyl ether to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 4 The compound obtained in Synthesis Example 4 was dissolved in dibutyl ether to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 5 The compound obtained in Synthesis Example 5 was dissolved in toluene to a concentration of 10 mass % to prepare a surface treatment agent.
• Example 6 The compound obtained in Synthesis Example 7 was dissolved in isononane to a concentration of 20% by mass to prepare a surface treatment agent.
• Example 7 The compound obtained in Synthesis Example 8 was dissolved in dibutyl ether to a concentration of 5 mass % to prepare a surface treatment agent.
• Example 8 The compound obtained in Synthesis Example 9 was dissolved in propylene glycol monomethyl ether acetate to a concentration of 30% by mass to prepare a surface treatment agent.
• Example 9 The compound obtained in Synthesis Example 10 was dissolved in toluene to a concentration of 80 mass % to prepare a surface treatment agent.
• Example 11 The compound obtained in Synthesis Example 12 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent.
• Example 12 The compound obtained in Synthesis Example 15 was dissolved in dibutyl ether to a concentration of 50 mass % to prepare a surface treatment agent.
• Example 13 The compound obtained in Synthesis Example 17 was dissolved in a 50/50 mixed solution of hexane/isooctane to a concentration of 20% by mass to prepare a surface treatment agent.
• Example 14 The compound obtained in Synthesis Example 18 was dissolved in toluene to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 15 The compound obtained in Synthesis Example 20 was dissolved in toluene to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 16 The compound obtained in Synthesis Example 21 was dissolved in dibutyl ether to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 17 The compound obtained in Synthesis Example 24 was dissolved in isooctane to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 18 The compound obtained in Synthesis Example 26 was dissolved in isooctane to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 19 The compound obtained in Synthesis Example 28 was dissolved in isooctane to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 20 The compound obtained in Synthesis Example 31 was dissolved in isooctane to a concentration of 20% by mass to prepare a surface treatment agent.
• Example 21 The compound obtained in Synthesis Example 32 was dissolved in propylene glycol monomethyl ether acetate to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 22 The compound obtained in Synthesis Example 14 was used as a surface treatment agent without dilution.
• Example 23 The compound obtained in Synthesis Example 30 was used as a surface treatment agent without dilution.
• the glass on which the cured coating was formed was evaluated for water repellency, slipperiness, dirt wiping ability, and abrasion resistance by the methods described below. Note that the same evaluation was carried out for Comparative Example 3, which was a glass without surface treatment, but with a 10 nm thick SiO2 coating on the outermost surface (Gorilla Glass, manufactured by Corning Incorporated).
• the glass having the cured coating formed thereon was evaluated for its slipperiness by the following method: The coefficient of dynamic friction of the glass having the cured coating formed thereon against a nonwoven fabric was measured in accordance with ASTM D1894 using a surface property tester TYPE: 14FW (manufactured by Shinto Scientific Co., Ltd.) under conditions of a load of 100 gf and a tensile speed of 500 mm/min. The results (coefficient of dynamic friction) are shown in Table 1. [Slipperiness evaluation conditions] Load: 100gf Stroke: 100mm Contact area: 1 x 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)
• the cured coatings of the surface treatment agents of Examples 1 to 23 exhibited water repellency due to the presence of two hydrocarbon chains of a specified carbon number at the molecular chain end of the compound used, and also improved molecular mobility, resulting in good slipperiness, ease of wiping off dirt, and abrasion resistance.
• the cured coating of the surface treatment agent of Comparative Example 1 exhibited water repellency due to the presence of one hydrocarbon chain in the compound used, but was poor in ease of wiping off dirt and abrasion resistance.
• the cured coating of the surface treatment agent of Comparative Example 2 exhibited high water repellency due to the compound used having a fluorohydrocarbon chain, but was poor in durability.
• Comparative Example 3 was a glass substrate that did not use a surface treatment agent, but since it was not surface-treated, it had none of the characteristics, and the effects of the Examples could be confirmed. As described above, with the surface treatment agents of the Examples, a cured coating that achieved high levels of water repellency, slipperiness, ease of wiping off dirt, and abrasion resistance was obtained by vapor deposition coating.
• Example 24 The compound obtained in Synthesis Example 1 was dissolved in dibutyl ether to a concentration of 0.1% by mass to prepare a surface treatment agent.
• Example 25 The compound obtained in Synthesis Example 3 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.
• Example 26 The compound obtained in Synthesis Example 17 was dissolved in isooctane to a concentration of 0.1% by mass to prepare a surface treatment agent.
• Example 27 The compound obtained in Synthesis Example 22 was dissolved in 50/50 hexane/isooctane to a concentration of 0.1% by mass to prepare a surface treatment agent.
• Example 28 The compound obtained in Synthesis Example 30 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.
• the glass on which the cured coating was formed was evaluated for water repellency, slipperiness, dirt wiping ability, and abrasion resistance by the methods described below. Note that the same evaluation was carried out for Comparative Example 6, which was a glass without surface treatment, but with a 10 nm thick SiO2 coating on the outermost surface (Gorilla Glass, manufactured by Corning Incorporated).
• the contact angle (water repellency) of the cured coating with respect to water was measured using a contact angle meter Drop Master (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 ⁇ l, temperature: 25° C., relative humidity: 40%). The measurement was performed by photographing the (stable) droplet 1 second after it was dropped with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using contact angle analysis software FAMAS attached to the contact angle meter to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the ⁇ /2 method.
• the analysis conditions were as follows.
• the glass having the cured coating prepared above was evaluated for its slipperiness by the following method, which evaluates its dynamic friction coefficient against nonwoven fabric.
• the dynamic friction coefficient of the glass having the cured coating formed thereon against nonwoven fabric was measured in accordance with ASTM D1894 using a surface property measuring instrument TYPE: 14FW (manufactured by Shinto Scientific Co., Ltd.) under conditions of a load of 100 gf and a tensile speed of 500 mm/min.
• the results (dynamic friction coefficient) are shown in Table 2.
• the cured coatings of the surface treatment agents of Examples 24 to 28 exhibited water repellency due to the presence of two hydrocarbon chains of a specified carbon number at the molecular chain end of the compound used, and also exhibited good slipperiness, ease of wiping off dirt, and abrasion resistance due to improved molecular mobility.
• the cured coating of the surface treatment agent of Comparative Example 4 exhibited water repellency due to the presence of one hydrocarbon chain in the compound used, but was poor in ease of wiping off dirt and abrasion resistance.
• the cured coating of the surface treatment agent of Comparative Example 5 exhibited high water repellency due to the compound used having a fluorohydrocarbon chain, but was poor in durability.
• Comparative Example 6 was a glass substrate that did not use a surface treatment agent, but since it was not surface-treated, it did not have any characteristics, and the effects of the Examples could be confirmed. As described above, with the surface treatment agents of the Examples, a cured coating that achieved high levels of water repellency, slipperiness, ease of wiping off dirt, and abrasion resistance could be obtained even with spray coating, which is an example of wet coating.
• Example 29 The compound obtained in Synthesis Example 39 was dissolved in ethylcyclohexane to a concentration of 10 mass % to prepare a surface treatment agent.
• Example 31 The compound obtained in Synthesis Example 42 was dissolved in toluene to a concentration of 20 mass % to prepare a surface treatment agent.
• Example 32 The compound obtained in Synthesis Example 43 was dissolved in butyl acetate to a concentration of 20 mass % to prepare a surface treatment agent.
• the glass on which the cured coating was formed was evaluated for water repellency, slipperiness, dirt wiping ability, and abrasion resistance by the methods described below. Note that the same evaluation was carried out for Comparative Example 3, which was a glass without surface treatment, but with a 10 nm thick SiO2 coating on the outermost surface (Gorilla Glass, manufactured by Corning Incorporated).
• the contact angle (water repellency) of the cured coating with respect to water was measured using a contact angle meter Drop Master (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 ⁇ l, temperature: 25° C., relative humidity: 40%). The measurement was performed by photographing the (stable) droplet 1 second after it was dropped with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using contact angle analysis software FAMAS attached to the contact angle meter to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the ⁇ /2 method.
• the analysis conditions were as follows.
• the cured coatings of the surface treatment agents of Examples 29 to 32 exhibited water repellency due to the presence of two hydrocarbon chains with a specified number of carbon atoms at the molecular chain terminals of the compounds used, and the improved molecular mobility resulted in good slipperiness, ease of wiping off dirt, and abrasion resistance.
• good chemical resistance means an immersion time in the above-mentioned chemical resistance test at which the water contact angle of the formed cured coating becomes less than 80° is 2 hours or more, more preferably 4 hours or more, and most preferably 5 hours or more.
• the cured coating of the surface treatment agent of the examples exhibited water repellency and good chemical resistance due to the presence of two hydrocarbon chains with a specified carbon number at the molecular chain end of the compound used.
• R 1 is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may contain at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, and may be linear, branched, or cyclic, or a combination thereof;
• R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms;
• R 1 or -Y-A U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group,
• V is a single bond or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and
• a surface treatment agent to form a cured coating film having chemical resistance.
• Chemical resistance test conditions Chemical: 30% by weight aqueous sodium hydroxide solution Temperature: 55°C Measure the immersion time until the water contact angle becomes less than 80°.
• the hydrocarbon terminal group-containing compound is represented by the following general formula (Z):
• R 1 ' is a monovalent hydrocarbon group having 13 to 32 carbon atoms which may be linear, branched, or cyclic, or a combination thereof
• R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms, R 1 , or -Y-A
• U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group
• V is a single bond, or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom
• Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to oc

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